CN110943144A - A kind of texturing cleaning method of heterojunction battery - Google Patents
A kind of texturing cleaning method of heterojunction battery Download PDFInfo
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- CN110943144A CN110943144A CN201911204253.XA CN201911204253A CN110943144A CN 110943144 A CN110943144 A CN 110943144A CN 201911204253 A CN201911204253 A CN 201911204253A CN 110943144 A CN110943144 A CN 110943144A
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- 238000004140 cleaning Methods 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 62
- 239000010703 silicon Substances 0.000 claims abstract description 62
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 2
- 235000021110 pickles Nutrition 0.000 claims 4
- 238000005554 pickling Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 2
- 238000012864 cross contamination Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002184 metal Substances 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/121—The active layers comprising only Group IV materials
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- 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
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
-
- 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
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
本发明公开了一种异质结电池的制绒清洗方法，该方法包括：采用SC1对原硅片预清洗；对硅片粗抛去损处理；臭氧体系溶液清洗；对硅片进行制绒；采用SC1或臭氧体系溶液清洗；对硅片腐蚀，进行光滑圆整处理；采用SC2或臭氧体系溶液清洗；烘干；并在SC1或臭氧体系溶液清洗、光滑圆整处理、SC2或臭氧体系溶液清洗、烘干流程前均增加HF酸洗流程。通过本发明的清洗方法，保证了硅片表面完全洁净，获得较优表面形貌，极大程度得提高了HJT电池的性能。The invention discloses a texturing and cleaning method for a heterojunction battery, which comprises the following steps: pre-cleaning the original silicon wafer by using SC1; rough throwing and removing damage to the silicon wafer; cleaning with an ozone system solution; and texturing the silicon wafer; Use SC1 or ozone system solution for cleaning; corrode the silicon wafer, carry out smooth rounding treatment; use SC2 or ozone system solution for cleaning; dry; and clean in SC1 or ozone system solution, smooth rounding treatment, SC2 or ozone system solution cleaning , The HF pickling process is added before the drying process. The cleaning method of the present invention ensures that the surface of the silicon wafer is completely clean, obtains a better surface morphology, and greatly improves the performance of the HJT battery.
Description
Technical Field
The invention relates to the field of heterojunction batteries, in particular to a texturing and cleaning method of a heterojunction battery.
Background
The development of solar photovoltaic power generation has profound strategic significance, the efficiency improvement and cost reduction are one of the key points of current research, the efficiency of the conventional structure battery has no great promotion space, and the high-efficiency crystalline silicon battery gradually becomes the mainstream of market research and development. The HJT battery is a high-efficiency crystalline silicon solar battery which adopts an amorphous silicon/crystalline silicon heterojunction structure and realizes low cost. The battery structure has the advantages of few process steps, low process temperature, no LID and PID effects, low temperature coefficient, high efficiency and the like.
The HJT battery takes n-type silicon with long service life as a substrate, and an intrinsic amorphous silicon film and a p-type amorphous silicon film are sequentially deposited on the front surface of a silicon wafer which is subjected to texturing cleaning, so that a p-n heterojunction is formed; depositing an intrinsic amorphous silicon film and an n-type amorphous silicon film on the back of the silicon wafer in sequence to form a back surface field; and depositing transparent conductive oxide films on two sides of the doped amorphous silicon film, and finally forming metal electrodes on two sides by a screen printing technology to form the HJT solar cell with a symmetrical structure.
The heterojunction cell is different from a conventional homojunction, the requirement on an interface is higher, the cleanliness of the surface of a silicon wafer is one of important factors influencing the quality of the interface of an intrinsic amorphous silicon film layer and an n-type silicon substrate, and therefore the surface of the silicon wafer needs to be sufficiently clean after texturing and cleaning. At present, the conventional texturing and cleaning process for preparing the heterojunction cell in the industry can meet the normal cleaning requirement of the heterojunction. However, conventional cleaning processes have not been satisfactory for the purpose of producing cells with higher surface cleanliness and higher conversion efficiency.
