US20110003425A1 - Process for making multi-crystalline silicon thin-film solar cells - Google Patents
Process for making multi-crystalline silicon thin-film solar cells Download PDFInfo
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- US20110003425A1 US20110003425A1 US12/007,154 US715408A US2011003425A1 US 20110003425 A1 US20110003425 A1 US 20110003425A1 US 715408 A US715408 A US 715408A US 2011003425 A1 US2011003425 A1 US 2011003425A1
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title description 47
- 239000010409 thin film Substances 0.000 title description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010936 titanium Substances 0.000 claims abstract description 71
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 25
- 238000002791 soaking Methods 0.000 claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 7
- 229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 28
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 20
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 16
- 229910000676 Si alloy Inorganic materials 0.000 claims description 15
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 15
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910033181 TiB2 Inorganic materials 0.000 claims description 2
- 229910034327 TiC Inorganic materials 0.000 claims description 2
- 229910008479 TiSi2 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000002161 passivation Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 95
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0368—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors
- H01L31/03682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic System
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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- H01L31/03921—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including only elements of Group IV of the Periodic System
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- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
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- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a process for making multi-crystalline silicon thin-film solar cells and, more particularly, to a high-temperature process for making multi-crystalline silicon thin-film solar cells based on plasma-enhanced chemical vapor deposition.
- Silicon-based solar cells are generally made in low-temperature processes based on plasma-enhanced chemical vapor deposition (“PECVD”).
- PECVD plasma-enhanced chemical vapor deposition
- An amorphous or microcrystalline silicon film is coated on a substrate of glass, aluminum, silicon, stainless steel or plastics.
- a back contact is made of aluminum, gold, silver or transparent conductive oxide such as indium-tin oxide (“ITO”) and zinc oxide.
- ITO indium-tin oxide
- the primary advantage of the low-temperature processes is the wide variety of materials that can be used to make the substrates. However, they suffer drawbacks such as defective silicon films, low photoelectrical conversion efficiencies and low light-soaking stability.
- a silicon material is highly diluted in hydrogen according to the following notion:
- the concentration or flow rate of H 2 is more than 15 times as high as that of SiH 4 .
- the problems with the PECVD include a low growth rate of the film, a long process and a high cost.
- SPC solid phase crystallization
- AIC aluminum-induced crystallization
- the SPC is based on the PECVD.
- an amorphous silicon film is deposited, intensively heated and annealed at a high temperature.
- a multi-crystalline silicon film with a grain size of 1 to 2 micrometers is made.
- a substrate 71 is coated with an aluminum film 72 .
- An amorphous silicon film 73 is coated on the aluminum film 72 based on the PECVD and annealed at a temperature of 575 degrees Celsius for a long time to form a seed film 74 . Then, it is subjected to an epitaxial process such as the PECVD or an electron cyclotron resonance chemical deposition (“ECR-CVD”) to make a multi-crystalline silicon film 75 .
- ECR-CVD electron cyclotron resonance chemical deposition
- the AIC however involves many steps and takes a long time.
- the resultant grain size is 0.1 to 10 micrometers.
- a conventional silicon-based tandem solar cell includes an upper laminate and a lower laminate.
- the upper laminate is an amorphous silicon p-i-n laminate.
- the lower laminate is a microcrystalline silicon p-i-n laminate.
- the present invention is therefore intended to obviate or at least alleviate the problems encountered in prior art.
- It is the primary objective of the present invention is to provide a process for making a tandem solar cell.
- a titanium-based alloy film is provided on a ceramic substrate.
- Dichlorosilane and diborane are deposited on the titanium-based alloy film to grow a p + type back surface field film.
- the temperature is raised to grow a p ⁇ type light-soaking film on the p + type back surface field film.
- Phosphine is deposited on the p ⁇ type light-soaking film to form an n + type emitter.
- an n + -p ⁇ -p + laminate is provided on the titanium-based alloy film.
- SiCNO:Ar plasma is used to passivate the n + -p ⁇ -p + laminate, thus forming an anti-reflection film of SiCN/SiO2 on the n + type emitter.
- the n + -p ⁇ -p + laminate is etched in a patterned mask process.
