CN116705918A - Silicon wafer processing method and solar cell - Google Patents
Silicon wafer processing method and solar cell Download PDFInfo
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- CN116705918A CN116705918A CN202310716761.6A CN202310716761A CN116705918A CN 116705918 A CN116705918 A CN 116705918A CN 202310716761 A CN202310716761 A CN 202310716761A CN 116705918 A CN116705918 A CN 116705918A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 207
- 239000010703 silicon Substances 0.000 title claims abstract description 207
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000005520 cutting process Methods 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000005498 polishing Methods 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000003749 cleanliness Effects 0.000 abstract description 14
- 235000012431 wafers Nutrition 0.000 description 181
- 239000000243 solution Substances 0.000 description 64
- 229910021417 amorphous silicon Inorganic materials 0.000 description 19
- 239000012535 impurity Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000002161 passivation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005247 gettering Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 238000000241 photoluminescence detection Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 150000003376 silicon Chemical class 0.000 description 1
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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
- H01L31/18—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 System
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
-
- 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
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar 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 application provides a silicon wafer processing method and a solar cell, wherein the silicon wafer processing method comprises the following steps: providing a silicon wafer; by using a catalyst containing H 2 O 2 And a first solution of alkali to clean the silicon wafer; carrying out surface saturation treatment on the cleaned silicon wafer by adopting a second solution containing HF and HCl; cutting the silicon wafer subjected to surface saturation treatment; and texturing the cut silicon wafer by adopting texturing liquid medicine. The treatment method of the application can effectively improve the cleanliness of the surface of the silicon wafer before cutting, avoid the pollution of the sucker of the cutting machine, reduce the bad sucker printing of the solar cell and reduce the cost of the solar cellAnd the yield and the photoelectric conversion efficiency of the solar cell are improved.
Description
Technical Field
The application relates to the technical field of solar cell production, in particular to a silicon wafer processing method and a solar cell.
Background
Heterojunction solar cells (Heterojunction with Intrinsic Thin Layer, HJT) are a special type of PN junction formed of amorphous silicon and crystalline silicon material on which an amorphous silicon thin film is deposited by some special methods. HJT the advantages of crystalline silicon cells and thin film cells are combined because the heterojunction is formed at low temperature using amorphous silicon thin film/crystalline silicon.
Compared with the traditional crystalline silicon solar cell, the HJT cell needs to deposit an intrinsic amorphous silicon layer, a doped amorphous silicon layer, a TCO (transparent conductive film) and a printed electrode on two sides of a monocrystalline silicon wafer respectively. HJT the battery adopts a silicon-based film to form a PN junction, so that the highest process temperature is only the forming temperature (200 ℃) of the amorphous silicon film. The lower process temperature can save energy, reduce thermal damage and deformation of the silicon wafer, and can use the thin silicon wafer as a substrate, thereby being beneficial to reducing the material cost. And, an intrinsic thin film i-a-Si is interposed between the crystalline silicon and the doped thin film silicon: and H, the defects on the surface of the crystal can be effectively passivated, so that higher photoelectric conversion efficiency is obtained. Meanwhile, as the HJT battery uses n-type monocrystalline silicon as a substrate, the problem of light attenuation caused by B-O pairs does not exist.
However, improvement of the yield and photoelectric conversion efficiency of the HJT battery is an important premise for mass production of the main current standard. The current HJT battery still has the problems of low yield and further improvement of photoelectric conversion efficiency, and the productivity and the large-scale application of the HJT battery are affected. Therefore, how to improve the yield and efficiency of HJT batteries has become one of the important research directions in the art.
Disclosure of Invention
Based on this, it is necessary to provide a processing method of a silicon wafer and a solar cell, so as to improve the production yield and the photoelectric conversion efficiency of the solar cell.
According to a first aspect of the present application, there is provided a method for processing a silicon wafer, comprising the steps of:
by using a catalyst containing H 2 O 2 And a first solution of alkali to clean the silicon wafer;
carrying out surface saturation treatment on the silicon wafer after the cleaning treatment by adopting a second solution containing HF and HCl;
cutting the silicon wafer subjected to surface saturation treatment; and
and texturing the cut silicon wafer by adopting texturing liquid medicine.
In any embodiment, the first solution is prepared from 40-50% of sodium hydroxide or potassium hydroxide solution, 25-35% of hydrogen peroxide and water according to a volume ratio of 1: (26-30): (200-269) mixing.
