CN113937184A - Manufacturing method of heterojunction solar cell adopting hydrogen treatment technology before passivation - Google Patents
Manufacturing method of heterojunction solar cell adopting hydrogen treatment technology before passivation Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 54
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- 239000013081 microcrystal Substances 0.000 claims description 3
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- 239000013078 crystal Substances 0.000 description 4
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- 238000012545 processing Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
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- 238000005240 physical vapour deposition Methods 0.000 description 3
- 101100042793 Gallus gallus SMC2 gene Proteins 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
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- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005137 deposition process Methods 0.000 description 1
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
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Abstract
The invention relates to a method for manufacturing a heterojunction solar cell by adopting a hydrogen treatment technology before passivation, which comprises a hydrogen treatment process, and specifically comprises the following steps: and (3) performing hydrogen treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method. The invention aims to provide a manufacturing method of a heterojunction solar cell by adopting a hydrogen treatment technology before 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 apply the cast monocrystalline silicon body and the cast polycrystalline silicon body 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 a hydrogen treatment technology before 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 by adopting a hydrogen treatment technology before 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 apply the cast monocrystalline silicon body and the cast polycrystalline silicon body 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 a hydrogen treatment technology before passivation comprises a hydrogen treatment process, which comprises the following specific steps: and (3) performing hydrogen treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method.
Compared with the prior art, the invention has the advantages that:
(1) by adopting hydrogen treatment, a high-cleanness layer with lower interstitial oxygen content and lower metal impurities 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 of the present invention using a pre-passivation hydrogen treatment technique.
Detailed Description
A manufacturing method of a heterojunction solar cell adopting a hydrogen treatment technology before passivation comprises a hydrogen treatment process, which comprises the following specific steps: and (3) performing hydrogen treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method.
The specific method of the hydrogen treatment process is that the surface of the semiconductor substrate after the texturing is put in a hydrogen environment and is subjected to hydrogen treatment by a plasma enhanced chemical vapor deposition method.
Putting the textured semiconductor substrate into plasma enhanced chemical vapor deposition equipment, and performing hydrogen treatment by using high-purity hydrogen with the purity of 99.9999%, wherein the hydrogen flow is 500-5000 sccm, the treatment power is 200-500W, the treatment time is 20-120s, the chamber pressure is 10-100 pa, and the chamber temperature is not more than 200 ℃, so that a clean layer is formed; after the hydrogen treatment process is finished, the semiconductor film layer deposition is directly carried out.
The specific method for depositing the semiconductor film layer comprises the steps of respectively depositing semiconductor layers with different conductivity types on the front surface and the back surface of the semiconductor substrate after the hydrogen treatment to form the cleaning layer; the conductivity type of the semiconductor layer is mainly N type and P type; the N-type semiconductor layer comprises an intrinsic layer and an N-type doped layer, and the P-type semiconductor layer comprises an intrinsic layer and a P-type doped layer.
The N-type semiconductor layer comprises an intrinsic amorphous silicon layer and an N-type doped amorphous silicon layer, and the P-type semiconductor layer comprises an intrinsic amorphous silicon layer and a P-type doped amorphous silicon layer; the process gas for depositing the intrinsic amorphous silicon layer is mainly SiH4、H2、CO2And CH4Is formed by combining a plurality of the components; the process gas for depositing the N-type doped amorphous silicon layer mainly comprises SiH4、H2And pH3Forming; the process gas for depositing the P-type doped amorphous silicon layer mainly comprises SiH4、H2、CO2、CH4And B2H6Are combined.
The deposition thickness of the intrinsic amorphous silicon layer or the N-type doped amorphous silicon layer is 100-200 angstroms; the P-type doped amorphous silicon layer is oxygen-containing microcrystalline muc-SiOx or amorphous silicon carbide a-SiC; the film forming speed of the oxygen-containing microcrystal mu c-SiOx H is controlled to be 0.2-1.5 angstroms/second, and the thickness of the textured surface is 40-200 angstroms.
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; 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.
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 a hydrogen treatment before 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 O can be introduced during the annealing process2And 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, after the texturing and cleaning step S3, carrying out PECVD (plasma enhanced chemical vapor deposition) hydrogen treatment and coating to prepare a surface passivation film layer (non-doped type) and a doped film layer. Firstly, hydrogen treatment is carried out on the front and back surfaces of a silicon wafer, a power supply of PECVD equipment adopts 13.56MHz, 26MHz or 40MHz, preferably adopts 13.56MHz, and the process gas for hydrogen treatment is high-purity hydrogen (purity)>99.9999%), the gas flow rate of H2 is 500sccm-5000sccm, the processing power is 200-500W, the processing time is 20-120s, and the chamber pressure is 10pa-100 pa. And then respectively plating a first semiconductor layer and a second semiconductor layer on two sides of the silicon wafer, wherein the front side and the back side of the silicon wafer can be respectively provided with the first semiconductor layer and the second semiconductor layer, and can also be respectively provided with the second semiconductor layer and the first semiconductor layer. The first semiconductor layer is intrinsic amorphous silicon and N-type doped amorphous silicon. 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 comprises Silane (SiH)4) Hydrogen (H)2) And Phosphane (PH)3). A second semiconductor intrinsic type amorphous silicon and a P-type doped wide gap material. The process gas for the intrinsic amorphous silicon film layer contains Silane (SiH)4) Hydrogen (H)2)、CO2And CH4In which the process gas for preparing the P-type doped film layer comprises Silane (SiH)4) Hydrogen (H)2)、CO2And CH4Diborane (B)2H6) TMB, all or a combination of several. The 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.
