CN111403561A - Silicon wafer texturing method - Google Patents
Silicon wafer texturing method Download PDFInfo
- Publication number
- CN111403561A CN111403561A CN202010334598.3A CN202010334598A CN111403561A CN 111403561 A CN111403561 A CN 111403561A CN 202010334598 A CN202010334598 A CN 202010334598A CN 111403561 A CN111403561 A CN 111403561A
- Authority
- CN
- China
- Prior art keywords
- silicon wafer
- cleaning
- solution
- wafer obtained
- putting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 180
- 239000010703 silicon Substances 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005406 washing Methods 0.000 claims abstract description 38
- 239000013256 coordination polymer Substances 0.000 claims abstract description 27
- 239000008213 purified water Substances 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 112
- 239000000243 solution Substances 0.000 claims description 90
- 239000007788 liquid Substances 0.000 claims description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 description 129
- 230000000052 comparative effect Effects 0.000 description 45
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 24
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
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
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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 invention discloses a silicon wafer texturing method, which comprises the following steps: s1, carrying out pre-oxidation treatment on the silicon wafer to be treated to remove pollutants on the surface of the silicon wafer; s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning; s3, placing the silicon wafer obtained in the S2 into an SDE groove for SDE treatment; s4, carrying out surface oxidation treatment on the silicon wafer obtained in the S3; s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning; s6, putting the silicon wafer obtained in the S5 into a TEX groove for texturing; s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning; s8, post-cleaning the silicon wafer obtained in the S7 for 1; s9, putting the silicon wafer obtained in the S8 into pure water, cleaning, and then carrying out CP; s10, washing the silicon wafer obtained in the step S9 with purified water, and then washing 2; s11, cleaning the silicon wafer obtained in the step S10 with purified water and then with hydrofluoric acid; and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying. The invention is suitable for surface cleaning and texturing of the heterojunction battery.
Description
Technical Field
The invention discloses a battery preparation process, and particularly relates to a silicon wafer texturing method.
Background
An shj (silicon heterojunction) silicon heterojunction battery, also called an hit (heterojunction with intrinsic thin layer) battery, has the characteristics of high efficiency, high Voc and the like, generally uses an N-type silicon wafer as a substrate, has particularly strict requirements on a silicon substrate interface (sensitive to surface cleanliness after texturing), and has the following general process steps: texturing, amorphous silicon, TCO, silk screen & testing.
At present, in the large-scale SHJ production, the texturing process of a silicon substrate generally adopts the flow of pre-cleaning → removing damage → texturing → post-cleaning → CP (chemical polishing) → HF cleaning → drying, and in the texturing process, the added texturing additive is generally divided into a hydrophobic texturing additive and a hydrophilic texturing additive, and the devices corresponding to different texturing additives are different, so that the enterprise burden is undoubtedly increased by purchasing two sets of devices, and in addition, the cleanliness of the surface of the textured silicon wafer greatly affects the deposition quality of amorphous silicon, thereby affecting the efficiency. Wherein, the post-cleaning cleans the organic matter on the surface of the textured silicon wafer, the CP can remove one layer of the surface of the silicon wafer, and the HF tank plays a role in removing SiO on the surface of the silicon wafer2While SiO can be removed2K, Na, etc. But before the HF groove is removed, the surface of the silicon wafer is not completely oxidized, the HF groove removes ions, and the capability of stripping particles is not completely reflected.