Therefore, in combination with the above problems, there is a need for providing a method for cleaning a heterojunction battery by etching, which is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a texturing cleaning method for a heterojunction battery, and the cleaning method provided by the invention ensures that the surface of a silicon wafer is completely clean, obtains a better surface appearance, greatly improves the performance of the HJT battery, can avoid cross contamination among main process reaction liquid medicines, and prolongs the service life of the liquid medicines.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a texturing and cleaning method for a heterojunction battery comprises the following steps:
s1, pre-cleaning the original silicon wafer by adopting SC 1;
s2, roughly polishing the silicon wafer, and removing a damage layer of the silicon wafer;
s3, cleaning the silicon wafer by adopting an ozone system solution;
s4, texturing the silicon wafer;
s5, performing first acid washing on the silicon wafer by adopting an HF solution;
s6, cleaning the silicon wafer by using SC1 or ozone system solution;
s7, performing secondary acid washing on the silicon wafer by adopting an HF solution;
s8, corroding the silicon wafer by adopting an HF + HNO3 solution or an HCl + HF ozone system solution, and performing smooth rounding treatment;
s9, carrying out acid washing on the silicon wafer for the third time by adopting an HF solution;
s10, cleaning the silicon wafer by using SC2 or ozone system solution;
s11, performing fourth acid washing on the silicon wafer by adopting an HF solution;
s12, drying;
wherein, the ozone system solution is a mixed solution of HCl and ozone.
Preferably, in the step S1, SC1 is a mixed solution of ammonia water and hydrogen peroxide, the volume ratio of NH4OH to H2O2 to H2O is 1:1:3-10, the pre-cleaning temperature is 65-85 ℃, and the time is 120-.
By adopting the preferable scheme, the invention has the beneficial effects that: the SC1 is adopted to pre-clean the original silicon wafer, and residues such as cutting fluid, oil stain, grease and the like in the cutting process of the original silicon wafer can be mainly removed.
Preferably, in the step S2, the damaged layer of the silicon wafer is removed by using an alkaline solution, wherein the mass concentration of the alkaline solution is 5-15%, the temperature is 60-80 ℃, and the time is 60-240S.
Preferably, the concentration of ozone in the step S3 is 10-20ppm, the HCl content is 0.05-0.1 wt%, and the cleaning time is 120-.
By adopting the preferable scheme, the invention has the beneficial effects that: neutralizing the residual alkali liquor after rough polishing, strengthening the function of pre-cleaning the silicon wafer, and compatibly meeting the requirements of texturing additives.
Preferably, in the step S4, the silicon wafer is immersed in a mixed solution of an alkaline solution and an alcohol-free texturing additive at a temperature of 70-90 ℃ for a time of 420-900S.
Preferably, the alkaline solution in step S4 is a KOH solution, and the mass concentration of KOH is 5%.
Preferably, the volume concentration of the alcohol-free texturing additive in the step S4 is 1%.
Preferably, in the step S6, SC1 is a mixed solution of ammonia water and hydrogen peroxide, the volume ratio of NH4OH to H2O2 to H2O is 1:1:3-10, the ozone concentration is 10-20ppm, the cleaning temperature is 65-85 ℃, and the cleaning time is 120-.
Preferably, in the step S8, the silicon wafer is immersed into a solution of HF and HNO3 with the volume ratio of 1:80-90 for corrosion at the temperature of 5-25 ℃ for 60-180S; the ozone concentration is 20-30ppm, and the time is 60-240 s.
Preferably, in the step S10, SC2 is a mixed solution of hydrochloric acid and hydrogen peroxide, the volume ratio of HCl to H2O2 to H2O is 1:1:3-10, the ozone concentration is 10-20ppm, the cleaning temperature is 65-85 ℃, and the cleaning time is 120-600S.
Preferably, the mass concentration of the HF solution used in the steps S5, S7 and S9 is 3-10%, and the cleaning time is 120-240S.
Preferably, the mass concentration of the HF solution used in the step S11 is 5-15%, and the cleaning time is 120-240S.