- a p ⁇ type ohmic contact is formed on the titanium-based alloy film.
- the anti-reflection film is etched in a patterned mask process.
- the n + type emitter is coated with a titanium/palladium/silver alloy film that is annealed in hydrogen. An n ⁇ type ohmic contact is formed on the n + type emitter.
- FIG. 1 is a flowchart of a process for making multi-crystalline silicon thin-film solar cells according to the preferred embodiment of the present invention.
- FIG. 2 is a side view of a ceramic substrate for use in the process shown in FIG. 1 .
- FIG. 3 is a side view of a titanium-based alloy film coated on the ceramic substrate in the process shown in FIG. 2 .
- FIG. 4 is an atmospheric chemical vapor deposition apparatus for processing the laminate shown in FIG. 3 .
- FIG. 5 is a side view of an amorphous silicon film coated on the titanium-based alloy film shown in FIG. 4 .
- FIG. 6 is a side view of a p + type multi-crystalline silicon back surface field converted from the amorphous silicon film and the titanium-based alloy film shown in FIG. 5 .
- FIG. 7 is a side view of an n-i-p multi-crystalline silicon laminate coated on the laminate shown in FIG. 6 .
- FIG. 8 is a side view of a plasma-enhanced chemical vapor deposition apparatus for providing SiCNO:Ar plasma to coat an anti-reflection film on the n-i-p multi-crystalline silicon laminate shown in FIG. 7 .
- FIG. 9 is a side view of a p ⁇ type ohm contact provided on the laminate shown in FIG. 6 .
- FIG. 10 is a side view of an n ⁇ type ohm contact connected to the anti-reflection film shown in FIG. 9 .
- FIG. 11 is a side view of a substrate for use in a conventional process for making a multi-crystalline silicon film.
- FIG. 12 is a side view of an aluminum film coated on the substrate shown in FIG. 11 .
- FIG. 13 is a side view of an amorphous silicon film coated on the aluminum film shown in FIG. 12 .
- FIG. 14 is a side view of the substrate coated with a seed film converted from the amorphous silicon film and the aluminum film of FIG. 13 .
- FIG. 15 is a side view of a multi-crystalline silicon film coated on the seed film shown in FIG. 14 .
- FIG. 1 there is shown a process for making multi-crystalline silicon thin-film solar cells according to the preferred embodiment of the present invention.
- a ceramic substrate 21 is provided.
- the ceramic substrate 21 is made of aluminum oxide.
- the thickness of the substrate 21 is 0.1 to 1.0 mm.
- the ceramic substrate 21 is coated with a titanium-based alloy film 24 ( FIG. 6 ).
- the titanium/silicon alloy film 24 may be made of TiSi 2 , TiN, TiC, TiB 2 or TiC x N y .
- the titanium-based alloy film 24 can be provided in three subroutines.
- a titanium film 22 is coated on the ceramic substrate 21 in an e-gun evaporation system at 250 degrees Celsius.
- the thickness of the titanium film 22 is 1000 to 5000 angstroms.
- dichlorosilane is deposited on the titanium film 22 in an atmospheric pressure chemical vapor deposition (“APCVD”) apparatus 4 , at 800 to 1100 degrees Celsius.
- APCVD atmospheric pressure chemical vapor deposition
- the dichlorosilane and the titanium film 22 exchange silicon atoms and titanium atoms to form the titanium/silicon alloy film 24 .
- the grain size of the titanium/silicon alloy film 24 is larger than 1 micrometer.
- the sheet resistance of the titanium/silicon ally film 24 is lower than ohm/cm 2 .
- a titanium film 22 is coated on the ceramic substrate 21 in an e-gun evaporation system at 250 degrees Celsius.
- the thickness of the titanium film 22 is 1000 to 5000 angstroms.
- an amorphous silicon film 23 is coated on the titanium film 22 in a plasma-enhanced chemical vapor deposition (“PECVD”) apparatus.
- PECVD plasma-enhanced chemical vapor deposition
- the amorphous silicon film 23 may be coated on the ceramic substrate 21 before the titanium film 22 is coated on the amorphous silicon film 23 . In either case, the ratio of the thickness of the amorphous silicon film 23 to the thickness of the titanium film 22 is 2:1.