Disclosure of Invention
In order to solve the problems, the invention provides a silicon wafer texturing method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silicon wafer texturing method comprises the following steps:
s1, carrying out pre-oxidation treatment on the silicon wafer to be treated to remove pollutants on the surface of the silicon wafer;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning;
s3, placing the silicon wafer obtained in the S2 into an SDE groove for SDE treatment;
s4, carrying out surface oxidation treatment on the silicon wafer obtained in the S3;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the S5 into a TEX groove for texturing;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning the silicon wafer obtained in the S7 for 1;
s9, washing the silicon wafer obtained in the step S8 in pure water, and then performing CP (chemical polishing);
s10, washing the silicon slice obtained in the step S9 with purified water, and then washing 2, wherein the washing 2 is SC2 washing liquid or O3Cleaning fluid;
s11, cleaning the silicon wafer obtained in the step S10 with purified water and then with hydrofluoric acid;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
Further, in S1, S4 and S8, the treating liquid used is O3Solution or SC1 solution. Further, in S4, when the treating liquid is O3In the case of solution, the treatment time is 180s, the temperature is room temperature, and O is3The concentration is 0.01-120ppm, and the pure water is in overflow state.
Further, in S3, in the SDE treatment, alkali liquor is adopted for removing the damage, the mass concentration of the alkali is 1-20%, the treatment temperature is 40-90 ℃, and the treatment time is 10-240S.
Further, O3The solution also comprises HCl and HNO3One or more of. At O3Adding HCl, HF and HNO in any proportion3Can increase the acidity of the solution and improve the solubility of ozone.
Further, the SC1 solution is characterized in that H2O2Mixed solution of solution and alkali, wherein the alkali can be NaOH, KOH, NH4One or more of OH.
Further, in S9, CP is O3CP or HF/HNO3CP; said O is3CP is O3Mixed solution of/HF, or O3Adding HCl and HNO into/HF mixed solution3One or two of them; the HF/HNO3CP is HF/HNO3Mixed solution, or HF/HNO3One or two mixed solutions of HCl and acetic acid are added into the solution.
Further, the hydrofluoric acid solution is an HF solution or an HF/HCl mixed solution.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, a pre-oxidation pretreatment-SDE-oxidation treatment-TEX process flow treatment method is adopted before texturing, in the pre-oxidation pretreatment process, the micro reaction is that hydrogen peroxide enables an oxide layer to be formed on the surface of a silicon wafer, potassium hydroxide corrodes the oxide layer, hydrogen peroxide reoxidizes the surface of the silicon wafer to form the oxide layer, and potassium hydroxide corrodes the oxide layer again, so that the cycle is repeated, therefore, the pre-oxidation process of the application carries out modification treatment on the surface of the silicon wafer while removing oil stains, and the silicon wafer is subjected to surface oxidation treatment again before texturing2The distribution is more uniform, so that the texture is more uniform, the FF of the battery is increased, and the efficiency gain is brought.
(2) The post-cleaning 2 of the invention is SC2 cleaning solution or O3The cleaning solution is used for the pre-HF bath oxidation treatment, and the pre-HF bath oxidation treatment forms a layer of complete SiO on the surface of the silicon wafer2Film, SiO the layer by HF acid2The film is washed off to remove particles, organic matters, ions and the like on the surface of the silicon wafer and make the surface of the silicon wafer hydrophobic; meanwhile, the post-cleaning 2 can directly oxidize the residual organic matters on the surface of the silicon wafer, so that the effect of directly removing the organic matters is achieved, and the improvement of Isc is facilitated.
(3) When CP liquid is O3Increasing HNO in/HF mixed solution3Or adding HCl and HNO3In the process, the pyramid structure formed on the textured silicon wafer has the effect of rounding the pyramid tips and the pyramid valleys simultaneously, the pyramid appearance of the textured silicon wafer of the solar cell is better modified, the silicon wafer with the pyramid tips and the pyramid valleys having a certain curvature radius is obtained, the reflectivity of the silicon wafer is improved, and the minority carrier lifetime is remarkably prolonged after an amorphous silicon passivation layer is deposited on the silicon waferHigh passivation quality of the silicon chip.
Drawings
FIG. 1 is an SEM photograph of a pyramidal cross-sectional profile of example 1;
FIG. 2 is an SEM photograph of a pyramidal cross-sectional morphology of comparative example 2.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. All other embodiments that can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention.
