WO2016145300A1 - Chemical sensor - Google Patents

Chemical sensor Download PDF

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Publication number
WO2016145300A1
WO2016145300A1 PCT/US2016/021988 US2016021988W WO2016145300A1 WO 2016145300 A1 WO2016145300 A1 WO 2016145300A1 US 2016021988 W US2016021988 W US 2016021988W WO 2016145300 A1 WO2016145300 A1 WO 2016145300A1
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WO
WIPO (PCT)
Prior art keywords
chemical sensor
chemical
sensor chip
nanoparticles
chemicals
Prior art date
Application number
PCT/US2016/021988
Other languages
French (fr)
Inventor
Sundip R. DOSHI
Heng Chia SU
Albert Chien-En CHEN
Dale Hutchins
Original Assignee
Nano Engineered Applications, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nano Engineered Applications, Inc. filed Critical Nano Engineered Applications, Inc.
Publication of WO2016145300A1 publication Critical patent/WO2016145300A1/en

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B21/00Alarms responsive to a single specified undesired or abnormal condition and not otherwise provided for
    • G08B21/02Alarms for ensuring the safety of persons
    • G08B21/12Alarms for ensuring the safety of persons responsive to undesired emission of substances, e.g. pollution alarms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0031General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • G01N33/0034General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array comprising neural networks or related mathematical techniques
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0073Control unit therefor
    • G01N33/0075Control unit therefor for multiple spatially distributed sensors, e.g. for environmental monitoring
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B31/00Predictive alarm systems characterised by extrapolation or other computation using updated historic data

Definitions

  • the invention generally relates to chemical sensors and, more particularly, to nanomaterial-based chemical sensors, including methods for making, testing and using such sensors.
  • Chemical sensors and devices have wide range of applications, including environmental monitoring, medical monitoring and disease detection, detection of harmful chemicals for homeland security and military applications, industrial health and safety and food and agriculture safety.
  • the present invention provides a chemical sensor system including a small and lightweight nanomaterial-based sensor device.
  • the sensor device provides detection and monitoring of multiple chemicals simultaneously as well as fast response time and high sensitivity, e.g. parts-per-billion (ppb).
  • Non-limiting examples of detected chemicals include, but are not limited to, airborne gases, volatile organic compounds (VOCs), airborne toxins, biomolecules and/or molds.
  • the invention provides a chemical sensor system comprising a nanomaterial based chemical sensor chip for detection of chemicals in gas, vapor, liquid and aerosol phase. Additionally the invention provides methods of fabricating the chemical sensor chip and sensing with the chip.
  • FIG. 1 is a schematic diagram showing certain embodiments of a chemical sensor system 100 of the invention comprising a chemical sensor device (10) accompanying software application (20) which may facilitate connections to the cloud system (30).
  • FIG. 2 A shows an embodiment of chemical sensor chips 11 fabricated on a substrate 110 in a low density arrangement.
  • FIG. 2B shows an embodiment of chemical sensor chips 11 fabricated on a substrate 110 in a high density arrangement.
  • FIG. 3 is a schematic a of a chemical sensor chip 11 of the invention comprising ten chemical sensor channels, on-chip reference electrodes and on-chip counter electrodes.
  • FIG. 4 is a schematic of a chemical sensor chip 11 of the invention comprising two chemical sensor channels.
  • FIG. 5 is a close-up schematic of a single chemical sensor channel 210.
  • FIG. 6A is a side-view schematic of a nanomaterial network on a single layer substrate.
  • the nanomaterial network is aligned between electrodes.
  • FIG. 6B is a side-view schematic of a nanomaterial network on a two-layer substrate.
  • the nanomaterial network is aligned between electrodes.
  • FIG. 6C is a top-view schematic a nanomaterial network.
  • nanomaterial network is aligned between electrodes.
  • FIG. 7A is a side-view schematic of a nanomaterial network functionalized with nanoparticles.
  • FIG. 7B is a top-view schematic of a nanomaterial network functionalized with nanoparticles.
  • FIG. 8 is a schematic showing the components of a Custom Alignment and Electrochemical Deposition System (CAES) 800 to fabricate chemical sensor chips.
  • CAES Custom Alignment and Electrochemical Deposition System
  • FIG. 9 is a schematic demonstrating the positioning of deposition wells and primary sensor chips in the CAES 800.
  • FIG. 1 OA is a schematic illustrating the deposition well in the CAES 800.
  • FIG. 10B is a top-view schematic sketch of the deposition well in the CAES 800.
  • FIG. 11 is a schematic showing the components of a Customized Sensing System (CSS) 1100 to perform gas sensing in a laboratory environment.
  • SCS Customized Sensing System
  • FIG. 12 is a schematic showing a sensing chamber of the CSS system. DETAILED DESCRIPTION
  • the present invention provides a nanomaterial-based chemical sensor system and methods for detection of chemicals with the chemical sensor system.
  • the chemical sensor system and its various embodiments of the present invention may be used for identification of chemicals and determination of chemical concentrations.
  • the chemicals may be, but are not limited to, airborne chemicals, vehicle-borne chemicals, VOCs, toxins, biomolecules, harmful or dangerous materials including explosives and chemical warfare agents, biological warfare agents, pharmaceutical substances including prescription drugs and over-the-counter drugs and/or substances of abuse.
  • biomolecules may include, but are not limited to, proteins, ligands, lipids, fats, nucleic acids, and/or antigens.
  • the chemical sensor system may be used for detection and monitoring of chemicals in a variety of fluids such as gas, vapor, liquid and aerosol.
  • a "fluid” is defined as a “substance that deforms (flows) under applied stress.
  • fluids include gases, vapors, liquids and aerosols.
  • the sensor system may detect chemicals at parts- per-million (ppm) concentration, parts-per-billion (ppb) concentration, or lower.
  • the chemical sensor system may comprise a plurality of features that serve to increase the number of chemicals detected and monitored simultaneously with fast response and/or high sensitivity.
  • the chemical sensor system of the invention comprises a nanomaterial- based chemical sensor device having an electronic detection mechanism.
  • the nanomaterial-based sensor may comprise one or multiple chemical sensor chips. These chemical sensor chips comprise a conductive nanomaterial network which may be functionalized with nanoparticles capable of interacting with chemicals to be detected. While not wishing to be bound by theory, it is believed that the
  • nanoparticles interact with chemicals adsorbed to the surface of the nanomaterial network.
  • the resultant interaction is observed as a change in a measurable electrical characteristic of the nanomaterial network. This allows detection of chemicals by measuring the electrical characteristics of the conductive nanomaterial network.
  • An electrical property measurement provides for real-time detection of the adsorbed chemicals.
  • Functionalization of the nanomaterial network with nanoparticles may provide selective and sensitive detection of chemicals.
  • a chemical sensor chip can identify and detect many chemicals. Additionally, by selection from a variety of nanoparticles, one sensor chip can be manufactured to accommodate different applications.
  • the chemical sensor system of the invention may be configured as to be portable, wearable, stationary, wireless and/or battery-supported.
  • the chemical sensor system may be configured to report detection and monitoring results and/or information as instant readouts, graphs or other visual manifestations.
  • the chemical sensor system of the invention may be used in wide variety of fields.
  • Non-limiting examples of the uses include detection and monitoring of indoor or outdoor air quality, monitoring toxic chemical levels in an industrial plant and monitoring and detection of health conditions by detecting VOCs in patient's breath.
  • the chemical sensor system may be employed as a stationary or as a portable sensor. Further non-limiting examples of use include monitoring VOC levels in crops for determination of a crop spoilage, detecting chemical leakages during industrial processes and detecting vapor traces of substances of abuse (e.g. drugs) at the state borders for the homeland security.
  • the chemical sensor may be employed as a wearable sensor for monitoring chemical levels surrounding the user. The user may be for example a person monitoring air pollutant levels for a health purpose, or a soldier monitoring presence of chemical warfare agents in a field setting.
  • the chemical sensor may be embedded in mobile vehicles such as drones, planes, automobiles, trains, and boats/ships for detecting specific application- based chemicals.
  • the current invention embraces methods for detection of chemicals with a chemical sensor system.
  • the methods comprise detection of chemicals from fluids.
  • Certain embodiments of the chemical sensor system may provide information to a user at a particular instance.
  • the user may command the system to gather data, report data or share data.
  • the user may trigger the system with a smart device via a software application.
  • Certain embodiments of the chemical sensor system may provide passive detection or monitoring of chemical levels in fluids.
  • the gathered information may be provided continuously or the user may obtain the data gathered continuously over a period of time at a particular instance.
  • Certain embodiments of the chemical system may provide detection or monitoring of chemicals in samples that are collected and then introduced to the sensor system.
  • the present invention describes methods of manufacturing the system, device and chips described here.
  • the methods include an alignment of suitable nanomaterials to form a nanomaterial network and functionalization of the network with nanoparticles used for selective and sensitive detection of different chemicals.
  • the described methods include features that may be used to control parameters of the sensor chips. Such parameters may include, but are not limited to, density of the nanomaterial in a network, and size, density and geometry of the nanoparticles.
  • the present invention also describes methods of manufacturing the system, device and chips described here and means of testing chemical sensing in an automated setting or environment.
  • Chemical sensor system [00040] According to the present invention, a chemical sensor system is provided.
  • the chemical sensor system 100 comprises a chemical sensor device 10, a software application 20 and a cloud system 30.
  • the cloud system 30 comprises one or more remote servers, a software, network protocols for communication and/or storing data to the cloud server.
  • the software application may be housed in the chemical sensor device or externally.
  • the software application may be a mobile application.
  • Mobile application refers to software that may be run on wireless computing devices and/or smart devices.
  • the software may be configured to run on a smartphone, a smartwatch, a personal computer (PC), a tablet computer, a cloud system 30, local area networks (LAN), wide area networks (WAN), television, hardware devices, hardware media, embedded systems and/or in any smart device.
  • the software application may be used for operations such as, but not limited to activating the sensor device, receiving data from the sensor device, analyzing data, reporting data and storing data.
  • the software application 20 may store, analyze and share data at the device level, localized level and/or at a cloud system 30 level.
  • the software application may communicate with the cloud system 30 via the internet.
  • the software application may be operated through an internet browser.
  • the software application may also include machine learning capabilities for predictive analysis and reporting.
  • a user may enter data to the software.
  • the data may include, but is not limited to, data related to environmental conditions, health conditions, geographical information and/or other data.
  • the software application may communicate with the chemical sensor device via a wireless or a wired transmitter 13 protocols.
  • the software application may be used for controlling operations of the chemical sensor system and performing operations by commands. Commands may be a series of commands specifying each individual action the sensor device makes or a command may run a function programmed into the sensor device firmware.
  • the software application may be used activate the sensor device automatically or a user can activate the sensor device to run an on-demand command. As an example, a user can set software application to run instant measurements, to run measurements continuously or over period of time and/or to give an alert when sensor has encountered a specific observation.
  • the application software may communicate with a pattern recognition algorithm for identification and analysis of chemical levels. The algorithm may be run either at the sensor device level, at the embedded systems level, at the software application level or at the cloud system level.
  • the application software may be used for reporting data as readouts, graphs, maps or other graphical or numerical manifestations.
  • the chemical sensor system 100 communicates with a cloud system 30.
  • the software may pass the data across a network using standard communication protocols (e.g., the internet protocol), custom communication protocols and/or any combination of these protocols.
  • the communication protocols used may be protocols defined by the wired or wireless communication standards from Institute of Electrical and Electronics Engineers Standards Association (IEEE- SA).
  • IEEE- SA Institute of Electrical and Electronics Engineers Standards Association
  • the data is passed to a cloud, which is a server, or a group of servers located remotely from the chemical sensor system.
  • the cloud may receive data, store data, process data, distribute data and/or share data.
  • the cloud system 30 may communicate with one or more chemical sensor systems 100.
  • the cloud system 30 may support receiving, storing, processing, distributing and/or sharing data with other external systems. These external systems may include commercial and consumer sources, and may be related to e.g. consumer health and/or environmental data.
  • the data may be in the form of a hard copy or a soft copy.
  • the data at the cloud system 30 may be accessed by the software application 20 of the chemical sensor system, or by other software applications such as internet browser based applications, smart device based application and/or other interfaces.
  • the data may be accessed by a user, a network of users or by third parties.
  • the cloud system 30 may provide automated alerts and/or predictive alerts based on the received and processed data.
  • Cloud- based systems for receiving, processing, storing, distributing and sharing data are discussed in Jeong et al. (US 2013/0160006), Chen et al. (US 2013/0282227), Williams (US 2013/0160006), Chen et al. (US 2013/0282227), Williams (US 2013/01
  • the user may view, store, distribute and/or share data.
  • the data may be stored in the cloud to a specific user account managed by the software application.
  • the software application may be used to share and view data among users.
  • the software application data may be shared to other users including, but not limited to, corporations, organizations, governments, and the general public.
  • the users may customize the received and shared information.
  • the users may enter health profiles to the software application and gain personalized alerts and/or predictive alerts.
  • Certain embodiments of the chemical sensor system 100 may include multiple sensor devices 10, each with the ability to detect specific chemicals and collect data, process data and communicate data with each other within the sensor network or with a centralized unit referred to as a wireless network sensor node.
  • Certain embodiments of the chemical sensor system 100 may be embedded in consumer and/or commercial electronic devices and/or other devices to support chemical sensing functionality.
  • Such devices may be, but are not limited to, cell phones, smartphones, smartwatches, tablet computers, laptop computers, personal computers, televisions, cameras, wearable technologies (e.g. health monitors, smartwatches, headphones), self-contained stationary devices, home appliances (e.g. coffee makers, air humidifiers, air purifiers, ranges, refrigerators etc.), lighting systems and devices, security devices and/or other devices.
  • wearable technologies e.g. health monitors, smartwatches, headphones
  • self-contained stationary devices e.g. coffee makers, air humidifiers, air purifiers, ranges, refrigerators etc.
  • lighting systems and devices e.g. coffee makers, air humidifiers, air purifiers, ranges, refrigerators etc.
  • the chemical sensor device 10 comprises one or more chemical sensor chips 11, a sensor controller 12, a wireless or a wired transmitter 13, a port 16, a power source 15, a pattern recognition module 14 and a housing 17.
  • the chemical sensor device 10 may be of different sizes and shapes.
  • Chemical sensor device may be a sphere, a cube, a cuboid, a cone, a hemisphere, a cylinder, a tetrahedron, an octahedron, a pyramid or a prism.
  • the size of the chemical sensor device may range from 0.5 cm 3 to 15,000 cm 3 : including, but not limited to, 0.5, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000, 12,000, 12,500 and/or 15,000 cm 3 .
  • the dimensions of a cuboid shaped chemical sensor device may be 1 cm x 1 cm x 0.5 cm.
  • the dimensions of a cubical chemical sensor device may be 2.5 cm x 2.5 cm x 2.5 cm.
  • the chemical sensor chip/chips 11 may be operably connected to a printed circuit board (PCB) through an industrial wire bonding or other connection process. Additionally, the sensor chip/chips 11 may be enclosed and protected by an integrated circuit packaging process. The sensor chip/chips 11 may be operably connected to the sensor controller unit 12 of the device. In some embodiments of the invention, the chemical sensor chip/chips 11 may be modular or replaceable, capable of being swapped for a separate or additional sensor chip. The number of chemicals detected can be increased by using one chemical sensor device having a plurality of sensor chips 11 comprising
  • the detection event may be a measurable change in an electrical characteristic of the sensor chips 11.
  • the change in electrical characteristics may be read and processed by the sensor controller unit 12.
  • the sensor controller unit 12 comprises of electronic components for reading and processing amplitude and modulation data of electrical changes occurring in the circuit.
  • modulation refers to an increase or a decrease in an electrical characteristic.
  • the components of the sensor controller unit may include, but are not limited to, a digital potentiometer or a rheostat, a microcontroller unit (MCU), analog-to-digital converters (ADC), multiplexers, edge connectors, voltage regulators, wires, resistors, capacitors, inductors, a ferrite bead, a Li-ion battery charger integrated circuit (IC), a temperature sensor and/or a humidity sensor.
  • MCU microcontroller unit
  • ADC analog-to-digital converters
  • IC Li-ion battery charger integrated circuit
  • IC temperature sensor and/or a humidity sensor.
  • the sensor controller unit 12 may include optional components such as, but not limited to, a gas filter, ultraviolet (UV) light-emitting diodes (LEDs), a gas sensing chamber, pumps, valves, a barometer, a heating element, buttons, an accelerometer, a gyroscope, an inertial measurement unit (IMU), a heartrate sensor, a liquid-crystal display (LCD), an UV index sensor and/or a global positioning system (GPS).
  • UV ultraviolet
  • LEDs ultraviolet light-emitting diodes
  • IMU inertial measurement unit
  • LCD liquid-crystal display
  • UV index sensor and/or a global positioning system
  • GPS global positioning system
  • Temperature and humidity sensors are included to account for variables that are encountered in the real world to compensate for data results from the laboratory, although those will be simulated as well.
  • Optional sensors such as an accelerometer, a heartrate sensor, an inertial measurement unit and an UV index sensor may further be incorporated to provide a user information regarding surrounding conditions.
  • a global positioning system (GPS) transmitter may be included for recording information regarding location and time of the detection event.
  • certain embodiments of the sensor controller unit 12 may include components that may alert a user. Such components may include, but are not limited to, a vibration motor and/or a speaker that may be a vocal or a tonal speaker.
  • the sensor controller unit 12 also includes firmware for the MCU to control various functions of the sensor controller unit.
  • the firmware may read the temperature and humidity sensors and operate other hardware components such as valves, pumps, LEDs, multiplexers, potentiometers and/or a UV index sensor.
  • Firmware may have low level software specific to the MCU that controls hardware components that the end user does not directly interface with.
  • the amplitude and modulation of the circuit comprising chemical sensor chip 11 is read by the sensor controller.
  • an input voltage Vin is applied and controlled by means of a voltage regulator (VRM).
  • VRM voltage regulator
  • the resolution may be set by adjusting the voltage.
  • a MCU controls the chemical sensor reading.
  • the initial resistance R po t is adjusted to match the resistance of the sensor to provide a maximum modulation measurable with a lower bit ADC.
  • Vout is read by ADC.
  • the resistance of the chemical sensor chip R se nsor can be calculated from the equation.
  • the electrical characteristics data read and processed by the sensor controller unit 12 may be transmitted via wireless and/or wired transmitter 13 to the software application 20.
  • the wired transmitter could be a standard serial port RS232, a Universal Serial Bus (USB), an Ethernet, a universal asynchronous receiver/transmitter (USART), a Serial Peripheral Interface (SPI) and an Inter-Integrated Circuit (I 2 C).
  • a stationary sensor device detecting hazardous gas at a manufacturing facility could be connected to a personal computer using a USB, a RS232 or an Ethernet connection.
  • the wireless transmitter 13 could be a short distance or a localized transmitter, such as a
  • the short distance transmitter may be implemented in a wearable sensor device when a user is located and reads the results in near proximity to the sensor.
  • the WI-FI (R) transmitter may be implemented in a chemical sensor device detecting or monitoring chemical levels in specific locations at a process factory and reporting results to a worker inside the factory.
  • Certain embodiments of the chemical sensor system 100 may include an active pump to provide regulated air flow exposure to the chemical sensor chip and/or an additional enclosed chamber to provide more controlled conditions.
  • the chemical sensor device 10 may comprise a pattern recognition module 14.
  • the pattern recognition module may be housed internally or externally to the sensor device 10.
  • the pattern recognition module may comprise an MCU, an integrated hardware component such as digital signal processor (DSP) or an application specific integrated circuit (ASIC), or a full system on chip (SOC).
  • DSP digital signal processor
  • ASIC application specific integrated circuit
  • SOC full system on chip
  • the pattern recognition module may be used to run one or more partem recognition algorithm formulas for analyzing the data read from chemical sensor chip. When the sensor device is exposed to a chemical, the partem recognition algorithm analyzes the electrical properties from the chemical sensor chip/chips to determine the identification and concentration of the chemical being detected.
  • the pattern recognition algorithm may be run at the sensor device level; within the partem recognition module 14; at an embedded systems level; at a software application level and/or at a cloud system 30 level.
  • the pattern recognition algorithm may identify each of the chemicals and their concentrations.
  • the chemical sensor device is powered by a power source 15 that may be any suitable power source.
  • the power source may be a battery.
  • the battery may be a rechargeable battery together with a battery charger integrated circuit.
  • the battery may be charged with a cable in connection with a port 16.
  • the port may be a USB port.
  • the battery may be a non-rechargeable, disposable battery. Batteries useful in the present invention may have different shapes, sizes, weights and properties including, but not limited to, power and lifetime.
  • the power source may be directly connected to other external power source such as an alternating current (AC) power socket.
  • AC alternating current
  • the chemical sensor device 10 may be enclosed within a housing 17.
  • the housing may have different shapes, sizes, thicknesses and weight.
  • the housing may be made of different materials and have different look and feel.
  • the housing may be made from plastic, composites, polymers, metals, ceramics and the like. The configuration of the embodiments inside the sensor device may differ, while still remaining functionally the same.
  • the chemical sensor device 10 may be wearable by a user.
  • the chemical sensor device may be incorporated into an article of clothing such as, but not limited to, a shirt, a coat, a belt, a shoe, a boot, a pant, and/or a hat or into a protective gear such as, but not limited to, a helmet, a glove, a mask a hazardous material (haz-mat) suit, or an apron.
  • the chemical sensor device may be incorporated into an accessory such as, but not limited to, a smartwatch, a bracelet, a ring, any jewelry, a pendant, an activity tracker or a wristband. Certain embodiments of a chemical sensor device 10 may be portable.
  • the chemical sensor device may be a small, lightweight handheld device allowing the user to be mobile.
  • the chemical sensor device 10 may be stationary.
  • the chemical sensor device may be installed at a location of interest.
  • the sensor device may be attached to a vehicle, a drone or a robot to detect airborne chemicals for purpose of air quality monitoring, airborne toxins, chemical and biological warfare agents, and/or estimating the performance of the vehicle.