- the titanium film 22 and the amorphous silicon film 23 are heated in a high-temperature annealing apparatus 5 at 700 to 900 degrees Celsius so that they exchange titanium atoms and silicon atoms, thus forming the titanium/silicon alloy film 24 . Then, the temperature in the APCVD apparatus 5 is raised to a value-higher than 1000 degrees Celsius for the epitaxial growth of the grains.
- the size of the grains of the titanium/silicon alloy film 24 is larger than 1 micrometer.
- the sheet resistance of the titanium/silicon alloy film 24 is lower than ohm/cm 2 .
- dichlorosilane and titanium tetrachloride are made to react with each other to form the titanium/silicon alloy film 24 in the APCVD apparatus 4 .
- dichlorosilane and diborane are made to exchange silicon atoms and boron atoms in the APCVD apparatus 4 at 900 to 1000 degrees Celsius, thus forming a type multi-crystalline silicon back surface field film 25 .
- the temperature in the APCVD apparatus 4 is raised to a value higher than 1000 degrees Celsius. More dichlorosilane and diborane are made to exchange silicon atoms and boron atoms, thus forming a p ⁇ type multi-crystalline silicon light-soaking film 26 on the p + type multi-crystalline silicon back surface field film 25 , which is used as a seed layer.
- the epitaxial growth of the p ⁇ type multi-crystalline silicon light-soaking film 26 is 0.5 micrometer/minute and lasts for 30 minutes.
- the thickness of the p ⁇ type multi-crystalline silicon light-soaking film 26 is 1 to 15 micrometers.
- the size of the grains 261 of the p ⁇ type multi-crystalline silicon light-soaking film 26 is larger than 10 micrometers.
- the concentration of the boron atoms in the p ⁇ type multi-crystalline silicon light-soaking film 26 is 10 16 to 10 17 #/cm 3 .
- phosphine is deposited on the p ⁇ type multi-crystalline silicon light-soaking film 26 , thus executing the n + type deposition of the phosphor atoms of the phosphine on the p ⁇ type multi-crystalline silicon light-soaking film 26 . That is, an n + type multi-crystalline silicon emitter 27 is form on the p ⁇ type multi-crystalline silicon light-soaking film 26 .
- the thickness of the n + type multi-crystalline silicon emitter 27 is smaller than 1000 angstroms.
- the concentration of the boron atoms in the n + type multi-crystalline silicon emitter 27 is 10 18 to 10 19 #/cm 3 .
- n + type multi-crystalline silicon emitter 27 the p ⁇ type multi-crystalline silicon light-soaking film 26 and the p + type multi-crystalline silicon back surface field film 25 together form a n + -p ⁇ -p + laminate 1 .
- SiCNO:Ar plasma is provided in a PECVD apparatus 6 .
- Silane, nitrous oxide and methane are used as the raw materials of the SiCNO:Ar plasma while argon is used as a carrier.
- the SiCNO:Ar plasma passivates the n + -p ⁇ -p + laminate 1 .
- the dangling bonds of the silicon atoms on the surface 271 of the n + type multi-crystalline silicon emitter 27 are filled.
- the dangling bonds of the silicon atoms at the grain boundaries 262 between the grains 261 of the p ⁇ type multi-crystalline silicon light-soaking film 26 are also filled.
- the dangling bonds of the silicon atoms in the p + type multi-crystalline silicon back surface field film 25 are also filled.
- an anti-reflection film 28 of SiCN/SiO 2 is coated on the n + type multi-crystalline silicon emitter 27 .
- potassium hydroxide solution is used to etch the multi-crystalline silicon laminate in a patterned mask process.
- the substrate 21 and the titanium/silicon alloy film 24 are not etched at all.
- a p ⁇ type ohmic contact 29 is made on the titanium/silicon alloy film 24 .
- the anti-reflection film 28 are etched in a patterned mask process so that ortions of the n + type multi-crystalline silicon emitter 27 are exposed from the anti-reflection film 28 .
- a titanium/palladium/silver alloy film 30 is provided in the exposed portions of the n + type multi-crystalline silicon emitter 27 and annealed in the high-temperature annealing apparatus 5 .