Example 1
A silicon wafer texturing method comprises the following steps:
s1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is SC1 solution, the volume fraction of KOH solution with the concentration of 45 wt% is 1.6%, and the concentration of H is 30 wt%2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 20 wt% and the balance of water, the temperature is 70 ℃, and the treatment time is 30S;
s4, placing the silicon chip obtained in the S3 into O3Cleaning in solution, O3The concentration is 120ppm, the treatment time is 180s, and the temperature is room temperature;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the step S5 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
S8、post-cleaning 1 is carried out on the silicon wafer obtained in the step S7, the cleaning solution of the post-cleaning 1 is SC1 cleaning solution, and the SC1 cleaning solution is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s9, washing the silicon wafer obtained in S8 in pure water, and then carrying out O3CP of said O3CP is O3/HF/HNO3Mixing the solution, wherein the mass fraction of nitric acid is 30%, the mass fraction of hydrofluoric acid is 0.8%, the concentration of ozone is 80ppm, the temperature is 20 ℃, and the time is 4 min;
s10, washing the silicon slice obtained in the step S9 with purified water, and adding O3Post-cleaning 2, O in a cleaning solution3The ozone concentration in the cleaning solution is 10ppm, and the time is 180 s;
s11, cleaning the silicon wafer obtained in the step S10 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
Example 2
A silicon wafer texturing method comprises the following steps:
s1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is SC1 solution, the volume fraction of which is 45 wt% NaOH solution is 1.6%, and the concentration of which is 30 wt% H2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 10 wt% and the balance of water, the temperature is 42 ℃, and the treatment time is 100S;
s4, placing the silicon chip obtained in the S3 into O3Cleaning in solution, O3Adding HCl and O with the mass fraction of 0.1% into the solution3The concentration of the mixed solution is 120ppm,the treatment time is 180s, and the temperature is room temperature;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the step S5 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning 1 the silicon wafer obtained in the step S7, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s9, washing the silicon wafer obtained in S8 in pure water, and then carrying out O3CP of said O3CP is O3The ozone concentration is 80ppm, the mass fraction of hydrofluoric acid is 0.8%, the temperature is 20 ℃, and the time is 4 min;
s10, washing the silicon slice obtained in the step S9 with purified water, and adding O3Post-cleaning 2, O in a cleaning solution3The ozone concentration in the cleaning solution is 10ppm, and the time is 180 s;
s11, cleaning the silicon wafer obtained in the step S10 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
Example 3
A silicon wafer texturing method comprises the following steps:
s1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is SC1 solution, and the NH concentration is 45 wt%4OH solution 1.6% by volume, 30% by weight of H2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is 2 wt% of KOH solution, and the balance is water, the temperature is 85 ℃, and the treatment time is 240S;
s4, placing the silicon chip obtained in the S3 into O3Cleaning in solution, O3Adding HNO with the mass fraction of 0.1% into the solution3，O3The concentration is 120ppm, the treatment time is 180s, and the temperature is room temperature;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the step S5 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning 1 the silicon wafer obtained in the step S7, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s9, washing the silicon wafer obtained in the S8 in pure water, and then carrying out HF/HNO3CP of the HF/HNO3CP is HF/HNO3Mixing the solution, wherein the mass fraction of nitric acid is 68%, the mass fraction of hydrofluoric acid is 0.2%, the temperature is 20 ℃, and the time is 4 min;
s10, washing the silicon slice obtained in the step S9 with purified water, and adding O3Post-cleaning 2, O in a cleaning solution3The ozone concentration in the cleaning solution is 10ppm, and the time is 180 s;
s11, cleaning the silicon wafer obtained in the step S10 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
Comparative example 1
S1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is KOH solution with the concentration of 45 wt%, the volume fraction of the KOH solution is 1.6%, and the concentration of H is 30 wt%2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 20 wt% and the balance of water, the temperature is 70 ℃, and the treatment time is 30S;
s4, putting the silicon wafer obtained in the step S3 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, post-cleaning 1 the silicon wafer obtained in the step S5, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s7, washing the silicon wafer obtained in S6 in pure water, and then carrying out O3CP of said O3CP is O3/HF/HNO3Mixing the solution, wherein the mass fraction of nitric acid is 30%, the mass fraction of hydrofluoric acid is 0.8%, the concentration of ozone is 80ppm, the temperature is 20 ℃, and the time is 4 min;
s8, cleaning the silicon wafer obtained in the step S7 with purified water, and then cleaning with hydrofluoric acid for 120S; HF with a concentration of 49 wt% in a volume fraction of 10%, the balance being water.