In any embodiment, the temperature of the washing treatment is 65 to 68 ℃ and the time is 320 to 400 seconds.
In any embodiment, the second solution is prepared from 30-40% of hydrochloric acid, 45-55% of hydrofluoric acid and water according to the volume ratio (0.3-0.6): (10-16): (20-35) and mixing.
In any embodiment, the surface saturation treatment is performed at a temperature of 20 to 30 ℃ for 180 to 240 seconds.
In any embodiment, after the surface saturation treatment and before the dicing, the treatment method further includes a step of slow-lift-dehydrating the silicon wafer after the surface saturation treatment.
In any embodiment, after the slow-pull dehydration and before the cutting, the processing method further comprises a step of drying the silicon wafer after the slow-pull dehydration.
In any embodiment, after the cutting and before the texturing, the processing method further comprises a step of rough polishing the cut silicon wafer by adopting alkali solution.
In any embodiment, after the rough polishing and before the texturing, the treatment method further comprises a step of ozone cleaning the silicon wafer after the rough polishing by adopting an acid solution containing ozone.
According to a second aspect of the present application, there is provided a solar cell comprising a silicon wafer treated by the treatment method of the first aspect of the present application.
Compared with the prior art, the application has the following beneficial effects:
the processing method of the silicon wafer comprises the steps of adopting a silicon wafer containing H before cutting the silicon wafer 2 O 2 The first solution of alkali is used for cleaning the silicon wafer, and the second solution containing HF and HCl is used for carrying out surface saturation treatment on the cleaned silicon wafer; the method can effectively improve the cleanliness of the surface of the silicon wafer before cutting, avoid the pollution of the sucker of the cutting machine in the cutting process, reduce the bad sucker printing of the solar cell, and improve the yield and the photoelectric conversion efficiency of the solar cell.
Drawings
FIG. 1 is a flow chart of a processing method according to an embodiment of the application;
FIG. 2 is a flow chart of a processing method according to another embodiment of the present application;
FIG. 3 is a PL image of a heterojunction solar cell with suction cup mark failure;
fig. 4 is a PL image of a heterojunction solar cell without suction cup mark failure.
Detailed Description
The detailed description of the present application will be provided to make the above objects, features and advantages of the present application more obvious and understandable. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The existing heterojunction solar cell still has the problems of low production yield and further improvement of photoelectric conversion efficiency, and the productivity and the large-scale application of the heterojunction solar cell are affected. In this regard, the application provides a silicon wafer processing method and a corresponding heterojunction solar cell, and the silicon wafer is subjected to a series of pretreatment before being cut and textured, so that the yield of the cell is effectively improved, and the photoelectric conversion efficiency of the heterojunction solar cell is improved.
Referring to fig. 1 and 2, an embodiment of the present application provides a method for processing a silicon wafer, which includes steps S100 to S900 as follows:
step S100: a silicon wafer is provided.
In some of these embodiments, the silicon wafer is an n-type monocrystalline silicon wafer. The silicon wafer can be used as a substrate of a heterojunction solar cell, and the heterojunction solar cell can be prepared by sequentially forming an intrinsic amorphous silicon layer, a doped amorphous silicon layer, TCO and an electrode on the front surface and the back surface of the silicon wafer.
Step S200: by using a catalyst containing H 2 O 2 And the first solution of alkali is used for cleaning the silicon wafer.
Generally, a silicon wafer supplier needs to perform a gettering annealing operation on a silicon wafer before the silicon wafer leaves the factory, so as to reduce the impurity content in the silicon wafer and improve the quality of the silicon wafer. During the silicon wafer production and gettering annealing steps, some organic impurities, metal impurities and dust fall are inevitably formed on the surface of the silicon wafer.
In the subsequent silicon wafer cutting process, the silicon wafer needs to be adsorbed and carried through the sucking disc of the cutting machine, and organic impurities, metal impurities and dust fall on the surface of the silicon wafer inevitably pollute the sucking nozzle on the sucking disc in the adsorption and carrying process, and the polluted sucking nozzle can form a sucking disc mark on the silicon wafer when the silicon wafer is carried. The sucker marks cannot be completely removed in the subsequent cleaning step, and the sucker marks can influence the uniformity of the texture surface in the silicon wafer texturing process, influence the film quality of an intrinsic amorphous silicon layer formed on a silicon wafer, seriously influence the yield and the photoelectric conversion efficiency of a battery piece and cause the increase of the production cost.
