CN104488087B - Passivating film, application type material, solar cell device and the silicon substrate with passivating film - Google Patents
Passivating film, application type material, solar cell device and the silicon substrate with passivating film Download PDFInfo
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- CN104488087B CN104488087B CN201380037776.4A CN201380037776A CN104488087B CN 104488087 B CN104488087 B CN 104488087B CN 201380037776 A CN201380037776 A CN 201380037776A CN 104488087 B CN104488087 B CN 104488087B
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- oxide
- silicon substrate
- passivating film
- vanadium
- film
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 144
- 239000010703 silicon Substances 0.000 title claims abstract description 144
- 239000000758 substrate Substances 0.000 title claims abstract description 142
- 239000000463 material Substances 0.000 title claims description 124
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 87
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 84
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 46
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 45
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims description 41
- 238000009792 diffusion process Methods 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 239000004411 aluminium Substances 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 25
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 7
- 239000010408 film Substances 0.000 description 242
- 210000004027 cell Anatomy 0.000 description 65
- 238000000034 method Methods 0.000 description 37
- 238000011160 research Methods 0.000 description 33
- 229910052751 metal Inorganic materials 0.000 description 31
- 239000002184 metal Substances 0.000 description 31
- 239000000126 substance Substances 0.000 description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 18
- 238000002161 passivation Methods 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 229910052581 Si3N4 Inorganic materials 0.000 description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000001419 dependent effect Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000002019 doping agent Substances 0.000 description 8
- 230000006798 recombination Effects 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000005669 field effect Effects 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 230000000415 inactivating effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910004440 Ta(OCH3)5 Inorganic materials 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- XCGKCPWIWFSADF-UHFFFAOYSA-N ethanol vanadium Chemical compound [V].C(C)O XCGKCPWIWFSADF-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- -1 tantalum oxide Compound Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019651 Nb(OC2H5)5 Inorganic materials 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- FESYJEAHUBWUOL-UHFFFAOYSA-N [V+5].C(C)O Chemical compound [V+5].C(C)O FESYJEAHUBWUOL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CWLKHIHGOBVTMS-UHFFFAOYSA-N ethanol;niobium(5+) Chemical compound [Nb+5].CCO CWLKHIHGOBVTMS-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UNMVMFALWBMKJA-UHFFFAOYSA-N methanol tantalum(5+) Chemical compound [Ta+5].CO UNMVMFALWBMKJA-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a kind of passivating film, its oxide comprising aluminum oxide and at least one kind of vanadium family element in the group being made up of vanadium oxide and tantalum oxide, the passivating film is used for the solar cell device with silicon substrate.
Description
Technical field
The present invention relates to passivating film, application type material, solar cell device and silicon substrate with passivating film.
Background technology
Solar cell device is the photo-electric conversion element for converting the solar into electric energy, as nuisanceless and can infinitely again
One of raw energy, will expect further to be popularized from now on.
Solar cell device generally includes p-type semiconductor and n-type semiconductor, by absorbing solar energy in semiconductor
Inside generation electron-hole pair.Herein, the electronics generated is moved to n-type semiconductor, and hole (hole) is moved to p-type semiconductor
Dynamic, they are collected in electrode, so as to utilize electric energy in outside.
On the other hand, in solar cell device, in order to be changed solar energy as much as possible, be output as electric energy, carry
High efficiency is critically important.In order to improve the efficiency of this solar cell device, electricity as much as possible is generated in the inside of semiconductor
Son-hole is to critically important.In addition, suppress the loss of generated electric charge and be drawn off also critically important to outside.
Produced by the loss of electric charge is due to a variety of causes.Particularly, pass through generated electronics and hole in conjunction with,
Generation electric charge disappears, so that the loss of electric charge can be produced.
In the crystal silicon solar energy battery element as main flow at present, as shown in figure 1, being referred to as texture using having
For the silicon substrate 11 of the p-type in the pyramid structure portion (omit diagram) that prevents reflection, n-layer 12 is formd in smooth surface, in the back of the body
Face forms p+Layer 14.And then, light surface side have as smooth surface passivating film silicon nitride (SiN) film 13, be formed with by
The silver-colored colelctor electrode of referred to as secondary grid line (finger) electrode 15.Overleaf the entire surface of side be formed with take into account suppress the back side light it is saturating
The electrode 16 for the aluminium crossed.
The n-layer 12 of above-mentioned silicon typically by make phosphorus from gas phase or solid-state diffusion into silicon substrate 11 formed by.The back side
P+Contact site when layer 14 is the formation by the electrode 16 of aluminium overleaf in aluminium and the silicon substrate of p-type 11 applies 700 DEG C
Formed by heat above.By the process, aluminium spreads in silicon substrate 11, generates alloy, forms p+Layer 14.
In the silicon substrate 11 and p of p-type+The interface of layer 14 forms the electric field from electrical potential difference.p+The electricity that layer 14 is produced
Field is main to be produced in the silicon substrate 11 of p-type, with following effects：In the hole and electronics at the back side is diffused into, by electron back
The inside of the silicon substrate 11 of p-type is incident upon, makes hole optionally through p+Layer 14.That is, the effect can bring following effect：Repel
Electronics, make hole and electronics solar cell device back side interface occur in conjunction with situation reduce.This back side possesses
The solar cell device of the existing mode of the alloy-layer of aluminium is widely used as being suitable for volume production due to relatively simple to manufacture
Solar cell device structure.
But, there is p at the above-mentioned back side+In the solar cell device of the existing mode of layer 14, for p+Layer 14 and the back of the body
The interface of the electrode 16 in face does not carry out the deactivation processing of any reduction interface recombination velocity.In addition, the p+Layer 14 with
The alloy of the aluminium of high-concentration dopant itself, i.e. aluminium silicon can form recombination center, therefore the presence density of recombination center is high, with
Other regions are compared, and are reduced as the quality of semiconductor.
In order to solve the problem, following substitute using the solar cell device of above-mentioned existing mode enters as target
The exploitation of passivating back type solar cell device is gone.Different from the solar cell device of above-mentioned existing mode, the back side is blunt
Change type solar cell device covers the back side of solar cell device by using passivating film, so as to so as to be originally present in silicon
The interface of substrate and passivating film and as in conjunction with the reason for uncombined key (dangling bonds) be used as terminal.That is, passivating back type
Solar cell device is not by p/p+The electric field that interface is produced reduces carrier recombination velocity, but makes the back side
In recombination center density itself reduction, reduce carrier (hole and electronics) in conjunction with.On the other hand, by by blunt
Changing the electric field of the generation of the fixed charge in film makes carrier concentration reduction, the passivating film quilt so as to suppress carrier recombination velocity
Referred to as field-effect passivating film.Particularly, overleaf in recombination center density it is big in the case of, load can be made using electric field
Stream from the remote field-effect passivating film of recombination center be effective.
It is used as field-effect passivating film, it is known that by ALD-CVD (Atomic Layer Deposition-Chemical Vapor
Deposition：Ald-chemical vapor deposition) the obtained pellumina of film forming.In addition, in order to reduce film forming cost,
The coated film of the known collosol and gel by aluminum oxide is used as the technology of passivating film (for example, International Publication No. is No. 2008/137174 small
Book, Japanese Unexamined Patent Publication 2009-194120 publications and B.Hoex, J.Schmidt, P.Poh1, M.C.M.van de Sanden,
W.M.M.Kesseles, " Silicon surface passivation by atomic layer deposited Al2O3 ",
J Appl.Phys, 104, p.44903 (2008)).In addition, it is also known that use dielectric coating material, polyamides comprising titanium and phosphorus
The other materials such as imide resin are as the technology of the passivating back material of application type (for example, International Publication No. 2009/052227
Pamphlet and Japanese Unexamined Patent Publication 2012-69592 publications).
But, in general the deposition velocity of ALD is slow, it is impossible to obtain high productive capacity, therefore presence is difficult to low cost
The problem of change.And then, after by pellumina film forming, it is necessary to for obtained by the electrode at the back side connection through hole, it is necessary to certain
Plant patterning techniques.
In addition, in order that the film forming cost degradation of pellumina, it is known that by the coated film of the collosol and gel of aluminum oxide etc
Technology as passivating film.
The content of the invention
The invention problem to be solved
But, the fixed charge born in the coated film of aluminum oxide is unstable, therefore utilizes CV (Capacitance-
Voltage：Capacitance voltage) method when with the tendency for being difficult to obtain negative fixed charge.
In view of the above problems, the invention solves the problems that the 1st problem be be realized with a low cost extension silicon substrate the carrier longevity
Life and the passivating film with negative fixed charge.2nd problem is to provide the application type material of the formation for realizing the passivating film.
3rd problem is to have used the inexpensive and efficient solar cell device of the passivating film to be realized with a low cost.4th problem is
To be realized with a low cost the carrier lifetime of extension silicon substrate and there is the silicon substrate with passivating film of negative fixed charge.
The above-mentioned problem and other problems and new feature of the present invention can by present specification contents and accompanying drawing
Clearly.
Scheme for solving problem
Scheme for solving above-mentioned problem includes following mode.
<1>A kind of passivating film, it includes aluminum oxide and at least one kind of in the group being made up of vanadium oxide and tantalum oxide
The oxide of vanadium family element, the passivating film is used for the solar cell device with silicon substrate.
