CN110943144A - Texturing and cleaning method for heterojunction battery - Google Patents

Texturing and cleaning method for heterojunction battery Download PDF

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Publication number
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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cleaning
silicon wafer
solution
time
ozone
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CN201911204253.XA
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Chinese (zh)
Inventor
张娟
王继磊
白焱辉
黄金
白星亮
冯乐
贾慧君
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Jinneng Clean Energy Technology Ltd
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Jinneng Clean Energy Technology Ltd
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Priority to CN201911204253.XA priority Critical patent/CN110943144A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment 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
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604Chemical etching
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a texturing and cleaning method of a heterojunction battery, which comprises the following steps: pre-cleaning a raw silicon wafer by using SC 1; roughly polishing and removing damage of the silicon wafer; cleaning with an ozone system solution; texturing a silicon wafer; cleaning with SC1 or ozone system solution; corroding the silicon wafer, and performing smooth rounding treatment; cleaning with SC2 or ozone system solution; drying; and an HF acid washing process is added before the processes of cleaning with an SC1 or ozone system solution, smoothing and rounding, cleaning with an SC2 or ozone system solution and drying. The cleaning method ensures that the surface of the silicon wafer is completely clean, obtains better surface appearance and greatly improves the performance of the HJT battery.

Description

Texturing and cleaning method for heterojunction battery
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)

1. A texturing and cleaning method for a heterojunction battery is characterized by comprising 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.
2. The method as claimed in claim 1, wherein in step S1, SC1 is a mixture of ammonia water and hydrogen peroxide, the volume ratio of NH4OH: H2O2: H2O is 1:1:3-10, the pre-cleaning temperature is 65-85 ℃, and the time is 120-.
3. The method as claimed in claim 1, wherein the ozone concentration in step S3 is 10-20ppm, the HCl is 0.05-0.1 wt%, and the cleaning time is 120-480S.
4. The method of claim 1, wherein the silicon wafer is immersed in the mixed solution of the alkaline solution and the alcohol-free texturing additive at 70-90 ℃ for 420-900S in step S4.
5. The method as claimed in claim 1, wherein in step S6, SC1 is a mixture 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-.
6. The method of claim 1, wherein in step S8, the silicon wafer is immersed in a solution of HF and HNO3 at a volume ratio of 1:80-90 for etching at 5-25 ℃ for 60-180S; the ozone concentration is 20-30ppm, and the time is 60-240 s.
7. The method as claimed in claim 1, wherein in step S10, SC2 is a mixture of hydrochloric acid and hydrogen peroxide, the volume ratio of HCl to H2O2 to H2O is 1:1:3-10, the concentration of ozone is 10-20ppm, the cleaning temperature is 65-85 ℃, and the cleaning time is 120-.
8. The method as claimed in claim 1, wherein the HF solution used in steps S5, S7 and S9 has a mass concentration of 3-10% and a cleaning time of 120-.
9. The method as claimed in claim 1, wherein the HF solution used in step S11 has a mass concentration of 5-15% and a cleaning time of 120-.
10. The method as claimed in claim 1, wherein the drying time in step S12 is 180-600S, and the temperature is 40-60 ℃.
CN201911204253.XA 2019-11-29 2019-11-29 Texturing and cleaning method for heterojunction battery Pending CN110943144A (en)

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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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