- an n ⁇ type ohmic contact 31 is provided on the titanium/palladium/silver alloy film 30 .
- the multi-crystalline silicon laminate 1 includes the ceramic substrate 21 and the titanium/silicon alloy film 24 used as the seed layer.
- the APCVD apparatus 6 is used in the high-temperature process for the exchange of the silicon atoms and the boron atoms, thus forming the p + type multi-crystalline silicon back surface field film 25 and the p ⁇ type multi-crystalline silicon light-soaking film 26 . Then, the phosphor atoms and the silicon atoms are exchanged so that the n + type multi-crystalline silicon emitter 28 is made.
- the SiCNO:Ar plasma is used to passivate the laminate 1 .
- the patterned mask process is used to make the p ⁇ type ohmic contact 29 on the titanium/silicon alloy film 24 .
- the patterned mask process is used to coat the titanium/palladium/silver alloy film 30 on the n + type multi-crystalline silicon emitter 27 and provide the n ⁇ type ohmic contact 31 on the n + type multi-crystalline silicon emitter 27 .
- the ceramic substrate 21 is inexpensive, refractory and chemically stable, and can be integrated with materials for construction.
- the titanium/silicon alloy film 24 is environmentally friendly, abundant and inexpensive.
- the titanium/silicon alloy film 24 ensures the integrity of the multi-crystalline silicon laminate 1 since its thermal expansion coefficient is matched with that of the ceramic substrate 21 and the p + type multi-crystalline silicon back surface field film 25 .
- the solar cells provide a high photoelectrical conversion efficiency and excellent light-soaking stability because the PEVCD apparatus 6 is used in the high-temperature process to passivate the multi-crystalline silicon films that would otherwise involve high mobility and a large diffusion length, and take long for recombination.
- the process of the present invention provides a high epitaxial growth rate and a high crystal quality.
Abstract
Description
- 1. Field of Invention
- The present invention relates to a process for making multi-crystalline silicon thin-film solar cells and, more particularly, to a high-temperature process for making multi-crystalline silicon thin-film solar cells based on plasma-enhanced chemical vapor deposition.
- 2. Related Prior Art
- Silicon-based solar cells are generally made in low-temperature processes based on plasma-enhanced chemical vapor deposition (“PECVD”). An amorphous or microcrystalline silicon film is coated on a substrate of glass, aluminum, silicon, stainless steel or plastics. A back contact is made of aluminum, gold, silver or transparent conductive oxide such as indium-tin oxide (“ITO”) and zinc oxide.
- The primary advantage of the low-temperature processes is the wide variety of materials that can be used to make the substrates. However, they suffer drawbacks such as defective silicon films, low photoelectrical conversion efficiencies and low light-soaking stability. In the PECVD, while coating the microcrystalline silicon film, a silicon material is highly diluted in hydrogen according to the following notion:
-
[H2]/[SiH4]>15 - That is, the concentration or flow rate of H2 is more than 15 times as high as that of SiH4. The problems with the PECVD include a low growth rate of the film, a long process and a high cost.
- Regarding the making of the multi-crystalline silicon solar cells, there are various techniques such as solid phase crystallization (“SPC”) and aluminum-induced crystallization (“AIC”).
- The SPC is based on the PECVD. In the SPC, an amorphous silicon film is deposited, intensively heated and annealed at a high temperature. Thus, a multi-crystalline silicon film with a grain size of 1 to 2 micrometers is made.
- There are however problems with the low-temperature processes for making multi-crystalline silicon solar cells based on the PECVD. Firstly, many defects occur in the silicon films. Secondly, the photoelectrical conversion efficiencies are low. Thirdly, the light soaking stabilities are low. Fourthly, the growth rates of the films are low. Sixthly, the processes are long. Seventhly, the costs are high.