Preferably, the drying time in the step S12 is 180-600S, and the temperature is 40-60 ℃.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the invention adopts the ozone system solution to clean the silicon wafer, and can meet the requirement of thoroughly cleaning the surface of the original silicon wafer under the condition of poor surface quality of the silicon wafer source; in addition, some additives need to nucleate and produce wool on the surface of the oxide layer at present, and the ozone system solution cleaning step added in the invention can simultaneously meet the requirements of cleaning and wool production.
An HF acid washing flow is added before the processes of cleaning with an SC 1/ozone system solution, smooth and round treatment, cleaning with an SC 2/ozone system solution and drying. By the cleaning method, the surface of the silicon wafer is completely clean, a better surface appearance is obtained, cross contamination among SC1 cleaning, smoothing and SC2 cleaning liquid medicine is avoided, and the service life of the liquid medicine is prolonged.
The cleaning method can improve the performance of the HJT battery to a great extent, the advantages are mainly reflected in Voc and FF, and the final efficiency can be improved by 0.2%.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment 1 of the invention discloses a texturing and cleaning method for a heterojunction battery, which adopts the following technical scheme:
a texturing and cleaning method for a heterojunction battery comprises the following steps:
the original silicon wafer is pre-cleaned by SC1, and the volume ratio of SC1 is NH4OH: H2O2: H2O is 1:1:5, the temperature is 80 ℃, and the time is 240 s;
adopting KOH solution to carry out rough polishing, wherein the mass concentration is 10 percent, the temperature is 80 ℃, and the time is 120 s;
cleaning with HCl ozone system solution with ozone concentration of 20ppm for 120 s;
immersing a silicon wafer into KOH with the mass concentration of 5 percent and alcohol-free texturing additive with the volume concentration of 1 percent for corrosion texturing, wherein the temperature is 80 ℃, and the time is 720 seconds;
pickling with HF solution, wherein the mass concentration of HF is 5%, and the time is 120 s;
cleaning with SC1, wherein the volume ratio of SC1 is NH4OH: H2O2: H2O is 1:1:5, the temperature is 80 ℃, and the time is 240 s;
pickling with HF solution, wherein the mass concentration of HF is 5%, and the time is 120 s;
adopting an HF + HNO3 solution to perform smooth and round treatment on the silicon wafer, and immersing the silicon wafer into the solution with the volume ratio of HF: corroding in a mixed solution with the HNO3 ratio of 1:90, and performing smooth rounding treatment at the temperature of 21 ℃ for 100 s;
pickling with HF solution, wherein the mass concentration of HF is 5%, and the time is 120 s;
cleaning with SC2, wherein the volume ratio of HCl to H2O2 to H2O of SC2 is as follows: 1:1:5, temperature 65 ℃, time 240 s;
pickling with HF solution, wherein the mass concentration of HF is 10%, and the time is 120 s;
drying the silicon chip for 450s at 50 ℃.
Example 2:
the embodiment 2 of the invention discloses a texturing and cleaning method for a heterojunction battery, which adopts the following technical scheme:
a texturing and cleaning method for a heterojunction battery comprises the following steps:
the original silicon wafer is pre-cleaned by SC1, and the volume ratio of SC1 is NH4OH: H2O2: H2O is 1:1:3, the temperature is 85 ℃, and the time is 120 s;
adopting KOH solution to carry out rough polishing, wherein the mass concentration is 10 percent, the temperature is 80 ℃, and the time is 120 s;
cleaning with HCl ozone system solution with ozone concentration of 15ppm for 480 s;
immersing a silicon wafer into KOH with the mass concentration of 5 percent and alcohol-free texturing additive with the volume concentration of 1 percent for corrosion texturing, wherein the temperature is 70 ℃, and the time is 900 s;
pickling with HF solution, wherein the mass concentration of HF is 3%, and the time is 240 s;
cleaning with SC1, wherein the volume ratio of SC1 is NH4OH: H2O2: H2O is 1:1:3, the temperature is 85 ℃, and the time is 120 s;
pickling with HF solution, wherein the mass concentration of HF is 3%, and the time is 240 s;
adopting an HF + HNO3 solution to perform smooth and round treatment on the silicon wafer, and immersing the silicon wafer into the solution with the volume ratio of HF: corroding in a mixed solution with the HNO3 ratio of 1:80, and performing smooth and round treatment at the temperature of 5 ℃ for 180 s;
pickling with HF solution, wherein the mass concentration of HF is 3%, and the time is 240 s;
cleaning with SC2, wherein the SC2 has the following composition in volume ratio of HCl to H2O2 to H2O: 1:1:3, the temperature is 85 ℃, and the time is 120 s;
pickling with an HF solution, wherein the mass concentration of HF is 5%, and the time is 240 s;
drying the silicon chip for 600s at 40 ℃.