  • the chemical sensor device 10 may be incorporated into other devices and/or systems such as, but not limited to, smart watches, health and fitness monitors, activity trackers, domestic appliances, home automation systems, air purifying systems, product manufacturing line systems, embedded systems, and/or other suitable devices or systems.
  • detection is passive.
  • the sensor device detects one or more fluids in near proximity to the sensor.
  • a user can have a wearable sensor that detects and monitors chemical levels from the surrounding air.
  • the user of such a wearable device may an asthma patient monitoring air quality, a soldier monitoring a threat of chemical warfare agents or an industrial worker monitoring chemical levels.
  • the sensor could be a stationary sensor attached to a wall in an office, or in proximity to a process line in industrial plant to, for example, monitor chemical levels in a particular location.
  • the detection is active.
  • the chemical sensor device 10 may have a sensing chamber where a volume of a sample fluid is actively moved through the device to be measured and analyzed.
  • a tube connected to a drone may actively draw gases from an agriculture site into a sensing chamber of the chemical sensor device 10 where the gases are exposed to the sensor chip/chips to be analyzed and chemicals measured for detection of crop spoilage, infestation or other metric.
  • FIG. 2-7 show embodiments of a chemical sensor chip 11 generally.
  • FIG. 2 A and FIG. 2B illustrate sensor chips 11 fabricated on a substrate 110 which may be made of a metallic, a semiconducting or a non-conductive material or other appropriate material known to those skilled in the art.
  • the substrate 110 may be rigid or flexible.
  • the substrate 110 material may comprise silicon, silicon oxide, aluminum oxide, hafnium oxide, plastic, paper and/or certain cloth or fabric materials.
  • the substrate may comprise of one, two or three layers of material. The material layers may be the same or different.
  • the substrate 110 may be a two layer substrate of silicon wafer with a passive silicon dioxide (SiC ) layer on top.
  • SiC passive silicon dioxide
  • the substrate 110 may be of any shape such as, but not limited to, round, rectangular, square or elliptical.
  • the substrate 110 may have different thicknesses and different sizes.
  • it may have a diameter from 1-18", including, but not limited to, 1", 2", 4", 6", 8", 10", 12", 14", 16" and/or 18", see FIG. 2A, element "A".
  • round the substrate 110 has a diameter A of 6".
  • the number of chemical sensor chips 11 fabricated on, or affixed to, the substrate 110 can range from 100 to 25, 000;
  • the substrate 110 may have 144 chemical sensor chips 11.
  • the substrate 110 may have 2,506 chemical sensor chips 11.
  • the substrate may have 4,156 chemical sensor chips. The substrate 110 can be cut into smaller pieces before or after fabrication, that have one or more chemical sensor chips 11.
  • FIG. 2B shows a source electrode 120 and a drain electrodes which are in connection with chemical sensor chips 11.
  • the source electrode 120 and the drain electrode 130 may be used for electrochemical deposition processes and/or for any other electrodeposition processes and/or for alignment of nanomaterials and/or connecting the chip to an electric circuit.
  • Certain embodiments of the chemical sensor chip 11 may comprise a heating element.
  • the chemical sensor chip 11 comprises chemical sensor channels 210.
  • the number of chemical sensor channels 210 may range from 1 to 100; including, but not limited to, 2, 6, 10, 24, 36, 48, 60, 72, 84, 96, 100 and/or any single unit value between 1 and 100.
  • a detailed schematic of a sensor chip 11 comprising ten chemical sensor channels 210 is shown in FIG. 3.
  • the chemical sensor chip 11 of the invention may have different sizes described by distances B and H.
  • the distances B and H of the sensor chip 11 may independently range from 5.000 mm to 10.000 mm; including, but not limited to, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 2.5, 4.0, 4.25, 4.5, 4.75, 5.0, 7.5,10.0, 12.5, 15.0, 17.5 and or 20.0 mm.
  • the distance B is about 5.0 mm and the distance H is about 10.0 mm.
  • the source electrode 120 and a drain electrode 130 are also shown. Ends or termini of the source and drain electrodes may have pads that are be used for connecting the electrodes to a circuit.
  • the electrode pad size is described by the distances F and G, shown in the FIG. 3. The distances F and G can range
  • the distance F is about 0.5 mm and the distance G is about 0.24 mm.
  • the distance I between the central axis of drain electrode 120 and the source electrode 130 can range from 0.2 mm to 2.0 mm including, but not limited to, about 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 1.8, 1.9 and/or about 2.0 mm. In some embodiments the distance I is about 0.75 mm.
  • the electrodes form a patterned structure referred to as a chemical sensor channel 210.
  • the distance between the central axes of the chemical sensor channels is described by distance C which can range from 1.0 mm to 5.0 mm; including, but not limited to, about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 1.8, 1.9, 2.0, 2.1, 2.2, 2.25, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 3.5, 4.0, 4.5 and/or about 5.0 mm. In some embodiments the distance C is about 1.75 mm.
  • the chemical sensor chip 11 may also comprise one or more on-chip reference electrodes 230 and one or more on-chip counter electrodes 220.
  • the distance D between the on-chip reference electrode 230 and the on-chip counter electrode 220 can range from 0.20 mm to 0.40; including but not limited to about 0.20, 0.21, 0.212, 0.213, 0.214, 0.215, 0.216, 0.217, 0.218, 0.219, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39 and/or about 0.4 mm. In some embodiments the distance D is about 0.218 mm.
  • the size of a sensor channel 210 described by the distances E and J can range independently from 0.1 mm to 0.4 mm; including, but not limited to about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 2.0, 2.1, 0.218, 2.2, 2.25, 2.3, 2.4,
  • the distance E is about 0.2 mm and distance J is about 0.218 mm.
  • FIG. 4 A detailed schematic of a sensor chip 11 comprising two chemical sensor channels 210 is shown in FIG. 4.
  • the sensor chip 11 configuration with two chemical sensor channels 210 may have different sizes described by distances H and B.
  • the distances H and B of the configuration may independently range from 0.1 mm to 2.5 mm; including, but not limited to, about 0.1,0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25 and/or about 2.5 mm.
  • the distance H is about 1.0 mm and the distance B is about 2.0 mm.
  • the electrode pad size is described by the distances F and G.
  • the distances F and G can range independently from about 0.1 mm to 1.0 mm; including, but not limited to, about 0.1, 0.15, 0.2, 0.24, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9 and/or about 1.000.
  • the distance F is about 0.5 mm and the distance G is about 0.25 mm.
  • the distance between the central axes of the chemical sensor channels is described by distance C.
  • the distance C can range from 0.1 mm to 0.32 mm; including, but not limited to, about 0.1, 0.12, 0.2, 0.22, 0.3 and/or about 0.32 mm. In some embodiments the distance C is about 0.22 mm.
  • the size of a sensor channel 210 described by the distances E and J can range independently from 0.1 mm to 0.4 mm; including, but not limited to, about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5,
  • the distance E is about 0.2 mm and distance J is about 0.218 mm.
  • the distance between the central axis or point of the source electrode 120 and drain electrode 130 is described by distance I.
  • the distance I can range from 0.1 mm to 0.5 mm; including, but not limited to, about 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 and/or about 0.5 mm. In some embodiments the distance I is about 0.25 mm.
  • Methods of a standard lift-off photolithography process and a standard thin film coating process such as an e-beam evaporation may be used for fabrication of the source electrode 120, the drain electrode 130, the chemical sensor chips 210, the on- chip reference electrodes 230 and the on-chip counter electrodes 220.
  • the material used for the source electrode 120 and drain electrode 130 electrode may be a metal such as, but not limited to, titanium (Ti), platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), chromium (Cr) and/or other similar material.
  • the electrodes may be fabricated from one metal or from a combination of two or more metals.
  • the electrode thicknesses may range from 10 nm to 500 nm, including but not limited to: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 275, 300, 350, 400, 450 and/or 500 nm.
  • the electrodes have thickness of 215 nm and are fabricated from a 25 nm layer of titanium and a 190 nm layer of platinum.
  • the electrodes have thickness of 215 nm and are fabricated from a 25 nm layer of titanium and a 190 nm layer of platinum.
  • the source electrode 120 and drain electrode 130 may be symmetric, meaning that the electrodes are fabricated from the same material.
  • the two electrodes may be asymmetric, meaning that they are independently fabricated from two different materials.
  • the on-chip counter electrode 220 may be fabricated from an inert metal such as, but not limited to, platinum.
  • the on-chip reference electrode 230 may be fabricated from silver (Ag) silver/silver chloride (Ag/AgCl), platinum, graphite or other suitable material. Reference and counter electrodes may be used during an electrochemical deposition. In some embodiments the on-chip counter electrode 220 and the on-chip reference electrodes 230 are optionally present. These electrodes can be applied externally.
  • the sensor channel 210 is formed from the source electrode 120 and drain electrode 130 deposited into a pattern with a narrow gap between them.
  • the gap is described by distance R which can range from 0.002 to 0.01 mm; including, but not limited to about 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, and/or about 0.010 mm. In some embodiments the distance R is about 0.003 mm.
  • FIG. 6A important to the function of the chemical sensor channel 210 of the present invention is the narrow gap which may be used for positioning a nanomaterial network formed from a conducting nanomaterial 510.
  • the gap is described as element "R" in FIG. 6A and FIG. 6C.
  • the gap defines the width of the nanomaterial network comprising the nanomaterial 510 non-functionalized or functionahzed with nanoparticles.
  • Nanomaterial-based sensors in the art are taught by Myung et al. (US8034222 and US2012/0080319) and Deshusses et al. (US8683672), the contents of which are incorporated herein by reference in their entirety. Such fabrication methods and materials may be used in the present invention.
  • the gap functionahzed with a nanomaterial network is shown in FIG. 6A and FIG. 6B from a side-view and in FIG. 6C from a top view.
  • the substrate 110 may consist one layer, two layer or three layers of material.
  • a substrate with one layer is shown in FIG. 6A and a substrate with two layers is shown in FIG. 6B.
  • the nanomaterial 510 is aligned between the source electrode 120 and drain electrode 130.
  • the nanomaterial 510 may be a one-dimensional
  • nanostructured material One-dimensional here refers to a structure with high length to width ratio, such as line, tube and/or wire. In certain embodiments the
  • nanomaterial 510 may be, but is not limited to, a nanotube, a nanowire, a nanoribbon, other nanomaterial and/or combinations thereof.
  • the nanowires and nanotubes may have diameters ranging from 0.5 to 350 nm; including, but not limited to, about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325 and/or about 350
  • the nanoribbons may have widths ranging from 10 to 100 nm; including, but not limited to, about 10, 20, 30, 40, 50, 60, 70, 80, 90 and/or aboutlOO nm.
  • the thickness of nanoribbons can range from a one atomic layer to five atomic layers; including 1, 2, 3, 4 and 5 atomic layers.
  • the lengths of the nanomaterials 510 may range from 100 nm to 1 mm; including, but not limited to, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 ⁇ , 1.2 ⁇ , 1.4 ⁇ , 1.6 ⁇ , 1.8 ⁇ , 2.0 ⁇ , 2.2 ⁇ , 2.4 ⁇ , 2.6 ⁇ , 2.8 ⁇ , 3.0 ⁇ , 3.2 ⁇ , 3.4 ⁇ , 3.6 ⁇ , 3.8 ⁇ , 4.0 ⁇ , 4.2 ⁇ , 4.4 ⁇ , 4.6 ⁇ , 4.8 ⁇ , 5.0 ⁇ , 5.5 ⁇ , 6.0 ⁇ , 6.5 ⁇ , 7.0 ⁇ , 7.5 ⁇ , 8.0 ⁇ , 8.5 ⁇ , 9.0 ⁇ , 9.5 ⁇ , 10 ⁇ , 15 ⁇ , 20 ⁇ , 25 ⁇ , 30 ⁇ , 35 ⁇ , 40 ⁇ , 10
  • the nanomaterials 510 can be metallic and/or semiconducting and/or a combination of metallic and semiconducting.
  • the nanomaterials 510 can be made of different materials such as, but not limited to, carbon, silicon, conducting polymers, metals, metal oxides and other suitable materials.
  • the nanomaterial 510 may be single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), silicon (Si) nanowires, zinc oxide (ZnO) nanostructures, tin oxide (SnC ) nanowires, indium oxide (ImC ) nanowires, boron nitride (BN) nanotubes, carbon nitride nanotubes (CN Ts), BxC3N2 nanotube structures, tellurium (Te) nanotube and nanowire structures, Te nanotube and nanowire structures with embedded gold (Au) nanoparticles, multisegmented metal nanowires such as cobalt-gold (Co/Au) or nickel/gold (Ni/Au) structures, polyaniline (PANI) nanowires, polypyrrole (Ppy) nanowires, multis
  • the nanomaterial network is made of SWNTs.
  • the diameter of SWNTs may be about 1.4 nm and the length may range from 2 to 3 ⁇ . In some embodiments the diameter of SWNTs may be about 1.4 nm and the length may range from 2 to 10 ⁇ .
  • the nanomaterial network may be non-functionalized or functionalized with a nanoparticles 610.
  • FIG. 7A shows a side-view schematic and
  • FIG. 7B shows a top-view schematic of a section of the chemical sensor channel gap having a nanomaterial network with nanoparticles 610.
  • a nanoparticle here refers to a nanoscale material that can be of different shapes.
  • Nanoparticles 610 include, but are not limited to, metal nanoparticles, metal oxide nanoparticles, metalloid
  • metal nanoparticles may include, but are not limited to, gold (Au), palladium (Pd), platinum (Pt) and/or other metal nanoparticles.
  • Metal oxide nanoparticles may include, but are not limited to, tin oxide (SnC ) or other metal oxides such as taught by Myung et al. (US2012/0080319) and Deshusses et al. (US8683672), the contents of which are incorporated here by reference in their entirety. Such materials may be used in the present invention.
  • metalloids may include nanoparticles of tellurium or other metalloids such as those taught by Myung and Zhang
  • Macromolecules may include, but are not limited to, porphyrins, phthalocyanines and/or other macromolecules.
  • Conductive polymer nanoparticles may include, but are not limited to, doped polymer nanoparticles such as polyaniline doped with a camphor-sulfonic acid (CSA), percholate (CIO4 " ), acrylic acid (C3H4O2), tetraethylammonium
  • CSA camphor-sulfonic acid
  • CIO4 percholate
  • acrylic acid C3H4O2
  • TEAPFOS perfluorooctane sulfonate
  • Biomolecules may include, but are not limited to, antibodies, proteins and protein fragments, polynucleotides, oligonucleotide sequences, DNA aptamers, nucleic acids, lipids, glycoproteins, hormones, pheromones and/or other biomolecules such as those taught by Myung et al. (US8034222), the contents of which are incorporated here by reference in their entirety.
  • biomolecules may be used in the present invention
  • Biomolecules may be natural or synthetic.
  • nanoparticles may be a combination of two or more materials, such as, but not limited to, metal and metal-oxide nanomaterials.
  • the nanoparticles characteristic refers to a property of a material to interact with adsorbed chemicals.
  • the interaction may be a covalent or a non-covalent interaction, including ionic interaction, hydrogen interaction, van der Waals interaction, dispersion force interaction, hydrophilic-hydrophobic interaction and/or combination of these interactions.
  • the nanoparticles 610 may adsorb specifically to certain chemicals.
  • the nanoparticles 610 may have different particle and/or molecule sizes, shapes and densities.
  • the nanomaterial network may be fabricated by aligning suspended carboxylated SWNTs (SWNT-COOH) in a chemical sensor channel 210 by applying an electric field. After the alignment process an
  • the nanoparticles may be deposited as nanoparticles or as molecules.
  • Some properties of the chemical sensor chip 11 may be varied by controlling the electrochemical deposition of the nanoparticles 610.
  • the density of the nanoparticles as well as the size and/or the geometry of the nanoparticles on the surface of the nanomaterial network may be controlled by adjusting the type of the an electrolyte, the concentration of an electrolyte, and the deposition time, potential and/or charge density during the electrochemical deposition.
  • the properties of the functionalized nanomaterials may affect the sensitivity, stability and/or the selectivity.
  • the nanomaterial network may be fabricated utilizing an inkjet printing technique, array er and/or a similar process such as those taught by Stetter et al. (US8795484), the contents of which are incorporated here by reference in their entirety.
  • a chemical sensor chip 11 may have tin dioxide (SnC ) nanoparticles deposited on nanomaterials 510 making the chip sensitive towards detection of e.g. nitrogen dioxide (NC ), ammonia (NH3), carbon monoxide (CO) and certain VOCs.
  • Certain embodiments of a chemical sensor chip 11 may have phthalocyanine macromolecules as the functionalizing moiety making the chip sensitive towards detection of ozone (O3) and sulfur dioxide (SO2).
  • a plurality of chemical sensor chips 11 with nanomaterial networks and nanoparticles fabricated from different materials may be combined when incorporated in a chemical sensor device.
  • the chemical sensor chip may detect chemicals at parts-per-million (ppm) concentration, parts-per-billion (ppb) concentration, or lower.
  • the chemical sensor system may comprise a plurality of features that serve to increase sensitivity, selectivity and stability.
  • the features include, but are not limited to, the use of sensing components fabricated from a one-dimensional nanomaterial network.
  • the present invention also describes methods for detecting chemicals using the chemical sensor chip 11.
  • the detection mechanism may be a measurable change in an electrical characteristic of the nanomaterial network.
  • the detected chemicals are adsorbed onto the surface of the functionalized or non-functionalized nanomaterial network and this adsorption is the trigger for the detection.
  • the molecules interact with the functionalized nanomaterial changing a measurable electrical characteristic.
  • the amplitude and modulation of the electrical characteristics is dependent on the properties of the detected chemical such as their electron donating or electron withdrawing ability.
  • the detection event such as an increase or a decrease in resistance and rate of change is read by the sensor controller unit 12, as described above and shown in FIG. 1.
  • the observed amplitude and modulation of the change is communicated to the pattern recognition module 14.
  • the detection method of the current invention provides for low power consumption.
  • the power consumption of the detection may be 1 mW or lower.
  • Features resulting to the low power consumption include the small sensor chip size due to the nanoscale sensing materials used, efficient conductivity due to the use of nanostructures, and/or no requirement for heating of the sensing materials.
  • the methods for manufacturing sensor chips 11 may be performed by a Custom Alignment and Electrochemical Deposition System (CAES).
  • CAES Custom Alignment and Electrochemical Deposition System
  • FIG. 8 One embodiment of the CAES 800 is shown in FIG. 8.
  • CAES is an automated setup for nanomaterial alignment, electrochemical deposition and electrical characteristics measurement for the sensor chips 11 with the chemical sensor channel 210 in micrometer scale.
  • the CAES of the present invention comprises CAES enclosure 700 and external systems 720.
  • the CAES enclosure 700 may comprise one or more of an alignment and deposition area 713, a heating/cooling module 714, a nanomaterial suspension reservoir 703, a water reservoir 704, one or more electrolyte reservoirs 705, a nitrogen (N 2 ) gas connector 706, one or more waste electrolyte reservoirs 708, a waste water reservoirs 708, a nanomaterial suspension waste reservoir 707, a processed tray hopper 715, conductive pathway pins 710, deposition wells 711, a robotic arm 701, a holding tray hopper 702 and/or variety of tubing 712.
  • These components may be arranged or configured in any orientation one of the skill in the art understands how to arrange such components for optimal automation and manufactory.
  • External systems 720 may comprise, but are not limited to, one or more potentiostat 721, a source measurement unit 722, a waveform function generator 723, a temperature control unit (with power supply) 714, a mass flow controller 725 and a water circulation system 726. All aspects of the CAES and the external instruments may be controlled through a control interface 716 by customized CAES software 727 such as LABVIEW (R) Software and/or other similar software.
  • CAES software 727 such as LABVIEW (R) Software and/or other similar software.
  • FIG. 9 shows the positioning of primary sensor chips 802 on a holding tray 801.
  • the automated robotic arm 701 can seize the holding tray 801 from the holding tray hopper (not shown) and move them to the alignment and deposition area 713 and processed tray hopper (not shown).
  • the holding tray hopper and the processed tray hopper may hold one or more holding trays 801.
  • the holding tray may have one or more primary sensor chips 802.
  • the primary sensor chip 802 here refers to a chip consisting of a source electrode and a drain electrode with sensor channels but no nanomaterial network.
  • the primary sensor chip 802 may or may not have on-chip reference electrodes and on-chip counter electrodes.
  • the robotic arm 701 is also used for positioning the primary sensor chips 802 in connection with conductive pathway pins 710 and below deposition wells 711.
  • the CAES may comprise a number of deposition wells ranging from 1 to 30: including, but not limited to 1, 2, 3, 5, 7, 9, 10, 15, 20, 25, and/or 30. In some embodiments the number of deposition wells may be nine.
  • FIG. 10A and FIG. 10B present a more detailed schematic of the deposition well 711.
  • FIG. 10A is a side-view schematic of the deposition well 711 positioned above a staging platform comprising the sensor tray 801 holding a primary sensor chip 802 in connection with conductive pathway pins 710.
  • FIG. 10B shows a top-view schematic of deposition well 711.
  • the deposition well 711 comprises inlets for the water reservoir 902, the nitrogen inflow 901, the nanomaterial reservoir 903 and the electrolyte reservoirs 906.
  • the deposition well contains a counter electrode 905 and a reference electrode 904.
  • the first part of manufacturing chemical sensor chip/chips 11 involves fabricating the nanomaterial network.
  • the primary sensor chips 802 are positioned in contact with the conductive pathway pins 710 and a volume of a dispersion or a solution of a nanomaterial from a reservoir 703 is collected and deposited onto the deposition wells 711 aligned with primary sensor chips 802.
  • An electric current may be applied by an external instrument such as, but not limited to, a waveform function generator 723 for a period of time for alignment of the nanomaterial network.
  • an electrochemical deposition of nanoparticles is performed onto the nanomaterial network.