- Referring to
FIGS. 11 through 15 , in the AIC, asubstrate 71 is coated with analuminum film 72. Anamorphous silicon film 73 is coated on thealuminum film 72 based on the PECVD and annealed at a temperature of 575 degrees Celsius for a long time to form aseed film 74. Then, it is subjected to an epitaxial process such as the PECVD or an electron cyclotron resonance chemical deposition (“ECR-CVD”) to make amulti-crystalline silicon film 75. The AIC however involves many steps and takes a long time. The resultant grain size is 0.1 to 10 micrometers. - A conventional silicon-based tandem solar cell includes an upper laminate and a lower laminate. The upper laminate is an amorphous silicon p-i-n laminate. The lower laminate is a microcrystalline silicon p-i-n laminate. Thus, the infrared and visible light of the sunlit can be converted into electricity. However, the photoelectrical conversion efficiency of the conventional silicon-based tandem solar cell deteriorates quickly.
- Concerning the process for making multi-crystalline silicon solar cells based on the AIC, the processes are long for including many steps and therefore expensive. As for the conventional silicon-based tandem solar cell, the photoelectrical conversion efficiency deteriorates quickly.
- The present invention is therefore intended to obviate or at least alleviate the problems encountered in prior art.
- It is the primary objective of the present invention is to provide a process for making a tandem solar cell.
- To achieve the primary objective, a titanium-based alloy film is provided on a ceramic substrate. Dichlorosilane and diborane are deposited on the titanium-based alloy film to grow a p+ type back surface field film. The temperature is raised to grow a p− type light-soaking film on the p+ type back surface field film. Phosphine is deposited on the p− type light-soaking film to form an n+ type emitter. Thus, an n+-p−-p+ laminate is provided on the titanium-based alloy film. SiCNO:Ar plasma is used to passivate the n+-p−-p+ laminate, thus forming an anti-reflection film of SiCN/SiO2 on the n+ type emitter. The n+-p−-p+ laminate is etched in a patterned mask process. A p− type ohmic contact is formed on the titanium-based alloy film. The anti-reflection film is etched in a patterned mask process. The n+ type emitter is coated with a titanium/palladium/silver alloy film that is annealed in hydrogen. An n− type ohmic contact is formed on the n+ type emitter.
- Other objectives, advantages and features of the present invention will become apparent from the following description referring to the attached drawings.
- The present invention will be described via the detailed illustration of the preferred embodiment referring to the drawings.
-
FIG. 1 is a flowchart of a process for making multi-crystalline silicon thin-film solar cells according to the preferred embodiment of the present invention. -
FIG. 2 is a side view of a ceramic substrate for use in the process shown inFIG. 1 . -
FIG. 3 is a side view of a titanium-based alloy film coated on the ceramic substrate in the process shown inFIG. 2 . -
FIG. 4 is an atmospheric chemical vapor deposition apparatus for processing the laminate shown inFIG. 3 . -
FIG. 5 is a side view of an amorphous silicon film coated on the titanium-based alloy film shown inFIG. 4 . -
FIG. 6 is a side view of a p+ type multi-crystalline silicon back surface field converted from the amorphous silicon film and the titanium-based alloy film shown inFIG. 5 . -
FIG. 7 is a side view of an n-i-p multi-crystalline silicon laminate coated on the laminate shown inFIG. 6 . -
FIG. 8 is a side view of a plasma-enhanced chemical vapor deposition apparatus for providing SiCNO:Ar plasma to coat an anti-reflection film on the n-i-p multi-crystalline silicon laminate shown inFIG. 7 . -
FIG. 9 is a side view of a p− type ohm contact provided on the laminate shown inFIG. 6 . -
FIG. 10 is a side view of an n− type ohm contact connected to the anti-reflection film shown inFIG. 9 . -
FIG. 11 is a side view of a substrate for use in a conventional process for making a multi-crystalline silicon film. -
FIG. 12 is a side view of an aluminum film coated on the substrate shown inFIG. 11 . -
FIG. 13 is a side view of an amorphous silicon film coated on the aluminum film shown inFIG. 12 . -
