CN113937185A - Method for manufacturing heterojunction solar cell adopting hydrogen passivation - Google Patents
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002161 passivation Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 51
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000004065 semiconductor Substances 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 50
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 38
- 238000000137 annealing Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 238000009792 diffusion process Methods 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005360 phosphosilicate glass Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 6
- 235000012431 wafers Nutrition 0.000 description 26
- 239000010408 film Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 101100042793 Gallus gallus SMC2 gene Proteins 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005922 Phosphane Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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 Table
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The invention relates to a method for manufacturing a heterojunction solar cell by adopting hydrogen passivation, which comprises a hydrogen passivation process, and specifically comprises the following steps: and performing hydrogen passivation and oxidation treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method, and cleaning to remove a film layer formed by the hydrogen passivation and oxidation treatment. The invention aims to provide a manufacturing method of a heterojunction solar cell adopting hydrogen passivation, which can improve the conversion efficiency of the heterojunction solar cell, solve the problems of low minority carrier lifetime, more impurity defects and the like of a cast monocrystalline silicon body and a cast polycrystalline silicon body, and be applied to the heterojunction solar cell, thereby further reducing the manufacturing cost of the heterojunction solar cell.
Description
Technical Field
The invention relates to a method for manufacturing a heterojunction solar cell by adopting hydrogen passivation.
Background
At present, the research and development and the manufacture of solar cells mainly develop in the direction of cost reduction and efficiency improvement, the improvement of the conversion efficiency of the solar cells is the foundation of the development of solar energy career, and the reduction of the manufacture cost of the solar cells is the foundation of the growth of the solar energy career and is a prerequisite condition for meeting the large-scale production.
The silicon wafer is a carrier used for producing silicon-based solar cells and is generally divided into monocrystalline silicon wafers, cast monocrystalline silicon wafers and polycrystalline silicon wafers. It is known that high-level surface passivation is a main factor for improving the conversion efficiency of heterojunction solar cells, and defects and impurities existing in the production process of silicon wafers greatly influence the passivation level of the silicon wafers, particularly defects existing in cast monocrystalline silicon wafers and polycrystalline silicon wafers.
The existing preparation method of the heterojunction solar cell can not improve the defects and impurities caused in the production process of the silicon wafer, so that the silicon-based heterojunction solar cell has higher requirements on the quality of the silicon wafer, the cell conversion efficiency is influenced, and the production cost of the silicon wafer is greatly increased.
Disclosure of Invention
The invention aims to provide a manufacturing method of a heterojunction solar cell adopting hydrogen passivation, which can improve the conversion efficiency of the heterojunction solar cell, solve the problems of low minority carrier lifetime, more impurity defects and the like of a cast monocrystalline silicon body and a cast polycrystalline silicon body, and be applied to the heterojunction solar cell, thereby further reducing the manufacturing cost of the heterojunction solar cell.
The purpose of the invention is realized by the following technical scheme:
a manufacturing method of a heterojunction solar cell adopting hydrogen passivation comprises a hydrogen passivation process, and specifically comprises the following steps: and performing hydrogen passivation and oxidation treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method, and cleaning to remove a film layer formed by the hydrogen passivation and oxidation treatment.
Compared with the prior art, the invention has the advantages that:
(1) after hydrogen passivation and oxidation treatment are adopted and corresponding cleaning and removal are carried out, a high-cleanness layer is formed on the surface of the silicon wafer, so that the surface passivation level is greatly improved.
(2) The PSG is used for gettering, so that metal impurities are released from crystal defects such as dislocation, grain boundaries and the like, and are diffused to the surface of the silicon wafer to be captured, the purpose of removing the impurities is achieved, and the bulk minority carrier lifetime of the silicon wafer can be prolonged.
(3) And the crystal grain dislocation is reformed by adopting a high-temperature annealing mode, so that the lattice defect is reduced, and finally, the cell efficiency of the heterojunction solar cell is improved.