In view of the above problems, the present application is directed to a method for dicing a silicon wafer by using a wafer containing H 2 O 2 And the first solution of alkali is used for cleaning the silicon wafer. By using H in the first solution 2 O 2 The strong oxidizing property of the catalyst is used for oxidizing the surface of the silicon wafer, so that organic impurities on the surface of the silicon wafer can be decomposed and removed, and other impurities and particulate matters on the surface of the silicon wafer can be removed; meanwhile, an oxide layer (silicon oxide) can be generated on the surface of the silicon wafer, so that the subsequent surface saturation treatment of the silicon wafer is facilitated.
Through carrying out foretell cleaning process to the silicon chip, can improve the cleanliness factor on silicon chip surface, reduce the pollution to the sucking disc when the silicon chip cuts, reduce battery piece sucking disc seal bad, be favorable to improving the matte homogeneity after the silicon chip texture making, improve the yield and the photoelectric conversion efficiency of battery piece. H 2 O 2 The chemical reaction equation for decomposing and oxidizing the surface of the silicon wafer is as follows:
H 2 O 2 ＝H 2 O+O 2
Si+2O 2 ＝SiO 2 +3O 2
in some embodiments, the first solution is prepared from 40-50% of sodium hydroxide or potassium hydroxide solution, 25-35% of hydrogen peroxide and water according to a volume ratio of 1: (26-30): (200-269) and mixing them together. The alkaline, hydrogen peroxide and water with the concentrations are prepared into the first solution according to the proportion, so that the cleanliness of the surface of the silicon wafer can be effectively improved, the bad printing of the sucker of the battery piece is reduced, and the yield and the photoelectric conversion efficiency of the battery piece are improved.
It is understood that the mass fraction of sodium hydroxide or potassium hydroxide solution used to formulate the first solution may be, but is not limited to, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%. The mass fraction of hydrogen peroxide used to formulate the first solution may be, but is not limited to 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%. The volume ratio of the sodium hydroxide or potassium hydroxide solution to the hydrogen peroxide may be, but is not limited to, 1:26, 1:27, 1:28, 1:29, 1:30. The volume ratio of sodium hydroxide or potassium hydroxide solution to water may be, but is not limited to, 1:200, 1: 210. 1:220, 1:230, 1:240, 1:250, 1:260, 1:269.
In some embodiments, the above-mentioned H-containing materials are used 2 O 2 And the first solution of alkali is used for cleaning the silicon wafer at the cleaning temperature of 65-68 ℃ for 320-400 s. Under the conditions, the cleanliness of the surface of the silicon wafer can be further improved, and meanwhile, an oxide layer with the thickness of 5-10 nm can be generated on the surface of the silicon wafer. It is understood that the temperature of the cleaning process may be, but is not limited to 65 ℃, 66 ℃, 67 ℃, 68 ℃; the time of the cleaning process may be, but is not limited to, 320s, 330s, 340s, 350s, 360s, 370s, 380s, 390s, 400s.
Step S300: and carrying out surface saturation treatment on the cleaned silicon wafer by adopting a second solution containing HF and HCl.
In the case of H-containing 2 O 2 The first solution of alkali is used for cleaning the silicon wafer, removing organic impurities and dust fall on the surface of the silicon wafer, and forming an oxide layer on the surface of the silicon wafer; and continuing to carry out surface saturation treatment on the silicon wafer by adopting a second solution containing HF and HCl.
HF in the second solution can react with an oxide layer on the surface of the silicon wafer to remove the oxide layer on the surface of the silicon wafer; meanwhile, HF can also react with silicon to generate hydrogen, and the hydrogen is combined with a suspension bond and a free radical on the surface of the silicon wafer to generate a stable surface state on the surface of the silicon wafer. Therefore, the surface of the silicon wafer can be saturated by hydrogen, so that the silicon wafer has good passivation performance, the hydrophobicity of the surface of the silicon wafer is increased, the surface of the silicon wafer has certain drainage, small particles and dust can not be adsorbed, and dirt can not be adhered, so that sucking disc marks on the silicon wafer can be avoided, and the yield and efficiency of the battery piece are improved. The chemical reaction equation for HF to react with silicon oxide layer and silicon is as follows:
SiO 2 +4HF＝SiF 4 ↑+2H 2 O
Si+4HF＝SiF 4 ↑+2H 2 ↑
HCl in the second solution can react with metal impurities on the surface of the silicon wafer, so that the metal impurities on the surface of the silicon wafer are removed, the cleanliness of the surface of the silicon wafer can be better improved by matching HCl with HF, the pollution of a sucker in the subsequent cutting step is better reduced, and the defect of sucker printing on the silicon wafer is avoided.