S5, applying PVD (physical vapor deposition) magnetron sputtering to prepare a transparent conductive film (TCO) after the deposition process of the S4 amorphous silicon film, wherein the TCO can be made of an indium oxide film doped with tin oxide, titanium oxide, zinc oxide or gallium oxide. Wherein is oxidizedIndium (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 S6, 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 monocrystalline silicon | Polycrystalline silicon |
| Preparation process of conventional heterojunction solar cell | 2510 | 215 | 96 |
| The invention optimizes the preparation process of the heterojunction solar cell | 3023 | 2446 | 895 |
TABLE 2 comparison of conversion efficiencies
| Scheme(s) | Silicon single crystal | Casting monocrystalline silicon | Polycrystalline silicon |
| Preparation process of conventional heterojunction solar cell | 23.8％ | 19.9％ | 14.7％ |
| The invention optimizes the preparation process of the heterojunction solar cell | 24.3％ | 23.6％ | 21.8％ |
Claims (11)
1. A method for manufacturing a heterojunction solar cell by using a hydrogen treatment technology before passivation is characterized in that: the method comprises a hydrogen treatment process, which specifically comprises the following steps: and (3) performing hydrogen treatment on the surface of the textured semiconductor substrate by adopting a plasma enhanced chemical vapor deposition method.
2. The method of claim 1 for fabricating a heterojunction solar cell using a hydrogen pre-passivation treatment technique, wherein: the specific method of the hydrogen treatment process is that the surface of the semiconductor substrate after the texturing is put in a hydrogen environment and is subjected to hydrogen treatment by a plasma enhanced chemical vapor deposition method.
3. The method of claim 2 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, wherein: putting the textured semiconductor substrate into plasma enhanced chemical vapor deposition equipment, and performing hydrogen treatment by using high-purity hydrogen with the purity of 99.9999%, wherein the hydrogen flow is 500-5000 sccm, the treatment power is 200-500W, the treatment time is 20-120s, the chamber pressure is 10-100 pa, and the chamber temperature is not more than 200 ℃, so that a clean layer is formed; after the hydrogen treatment process is finished, the semiconductor film layer deposition is directly carried out.
4. The method of claim 2 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, wherein: the specific method for depositing the semiconductor film layer comprises the steps of respectively depositing semiconductor layers with different conductivity types on the front surface and the back surface of the semiconductor substrate after hydrogen treatment; the conductivity type of the semiconductor layer is mainly N type and P type; the N-type semiconductor layer comprises an intrinsic layer and an N-type doped layer, and the P-type semiconductor layer comprises an intrinsic layer and a P-type doped layer.
5. Root of herbaceous plantThe method of claim 4 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, wherein: the N-type semiconductor layer comprises an intrinsic amorphous silicon layer and an N-type doped amorphous silicon layer, and the P-type semiconductor layer comprises an intrinsic amorphous silicon layer and a P-type doped amorphous silicon layer; the process gas for depositing the intrinsic amorphous silicon layer is mainly SiH4、H2、CO2And CH4Is formed by combining a plurality of the components; the process gas for depositing the N-type doped amorphous silicon layer mainly comprises SiH4、H2And pH3Forming; the process gas for depositing the P-type doped amorphous silicon layer mainly comprises SiH4、H2、CO2、CH4And B2H6Are combined.
6. The method of claim 5 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, wherein: the deposition thickness of the intrinsic amorphous silicon layer or the N-type doped amorphous silicon layer is 100-200 angstroms; the P-type doped amorphous silicon layer is oxygen-containing microcrystalline muc-SiOx or amorphous silicon carbide a-SiC; the film forming speed of the oxygen-containing microcrystal mu c-SiOx H is controlled to be 0.2-1.5 angstroms/second, and the thickness of the textured surface is 40-200 angstroms.
7. The method of fabricating a heterojunction solar cell employing a hydrogen pre-passivation treatment technique 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 claim 7 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, 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 claim 7 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, 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 claim 7 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, 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 claim 10 for fabricating a heterojunction solar cell using a hydrogen pre-passivation technique, 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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