Drawings
Figure 1 is a simplified flow diagram of an embodiment of a method of fabricating a heterojunction solar cell employing hydrogen passivation in accordance with the present invention.
Detailed Description
A method of fabricating a heterojunction solar cell employing hydrogen passivation, comprising: the method comprises a hydrogen passivation process, which specifically comprises the following steps: and performing hydrogen passivation and oxidation treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method, and cleaning to remove a film layer formed by the hydrogen passivation and oxidation treatment.
The specific method of the hydrogen passivation and oxidation treatment comprises the following steps of depositing an intrinsic amorphous silicon layer or an impurity-doped amorphous silicon layer on the surface of a textured semiconductor substrate by adopting plate-type plasma enhanced chemical vapor deposition equipment, and carrying out annealing treatment; or depositing an intrinsic amorphous silicon layer or depositing a doped amorphous silicon layer on the surface of the semiconductor substrate by adopting tubular plasma enhanced chemical vapor deposition equipment for the textured semiconductor substrate or directly introducing hydrogen for treatment. At present, the intrinsic amorphous silicon layer deposited by the plasma enhanced chemical vapor deposition method or the doped amorphous silicon layer deposited by the plasma enhanced chemical vapor deposition method is hydrogenated amorphous silicon, and hydrogen is bound to participate in the deposition process. When the tubular plasma enhanced chemical vapor deposition equipment is used for hydrogen passivation and oxidation treatment, the working temperature of the tubular plasma enhanced chemical vapor deposition equipment is usually 400-500 ℃, so that annealing treatment is not needed.
The annealing treatment in the hydrogen passivation procedure has the annealing temperature of 400-500 ℃ and the annealing time of 20-30 minutes.
The process gas for depositing the intrinsic amorphous silicon layer or the doped amorphous silicon layer is SiH4、H2、CO2、CH4、PH3、B2H6The thickness of the intrinsic amorphous silicon layer or the doped amorphous silicon layer is 100-200 angstroms; the power supply of the plate-type plasma enhanced chemical vapor deposition equipment adopts 13.56MHz, 26MHz or 40 MHz; the power density of the tubular plasma enhanced chemical vapor deposition equipment is 500-2000Mw/cm2The power frequency is 10MHz-100 MHz; the specific method for treating by directly introducing hydrogen into the tubular plasma enhanced chemical vapor deposition equipment comprises the steps of placing the textured semiconductor substrate into a deposition chamber of the tubular plasma enhanced chemical vapor deposition equipment, and introducing hydrogen at the temperature of 400-500 DEG CThe treatment is carried out for 20-30 minutes, and the pressure of the deposition chamber is kept at 10-500 pa.
Annealing treatment, intrinsic amorphous silicon layer deposition treatment, doped amorphous silicon layer deposition treatment or direct hydrogen treatment are carried out at the temperature of 400-500 ℃, so that oxidation reaction is generated and the release of interstitial oxygen is promoted.
And the cleaning after the hydrogen passivation and oxidation treatment is to remove the film layer formed by the hydrogen passivation and oxidation treatment by adopting an acidic solution or an alkaline solution and then carry out acid cleaning.
The specific method for cleaning after hydrogen passivation and oxidation treatment comprises the steps of removing a film layer formed by hydrogen passivation and oxidation treatment by using a mixed solution of hydrofluoric acid and nitric acid, and cleaning by using a hydrofluoric acid solution, wherein the total mass percentage of hydrofluoric acid and nitric acid in the mixed solution of hydrofluoric acid and nitric acid is 15-30%, and the mass percentage of hydrofluoric acid in the hydrofluoric acid solution is 5-20%; or, removing the film layer formed by hydrogen passivation and oxidation treatment by using a sodium hydroxide solution or a potassium hydroxide solution, and then cleaning the silicon wafer by using a hydrochloric acid hydrogen peroxide solution and a hydrofluoric acid solution in sequence, wherein the mass percent of sodium hydroxide in the sodium hydroxide solution is 5-25%, the mass percent of potassium hydroxide in the potassium hydroxide solution is 5-25%, the total mass percent of hydrochloric acid hydrogen peroxide in the hydrochloric acid hydrogen peroxide solution is 15-30%, and the mass percent of hydrofluoric acid in the hydrofluoric acid solution is 5-20%.