  • the electrochemical deposition is performed by using the source and drain electrodes as a working electrode together with counter and reference electrodes.
  • the source and drain electrodes act as the working electrode in the electrochemical deposition process and are positioned in contact with conductive pathway pins 710.
  • the on-chip reference electrode pads and on-chip counter electrode pads are also positioned in contact with the conductive pathway pins 710.
  • the counter electrode 905 and the reference electrode 904 are introduced as components of the CAES 800, as shown in FIG. 10A and FIG. 10B.
  • a volume of electrolyte is collected from an electrolyte reservoir 705 through tubing 712 and deposited onto deposition wells 711.
  • the CAES may comprise one or more electrolyte reservoirs and electrolyte waste reservoirs.
  • Appropriate potential and current is applied by an external instrument such as, but not limited to, a potentiostat 721 and charge is measured...
  • the particle size and the density of the functionalized nanomaterial may be controlled by the concentration of the electrolyte and/or the deposition potential, charge density and time.
  • Some electrolytes may require an elevated temperature that can be adjusted with a heating/cooling module 714 controlled by an external temperature controller 724. After deposition, the excess electrolyte is removed, and the sensor chips are rinsed with water and treated with nitrogen gas for drying.
  • a substrate may contain four or more chemical sensor chips each of which has a nanomaterial network fabricated from different nanomaterials.
  • the nanomaterial networks may further be functionalized with different nanoparticles.
  • Electronic characteristics may include, but are not limited to, conductivity, resistance, voltage, current, capacitance, inductance, and field-effect transistor (FET) properties.
  • the chemical sensor chip/chips are positioned in contact with the conductive pathway pins 710.
  • the electrical characteristics of each chemical sensor chip is measured with use of an external source measurement unit 722.
  • the measurements are recorded by the customized CAES software 727.
  • methods of gas sensing with the chemical sensor chip is also provided.
  • the methods enable an automated sensing method in a laboratory environment.
  • the gas sensing may be performed with a Custom Sensing System (CSS).
  • One embodiment of the CSS 1100 is shown in FIG. 11.
  • the CSS is an automated setup for determining the amplitude and modulation of electrical properties when chemical sensor chips 11 are exposed to gas chemicals.
  • the CSS of the invention is an automated system that may control multiple variables impacting the electrical properties of the nanomaterial network, such as a
  • the CSS comprises an analytes and cylinders unit 1010, a mass flow control (MFC) and valves unit 1020, a gas pre-treatment chamber unit 1030, sensing chamber unit 1040, an external equipment unit 1050, temperature control units 1060 and/or humidity control units 1070.
  • MFC mass flow control
  • the external equipment unit controls the operations of the CSS via a control interface 1051. All aspects of the CSS processes are controlled by a CSS customized software 1059 such as LAB VIEW (R) software and/or other similar software.
  • the analytes and gas cylinders unit 1010 contains the sources for the chemicals and gases used during sensing.
  • the analytes and gas cylinders unit 1010 may contain multiple gas cylinders 1012, a synthetic air cylinder 1013, a VOC generator 1011 controlled by an external VOC generator control unit 1053 and an ozone generator 1014 controlled by an external ozone generation control unit 1057.
  • Individual chemicals or a combination of chemicals from the analytes and cylinders unit may be used. Synthetic air here refers to purified air with zero humidity.
  • the selection of chemicals and their concentrations may be controlled by a valve control mechanism and mass flow controllers (MFCs) controlled by a mass flow control unit 1056 and a valve control unit 1052.
  • MFCs mass flow controllers
  • the chemicals from analytes and cylinders unit 1010 are directed through the mass flow control and valves unit 1020 which controls the type and amount of gas flow entering the gas pre-treatment chamber unit 1030.
  • the gas pre-treatment chamber comprises a number of gas mixture chambers 1031 and dry air chambers 1032.
  • the pre-treatment chamber is utilized to mix the selected gases and to adjust temperature and humidity conditions. The temperature and the humidity are adjusted and controlled by temperature control units 1060 and humidity control units 1070.
  • the gas pre-treatment chamber 1030 and the sensing chamber 1041 may be fabricated from material such as TEFLON (R), AFLAS (R) and/or other suitable material.
  • the number of sensing chambers can range from 1 to 30; including but not limited to 1, 2, 3, 5, 7, 9, 10, 15, 20, 25, and/or 30. In some embodiments there are three sensing chambers.
  • a schematic of the sensing chamber 1041 is shown in FIG. 12.
  • a sensor tray 1109 holding a number of chemical sensor chips 11 may be placed under the sensing chamber housing 1104 and sealed with a rubber O-ring 1101.
  • the sensor tray 1109 may be fabricated from quartz, ceramic or other suitable material.
  • the drain and source electrodes are connected via sensing chamber conductive pins 1106.
  • a gas flow from the gas pre-treatment chamber 1030 is directed to sensing chamber 1041 through gas inlet 1102 and removed through gas outlet 1108.
  • the temperature is controlled by temperature control units 1060 connected to a sensing chamber heating module 1110 which may be a peltier thermoelectric temperature module or other suitable temperature controller.
  • the humidity is controlled by control units 1070 via humidity control unit inlet 1103 and outlet 1107 paths.
  • the sensing chamber may be illuminated with LED lights 1105 controlled by an LED light control unit 1054.
  • the LED lights may be UV or tricolor RGB (red-green-blue) LEDs.
  • electrical properties such as, but not limited to, conductivity, resistance, voltage, current, capacitance, inductance, and (FET) properties, may be continuously detected using source measurement unit 1055 and CSS customized software 1059. Uses
  • the chemical sensor system may be used to detect and monitor chemicals associated with air pollution, effluents, molds, toxic spills and hazardous gases. Such chemicals can cause harm, diseases, death to humans, damage to other living organisms such as, but not limited to, food crops and natural environment.
  • the detected chemicals may be, but are not limited to, hydrogen sulfide (H2S), carbon dioxide (CO2), nitrogen oxide (NO), nitrogen dioxide (NO2), ozone O3, sulphur dioxide (SO2), carbon monoxide (CO) or any volatile organic compounds (VOCs).
  • the sensor device could be stationary for monitoring air quality in a specific location, such as in an office room, in a city center or in an industrial neighborhood.
  • the sensor system may be wearable or portable and may be applied for monitoring air quality surrounding a user.
  • Such application may have importance for users trying to avoid poor air quality spaces.
  • Such users could be for example patients with a stroke, a heart disease, a lung cancer or a chronic and acute respiratory disease, such as an asthma, chronic obstructive pulmonary disease (COPD), emphysema, etc.
  • COPD chronic obstructive pulmonary disease
  • emphysema etc.
  • the chemical sensor system may be used to detect and monitor ammonia (NH3) emissions in agriculture.
  • NH3 ammonia
  • Air quality issues have become an increasing concern for the agriculture industry. Excessive ammonia emissions, a byproduct of livestock and poultry operations, can be harmful to livestock, humans and environment as a whole.
  • a personally worn chemical sensor system may be used to alert agricultural workers and their superiors when workers are reaching their permissible exposure limit to ammonia in a given work day, as set by U. S.
  • Occupational Safety and Health Administration OSHA
  • a stationary sensor system could monitor ammonia levels within animal facilities in order to alert workers regarding risks to the welfare of the animals.
  • the chemical sensor system may be used to detect and monitor ripeness and other conditions of crops (e.g. fruits, vegetables, grains etc.) in agricultural production.
  • crops e.g. fruits, vegetables, grains etc.
  • Certain amount of carbon emitted into the atmosphere by plants is in the form of VOCs.
  • the VOC profiles emitted by plants undergo changes when conditions change.
  • the VOC profiles may be used to provide information regarding the conditions of crops such as ripeness, spoilage, plant disease and pests.
  • the chemical sensor system may be used to detect and monitor the presence of pesticides and/or pest control chemicals of crops in agricultural production.
  • pesticides and/or pest control chemicals may include insecticides, insect repellents, herbicides, fungicides, bactericides, animal repellents and/or other chemicals.
  • the chemical sensor system may be used to detect and monitor gases such as carbon dioxide (CO2 ) that are used in the process of inspection, manufacturing and sealing food items for distribution to consumers.
  • CO2 carbon dioxide
  • the chemical sensor system could be used to monitor permissible gas levels and leakages.
  • the chemical sensor system may be used to detect food spoilage. For example, spoilage of fish and seafood may be detected and monitored by sensing trimethylamine ((C]3 ⁇ 4)3N), dimethylamine ((CH3)2NH) and/or ammonia (NH3).
  • the spoilage of meat may be detected and monitored by sensing hydrogen sulfide (H2S), dimethylsulfide ((CH 3 )2S), cis-3-nonenal (H UC ⁇ ⁇ : ⁇ ⁇ ,( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ). trans-6-nonenals (( ⁇ ⁇ ⁇ ! ,( ⁇ ( ' ⁇ « l !, ; ,( ' ! !()).
  • oct-l-en-3-one C! hCMC ⁇ ⁇ ⁇ m ' M . and/or bis(methylthio) methane (CH3SCH2SCH3).
  • the chemical sensor system may be used in various settings of significance to Homeland Security, including, but not limited to, at ports of entry and in a border patrol, at governmental locations or at large event locations.
  • the chemical sensor system could be applied to monitor trafficking of substances of abuse by detecting chemical traces of these drugs.
  • the chemical sensor system could be applied to monitor the threat of chemical warfare agents, biological warfare agents or explosives.
  • Chemical warfare agents detected could include, but are not limited to, sarin, chlorine (Cb) or phosgene.
  • the chemical sensor system may be used in industrial plants and/or facilities that produce or utilize hazardous and toxic chemicals that could place their employees and local residents at risk.
  • the chemical sensor system could detect the buildup of such chemicals in order to decrease risks.
  • the emission of hydrogen sulfide from an industrial plant to the atmosphere could be monitored by the chemical sensor system to detect excessive or levels above OSHA that may be detrimental to the health of workers and/or nearby residents.
  • the industrial facilities may include manufacturing facilities, mining facilities, gas industry facilities, oil industry facilities and/or other industrial facilities.
  • the chemical sensor system may be used by military and defense.
  • the chemical sensor system may be applied to purposes of maintaining military vehicles or maintaining the welfare of soldiers.
  • U.S. Air Force uses chemical sensors for detecting jet fuel leaks
  • U.S. Navy uses chemical sensors for detection of hydrogen sulfide (H2S) gas on all surface vessels in spaces containing sanitary waste equipment.
  • chemical sensors may be embedded into military vehicles, drones, planes, etc. to detect chemical and biological warfare agents, explosives and/or toxic industrial gases.
  • the chemical sensor system may be used in water and wastewater treatment plants. Water and wastewater treatment processes often release harmful amounts of chemicals into the air.
  • the chemical sensor system may be applied to protect employees and the community from toxic and combustible gas hazards such as ammonia (NH3), carbon monoxide (CO), chlorine (Ch), hydrogen sulfide (H2S), nitrogen oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2) and others.
  • the chemical sensor system may be used to detect and monitor human phenotypic characteristics related to VOC profiles of breath, body odor and/or body fluids. Some embodiments of the chemical sensor system may be used to detect and monitor certain medical and health conditions non-invasively from breath. For example breath contains VOCs that in some cases contain early-detection biomarkers or indicators of certain medical conditions and diseases. Examples include, but are not limited to, organ failure, cancers, such as lung cancer and breast cancer and/or infections such as mouth and teeth related infections, respiratory tract infections, nasal cavity infections and/or gastrointestinal tract infections. [000109] The chemical sensor may be used for monitoring public health threats by non-invasive testing of e.g. tuberculosis.
  • the chemical sensor system may be used to detect chemicals related to bad breath (halitosis).
  • Detected chemicals may be, but are not limited to, hydrogen sulfide H2S, methyl mercaptan CH3SH and/or dimethylsulfide ((CH3)2S).
  • the chemical sensor system may be used to detect human body odors. Body odors present in humans may be influenced various health conditions and diseases, hormonal changes, nutrition, and/or substance usage such as pharmaceutical substances, illegal drugs, alcohol and/or tobacco.
  • Detected chemicals may be, but are not limited to, isovaleric acid (( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . trans-3-Methyl-2-hexenoic acid
  • pheromones such as androstetones including 5a- androst-16-en-3-one. Additionally, detection of phenotypic characteristics of body odor and/or breath may be applied to forensic analyses, lie detectors, and/or breathalyzers and/or port-mortem analyses.
  • the chemical sensor system may be used as an electronic olfaction sensor referred to an electronic nose.
  • An electronic nose imitates the human's capability to smell.
  • smells such as VOCs or chemicals with odor such as esters, are detected and identified by means of a pattern recognition algorithm.
  • Fields of applications may include industries where the smell of the product or the smell released during a process provides specific information related to the quality of the product or process.
  • Non-limiting examples of applications for electronic nose are quality control, consistency control, raw material identification, identification of raw material origin and/or storage condition monitoring in variety of industries such as, but not limited to, paint, lacquer and coatings industry, the wood industry, the chemical and solvent industry, the food and beverage industry (e.g.
  • the chemical sensor system may be applied for detection of wine ageing, monitoring the aroma, and/or classification and discrimination of wines (e.g. detection of wine origin and type of wine) and for detection of cheese ageing, type of cheese, detection of cheese origin and discrimination of cheeses.
  • the chemical sensor system may be applied in the monitoring the quality and/or consistency of brewed coffee when incorporated to coffee machines at home, at restaurants and/or at coffee shops.
  • the chemical sensor system may be applied to detect paint and lacquer odors for quality and consistency control as well as to ensure comfortable smell that pleases a user.
  • the chemical sensor system may be applied to an emergency -response system for detection of potential harmful chemicals for emergency personnel.
  • Emergency personnel such as firefighters and/or security and law enforcement personnel may be exposed to various harmful chemicals and airborne toxins such as such as hydrogen cyanide (HCN), carbon monoxide (CO), hydrocarbons, and VOCs.
  • the sensor system may alert about potential airborne toxins around the area of a fire, a spill, or a gas leak.
  • the alert may include warning of a potential risk for an explosion in a situation where a methane or a propane gas leak is present.
  • Aerosol refers to a substance consisting of gas or colloids of fine liquid droplets, e.g. fog as a natural aerosol. Aerosol here excludes solid particulate matter e.g. dust.
  • Airborne sensor refers to an instrument or system that detects chemicals in air.
  • ANN Artificial neural networks
  • Biological warfare agent is a biological substance used as a weapon.
  • Biomarker refers to a substance that can be an indicator of a disease or a health condition. Biomarker can be used for monitoring or detecting health conditions and/or diseases.
  • Biomolecule refers to a molecule present in living organisms and may be natural or synthetic. Biomolecules include e.g. proteins, ligands, polysaccharides, lipids, fats, antibodies and nucleic acids.
  • BLUETOOTH is a wireless technology standard for transferring data over short distances using short-wavelength ultra-high frequency waves.
  • BL UETOOTH SMART is a low energy technology standard for transferring data over short distances using short-wavelength ultra-high frequency waves.
  • Capacitor refers to an electric component in a circuit to store energy electrostatically.
  • Chemical is a form of matter with constant chemical composition.
  • Chemicals may include elements, molecules, compounds, alloys, macromolecules and biomolecules.
  • Chemical sensor channel is a micro-scale component of a sensor chip comprising of two patterned electrodes separated by a gap.
  • the gap may have a nanomaterial network.
  • Chemical sensor chip is a component of the sensor device comprising one or more sensor channels on a substrate.
  • Chemical warfare agent is a chemical substance used as a weapon.
  • Cloud system refers to a system comprising one or more remotely or centrally located servers, software, and networks protocols for communication with the servers.
  • the cloud can be used for processing data, storing data, distributing data and/or sharing data.
  • Counter electrode is an electrode used in a three electrode electrochemical cell for voltammetric analysis or other reactions in which an electrical current is expected to flow.
  • a counter electrode is distinct from a reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place.
  • Custom alignment and deposition system refers to a system for manufacturing chemical sensor chips in an automated protocol.
  • the system can align a nanomaterial network, deposit nanoparticles electrochemically, and test electrical characteristics of the network.
  • Edge connecter refers to the portion of a printed circuit board (PCB) consisting of traces leading to the edge of the board that are intended to plug into a matching socket.
  • PCB printed circuit board
  • Electrical characteristic refers to a measurable property of a circuit or component such as, but not limited to conductivity, resistance, voltage, current, capacitance, inductance, and FET properties.
  • FET Field-Effect Transistor
  • Fluid is a substance that deforms (flows) under applied stress. Fluids include gases, vapors, liquids and aerosols.
  • Gas is a substance defined as a state of matter with low density and low viscosity.
  • a gas will freely fill up the space that it is in and the volume can be influenced by pressure or/or temperature.
  • a gas can consist of an element, a compound or a mixture of compounds.
  • GPS Global positioning system
  • Harmful refers to a propensity of a substance to cause damage or pain to an organism, such as a human, an animal, a bacterium or a plant.
  • LED Light-emitting diode
  • LED here refers to a semiconducting diode that is a light source.
  • Microcontroller unit refers to a small computer on a single integrated circuit.
  • Multiplexer refers to an electronic component that allows the selection of one output signal from multiple input signals.
  • Multi-walled carbon nanotube is a concentric tube rolled of multiple layers of graph ene
  • Nanomaterial network refers to nanomaterials deposited on a sensor channel between electrodes.
  • the nanomaterial forming the network maybe a nanowire, a nanotube, a nanoribbon, or other nanometer-scale material.
  • Nanometer refers to distance of 10 "9 meters.
  • Nanometer -scale refers to distances ranging from one to hundreds of nanometers.
  • Nanoparticle is a particle with size ranging from one to hundreds of nanometers.
  • Nanoribbon is a one-dimensional nanometer-scale strip of a thin film with nanometer-scale thickness.
  • Nanotube is a one-dimensional hollow cylindrical structure with diameter constrained to nanometer-scale.
  • Nanowire is a one-dimensional nanostructure with diameter constrained to nanometer-scale.
  • On-chip counter electrode here refers to a counter electrode that is deposited on a chemical sensor chip.
  • On-chip reference electrode here refers to a reference electrode that is deposited on a chemical sensor chip.
  • Parts -per -billion is one part of solute per one billion parts solvent.
  • the function of a pattern recognition algorithm is to provide "most likely" match of input taking into account their statistical variation.
  • Port refers to a cable connection interface between an electronic device and a computer.
  • a port can be used for power supply, data transfer and
  • Portable refers to an electronic device that can be transported by carrying during normal usage.
  • the size and the weight of the device is such that an individual person can carry it.
  • Potentiometer refers to a voltage divider used for measuring electric potential.
  • Potentiostat is an electronic hardware required to control a three electrode cell and run most electroanalytical experiments.
  • a potentiostat is an electronic instrument that controls the voltage difference between a working electrode and a reference electrode. Both electrodes are contained in an electrochemical cell.
  • Primary Chip comprises a substrate with a source and a drain electrodes and chemical sensor channels.
  • the primary chip can be used as a basis for manufacturing a chemical sensor chip.
  • PCB Printed Circuit Board
  • PCB refers to a non-conductive substrate with embedded conductive features. PCB is generally used in electronic devices for connecting components.
  • Real-time here refers to a short period of time during which data is collected, processed and reported to the user.
  • the period is so short that data is available to the user virtually immediately.
  • the time period may be seconds or milliseconds.
  • Reference electrode is used in a three electrode electrochemical cell setup during electrochemical deposition reaction.
  • Reference electrode is made of material with stable electrode potential and other electrode potentials are measured against reference electrode.
  • Resistor refers to an electric component in a circuit to implement resistance.
  • Rheostat refers to a resistor for regulating current by means of variable resistance.
  • Sensitivity refers to a capacity of a substance to interact with chemicals.
  • SWNT Single-Walled Carbon Nanotube
  • Smart device is an electronic device generally connected to other electronic devices or networks via wireless protocols. Examples of smart devices are smartphones, smartwatches, smart bands, smart key chains, tablet computers, smart pads and/or other devices.
  • Software application refers to a computer program to carry out operations of a sensor system. Software application communicates with the sensor device.
  • Software application may be run on various devices such as, but not limited to, cell phones, smartphones, smartwatches, tablet computers, personal computers, self- contained stationary devices, televisions, cameras, hardware devices, hardware media and/or other devices. Additionally, the software application may be run through an internet browser.
  • Source measurement unit is an instrument that can provide a constant current or a constant voltage source and simultaneously measure a current or a voltage across those terminals.
  • Selectivity here refers to a capacity of a substance to interact with a specific chemical.
  • Stationary refers to an electronic device that is held in one place during normal usage.
  • Substrate refers to a substance that may be used to mechanically support other substances.
  • the substrate may be rigid or flexible.
  • Support vector machine refers to a machine learning technique associated with learning algorithms. SVM may be used to pattern recognition. By using a given training examples in different categories, SVM training algorithm builds a model to predict a category for new input data accordingly.
  • Toxic refers to a property of a substance to cause damage to an organism, such as a human, an animal, a bacterium, and a plant.
  • Trace here refers to a very small amount of chemical detected at ppm, ppb or ppt (parts-per-trillion) concentration level. Trace could be a vapor of an illegal drug or chemical warfare agent.
  • USB Universal Serial Bus
  • Vapor is a substance in the gas phase at a temperature at which it can be condensed to a liquid by increasing its pressure without reducing the temperature.
  • Vehicle-borne sensor refers to an instrument or system that detects chemicals as part of a vehicle.
  • VOC Volatile organic compound
  • VOCs are organic chemical that have high vapor pressure at ambient room temperature. VOCs typically have low boiling point. VOCs can be either naturally occurring or chemically processed. Common examples of VOC sources include common household and workplace items such as paints and lacquers, paint strippers, aerosol sprays, stored fuels, cleaning supplies, pesticides, building materials, furnishings, permanent markers, copiers, printers and craft materials including glues and adhesives.
  • Voltage regulator refers to a component for maintaining constant voltage level of a system.
