CN111151489A - Method for cleaning silicon wafer in spraying mode through ozone - Google Patents
Method for cleaning silicon wafer in spraying mode through ozone Download PDFInfo
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- CN111151489A CN111151489A CN201911418609.XA CN201911418609A CN111151489A CN 111151489 A CN111151489 A CN 111151489A CN 201911418609 A CN201911418609 A CN 201911418609A CN 111151489 A CN111151489 A CN 111151489A
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- 238000004140 cleaning Methods 0.000 title claims abstract description 161
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000010703 silicon Substances 0.000 title claims abstract description 120
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 120
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000005507 spraying Methods 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007921 spray Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 35
- 238000005406 washing Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012670 alkaline solution Substances 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000013256 coordination polymer Substances 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 91
- 239000007789 gas Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000005498 polishing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/02—Cleaning by the force of jets or sprays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B13/00—Accessories or details of general applicability for machines or apparatus for cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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 Table
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B2203/00—Details of cleaning machines or methods involving the use or presence of liquid or steam
- B08B2203/02—Details of machines or methods for cleaning by the force of jets or sprays
- B08B2203/0217—Use of a detergent in high pressure cleaners; arrangements for supplying the same
-
- 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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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a method for cleaning a silicon wafer in a spraying manner by ozone, which comprises the following steps: pouring the prepared cleaning solution into a cleaning tank of a silicon wafer cleaning device for later use; then, placing the silicon wafer to be cleaned in a silicon wafer basket in a cleaning tank and then covering a tank cover; then introducing ozone gas into the cleaning tank; then, the cleaning solution in the cleaning tank flows back to the cleaning tank in a spraying mode through a liquid circulating device to clean the silicon wafer; and finally, putting the silicon wafer which is cleaned by the ozone in the previous step into pure water for washing. According to the invention, alkaline liquid is sprayed on the surface of the silicon wafer in the cleaning tank filled with ozone gas, so that the problems that the decomposition speed of ozone and free radicals in the alkaline solution is high, the ozone and the free radicals cannot reach the surface of the silicon wafer and react with organic contamination are solved, and the hydrofluoric acid solution is sprayed in the cleaning tank, so that the ozone on the surface of the silicon wafer reaches high concentration, the corrosion rate of ozone CP is increased, the process time is shortened, and the productivity is improved.
Description
Technical Field
The invention relates to the technical field of semiconductor manufacturing, in particular to a method for cleaning a silicon wafer in a spraying mode by ozone.
Background
The silicon wafer is a carrier of the solar cell, and in the manufacturing process of the solar cell, the silicon wafer is used as a core component of the solar cell, and various performance parameters of the silicon wafer directly influence the photoelectric conversion efficiency of the solar cell, such as rapid increase of reverse current in the performance of a device, failure of the device and the like, so that the cleaning of the silicon wafer is important. The silicon wafer is cleaned to achieve a good cleaning effect, and the method has important significance for improving the photoelectric conversion efficiency of a solar cell finished product.
During the process of cutting silicon wafers, impurities possibly contaminated on the surfaces of the silicon wafers can be roughly classified into three types: (1) organic substances such as grease, rosin, wax, epoxy resin, polyethylene glycol and the like; (2) metals, metal ions and some inorganic compounds; (3) dust and other particles, and the like. In the prior art, a chemical cleaning method is usually adopted for cleaning a silicon wafer, and the traditional RCA method for cleaning the silicon wafer involves the use and discharge of chemicals such as ammonia water, hydrogen peroxide, potassium hydroxide and the like, thereby causing great pollution to the environment; the ozone cleaning method is widely applied to the field of silicon wafer cleaning, and can replace the traditional RCA cleaning by ozone cleaning in the silicon wafer cleaning process in the solar cell manufacturing.
Nitric acid is needed in a CP (chemical polishing) process after texturing, and the use and discharge of chemicals such as ammonia water, hydrogen peroxide, nitric acid and the like can be avoided by using an ozone cleaning process, so that the production cost is greatly reduced, and the cleaning method is green and environment-friendly. The common ozone cleaning mode is to introduce ozone into an aqueous solution containing hydrochloric acid or hydrofluoric acid, the concentration of the ozone dissolved in the water is generally 10-100ppm, and the silicon wafer is cleaned in the solution containing the ozone, so that the aim of cleaning the silicon wafer or chemically polishing the silicon wafer is fulfilled. Compared with the RCA cleaning process, the acidic ozone cleaning solution has weaker oxidizing capability and low capability of removing stains on the silicon wafer; compared with the nitric acid CP process, the ozone CP process has the advantages of low corrosion rate and long process time.