And depositing a phosphorosilicate glass layer on the surface of the semiconductor substrate at a high temperature before texturing, and annealing.
B, depositing the phosphosilicate glass layer in the PSG at the high temperature by adopting a phosphorus oxychloride diffusion method; the diffusion temperature is 800-1100 deg.C, the diffusion pressure is 50-300 mbar, the diffusion time is 5-30 min, and POCL is introduced during the high-temperature diffusion process3、O2、N2，POCL3The gas flow is 50sccm-500sccm, O2The gas flow is 200sccm-2000sccm, N2The gas flow rate is 500sccm to 5000 sccm.
The annealing in the step B of high-temperature deposition of PSG is specifically carried out at the annealing temperature of 700-1000 ℃ and the cooling rate of 2-10 ℃/min; annealing pressure of 100mbar-500mbar, annealing time is 60min-180 min; introducing O in the annealing process2And N2，O2And N2The gas flow rate of the gas is 500sccm to 5000sccm, respectively.
And (3) carrying out acid cleaning on the semiconductor substrate subjected to the high-temperature deposition phosphorosilicate glass layer and the annealing treatment.
The semiconductor substrate after the high-temperature deposition phosphorosilicate glass layer and the annealing treatment is cleaned by hydrofluoric acid solution, the treatment time is 5-10 minutes, the treatment temperature is 20-30 ℃, the hydrofluoric acid solution contains 5-20% by mass of hydrofluoric acid and the balance of deionized water.
The invention is described in detail below with reference to the drawings and examples of the specification:
fig. 1 is a schematic diagram of an embodiment of a method for manufacturing a heterojunction solar cell using hydrogen passivation according to the present invention.
The invention provides a preparation method of a cast monocrystalline silicon heterojunction solar cell, which comprises the following steps:
s1, cleaning to remove oil stain, metal particles and other impurities on the surface, wherein the cleaning mode can be one or more of pure water washing, ultrasonic cleaning and acid solution cleaning, preferably acid solution cleaning, and the silicon wafer is immersed into SCI and SCII solution for rinsing sequentially, and the ratio of the SCI solution to the SCI solution is VNH3.H2O∶VH2O2∶VDI-water1: 6, and the ratio of SCII solution is VHCl∶VH2O2∶VDI-waterRinsing in the solution at 80 deg.C for 10min at a ratio of 1: 5; cleaning the surface of the substrate for 180-300 seconds by using an acid solution, and finally cleaning the surface of the substrate for 120-240 seconds by using deionized water and drying until no water residue is left on the surface, wherein the drying temperature is 50-90 ℃, and the drying time is 3-5 min; wherein the acid solution is one or a combination of more of HF acid, hydrochloric acid and nitric acid, and the total mass percentage of the acid is 5-15%.
S2, performing high-temperature phosphorus-containing layer coating and annealing treatment on the silicon wafer cleaned in the S1, preferably using a phosphorus oxychloride diffusion method, and introducing POCL into the silicon wafer in the high-temperature diffusion process3、O2、N2(ii) a During the annealing processIn which O can be introduced2And N2. The diffusion temperature range is 800-1100 ℃, the annealing temperature range is 700-1000 ℃, and the cooling rate range is 2-10 ℃/min; POCL3The gas flow is 50sccm-500 sccm; o is2The gas flow is 200sccm-2000 sccm; n is a radical of2The gas flow is 500sccm-5000 sccm; the flow rate of the annealing gas is 500sccm-5000 sccm; the pressure diffusion of the furnace tube is between 50mbar and 300mbar, and the annealing is between 100mbar and 500 mbar; the diffusion time is controlled to be 5min-30min, and the annealing time is controlled to be 60min-180 min;
s3, adopting an HF acid solution to re-clean the silicon wafer treated by the S2; wherein, the mass percent of the HF acid is 5-20%, the mass percent of the deionized water is 80-95%, the processing time of the silicon chip in the HF acid solution is 5-10 minutes, and the processing temperature is 20-30 ℃; and then, treating the cast monocrystalline silicon wafer with HF acid solution to perform surface texture etching, wherein the alkaline solution used for texture etching is one of KOH or NaOH, the mass percent of the alkaline solution is 0.5-3%, the texture etching time of the silicon wafer in the alkaline solution is 15-40 minutes, and the treatment temperature is 75-85 ℃.