  • Waveform function generator refers to an instrument which can provide electric currents with different waveforms at wide range of frequencies.
  • Wearable refers to an electronic device that can be implemented as part of a clothing of accessories.
  • WI-FI (R) is a wireless technology used for computer networking. WI-FI (R) may be used for local communication between computers and devices.
  • Wireless transmitter is an electric device that transfers information without the use of wires and rather over radio waves.
  • the transmitters can work over both short and long distances.
  • Working electrode is the electrode in an electrochemical system on which the reaction of interest is occurring.
  • any particular embodiment of the present invention that falls within the prior art may be explicitly excluded from any one or more of the claims. Since such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the compositions of the invention (e.g., any nucleic acid or protein encoded thereby; any method of production; any method of use; etc.) can be excluded from any one or more claims, for any reason, whether or not related to the existence of prior art.
  • CAES Custom Alignment and Electrochemical Deposition System
  • This process involves deposition and an "alignment" of SWNTs solution onto each of the chemical sensor channels in each of the sensor chip.
  • the primary sensor chips 802 are placed on a holding tray 801, as shown in FIG. 9.
  • the robotic arm 701 automatically seizes one of the holding trays 801 from the holding tray hopper 702 and places the tray in the alignment and deposition area 713.
  • the primary sensor chips 802 are positioned in connection with the conductive pathway pins 710. Individual pins are connected to the source and drain electrode pads.
  • FIG. 10A shows a schematic of the complete design of the deposition well 711.
  • FIG. 10B shows the position of inlets for the water reservoir 902, the nitrogen inflow 901, the nanomaterial reservoir 903 and the electrolyte reservoirs 906.
  • the deposition well contains a counter electrode 905 and a reference electrode 904.
  • the robotic arm 701 deposits carboxylated SWNT suspension in dimethylformamide (DMF) through an inlet 903 from the SWNTs reservoir 703 onto the deposition wells 711.
  • DMF dimethylformamide
  • the SWNT suspension in DMF is previously prepared through a one hour ultra-sonication treatment.
  • the necessary electric field to "align" the SWNTs is provided by an external waveform function generator 711.
  • the robotic arm 701 removes the holding tray 801 from the deposition area and positions it into the processed tray hopper 715.
  • the chips are dried with nitrogen (N 2 ) and annealed under forming gas mixture of nitrogen and hydrogen (95 % N2 + 5 % H2) at 300 °C for one hour to remove the organic solvent and secure the contact between the SWNTs and the electrodes.
  • the process of manufacturing the chemical sensor chip involves resistance and FET characteristic measurement of the nanomaterial network utilizing the source and the drain electrodes for each of the sensor chip.
  • the measurements are performed with the external Source Measurement Unit (SMU) 722.
  • the robotic arm 701 places one holding tray 801 in the alignment and deposition area 713 to be measured.
  • the conductive pathway pins 710 are lowered to connect with each sensor chip 11.
  • Each nanomaterial network is measured for its resistance and FET characteristics.
  • the applied potential is -1 to 1 V.
  • FET a sweep voltage from -20 V to 20 V is applied and the current is measured every 5V (or any interval).
  • the voltage applied may be from -40 to 40 V.
  • the robotic arm 701 removes the holding tray 801 from the deposition area and places it into the processed tray hopper 715.
  • the robotic arm 701 places one holding tray 801 with chemical sensor chip 11 from the holding tray hopper 702 to the alignment and deposition area 713.
  • the robotic arm lowers the conductive pathway pins 710 to make connections to each of chemical sensor chips.
  • the deposition for each of the channels is done in parallel.
  • Electrolytes from the electrolyte reservoirs 705 are deposited through the electrolyte reservoir inlet 906.
  • the electrochemical deposition is performed with a three electrode cell setup.
  • the reference electrode 904 and counter electrode 905 are placed in contact with an electrolyte through deposition well. Potential and current are applied by an external potentiostat 721.
  • the robotic arm 701 Upon completion of the deposition process, the robotic arm 701 removes excess electrolytes to a waste electrolyte reservoir 708 and flushes each chip 802 with deionized water from a water reservoir 704 and drains it to a waste water reservoir 708. Next, the chips 802 are dried with ultra-high purity (UHP) nitrogen (N 2 ) through the gas connector 706 controlled by an external mass flow controller 725. The robotic arm 701 then removes the holding tray 801 from the alignment and deposition area 713 and places it into the processed tray hopper 715.
  • UHP ultra-high purity
  • nanomaterials require an annealing process after drying, such as 4 hours at 500 °C under an inert gas such as nitrogen or argon (Ar).
  • an inert gas such as nitrogen or argon (Ar).
  • sensing is performed with ammonia (NEb).
  • Ammonia is mixed with synthetic air to gain the desired concentrations.
  • a set of measurements are performed with concentrations varying between 0.5 ppm and 200 ppm by volume, with 1 ppm interval. It is noted that the permissible exposure limit (PEL) set by OSHA standards for ammonia is 50 ppm.
  • PEL permissible exposure limit
  • the flow rates of 1012 and synthetic air 1013 from cylinders are controlled by mass flow controllers and valves unit 1020.
  • the gases are directed to a gas pre-treatment chamber unit 1030 where the temperature and the humidity are adjusted with temperature control unit 1060 and a humidity control unit 1070.
  • Measurements with different temperature and humidity are performed.
  • the temperature is varied from -10 °C to 60 °C with interval of 1 °C, and the relative humidity is varied from 0% to 95 % with interval of 1-5 %.
  • the sensor channels are first stabilized in synthetic air for 60 minutes, and then exposed with different concentrations of ammonia with 1-15 minutes with 30 second intervals exposure and 1-20 minutes with intervals of 1 minute recovery times.
  • the resistance is measured before, during and after exposure to ammonium by the source measurement unit 1055 and the amplitude and the modulation of the resistance is recorded. 15-20 cycles of measurements are carried out for each concentration, temperature and humidity settings.
  • the sensor is allowed to recover in synthetic air flow for 60 min.
  • a response time for the sensor chips is then calculated.
  • a response is defined as the time for the sensor channel to reach 90% of its steady-state value, and the recovery time is identified as the time required for the sensor channel after the exposure to return to 50% of its maximum response.
  • the chemical sensor chip 11 has a nanomaterial network functionalized with tin dioxide (SnC ) nanoparticles. The conductivity of tin dioxide may be altered when illuminated and therefore light can impact the sensing measurement.
  • the photoelectric measurements are performed with and without exposure to light to understand the impact of light on sensing.
  • the chemical sensor chips 11 are first stabilized in the synthetic air for 60 minutes, and then the chips are illuminated with LED lights 1105 for 1-15 minutes in 30 second intervals under synthetic air. Then LEDs 1105 are turned off to allow a 20 minute recovery time. Three cycles of measurements are performed and then the sensor chips 11 are allowed to recover for 60 min.
  • Example 2 These measurements which simulate known concentrations of chemicals at different temperature and humidity conditions are used to build a chemical sensing database.
  • All parameters of the tests including, but not limited to, chemical concentration, temperature, relative humidity, rate of change, rate of recovery, point of saturation, baseline level and/or presence of light together with the readings of electrical characteristics measured are recorded to the database.
  • Various mathematical and learning algorithms including, but not limited to, pattern recognition algorithms and/or machine learning algorithms such as Support Vector Machines (SVMs) and/or Artificial Neural Networks (ANNs) are used to develop a pattern recognition algorithm.
  • the partem recognition algorithm may be developed by supervised and/or unsupervised learning methods.
  • Supervised learning refers to a learning method where one or more relevant and known training sets are used to develop the pattern recognition algorithm.
  • Unsupervised learning refers to a learning method where relevant and known training sets are not used but patterns are rather developed by discovering hidden patterns in a data.
  • the described chemical sensor system is applied to monitoring air quality surrounding an individual user.
  • the detected chemicals are for example sulfur dioxide (SC ), nitrogen dioxide (NC ), ozone (O3), carbon monoxide (CO), molds and certain VOCs typical for urban air.
  • SC sulfur dioxide
  • NC nitrogen dioxide
  • O3 ozone
  • CO carbon monoxide
  • the users may also monitor and track fitness-related metrics in addition to knowing about toxic and harmful airborne gas levels around them.
  • the users may be fitness- and health-conscious consumers and/or people with certain health conditions such as an asthma or a heart disease. Users can use the information of chemical levels surrounding them to avoid places with poor air quality both indoors and outdoors. Users monitor the air quality of their homes or work places and adjust the need for e.g. air purifiers and ventilation accordingly.
  • the chemical sensor device When the chemical sensor device is wearable, the users carry it for example as a wristband, a bracelet or a pendant.
  • the dimensions of the wearable sensor device are expected to be about 25 mm wide x 55 mm long x 12 mm high.
  • Users would control and read data from a software application on a smartphone or a tablet.
  • the software will also allow the users to share information regarding the air quality in their surroundings at different locations to the cloud. This way the user can identify for example locations in the city where the air quality is poor at certain times of the day and avoid those locations.
  • the software application also includes machine learning capabilities of providing predictive alerts to the end user. Examples include alerting the user of a certain toxic air environment that may not be conducive to the user's health based on the user health profile and/or past user experiences in this type of environment.
  • Example 5 Monitoring carbon monoxide (CO) and hydrogen cyanide (HCN)
  • CO is a colorless, odorless and tasteless gas produced by an incomplete combustion of hydrocarbons. It is harmful to humans when inhaled causing symptoms such as headache, dizziness, nausea, chest pain and in worst cases coma or even death.
  • Prockop LD Chichkora RI, “Carbon monoxide intoxication: an updated review", Journal of Neurological Sciences 262 (l-2)m 122-130, 2007
  • Concentrations of CO above 100 ppm are considered dangerous.
  • HCN is a poisonous gas, liquid or solid used widely in industry as solvents and in manufacturing of plastics.
  • HCN poisoning may cause airway irritation, cardiovascular collapse and death within minutes. Firefighters are exposed to CO and HCN when operating on fires. HCN is present especially in residential and industrial fires.
  • the described sensor system is used to for monitor CO and/or HCN exposure of firefighters, as they work in the field.
  • the lightweight and small detector is attached to gear, such as a helmet or a uniform.
  • the sensor system alerts firefighter and their superiors when the firefighter is in a location with dangerously high CO and/or HCN concentration.
  • the sensor system collects data of the firefighter's exposure to CO and/or HCN throughout a period of time. The data is then used to identify situations where the exposure either instantly or over a period of time has been harmful and dangerous. The data is useful for identification of CO and/or HCN intoxication or poisoning and enhance the treatment and care.
  • the described chemical sensor system is used for the monitoring glucose level in a non-invasive way.
  • a statistical analysis done by World Health Organization (WHO) indicates that an estimate 1.5 million deaths owing to the direct cause of diabetes in 2012.
  • WHO World Health Organization
  • 9 % of the global human population of age 18+ has diabetes. Diabetes can cause damage to heart, blood vessels, eyes, kidneys, and nerves over time.
  • the described non-invasive glucose chemical sensor device is lightweight portable device and can communicate to smart device through USB cable or wirelessly.
  • the glucose level may be measured from such as, but not limited to, saliva, sweat, and urine.
  • the combination of pattern recognition algorithm and software application can provide in situ reading for the glucose level, storage the measurement result, and view the history of the glucose level which will improve patient care.
  • biomolecules and/or biomarkers are also measured. These include hormones, pheromones and ketone bodies.
  • the described chemical sensor system is connected to a cloud system for processing, storing, distributing and/or sharing information.
  • Users have a chemical sensor system embedded in their smartphones.
  • the chemical sensor system collects data of chemicals (e.g. sulfur dioxide (SO2), nitrogen dioxide (NO2), ozone (O3), carbon monoxide (CO) and certain VOCs), as well as temperature, humidity and UV index information as the users move around during a day.
  • the data is combined with the location information provided by the GPS navigation embedded in the smartphone.
  • the data is continuously collected and communicated to the cloud system that processes the data, stores the data and shares the data.
  • Users including the users of the network as well as third party users, can access the data from their smartphone software application or through an internet browser application.
  • the third party users are industrial, commercial or governmental organizations interested in statistical data of chemical levels in an area.
  • the data is presented as graphs, readouts and as interactive maps.
  • a user may log on to their personalized account to get a summary of the chemical exposure they are encountering at that moment, or e.g. during the past 24 hours. In addition, they can review their past exposure to these chemicals. They can also see statistical data on chemical levels in their living area over a period of time e.g. days, weeks, months, years. Users can review the data on an interactive map that demonstrates with color the areas with most pollution. The user can also set an alert that allows their smartphone to indicate when the chemical levels in their living area are exceptionally high, or when they enter an area where the chemical levels are exceptionally high. The alert could be a text message, an email or a pop-up message on the smartphone screen. The user may also enter personalized health information and remarks about their health condition to the software. This allows them to understand the relationship between their timely exposures to chemicals and their health.

Abstract

The invention provides a chemical sensor system comprising a nanomaterial based chemical sensor chip for detection of chemicals in gas, vapor, liquid and aerosol phase utilizing pattern recognition algorithms. Additionally the invention provides methods of fabricating the chemical sensor chip and sensing with the chip. Additionally the invention provides methods for collecting, storing, sharing and distributing data utilizing automated and predictive algorithms.

Description

CHEMICAL SENSOR
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62/131,586, entitled Chemical Sensor, filed March 11, 2015 and U.S. Provisional Patent Application No. 62/175,640, entitled Chemical Sensor, filed June 15, 2015; the contents of each of which is herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention generally relates to chemical sensors and, more particularly, to nanomaterial-based chemical sensors, including methods for making, testing and using such sensors.
BACKGROUND OF THE INVENTION
[0003] Chemical sensors and devices have wide range of applications, including environmental monitoring, medical monitoring and disease detection, detection of harmful chemicals for homeland security and military applications, industrial health and safety and food and agriculture safety.
[0004] For detection and monitoring of chemical levels in the immediate surroundings of an individual or at a specific location, stationary or portable, chemical sensors and devices with high sensitivity, small size, low power usage, lightweight as well as fast recovery and response time are desired. For many applications a wearable or a portable sensor would be preferred so that information can be gathered in the immediate proximity of the user. Sensors that can detect a wide variety of chemicals instantly in the form of gas, vapor, aerosol and/or liquid are highly desirable due to their versatile usage. Additionally, sensors that can simultaneously detect and monitor multiple chemicals at different sensitivity ranges are of high interest.
[0005] The present invention provides a chemical sensor system including a small and lightweight nanomaterial-based sensor device. The sensor device provides detection and monitoring of multiple chemicals simultaneously as well as fast response time and high sensitivity, e.g. parts-per-billion (ppb). Non-limiting examples of detected chemicals include, but are not limited to, airborne gases, volatile organic compounds (VOCs), airborne toxins, biomolecules and/or molds. SUMMARY OF THE INVENTION
[0006] The invention provides a chemical sensor system comprising a nanomaterial based chemical sensor chip for detection of chemicals in gas, vapor, liquid and aerosol phase. Additionally the invention provides methods of fabricating the chemical sensor chip and sensing with the chip.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The foregoing and other objects, features and advantages will be apparent from the following description of particular embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of various embodiments of the invention.
[0008] FIG. 1 is a schematic diagram showing certain embodiments of a chemical sensor system 100 of the invention comprising a chemical sensor device (10) accompanying software application (20) which may facilitate connections to the cloud system (30).
[0009] FIG. 2 A shows an embodiment of chemical sensor chips 11 fabricated on a substrate 110 in a low density arrangement.
[00010] FIG. 2B shows an embodiment of chemical sensor chips 11 fabricated on a substrate 110 in a high density arrangement.
[00011] FIG. 3 is a schematic a of a chemical sensor chip 11 of the invention comprising ten chemical sensor channels, on-chip reference electrodes and on-chip counter electrodes.
[00012] FIG. 4 is a schematic of a chemical sensor chip 11 of the invention comprising two chemical sensor channels.
[00013] FIG. 5 is a close-up schematic of a single chemical sensor channel 210.
[00014] FIG. 6A is a side-view schematic of a nanomaterial network on a single layer substrate. The nanomaterial network is aligned between electrodes.
[00015] FIG. 6B is a side-view schematic of a nanomaterial network on a two-layer substrate. The nanomaterial network is aligned between electrodes.
[00016] FIG. 6C is a top-view schematic a nanomaterial network. The
nanomaterial network is aligned between electrodes.
[00017] FIG. 7A is a side-view schematic of a nanomaterial network functionalized with nanoparticles. [00018] FIG. 7B is a top-view schematic of a nanomaterial network functionalized with nanoparticles.
[00019] FIG. 8 is a schematic showing the components of a Custom Alignment and Electrochemical Deposition System (CAES) 800 to fabricate chemical sensor chips.
[00020] FIG. 9 is a schematic demonstrating the positioning of deposition wells and primary sensor chips in the CAES 800.
[00021] FIG. 1 OA is a schematic illustrating the deposition well in the CAES 800.
[00022] FIG. 10B is a top-view schematic sketch of the deposition well in the CAES 800.
[00023] FIG. 11 is a schematic showing the components of a Customized Sensing System (CSS) 1100 to perform gas sensing in a laboratory environment.
[00024] FIG. 12 is a schematic showing a sensing chamber of the CSS system. DETAILED DESCRIPTION
Overview
[00025] The present invention provides a nanomaterial-based chemical sensor system and methods for detection of chemicals with the chemical sensor system. The chemical sensor system and its various embodiments of the present invention may be used for identification of chemicals and determination of chemical concentrations. The chemicals may be, but are not limited to, airborne chemicals, vehicle-borne chemicals, VOCs, toxins, biomolecules, harmful or dangerous materials including explosives and chemical warfare agents, biological warfare agents, pharmaceutical substances including prescription drugs and over-the-counter drugs and/or substances of abuse.
[00026] According to the present invention, biomolecules may include, but are not limited to, proteins, ligands, lipids, fats, nucleic acids, and/or antigens.
[00027] The chemical sensor system may be used for detection and monitoring of chemicals in a variety of fluids such as gas, vapor, liquid and aerosol. As used herein, a "fluid" is defined as a "substance that deforms (flows) under applied stress. For purposes of the present invention fluids include gases, vapors, liquids and aerosols.
[00028] In some embodiments, the sensor system may detect chemicals at parts- per-million (ppm) concentration, parts-per-billion (ppb) concentration, or lower. The chemical sensor system may comprise a plurality of features that serve to increase the number of chemicals detected and monitored simultaneously with fast response and/or high sensitivity. [00029] The chemical sensor system of the invention comprises a nanomaterial- based chemical sensor device having an electronic detection mechanism. The nanomaterial-based sensor may comprise one or multiple chemical sensor chips. These chemical sensor chips comprise a conductive nanomaterial network which may be functionalized with nanoparticles capable of interacting with chemicals to be detected. While not wishing to be bound by theory, it is believed that the
nanoparticles interact with chemicals adsorbed to the surface of the nanomaterial network. The resultant interaction is observed as a change in a measurable electrical characteristic of the nanomaterial network. This allows detection of chemicals by measuring the electrical characteristics of the conductive nanomaterial network.
[00030] An electrical property measurement provides for real-time detection of the adsorbed chemicals. Functionalization of the nanomaterial network with nanoparticles may provide selective and sensitive detection of chemicals. By combining different functionalizing nanoparticles, a chemical sensor chip can identify and detect many chemicals. Additionally, by selection from a variety of nanoparticles, one sensor chip can be manufactured to accommodate different applications.
[00031] The chemical sensor system of the invention may be configured as to be portable, wearable, stationary, wireless and/or battery-supported. The chemical sensor system may be configured to report detection and monitoring results and/or information as instant readouts, graphs or other visual manifestations.
[00032] The chemical sensor system of the invention may be used in wide variety of fields. Non-limiting examples of the uses include detection and monitoring of indoor or outdoor air quality, monitoring toxic chemical levels in an industrial plant and monitoring and detection of health conditions by detecting VOCs in patient's breath.
[00033] The chemical sensor system may be employed as a stationary or as a portable sensor. Further non-limiting examples of use include monitoring VOC levels in crops for determination of a crop spoilage, detecting chemical leakages during industrial processes and detecting vapor traces of substances of abuse (e.g. drugs) at the state borders for the homeland security. The chemical sensor may be employed as a wearable sensor for monitoring chemical levels surrounding the user. The user may be for example a person monitoring air pollutant levels for a health purpose, or a soldier monitoring presence of chemical warfare agents in a field setting. [00034] The chemical sensor may be embedded in mobile vehicles such as drones, planes, automobiles, trains, and boats/ships for detecting specific application- based chemicals.
[00035] The current invention embraces methods for detection of chemicals with a chemical sensor system. The methods comprise detection of chemicals from fluids.
[00036] Certain embodiments of the chemical sensor system may provide information to a user at a particular instance. The user may command the system to gather data, report data or share data. The user may trigger the system with a smart device via a software application. Certain embodiments of the chemical sensor system may provide passive detection or monitoring of chemical levels in fluids. The gathered information may be provided continuously or the user may obtain the data gathered continuously over a period of time at a particular instance. Certain embodiments of the chemical system may provide detection or monitoring of chemicals in samples that are collected and then introduced to the sensor system.
[00037] Additionally, the present invention describes methods of manufacturing the system, device and chips described here. The methods include an alignment of suitable nanomaterials to form a nanomaterial network and functionalization of the network with nanoparticles used for selective and sensitive detection of different chemicals. The described methods include features that may be used to control parameters of the sensor chips. Such parameters may include, but are not limited to, density of the nanomaterial in a network, and size, density and geometry of the nanoparticles.
[00038] The present invention also describes methods of manufacturing the system, device and chips described here and means of testing chemical sensing in an automated setting or environment.
[00039] Embodiments of the present invention will now be described with reference to the drawings. A number of features that may be incorporated into alternative embodiments will be described during the course of the description of the example embodiments. The skilled person will recognize that these alternative embodiments are also within the scope of the invention. Similar reference characters refer to similar parts throughout the different views. The drawings are not necessarily to scale and emphasis is instead placed upon illustrating the principles of this particular embodiment and other aspects of the invention.