Pass through the oxygen of at least one kind of vanadium family element comprising aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide
Compound, can extend the carrier lifetime of silicon substrate and with negative fixed charge.The reasons why carrier lifetime extends still is failed to understand
One of really, but as its reason, it is contemplated that the terminal of dangling bonds.
<2>According to<1>Described passivating film, wherein, the mass ratio of the oxide of the vanadium family element and the aluminum oxide
(oxide/aluminum oxide of vanadium family element) is 30/70~90/10.
Thus, it is possible to big and stable negative fixed charge.
<3>According to<1>Or<2>Described passivating film, wherein, the oxide of the vanadium family element and the aluminum oxide it is total
Content is more than 90%.
<4>According to<1>~<3>Any one of passivating film, wherein, be used as the oxide of the vanadium family element, bag
Oxide containing the 2 kinds or 3 kinds vanadium family elements in the group being made up of vanadium oxide, niobium oxide and tantalum oxide.
<5>According to<1>~<4>Any one of passivating film, its be application type material heat treatment thing, the application type
The salic precursor of material bag and at least one kind of vanadium in the group being made up of the precursor of vanadium oxide and the precursor of tantalum oxide
The precursor of the oxide of race's element.
Application type material of the invention for solving the 2nd problem is as described below.
<6>A kind of application type material, it wraps salic precursor and selected from before the precursor and tantalum oxide of vanadium oxide
The precursor of the oxide of at least one kind of vanadium family element in the group of body composition, the application type material is used for the sun with silicon substrate
The formation of the passivating film of energy cell device.
Solar cell device of the invention for solving the 3rd problem is as described below.
<7>A kind of solar cell device, it possesses：
The silicon substrate of p-type；
The impurity diffusion layer of the n-type formed in the 1st surface side of the light surface side as the silicon substrate；
The 1st electrode formed on the impurity diffusion layer；
Formed in 2nd surface side opposite with the light surface side of the silicon substrate and there is the passivating film of opening portion；With
Formed in the 2nd surface side of the silicon substrate and by the opening portion of the passivating film with the 2nd of the silicon substrate the
2nd electrode of surface side electrical connection,
At least one kind of vanadium family member of the passivating film comprising aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide
The oxide of element.
<8>According to<7>Described solar cell device, it has the impurity diffusion layer of p-type, the impurity diffusion of the p-type
Layer with the addition of impurity compared with the silicon substrate in part or all of formation of the 2nd surface side of the silicon substrate with high concentration,
2nd electrode is electrically connected by the opening portion of the passivating film with the impurity diffusion layer of the p-type.
<9>A kind of solar cell device, it possesses：
The silicon substrate of n-type；
The impurity diffusion layer of the p-type formed in the 1st surface side of the light surface side as the silicon substrate；
The 1st electrode formed on the impurity diffusion layer；
Formed in 2nd surface side opposite with the light surface side of the silicon substrate and there is the passivating film of opening portion；With
With formed in the 2nd surface side of the silicon substrate and by the opening portion of the passivating film with the silicon substrate the
2nd electrode of 2 surface sides electrical connection,
At least one kind of vanadium family member of the passivating film comprising aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide
The oxide of element.
<10>According to<9>Described solar cell device, it has the impurity diffusion layer of n-type, the impurity diffusion of the n-type
Layer with the addition of impurity compared with the silicon substrate in part or all of formation of the 2nd surface side of the silicon substrate with high concentration,
2nd electrode is electrically connected by the opening portion of the passivating film with the impurity diffusion layer of the n-type.
<11>According to<7>~<10>Any one of solar cell device, wherein, the vanadium of the passivating film
The mass ratio of the oxide of race's element and the aluminum oxide is 30/70~90/10.
<12>According to<7>~<11>Any one of solar cell device, wherein, the vanadium of the passivating film
The total content of the oxide of race's element and the aluminum oxide is more than 90%.
<13>According to<7>~<12>Any one of solar cell device, wherein, be used as the vanadium family element
Oxide, includes the oxide of the 2 kinds or 3 kinds vanadium family elements in the group being made up of vanadium oxide, niobium oxide and tantalum oxide.
The silicon substrate of the invention with passivating film for solving the 4th problem is as described below.
<14>A kind of silicon substrate with passivating film, it has：
Silicon substrate；With
The entire surface that is arranged on the silicon substrate or a part<1>~<5>Any one of solar cell
Element passivating film.
Invention effect
In accordance with the invention it is possible to which with the carrier lifetime for being realized with a low cost extension silicon substrate and there is negative fixed charge
Passivating film.Furthermore it is possible to provide the application type material of the formation for realizing the passivating film.This has been used in addition, can realize
The inexpensive and efficient solar cell device of passivating film.In addition, can be realized with a low cost extension silicon substrate current-carrying
Sub- life-span and the silicon substrate with passivating film with negative fixed charge.
Brief description of the drawings
Fig. 1 is the profile of the structure for the solar cell device for showing existing double-face electrode type.
Fig. 2 is to show that the back side has used the profile of the 1st configuration example of the solar cell device of passivating film.
Fig. 3 is to show that the back side has used the profile of the 2nd configuration example of the solar cell device of passivating film.
Fig. 4 is to show that the back side has used the profile of the 3rd configuration example of the solar cell device of passivating film.
Fig. 5 is to show that the back side has used the profile of the 4th configuration example of the solar cell device of passivating film.
Fig. 6 is to show that smooth surface has used the profile of the configuration example of the solar cell device of passivating film.
Embodiment
In this specification, term " process " is not only independent process, but also has and can not clearly be different from other processes
Situation, as long as the expected purpose of the process can be realized in this case, be then also contained in this term.In addition, this specification
It is middle to use the numerical value that "~" number range for showing represents the front and rear record containing "~" respectively as minimum value and maximum
Scope.And then, the content in this specification on each composition in composition exists a variety of equivalent to each composition in the composition
Material in the case of, unless otherwise specified, then each mean the total amount of many kinds of substance present in composition.In addition,
In addition to the composition for the shape for being formed at entire surface when term " layer " is observed except being included in as top view in this specification, in addition to
The composition of the shape formed in a part.
(embodiment 1)
The passivating film of present embodiment is the passivating film for silicon solar cell element, comprising aluminum oxide and selected from by
The oxide of at least one kind of vanadium family element in the group of vanadium oxide and tantalum oxide composition.
By making passivating film include aluminum oxide and at least one kind of vanadium family in the group being made up of vanadium oxide and tantalum oxide
The oxide of element, can extend the carrier lifetime of silicon substrate, and with negative fixed charge.Thus, passivation of the invention
Film can improve the photoelectric transformation efficiency of silicon solar cell element.And then, passivating film of the invention is due to that can utilize coating
Method or print process are formed, therefore film formation process is simple, and the production capacity of film forming is high.As a result, also easy, the Ke Yishi of pattern formation
Existing cost degradation.
In addition, in present embodiment, by changing the composition of passivating film, the fixed charge that passivating film can be controlled to have
Amount.Herein, vanadium family element refers to the 5th race's element of the periodic table of elements, for the element in vanadium, niobium and tantalum.
As the function of general passivating film, there are (1) dangling bonds terminal, (2) can band caused by the fixed charge in film
Bending.Wherein, the passivating film of the function of band curvature caused by the fixed charge in film of (2) has been used to be referred to as field-effect
Passivating film, with any one of hole and electronics are driven away by the electric charge and prevent in conjunction with effect.It is common to have used p
In the solar cell device of the silicon substrate of type, in the carrier generated, electronics is gone out from smooth surface side draw, by hole from
Rear side is taken out.Therefore, as the passivating film of the rear side in the silicon substrate of p-type, in order to electronics is come back into light surface side, it is necessary to
Field-effect passivating film (for example, Japanese Unexamined Patent Publication 2012-33759 publications) with negative fixed charge.
On the other hand, in present embodiment, by sharing the oxide and aluminum oxide of vanadium family element, passivating film can be made
Fixed charge is negative, and then, adjust mass ratio [oxide/oxidation of vanadium family element of the oxide and aluminum oxide of vanadium family element
Aluminium], so as to so that the fixed charge of passivating film is stably negative.Specifically, by making the oxide and oxygen of vanadium family element
Change oxide/aluminum oxide of the quality than vanadium family element of aluminium] it is 30/70~90/10, it is big and stabilized negative with can be achieved
The tendency of fixed charge.Also, as described above, the passivating film of the present invention can be formed using rubbing method or print process, therefore into
Membrane process is simple, and the production capacity of film forming is high.As a result, in present embodiment, pattern formation is also easy, it is possible to achieve low cost
Change.
In addition, from can make from the viewpoint of negative fixed charge stabilizes, the oxide of vanadium family element and aluminum oxide
Mass ratio is more preferably 35/65~90/10.More preferably 50/50~90/10.
The oxide of vanadium family element in passivating film and the mass ratio of aluminum oxide can pass through energy dispersion type X-ray spectrum
Method (EDX), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) are measured.On specific
Condition determination, such as it is as described below in the case of ICP-MS.Passivating film is dissolved in acid or aqueous alkali, makes the solution
To be vaporific and be directed into Ar plasmas, the light released when the element excited is returned into ground state carries out light splitting and simultaneously determines wavelength
And intensity, the qualitative of row element is entered by resulting wavelength, quantified by resulting intensity.