Disclosure of Invention
The invention aims to overcome the problems of insufficient cleaning capability of ozone cleaning, slow corrosion rate of an ozone CP process and long process time in the prior art, and provides a method for cleaning a silicon wafer in a spraying mode by using ozone.
The purpose of the invention is realized by the following technical scheme:
a method for cleaning a silicon wafer in a spraying mode and containing ozone is completed by using a cleaning device, and the method comprises a cleaning tank and a liquid circulating device, wherein a liquid inlet and a liquid outlet are formed in the cleaning tank, the liquid inlet and the liquid outlet are respectively connected with the liquid circulating device, the device for cleaning the silicon wafer further comprises an ozone generator, the air outlet end of the ozone generator is connected with the cleaning tank through an air inlet pipe, the liquid circulating device comprises a plurality of spray heads, and the spray heads are uniformly distributed on the inner wall of the cleaning tank;
the method specifically comprises the following steps:
s1: pouring the prepared cleaning solution into a cleaning tank of a silicon wafer cleaning device for later use;
s2: placing a silicon wafer to be cleaned in a cleaning tank;
s3: introducing ozone gas into the cleaning tank through an ozone generator;
s4: enabling the cleaning solution in the cleaning tank to flow back to the cleaning tank in a spraying mode through a liquid circulating device to clean the silicon wafer for 1-15 min;
s5: the silicon wafer after completion of the ozone cleaning in S4 was put into pure water and cleaned to remove the residual cleaning liquid.
Preferably, the cleaning solution is an alkali solution, and the alkali solution is prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the cleaning solution is an acid solution, and the acid solution is a hydrofluoric acid solution.
Preferably, the pH value of the alkali liquor is more than or equal to 8, and the pH value of the acid liquor is less than or equal to 6.
Preferably, the temperature of the cleaning solution is 5-95 ℃.
Preferably, the concentration of the ozone is more than or equal to 0.1 percent.
Preferably, a porous flow equalizing plate is arranged in the cleaning tank, the porous flow equalizing plate is parallel to the bottom plate of the cleaning tank, an air inlet pipe of the ozone generator penetrates from the outer wall of the cleaning tank to the inner wall of the cleaning tank, the air inlet pipe is located below the porous flow equalizing plate, ozone generated in the ozone generator is introduced below the porous flow equalizing plate, and then the ozone is uniformly dispersed in the cleaning tank through the flow equalizing plate.
Preferably, the liquid circulation device still includes circulating pump and line heater, the liquid outlet with the input of circulating pump is connected, line heater one end with be connected with the output of circulating pump, the line heater other end passes through the inlet is with a plurality of the shower nozzle is connected. Wherein liquid passes through circulating pump to line formula heater from the liquid outlet and carries out the fountain to the silicon chip in the washing tank after heating liquid again, has better cleaning performance.
Preferably, the cleaning device also comprises a silicon wafer basket, the silicon wafer basket is positioned in the cleaning tank, and the silicon wafers to be cleaned are placed through the silicon wafer basket, so that the cleaning efficiency of the silicon wafers is improved, and the cleaning effect is prevented from being influenced by direct contact with the porous flow equalizing plate or the cleaning tank; still include the capping, the capping covers the outer tank top, the capping with the contact site of washing tank is provided with the sealing strip, through setting up the capping, can prevent on the one hand that the dust in the air from getting into the washing tank in, influences the cleaning performance, and on the other hand can prevent that ozone gas from causing ozone generator's extra consumption to the outer loss of washing tank.
The invention has the beneficial effects that: the invention sprays alkaline liquid on the surface of the silicon wafer in the cleaning tank filled with ozone gas, so that a large amount of gas, liquid and solid three-phase reaction interfaces are generated on the surface of the silicon wafer, the problem that the ozone and free radicals are decomposed in the alkaline solution too fast to reach the surface of the silicon wafer to react with organic contamination is solved, and the ozone on the surface of the silicon wafer can reach high concentration by spraying hydrofluoric acid solution in the cleaning tank, so that the corrosion rate of ozone CP is improved, the process time is shortened, and the productivity is improved.