In some embodiments, the second solution is prepared from 30-40% hydrochloric acid, 45-55% hydrofluoric acid and water according to a volume ratio (0.3-0.6): (10-16): and (20-35) in a proportion. The second solution is prepared from the hydrochloric acid, the hydrofluoric acid and the water with the concentrations according to the proportion, so that a stable surface state can be generated on the surface of the silicon wafer more effectively, the passivation performance and the surface cleanliness of the silicon wafer are improved, and the yield and the efficiency of the battery piece are improved better.
It is understood that the mass fraction of hydrochloric acid used to form the second solution may be, but is not limited to, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%; the mass fraction of hydrofluoric acid used to form the second solution may be, but is not limited to, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%; the volume ratio of hydrochloric acid, hydrofluoric acid, and water used to form the second solution may be, but is not limited to, 0.3:10:20, 0.3:13:30, 0.3:16:35, 0.4:10:20, 0.4:14:28, 0.4:14:35, 0.6:10:20, 0.6:15:25, 0.6:16:35.
In some of these embodiments, the surface saturation treatment is performed at a temperature of 20 ℃ to 30 ℃ for a time of 180s to 240s. Under the process condition, stable surface states can be better generated on the surface of the silicon wafer, the passivation performance and the surface cleanliness of the silicon wafer are further improved, and the yield and the efficiency of the battery piece are better improved.
It is understood that the temperature of the surface saturation treatment may be, but is not limited to, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃; the time of the surface saturation treatment may be, but is not limited to, 180s, 190s, 200s, 210s, 220s, 230s, 240s.
Step S400: and slowly lifting and dehydrating the silicon wafer subjected to surface saturation treatment.
After the surface saturation treatment is carried out on the silicon wafer by adopting the second solution containing HF and HCl, the silicon wafer is placed in a slow-pulling groove for slow-pulling dehydration treatment, and the water on the surface of the silicon wafer is removed as much as possible while the residual liquid medicine on the surface of the silicon wafer is effectively removed. It is understood that the process parameters of the slow-pull dehydration, such as temperature, time, and pull speed, may be set according to actual production conditions, which are not particularly limited in the present application.
Step S500: and drying the slowly pulled and dehydrated silicon wafer.
After the slow-lifting dehydration treatment, the silicon wafer is placed in a drying groove for drying treatment so as to dry residual water on the surface of the silicon wafer, avoid water stain on the surface of the silicon wafer and further improve the cleanliness of the surface of the silicon wafer. It is understood that the process parameters such as temperature, time, etc. of the drying process may be set according to the actual production conditions, and are not particularly limited in the present application.
Step S600: and cutting the dried silicon wafer.
And (3) placing the dried silicon wafer in a cutting machine for cutting, and cutting the whole silicon wafer into half silicon wafers. The silicon wafer can be adsorbed and carried through the sucking disc of the cutting machine in the cutting process. The sucking disc is provided with a sucking nozzle for sucking the silicon wafer.
Since the application adopts the silicon wafer containing H before cutting 2 O 2 And the first solution of alkali is used for cleaning the silicon wafer, the second solution containing HF and HCl is used for carrying out surface saturation treatment on the cleaned silicon wafer, and the silicon wafer is slowly pulled to dehydrate and dry, so that impurities on the surface of the silicon wafer are effectively removed, and the cleanliness of the surface of the silicon wafer is improved; therefore, the suction nozzle of the cutting machine cannot be polluted in the process of adsorbing and carrying the silicon wafer, and suction cup marks cannot be formed on the silicon wafer, so that the yield and the photoelectric conversion efficiency of the battery piece can be effectively improved.
Step S700: and performing rough polishing on the cut silicon wafer.
Specifically, the cut silicon wafer is placed in a rough polishing groove, rough polishing treatment is carried out on the surface of the silicon wafer by utilizing alkali solution, and the cutting marks and the mechanical damage layers remained on the surface of the silicon wafer are etched. It is understood that the alkaline solution used in the rough polishing process may be a conventional rough polishing liquid.