The oxide of vanadium family element in passivating film and the total content of aluminum oxide be preferably more than 80 mass %, from can tie up
From the viewpoint of holding good characteristic, more preferably more than 90 mass %.If the oxide and oxygen of the vanadium family element in passivating film
The composition for changing aluminium becomes many, then the effect increase of negative fixed charge.
In addition, from the viewpoint of the raising of film quality or the adjustment of modulus of elasticity, vanadium family member can be included in passivating film
Composition beyond the oxide and aluminum oxide of element is used as organic principle.The presence of organic principle in passivating film can be by element point
The FT-IR of analysis and film measure confirms.
As the oxide of the vanadium family element, from the viewpoint of bigger negative fixed charge is obtained, preferably select
Vanadium oxide (V2O5).Because vanadium oxide has bigger negative fixed charge compared with tantalum oxide, thus it can more efficiently prevent from
Carrier in conjunction with.
The passivating film can include 2 kinds or 3 kinds of vanadium families in the group being made up of vanadium oxide, niobium oxide and tantalum oxide
The oxide of element as vanadium family element oxide.
The passivating film is preferably obtained by being heat-treated to application type material, more preferably utilizes rubbing method or printing
Method afterwards removes organic principle application type material filming by being heat-treated, so as to obtain the passivating film.That is, passivating film
It can be obtained as the heat treatment thing of the application type material of the precursor comprising alumina precursor and the oxide of vanadium family element.Below
Illustrate the details of application type material.
(embodiment 2)
The application type material of present embodiment is the painting of the passivating film for the solar cell device with silicon substrate
Cloth section bar material, wrap salic precursor and in the group being made up of the precursor of vanadium oxide and the precursor of tantalum oxide at least 1
Plant the precursor of the oxide of vanadium family element.As the precursor of the oxide of the vanadium family element contained by application type material, from by applying
From the viewpoint of the negative fixed charge of the passivating film of cloth material formation, vanadium oxide (V is preferably selected2O5) precursor.It is coated with section bar
Material can also include 2 kinds or 3 kinds in the group being made up of the precursor of the precursor of vanadium oxide, the precursor of niobium oxide and tantalum oxide
The precursor of the oxide of vanadium family element as the oxide of vanadium family element precursor.
As long as alumina precursor can generate aluminum oxide, it can be not particularly limited to use.As alumina precursor,
From make aluminum oxide be homogeneously dispersed on silicon substrate in terms of and chemically stable aspect, preferably use the oxidation of organic system
Aluminum precursor.As the example of the alumina precursor of organic system, aluminum isopropylate (structural formula can be enumerated：Al(OCH(CH3)2)3)、
(strain) high-purity chemical research institute SYM-AL04.
As long as the precursor of the oxide of vanadium family element can generate the oxide of vanadium family element, it can be not particularly limited
Ground is used.As the precursor of the oxide of vanadium family element, from make aluminum oxide be homogeneously dispersed on silicon substrate in terms of and chemistry
Stable aspect is set out, and preferably uses the precursor of the oxide of the vanadium family element of organic system.
As the example of the precursor of the vanadium oxide of organic system, three ethanol vanadium (V) (structural formulas of oxidation can be enumerated：VO
(OC2H5)3, molecular weight：202.13), (strain) high-purity chemical research institute V-02.It is used as the example of the precursor of the tantalum oxide of organic system
Son, can enumerate methanol tantalum (V) (structural formula：Ta(OCH3)5, molecular weight：336.12), (strain) high-purity chemical research institute, Ta-
10-P.As the example of the niobium oxide precursor of organic system, ethanol niobium (V) (structural formula can be enumerated：Nb(OC2H5)5, molecular weight：
318.21), (strain) high-purity chemical research institute Nb-05.
Using rubbing method or print process by the oxidation of the precursor of the oxide of the vanadium family element comprising organic system and organic system
The application type material filming of aluminum precursor, the heat treatment after removes organic principle, so as to obtain passivating film.Cause
This, as a result, can be the passivating film for including machine composition.The content of organic principle in passivating film is more preferably less than 10 matter
Measure %, more preferably below 5 mass %, particularly preferably below 1 mass %.
(embodiment 3)
Vicinity of the solar cell device (photoelectric conversion device) of present embodiment at the opto-electronic conversion interface of silicon substrate
With the passivating film (dielectric film, protection dielectric film) illustrated in above-mentioned embodiment 1, i.e., comprising aluminum oxide and select free oxidation
The film of the oxide of at least one kind of vanadium family element in the group of vanadium and tantalum oxide composition.By comprising aluminum oxide and selecting free oxidation
The oxide of at least one kind of vanadium family element in the group of vanadium and tantalum oxide composition, can extend the carrier lifetime of silicon substrate, and tool
There is negative fixed charge, the characteristic (photoelectric transformation efficiency) of solar cell device can be improved.
<Structure explanation>
First, 2~Fig. 5 of reference picture is illustrated to the structure of the solar cell device of present embodiment.Fig. 2~Fig. 5
It is the profile of the 1st~the 4th configuration example of the solar cell device for overleaf having used passivating film for showing present embodiment.
As the silicon substrate (crystalline silicon substrates, semiconductor substrate) used in present embodiment, can use monocrystalline silicon or
Any of polysilicon.Further, it is possible to use crystalline silicon substrates or conductivity type that conductivity type is p-type are the crystal silicon substrate of n-type
Any of plate.As silicon substrate 1, during the crystalline silicon or conductivity type that conductivity type can be used to be p-type are the crystalline silicon of n-type
It is any.From the viewpoint of the further effect for playing the present invention, conductivity type is more suitable for the crystalline silicon of p-type.
In following Fig. 2~Fig. 5, the example using p-type monocrystalline silicon as silicon substrate 1 is illustrated.Need
Bright, the monocrystalline silicon or polysilicon used in the silicon substrate 1 can be arbitrary material, and preferably resistivity is 0.5 Ω cm
~10 Ω cm monocrystalline silicon or polysilicon.
As shown in Fig. 2 (the 1st configuration example), in light surface side (upside, the 1st face, surface in figure) shape of the silicon substrate 1 of p-type
Into the diffusion layer 2 for the n-type for being doped with the V group elements such as phosphorus.Also, form pn-junction between silicon substrate 1 and diffusion layer 2.In diffusion
The surface of layer 2 forms the smooth surface antireflection films 3 such as silicon nitride (SiN) film and has used the (smooth surface of the 1st electrode 5 of silver-colored (Ag) etc.
The electrode of side, the 1st face electrode, overlying electrode, surface electrode).Smooth surface antireflection film 3 can also have concurrently and is passivated as smooth surface
The function of film.By using SiN film, both functions of smooth surface antireflection film and smooth surface passivating film can be had concurrently.
It should be noted that the solar cell device of the present invention can be with or without smooth surface antireflection film 3.Separately
Outside, in order to reduce the reflectivity on surface, preferably the smooth surface formation concaveconvex structure (texture structure) in solar cell device, but
The solar cell device of the present invention can be with or without texture structure.
On the other hand, the IIIs such as aluminium, boron are doped with rear side (downside, the 2nd face, the back side in the figure) formation of silicon substrate 1
The layer of element is BSF (Back Surface Field, back surface field) layer 4.But, solar cell device of the invention can have
Or without BSF layers 4.
(electricity is contacted in order to be obtained with BSF layers 4 (being the surface of the rear side of silicon substrate 1 in the case of BSF layers 4 are not present)
Connection), the 2nd electrode 6 (electrode of rear side, the 2nd face electrode, the back side being made up of aluminium etc. are formd in the rear side of silicon substrate 1
Electrode).
And then, (it is being the rear side of silicon substrate 1 in the case of no BSF layers 4 except BSF layers 4 in Fig. 2 (the 1st configuration example)
Surface) part of the contact area (opening portion OA) that is electrically connected with the 2nd electrode 6 outside form comprising aluminum oxide and selected from by
The passivating film 7 (passivation layer) of the oxide of at least one kind of vanadium family element in the group of vanadium oxide and tantalum oxide composition.Such as in embodiment party
As being described in detail in formula 1, passivating film 7 of the invention can have negative fixed charge.By the fixed charge, make because of light
And rebounded face side as the electronics of minority carrier in the carrier produced in the silicon substrate 1.Therefore, short circuit current flow increase,
It can expect that photoelectric transformation efficiency is improved.
Then, the 2nd configuration example shown in Fig. 3 is illustrated.In Fig. 2 (the 1st configuration example), the 2nd electrode 6 is in contact zone
Formed in entire surface on domain (opening portion OA) and passivating film 7, but in Fig. 3 (the 2nd configuration example), only in contact area (opening
Portion OA) form the 2nd electrode 6.The can also be formed with for a part only on contact area (opening portion OA) and passivating film 7
The composition of 2 electrodes 6.Even the solar cell device of the composition shown in Fig. 3, it can also obtain same with Fig. 2 (the 1st configuration example)
The effect of sample.