Chemical sensor system [00040] According to the present invention, a chemical sensor system is provided. One embodiment of the system is shown in FIG. 1. In one embodiment, the chemical sensor system 100 comprises a chemical sensor device 10, a software application 20 and a cloud system 30. The cloud system 30 comprises one or more remote servers, a software, network protocols for communication and/or storing data to the cloud server.
[00041] The software application may be housed in the chemical sensor device or externally. The software application may be a mobile application. Mobile application refers to software that may be run on wireless computing devices and/or smart devices. When external to the chemical sensor device the software may be configured to run on a smartphone, a smartwatch, a personal computer (PC), a tablet computer, a cloud system 30, local area networks (LAN), wide area networks (WAN), television, hardware devices, hardware media, embedded systems and/or in any smart device. The software application may be used for operations such as, but not limited to activating the sensor device, receiving data from the sensor device, analyzing data, reporting data and storing data. The software application 20 may store, analyze and share data at the device level, localized level and/or at a cloud system 30 level. The software application may communicate with the cloud system 30 via the internet. In some embodiments, the software application may be operated through an internet browser. In some embodiments, the software application may also include machine learning capabilities for predictive analysis and reporting. Additionally, a user may enter data to the software. The data may include, but is not limited to, data related to environmental conditions, health conditions, geographical information and/or other data.
[00042] The software application may communicate with the chemical sensor device via a wireless or a wired transmitter 13 protocols. The software application may be used for controlling operations of the chemical sensor system and performing operations by commands. Commands may be a series of commands specifying each individual action the sensor device makes or a command may run a function programmed into the sensor device firmware. The software application may be used activate the sensor device automatically or a user can activate the sensor device to run an on-demand command. As an example, a user can set software application to run instant measurements, to run measurements continuously or over period of time and/or to give an alert when sensor has encountered a specific observation. The application software may communicate with a pattern recognition algorithm for identification and analysis of chemical levels. The algorithm may be run either at the sensor device level, at the embedded systems level, at the software application level or at the cloud system level. The application software may be used for reporting data as readouts, graphs, maps or other graphical or numerical manifestations.
[00043] In some embodiments, the chemical sensor system 100 communicates with a cloud system 30. The software may pass the data across a network using standard communication protocols (e.g., the internet protocol), custom communication protocols and/or any combination of these protocols. The communication protocols used may be protocols defined by the wired or wireless communication standards from Institute of Electrical and Electronics Engineers Standards Association (IEEE- SA). The data is passed to a cloud, which is a server, or a group of servers located remotely from the chemical sensor system. The cloud may receive data, store data, process data, distribute data and/or share data. The cloud system 30 may communicate with one or more chemical sensor systems 100.
[00044] Additionally, the cloud system 30 may support receiving, storing, processing, distributing and/or sharing data with other external systems. These external systems may include commercial and consumer sources, and may be related to e.g. consumer health and/or environmental data. The data may be in the form of a hard copy or a soft copy. The data at the cloud system 30 may be accessed by the software application 20 of the chemical sensor system, or by other software applications such as internet browser based applications, smart device based application and/or other interfaces. The data may be accessed by a user, a network of users or by third parties. The cloud system 30 may provide automated alerts and/or predictive alerts based on the received and processed data. Cloud- based systems for receiving, processing, storing, distributing and sharing data are discussed in Jeong et al. (US 2013/0160006), Chen et al. (US 2013/0282227), Williams (US
2014/0257833), Kain et al. (US 2013/0274148) and Wu et al. (US 2013/0317381), the contents of which are incorporated herein by reference in their entirety.
[00045] The user may view, store, distribute and/or share data. The data may be stored in the cloud to a specific user account managed by the software application. The software application may be used to share and view data among users. The software application data may be shared to other users including, but not limited to, corporations, organizations, governments, and the general public. The users may customize the received and shared information. The users may enter health profiles to the software application and gain personalized alerts and/or predictive alerts.
[00046] Certain embodiments of the chemical sensor system 100 may include multiple sensor devices 10, each with the ability to detect specific chemicals and collect data, process data and communicate data with each other within the sensor network or with a centralized unit referred to as a wireless network sensor node.
[00047] Certain embodiments of the chemical sensor system 100 may be embedded in consumer and/or commercial electronic devices and/or other devices to support chemical sensing functionality. Such devices may be, but are not limited to, cell phones, smartphones, smartwatches, tablet computers, laptop computers, personal computers, televisions, cameras, wearable technologies (e.g. health monitors, smartwatches, headphones), self-contained stationary devices, home appliances (e.g. coffee makers, air humidifiers, air purifiers, ranges, refrigerators etc.), lighting systems and devices, security devices and/or other devices. In one embodiment chemical sensors in multiple devices may communicate with each other.
Chemical sensor device
[00048] In one embodiment the chemical sensor device 10 comprises one or more chemical sensor chips 11, a sensor controller 12, a wireless or a wired transmitter 13, a port 16, a power source 15, a pattern recognition module 14 and a housing 17. The chemical sensor device 10 may be of different sizes and shapes. Chemical sensor device may be a sphere, a cube, a cuboid, a cone, a hemisphere, a cylinder, a tetrahedron, an octahedron, a pyramid or a prism. The size of the chemical sensor device may range from 0.5 cm3 to 15,000 cm3: including, but not limited to, 0.5, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10,000, 12,000, 12,500 and/or 15,000 cm3. In some embodiments the dimensions of a cuboid shaped chemical sensor device may be 1 cm x 1 cm x 0.5 cm. In some embodiments the dimensions of a cubical chemical sensor device may be 2.5 cm x 2.5 cm x 2.5 cm.
[00049] In the chemical sensor device 10, the chemical sensor chip/chips 11 may be operably connected to a printed circuit board (PCB) through an industrial wire bonding or other connection process. Additionally, the sensor chip/chips 11 may be enclosed and protected by an integrated circuit packaging process. The sensor chip/chips 11 may be operably connected to the sensor controller unit 12 of the device. In some embodiments of the invention, the chemical sensor chip/chips 11 may be modular or replaceable, capable of being swapped for a separate or additional sensor chip. The number of chemicals detected can be increased by using one chemical sensor device having a plurality of sensor chips 11 comprising
functionalized or non-functionalized nanomaterials. Additionally, a damaged chemical sensor chip/chips 11 may be replaced.
Detection
[00050] The detection event may be a measurable change in an electrical characteristic of the sensor chips 11.
[00051] According to the present invention, the change in electrical characteristics may be read and processed by the sensor controller unit 12. The sensor controller unit 12 comprises of electronic components for reading and processing amplitude and modulation data of electrical changes occurring in the circuit. As used herein, modulation refers to an increase or a decrease in an electrical characteristic. The components of the sensor controller unit may include, but are not limited to, a digital potentiometer or a rheostat, a microcontroller unit (MCU), analog-to-digital converters (ADC), multiplexers, edge connectors, voltage regulators, wires, resistors, capacitors, inductors, a ferrite bead, a Li-ion battery charger integrated circuit (IC), a temperature sensor and/or a humidity sensor. Certain embodiments of the sensor controller unit 12 may include optional components such as, but not limited to, a gas filter, ultraviolet (UV) light-emitting diodes (LEDs), a gas sensing chamber, pumps, valves, a barometer, a heating element, buttons, an accelerometer, a gyroscope, an inertial measurement unit (IMU), a heartrate sensor, a liquid-crystal display (LCD), an UV index sensor and/or a global positioning system (GPS). Temperature and humidity sensors are included to account for variables that are encountered in the real world to compensate for data results from the laboratory, although those will be simulated as well. Optional sensors, such as an accelerometer, a heartrate sensor, an inertial measurement unit and an UV index sensor may further be incorporated to provide a user information regarding surrounding conditions. In certain embodiments, a global positioning system (GPS) transmitter may be included for recording information regarding location and time of the detection event. Additionally, certain embodiments of the sensor controller unit 12 may include components that may alert a user. Such components may include, but are not limited to, a vibration motor and/or a speaker that may be a vocal or a tonal speaker. The sensor controller unit 12 also includes firmware for the MCU to control various functions of the sensor controller unit. For example, the firmware may read the temperature and humidity sensors and operate other hardware components such as valves, pumps, LEDs, multiplexers, potentiometers and/or a UV index sensor. Firmware may have low level software specific to the MCU that controls hardware components that the end user does not directly interface with.
[00052] The amplitude and modulation of the circuit comprising chemical sensor chip 11 is read by the sensor controller. As a non- limiting example, an input voltage Vin is applied and controlled by means of a voltage regulator (VRM). The resolution may be set by adjusting the voltage. Here, a MCU controls the chemical sensor reading. The initial resistance Rpot is adjusted to match the resistance of the sensor to provide a maximum modulation measurable with a lower bit ADC. An equation to calculate the resistance of the sensor using voltage bridge circuit is presented in Equation 1
in * R s. ensor
Vout (Equation 1),
sensor pot
where Vout is read by ADC. The resistance of the chemical sensor chip Rsensor can be calculated from the equation. One method for receiving, analyzing and
communicating of chemical detection data is discussed in Li et al. (US7968054), the contents of which are incorporated herein by reference in their entirety.
[00053] The electrical characteristics data read and processed by the sensor controller unit 12 may be transmitted via wireless and/or wired transmitter 13 to the software application 20. In some embodiments, the wired transmitter could be a standard serial port RS232, a Universal Serial Bus (USB), an Ethernet, a universal asynchronous receiver/transmitter (USART), a Serial Peripheral Interface (SPI) and an Inter-Integrated Circuit (I2C). As an example, a stationary sensor device detecting hazardous gas at a manufacturing facility could be connected to a personal computer using a USB, a RS232 or an Ethernet connection. In some embodiments the wireless transmitter 13 could be a short distance or a localized transmitter, such as a
BLUETOOTH (R), a BLUETOOTH SMART (R) (Bluetooth low energy), a near- field communicator (NFC), a radio frequency identification (RFID), a radio frequency (RF), a WI-FI (R) transmitter or any cellular based transmitter. As an example, the short distance transmitter may be implemented in a wearable sensor device when a user is located and reads the results in near proximity to the sensor. As an example, the WI-FI (R) transmitter may be implemented in a chemical sensor device detecting or monitoring chemical levels in specific locations at a process factory and reporting results to a worker inside the factory.
[00054] Certain embodiments of the chemical sensor system 100 may include an active pump to provide regulated air flow exposure to the chemical sensor chip and/or an additional enclosed chamber to provide more controlled conditions.
[00055] In some embodiments the chemical sensor device 10 may comprise a pattern recognition module 14. The pattern recognition module may be housed internally or externally to the sensor device 10. The pattern recognition module may comprise an MCU, an integrated hardware component such as digital signal processor (DSP) or an application specific integrated circuit (ASIC), or a full system on chip (SOC). The pattern recognition module may be used to run one or more partem recognition algorithm formulas for analyzing the data read from chemical sensor chip. When the sensor device is exposed to a chemical, the partem recognition algorithm analyzes the electrical properties from the chemical sensor chip/chips to determine the identification and concentration of the chemical being detected. In certain
embodiments the pattern recognition algorithm may be run at the sensor device level; within the partem recognition module 14; at an embedded systems level; at a software application level and/or at a cloud system 30 level. When a sensor device comprising multiple sensor chips is exposed to a mixture of chemicals, the pattern recognition algorithm may identify each of the chemicals and their concentrations.
[00056] The chemical sensor device is powered by a power source 15 that may be any suitable power source. In some embodiments the power source may be a battery. In some embodiments, the battery may be a rechargeable battery together with a battery charger integrated circuit. The battery may be charged with a cable in connection with a port 16. In some embodiments the port may be a USB port. In some embodiments the battery may be a non-rechargeable, disposable battery. Batteries useful in the present invention may have different shapes, sizes, weights and properties including, but not limited to, power and lifetime. In some embodiments, the power source may be directly connected to other external power source such as an alternating current (AC) power socket.
[00057] In some embodiments the chemical sensor device 10 may be enclosed within a housing 17. The housing may have different shapes, sizes, thicknesses and weight. The housing may be made of different materials and have different look and feel. In some embodiments the housing may be made from plastic, composites, polymers, metals, ceramics and the like. The configuration of the embodiments inside the sensor device may differ, while still remaining functionally the same.
[00058] The chemical sensor device 10 may be wearable by a user. The chemical sensor device may be incorporated into an article of clothing such as, but not limited to, a shirt, a coat, a belt, a shoe, a boot, a pant, and/or a hat or into a protective gear such as, but not limited to, a helmet, a glove, a mask a hazardous material (haz-mat) suit, or an apron. Additionally, the chemical sensor device may be incorporated into an accessory such as, but not limited to, a smartwatch, a bracelet, a ring, any jewelry, a pendant, an activity tracker or a wristband. Certain embodiments of a chemical sensor device 10 may be portable. The chemical sensor device may be a small, lightweight handheld device allowing the user to be mobile. In certain embodiments, the chemical sensor device 10 may be stationary. The chemical sensor device may be installed at a location of interest. In certain embodiments, the sensor device may be attached to a vehicle, a drone or a robot to detect airborne chemicals for purpose of air quality monitoring, airborne toxins, chemical and biological warfare agents, and/or estimating the performance of the vehicle.
[00059] In certain embodiments, the chemical sensor device 10 may be incorporated into other devices and/or systems such as, but not limited to, smart watches, health and fitness monitors, activity trackers, domestic appliances, home automation systems, air purifying systems, product manufacturing line systems, embedded systems, and/or other suitable devices or systems.
[00060] In some embodiments detection is passive. As such, the sensor device detects one or more fluids in near proximity to the sensor. For example, a user can have a wearable sensor that detects and monitors chemical levels from the surrounding air. The user of such a wearable device may an asthma patient monitoring air quality, a soldier monitoring a threat of chemical warfare agents or an industrial worker monitoring chemical levels. As another example, the sensor could be a stationary sensor attached to a wall in an office, or in proximity to a process line in industrial plant to, for example, monitor chemical levels in a particular location.
[00061] In some embodiments the detection is active. To this end, the chemical sensor device 10 may have a sensing chamber where a volume of a sample fluid is actively moved through the device to be measured and analyzed. As an example, a tube connected to a drone may actively draw gases from an agriculture site into a sensing chamber of the chemical sensor device 10 where the gases are exposed to the sensor chip/chips to be analyzed and chemicals measured for detection of crop spoilage, infestation or other metric.
Chemical sensor chip
[00062] FIG. 2-7 show embodiments of a chemical sensor chip 11 generally. FIG. 2 A and FIG. 2B illustrate sensor chips 11 fabricated on a substrate 110 which may be made of a metallic, a semiconducting or a non-conductive material or other appropriate material known to those skilled in the art. The substrate 110 may be rigid or flexible. In certain embodiments the substrate 110 material may comprise silicon, silicon oxide, aluminum oxide, hafnium oxide, plastic, paper and/or certain cloth or fabric materials. The substrate may comprise of one, two or three layers of material. The material layers may be the same or different. In some embodiments the substrate 110 may be a two layer substrate of silicon wafer with a passive silicon dioxide (SiC ) layer on top. In certain embodiments the substrate 110 may be of any shape such as, but not limited to, round, rectangular, square or elliptical. The substrate 110 may have different thicknesses and different sizes. In certain embodiments, where substrate is round, it may have a diameter from 1-18", including, but not limited to, 1", 2", 4", 6", 8", 10", 12", 14", 16" and/or 18", see FIG. 2A, element "A". In some embodiments round the substrate 110 has a diameter A of 6". The number of chemical sensor chips 11 fabricated on, or affixed to, the substrate 110 can range from 100 to 25, 000;
including, but not limited to, at least 100, 120, 144, 200, 250, 300, 350, 400, 450, 500, 750, 1,000, 1,250, 2,500, 2,506, 2,750, 3,000, 3,500, 4,000, 4,500, 5,000, 7,500, 10,000, 12,500, 15,000, 17,500, 20,000, 22,500, and/or at least 25,000. In some embodiments the substrate 110 may have 144 chemical sensor chips 11. In some embodiments the substrate 110 may have 2,506 chemical sensor chips 11. In some embodiments the substrate may have 4,156 chemical sensor chips. The substrate 110 can be cut into smaller pieces before or after fabrication, that have one or more chemical sensor chips 11. For example, a silicon wafer substrate can be cut into smaller pieces accurately with a method of wafer dicing using a dicing saw or a laser. FIG. 2B shows a source electrode 120 and a drain electrodes which are in connection with chemical sensor chips 11. The source electrode 120 and the drain electrode 130 may be used for electrochemical deposition processes and/or for any other electrodeposition processes and/or for alignment of nanomaterials and/or connecting the chip to an electric circuit. Certain embodiments of the chemical sensor chip 11 may comprise a heating element.
[00063] Turning to FIG. 3 and FIG. 4, the chemical sensor chip 11 comprises chemical sensor channels 210. In certain embodiments of the chemical sensor chip 11 the number of chemical sensor channels 210 may range from 1 to 100; including, but not limited to, 2, 6, 10, 24, 36, 48, 60, 72, 84, 96, 100 and/or any single unit value between 1 and 100. In some embodiments there are ten chemical sensor channels 210 in a single chemical sensor chip 11. In some embodiments there are two chemical sensor channels 210 in one sensor chip 11. A detailed schematic of a sensor chip 11 comprising ten chemical sensor channels 210 is shown in FIG. 3. The chemical sensor chip 11 of the invention may have different sizes described by distances B and H. The distances B and H of the sensor chip 11 may independently range from 5.000 mm to 10.000 mm; including, but not limited to, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 2.5, 4.0, 4.25, 4.5, 4.75, 5.0, 7.5,10.0, 12.5, 15.0, 17.5 and or 20.0 mm. In some embodiments, the distance B is about 5.0 mm and the distance H is about 10.0 mm.
[00064] Also shown are the source electrode 120 and a drain electrode 130. Ends or termini of the source and drain electrodes may have pads that are be used for connecting the electrodes to a circuit. The electrode pad size is described by the distances F and G, shown in the FIG. 3. The distances F and G can range
independently from 0.1 mm to 1.0 mm; including, but not limited to, about 0.1, 0.15, 0.2, 0.24, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9 and/or about 1.0. In some embodiments the distance F is about 0.5 mm and the distance G is about 0.24 mm. The distance I between the central axis of drain electrode 120 and the source electrode 130 can range from 0.2 mm to 2.0 mm including, but not limited to, about 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 1.8, 1.9 and/or about 2.0 mm. In some embodiments the distance I is about 0.75 mm. The electrodes form a patterned structure referred to as a chemical sensor channel 210. The distance between the central axes of the chemical sensor channels is described by distance C which can range from 1.0 mm to 5.0 mm; including, but not limited to, about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 1.8, 1.9, 2.0, 2.1, 2.2, 2.25, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 3.5, 4.0, 4.5 and/or about 5.0 mm. In some embodiments the distance C is about 1.75 mm. The chemical sensor chip 11 may also comprise one or more on-chip reference electrodes 230 and one or more on-chip counter electrodes 220. The distance D between the on-chip reference electrode 230 and the on-chip counter electrode 220 can range from 0.20 mm to 0.40; including but not limited to about 0.20, 0.21, 0.212, 0.213, 0.214, 0.215, 0.216, 0.217, 0.218, 0.219, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39 and/or about 0.4 mm. In some embodiments the distance D is about 0.218 mm. The size of a sensor channel 210 described by the distances E and J can range independently from 0.1 mm to 0.4 mm; including, but not limited to about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5, 1.6, 1.7, 1.75, 2.0, 2.1, 0.218, 2.2, 2.25, 2.3, 2.4,
2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, 4.75 and/or about 5.0 mm. In some embodiments the distance E is about 0.2 mm and distance J is about 0.218 mm.
[00065] A detailed schematic of a sensor chip 11 comprising two chemical sensor channels 210 is shown in FIG. 4. The sensor chip 11 configuration with two chemical sensor channels 210 may have different sizes described by distances H and B. The distances H and B of the configuration may independently range from 0.1 mm to 2.5 mm; including, but not limited to, about 0.1,0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25 and/or about 2.5 mm. In some embodiments the distance H is about 1.0 mm and the distance B is about 2.0 mm.
[00066] The electrode pad size is described by the distances F and G. The distances F and G can range independently from about 0.1 mm to 1.0 mm; including, but not limited to, about 0.1, 0.15, 0.2, 0.24, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9 and/or about 1.000. In some embodiments the distance F is about 0.5 mm and the distance G is about 0.25 mm.
[00067] The distance between the central axes of the chemical sensor channels is described by distance C. In certain embodiments the distance C can range from 0.1 mm to 0.32 mm; including, but not limited to, about 0.1, 0.12, 0.2, 0.22, 0.3 and/or about 0.32 mm. In some embodiments the distance C is about 0.22 mm. The size of a sensor channel 210 described by the distances E and J can range independently from 0.1 mm to 0.4 mm; including, but not limited to, about 1.0, 1.1, 1.2, 1.25, 1.3, 1.4, 1.5,
1.6, 1.7, 1.75, 2.0, 2.1, 0.218, 2.2, 2.25, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, 4.75 and/or about 5.0 mm. In some embodiments the distance E is about 0.2 mm and distance J is about 0.218 mm.
[00068] The distance between the central axis or point of the source electrode 120 and drain electrode 130 is described by distance I. In certain embodiments the distance I can range from 0.1 mm to 0.5 mm; including, but not limited to, about 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 and/or about 0.5 mm. In some embodiments the distance I is about 0.25 mm.