Comparative example 1 differs from example 1 in that comparative example 1 was not subjected to surface oxidation before texturing, and in that no post-cleaning 2 was performed after texturing and before cleaning with hydrofluoric acid, i.e., no surface oxidation was performed before the hydrofluoric acid cleaning.
The silicon wafers prepared in example 1 and comparative example 1 were used to prepare batteries, and the performance of the batteries was measured, and the measurement results are shown in table 1. As can be seen from table 1, the cell efficiency of the present invention is improved, mainly from Isc and FF.
Table 1 test results of silicon wafer fabricated batteries obtained by post-treating example 1 and comparative example 1
| Conditions of the experiment | Number of | Eta | Voc | Isc | FF |
| Example 1 | 200 | 23.28 | 0.7371 | 9.4221 | 81.582 |
| Comparative example 1 | 200 | 23.23 | 0.737 | 9.4103 | 81.503 |
Comparative example 2
S1, pre-oxidizing the silicon wafer to be processedRemoving the pollutants on the surface of the silicon wafer by using a cleaning solution SC1 solution, wherein the volume fraction of KOH solution with the concentration of 45 wt% is 1.6%, and the volume fraction of H with the concentration of 30 wt% is2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 20 wt% and the balance of water, the temperature is 70 ℃, and the treatment time is 30S;
s4, placing the silicon chip obtained in the S3 into O3Cleaning in solution, O3The concentration is 120ppm, the treatment time is 180s, and the temperature is room temperature;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the step S5 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning 1 the silicon wafer obtained in the step S7, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s9, washing the silicon wafer obtained in S8 in pure water, and then carrying out O3CP of said O3CP is O3The ozone concentration is 80ppm, the mass fraction of hydrofluoric acid is 0.8%, the temperature is 20 ℃, and the time is 4 min;
s10, washing the silicon slice obtained in the step S9 with purified water, and adding O3Post-cleaning 2, O in a cleaning solution3The ozone concentration in the cleaning solution is 10ppm, and the time is 180 s;
s11, cleaning the silicon wafer obtained in the step S10 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
Comparative example 2 compares to example 1 with the difference that, in the case of CP, O is used in comparative example 23CP is O3HF mixture solution, O used in example 13CP is O3/HF/HNO3The solution was mixed.
The SEM photograph of comparative example 2 shows that the pyramid tops were rounded and the pyramid valleys were still relatively sharp, as shown in fig. 2. The SEM photograph of example 1 shows that the pyramids and valleys are rounded as shown in fig. 1.
An amorphous silicon thin film was deposited on the silicon wafer cleaned and dried in example 1 and comparative example 2 using a Plasma Enhanced Chemical Vapor Deposition (PECVD) apparatus, an amorphous silicon passivation layer having a thickness of 10nm was deposited on both front and back sides, and then the minority carrier lifetime and the implanted Voc (theoretical open circuit voltage) were measured on a Sinton WCT-120 tester, and the test results are shown in table 2. Under the same silicon wafer and test conditions, the higher the minority carrier lifetime and the amplified Voc, the lower the defect state density of the amorphous silicon film, and the better the passivation quality. The minority carrier lifetime and the amplified Voc of the embodiment 1 are both higher than those of the comparative example 2, which shows that the method can better modify the pyramid morphology of the solar cell textured silicon wafer, is beneficial to the deposition of an amorphous silicon film and improves the passivation quality.