Then, the 3rd configuration example shown in Fig. 4 is illustrated.In the 3rd configuration example shown in Fig. 4, BSF layers 4 are only in bag
The part formation of rear side containing the contact area (opening portion OA portions) with the 2nd electrode 6, is not such as Fig. 2 (the 1st configuration example)
Overleaf the entire surface of side is formed like that.Even the solar cell device (Fig. 4) of this composition, can also be obtained and Fig. 2
(the 1st configuration example) same effect.In addition, according to the solar cell device of Fig. 4 the 3rd configuration example, BSF layers 4, i.e. by mixing
The element of the IIIs such as miscellaneous aluminium, boron and with high-concentration dopant, the region of impurity is few compared with silicon substrate 1, therefore can be compared
Photoelectric transformation efficiency higher Fig. 2 (the 1st configuration example).
Then, the 4th configuration example shown in Fig. 5 is illustrated.In Fig. 4 (the 3rd configuration example), the 2nd electrode 6, which is formed at, to be connect
The entire surface on region (opening portion OA) and passivating film 7 is touched, but in Fig. 5 (the 4th configuration example), only in contact area (opening portion
OA) it is formed with the 2nd electrode 6.The 2nd can also be formed with for the part only on contact area (opening portion OA) and passivating film 7
The composition of electrode 6.Even the solar cell device of the composition shown in Fig. 5, it can also obtain same with Fig. 4 (the 3rd configuration example)
The effect of sample.
In addition, being coated with the 2nd electrode 6 by using print process and in high temperature burn till so that overleaf the entire surface of side is formed
In the case of, convex warpage easily occurs in temperature-fall period.This warpage causes the broken of solar cell device sometimes
Damage, yield is likely to decrease.In addition, when the filming of silicon substrate is carried out, becoming the problem of warpage big.The reason for warpage, exists
In：Compared with silicon substrate, the thermal coefficient of expansion of the 2nd electrode 6 formed by metal (such as aluminium) is big, thus the receipts in temperature-fall period
Contracting is big, so producing stress.
In summary, the not overleaf entire surface formation the of side as Fig. 3 (the 2nd configuration example) and Fig. 5 (the 4th configuration example)
During 2 electrode 6, electrode structure is easily symmetrical above and below, it is difficult to because the difference of thermal coefficient of expansion produces stress, therefore preferably.Wherein, the feelings
Under condition, reflecting layer is preferably separately set.
<Preparation method explanation>
Then, to the manufacture method of the solar cell device (Fig. 2~Fig. 5) of the present embodiment with above-mentioned composition
One illustrates.Wherein, the invention is not restricted to the solar cell device made using method described below.
First, texture structure is formed on the surface of the silicon substrate 1 shown in Fig. 2 etc..The formation of texture structure can be in silicon substrate
The two-sided formation of plate 1, can also be only in one side (light surface side) formation.In order to form texture structure, first, silicon substrate 1 is soaked
Stain removes the damage layer of silicon substrate 1 into the solution of heated potassium hydroxide or sodium hydroxide.Afterwards, it is impregnated into hydrogen
In potassium oxide and the solution that isopropanol is main component, so that in two-sided or one side (light surface side) the formation texture of silicon substrate 1
Structure.It should be noted that as described above, the solar cell device of the present invention can have texture structure, can not also have
Textured structure, therefore this process can be omitted.
Then, silicon substrate 1 is cleaned with solution such as hydrochloric acid, hydrofluoric acid, passes through POCl3 (POCl afterwards3) etc. thermal diffusion
Phosphorus-diffused layer (the n as diffusion layer 2 is formed in silicon substrate 1+Layer).Phosphorus-diffused layer for example can be by by the application type comprising phosphorus
Dopant solution coating is to silicon substrate 1 and is heat-treated and is formed., will be in surface shape with acid such as hydrofluoric acid after heat treatment
Into phosphorus glass layer remove, so as to form the phosphorus-diffused layer (n as diffusion layer 2+Layer).Do not have to the method for forming phosphorus-diffused layer
There is special limitation.Scope, thin-film electro of the phosphorus-diffused layer preferably according to the depth from the surface of silicon substrate 1 for 0.2 μm~0.5 μm
The mode hindered for 40 Ω/~100 Ω/ (ohm/square) scope is formed.
Afterwards, the solution of the dopant for the application type for including boron, aluminium etc. in the rear side coating of silicon substrate 1 simultaneously carries out hot place
Reason, so as to form the BSF layers 4 of rear side.Coating can use the methods such as silk-screen printing, ink-jet, distribution, spin coating.After heat treatment,
The layer of the boron glass overleaf formed, aluminium etc. is removed using hydrofluoric acid, hydrochloric acid etc., so as to form BSF layers 4.To forming BSF layers
4 method is not particularly limited.It is preferred that being 10 according to the concentration range of boron, aluminium etc.18cm-3~1022cm-3Mode form BSF layers
4, preferably with point-like or wire formation BSF layers 4.It should be noted that the solar cell device of the present invention can have or not
With BSF layers 4, therefore this process can be omitted.
In addition, the feelings that the diffusion layer 2 of smooth surface and the BSF layers 4 at the back side are formed using the solution of the dopant of application type
Under condition, the solution of above-mentioned dopant can be respectively coated two-sided to silicon substrate 1, the phosphorus expansion as diffusion layer 2 is carried out in the lump
Dissipate layer (n+Layer) and BSF layers 4 formation, afterwards, the phosphorus glass formed on surface, boron glass etc. are removed in the lump.
Afterwards, the silicon nitride film as smooth surface antireflection film 3 is formed on diffusion layer 2.To forming smooth surface antireflection
The method of film 3 is not particularly limited.Scope that smooth surface antireflection film 3 is preferably 50nm~100nm according to thickness, refractive index are
The mode of 1.9~2.2 scope is formed.Smooth surface antireflection film 3 is not limited to silicon nitride film, or silicon dioxide film, oxygen
Change aluminium film, titanium dioxide film etc..The surface such as silicon nitride film antireflection film 3 can utilize the method systems such as plasma CVD, hot CVD
Make, made preferably by the plasma CVD that can be formed in 350 DEG C~500 DEG C of temperature range.
Then, passivating film 7 is formed.Passivating film 7 is comprising aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide
The oxide of at least one kind of vanadium family element, for example, formed by following manner：Coating includes to obtain the organic of aluminum oxide after burning till
Metal decomposes application type material for the alumina precursor of representative and to obtain being selected from what is be made up of vanadium oxide and tantalum oxide after burning till
The commercially available organic metal of the oxide of at least one kind of vanadium family element in group decomposes material of the application type material for the precursor of representative
(passivating material), and be heat-treated and (burnt till), so as to form the passivating film 7 (with reference to embodiment 1).
The formation of passivating film 7 can be for example carried out as follows.Eliminated in advance for 0.49 mass % hydrofluoric acid with concentration
The one side rotation of 725 μ m-thicks of natural oxide film, the silicon substrate (8 Ω cm~12 Ω cm) of the p-type of 8 inches (20.32cm)
Above-mentioned application type material is coated with, 120 DEG C, the prebake of 3 minutes are carried out on hot plate.Afterwards, 650 are carried out in a nitrogen atmosphere
DEG C, the heat treatment of 1 hour.In this case, obtain comprising aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide extremely
The passivating film 7 of the oxide of few a kind of vanadium family element.The film measured by ellipsometer of the passivating film 7 formed using the above method
Thickness is usually tens nm or so.
For above-mentioned application type material, by silk-screen printing, hectographic printing, the printing based on ink-jet, based on distributor
The methods such as printing, are coated into the specific pattern for including contact area (opening portion OA).It should be noted that for above-mentioned application type
Material, the preferably scope after coating in 80 DEG C~180 DEG C carry out prebake, evaporate solvent, afterwards in a nitrogen atmosphere or empty
Implement the heat treatment (annealing) of 30 minutes~3 hours or so in 600 DEG C~1000 DEG C in gas, be made passivating film 7 (oxide
Film).
And then, opening portion (hole of contact) OA is preferably formed on BSF layers 4 with point-like or wire.
It is used as the passivating film 7 used in above-mentioned solar cell device, as described in detail in embodiment 1, vanadium
The oxide of race's element and the mass ratio (oxide/aluminum oxide of vanadium family element) of aluminum oxide are preferably 30/70~90/10 model
In enclosing, in the range of more preferably 35/65~90/10, in the range of more preferably 50/50~90/10.Thus, it is possible to
Stabilize negative fixed charge.
In addition, in passivating film 7, the oxide of vanadium family element and the total content of aluminum oxide are preferably more than 90%.
Then, the 1st electrode 5 of the electrode as light surface side is formed.1st electrode 5 is formed by following manner：Utilize silk
Net is printed on to be formed on smooth surface antireflection film 3 is the paste of main component with silver-colored (Ag), and is heat-treated (burn-through), so that
Form the 1st electrode 5.The shape of 1st electrode 5 can be arbitrary shape, for example, can be by secondary gate line electrode and main gate line
The known shape that (bus bar) electrode is constituted.
Then, the 2nd electrode 6 of the electrode as rear side is formed.2nd electrode 6 can be formed by following manner：Utilize
Silk-screen printing or distributor are coated with the paste using aluminium as main component, it are heat-treated, so as to form the 2nd electrode 6.
In addition, the shape identical shape, the shape of the entire surface of covering rear side, comb that are preferably shaped to BSF layers 4 of the 2nd electrode 6
Type shape, clathrate etc..It should be noted that first carrying out respectively for forming the 1st electrode 5 and as the electrode of light surface side
The printing of the paste of 2 electrodes 6, is heat-treated (burn-through) afterwards, so that the 1st electrode 5 and the 2nd electrode 6 can also be formed in the lump.