[00069] Methods of a standard lift-off photolithography process and a standard thin film coating process such as an e-beam evaporation may be used for fabrication of the source electrode 120, the drain electrode 130, the chemical sensor chips 210, the on- chip reference electrodes 230 and the on-chip counter electrodes 220. The material used for the source electrode 120 and drain electrode 130 electrode may be a metal such as, but not limited to, titanium (Ti), platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), chromium (Cr) and/or other similar material. The electrodes may be fabricated from one metal or from a combination of two or more metals. The electrode thicknesses may range from 10 nm to 500 nm, including but not limited to: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 275, 300, 350, 400, 450 and/or 500 nm. In some embodiments the electrodes have thickness of 215 nm and are fabricated from a 25 nm layer of titanium and a 190 nm layer of platinum. In some embodiments the electrodes have thickness of 215 nm and are fabricated from a 25 nm layer of titanium and a 190 nm layer of platinum. In certain embodiments, the source electrode 120 and drain electrode 130 may be symmetric, meaning that the electrodes are fabricated from the same material. In some embodiments the two electrodes may be asymmetric, meaning that they are independently fabricated from two different materials.
Asymmetric gas sensors in the art are taught by Myung and Brooks in US publication (US2014/0145736), the contents of which are incorporated herein by reference in their entirety. Such fabrication methods and materials may be used in the present invention. The on-chip counter electrode 220 may be fabricated from an inert metal such as, but not limited to, platinum. The on-chip reference electrode 230 may be fabricated from silver (Ag) silver/silver chloride (Ag/AgCl), platinum, graphite or other suitable material. Reference and counter electrodes may be used during an electrochemical deposition. In some embodiments the on-chip counter electrode 220 and the on-chip reference electrodes 230 are optionally present. These electrodes can be applied externally.
[00070] A detailed schematic of a sensor channel 210 is shown in FIG. 5. The sensor channel 210 is formed from the source electrode 120 and drain electrode 130 deposited into a pattern with a narrow gap between them. The gap is described by distance R which can range from 0.002 to 0.01 mm; including, but not limited to about 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, and/or about 0.010 mm. In some embodiments the distance R is about 0.003 mm.
[00071] Turning now to FIG. 6A, important to the function of the chemical sensor channel 210 of the present invention is the narrow gap which may be used for positioning a nanomaterial network formed from a conducting nanomaterial 510. The gap is described as element "R" in FIG. 6A and FIG. 6C. The gap defines the width of the nanomaterial network comprising the nanomaterial 510 non-functionalized or functionahzed with nanoparticles. Nanomaterial-based sensors in the art are taught by Myung et al. (US8034222 and US2012/0080319) and Deshusses et al. (US8683672), the contents of which are incorporated herein by reference in their entirety. Such fabrication methods and materials may be used in the present invention. The gap functionahzed with a nanomaterial network is shown in FIG. 6A and FIG. 6B from a side-view and in FIG. 6C from a top view. The substrate 110 may consist one layer, two layer or three layers of material. A substrate with one layer is shown in FIG. 6A and a substrate with two layers is shown in FIG. 6B. The nanomaterial 510 is aligned between the source electrode 120 and drain electrode 130.
[00072] In general, the nanomaterial 510 may be a one-dimensional
nanostructured material. One-dimensional here refers to a structure with high length to width ratio, such as line, tube and/or wire. In certain embodiments the
nanomaterial 510 may be, but is not limited to, a nanotube, a nanowire, a nanoribbon, other nanomaterial and/or combinations thereof. The nanowires and nanotubes may have diameters ranging from 0.5 to 350 nm; including, but not limited to, about 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 11.0, 12.0, 13.0, 14.0, 15.0, 16.0, 17.0, 18.0, 19.0, 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325 and/or about 350 nm. The nanoribbons may have widths ranging from 10 to 100 nm; including, but not limited to, about 10, 20, 30, 40, 50, 60, 70, 80, 90 and/or aboutlOO nm. The thickness of nanoribbons can range from a one atomic layer to five atomic layers; including 1, 2, 3, 4 and 5 atomic layers.
[00073] The lengths of the nanomaterials 510 may range from 100 nm to 1 mm; including, but not limited to, about 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 μιη, 1.2 μιη, 1.4 μιη, 1.6 μιη, 1.8 μιη, 2.0 μιη, 2.2 μηι, 2.4 μηι, 2.6 μηι, 2.8 μηι, 3.0 μηι, 3.2 μηι, 3.4 μηι, 3.6 μηι, 3.8 μηι, 4.0 μηι, 4.2 μηι, 4.4 μηι, 4.6 μηι, 4.8 μηι, 5.0 μηι, 5.5 μηι, 6.0 μηι, 6.5 μηι, 7.0 μηι, 7.5 μηι, 8.0 μηι, 8.5 μηι, 9.0 μηι, 9.5 μηι, 10 μηι, 15 μηι, 20 μηι, 25 μηι, 30 μηι, 35 μηι, 40 μηι, 45 μηι, 50 μηι, 55 μηι, 60 μηι, 65 μηι, 70 μηι, 75 μηι, 80 μηι, 85 μηι, 90 μηι, 95 μηι, 100 μηι, 150 μηι, 200 μηι, 250 μηι, 300 μηι, 350 μηι, 400 μηι, 450 μηι, 500 μηι, 550 μηι, 600 μηι, 650 μηι, 700 μηι, 750 μηι, 800 μηι, 850 μηι, 900 μηι and/or about 1000 μηι. The nanomaterials applied may have a narrow, moderate or wide distribution and/or may be a combination of different lengths.
[00074] The nanomaterials 510 can be metallic and/or semiconducting and/or a combination of metallic and semiconducting.
[00075] The nanomaterials 510 can be made of different materials such as, but not limited to, carbon, silicon, conducting polymers, metals, metal oxides and other suitable materials. In certain embodiments the nanomaterial 510 may be single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), silicon (Si) nanowires, zinc oxide (ZnO) nanostructures, tin oxide (SnC ) nanowires, indium oxide (ImC ) nanowires, boron nitride (BN) nanotubes, carbon nitride nanotubes (CN Ts), BxC3N2 nanotube structures, tellurium (Te) nanotube and nanowire structures, Te nanotube and nanowire structures with embedded gold (Au) nanoparticles, multisegmented metal nanowires such as cobalt-gold (Co/Au) or nickel/gold (Ni/Au) structures, polyaniline (PANI) nanowires, polypyrrole (Ppy) nanowires and/or other nanostructures. The fabrication of Te nanotubes and wires and multisegmented nanostructures are taught by Myung and Hangarter
(US2012/0021248) and the fabrication of conducting polymer e.g. PANI and Ppy nanowires is taught by Myung et al. (US8034222), the contents of which are incorporated here by reference in their entirety. Such fabrication methods may be used in the present invention. In some embodiments the nanomaterial network is made of SWNTs. In some embodiments the diameter of SWNTs may be about 1.4 nm and the length may range from 2 to 3 μηι. In some embodiments the diameter of SWNTs may be about 1.4 nm and the length may range from 2 to 10 μηι.
[00076] The nanomaterial network may be non-functionalized or functionalized with a nanoparticles 610. FIG. 7A shows a side-view schematic and FIG. 7B shows a top-view schematic of a section of the chemical sensor channel gap having a nanomaterial network with nanoparticles 610. A nanoparticle here refers to a nanoscale material that can be of different shapes. Nanoparticles 610 include, but are not limited to, metal nanoparticles, metal oxide nanoparticles, metalloid
nanostructures, macromolecules, conductive polymer nanoparticles, biomolecules, sugars, ketones and/or or other suitable materials. According to the present invention, metal nanoparticles may include, but are not limited to, gold (Au), palladium (Pd), platinum (Pt) and/or other metal nanoparticles. Metal oxide nanoparticles may include, but are not limited to, tin oxide (SnC ) or other metal oxides such as taught by Myung et al. (US2012/0080319) and Deshusses et al. (US8683672), the contents of which are incorporated here by reference in their entirety. Such materials may be used in the present invention. In the in context metalloids may include nanoparticles of tellurium or other metalloids such as those taught by Myung and Zhang
(US2014/0103330), the contents of which are incorporated here by reference in their entirety. Such nanostructures may be used in the present invention. Macromolecules may include, but are not limited to, porphyrins, phthalocyanines and/or other macromolecules.
[00077] Conductive polymer nanoparticles may include, but are not limited to, doped polymer nanoparticles such as polyaniline doped with a camphor-sulfonic acid (CSA), percholate (CIO4"), acrylic acid (C3H4O2), tetraethylammonium
perfluorooctane sulfonate (TEAPFOS), and/or para-toluene sulfonic acid
(CH3C6H4SO3H) and/or other conducting polymers or doped polymers such as those thought by Deshusses et al. (US8683672), the contents of which are incorporated here by reference in their entirety. Such nanoparticles may be used in the present invention.
[00078] Biomolecules may include, but are not limited to, antibodies, proteins and protein fragments, polynucleotides, oligonucleotide sequences, DNA aptamers, nucleic acids, lipids, glycoproteins, hormones, pheromones and/or other biomolecules such as those taught by Myung et al. (US8034222), the contents of which are incorporated here by reference in their entirety. Such biomolecules may be used in the present invention Biomolecules may be natural or synthetic.
[00079] In certain embodiments, nanoparticles may be a combination of two or more materials, such as, but not limited to, metal and metal-oxide nanomaterials. In general, the nanoparticles characteristic refers to a property of a material to interact with adsorbed chemicals. The interaction may be a covalent or a non-covalent interaction, including ionic interaction, hydrogen interaction, van der Waals interaction, dispersion force interaction, hydrophilic-hydrophobic interaction and/or combination of these interactions. The nanoparticles 610 may adsorb specifically to certain chemicals. The nanoparticles 610 may have different particle and/or molecule sizes, shapes and densities.
[00080] In some embodiment, the nanomaterial network may be fabricated by aligning suspended carboxylated SWNTs (SWNT-COOH) in a chemical sensor channel 210 by applying an electric field. After the alignment process an
electrochemical deposition or other deposition process of a nanoparticle to form a functionalized nanomaterial is performed. The nanoparticles may be deposited as nanoparticles or as molecules. Some properties of the chemical sensor chip 11 may be varied by controlling the electrochemical deposition of the nanoparticles 610. As an example, the density of the nanoparticles as well as the size and/or the geometry of the nanoparticles on the surface of the nanomaterial network may be controlled by adjusting the type of the an electrolyte, the concentration of an electrolyte, and the deposition time, potential and/or charge density during the electrochemical deposition. The properties of the functionalized nanomaterials may affect the sensitivity, stability and/or the selectivity.
[00081] In some embodiment, the nanomaterial network may be fabricated utilizing an inkjet printing technique, array er and/or a similar process such as those taught by Stetter et al. (US8795484), the contents of which are incorporated here by reference in their entirety.
[00082] The selection of the nanoparticles defines the type of chemicals the chemical sensor chip may detect and/or monitor. As an example, certain embodiments of a chemical sensor chip 11 may have tin dioxide (SnC ) nanoparticles deposited on nanomaterials 510 making the chip sensitive towards detection of e.g. nitrogen dioxide (NC ), ammonia (NH3), carbon monoxide (CO) and certain VOCs. Certain embodiments of a chemical sensor chip 11 may have phthalocyanine macromolecules as the functionalizing moiety making the chip sensitive towards detection of ozone (O3) and sulfur dioxide (SO2). A plurality of chemical sensor chips 11 with nanomaterial networks and nanoparticles fabricated from different materials may be combined when incorporated in a chemical sensor device.
[00083] In certain embodiments, the chemical sensor chip may detect chemicals at parts-per-million (ppm) concentration, parts-per-billion (ppb) concentration, or lower. The chemical sensor system may comprise a plurality of features that serve to increase sensitivity, selectivity and stability. The features include, but are not limited to, the use of sensing components fabricated from a one-dimensional nanomaterial network.
[00084] The present invention also describes methods for detecting chemicals using the chemical sensor chip 11. The detection mechanism may be a measurable change in an electrical characteristic of the nanomaterial network. The detected chemicals are adsorbed onto the surface of the functionalized or non-functionalized nanomaterial network and this adsorption is the trigger for the detection. The molecules interact with the functionalized nanomaterial changing a measurable electrical characteristic. The amplitude and modulation of the electrical characteristics is dependent on the properties of the detected chemical such as their electron donating or electron withdrawing ability. The detection event such as an increase or a decrease in resistance and rate of change is read by the sensor controller unit 12, as described above and shown in FIG. 1. The observed amplitude and modulation of the change is communicated to the pattern recognition module 14.
[00085] The detection method of the current invention provides for low power consumption. In certain embodiments the power consumption of the detection may be 1 mW or lower. Features resulting to the low power consumption include the small sensor chip size due to the nanoscale sensing materials used, efficient conductivity due to the use of nanostructures, and/or no requirement for heating of the sensing materials.
Manufacture of a chemical sensor chip
[00086] According to the present invention, methods of manufacturing chemical sensor chips 11 and testing electronic characteristics of the chips are also provided. The described methods enable automation of manufacturing with consistency, precision and accuracy.
[00087] The methods for manufacturing sensor chips 11 may be performed by a Custom Alignment and Electrochemical Deposition System (CAES). One embodiment of the CAES 800 is shown in FIG. 8. CAES is an automated setup for nanomaterial alignment, electrochemical deposition and electrical characteristics measurement for the sensor chips 11 with the chemical sensor channel 210 in micrometer scale. The CAES of the present invention comprises CAES enclosure 700 and external systems 720. The CAES enclosure 700 may comprise one or more of an alignment and deposition area 713, a heating/cooling module 714, a nanomaterial suspension reservoir 703, a water reservoir 704, one or more electrolyte reservoirs 705, a nitrogen (N2) gas connector 706, one or more waste electrolyte reservoirs 708, a waste water reservoirs 708, a nanomaterial suspension waste reservoir 707, a processed tray hopper 715, conductive pathway pins 710, deposition wells 711, a robotic arm 701, a holding tray hopper 702 and/or variety of tubing 712. These components may be arranged or configured in any orientation one of the skill in the art understands how to arrange such components for optimal automation and manufactory.
[00088] External systems 720 may comprise, but are not limited to, one or more potentiostat 721, a source measurement unit 722, a waveform function generator 723, a temperature control unit (with power supply) 714, a mass flow controller 725 and a water circulation system 726. All aspects of the CAES and the external instruments may be controlled through a control interface 716 by customized CAES software 727 such as LABVIEW (R) Software and/or other similar software.
[00089] FIG. 9 shows the positioning of primary sensor chips 802 on a holding tray 801. The automated robotic arm 701 can seize the holding tray 801 from the holding tray hopper (not shown) and move them to the alignment and deposition area 713 and processed tray hopper (not shown). The holding tray hopper and the processed tray hopper may hold one or more holding trays 801. The holding tray may have one or more primary sensor chips 802. The primary sensor chip 802 here refers to a chip consisting of a source electrode and a drain electrode with sensor channels but no nanomaterial network. The primary sensor chip 802 may or may not have on-chip reference electrodes and on-chip counter electrodes. The robotic arm 701 is also used for positioning the primary sensor chips 802 in connection with conductive pathway pins 710 and below deposition wells 711. The CAES may comprise a number of deposition wells ranging from 1 to 30: including, but not limited to 1, 2, 3, 5, 7, 9, 10, 15, 20, 25, and/or 30. In some embodiments the number of deposition wells may be nine. FIG. 10A and FIG. 10B present a more detailed schematic of the deposition well 711. FIG. 10A is a side-view schematic of the deposition well 711 positioned above a staging platform comprising the sensor tray 801 holding a primary sensor chip 802 in connection with conductive pathway pins 710. FIG. 10B shows a top-view schematic of deposition well 711. The deposition well 711 comprises inlets for the water reservoir 902, the nitrogen inflow 901, the nanomaterial reservoir 903 and the electrolyte reservoirs 906. In addition the deposition well contains a counter electrode 905 and a reference electrode 904.
[00090] The first part of manufacturing chemical sensor chip/chips 11 involves fabricating the nanomaterial network. The primary sensor chips 802 are positioned in contact with the conductive pathway pins 710 and a volume of a dispersion or a solution of a nanomaterial from a reservoir 703 is collected and deposited onto the deposition wells 711 aligned with primary sensor chips 802. An electric current may be applied by an external instrument such as, but not limited to, a waveform function generator 723 for a period of time for alignment of the nanomaterial network.
[00091] Following deposition an electrochemical deposition of nanoparticles is performed onto the nanomaterial network. The electrochemical deposition is performed by using the source and drain electrodes as a working electrode together with counter and reference electrodes. The source and drain electrodes act as the working electrode in the electrochemical deposition process and are positioned in contact with conductive pathway pins 710. In some embodiments the on-chip reference electrode pads and on-chip counter electrode pads are also positioned in contact with the conductive pathway pins 710. In some embodiments the counter electrode 905 and the reference electrode 904 are introduced as components of the CAES 800, as shown in FIG. 10A and FIG. 10B. A volume of electrolyte is collected from an electrolyte reservoir 705 through tubing 712 and deposited onto deposition wells 711. The CAES may comprise one or more electrolyte reservoirs and electrolyte waste reservoirs. Appropriate potential and current is applied by an external instrument such as, but not limited to, a potentiostat 721 and charge is measured... The particle size and the density of the functionalized nanomaterial may be controlled by the concentration of the electrolyte and/or the deposition potential, charge density and time. Some electrolytes may require an elevated temperature that can be adjusted with a heating/cooling module 714 controlled by an external temperature controller 724. After deposition, the excess electrolyte is removed, and the sensor chips are rinsed with water and treated with nitrogen gas for drying.
[00092] The above described methods may be applied to manufacture a plurality of chemical sensor chips on a substrate consisting of channels with functionalized nanomaterial networks of different materials. As an example, a substrate may contain four or more chemical sensor chips each of which has a nanomaterial network fabricated from different nanomaterials. The nanomaterial networks may further be functionalized with different nanoparticles.
[00093] Method for testing electronic characteristics of the manufactured chemical sensor chip are also provided by the present invention. Electronic characteristics may include, but are not limited to, conductivity, resistance, voltage, current, capacitance, inductance, and field-effect transistor (FET) properties. The chemical sensor chip/chips are positioned in contact with the conductive pathway pins 710. The electrical characteristics of each chemical sensor chip is measured with use of an external source measurement unit 722. The measurements are recorded by the customized CAES software 727.
Gas Sensing
[00094] According to the present invention, methods of gas sensing with the chemical sensor chip is also provided. The methods enable an automated sensing method in a laboratory environment. The gas sensing may be performed with a Custom Sensing System (CSS). One embodiment of the CSS 1100 is shown in FIG. 11. The CSS is an automated setup for determining the amplitude and modulation of electrical properties when chemical sensor chips 11 are exposed to gas chemicals. The CSS of the invention is an automated system that may control multiple variables impacting the electrical properties of the nanomaterial network, such as a
concentration of a chemical, temperature, relative humidity and an intensity of ultraviolet (UV) light. The CSS comprises an analytes and cylinders unit 1010, a mass flow control (MFC) and valves unit 1020, a gas pre-treatment chamber unit 1030, sensing chamber unit 1040, an external equipment unit 1050, temperature control units 1060 and/or humidity control units 1070.
[00095] The external equipment unit controls the operations of the CSS via a control interface 1051. All aspects of the CSS processes are controlled by a CSS customized software 1059 such as LAB VIEW (R) software and/or other similar software. The analytes and gas cylinders unit 1010 contains the sources for the chemicals and gases used during sensing. The analytes and gas cylinders unit 1010 may contain multiple gas cylinders 1012, a synthetic air cylinder 1013, a VOC generator 1011 controlled by an external VOC generator control unit 1053 and an ozone generator 1014 controlled by an external ozone generation control unit 1057. Individual chemicals or a combination of chemicals from the analytes and cylinders unit may be used. Synthetic air here refers to purified air with zero humidity. The selection of chemicals and their concentrations may be controlled by a valve control mechanism and mass flow controllers (MFCs) controlled by a mass flow control unit 1056 and a valve control unit 1052.
[00096] The chemicals from analytes and cylinders unit 1010 are directed through the mass flow control and valves unit 1020 which controls the type and amount of gas flow entering the gas pre-treatment chamber unit 1030. The gas pre-treatment chamber comprises a number of gas mixture chambers 1031 and dry air chambers 1032. The pre-treatment chamber is utilized to mix the selected gases and to adjust temperature and humidity conditions. The temperature and the humidity are adjusted and controlled by temperature control units 1060 and humidity control units 1070.
[00097] During the adjustment process the gases are directed to flow out to a fume hood 1058 and after adjustments are achieved the gases are directed to enter a sensing chamber unit 1040 comprising sensing chambers 1041. The gas pre-treatment chamber 1030 and the sensing chamber 1041 may be fabricated from material such as TEFLON (R), AFLAS (R) and/or other suitable material. The number of sensing chambers can range from 1 to 30; including but not limited to 1, 2, 3, 5, 7, 9, 10, 15, 20, 25, and/or 30. In some embodiments there are three sensing chambers.
[00098] A schematic of the sensing chamber 1041 is shown in FIG. 12. A sensor tray 1109 holding a number of chemical sensor chips 11 may be placed under the sensing chamber housing 1104 and sealed with a rubber O-ring 1101. The sensor tray 1109 may be fabricated from quartz, ceramic or other suitable material. The drain and source electrodes are connected via sensing chamber conductive pins 1106. A gas flow from the gas pre-treatment chamber 1030 is directed to sensing chamber 1041 through gas inlet 1102 and removed through gas outlet 1108. The temperature is controlled by temperature control units 1060 connected to a sensing chamber heating module 1110 which may be a peltier thermoelectric temperature module or other suitable temperature controller. The humidity is controlled by control units 1070 via humidity control unit inlet 1103 and outlet 1107 paths. The sensing chamber may be illuminated with LED lights 1105 controlled by an LED light control unit 1054. The LED lights may be UV or tricolor RGB (red-green-blue) LEDs. As the chemical sensor chips 11 are exposed to the gas mixtures, electrical properties such as, but not limited to, conductivity, resistance, voltage, current, capacitance, inductance, and (FET) properties, may be continuously detected using source measurement unit 1055 and CSS customized software 1059. Uses
Air Quality Monitoring
[00099] In some embodiments of the present invention the chemical sensor system may be used to detect and monitor chemicals associated with air pollution, effluents, molds, toxic spills and hazardous gases. Such chemicals can cause harm, diseases, death to humans, damage to other living organisms such as, but not limited to, food crops and natural environment. The detected chemicals may be, but are not limited to, hydrogen sulfide (H2S), carbon dioxide (CO2), nitrogen oxide (NO), nitrogen dioxide (NO2), ozone O3, sulphur dioxide (SO2), carbon monoxide (CO) or any volatile organic compounds (VOCs). In some embodiments the sensor device could be stationary for monitoring air quality in a specific location, such as in an office room, in a city center or in an industrial neighborhood. In some embodiments the sensor system may be wearable or portable and may be applied for monitoring air quality surrounding a user. Such application may have importance for users trying to avoid poor air quality spaces. Such users could be for example patients with a stroke, a heart disease, a lung cancer or a chronic and acute respiratory disease, such as an asthma, chronic obstructive pulmonary disease (COPD), emphysema, etc.