Drawings
FIG. 1 is a process flow diagram of a method for cleaning silicon wafers by spraying ozone-containing solution according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an apparatus for performing a method of cleaning a silicon wafer by spraying ozone;
in the figure, 1-a spray head, 2-a cleaning tank, 3-a tank cover, 4-a silicon wafer basket, 5-a porous flow equalizing plate, 6-a line heater, 7-a circulating pump, 8-an ozone generator, 9-a liquid outlet, 10-a liquid inlet, 11-an air outlet, 12-an air inlet pipe and 13-a sealing strip.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
The principle of cleaning the silicon wafer by using the ozone-containing spray type silicon wafer comprises the following steps: because the concentration of ozone directly introduced into the acidic solution is low, the ozone is directly introduced into the alkaline solution to react with the alkaline solution to generate hydroxyl free radicals (. OH) and oxidized hydroxyl free radicals (. O)2H) The silicon wafer cleaning effect is poor due to the fact that the decomposition speed is high, the half-life period is short, and the like, in order to improve the concentration of ozone on the surface of the silicon wafer in an acidic solution or improve the concentration of free radicals in an alkaline solution, the alkaline solution or the acidic solution is sprayed on the surface of the silicon wafer in an ozone atmosphere, so that a gas-liquid-solid three-phase reaction interface is formed on the surface of the silicon wafer, the concentrations of the ozone and the free radicals on the surface of the silicon wafer are effectively improved, and the removal capacity of organic.
Example 1
The method for cleaning a solar cell silicon wafer according to the present invention will be described in detail with reference to the following embodiments of the respective steps.
As shown in figure 1, the method for cleaning the silicon wafer by spraying ozone comprises the following specific steps:
step 110: pouring the prepared cleaning solution into a cleaning tank of a silicon wafer cleaning device for later use;
specifically, the cleaning solution can be an alkali solution, wherein the alkali solution is prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water; the cleaning liquid can be acid liquid, and the acid liquid is hydrofluoric acid solution.
More specifically, the pH value of the alkali liquor is more than or equal to 8, and the pH value of the hydrofluoric acid solution is less than or equal to 6.
The hydrofluoric acid solution, ozone gas and silicon surface react as follows:
Si+O3→SiOx
SiOx+HF→H2SiF6+H2O
under the combined action of ozone and hydrofluoric acid, a layer of silicon wafer is corroded on the surface, stains on the surface of the silicon wafer fall off along with the silicon wafer, the surface cleaning effect can be achieved, the silicon wafer after texturing is treated, the smooth pyramid effect can be achieved, and the efficiency is higher.
Step 111: placing a silicon wafer to be cleaned in a cleaning tank;
specifically, the silicon wafer to be cleaned is placed in the cleaning tank through the silicon wafer basket, so that the cleaning efficiency of the silicon wafer is improved, and meanwhile, the cleaning effect is prevented from being influenced by direct contact with the porous flow equalizing plate or the cleaning tank.
Step 112: introducing ozone gas into the cleaning tank to fill the cleaning tank with the ozone gas;
specifically, the concentration of the ozone is more than or equal to 0.1%.
Step 113: enabling the cleaning solution in the cleaning tank to flow back to the cleaning tank in a spraying mode through a liquid circulating device to clean the silicon wafer for 1-15 min;
specifically, the temperature of the cleaning solution is 5-95 ℃, and the solution degree of ozone in the solution can be increased by heating.
Step 114: putting the silicon wafer subjected to ozone cleaning in the step 113 into pure water for cleaning so as to remove residual cleaning liquid
In actual operation, a plurality of silicon wafers to be cleaned can be placed in a silicon wafer basket, the silicon wafer basket is placed in an ozone atmosphere, cleaning liquid is sprayed onto the silicon wafers through a liquid circulation system in a spraying mode, after cleaning is carried out for 1-15min, residual alkali liquor on the surfaces of the silicon wafers is washed away through pure water, and finally clean silicon wafers are obtained.