In addition, by being used in the formation of the 2nd electrode 6 with the paste that aluminium (Al) is main component, so that aluminium is as mixing
Miscellaneous dose of diffusion, the contact site by adjust automatically in the 2nd electrode 6 and silicon substrate 1 forms BSF layers 4.It should be noted that as before
It is described, the solution of the dopant of the application type of boron, aluminium etc. can also be included in the rear side coating of silicon substrate 1, and it is carried out
Heat treatment, so as to separately form BSF layers 4.
It should be noted that showing that silicon substrate 1 has used the configuration example and preparation method example of the silicon of p-type in above-mentioned, but also may be used
To use the silicon substrate of n-type to be used as silicon substrate 1.In this case, the layer that diffusion layer 2 can be doped with the group-III elements such as boron is formed,
BSF layers 4 are formed by V group elements such as the phosphorus that adulterates.Wherein, in this case, leakage current by because of negative fixed charge
Interface formed inversion layer and rear side metal contact part and flow, conversion efficiency is difficult to improve sometimes, to the point should
Work as attention.
In addition using n-type silicon substrate in the case of, as shown in fig. 6, can light surface side use comprising aluminum oxide,
With the passivating film 7 of the oxide of at least one kind of vanadium family element in the group being made up of vanadium oxide and tantalum oxide.Fig. 6 is to show
The profile of the configuration example of the solar cell device of the smooth surface passivating film of present embodiment is used.
In this case, light surface side diffusion layer 2 doping boron and form p-type, in the carrier generated, make hole collection
In in light surface side, make electron concentration overleaf side.It is therefore preferable that the passivating film 7 with negative fixed charge is located at smooth surface
Side.
On passivating film 7, the antireflection film that further can be made up of using the formation such as CVD SiN etc..
(embodiment 4)
The silicon substrate with passivating film of present embodiment has silicon substrate and the entire surface being arranged on silicon substrate or one
Point above-mentioned embodiment 1 in illustrate passivating film, include aluminum oxide and in the group being made up of vanadium oxide and tantalum oxide
At least one kind of vanadium family element oxide film.By making passivating film comprising aluminum oxide and selected from by vanadium oxide and tantalum oxide group
Into group at least one kind of vanadium family element oxide, can extend the carrier lifetime of silicon substrate, and with negative fixed electricity
Lotus, can improve the characteristic (photoelectric transformation efficiency) of solar cell device.
Embodiment
Below, it is described in detail with reference to embodiment and comparative example.
<The situation of the oxide of vanadium family element is used as using vanadium oxide>
[embodiment 1]
Aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal decompose application type material [(strain)
High-purity chemical research institute SYM-AL04, the mass % of concentration 2.3] 3.0g and by be heat-treated (burning till) obtain vanadium oxide (V2O5)
Commercially available organic metal decompose application type material [(strain) high-purity chemical research institute, V-02, the mass % of concentration 2] 6.0g and mix
Close, prepare the passivating material (a-1) as application type material.
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
The one side rotary coating passivating material (a-1) of silicon substrate (8 Ω cm~12 Ω cm), carries out 120 DEG C, 3 points on hot plate
The prebake of clock.Afterwards, 700 DEG C, 30 minutes of heat treatment (burning till) is carried out in a nitrogen atmosphere, obtains including aluminum oxide and oxidation
The passivating film [vanadium oxide/aluminum oxide=63/37 (quality %)] of vanadium.Thickness is determined using ellipsometer, is as a result 51nm.Determine
The FT-IR of passivating film, as a result in 1200cm-1Nearby it is found that the minimal amount of peak due to alkyl.
Then, across metal mask, multiple a diameter of 1mm aluminium electrode is formed on above-mentioned passivating film by being deposited, is made
Make MIS (Metal-Insulator-Semiconductor；Metal-insulator semiconductor) structure capacitor.Utilize city
Detector and the LCR meter (Hewlett-Packard Corporation, 4275A) sold determine the voltage-dependent (C-V characteristics) of the electrostatic capacitance of the capacitor.
As a result, distinguishing that flat-band voltage (Vfb) is moved to+0.02V from the -0.81V of ideal value.From the amount of movement, by passivation material
The passivating film that material (a-1) is obtained is -5.2 × 10 in fixed charge density (Nf)11cm-2When show negative fixed charge.
As described above, passivating material (a-1) is applied to two-sided, the progress prebake of the silicon substrate of 8 inches of p-type,
And 650 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated what film was covered
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Determine.As a result, carrier lifetime is 400 μ s.In order to be compared, the silicon of the p-type of 8 inches of identical is made using iodine deactivation method
Substrate is passivated and is determined, and as a result carrier lifetime is 1100 μ s.In addition, being determined again after 14 days after sample making
Carrier lifetime, as a result carrier lifetime is 380 μ s.It follows that the reduction of carrier lifetime (from 400 μ s to 380 μ s)
Within -10%, the reduction of carrier lifetime is small.
In summary, it is known that：Passivating film obtained from passivating material (a-1) is heat-treated and (burnt till) shows certain
The inactivating performance of degree, shows negative fixed charge.
[embodiment 2]
Similarly to Example 1, for obtaining aluminum oxide (Al by being heat-treated (burning till)2O3) commercially available organic metal
Decompose application type material [high-purity chemical research institute of Co., Ltd., SYM-AL04, the mass % of concentration 2.3] and by heat treatment
(burning till) obtains vanadium oxide (V2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute, V-
02nd, the mass % of concentration 2], change ratio and mixed, prepare passivating material (a-2)~(a-7) shown in table 1.
Similarly to Example 1, passivating material (a-2)~(a-7) is respectively coated to the one side of the silicon substrate of p-type, entered
Row is heat-treated (burning till) and produces passivating film.The voltage-dependent of the electrostatic capacitance of passivating film obtained by determining, is thus counted
Calculate fixed charge density.
And then, similarly to Example 1, passivating material is applied to silicon substrate two-sided of p-type and is heat-treated and (is burnt
Into), determine carrier lifetime using resulting sample.
Resulting result is summarized in table 1.In addition, carrier lifetime is determined again after 14 days after sample making,
As a result understand, on the reduction of carrier lifetime, used the passivating film of passivating material (a-2)~(a-7) shown in table 1 equal
Within -10%, the reduction of carrier lifetime is small.
It is different results according to the ratio (mass ratio) of vanadium oxide/aluminum oxide after heat treatment (burning till), on blunt
Change material (a-2)~(a-7), due to showing negative fixed charge after heat treatment (burning till), carrier lifetime is displayed that
Go out value to a certain degree, thus hint is used as passivating film function.The passivating film obtained by passivating material (a-2)~(a-7)
Stably show negative fixed charge, it is known that the passivation of the silicon substrate of p-type can be preferably used as.
[table 1]
[embodiment 3]
Vanadium oxide (V will be obtained as by being heat-treated (burning till)2O5) compound the commercially available ethanol vanadium of oxidation three (knot
Structure formula：VO(OC2H5)3, molecular weight：202.13) 1.02g (0.010mol) and conduct obtain aluminum oxide by being heat-treated (burning till)
(Al2O3) compound commercially available aluminum isopropylate (structural formula：Al(OCH(CH3)2)3, molecular weight：204.25)2.04g
(0.010mol) is dissolved in hexamethylene 60g, prepares the passivating material (b-1) that concentration is 5 mass %.
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
The one side rotary coating passivating material (b-1) of silicon substrate (8 Ω cm~12 Ω cm), carries out 120 DEG C, 3 points on hot plate
The prebake of clock.Afterwards, 650 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, obtains including aluminum oxide and oxidation
The passivating film of vanadium.Thickness is determined using ellipsometer, is as a result 60nm.The result of elementary analysis, it is known that V/Al/C=64/33/3
(quality %).The FT-IR of passivating film is determined, as a result in 1200cm-1Nearby it is found that the minimal amount of peak due to alkyl.
Then, across metal mask, multiple a diameter of 1mm aluminium electrode is formed on above-mentioned passivating film by being deposited, is made
Make MIS (Metal-Insulator-Semiconductor；Metal-insulator semiconductor) structure capacitor.Utilize city
Detector and the LCR meter (Hewlett-Packard Corporation, 4275A) sold determine the voltage-dependent (C-V characteristics) of the electrostatic capacitance of the capacitor.
As a result, distinguishing that flat-band voltage (Vfb) is moved to+0.10V from the -0.81V of ideal value.From the amount of movement, by passivation material
The passivating film that material (b-1) is obtained is -6.2 × 10 in fixed charge density (Nf)11cm-2When show negative fixed charge.
As described above, passivating material (b-1) is applied to two-sided, the progress prebake of the silicon substrate of 8 inches of p-type,
And 600 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated what film was covered
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Determine.As a result, carrier lifetime is 400 μ s.In order to be compared, the silicon of the p-type of 8 inches of identical is made using iodine deactivation method
Substrate is passivated and is determined, and as a result carrier lifetime is 1100 μ s.
In summary, it is known that：Passivating film obtained from passivating material (b-1) is heat-treated and (burnt till) shows certain
The inactivating performance of degree, shows negative fixed charge.