Example 3:
a texturing and cleaning method for a heterojunction battery comprises the following steps:
the original silicon wafer is pre-cleaned by SC1, and the volume ratio of SC1 is NH4OH: H2O2: H2O is 1:1: 10, the temperature is 65 ℃, and the time is 600 s;
adopting KOH solution to carry out rough polishing, wherein the mass concentration is 10 percent, the temperature is 80 ℃, and the time is 120 s;
cleaning with HCl ozone system solution with ozone concentration of 10ppm for 260 s;
immersing a silicon wafer into KOH with the mass concentration of 5 percent and the volume concentration of alcohol-free texturing additive of 1 percent for corrosion texturing, wherein the temperature is 90 ℃ and the time is 420 s;
pickling with HF solution, wherein the mass concentration of HF is 10%, and the time is 180 s;
cleaning with ozone system solution, wherein the concentration of ozone is 15ppm, the cleaning temperature is 65 ℃, and the cleaning time is 600 s;
pickling with HF solution, wherein the mass concentration of HF is 10%, and the time is 180 s;
corroding the silicon wafer by adopting HCl + HF ozone system solution, and performing smooth rounding treatment, wherein the ozone concentration is 20-30ppma, and the time is 60-240 s;
pickling with HF solution, wherein the mass concentration of HF is 10%, and the time is 180 s;
cleaning with ozone system solution, wherein the concentration of ozone is 15ppm, the cleaning temperature is 65 ℃, and the cleaning time is 600 s;
pickling with HF solution, wherein the mass concentration of HF is 15%, and the time is 180 s;
drying the silicon wafer for 180s at 60 ℃.
Comparative analysis of the electrical properties by means of 3 examples, the results are as follows: example 2 is essentially the same as example 3; example 1 has 0.21% higher efficiency than examples 2 and 3, mainly the Uoc and FF gains.
The efficiency of the battery plate prepared by the technical scheme of the embodiment is 0.21% higher than that of the conventional heterojunction cleaning process.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
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| CN111403561A (en) * | 2020-04-24 | 2020-07-10 | 中威新能源(成都)有限公司 | Silicon wafer texturing method |
| CN111554758A (en) * | 2020-04-24 | 2020-08-18 | 中威新能源(成都)有限公司 | System and method for texturing pretreatment suitable for different texturing additives |
| CN112768555A (en) * | 2020-12-31 | 2021-05-07 | 中建材浚鑫(桐城)科技有限公司 | Method for manufacturing solar cell suede |
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| CN111403561A (en) * | 2020-04-24 | 2020-07-10 | 中威新能源(成都)有限公司 | Silicon wafer texturing method |
| CN111554758A (en) * | 2020-04-24 | 2020-08-18 | 中威新能源(成都)有限公司 | System and method for texturing pretreatment suitable for different texturing additives |
| WO2021213168A1 (en) * | 2020-04-24 | 2021-10-28 | 中威新能源(成都)有限公司 | Monocrystalline silicon wafer having rounded pyramid structure and preparation method |
| CN112768555A (en) * | 2020-12-31 | 2021-05-07 | 中建材浚鑫(桐城)科技有限公司 | Method for manufacturing solar cell suede |
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