TABLE 2 minority carrier lifetime and Impled Voc test
| Item | Minority carrier lifetime (mu s) | Implied Voc(V) |
| Example 1 | 6856 | 0.740 |
| Comparative example 2 | 1123 | 0.735 |
Comparative example 3
S1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is SC1 solution, the volume fraction of KOH solution with the concentration of 45 wt% is 1.6%, and the concentration of H is 30 wt%2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 20 wt% and the balance of water, the temperature is 70 ℃, and the treatment time is 30S;
s4, placing the silicon chip obtained in the S3 into O3Cleaning in solution, O3The concentration is 120ppm, the treatment time is 180s, and the temperature is room temperature;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the step S5 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning 1 the silicon wafer obtained in the step S7, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s9, washing the silicon wafer obtained in S8 in pure water, and then carrying out O3CP of said O3CP is O3/HF/HNO3Mixing the solution, wherein the mass fraction of nitric acid is 30%, the mass fraction of hydrofluoric acid is 0.8%, the concentration of ozone is 80ppm, the temperature is 20 ℃, and the time is 4 min;
s10, cleaning the silicon wafer obtained in the step S9 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S11, washing the silicon wafer obtained in the step S10 with purified water, and drying.
Comparative example 3 differs from example 1 in that comparative example 3 was subjected to hydrofluoric acid cleaning directly after CP without surface oxidation. The silicon wafers after texturing were post-treated in the methods of example 1 and comparative example 3 to obtain batteries, which were tested, and the test results are shown in table 3. As can be seen from Table 3, the Isc of the present invention is improved.
Table 3 test results of silicon wafer fabricated batteries obtained by post-treating example 1 and comparative example 3
| Conditions of the experiment | Number of | Eta | Voc | Isc | FF |
| Example 1 | 200 | 23.28 | 0.7371 | 9.4221 | 81.582 |
| Comparative example 3 | 200 | 23.25 | 0.737 | 9.4103 | 81.58 |
Comparative example 4
S1, pre-oxidizing the silicon wafer to be treated to remove the pollutants on the surface of the silicon wafer, wherein the cleaning solution is SC1 solution, the volume fraction of KOH solution with the concentration of 45 wt% is 1.6%, and the concentration of H is 30 wt%2O2The volume fraction of the aqueous solution is 10 percent, the balance is water, the temperature is 60 ℃, and the time is 5 min;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning, and washing off the residual cleaning liquid in the step S1 on the surface of the silicon wafer;
s3, putting the silicon wafer obtained in the step S2 into an SDE (sodium dodecyl sulfate) tank for damage removal treatment, wherein the solution in the SDE tank is a KOH solution with the concentration of 20 wt% and the balance of water, the temperature is 70 ℃, and the treatment time is 30S;
s4, putting the silicon wafer obtained in the step S3 into pure water for cleaning;
s5, putting the silicon wafer obtained in the step S4 into a TEX groove for texturing, wherein the mass fraction of KOH in texturing liquid is 7%, the mass fraction of a hydrophobic texturing additive MT-053 is 30%, the temperature is 80 ℃, and the time is 15 min;
s6, putting the silicon wafer obtained in the step S5 into pure water for cleaning;
s7, post-cleaning 1 the silicon wafer obtained in the step S6, wherein the cleaning liquid of the post-cleaning 1 is SC1 cleaning liquid, and the SC1 cleaning liquid is KOH and H2O2The mixed solution of (1), wherein the volume fraction of KOH having a concentration of 45 wt% is 1.6%, and the concentration of H having a concentration of 30 wt% is2O2The volume fraction of (1) is 10%, the rest is water, the temperature is 60 ℃, and the time is 5 min;
s8, washing the silicon wafer obtained in S7 in pure water, and then carrying out O3CP of said O3CP is O3/HF/HNO3Mixing the solution, wherein the mass fraction of nitric acid is 30%, the mass fraction of hydrofluoric acid is 0.8%, the concentration of ozone is 80ppm, the temperature is 20 ℃, and the time is 4 min;
s9, washing the silicon slice obtained in the step S8 with purified water, and adding O3Post-cleaning 2, O in a cleaning solution3The ozone concentration in the cleaning solution is 10ppm, and the time is 180 s;
s10, cleaning the silicon wafer obtained in the step S9 with purified water, and then cleaning with hydrofluoric acid solution for 120S, wherein the HF with the concentration of 49 wt% accounts for 10% by volume, and the balance is water;
and S11, washing the silicon wafer obtained in the step S10 with purified water, and drying.