Device applying the method
Example 2
As shown in fig. 2, the cleaning device comprises a cleaning tank 2, a liquid circulation device and an ozone generator 8; a liquid inlet 10 and a liquid outlet 9 are arranged on the cleaning tank, and the liquid inlet 10 and the liquid outlet 9 are respectively connected with the liquid circulating device; the liquid circulation device comprises a circulation pump 7 and a line heater 6, wherein a liquid outlet 9 is connected with the input end of the circulation pump 7, one end of the line heater 6 is connected with the output end of the circulation pump 7, and the other end of the line heater is connected with a liquid inlet 10.
The device for cleaning the silicon wafer further comprises an ozone generator 8, wherein an air outlet end 11 of the ozone generator 8 is connected with the cleaning tank 2 through an air inlet pipe 12, and ozone gas is filled into the cleaning tank 2, so that the cleaning tank 2 is in an ozone atmosphere.
Specifically, a porous flow equalizing plate 5 is arranged in the cleaning tank 2, the porous flow equalizing plate 5 is arranged in parallel to the bottom plate of the cleaning tank 2, an air inlet pipe 12 of an ozone generator 8 penetrates from the outer wall of the cleaning tank 2 to the inner wall of the cleaning tank 2, the air inlet pipe 12 is located below the porous flow equalizing plate 5, ozone generated in the ozone generator 8 is introduced below the porous flow equalizing plate 5, and then is uniformly dispersed in the cleaning tank 2 through the porous flow equalizing plate 5.
It is specific, liquid circulation device still includes a shower nozzle 11, and is a plurality of shower nozzle 1 through feed liquor pipe 12 with line formula heater 7 is connected, and is a plurality of shower nozzle 1 equipartition in 2 inner walls of washing tank, the washing liquid is through a plurality of shower nozzle 1 can be even spray treat abluent silicon chip on, specific, treat abluent silicon chip and arrange the silicon chip basket of flowers 4 in washing tank 2 in, treat abluent silicon chip and hold through silicon chip basket of flowers 4, improved the cleaning efficiency of silicon chip, prevent simultaneously that direct and porous flow equalizing plate 5 or washing tank 2 from contacting and influence the cleaning performance.
Specifically, washing tank 2 still includes capping 3, capping 3 covers washing tank 2 top, capping 3 with the contact site of washing tank 2 is provided with sealing strip 13, through setting up capping 3, can prevent that the dust in the air from getting into washing tank 2 on the one hand and influencing the cleaning performance, and on the other hand can prevent that ozone gas from spilling outside washing tank 2 and causing ozone generator 8's extra consumption.
The working principle is as follows: the method comprises the steps of putting a silicon wafer to be cleaned into a silicon wafer basket in a cleaning tank, pouring cleaning liquid into the cleaning tank, covering a tank cover and the cleaning tank tightly, then introducing ozone gas into the cleaning tank, starting a liquid circulation system after the ozone gas reaches a certain concentration, and spraying the cleaning liquid onto the silicon wafer in the cleaning tank under the ozone atmosphere, so that the silicon wafer is cleaned, the corrosion efficiency is increased in the chemical polishing process, and the process time is shortened.
Example 3
The method is used for pre-cleaning the silicon wafer in the manufacturing of the solar cell, wherein the pre-cleaning of the silicon wafer refers to the first step of cleaning the purchased original silicon wafer. Preparing NaOH solution, using NaOH with the mass concentration of 45%, wherein the volume ratio of NaOH to pure water is 2:100, carrying out ozone spray type cleaning on purchased original silicon wafers in alkaline solution, wherein the solution temperature is 45 ℃, the cleaning time is 7min, rinsing the silicon wafers by using pure water after the ozone cleaning is finished, and removing alkali liquor remained on the surfaces of the silicon wafers to obtain clean silicon wafers.
Example 4
The method is used for cleaning the silicon wafer after texturing in the manufacture of the solar cell. After the silicon wafer is subjected to the texturing process, a layer of texturing additive is adsorbed on the surface of the silicon wafer, and the organic matter needs to be decomposed and removed, so that the cleanliness of the silicon wafer is improved. Preparing NaOH solution, using NaOH with the mass concentration of 45%, wherein the volume ratio of NaOH to pure water is 2:100, carrying out ozone spray type cleaning on purchased original silicon wafers in alkaline solution, wherein the solution temperature is 45 ℃, the cleaning time is 7min, rinsing the silicon wafers by using pure water after the ozone cleaning is finished, and removing alkali liquor remained on the surfaces of the silicon wafers to obtain clean silicon wafers.