Step S800: and (3) carrying out ozone cleaning on the roughly polished silicon wafer.
The solution containing ozone, HF and HCl is adopted to carry out ozone cleaning treatment on the roughly polished silicon wafer, oxygen generated by ozone decomposition is utilized to react with silicon to form a silicon oxide layer on the surface of the silicon wafer, metal impurities on the surface of the silicon wafer are adsorbed, and the HF and HCl are used to remove the oxide layer and the metal impurities on the surface of the silicon wafer, so that the metal impurities on the surface of the silicon wafer are further removed, and the cleanliness of the surface of the silicon wafer is improved.
It will be appreciated that the amounts of ozone, HF and HCl used in the solution used in the ozone cleaning step may be specifically set depending on the actual production situation.
Step S900: and (3) texturing the silicon wafer after ozone cleaning by adopting texturing liquid medicine.
After the silicon wafer is subjected to ozone cleaning treatment, the silicon wafer subjected to ozone cleaning is subjected to texturing treatment by adopting texturing liquid medicine, anti-reflection textured surfaces in a pyramid shape which are densely distributed can be formed on the surface of the silicon wafer, the light trapping principle of the textured structure is utilized, the generation of photo-generated carriers is increased, and the photoelectric conversion efficiency of the battery piece is improved.
In the application, the silicon wafer is subjected to cleaning treatment and surface saturation treatment before being cut, so that organic impurities and particles on the surface of the silicon wafer are cleaned in advance; therefore, after ozone cleaning and before texturing, the conventional alkaline solution and hydrogen peroxide pre-cleaning treatment is not required to be carried out on the silicon wafer. The silicon wafer may be textured after ozone cleaning.
It is understood that the texturing solution used in the texturing process may be one commonly used in the art. Generally, the texturing liquid comprises alkali and a texturing additive. The technological parameters of the texturing step can also be specifically set according to actual production conditions.
In the silicon wafer processing method of the present application, after the silicon wafer is textured, the silicon wafer may be sequentially subjected to post-cleaning, smoothing, passivation and drying. Wherein, the rear partThe cleaning comprises alkali and H 2 O 2 Cleaning the silicon wafer after texturing so as to completely clean the residues of the texturing additive on the surface of the silicon wafer; the smooth treatment adopts a solution containing ozone and HF to treat the silicon wafer, uses the ozone and HF to carry out isotropic corrosion on the silicon wafer, and polishes the surface of the pyramid so as to adapt to the subsequent amorphous silicon coating; the passivation step adopts a solution containing HF to treat the silicon wafer, removes an oxide layer on the surface of the silicon wafer, and ensures that the silicon wafer has good passivation performance, and can prevent the silicon wafer from being oxidized to a certain extent. The agents used in the post-cleaning, rounding and passivation steps may be the corresponding conventional agents in the art; the technological parameters of the steps of post-cleaning, smoothing, passivation and drying can be set according to actual conditions.
In general, the silicon wafer processing method of the present application is carried out by employing a wafer containing H before dicing the wafer 2 O 2 And the first solution of alkali is used for cleaning the silicon wafer, and the second solution containing HF and HCl is used for carrying out surface saturation treatment on the cleaned silicon wafer, so that the cleanliness of the surface of the silicon wafer before cutting can be effectively improved, the suction cup of the cutting machine is prevented from being polluted, the defective suction cup printing of the battery piece is reduced, and the yield and the photoelectric conversion efficiency of the battery piece are improved. PL (photoluminescence) images of heterojunction solar cells with suction cup print defects are shown in fig. 3; PL images of heterojunction solar cells without suction cup mark failure are shown in fig. 4.
An embodiment of the present application provides a solar cell, which includes a silicon wafer processed by the silicon wafer processing method of the present application. The solar cell adopts the silicon wafer processed by the silicon wafer processing method disclosed by the application, so that bad sucker printing is reduced, and the solar cell has higher yield and photoelectric conversion efficiency.
In some of these embodiments, the solar cell is a heterojunction solar cell. The silicon wafer treated by the silicon wafer treatment method provided by the application is used as a substrate of a heterojunction solar cell. The front surface of the silicon wafer is sequentially provided with an intrinsic amorphous silicon layer, an n-type doped amorphous silicon layer, a TCO and an electrode from inside to outside, and the back surface of the silicon wafer is sequentially provided with an intrinsic amorphous silicon layer, a p-type doped amorphous silicon layer, a TCO and an electrode from inside to outside.