[embodiment 4]
By the commercially available ethanol vanadium (structural formula of oxidation three：VO(OC2H5)3, molecular weight：202.13)1.52g(0.0075mol)、
Commercially available aluminum isopropylate (structural formula：Al(OCH(CH3)2)3, molecular weight：204.25) 1.02g (0.005mol) and phenolic aldehyde are clear
Coating resins 10g is dissolved in butyl carbitol acetate 10g and hexamethylene 10g, prepares passivating material (b-2).
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
The one side rotary coating passivating material (b-2) of silicon substrate (8 Ω cm~12 Ω cm), carries out 120 DEG C, 3 points on hot plate
The prebake of clock.Afterwards, 650 DEG C, the heating of 1 hour are carried out in a nitrogen atmosphere, obtain the passivation comprising aluminum oxide and vanadium oxide
Film.Thickness is determined using ellipsometer, is as a result 22nm.The result of elementary analysis, it is known that V/Al/C=71/22/7 (matter
Measure %).The FT-IR of passivating film is determined, as a result in 1200cm-1Nearby it is found that the minimal amount of peak due to alkyl.
Then, across metal mask, multiple a diameter of 1mm aluminium electrode is formed on above-mentioned passivating film by being deposited, is made
Make MIS (Metal-Insulator-Semiconductor；Metal-insulator semiconductor) structure capacitor.Utilize city
Detector and the LCR meter (Hewlett-Packard Corporation, 4275A) sold determine the voltage-dependent (C-V characteristics) of the electrostatic capacitance of the capacitor.
As a result, distinguishing that flat-band voltage (Vfb) is moved to+0.03V from the -0.81V of ideal value.From the amount of movement, by passivation material
The passivating film that material (b-2) is obtained is -2.0 × 10 in fixed charge density (Nf)11cm-2When show negative fixed charge.
As described above, the p-type that passivating material (b-2) is applied to 8 inches silicon substrate it is two-sided, carry out pre-
Roasting, and 600 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated film covering
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Measure.As a result, carrier lifetime is 170 μ s.In order to be compared, the p-type of 8 inches of identical is made using iodine deactivation method
Silicon substrate is passivated and is determined, and as a result carrier lifetime is 1100 μ s.
In summary, it is known that：Passivating film obtained from passivating material (b-2) solidification shows assivation property to a certain degree
Can, show negative fixed charge.
<The situation of the oxide of vanadium family element is used as using tantalum oxide>
[embodiment 5]
For obtaining aluminum oxide (Al by being heat-treated (burning till)2O3) commercially available organic metal film coated section bar material
[(strain) high-purity chemical research institute, SYM-AL04, the mass % of concentration 2.3] and by being thermally treated resulting in tantalum oxide (Ta2O5) city
The organic metal film coated section bar material [(strain) high-purity chemical research institute, Ta-10-P, the mass % of concentration 10] sold, changes ratio
Example and mixed, prepare passivating material (c-1)~(c-6) shown in table 2.
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
One side difference rotary coating passivating material (c-1)~(c-6) of silicon substrate (8 Ω cm~12 Ω cm), is placed in heating plate
Carry out 120 DEG C, the prebake of 3 minutes.Afterwards, 700 DEG C, 30 minutes of heat treatment (burning till) is carried out in a nitrogen atmosphere, is wrapped
Salic and tantalum oxide passivating film.The voltage-dependent of static capacity is determined using the passivating film, is thus calculated solid
Determine charge density.
Then, passivating material (c-1)~(c-6) is respectively coated two-sided to the silicon substrate of 8 inches of p-type, carried out pre-
Roasting, and 650 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated film covering
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Measure.
Resulting result is summarized in table 2.In addition, carrier lifetime is determined again after 14 days after sample making,
As a result understand, any of the reduction of carrier lifetime in the passivating film for having used passivating material (c-1)~(c-6) shown in table 2
In the case of be that within -10%, the reduction of carrier lifetime is small.
It is different results according to the ratio (mass ratio) of tantalum oxide/aluminum oxide after heat treatment (burning till), on blunt
Change material (c-1)~(c-6), due to showing negative fixed charge after heat treatment (burning till), carrier lifetime is displayed that
Go out value to a certain degree, thus hint is used as passivating film function.
[table 2]
[embodiment 6]
Tantalum oxide (Ta will be obtained as by being heat-treated (burning till)2O5) compound commercially available methanol tantalum (structural formula：
Ta(OCH3)5, molecular weight：336.12) 1.18g (0.0025mol) and conduct obtain aluminum oxide by being heat-treated (burning till)
(Al2O3) compound commercially available aluminum isopropylate (structural formula：Al(OCH(CH3)2)3, molecular weight：204.25)2.04g
(0.010mol) is dissolved in hexamethylene 60g, prepares the passivating material (d-1) that concentration is 5 mass %.
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
The one side rotary coating passivating material (d-1) of silicon substrate (8 Ω cm~12 Ω cm), carries out 120 DEG C, 3 points on hot plate
The prebake of clock.Afterwards, 700 DEG C, the heating of 1 hour are carried out in a nitrogen atmosphere, obtain the passivation comprising aluminum oxide and tantalum oxide
Film.Thickness is determined using ellipsometer, is as a result 40nm.The result of elementary analysis, it is known that Ta/Al/C=75/22/3 (wt%).
The FT-IR of passivating film is determined, as a result in 1200cm-1Nearby it is found that the minimal amount of peak due to alkyl.
Then, across metal mask, multiple a diameter of 1mm aluminium electrode is formed on above-mentioned passivating film by being deposited, is made
Make MIS (Metal-Insulator-Semiconductor；Metal-insulator semiconductor) structure capacitor.Utilize city
Detector and the LCR meter (Hewlett-Packard Corporation, 4275A) sold determine the voltage-dependent (C-V characteristics) of the electrostatic capacitance of the capacitor.
As a result, distinguishing that flat-band voltage (Vfb) is moved to -0.30V from the -0.81V of ideal value.From the amount of movement, by passivation material
The passivating film that material (d-1) is obtained is -6.2 × 10 in fixed charge density (Nf)10cm-2When show negative fixed charge.
As described above, passivating material (d-1) is applied to two-sided, the progress prebake of the silicon substrate of 8 inches of p-type,
And 600 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated what film was covered
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Determine.As a result, carrier lifetime is 610 μ s.In order to be compared, the silicon of the p-type of 8 inches of identical is made using iodine deactivation method
Substrate is passivated and is determined, and as a result carrier lifetime is 1100 μ s.
In summary, it is known that：Passivating film obtained from passivating material (d-1) is heat-treated is shown to a certain degree
Inactivating performance, shows negative fixed charge.
[embodiment 7]
Tantalum oxide (Ta will be obtained as by being heat-treated (burning till)2O5) compound commercially available methanol tantalum (structural formula：
Ta(OCH3)5, molecular weight：336.12) 1.18g (0.005mol), as by be heat-treated (burning till) obtain aluminum oxide (Al2O3)
Compound commercially available aluminum isopropylate (structural formula：Al(OCH(CH3)2)3, molecular weight：204.25)1.02g
(0.005mol) and novolac resin 10g are dissolved in butyl carbitol acetate 10g and hexamethylene 10g mixture
In, prepare passivating material (d-2).
725 μ m-thicks of natural oxide film, 8 inches of p-type are being eliminated with the mass % of concentration 0.49 hydrofluoric acid in advance
The one side rotary coating passivating material (d-2) of silicon substrate (8 Ω em~12 Ω cm), carries out 120 DEG C, 3 points on hot plate
The prebake of clock.Afterwards, 650 DEG C, the heating of 1 hour are carried out in a nitrogen atmosphere, obtain the passivation comprising aluminum oxide and tantalum oxide
Film.Thickness is determined using ellipsometer, is as a result 18nm.The result of elementary analysis, it is known that Ta/Al/C=72/20/8 (wt%).
The FT-IR of passivating film is determined, as a result in 1200cm-1Nearby it is found that the minimal amount of peak due to alkyl.
Then, across metal mask, multiple a diameter of 1mm aluminium electrode is formed on above-mentioned passivating film by being deposited, is made
Make MIS (Metal-Insulator-Semiconductor；Metal-insulator semiconductor) structure capacitor.Utilize city
Detector and the LCR meter (Hewlett-Packard Corporation, 4275A) sold determine the voltage-dependent (C-V characteristics) of the electrostatic capacitance of the capacitor.
As a result, distinguishing that flat-band voltage (Vfb) is moved to -0.43V from the -0.81V of ideal value.From the amount of movement, by passivation material
The passivating film that material (d-2) is obtained is -5.5 × 10 in fixed charge density (Nf)10cm-2When show negative fixed charge.
As described above, passivating material (d-2) is applied to two-sided, the progress prebake of the silicon substrate of 8 inches of p-type,
And 600 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated what film was covered
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Determine.As a result, carrier lifetime is 250 μ s.In order to be compared, the silicon of the p-type of 8 inches of identical is made using iodine deactivation method
Substrate is passivated and is determined, and as a result carrier lifetime is 1100 μ s.
In summary, it is known that：Passivating film obtained from passivating material (d-2) is heat-treated and (burnt till) shows certain
The inactivating performance of degree, shows negative fixed charge.