Comparative example 1
Pre-cleaning silicon wafers of the same batch by adopting a conventional ozone cleaning method, wherein the concentration of hydrofluoric acid in a prepared cleaning solution is 2%, the concentration of ozone is 40ppm, the temperature of the solution is 45 ℃, the cleaning time is 7min, and then rinsing the silicon wafers by using pure water to obtain clean silicon wafers.
Through the experiments, the minority carrier lifetime of the cleaned and dried silicon wafer is tested, the test instrument is Sinton WCT-120, and the test results are shown in the following table 1:
TABLE 1 minority carrier lifetime test
| Item | Minority carrier lifetime (mu s) |
| Example 3 | 28.7 |
| Example 4 | 29.1 |
| Comparative example 1 | 14.2 |
The minority carrier lifetime value in the table is the average value of the test results of 30 silicon wafers, and the above test silicon wafers are all purchased from the same batch.
Under the same silicon wafer and test conditions, the higher minority carrier lifetime indicates higher cleanliness of the silicon wafer surface, so the cleanliness of the silicon wafers of the examples 3 and 4 is better than that of the comparative example, and the method and the device have practical value.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for cleaning a silicon wafer by spraying ozone, which is characterized in that,
the method comprises the following steps:
and (3) putting the silicon wafer to be cleaned in an ozone gas atmosphere, and spraying cleaning liquid on the surface of the silicon wafer for ozone cleaning.
2. The method of claim 1, wherein the cleaning step comprises the steps of: the method for cleaning the silicon wafer is completed in a cleaning device, the cleaning device comprises a cleaning tank and a liquid circulation device, a liquid inlet and a liquid outlet are formed in the cleaning tank, the liquid inlet and the liquid outlet are respectively connected with the liquid circulation device, the device for cleaning the silicon wafer further comprises an ozone generator, the air outlet end of the ozone generator is connected with the cleaning tank through an air inlet pipe, the liquid circulation device comprises a plurality of spray heads, and the spray heads are evenly distributed on the inner wall of the cleaning tank.
3. The method of claim 1, wherein the cleaning step comprises the steps of: the cleaning solution is an alkali solution or an acid solution, and the alkali solution is prepared from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water; the acid solution is hydrofluoric acid solution.
4. The method according to claim 3, wherein the silicon wafer is subjected to the spray cleaning with ozone, and the method comprises the following steps: the pH value of the alkali liquor is more than or equal to 8, and the pH value of the acid liquor is less than or equal to 6.
5. The method of claim 1, wherein the cleaning step comprises the steps of: the concentration of the ozone is more than or equal to 0.1 percent.
6. The method of claim 1, wherein the cleaning step comprises the steps of: the temperature of the cleaning liquid is 5-95 ℃.
7. The method of claim 2, wherein the silicon wafer is subjected to the spray cleaning with ozone, and the method comprises the following steps: the cleaning tank is characterized in that a porous flow equalizing plate is arranged in the cleaning tank, the porous flow equalizing plate is parallel to the bottom plate of the cleaning tank, an air inlet pipe of the ozone generator penetrates from the outer wall of the cleaning tank to the inner wall of the cleaning tank, and the air inlet pipe is located below the porous flow equalizing plate.
8. The method of claim 2, wherein the silicon wafer is subjected to the spray cleaning with ozone, and the method comprises the following steps: the liquid circulating device further comprises a circulating pump and a line heater, the liquid outlet is connected with the input end of the circulating pump, one end of the line heater is connected with the output end of the circulating pump, and the other end of the line heater is connected with the plurality of nozzles through the liquid inlet.
9. The method of claim 2, wherein the silicon wafer is subjected to the spray cleaning with ozone, and the method comprises the following steps: the cleaning device further comprises a silicon wafer basket and a tank cover, the silicon wafer basket is located in the cleaning tank, the tank cover covers the top of the outer tank, and a sealing strip is arranged at the contact position of the tank cover and the cleaning tank.
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