FIG. 14 is a side view of the substrate coated with a seed film converted from the amorphous silicon film and the aluminum film ofFIG. 13 . -
FIG. 15 is a side view of a multi-crystalline silicon film coated on the seed film shown inFIG. 14 . - Referring to
FIG. 1 , there is shown a process for making multi-crystalline silicon thin-film solar cells according to the preferred embodiment of the present invention. - Referring to
FIGS. 1 and 2 , at 11, aceramic substrate 21 is provided. Theceramic substrate 21 is made of aluminum oxide. The thickness of thesubstrate 21 is 0.1 to 1.0 mm. - The
ceramic substrate 21 is coated with a titanium-based alloy film 24 (FIG. 6 ). The titanium/silicon alloy film 24 may be made of TiSi2, TiN, TiC, TiB2 or TiCxNy. The titanium-basedalloy film 24 can be provided in three subroutines. - In the first subroutine, at 12 (
FIGS. 1 and 3 ), atitanium film 22 is coated on theceramic substrate 21 in an e-gun evaporation system at 250 degrees Celsius. The thickness of thetitanium film 22 is 1000 to 5000 angstroms. - At 13 a (
FIGS. 1 and 4 ), dichlorosilane is deposited on thetitanium film 22 in an atmospheric pressure chemical vapor deposition (“APCVD”)apparatus 4, at 800 to 1100 degrees Celsius. The dichlorosilane and thetitanium film 22 exchange silicon atoms and titanium atoms to form the titanium/silicon alloy film 24. The grain size of the titanium/silicon alloy film 24 is larger than 1 micrometer. The sheet resistance of the titanium/silicon ally film 24 is lower than ohm/cm2. - In the second subroutine, at 12 (
FIGS. 1 and 3 ), atitanium film 22 is coated on theceramic substrate 21 in an e-gun evaporation system at 250 degrees Celsius. The thickness of thetitanium film 22 is 1000 to 5000 angstroms. At 13 b (FIGS. 1 and 5 ), anamorphous silicon film 23 is coated on thetitanium film 22 in a plasma-enhanced chemical vapor deposition (“PECVD”) apparatus. Alternatively, theamorphous silicon film 23 may be coated on theceramic substrate 21 before thetitanium film 22 is coated on theamorphous silicon film 23. In either case, the ratio of the thickness of theamorphous silicon film 23 to the thickness of thetitanium film 22 is 2:1. - The
titanium film 22 and theamorphous silicon film 23 are heated in a high-temperature annealing apparatus 5 at 700 to 900 degrees Celsius so that they exchange titanium atoms and silicon atoms, thus forming the titanium/silicon alloy film 24. Then, the temperature in the APCVD apparatus 5 is raised to a value-higher than 1000 degrees Celsius for the epitaxial growth of the grains. The size of the grains of the titanium/silicon alloy film 24 is larger than 1 micrometer. The sheet resistance of the titanium/silicon alloy film 24 is lower than ohm/cm2. - In the third subroutine, dichlorosilane and titanium tetrachloride are made to react with each other to form the titanium/
silicon alloy film 24 in theAPCVD apparatus 4. - Referring to
FIGS. 1 and 7 , at 15, dichlorosilane and diborane are made to exchange silicon atoms and boron atoms in theAPCVD apparatus 4 at 900 to 1000 degrees Celsius, thus forming a type multi-crystalline silicon backsurface field film 25. - The temperature in the
APCVD apparatus 4 is raised to a value higher than 1000 degrees Celsius. More dichlorosilane and diborane are made to exchange silicon atoms and boron atoms, thus forming a p− type multi-crystalline silicon light-soakingfilm 26 on the p+ type multi-crystalline silicon backsurface field film 25, which is used as a seed layer. The epitaxial growth of the p− type multi-crystalline silicon light-soakingfilm 26 is 0.5 micrometer/minute and lasts for 30 minutes. The thickness of the p− type multi-crystalline silicon light-soakingfilm 26 is 1 to 15 micrometers. The size of thegrains 261 of the p− type multi-crystalline silicon light-soakingfilm 26 is larger than 10 micrometers. The concentration of the boron atoms in the p− type multi-crystalline silicon light-soakingfilm 26 is 1016 to 1017 #/cm3. - At 800 to 1000 degrees Celsius, phosphine is deposited on the p− type multi-crystalline silicon light-soaking