Comparative example 4 differs from example 1 in that comparative example 4 does not oxidize the wafer surface prior to texturing. The silicon wafers after texturing were post-treated in the methods of example 1 and comparative example 4 to prepare batteries, which were tested, and the test results are shown in table 4.
Table 4 test results of silicon wafer fabricated batteries obtained by post-treating example 1 and comparative example 4
| Conditions of the experiment | Number of | Eta | Voc | Isc | FF |
| Example 1 | 200 | 23.28 | 0.7371 | 9.4221 | 81.582 |
| Comparative example 4 | 200 | 23.24 | 0.7361 | 9.4178 | 81.52 |
Compared with the comparative example 1, the battery efficiency of the embodiment 1 of the invention is improved, mainly from Isc and FF; example 1 cell efficiency was improved compared to comparative example 3, mainly from Isc; example 1 shows an improvement in cell efficiency, mainly due to FF, over comparative example 4. The difference between the comparative example 3 and the comparative example 1 is that the surface of the silicon wafer is oxidized before texturing in the comparative example 3, so that the surface of the silicon wafer is hydrophilic, and compared with the comparative example 1, the cell efficiency of the comparative example 3 is improved by 0.02%; the difference between the comparative example 4 and the comparative example 1 is that the comparative example 4 oxidizes the surface of the silicon wafer before hydrofluoric acid cleaning after texturing, and compared with the comparative example 1, the battery efficiency of the comparative example 4 is improved by 0.01%; example 1 is different from comparative example 1 in that comparative example 1 is not subjected to surface oxidation before texturing and is not subjected to surface oxidation before cleaning with hydrofluoric acid after texturing, and the cell efficiency of example 1 is improved by 0.05% compared to comparative example 1. Comparing comparative example 1, comparative example 3 and comparative example 4 together, it was found that the improvement of the battery efficiency is small when only the oxidation of the front surface before the texturing or the oxidation of the front surface before the hydrofluoric acid cleaning after the texturing is performed, whereas the improvement of the battery efficiency is large when the oxidation of the front surface before the texturing and the oxidation of the front surface before the hydrofluoric acid cleaning after the texturing are simultaneously performed in example 1 of the present invention.
Claims (7)
1. A silicon wafer texturing method is characterized by comprising the following steps:
s1, carrying out pre-oxidation treatment on the silicon wafer to be treated to remove pollutants on the surface of the silicon wafer;
s2, putting the silicon wafer obtained in the step S1 into pure water for cleaning;
s3, placing the silicon wafer obtained in the S2 into an SDE groove for SDE treatment;
s4, carrying out surface oxidation treatment on the silicon wafer obtained in the S3;
s5, putting the silicon wafer obtained in the step S4 into pure water for cleaning;
s6, putting the silicon wafer obtained in the S5 into a TEX groove for texturing;
s7, putting the silicon wafer obtained in the step S6 into pure water for cleaning;
s8, post-cleaning the silicon wafer obtained in the S7 for 1;
s9, putting the silicon wafer obtained in the S8 into pure water, cleaning, and then carrying out CP;
s10, washing the silicon slice obtained in the step S9 with purified water, and then washing 2, wherein the washing 2 is SC2 washing liquid or O3Cleaning fluid;
s11, cleaning the silicon wafer obtained in the step S10 with purified water, and then cleaning with hydrofluoric acid solution;
and S12, washing the silicon wafer obtained in the step S11 with purified water, and drying.