Agricultural safety
[000100] In some embodiments, the chemical sensor system may be used to detect and monitor ammonia (NH3) emissions in agriculture. Air quality issues have become an increasing concern for the agriculture industry. Excessive ammonia emissions, a byproduct of livestock and poultry operations, can be harmful to livestock, humans and environment as a whole. A personally worn chemical sensor system may be used to alert agricultural workers and their superiors when workers are reaching their permissible exposure limit to ammonia in a given work day, as set by U. S.
Occupational Safety and Health Administration (OSHA) standards. A stationary sensor system could monitor ammonia levels within animal facilities in order to alert workers regarding risks to the welfare of the animals.
Agricultural production
[000101] In some embodiments, the chemical sensor system may be used to detect and monitor ripeness and other conditions of crops (e.g. fruits, vegetables, grains etc.) in agricultural production. Certain amount of carbon emitted into the atmosphere by plants is in the form of VOCs. The VOC profiles emitted by plants undergo changes when conditions change. The VOC profiles may be used to provide information regarding the conditions of crops such as ripeness, spoilage, plant disease and pests.
[000102] In some embodiments, the chemical sensor system may be used to detect and monitor the presence of pesticides and/or pest control chemicals of crops in agricultural production. The pesticides and/or pest control chemicals may include insecticides, insect repellents, herbicides, fungicides, bactericides, animal repellents and/or other chemicals.
Food Packaging & Food Safety
[000103] In some embodiments, the chemical sensor system may be used to detect and monitor gases such as carbon dioxide (CO2 ) that are used in the process of inspection, manufacturing and sealing food items for distribution to consumers. The chemical sensor system could be used to monitor permissible gas levels and leakages. In some embodiments, the chemical sensor system may be used to detect food spoilage. For example, spoilage of fish and seafood may be detected and monitored by sensing trimethylamine ((C]¾)3N), dimethylamine ((CH3)2NH) and/or ammonia (NH3). The spoilage of meat may be detected and monitored by sensing hydrogen sulfide (H2S), dimethylsulfide ((CH3)2S), cis-3-nonenal (H UC Π · :· ·,( Ί Κ Ί ΙΠ Ί ίϋ). trans-6-nonenals ((Ί Ι Π ! ,( Ή(' Π« l !, ; ,(' ! !()). oct-l-en-3-one (C! hCMC ί ϋκΠ ί m 'M . and/or bis(methylthio) methane (CH3SCH2SCH3).
Homeland Security
[000104] In some embodiments, the chemical sensor system may be used in various settings of significance to Homeland Security, including, but not limited to, at ports of entry and in a border patrol, at governmental locations or at large event locations. As an example, the chemical sensor system could be applied to monitor trafficking of substances of abuse by detecting chemical traces of these drugs. As another example, the chemical sensor system could be applied to monitor the threat of chemical warfare agents, biological warfare agents or explosives. Chemical warfare agents detected could include, but are not limited to, sarin, chlorine (Cb) or phosgene.
Industrial
[000105] In some embodiments, the chemical sensor system may be used in industrial plants and/or facilities that produce or utilize hazardous and toxic chemicals that could place their employees and local residents at risk. The chemical sensor system could detect the buildup of such chemicals in order to decrease risks. As an example, the emission of hydrogen sulfide from an industrial plant to the atmosphere could be monitored by the chemical sensor system to detect excessive or levels above OSHA that may be detrimental to the health of workers and/or nearby residents. The industrial facilities may include manufacturing facilities, mining facilities, gas industry facilities, oil industry facilities and/or other industrial facilities.
Military and Defense
[000106] In some embodiments, the chemical sensor system may be used by military and defense. In addition to applying the chemical sensor system for detection of chemical warfare agents, biological warfare agents and explosives, the chemical sensor system may be applied to purposes of maintaining military vehicles or maintaining the welfare of soldiers. As an example, U.S. Air Force uses chemical sensors for detecting jet fuel leaks and U.S. Navy uses chemical sensors for detection of hydrogen sulfide (H2S) gas on all surface vessels in spaces containing sanitary waste equipment. As another example, chemical sensors may be embedded into military vehicles, drones, planes, etc. to detect chemical and biological warfare agents, explosives and/or toxic industrial gases.
Water Treatment Plants
[000107] In some embodiments, the chemical sensor system may be used in water and wastewater treatment plants. Water and wastewater treatment processes often release harmful amounts of chemicals into the air. The chemical sensor system may be applied to protect employees and the community from toxic and combustible gas hazards such as ammonia (NH3), carbon monoxide (CO), chlorine (Ch), hydrogen sulfide (H2S), nitrogen oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2) and others.
Human disease and diagnostics
[000108] In some embodiments, the chemical sensor system may be used to detect and monitor human phenotypic characteristics related to VOC profiles of breath, body odor and/or body fluids. Some embodiments of the chemical sensor system may be used to detect and monitor certain medical and health conditions non-invasively from breath. For example breath contains VOCs that in some cases contain early-detection biomarkers or indicators of certain medical conditions and diseases. Examples include, but are not limited to, organ failure, cancers, such as lung cancer and breast cancer and/or infections such as mouth and teeth related infections, respiratory tract infections, nasal cavity infections and/or gastrointestinal tract infections. [000109] The chemical sensor may be used for monitoring public health threats by non-invasive testing of e.g. tuberculosis. In some embodiment, the chemical sensor system may be used to detect chemicals related to bad breath (halitosis). Detected chemicals may be, but are not limited to, hydrogen sulfide H2S, methyl mercaptan CH3SH and/or dimethylsulfide ((CH3)2S). In some embodiments, the chemical sensor system may be used to detect human body odors. Body odors present in humans may be influenced various health conditions and diseases, hormonal changes, nutrition, and/or substance usage such as pharmaceutical substances, illegal drugs, alcohol and/or tobacco. Detected chemicals may be, but are not limited to, isovaleric acid ((ί Π ί ΠΠ Κ ·Π }. trans-3-Methyl-2-hexenoic acid
(CH3(CH2)2C(CH3)CHCOOH), pheromones such as androstetones including 5a- androst-16-en-3-one. Additionally, detection of phenotypic characteristics of body odor and/or breath may be applied to forensic analyses, lie detectors, and/or breathalyzers and/or port-mortem analyses.
Olfactory Applications (Artificial Nose)
[000110] In some embodiments, the chemical sensor system may be used as an electronic olfaction sensor referred to an electronic nose. An electronic nose imitates the human's capability to smell. In this application smells, such as VOCs or chemicals with odor such as esters, are detected and identified by means of a pattern recognition algorithm. Fields of applications may include industries where the smell of the product or the smell released during a process provides specific information related to the quality of the product or process. Non-limiting examples of applications for electronic nose are quality control, consistency control, raw material identification, identification of raw material origin and/or storage condition monitoring in variety of industries such as, but not limited to, paint, lacquer and coatings industry, the wood industry, the chemical and solvent industry, the food and beverage industry (e.g. food and wine tasting, etc.), the fragrance industry, and the cosmetics and toiletries industry. As an example, the chemical sensor system may be applied for detection of wine ageing, monitoring the aroma, and/or classification and discrimination of wines (e.g. detection of wine origin and type of wine) and for detection of cheese ageing, type of cheese, detection of cheese origin and discrimination of cheeses. As an example, the chemical sensor system may be applied in the monitoring the quality and/or consistency of brewed coffee when incorporated to coffee machines at home, at restaurants and/or at coffee shops. As another example, the chemical sensor system may be applied to detect paint and lacquer odors for quality and consistency control as well as to ensure comfortable smell that pleases a user.
Emergency-Response Sensors
[000111] In some embodiments, the chemical sensor system may be applied to an emergency -response system for detection of potential harmful chemicals for emergency personnel. Emergency personnel such as firefighters and/or security and law enforcement personnel may be exposed to various harmful chemicals and airborne toxins such as such as hydrogen cyanide (HCN), carbon monoxide (CO), hydrocarbons, and VOCs. The sensor system may alert about potential airborne toxins around the area of a fire, a spill, or a gas leak. The alert may include warning of a potential risk for an explosion in a situation where a methane or a propane gas leak is present.
DEFINITIONS
[000112] About refers to +/- 10% of the recited value.
[000113] Aerosol refers to a substance consisting of gas or colloids of fine liquid droplets, e.g. fog as a natural aerosol. Aerosol here excludes solid particulate matter e.g. dust.
[000114] Airborne sensor refers to an instrument or system that detects chemicals in air.
[000115] Artificial neural networks (ANN) refers to a statistical learning algorithm and may be used to estimate or approximate functions that depend on large number of inputs.
[000116] Biological warfare agent is a biological substance used as a weapon.
[000117] Biomarker refers to a substance that can be an indicator of a disease or a health condition. Biomarker can be used for monitoring or detecting health conditions and/or diseases.
[000118] Biomolecule refers to a molecule present in living organisms and may be natural or synthetic. Biomolecules include e.g. proteins, ligands, polysaccharides, lipids, fats, antibodies and nucleic acids.
[000119] BLUETOOTH (R) is a wireless technology standard for transferring data over short distances using short-wavelength ultra-high frequency waves. [000120] BL UETOOTH SMART (R) is a low energy technology standard for transferring data over short distances using short-wavelength ultra-high frequency waves.
[000121] Capacitor refers to an electric component in a circuit to store energy electrostatically.
[000122] Chemical is a form of matter with constant chemical composition.
Chemicals may include elements, molecules, compounds, alloys, macromolecules and biomolecules.
[000123] Chemical sensor channel is a micro-scale component of a sensor chip comprising of two patterned electrodes separated by a gap. The gap may have a nanomaterial network.
[000124] Chemical sensor chip is a component of the sensor device comprising one or more sensor channels on a substrate.
[000125] Chemical warfare agent is a chemical substance used as a weapon.
[000126] Cloud system refers to a system comprising one or more remotely or centrally located servers, software, and networks protocols for communication with the servers. The cloud can be used for processing data, storing data, distributing data and/or sharing data.
[000127] Counter electrode is an electrode used in a three electrode electrochemical cell for voltammetric analysis or other reactions in which an electrical current is expected to flow. A counter electrode is distinct from a reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place.
[000128] Custom alignment and deposition system (CAES) refers to a system for manufacturing chemical sensor chips in an automated protocol. The system can align a nanomaterial network, deposit nanoparticles electrochemically, and test electrical characteristics of the network.
[000129] Edge connecter refers to the portion of a printed circuit board (PCB) consisting of traces leading to the edge of the board that are intended to plug into a matching socket.
[000130] Electrical characteristic refers to a measurable property of a circuit or component such as, but not limited to conductivity, resistance, voltage, current, capacitance, inductance, and FET properties. [000131] Field-Effect Transistor (FET) is a transistor that uses an electric field to control the shape and hence the conductivity of a channel of one type of charge carrier in a semiconductor material.
[000132] Fluid is a substance that deforms (flows) under applied stress. Fluids include gases, vapors, liquids and aerosols.
[000133] Gas is a substance defined as a state of matter with low density and low viscosity. A gas will freely fill up the space that it is in and the volume can be influenced by pressure or/or temperature. A gas can consist of an element, a compound or a mixture of compounds.
[000134] Global positioning system (GPS) is a satellite navigation system that provides information regarding location and time.
[000135] Harmful refers to a propensity of a substance to cause damage or pain to an organism, such as a human, an animal, a bacterium or a plant.
[000136] Light-emitting diode (LED) here refers to a semiconducting diode that is a light source.
[000137] Microcontroller unit (MCU) refers to a small computer on a single integrated circuit.
[000138] Multiplexer refers to an electronic component that allows the selection of one output signal from multiple input signals.
[000139] Multi-walled carbon nanotube (MWNT) is a concentric tube rolled of multiple layers of graph ene,
[000140] Nanomaterial network refers to nanomaterials deposited on a sensor channel between electrodes. The nanomaterial forming the network maybe a nanowire, a nanotube, a nanoribbon, or other nanometer-scale material.
[000141] Nanometer refers to distance of 10"9 meters.
[000142] Nanometer -scale refers to distances ranging from one to hundreds of nanometers.
[000143] Nanoparticle is a particle with size ranging from one to hundreds of nanometers.
[000144] Nanoribbon is a one-dimensional nanometer-scale strip of a thin film with nanometer-scale thickness.
[000145] Nanotube is a one-dimensional hollow cylindrical structure with diameter constrained to nanometer-scale. [000146] Nanowire is a one-dimensional nanostructure with diameter constrained to nanometer-scale.
[000147] On-chip counter electrode here refers to a counter electrode that is deposited on a chemical sensor chip.
[000148] On-chip reference electrode here refers to a reference electrode that is deposited on a chemical sensor chip.
[000149] Parts -per -billion (ppb) is one part of solute per one billion parts solvent.
[000150] Parts -per -million (ppm) is one part of solute per one million parts solvent.
[000151] The function of a pattern recognition algorithm is to provide "most likely" match of input taking into account their statistical variation.
[000152] Port refers to a cable connection interface between an electronic device and a computer. A port can be used for power supply, data transfer and
communication.
[000153] Portable refers to an electronic device that can be transported by carrying during normal usage. The size and the weight of the device is such that an individual person can carry it.
[000154] Potentiometer refers to a voltage divider used for measuring electric potential.
[000155] Potentiostat is an electronic hardware required to control a three electrode cell and run most electroanalytical experiments. A potentiostat is an electronic instrument that controls the voltage difference between a working electrode and a reference electrode. Both electrodes are contained in an electrochemical cell.
[000156] Primary Chip comprises a substrate with a source and a drain electrodes and chemical sensor channels. The primary chip can be used as a basis for manufacturing a chemical sensor chip.
[000157] Printed Circuit Board (PCB) refers to a non-conductive substrate with embedded conductive features. PCB is generally used in electronic devices for connecting components.
[000158] Real-time here refers to a short period of time during which data is collected, processed and reported to the user. The period is so short that data is available to the user virtually immediately. The time period may be seconds or milliseconds.
[000159] Reference electrode is used in a three electrode electrochemical cell setup during electrochemical deposition reaction. Reference electrode is made of material with stable electrode potential and other electrode potentials are measured against reference electrode.
[000160] Resistor refers to an electric component in a circuit to implement resistance.
[000161] Rheostat refers to a resistor for regulating current by means of variable resistance.
[000162] Sensitivity refers to a capacity of a substance to interact with chemicals.
[000163] Single-Walled Carbon Nanotube (SWNT) is a one-dimensional tube structure with one-atom-layer of graphene.
[000164] Smart device is an electronic device generally connected to other electronic devices or networks via wireless protocols. Examples of smart devices are smartphones, smartwatches, smart bands, smart key chains, tablet computers, smart pads and/or other devices.
[000165] Software application refers to a computer program to carry out operations of a sensor system. Software application communicates with the sensor device.
Software application may be run on various devices such as, but not limited to, cell phones, smartphones, smartwatches, tablet computers, personal computers, self- contained stationary devices, televisions, cameras, hardware devices, hardware media and/or other devices. Additionally, the software application may be run through an internet browser.
[000166] Source measurement unit (SMU) is an instrument that can provide a constant current or a constant voltage source and simultaneously measure a current or a voltage across those terminals.
[000167] Selectivity here refers to a capacity of a substance to interact with a specific chemical.
[000168] Stationary refers to an electronic device that is held in one place during normal usage.
[000169] Substrate refers to a substance that may be used to mechanically support other substances. The substrate may be rigid or flexible.
[000170] Support vector machine (SVM) refers to a machine learning technique associated with learning algorithms. SVM may be used to pattern recognition. By using a given training examples in different categories, SVM training algorithm builds a model to predict a category for new input data accordingly. [000171] Toxic refers to a property of a substance to cause damage to an organism, such as a human, an animal, a bacterium, and a plant.
[000172] Trace here refers to a very small amount of chemical detected at ppm, ppb or ppt (parts-per-trillion) concentration level. Trace could be a vapor of an illegal drug or chemical warfare agent.
[000173] Universal Serial Bus (USB) is an industry standard defining cables, connectors and communication protocols for connection, communication and powering between computers and electronic devices.
[000174] Vapor is a substance in the gas phase at a temperature at which it can be condensed to a liquid by increasing its pressure without reducing the temperature.
[000175] Vehicle-borne sensor refers to an instrument or system that detects chemicals as part of a vehicle.
[000176] Volatile organic compound (VOC) is an organic chemical that have high vapor pressure at ambient room temperature. VOCs typically have low boiling point. VOCs can be either naturally occurring or chemically processed. Common examples of VOC sources include common household and workplace items such as paints and lacquers, paint strippers, aerosol sprays, stored fuels, cleaning supplies, pesticides, building materials, furnishings, permanent markers, copiers, printers and craft materials including glues and adhesives.
[000177] Voltage regulator refers to a component for maintaining constant voltage level of a system.
[000178] Waveform function generator refers to an instrument which can provide electric currents with different waveforms at wide range of frequencies.
[000179] Wearable refers to an electronic device that can be implemented as part of a clothing of accessories.
[000180] WI-FI (R) is a wireless technology used for computer networking. WI-FI (R) may be used for local communication between computers and devices.
[000181] Wireless transmitter is an electric device that transfers information without the use of wires and rather over radio waves. The transmitters can work over both short and long distances.
[000182] Working electrode is the electrode in an electrochemical system on which the reaction of interest is occurring.
Equivalents and Scope [000183] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments in accordance with the invention described herein. The scope of the present invention is not intended to be limited to the above Description, but rather is as set forth in the appended claims.
[000184] In the claims, articles such as "a," "an," and "the" may mean one or more than one unless indicated to the contrary or otherwise evident from the context.
Claims or descriptions that include "or" between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The invention includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The invention includes
embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.
[000185] It is also noted that the term "comprising" is intended to be open and permits but does not require the inclusion of additional elements or steps. When the term "comprising" is used herein, the term "consisting of is thus also encompassed and disclosed.
[000186] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Methods and materials are described herein for use in the present disclosure; other, suitable methods and materials known in the art can also be used.
[000187] Where ranges are given, endpoints are included. Furthermore, it is to be understood that unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or subrange within the stated ranges in different embodiments of the invention, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.
[000188] In addition, it is to be understood that any particular embodiment of the present invention that falls within the prior art may be explicitly excluded from any one or more of the claims. Since such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the compositions of the invention (e.g., any nucleic acid or protein encoded thereby; any method of production; any method of use; etc.) can be excluded from any one or more claims, for any reason, whether or not related to the existence of prior art.
[000189] All cited sources, for example, references, publications, databases, database entries, and art cited herein, are incorporated into this application by reference, even if not expressly stated in the citation. In case of conflicting statements of a cited source and the instant application, the statement in the instant application shall control.
[000190] Section and table headings are not intended to be limiting.
EXAMPLES
[000191] The foregoing description will be more fully understood with reference to the following examples. These examples, are, however, exemplary of methods of making and using certain aspects of the present invention and are not intended to impose limits on the scope of the invention as defined by the appended claims.
Example 1. Manufacture of Chemical Sensor Chips and Testing its Electrical Characteristics
[000192] The following is an example of the manufacture of a chemical sensor chip described above and testing of electrical characteristics. Manufacture of chemical sensor chip is performed with the automated Custom Alignment and Electrochemical Deposition System (CAES) 800 described in FIG. 8. All aspects of the process, including operations, are controlled by a customized CAES software 727 such as LABVIEW (R).
[000193] This process involves deposition and an "alignment" of SWNTs solution onto each of the chemical sensor channels in each of the sensor chip. The primary sensor chips 802 are placed on a holding tray 801, as shown in FIG. 9. By command given by the customized CAES software 727, the robotic arm 701 automatically seizes one of the holding trays 801 from the holding tray hopper 702 and places the tray in the alignment and deposition area 713. The primary sensor chips 802 are positioned in connection with the conductive pathway pins 710. Individual pins are connected to the source and drain electrode pads.
[000194] The primary sensor chips/chips 802 are placed under deposition wells 711. FIG. 10A shows a schematic of the complete design of the deposition well 711. A top-view of the deposition well 711 is shown in FIG. 10B demonstrating the position of inlets for the water reservoir 902, the nitrogen inflow 901, the nanomaterial reservoir 903 and the electrolyte reservoirs 906. In addition the deposition well contains a counter electrode 905 and a reference electrode 904.
[000195] Next, the robotic arm 701 deposits carboxylated SWNT suspension in dimethylformamide (DMF) through an inlet 903 from the SWNTs reservoir 703 onto the deposition wells 711. The SWNT suspension in DMF is previously prepared through a one hour ultra-sonication treatment. The necessary electric field to "align" the SWNTs is provided by an external waveform function generator 711.
[000196] The excess SWNT suspension is drained to a nanomaterial waste reservoir
707 and upon completion, the robotic arm 701 removes the holding tray 801 from the deposition area and positions it into the processed tray hopper 715.
[000197] The chips are dried with nitrogen (N2) and annealed under forming gas mixture of nitrogen and hydrogen (95 % N2 + 5 % H2) at 300 °C for one hour to remove the organic solvent and secure the contact between the SWNTs and the electrodes.