film 26, thus executing the n+ type deposition of the phosphor atoms of the phosphine on the p− type multi-crystalline silicon light-soakingfilm 26. That is, an n+ typemulti-crystalline silicon emitter 27 is form on the p− type multi-crystalline silicon light-soakingfilm 26. The thickness of the n+ typemulti-crystalline silicon emitter 27 is smaller than 1000 angstroms. The concentration of the boron atoms in the n+ typemulti-crystalline silicon emitter 27 is 1018 to 1019 #/cm3. The n+ typemulti-crystalline silicon emitter 27, the p− type multi-crystalline silicon light-soakingfilm 26 and the p+ type multi-crystalline silicon backsurface field film 25 together form a n+-p−-p+ laminate 1. - Referring to
FIGS. 1 and 8 , at 16, SiCNO:Ar plasma is provided in aPECVD apparatus 6. Silane, nitrous oxide and methane are used as the raw materials of the SiCNO:Ar plasma while argon is used as a carrier. The SiCNO:Ar plasma passivates the n+-p−-p+ laminate 1. Hence, the dangling bonds of the silicon atoms on thesurface 271 of the n+ typemulti-crystalline silicon emitter 27 are filled. The dangling bonds of the silicon atoms at thegrain boundaries 262 between thegrains 261 of the p− type multi-crystalline silicon light-soakingfilm 26 are also filled. The dangling bonds of the silicon atoms in the p+ type multi-crystalline silicon backsurface field film 25 are also filled. Moreover, ananti-reflection film 28 of SiCN/SiO2 is coated on the n+ typemulti-crystalline silicon emitter 27. - Referring to
FIGS. 1 and 9 , at 17, potassium hydroxide solution is used to etch the multi-crystalline silicon laminate in a patterned mask process. Thesubstrate 21 and the titanium/silicon alloy film 24 are not etched at all. A p− typeohmic contact 29 is made on the titanium/silicon alloy film 24. - Referring to
FIGS. 1 and 10 , at 18, theanti-reflection film 28 are etched in a patterned mask process so that ortions of the n+ typemulti-crystalline silicon emitter 27 are exposed from theanti-reflection film 28. A titanium/palladium/silver alloy film 30 is provided in the exposed portions of the n+ typemulti-crystalline silicon emitter 27 and annealed in the high-temperature annealing apparatus 5. Finally, an n− typeohmic contact 31 is provided on the titanium/palladium/silver alloy film 30. - As discussed above, the
multi-crystalline silicon laminate 1 includes theceramic substrate 21 and the titanium/silicon alloy film 24 used as the seed layer. TheAPCVD apparatus 6 is used in the high-temperature process for the exchange of the silicon atoms and the boron atoms, thus forming the p+ type multi-crystalline silicon backsurface field film 25 and the p− type multi-crystalline silicon light-soakingfilm 26. Then, the phosphor atoms and the silicon atoms are exchanged so that the n+ typemulti-crystalline silicon emitter 28 is made. The SiCNO:Ar plasma is used to passivate thelaminate 1. The patterned mask process is used to make the p− typeohmic contact 29 on the titanium/silicon alloy film 24. The patterned mask process is used to coat the titanium/palladium/silver alloy film 30 on the n+ typemulti-crystalline silicon emitter 27 and provide the n− typeohmic contact 31 on the n+ typemulti-crystalline silicon emitter 27. - Solar cells made in the process according to the present invention exhibits several advantages. The
ceramic substrate 21 is inexpensive, refractory and chemically stable, and can be integrated with materials for construction. - The titanium/
silicon alloy film 24 is environmentally friendly, abundant and inexpensive. The titanium/silicon alloy film 24 ensures the integrity of themulti-crystalline silicon laminate 1 since its thermal expansion coefficient is matched with that of theceramic substrate 21 and the p+ type multi-crystalline silicon backsurface field film 25. - The solar cells provide a high photoelectrical conversion efficiency and excellent light-soaking stability because the
PEVCD apparatus 6 is used in the high-temperature process to passivate the multi-crystalline silicon films that would otherwise involve high mobility and a large diffusion length, and take long for recombination. - Moreover, the process of the present invention provides a high epitaxial growth rate and a high crystal quality.
- The present invention has been described via the detailed illustration of the preferred embodiment. Those skilled in the art can derive variations from the preferred embodiment without departing from the scope of the present invention. Therefore, the preferred embodiment shall not limit the scope of the present invention defined in the claims.
Claims (19)
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