The present application will be further described with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the application.
Example 1:
45% sodium hydroxide solution, 30% hydrogen peroxide and water in a volume ratio of 1:28:210 forming a first solution; cleaning the n-type monocrystalline silicon wafer for 330s at 65 ℃ by adopting the first solution;
hydrochloric acid with the mass fraction of 35 percent, hydrofluoric acid with the mass fraction of 50 percent and water are mixed according to the volume ratio of 0.4:12:24 forming a second solution; carrying out surface saturation treatment on the silicon wafer subjected to the cleaning treatment for 200s at 25 ℃ by adopting the second solution;
slowly lifting and dehydrating the silicon wafer subjected to surface saturation treatment for 60s, further drying for 900s in a drying groove at 65 ℃, and then placing the silicon wafer in a cutting machine for cutting treatment, so that the whole silicon wafer is cut into half silicon wafers; performing rough polishing treatment on the cut silicon wafer by adopting an alkali solution with the volume concentration (namely the proportion of the alkali solution volume to the volume of the whole mixed solution in the rough polishing tank) of 2.09 percent and the temperature of 70 ℃; then ozone cleaning treatment is carried out on the roughly polished silicon wafer by adopting normal-temperature solution of ozone with the mass concentration of 30-45 ppm, HF with the volume concentration of 0.96% and HCl with the volume concentration of 0.02%; performing 600s texturing on the silicon wafer after ozone cleaning by adopting a texturing liquid medicine at 80 ℃;
an alkaline solution with a volume concentration of 1.12% and H with a volume concentration of 4.44% are used 2 O 2 Carrying out 180s post-cleaning on the silicon wafer after texturing; carrying out 200s of smooth treatment on the silicon wafer after the post-cleaning by adopting a solution containing 30-45 ppm of ozone and HF with the volume concentration of 0.30%; passivating the silicon wafer for 200 seconds by adopting normal-temperature solution containing HF with the volume concentration of 5.35%; then drying the silicon wafer in a drying groove at 65 ℃ for 900 seconds;
the n-type monocrystalline silicon wafer treated by the steps is used as a substrate, and an intrinsic amorphous silicon layer, an n-type doped amorphous silicon layer, a TCO and an electrode are sequentially formed on the front surface of the silicon wafer; and sequentially forming an intrinsic amorphous silicon layer, a p-type doped amorphous silicon layer, TCO and an electrode on the back surface of the silicon wafer, thereby forming the heterojunction solar cell.
Example 2:
this embodiment is substantially the same as embodiment 1, except that: the temperature of the cleaning treatment of the silicon wafer by adopting the first solution is different. In this example, the temperature at which the first solution performs the cleaning process on the silicon wafer is 67 ℃.
Example 3:
this embodiment is substantially the same as embodiment 1, except that: the time for cleaning the silicon wafer by the first solution is different. In this embodiment, the time for the first solution to perform the cleaning process on the silicon wafer is 340s.
Example 4:
this embodiment is substantially the same as embodiment 1, except that: the first solution has a different composition. In the embodiment, a sodium hydroxide solution with the mass fraction of 46%, hydrogen peroxide with the mass fraction of 31% and water are mixed according to the volume ratio of 1:29:220 to form a first solution. The time for cleaning the silicon wafer by the first solution is 345s.
Example 5:
this embodiment is substantially the same as embodiment 1, except that: and adopting the second solution to carry out surface saturation treatment on the silicon wafer at different temperatures. In this example, the surface saturation treatment of the silicon wafer by the second solution was carried out at 28 ℃.
Example 6:
this embodiment is substantially the same as embodiment 1, except that: and carrying out surface saturation treatment on the silicon wafer by adopting the second solution for different time. In this embodiment, the second solution performs surface saturation treatment on the silicon wafer for 205s.
Example 7:
this embodiment is substantially the same as embodiment 1, except that: the composition of the second solution is different. In this example, hydrochloric acid with a mass fraction of 37%, hydrofluoric acid with a mass fraction of 47% and water were mixed in a volume ratio of 0.5:13:25 to form a second solution.
Comparative example 1:
this comparative example is substantially identical to example 1, except that: before cutting the silicon wafer, the silicon wafer is not subjected to cleaning treatment, surface saturation treatment, slow lifting and drying; and after ozone cleaning and before texturing, the method adopts the method containing H 2 O 2 The pre-cleaning step is carried out on the silicon wafer by the alkali solution.