S4, performing hydrogen passivation and oxidation treatment on the surface of the silicon wafer subjected to the S3 cleaning and texturing, performing hydrogen passivation and oxidation treatment by adopting a plate-type PECVD system or a tubular PECVD system, plating an intrinsic or doped amorphous silicon layer by adopting plate-type PECVD, and performing a series of annealing treatments, wherein the power supply of PECVD equipment adopts 13.56MHz, 26MHz or 40 MHz; preferably, 13.56MHz is used. The process gas for the amorphous silicon film layer contains Silane (SiH)4) Hydrogen (H)2)、CO2、CH4、PH3Or B2H6The annealing temperature is 400-500 ℃, and the annealing time is 30M; or directly plating the amorphous silicon layer at 400-2000 ℃ by adopting tubular PECVD or directly performing hydrogen treatment, wherein the power density is 500-2000Mw/cm2The power frequency is 10MHz-100MHz, and the process gas of the amorphous silicon film layer contains Silane (SiH)4) Hydrogen (H)2)、CO2、CH4、PH3Or B2H6The hydrogen treatment process gas is hydrogen.
S5, passivating and oxidizing the silicon wafer by hydrogenPerforming secondary cleaning, wherein the amorphous silicon layer can be removed by acid solution or alkaline solution, and the acid solution can be HF, HNO3Removing the amorphous silicon layer by using the mixed solution, and then cleaning by using HF; wherein HF is HNO3The total mass percentage of the mixed acid is 15-30%. HF acid 5-20 wt%, sodium hydroxide or potassium hydroxide solution as alkaline solution for removing amorphous silicon layer, and hydrogen chloride hydrogen peroxide solution and hydrofluoric acid solution for cleaning silicon wafer, wherein the alkaline solution has a mass solubility of 5-25%, and HCl is H2O2The total mass percent of the mixed acid is 15-30%, and the mass percent of the HF acid is 5-20%.
S6, after removing the amorphous silicon film layer at S5, preparing a surface passivation film layer (non-doped type) and a doped film layer by PECVD (plasma enhanced chemical vapor deposition) film coating. The back side of the silicon wafer is coated with the intrinsic type amorphous silicon and then the N type doped amorphous silicon in sequence. The power supply of the PECVD equipment adopts 13.56MHz, 26MHz or 40MHz, and preferably adopts 13.56 MHz. The process gas for the intrinsic amorphous silicon film layer contains Silane (SiH)4) Hydrogen (H)2)、CO2And CH4All or a combination of several of them. The process gas for preparing N-type doped amorphous silicon contains SiH4、H2And Phosphane (PH)3). The front surface of the silicon wafer is coated with the intrinsic amorphous silicon and then the P-type doped wide-energy-gap material in sequence. The process gas for the front (light incident) intrinsic amorphous silicon comprises Silane (SiH)4) Hydrogen (H)2)、CO2And CH4All or a combination of several of them. The process gas for preparing the P-type doped film layer contains SiH4、H2、CO2、CH4Diborane (B)2H6) TMB, all or a combination of several. The positive P-type doped film layer can be oxygen-containing microcrystalline muc-SiOx: H or amorphous silicon carbide a-SiC. The film forming speed of the oxygen-containing type microcrystals muc-SiOx H (P) is controlled to 0.2 to 1.5A/sec, preferably 0.6 to 0.8A/sec. The oxygen-containing microcrystalline muc-SiOx H (P) has a thickness of 40 to 200 angstroms, preferably 60 to 120 angstroms, on the textured surface.