<Use the situation of the oxide of vanadium family element of more than two kinds>
As shown in above-mentioned embodiment 1~7, it is known that：Passivating film comprising aluminum oxide and vanadium oxide and include aluminum oxide and oxygen
In the passivating film for changing tantalum, negative fixed charge is shown, the effect improved with carrier lifetime caused by passivation.
In addition, the present inventor has found in the application (Japanese Patent Application 2012-160336) having pointed out：Include aluminum oxide and oxygen
The passivating film for changing niobium shows negative fixed charge, the effect improved with carrier lifetime caused by passivation.
Therefore, it is as follows, to comprising aluminum oxide and as vanadium family element oxide be selected from by vanadium oxide, niobium oxide
And the passivating film of the oxide of 2 kinds or 3 kinds vanadium family elements in the group of tantalum oxide composition is discussed.
[embodiment 8]
Aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal film coated section bar material [(strain)
High-purity chemical research institute, SYM-AL04, the mass % of concentration 2.3], by be heat-treated (burning till) obtain vanadium oxide (V2O5) city
The organic metal film coated section bar material [(strain) high-purity chemical research institute, V-02, the mass % of concentration 2] sold and by heat at
Reason (burning till) obtains tantalum oxide (Ta2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute,
Ta-10-P, the mass % of concentration 10] mixing, prepare the passivating material (e-1) as application type material (with reference to table 3).
Aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal film coated section bar material [(strain)
High-purity chemical research institute SYM-AL04, the mass % of concentration 2.3], by be heat-treated (burning till) obtain vanadium oxide (V2O5) it is commercially available
Organic metal film coated section bar material [(strain) high-purity chemical research institute V-02, the mass % of concentration 2] and pass through heat treatment
(burning till) obtains niobium oxide (Nb2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute, Nb-
05th, the mass % of concentration 5] mixing, prepare the passivating material (e-2) as application type material (with reference to table 3).
Aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal film coated section bar material [(strain)
High-purity chemical research institute SYM-AL04, the mass % of concentration 2.3], by be heat-treated (burning till) obtain tantalum oxide (Ta2O5) city
The organic metal film coated section bar material [(strain) high-purity chemical research institute Ta-10-P, the mass % of concentration 10] sold and by heat
Processing (burning till) obtains niobium oxide (Nb2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute
Nb-05, the mass % of concentration 5] mixing, prepare the passivating material (e-3) as application type material (with reference to table 3).
Aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal film coated section bar material [(strain)
High-purity chemical research institute SYM-AL04, the mass % of concentration 2.3], by be heat-treated (burning till) obtain vanadium oxide (V2O5) it is commercially available
Organic metal film coated section bar material [(strain) high-purity chemical research institute V-02, the mass % of concentration 2], pass through heat treatment (burn
Into) obtain tantalum oxide (Ta2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute Ta-10-
P, the mass % of concentration 10] and by be heat-treated (burning till) obtain niobium oxide (Nb2O5) commercially available organic metal film coated type
Material [(strain) high-purity chemical research institute Nb-05, the mass % of concentration 5] is mixed, and prepares the passivation material as application type material
Expect (e-4) (with reference to table 3).
Similarly to Example 1,725 μm of natural oxide film are being eliminated in advance with the mass % of concentration 0.49 hydrofluoric acid
One side difference rotary coating passivating material (e-1)~(e- of the silicon substrate (8 Ω cm~12 Ω cm) of thick, 8 inches of p-type
4), it is placed in heating plate and carries out 120 DEG C, the prebake of 3 minutes.Afterwards, at the heat that 650 DEG C, 1 hour are carried out in a nitrogen atmosphere
Manage (burning till), obtain the passivating film of the oxide comprising aluminum oxide and vanadium family element of more than two kinds.
The voltage-dependent of static capacity is determined using passivating film obtained above, fixed charge density is thus calculated.
Then, passivating material (e-1)~(e-4) is applied to the two-sided and progress of silicon substrate for the p-type for being filled to 8 inches respectively in advance
Roast, 650 DEG C, 1 hour of heat treatment (burning till) is carried out in a nitrogen atmosphere, produce the two-sided of silicon substrate and be passivated what film was covered
Sample.The carrier lifetime of the sample has been carried out by biometrics device (Co., Ltd.'s KOBELCO scientific researches, RTA-540)
Determine.
Resulting result is summarized in table 3.
According to the oxide of vanadium family element of more than two kinds and the ratio (mass ratio) of aluminum oxide after heat treatment (burning till)
For different results, the passivating film on having used passivating material (e-1)~(e-4), due to showing after heat treatment (burning till)
Negative fixed charge is shown, carrier lifetime also shows that value to a certain degree, thus hint is used as passivating film function.
[table 3]
[embodiment 9]
Similarly to Example 1, aluminum oxide (Al will be obtained by being heat-treated (burning till)2O3) commercially available organic metal it is thin
Film application type material [(strain) high-purity chemical research institute, SYM-AL04, the mass % of concentration 2.3], by being heat-treated (burning till)
To vanadium oxide (V2O5) commercially available organic metal film coated section bar material [(strain) high-purity chemical research institute, V-02, the matter of concentration 2
Amount %] or by be heat-treated (burning till) obtain tantalum oxide (Ta2O5) commercially available organic metal film coated section bar material [(strain) is high
Purity chemical research institute, Ta-10-P, the mass % of concentration 10] mixing, prepare the passivating material (f-1) as application type material
~(f-8) (with reference to table 4).
In addition, preparing the passivating material (f-9) that aluminum oxide has been used alone (with reference to table 4).
Similarly to Example 1, passivating material (f-1)~(f-9) is respectively coated to the one side of the silicon substrate of p-type, it
It is heat-treated and (is burnt till) afterwards, produce passivating film, the voltage-dependent of static capacity is determined using the passivating film, is thus calculated
Go out fixed charge density.
And then, similarly to Example 1, passivating material (f-1)~(f-9) is respectively coated to pair of the silicon substrate of p-type
Face, is heat-treated and (is burnt till) and obtain sample, carrier lifetime is determined using the sample.Resulting result is summarized in
Table 4.
As shown in table 4, it can confirm that：Aluminum oxide/vanadium oxide or tantalum oxide in passivating material are 90/10 and 80/20
In the case of, the deviation of the value of fixed charge density is big, it is impossible to stably obtain negative fixed charge density, but by using oxygen
Change aluminium and niobium oxide, it is possible to achieve negative fixed charge density.It is 90/10 and 80/20 using aluminum oxide/vanadium oxide or tantalum oxide
Passivating material when being measured by CV methods, can according to circumstances turn into the passivating film for showing positive fixed charge, thus sentence
It is bright not up to stably to show negative fixed charge.It should be noted that showing that the passivating film of positive fixed charge can be with
Used as the passivating film of the silicon substrate of n-type.
On the other hand, in the case of passivating material (f-9) of the aluminum oxide for 100 mass %, it is impossible to obtain negative fixation
Charge density.
[table 4]
<Summarize>
Result more than can investigate the description below.
(1) in the passivating film comprising aluminum oxide and vanadium oxide and the passivating film comprising aluminum oxide and tantalum oxide, show
Negative fixed charge, the effect improved with carrier lifetime caused by passivation.
(2) on vanadium oxide and the mass ratio of aluminum oxide, when being 30/70~90/10, more preferably 35/65~90/10,
It is preferred from the viewpoint of the raising that can take into account carrier lifetime and stable negative fixed charge.
(3) on tantalum oxide and the mass ratio of aluminum oxide, when being 30/70~90/10, more preferably 35/65~90/10,
It is preferred from the viewpoint of the raising that can take into account carrier lifetime and stable negative fixed charge.
(4) in passivating film, from elementary analysis or the FT-IR of film measurement result, film is included as organic principle
In vanadium family element oxide (being herein vanadium oxide or tantalum oxide) and aluminum oxide beyond composition, but the vanadium family in passivating film
The oxide (being herein vanadium oxide or tantalum oxide) of element and the content (quality) of aluminum oxide if more than 90%, more preferably
More than 95%, then with the tendency of better characteristics can be maintained as passivating film.
(5) passivating film on the oxide comprising aluminum oxide and vanadium family element of more than two kinds, shows negative fixed electricity
Lotus, the effect improved with carrier lifetime caused by passivation.
[embodiment 10]
As silicon substrate 1, as the monocrystalline silicon substrate of dopant, the sun of the structure shown in Fig. 4 is produced using using boron
Can cell device.After texture processing is carried out to the surface of silicon substrate 1, the phosphorus diffusion material of application type is only coated with light surface side
Material, diffusion layer 2 (phosphorus-diffused layer) is formd by heat treatment.Afterwards, the phosphorus diffusion material of application type is eliminated using diluted hydrofluoric acid
Material.
Then, as smooth surface antireflection film 3, SiN film is formd using plasma CVD in light surface side.Afterwards, exist
The passivating material (a-1) prepared in embodiment 1, is applied to except contact area (opening by the rear side of silicon substrate 1 by ink-jet method
Portion OA) outer region.Afterwards, it is heat-treated, forms the passivating film 7 with opening portion OA.In addition, as passivating film 7, also
The sample using the passivating material (c-1) prepared in embodiment 5 is separately made.