PL detection was performed on the heterojunction solar cell pieces prepared in each of the above examples and comparative examples, and whether or not there was a "suction cup print" defect on the cell piece in the PL image was observed; and the photoelectric conversion efficiency of the battery piece is tested. The PL detection method is to excite the solar cell by using a light source to make the silicon solar cell emit light with specific wavelength, then collect the light signal of the emitted light with specific wavelength through a light filtering and special photosensitive element, and finally obtain the defect condition of the surface of the solar cell through data processing. The PL device employed was DP100. The photoelectric conversion efficiency test adopts a Hall machine table, and the light intensity is under the standard (the test temperature is 1000W/m under the 25 ℃ state) 2 ) By applying different voltages to the battery cells and measuring the current; the values of these voltages and currents are recorded and plotted as a graph, called an I-V curve; this curve shows the relationship between the current and voltage of the component, which can be used to evaluate the photoelectric conversion efficiency of the battery cell.
The parameters and performance test results of each example and comparative example are shown in table 1.
TABLE 1
As can be seen from the data in table 1:
1) The application adopts the method containing H before cutting the silicon wafer 2 O 2 And alkali ofThe silicon wafer is cleaned by one solution, and the surface of the cleaned silicon wafer is saturated by a second solution containing HF and HCl, so that the cleanliness of the surface of the silicon wafer before cutting can be effectively improved, and the bad sucker printing of the battery piece is reduced. Compared with the traditional silicon wafer treatment method in the comparative example, the production line sucker mark defect ratio in the embodiment of the application is obviously reduced, the overall yield of the heterojunction cell is improved by more than 2.65%, and the yield is obviously improved.
2) The photoelectric conversion efficiency of the battery piece of the embodiment of the application is improved compared with that of the comparative example. The reason for this is mainly: the sucker dirt of the battery piece prepared by the embodiment of the application is obviously reduced, the cleanliness is greatly improved, the film plating and depositing effects are better, the composite center in the battery piece is reduced, and the photoelectric conversion efficiency of the battery piece is improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the application and are described in detail herein without thereby limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of the application should be assessed as that of the appended claims.
Claims (10)
1. The processing method of the silicon wafer is characterized by comprising the following steps:
by using a catalyst containing H 2 O 2 And a first solution of alkali to clean the silicon wafer;
carrying out surface saturation treatment on the silicon wafer after the cleaning treatment by adopting a second solution containing HF and HCl;
cutting the silicon wafer subjected to surface saturation treatment; and
and texturing the cut silicon wafer by adopting texturing liquid medicine.
2. The method for processing the silicon wafer according to claim 1, wherein the first solution is prepared from 40-50% of sodium hydroxide or potassium hydroxide solution, 25-35% of hydrogen peroxide and water according to a volume ratio of 1: (26-30): (200-269) mixing.
3. The method for treating a silicon wafer according to claim 1, wherein the cleaning treatment is carried out at a temperature of 65 to 68 ℃ for 320 to 400 seconds.
4. The method for processing a silicon wafer according to claim 1, wherein the second solution is prepared from 30 to 40% by mass of hydrochloric acid, 45 to 55% by mass of hydrofluoric acid and water in a volume ratio of (0.3 to 0.6): (10-16): (20-35) and mixing.
5. The method for treating a silicon wafer according to claim 1, wherein the surface saturation treatment is performed at a temperature of 20 to 30 ℃ for 180 to 240 seconds.
6. The method according to any one of claims 1 to 5, wherein after the surface saturation treatment and before the dicing, the method further comprises a step of subjecting the silicon wafer after the surface saturation treatment to slow-pull dehydration.
7. The method of processing a silicon wafer according to claim 6, wherein after the slow-pull dehydration and before the dicing, the method further comprises a step of drying the silicon wafer after the slow-pull dehydration.
8. The method of any one of claims 1 to 5 and 7, further comprising the step of rough polishing the cut silicon wafer with an alkali solution after the cutting and before the texturing.
9. The method according to any one of claims 1 to 5 and 7, wherein after the rough polishing and before the texturing, the method further comprises a step of ozone-cleaning the silicon wafer after the rough polishing with an acid solution containing ozone.
10. A solar cell comprising a silicon wafer treated by the treatment method according to any one of claims 1 to 9.
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