2. The method of claim 1, wherein the treating solution used in S1, S4, S8 is O3Solution or SC1 solution.
3. The silicon wafer texturing method according to claim 1, wherein in S3, in the SDE treatment, alkali liquor is used for removing damage, the mass concentration of the alkali is 1-20%, the treatment temperature is 40-90 ℃, and the treatment time is 10-240S.
4. The silicon wafer texturing method of claim 2, wherein O is3The solution also comprises HCl and HNO3One or more of.
5. According to the claimsThe silicon wafer texturing method according to claim 2, wherein the SC1 solution is H2O2Mixed solution of solution and alkali, wherein the alkali can be NaOH, KOH, NH4One or more of OH.
6. The silicon wafer texturing method of claim 1, wherein in S9, CP is O3CP or HF/HNO3CP; said O is3CP is O3Mixed solution of/HF, or O3Adding HCl and HNO into/HF mixed solution3One or two of them; the HF/HNO3CP is HF/HNO3Mixed solution, or HF/HNO3One or two mixed solutions of HCl and acetic acid are added into the solution.
7. The method of claim 1, wherein the hydrofluoric acid solution in S11 is HF solution or HF/HCl mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010334598.3A CN111403561A (en) | 2020-04-24 | 2020-04-24 | Silicon wafer texturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010334598.3A CN111403561A (en) | 2020-04-24 | 2020-04-24 | Silicon wafer texturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111403561A true CN111403561A (en) | 2020-07-10 |
Family
ID=71437156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010334598.3A Pending CN111403561A (en) | 2020-04-24 | 2020-04-24 | Silicon wafer texturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111403561A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900232A (en) * | 2020-08-03 | 2020-11-06 | 中威新能源(成都)有限公司 | Bad reworking method in production of SHJ battery |
| CN113066903A (en) * | 2021-03-26 | 2021-07-02 | 常州时创能源股份有限公司 | Silicon wafer texturing process |
| CN114392966A (en) * | 2021-12-29 | 2022-04-26 | 江苏时代华宜电子科技有限公司 | Automatic cleaning equipment and cleaning method for molybdenum alloy substrate |
| CN115207154A (en) * | 2021-04-12 | 2022-10-18 | 福建金石能源有限公司 | Heterojunction solar cell texturing and cleaning method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938431A (en) * | 2012-10-19 | 2013-02-20 | 上海中智光纤通讯有限公司 | Silicon wafer cleaning flocking method of solar battery |
| CN110416369A (en) * | 2019-08-21 | 2019-11-05 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | PERC battery cleaning and texturing technique and system |
| CN110459647A (en) * | 2019-08-09 | 2019-11-15 | 江苏日托光伏科技股份有限公司 | A kind of method and apparatus improving large-sized silicon wafers making herbs into wool uniformity |
| CN110828299A (en) * | 2019-11-20 | 2020-02-21 | 常州捷佳创精密机械有限公司 | Texturing cleaning method and heterojunction battery |
| CN110943144A (en) * | 2019-11-29 | 2020-03-31 | 晋能清洁能源科技股份公司 | Texturing and cleaning method for heterojunction battery |
| CN210325830U (en) * | 2019-08-22 | 2020-04-14 | 环晟光伏(江苏)有限公司 | Large-size laminated tile battery texturing equipment |
-
2020
- 2020-04-24 CN CN202010334598.3A patent/CN111403561A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938431A (en) * | 2012-10-19 | 2013-02-20 | 上海中智光纤通讯有限公司 | Silicon wafer cleaning flocking method of solar battery |
| CN110459647A (en) * | 2019-08-09 | 2019-11-15 | 江苏日托光伏科技股份有限公司 | A kind of method and apparatus improving large-sized silicon wafers making herbs into wool uniformity |