Then, it is being formed on the smooth surface antireflection film 3 (SiN film) of the light surface side of silicon substrate 1, with specific secondary grid
The shape silk-screen printing of line electrode and main grid line electrode is using silver as the paste of main component.The overleaf entire surface screen printing of side
The paste using aluminium as main component is brushed.Afterwards, it is heat-treated (burn-through) at 850 DEG C, forms electrode (the 1st electrode 5 and the 2nd
Electrode 6), and make aluminium diffuse to the back side opening portion OA part, form BSF layers 4, form structure shown in Fig. 4 too
Positive energy cell device.
It should be noted that herein, on the formation of the silver electrode of smooth surface, describing the burn-through not in SiN film perforate
Process, but silver electrode can also be formed afterwards first by etching etc. in SiN film formation opening portion OA.
In order to be compared, in above-mentioned production process, without the formation of passivating film 7, and the overleaf entire surface of side
Aluminum Paste is printed, in entire surface formation and the corresponding p of BSF layers 4+Layer 14 and electrode 16 corresponding with the 2nd electrode, form Fig. 1's
The solar cell device of structure.On these solar cell devices, carried out evaluating characteristics (short circuit current flow, open-circuit voltage,
Fill factor and conversion efficiency).Evaluating characteristics enter according to JIS-C-8913 (2005 year) and JIS-C-8914 (2005 year)
Row is determined.It the results are shown in table 5.
Distinguished by table 5, compared with the solar cell device without passivating film, the sun of the passivating film with the present invention
The short circuit current flow and open-circuit voltage of energy cell device increase, and conversion efficiency (photoelectric transformation efficiency) maximum improves 0.6%, can obtain
To the effect of the present invention.
[table 5]
More than, the invention carried out by the present inventor is illustrated based on embodiments thereof and embodiment, but this
Invention is not limited to above-mentioned embodiment and embodiment, and various changes can be carried out in the range of its purport is not departed from.
For in the disclosure of Japanese publication No. 2012-160336, No. 2012-218389 and No. 2013-011934
Hold, its entirety is incorporated into this specification as reference.Whole documents, patent application and technology described in this specification
Standard with it is specific and describe respectively the situation of each document, patent application and technical standard with degree as with reference to quote in
In this specification.
Claims (12)
1. a kind of passivating film, it is comprising aluminum oxide and containing at least one kind of in the group being made up of vanadium oxide and tantalum oxide
The oxide of vanadium family element, the mass ratio of the oxide of the vanadium family element and the aluminum oxide be the oxide of vanadium family element/
Aluminum oxide is 30/70~90/10, and the passivating film is used for the solar cell device with silicon substrate.
2. passivating film according to claim 1, wherein, the total content of the oxide of the vanadium family element and the aluminum oxide
For more than 90%.
3. passivating film according to claim 1 or 2, wherein, the oxide of the vanadium family element include be selected from by vanadium oxide,
The oxide of 2 kinds or 3 kinds vanadium family elements in the group of niobium oxide and tantalum oxide composition.
4. passivating film according to claim 1 or 2, it is the heat treatment thing of application type material, and the application type material is included：
The precursor of aluminum oxide and contain at least one kind of vanadium family in the group being made up of the precursor of vanadium oxide and the precursor of tantalum oxide
The precursor of the oxide of element.
5. a kind of application type material, it wraps salic precursor and containing selected from before the precursor and tantalum oxide of vanadium oxide
The precursor of the oxide of at least one kind of vanadium family element in the group of body composition, the application type material is used in Claims 1 to 4
The formation of passivating film described in any one.
6. a kind of solar cell device, it possesses：
The silicon substrate of p-type；
The impurity diffusion layer of the n-type formed in the 1st surface side of the light surface side as the silicon substrate；
The 1st electrode formed on the impurity diffusion layer；
Formed in 2nd surface side opposite with the light surface side of the silicon substrate and there is the passivating film of opening portion；With
Formed in the 2nd surface side of the silicon substrate and the opening portion by the passivating film and the 2nd surface side electricity of the silicon substrate
2nd electrode of connection,
The passivating film is comprising aluminum oxide and contains at least one kind of vanadium family in the group being made up of vanadium oxide and tantalum oxide
The mass ratio of the oxide of element, the oxide of the vanadium family element and the aluminum oxide is oxide/oxidation of vanadium family element
Aluminium is 30/70~90/10.
7. solar cell device according to claim 6, it has the impurity diffusion layer of p-type, the impurity diffusion of the p-type
Layer with the addition of impurity compared with the silicon substrate in part or all of formation of the 2nd surface side of the silicon substrate with high concentration,
2nd electrode is electrically connected by the opening portion of the passivating film with the impurity diffusion layer of the p-type.
8. a kind of solar cell device, it possesses：
The silicon substrate of n-type；
The impurity diffusion layer of the p-type formed in the 1st surface side of the light surface side as the silicon substrate；
The 1st electrode formed on the impurity diffusion layer；
Formed in 2nd surface side opposite with the light surface side of the silicon substrate and there is the passivating film of opening portion；With
Formed in the 2nd surface side of the silicon substrate and the opening portion by the passivating film and the 2nd surface side electricity of the silicon substrate
2nd electrode of connection,
The passivating film is comprising aluminum oxide and contains at least one kind of vanadium family in the group being made up of vanadium oxide and tantalum oxide
The mass ratio of the oxide of element, the oxide of the vanadium family element and the aluminum oxide is oxide/oxidation of vanadium family element
Aluminium is 30/70~90/10.
9. solar cell device according to claim 8, it has the impurity diffusion layer of n-type, the impurity diffusion of the n-type
Layer with the addition of impurity compared with the silicon substrate in part or all of formation of the 2nd surface side of the silicon substrate with high concentration,
2nd electrode is electrically connected by the opening portion of the passivating film with the impurity diffusion layer of the n-type.
10. the solar cell device according to any one of claim 6~9, wherein, the vanadium family of the passivating film
The total content of the oxide of element and the aluminum oxide is more than 90%.
11. the solar cell device according to any one of claim 6~9, wherein, the oxide of the vanadium family element
Include the oxide of the 2 kinds or 3 kinds vanadium family elements in the group being made up of vanadium oxide, niobium oxide and tantalum oxide.
12. a kind of silicon substrate with passivating film, it has：
Silicon substrate；With
The entire surface or the passivating film according to any one of claims 1 to 4 of a part being arranged on the silicon substrate.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012160336 | 2012-07-19 | ||
| JP2012-160336 | 2012-07-19 | ||
| JP2012218389 | 2012-09-28 | ||
| JP2012-218389 | 2012-09-28 | ||
| JP2013-011934 | 2013-01-25 | ||
| JP2013011934 | 2013-01-25 | ||
| PCT/JP2013/069706 WO2014014116A1 (en) | 2012-07-19 | 2013-07-19 | Passivation film, coating material, solar-cell element, and silicon substrate with passivation film attached thereto |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104488087A CN104488087A (en) | 2015-04-01 |
| CN104488087B true CN104488087B (en) | 2017-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380037776.4A Expired - Fee Related CN104488087B (en) | 2012-07-19 | 2013-07-19 | Passivating film, application type material, solar cell device and the silicon substrate with passivating film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6434310B2 (en) |
| KR (1) | KR20150038021A (en) |
| CN (1) | CN104488087B (en) |
| TW (1) | TWI599064B (en) |
| WO (1) | WO2014014116A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107425083A (en) * | 2017-07-26 | 2017-12-01 | 顺德中山大学太阳能研究院 | A kind of lamination back of the body passivation solar cell and preparation method thereof |
| CN108389928B (en) * | 2018-03-30 | 2020-08-25 | 顺德中山大学太阳能研究院 | Solar cell and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6548912B1 (en) * | 1999-10-25 | 2003-04-15 | Battelle Memorial Institute | Semicoductor passivation using barrier coatings |
| JP5464775B2 (en) * | 2004-11-19 | 2014-04-09 | エイエスエム インターナショナル エヌ．ヴェー． | Method for producing metal oxide film at low temperature |
| JPWO2009145140A1 (en) * | 2008-05-27 | 2011-10-13 | コニカミノルタホールディングス株式会社 | Dye-sensitized solar cell |
| JP5655206B2 (en) * | 2010-09-21 | 2015-01-21 | 株式会社ピーアイ技術研究所 | Polyimide resin composition for forming back surface reflective layer of solar cell and method for forming back surface reflective layer of solar cell using the same |
-
2013
- 2013-07-19 KR KR20157003336A patent/KR20150038021A/en active IP Right Grant
- 2013-07-19 JP JP2014525900A patent/JP6434310B2/en not_active Expired - Fee Related
- 2013-07-19 CN CN201380037776.4A patent/CN104488087B/en not_active Expired - Fee Related
- 2013-07-19 TW TW102125997A patent/TWI599064B/en not_active IP Right Cessation
- 2013-07-19 WO PCT/JP2013/069706 patent/WO2014014116A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP6434310B2 (en) | 2018-12-05 |
| TW201409730A (en) | 2014-03-01 |
| JPWO2014014116A1 (en) | 2016-07-07 |
| KR20150038021A (en) | 2015-04-08 |
| CN104488087A (en) | 2015-04-01 |
| WO2014014116A1 (en) | 2014-01-23 |
| TWI599064B (en) | 2017-09-11 |
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