S7, preparing a transparent conductive film (TCO) by applying PVD (physical vapor deposition) magnetron sputtering after the deposition process of the S6 amorphous silicon thin filmThe material may be a thin film of indium oxide doped with tin oxide, titanium oxide, zinc oxide or gallium oxide. Wherein indium oxide (In)2O3) Is a main material, and accounts for more than 90 percent by weight. Preferably, the doping material contains at least one of tin oxide, titanium oxide, zinc oxide or gallium oxide in an amount of 0 to 10% by weight. The target material used in PVD can also be pure indium oxide, and then H is introduced into the process2Or water vapor, to form doped In2O3H film. Cell designs with a P-doped layer in front require a thinner wide bandgap P-window layer to reduce optical absorption and enhance front side passivation. Accordingly, a high Work Function (WF) TCO is required as a contact layer to reduce contact resistance. For the intrinsic pair of TCO materials taking indium oxide as a main body, the Fermi surface position (or work function) of the TCO materials can be adjusted by adjusting effective doping. Effective doping is reduced, the infrared absorption of the TCO material can be reduced while the P-surface contact resistance is reduced, and the FF and the Isc are favorably improved, so that the conversion efficiency is improved
And S8, integrating the metal grid lines, and transferring the metal grid line pattern to the surface of the battery piece in a screen printing mode. The metal paste matched with the heterojunction process is low-temperature silver paste, and the annealing temperature is between 170-220 ℃, preferably in the range of 180-200 ℃.
Comparative experiment: according to the optimized process parameters, compared with the minority carrier lifetime of the conventional heterojunction process, the conversion efficiency is improved to a greater extent, as shown in the following table 1 and table 2:
TABLE 1 comparison of minority carrier lifetime after amorphous silicon coating
| Name of experiment | Silicon single crystal | Casting sheetCrystalline silicon | Polycrystalline silicon |
| Preparation process of conventional heterojunction solar cell | 2534 | 237 | 89 |
| The invention optimizes the preparation process of the heterojunction solar cell | 3123 | 2346 | 795 |
TABLE 2 comparison of conversion efficiencies
| Scheme(s) | Silicon single crystal | Casting monocrystalline silicon | Polycrystalline silicon |
| Preparation process of conventional heterojunction solar cell | 23.9％ | 19.8％ | 14.74％ |
| The invention optimizes the preparation process of the heterojunction solar cell | 24.4％ | 23.5％ | 21.81％ |
Claims (11)
1. A method of fabricating a heterojunction solar cell employing hydrogen passivation, comprising: the method comprises a hydrogen passivation process, which specifically comprises the following steps: and performing hydrogen passivation and oxidation treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method, and cleaning to remove a film layer formed by the hydrogen passivation and oxidation treatment.
2. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 1, wherein: the specific method of the hydrogen passivation and oxidation treatment comprises the following steps of depositing an intrinsic amorphous silicon layer or an impurity-doped amorphous silicon layer on the surface of a textured semiconductor substrate by adopting plate-type plasma enhanced chemical vapor deposition equipment, and carrying out annealing treatment; or depositing an intrinsic amorphous silicon layer or depositing a doped amorphous silicon layer on the surface of the semiconductor substrate by adopting tubular plasma enhanced chemical vapor deposition equipment for the textured semiconductor substrate or directly introducing hydrogen for treatment.
3. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 2, wherein: the annealing treatment in the hydrogen passivation procedure has the annealing temperature of 400-500 ℃ and the annealing time of 20-30 minutes.
4. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 2, wherein: the process gas for depositing the intrinsic amorphous silicon layer or the doped amorphous silicon layer is SiH4、H2、CO2、CH4、PH3、B2H6The thickness of the intrinsic amorphous silicon layer or the doped amorphous silicon layer is 100-200 angstroms; the power supply of the plate-type plasma enhanced chemical vapor deposition equipment adopts a voltage of 13.56MHz,26MHz or 40 MHz; the power density of the tubular plasma enhanced chemical vapor deposition equipment is 500-2000Mw/cm2The power frequency is 10MHz-100 MHz; the specific method for directly introducing hydrogen into the tubular plasma enhanced chemical vapor deposition equipment for treatment comprises the steps of placing the textured semiconductor substrate into a deposition chamber of the tubular plasma enhanced chemical vapor deposition equipment, introducing hydrogen at the temperature of 400-500 ℃ for treatment for 20-30 minutes, and keeping the pressure of the deposition chamber at 10-500 pa.
5. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 1, wherein: and the cleaning after the hydrogen passivation and oxidation treatment is to remove the film layer formed by the hydrogen passivation and oxidation treatment by adopting an acidic solution or an alkaline solution and then carry out acid cleaning.
6. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 5, wherein: the specific method for cleaning after hydrogen passivation and oxidation treatment comprises the steps of removing a film layer formed by hydrogen passivation and oxidation treatment by using a mixed solution of hydrofluoric acid and nitric acid, and cleaning by using a hydrofluoric acid solution, wherein the total mass percentage of hydrofluoric acid and nitric acid in the mixed solution of hydrofluoric acid and nitric acid is 15-30%, and the mass percentage of hydrofluoric acid in the hydrofluoric acid solution is 5-20%; or, removing the film layer formed by hydrogen passivation and oxidation treatment by using a sodium hydroxide solution or a potassium hydroxide solution, and then cleaning the silicon wafer by using a hydrochloric acid hydrogen peroxide solution and a hydrofluoric acid solution in sequence, wherein the mass percent of sodium hydroxide in the sodium hydroxide solution is 5-25%, the mass percent of potassium hydroxide in the potassium hydroxide solution is 5-25%, the total mass percent of hydrochloric acid hydrogen peroxide in the hydrochloric acid hydrogen peroxide solution is 15-30%, and the mass percent of hydrofluoric acid in the hydrofluoric acid solution is 5-20%.
7. The method of fabricating a heterojunction solar cell with hydrogen passivation according to any of claims 1 to 6, wherein: and depositing a phosphorosilicate glass layer on the surface of the semiconductor substrate at a high temperature before texturing, and annealing.
8. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 7, wherein: b, depositing the phosphosilicate glass layer in the PSG at the high temperature by adopting a phosphorus oxychloride diffusion method; the diffusion temperature is 800-1100 deg.C, the diffusion pressure is 50-300 mbar, the diffusion time is 5-30 min, and POCL is introduced during the high-temperature diffusion process3、O2、N2，POCL3The gas flow is 50sccm-500sccm, O2The gas flow is 200sccm-2000sccm, N2The gas flow rate is 500sccm to 5000 sccm.
9. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 7, wherein: the annealing in the step B of high-temperature deposition of PSG is specifically carried out at the annealing temperature of 700-1000 ℃ and the cooling rate of 2-10 ℃/min; the annealing pressure is 100mbar-500mbar, and the annealing time is 60min-180 min; introducing O in the annealing process2And N2，O2And N2The gas flow rate of the gas is 500sccm to 5000sccm, respectively.
10. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 7, wherein: and (3) carrying out acid cleaning on the semiconductor substrate subjected to the high-temperature deposition phosphorosilicate glass layer and the annealing treatment.
11. The method of manufacturing a heterojunction solar cell with hydrogen passivation according to claim 10, wherein: the semiconductor substrate after the high-temperature deposition phosphorosilicate glass layer and the annealing treatment is cleaned by hydrofluoric acid solution, the treatment time is 5-10 minutes, the treatment temperature is 20-30 ℃, the hydrofluoric acid solution contains 5-20% by mass of hydrofluoric acid and the balance of deionized water.
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