| CN110416369A (en) * | 2019-08-21 | 2019-11-05 | 青海黄河上游水电开发有限责任公司光伏产业技术分公司 | PERC battery cleaning and texturing technique and system |
| CN210325830U (en) * | 2019-08-22 | 2020-04-14 | 环晟光伏(江苏)有限公司 | Large-size laminated tile battery texturing equipment |
| CN110828299A (en) * | 2019-11-20 | 2020-02-21 | 常州捷佳创精密机械有限公司 | Texturing cleaning method and heterojunction battery |
| CN110943144A (en) * | 2019-11-29 | 2020-03-31 | 晋能清洁能源科技股份公司 | Texturing and cleaning method for heterojunction battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900232A (en) * | 2020-08-03 | 2020-11-06 | 中威新能源(成都)有限公司 | Bad reworking method in production of SHJ battery |
| CN113066903A (en) * | 2021-03-26 | 2021-07-02 | 常州时创能源股份有限公司 | Silicon wafer texturing process |
| CN115207154A (en) * | 2021-04-12 | 2022-10-18 | 福建金石能源有限公司 | Heterojunction solar cell texturing and cleaning method |
| CN114392966A (en) * | 2021-12-29 | 2022-04-26 | 江苏时代华宜电子科技有限公司 | Automatic cleaning equipment and cleaning method for molybdenum alloy substrate |
| CN114392966B (en) * | 2021-12-29 | 2024-04-19 | 江苏时代华宜电子科技有限公司 | Automatic cleaning equipment and cleaning method for molybdenum alloy substrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111403561A (en) | Silicon wafer texturing method | |
| CN104393118B (en) | The crystal silicon solar batteries Wet chemical processing method that making herbs into wool is carried out with cleaning substep | |
| WO2021213168A1 (en) | Monocrystalline silicon wafer having rounded pyramid structure and preparation method | |
| CN112542531B (en) | Silicon wafer pretreatment and heterojunction battery preparation method | |
| CN108231540A (en) | A kind of rear cleaning applied to solar cell making herbs into wool | |
| CN110165015B (en) | Solar monocrystalline cell texturing process | |
| CN103441182B (en) | The matte processing method of solar cell and solar cell | |
| CN111508824B (en) | Wool making cleaning method and heterojunction battery | |
| CN111900232B (en) | Bad reworking method in production of SHJ battery | |
| CN109037112B (en) | Method for etching crystalline silicon solar SE battery by using inorganic alkali | |
| CN110943144A (en) | Texturing and cleaning method for heterojunction battery | |
| CN103606595B (en) | The recycling of the rear defective Monocrystalline silicon cell piece of sintering and grid line recovery method thereof | |
| CN113823709A (en) | Texturing and cleaning method for solar cell | |
| CN110993724A (en) | Texturing and cleaning method for heterojunction solar cell | |
| CN110165018A (en) | A kind of polycrystalline cleaning process of decline electric leakage raising efficiency | |
| CN114628547B (en) | Solar cell with back surface local morphology and preparation method thereof | |
| CN109148262B (en) | Cleaning method of solar polycrystalline black silicon wafer | |
| CN216488101U (en) | Chain type alkali polishing system | |
| CN214384756U (en) | Texturing apparatus | |
| CN114335247A (en) | Double-texturing cleaning process and device for heterojunction battery | |
| CN109887841B (en) | PERC battery back polishing process | |
| CN113990981A (en) | Single crystal suede smooth and round treatment process | |
| CN113539813A (en) | Monocrystalline silicon piece back polishing method and silicon piece | |
| CN113437176A (en) | Preparation method of heterojunction battery | |
| CN111554774A (en) | Silicon wafer texturing post-treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200710 |