[000198] The process of manufacturing the chemical sensor chip involves resistance and FET characteristic measurement of the nanomaterial network utilizing the source and the drain electrodes for each of the sensor chip. The measurements are performed with the external Source Measurement Unit (SMU) 722. The robotic arm 701 places one holding tray 801 in the alignment and deposition area 713 to be measured. The conductive pathway pins 710 are lowered to connect with each sensor chip 11. Each nanomaterial network is measured for its resistance and FET characteristics. The applied potential is -1 to 1 V. For FET, a sweep voltage from -20 V to 20 V is applied and the current is measured every 5V (or any interval). For some substrates, such as hafnium dioxide (HfC ), the voltage applied may be from -40 to 40 V. Upon completion, the robotic arm 701 removes the holding tray 801 from the deposition area and places it into the processed tray hopper 715.
[000199] For electrochemical deposition of the nanoparticles onto the nanomaterial network, again the robotic arm 701 places one holding tray 801 with chemical sensor chip 11 from the holding tray hopper 702 to the alignment and deposition area 713. The robotic arm lowers the conductive pathway pins 710 to make connections to each of chemical sensor chips. The deposition for each of the channels is done in parallel. Electrolytes from the electrolyte reservoirs 705 are deposited through the electrolyte reservoir inlet 906. The electrochemical deposition is performed with a three electrode cell setup. The reference electrode 904 and counter electrode 905 are placed in contact with an electrolyte through deposition well. Potential and current are applied by an external potentiostat 721.
[000200] The selection of an electrode, the applied potential and the charge density for a specific chemical sensor channel is controlled by the CAES customized software 727 such as LABVIEW (R). The temperature of an electrolyte during deposition is controlled by the external temperature control unit 724 and applied by the
heating/cooling module 714.
[000201] Upon completion of the deposition process, the robotic arm 701 removes excess electrolytes to a waste electrolyte reservoir 708 and flushes each chip 802 with deionized water from a water reservoir 704 and drains it to a waste water reservoir 708. Next, the chips 802 are dried with ultra-high purity (UHP) nitrogen (N2) through the gas connector 706 controlled by an external mass flow controller 725. The robotic arm 701 then removes the holding tray 801 from the alignment and deposition area 713 and places it into the processed tray hopper 715.
[000202] It is noted that some nanomaterials require an annealing process after drying, such as 4 hours at 500 °C under an inert gas such as nitrogen or argon (Ar).
Example 2. Chemical Sensor Chip Gas Sensing
[000203] The following is an example of gas sensing with a chemical sensor chip in a laboratory environment using the Customized Sensing System (CSS). In this example, the gas sensing process is automated and all operations of the process are controlled by a CSS customized software 1059 such as LABVIEW (R).
[000204] Three chemical sensor chips 11 on a sensor tray 1109 are placed in a sensing chamber 1041. The source electrode 120 and the drain electrode 130 pads of the sensor chips 11 are set in connection with the sensing chamber conductive pins 1106. In this example the sensing is performed with ammonia (NEb). Ammonia is mixed with synthetic air to gain the desired concentrations. A set of measurements are performed with concentrations varying between 0.5 ppm and 200 ppm by volume, with 1 ppm interval. It is noted that the permissible exposure limit (PEL) set by OSHA standards for ammonia is 50 ppm. The flow rates of 1012 and synthetic air 1013 from cylinders are controlled by mass flow controllers and valves unit 1020. The gases are directed to a gas pre-treatment chamber unit 1030 where the temperature and the humidity are adjusted with temperature control unit 1060 and a humidity control unit 1070.
[000205] Measurements with different temperature and humidity are performed. The temperature is varied from -10 °C to 60 °C with interval of 1 °C, and the relative humidity is varied from 0% to 95 % with interval of 1-5 %. The sensor channels are first stabilized in synthetic air for 60 minutes, and then exposed with different concentrations of ammonia with 1-15 minutes with 30 second intervals exposure and 1-20 minutes with intervals of 1 minute recovery times. The resistance is measured before, during and after exposure to ammonium by the source measurement unit 1055 and the amplitude and the modulation of the resistance is recorded. 15-20 cycles of measurements are carried out for each concentration, temperature and humidity settings. After a cycle, the sensor is allowed to recover in synthetic air flow for 60 min. A response time for the sensor chips is then calculated. A response is defined as the time for the sensor channel to reach 90% of its steady-state value, and the recovery time is identified as the time required for the sensor channel after the exposure to return to 50% of its maximum response.
[000206] Another test involving a photoelectrical measurement for testing sensing in the presence of light is performed. The purpose of the measurement is to realize the effect of light illumination on sensing performance. The lighting was contributed by a RGB and UV LEDs 1105. The chemical sensor chip 11 has a nanomaterial network functionalized with tin dioxide (SnC ) nanoparticles. The conductivity of tin dioxide may be altered when illuminated and therefore light can impact the sensing measurement. The photoelectric measurements are performed with and without exposure to light to understand the impact of light on sensing. The chemical sensor chips 11 are first stabilized in the synthetic air for 60 minutes, and then the chips are illuminated with LED lights 1105 for 1-15 minutes in 30 second intervals under synthetic air. Then LEDs 1105 are turned off to allow a 20 minute recovery time. Three cycles of measurements are performed and then the sensor chips 11 are allowed to recover for 60 min.
[000207] To understand the sensing performance of sensor channels in the presence of light, a sensing test is performed with LED lights turned on continuously during the measurement process. Sensor chips are first stabilized in synthetic air for 60 minutes, and then exposed to different concentrations of chemicals with 1-15 minutes (30 second intervals) exposure and 1-20 minutes recovery times (with 1 minute interval). After the last sensing cycle, sensors chips are allowed to recover in the synthetic air for additional 60 minutes.
Example 3. Development of a Pattern Recognition Algorithm
[000208] Large data sets are collected in laboratory measurements described in
Example 2. These measurements which simulate known concentrations of chemicals at different temperature and humidity conditions are used to build a chemical sensing database.
[000209] All parameters of the tests including, but not limited to, chemical concentration, temperature, relative humidity, rate of change, rate of recovery, point of saturation, baseline level and/or presence of light together with the readings of electrical characteristics measured are recorded to the database. Various mathematical and learning algorithms including, but not limited to, pattern recognition algorithms and/or machine learning algorithms such as Support Vector Machines (SVMs) and/or Artificial Neural Networks (ANNs) are used to develop a pattern recognition algorithm. The partem recognition algorithm may be developed by supervised and/or unsupervised learning methods. Supervised learning refers to a learning method where one or more relevant and known training sets are used to develop the pattern recognition algorithm. Unsupervised learning refers to a learning method where relevant and known training sets are not used but patterns are rather developed by discovering hidden patterns in a data.
[000210] Additionally, real world trials where the sensor chips are exposed to airborne chemicals outside laboratory environment are stored in the chemical sensing database. The partem recognition algorithm may further be improved by chemical detection data reported by users. The pattern recognition algorithm improvement data may be processed at the cloud system level.
Example 4. Monitoring Air Quality
[000211] The described chemical sensor system is applied to monitoring air quality surrounding an individual user. The detected chemicals are for example sulfur dioxide (SC ), nitrogen dioxide (NC ), ozone (O3), carbon monoxide (CO), molds and certain VOCs typical for urban air. The users may also monitor and track fitness-related metrics in addition to knowing about toxic and harmful airborne gas levels around them. The users may be fitness- and health-conscious consumers and/or people with certain health conditions such as an asthma or a heart disease. Users can use the information of chemical levels surrounding them to avoid places with poor air quality both indoors and outdoors. Users monitor the air quality of their homes or work places and adjust the need for e.g. air purifiers and ventilation accordingly.
[000212] When the chemical sensor device is wearable, the users carry it for example as a wristband, a bracelet or a pendant. The dimensions of the wearable sensor device are expected to be about 25 mm wide x 55 mm long x 12 mm high. Users would control and read data from a software application on a smartphone or a tablet. The software will also allow the users to share information regarding the air quality in their surroundings at different locations to the cloud. This way the user can identify for example locations in the city where the air quality is poor at certain times of the day and avoid those locations.
[000213] The software application also includes machine learning capabilities of providing predictive alerts to the end user. Examples include alerting the user of a certain toxic air environment that may not be conducive to the user's health based on the user health profile and/or past user experiences in this type of environment.
Example 5. Monitoring carbon monoxide (CO) and hydrogen cyanide (HCN)
[000214] The described chemical sensor system is used for monitoring CO and HCN in rescue operations where firefighters battle a fire. CO is a colorless, odorless and tasteless gas produced by an incomplete combustion of hydrocarbons. It is harmful to humans when inhaled causing symptoms such as headache, dizziness, nausea, chest pain and in worst cases coma or even death. ( Ref. Prockop LD, Chichkora RI, "Carbon monoxide intoxication: an updated review", Journal of Neurological Sciences 262 (l-2)m 122-130, 2007) Concentrations of CO above 100 ppm are considered dangerous.
[000215] HCN is a poisonous gas, liquid or solid used widely in industry as solvents and in manufacturing of plastics. (Ref. Leybell et al., "Cyanide Toxicity", Medscape Reference Drugs, Diseases & Procedures, version 7/21/2014) HCN poisoning may cause airway irritation, cardiovascular collapse and death within minutes. Firefighters are exposed to CO and HCN when operating on fires. HCN is present especially in residential and industrial fires.
[000216] The described sensor system is used to for monitor CO and/or HCN exposure of firefighters, as they work in the field. The lightweight and small detector is attached to gear, such as a helmet or a uniform. The sensor system alerts firefighter and their superiors when the firefighter is in a location with dangerously high CO and/or HCN concentration. Additionally, the sensor system collects data of the firefighter's exposure to CO and/or HCN throughout a period of time. The data is then used to identify situations where the exposure either instantly or over a period of time has been harmful and dangerous. The data is useful for identification of CO and/or HCN intoxication or poisoning and enhance the treatment and care.
Example 6. Non-invasive Glucose Sensor
[000217] The described chemical sensor system is used for the monitoring glucose level in a non-invasive way. A statistical analysis done by World Health Organization (WHO) indicates that an estimate 1.5 million deaths owing to the direct cause of diabetes in 2012. In 2014, 9 % of the global human population of age 18+ has diabetes. Diabetes can cause damage to heart, blood vessels, eyes, kidneys, and nerves over time.
[000218] The described non-invasive glucose chemical sensor device is lightweight portable device and can communicate to smart device through USB cable or wirelessly. The glucose level may be measured from such as, but not limited to, saliva, sweat, and urine. The combination of pattern recognition algorithm and software application can provide in situ reading for the glucose level, storage the measurement result, and view the history of the glucose level which will improve patient care.
[000219] Other biomolecules and/or biomarkers are also measured. These include hormones, pheromones and ketone bodies.
Example 7. Cloud-base data
[000220] The described chemical sensor system is connected to a cloud system for processing, storing, distributing and/or sharing information. Users have a chemical sensor system embedded in their smartphones. The chemical sensor system collects data of chemicals (e.g. sulfur dioxide (SO2), nitrogen dioxide (NO2), ozone (O3), carbon monoxide (CO) and certain VOCs), as well as temperature, humidity and UV index information as the users move around during a day. The data is combined with the location information provided by the GPS navigation embedded in the smartphone. The data is continuously collected and communicated to the cloud system that processes the data, stores the data and shares the data. Users, including the users of the network as well as third party users, can access the data from their smartphone software application or through an internet browser application. The third party users are industrial, commercial or governmental organizations interested in statistical data of chemical levels in an area. The data is presented as graphs, readouts and as interactive maps.
[000221] A user may log on to their personalized account to get a summary of the chemical exposure they are encountering at that moment, or e.g. during the past 24 hours. In addition, they can review their past exposure to these chemicals. They can also see statistical data on chemical levels in their living area over a period of time e.g. days, weeks, months, years. Users can review the data on an interactive map that demonstrates with color the areas with most pollution. The user can also set an alert that allows their smartphone to indicate when the chemical levels in their living area are exceptionally high, or when they enter an area where the chemical levels are exceptionally high. The alert could be a text message, an email or a pop-up message on the smartphone screen. The user may also enter personalized health information and remarks about their health condition to the software. This allows them to understand the relationship between their timely exposures to chemicals and their health.

Claims

A chemical sensor system comprising:
(a) a chemical sensor device, comprising
i. a housing, having therein,
1. a sensor controller unit;
2. one or more chemical sensor chips, each operably
connected to the sensor controller unit;
3. a power source; and
4. a wireless or a wired transmitter;
ii. a port, operable integrated into the housing; and
(b) a partem recognition module, optionally contained within the chemical sensor device.
The chemical sensor system of claim 1, further comprising a software application.
The chemical sensor system of claim 1, optionally comprising a chamber with a pump providing a regulated air flow exposure to the chemical sensor chip. The chemical sensor system of claim 1, wherein in the chemical sensor chip is replaceable.
The chemical sensor system of claim 1, wherein the chemical sensor system is embedded to consumer electronics, commercial electronics, home appliances, security devices, lighting, or devices supporting chemical sensing
functionality.
The chemical sensor system of claim 1, wherein two or more chemical sensor systems are in a network.
A chemical sensor chip comprising
(a) a substrate;
(b) two or more chemical sensor channels permanently configured on the surface of the substrate, each chemical sensor channel formed by the co- configuration of at least one source electrode and one drain electrode; wherein each of said chemical sensor channels comprises a nanomaterial network formed from a conducting nanomaterial; and
(c) optionally, at least one on-chip reference electrode and at least one on-chip counter electrode for each chemical sensor channel.
8. The chemical sensor chip of claim 7, wherein the width of the chemical sensor channel formed between said source electrode and said drain electrode is between 0.002 mm to 0.01 mm.
9. The chemical sensor chip of claim 7, wherein the substrate comprises two or more layers.
10. The chemical sensor chip of claim 7, wherein the nanomaterial network is functionalized with nanoparticles.
1 1. The chemical sensor chip of claim 7, wherein the nanomaterial network is in the form of a nanotube, a nanowire, a nanoribbon, and/or combinations thereof.
12. The chemical sensor chip of claim 7, wherein the conducting nanomaterial comprises a material selected from the group consisting of carbon, silicon, conducting polymers, metals and metal oxides.
13. The chemical sensor chip of claim 7, wherein the nanomaterial network
comprises a material selected from the group consisting of single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), silicon (Si) nanowires, zinc oxide (ZnO) nanostructures, tin oxide (Sn02) nanowires, indium oxide (In203) nanowires, boron nitride (BN) nanotubes, carbon nitride nanotubes (CN Ts), BxC3N2 nanotube structures, tellurium (Te) nanotube and nanowire structures, Te nanotube and nanowire structures with embedded gold (Au) nanoparticles, multi-segmented metal nanowires such as cobalt-gold (Co/Au) or nickel/gold (Ni/Au) structures, polyaniline (PANI) nanowire structures and poly pyrrole (Ppy) nanowire structures.
14. The chemical sensor chip of claim 10, wherein the nanoparticles are selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metalloid nanostructures, macromolecules, conductive polymer nanoparticles, biomolecules.
15. The chemical sensor chip of claim 14, wherein the nanoparticles are
biomolecules and the biomolecules are selected from the group consisting of proteins, lipids, nucleic acids, sugars and glycoproteins.
16. The chemical sensor chip of claim 14, wherein the nanoparticles are metals and the metals are selected from the group consisting of gold (Au), palladium (Pd), platinum (Pt) and/or other metal nanoparticles.
17. The chemical sensor chip of claim 14, wherein the nanoparticles are metal oxide nanoparticles and the metal oxide particles are selected from the group consisting of tin oxide (Sn02) and other metal oxides.
18. The chemical sensor chip of claim 7, wherein each of the source and drain electrodes are independently fabricated of a metal selected from the group consisting of titanium (Ti), platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), chromium (Cr), and combinations thereof.
19. A method of detecting a chemical comprising exposing the chemical sensor system of claim 1 to an area, zone or environment suspected of containing the chemical.
20. The method of claim 19, wherein the chemical is in a form of gas, vapor, liquid or aerosol.
21. The method of claim 19, wherein the chemical is a volatile organic compound.
22. The method of claim 19, wherein the chemical is considered dangerous to human health or is a health concern.
23. The method of claim 19, wherein the chemical is associated with food
spoilage.
24. The method of claim 19, wherein the chemical is an indicator of food or
beverage quality.
25. The method of claim 19, wherein the chemical is an explosive, a chemical warfare agent or a biological warfare agent.
26. The method of claim 19, wherein the chemical is a substance of abuse.
27. The method of claim 19, wherein the chemical is an indicator of product
contamination, quality or consistency.
28. The method of claim 19, wherein the chemical is a pesticide or a pest control chemical.
29. The method of claim 19, wherein the chemical is an indicator of a plant
disease.
30. The method of claim 19, wherein the chemical is present in facilities
associated with manufacturing, mining, industry, and oil and gas industry.
31. A pattern recognition algorithm comprising one or more formulas to provide identification and concentration values or measurement of a chemical detected by method of claim 19.
32. The pattern recognition algorithm of claim 31 , wherein the formula is developed from gas detection data measured using different chemicals, concentrations, temperatures and humidity levels.
33. The pattern recognition algorithm of claim 31 , wherein the formula is
developed by supervised and unsupervised machine learning methodologies.
34. A predictive analysis algorithm comprising one or more formulas to provide predictive and automated alerts based on one or more chemicals detected by method of claim 19.
35. A method of fabricating the chemical sensor chip of claim 7 in comprising the steps of
(a) automated electrochemical deposition and alignment of a nanomaterial network.
(b) automated electrochemical deposition of nanoparticles on the
nanomaterial network; and
(c) automated measurement of one or more electrical properties of the chemical sensor chip.
36. The method of claim 35, wherein the nanomaterial network is deposited and aligned between the gap within the electrodes in the chemical sensor channel.
37. The method of claim 35, wherein the electrochemical deposition of
nanoparticles comprises steps of
(a) adding an electrolyte on the nanomaterial network, and
(b) synthesizing nanoparticles from an electrolyte by an electrochemical deposition technique.
38. The method of claim 35, wherein the electrical property is a conductivity, a resistance, a voltage, a current, a capacitance, an inductance, or a field-effect transistor property.
39. An apparatus to perform the method claim 35 comprising
(a) deposition wells,
(b) reservoirs to hold water, nanomaterials and electrolytes,
(c) reservoirs to hold water, nanomaterial and electrolyte waste,
(d) conductive pathway pins,
(e) nitrogen gas connector,
(f) tubing,
(g) heating and cooling module, (h) alignment and deposition area,
(i) tray hoppers,
(j) robotics and automation,
(k) an external software to control operations of the apparatus,
(1) one or more external equipment, and
(m) an electronic interface board to perform communication between the apparatus and the external equipment (1) and the external software (k). The apparatus of claim 39, wherein the external equipment comprises a potentiostat, a source measurement unit, a waveform function generator, a temperature control unit, and a mass flow controller.
A method of sensing chemicals with the chemical sensor chip of claim 7 in laboratory comprising the steps of
(a) recording one or more electrical properties of the chemical sensor chip;
(b) exposing the chemical sensor chip to a chemical or to a mixture of two or more chemicals with concentrations in a range from ppb to ppm;
(c) recording changes in one or more electrical properties of the chemical sensor chip while exposing the chemical sensor chip to a chemical or to a mixture of two or more chemicals;
(d) adjusting and controlling the concentration of the chemicals;
(e) adjusting and controlling the temperature, humidity and light exposure during a measurement.
The method of claim 41, wherein the steps (a) to (e) are performed in an automated manner.
The method of claim 41, wherein the electrical property is a conductivity, a resistance, a voltage, a current, a capacitance, an inductance, or a field-effect transistor property.
The method of claim 41, wherein the chemicals comprise chemicals of claims 20- 30.
An apparatus to perform the method of claim 41 comprising
(a) robotics and automation to control all operations of the apparatus,
(b) a volatile organic compound generator,
(c) one or more gas cylinders,
(d) an air cylinder,
(e) an ozone generator, (f) valves,
(g) one or more mass flow controllers,
(h) one or more temperature controller,
(i) one or more humidity controller,
j) light-emitting diodes providing ultraviolet and visible light,
(k) one or more pre-treatment chambers for adjusting conditions of the samples prior to measurement,
(1) one or more sensing chambers for measuring the sample under desired conditions,
(m) an external software to control operations of the apparatus,
(n) one or more external equipment, and
(o) an electronic interface board to perform communication between the apparatus and the external equipment (g) and the external software (f). The apparatus of method 45, wherein the external equipment comprises a valve control unit, a volatile organic compound generator control unit, a light emitting diode control unit, a source measurement unit, a mass flow control unit, an ozone generator control unit and a fume hood.
A method of communicating, processing and storing data from a chemical sensor system of claim 2 to one or more remote servers through one or more communication protocols, comprising the steps of
(a) transmitting chemical detection data from the chemical sensor system to one or more remote devices;
(b) processing chemical detection data at the remote server;
(c) storing the chemical detection data to the remote server; and
(d) distributing and sharing the chemical detection data to users.
The method of claim 47, wherein in the communication protocol is a wired or wireless Institute of Electrical and Electronics Engineers Standards
Association (IEEE-SA) standard.
The method of claim 47, wherein in data processing is performed by a pattern recognition algorithm of claim 31.
The method of claim 47, wherein the data is distributed or shared through software applications using a standard internet protocol.
The method of claim 50, wherein the software is an internet browser application.
52. The method of claim 50, wherein the software is an end user application.
53. The method of claim 50, wherein the software application is on a smartphone, a smartwatch, a tablet computer, a personal computer or a standalone system.
54. The method of claim 49, wherein in the data is from other commercial and consumer sources.
55. The chemical sensor system of claim 2, wherein the software application is accessed through the internet by mobile applications, personal computers, televisions, hardware devices or hardware media.
56. The chemical sensor system of claim 2, wherein the software application is used to customize information that is received, distributed or shared to the public through the cloud system.
57. The chemical sensor system of claim 2, wherein the software application is used to provide personalized alerts and predictive alerts based on entered user profiles and use cases.
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