CN112646671A - Silicon wafer cleaning method - Google Patents
Silicon wafer cleaning method Download PDFInfo
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- CN112646671A CN112646671A CN201910959761.2A CN201910959761A CN112646671A CN 112646671 A CN112646671 A CN 112646671A CN 201910959761 A CN201910959761 A CN 201910959761A CN 112646671 A CN112646671 A CN 112646671A
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- silicon wafer
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- 238000004140 cleaning Methods 0.000 title claims abstract description 236
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 154
- 239000010703 silicon Substances 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000012459 cleaning agent Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims description 87
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 15
- 238000005202 decontamination Methods 0.000 abstract description 2
- 230000003588 decontaminative effect Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 152
- 235000012431 wafers Nutrition 0.000 description 130
- 239000000126 substance Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011109 contamination Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000011863 silicon-based powder Substances 0.000 description 9
- 239000003814 drug Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000002173 cutting fluid Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- 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
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
-
- C11D2111/22—
Abstract
The invention provides a silicon wafer cleaning method, which comprises the following steps: cleaning the silicon wafer by using a cleaning solution A, a cleaning solution B and a cleaning solution C in sequence; the cleaning solution A comprises a silicon wafer cleaning agent; the cleaning solution B comprises a silicon wafer cleaning agent and KOH; the cleaning solution C comprises hydrogen peroxide and KOH. The silicon wafer cleaning method provided by the invention is used for cleaning the silicon wafer, the decontamination effect of the silicon wafer is good, and the cleaning time can be shortened.
Description
Technical Field
The invention belongs to the field of cleaning, and relates to a silicon wafer cleaning method.
Background
In the existing cleaning process of the polycrystalline silicon wafer, cleaning → medicament washing → rinsing → draining → drying, wherein 3 to 4 medicament grooves are arranged, which is the most important step in the cleaning process and aims to remove chemical substances such as silicon powder, cutting fluid and the like attached to the surface of the polycrystalline silicon wafer through physical and chemical reactions; in the prior art, a single-component cleaning agent is added into a chemical tank, the selected chemical is an organic strong alkaline substance generally, although part of impurities such as silicon powder and cutting fluid can be cleaned, the cleaning time is long (the single tank is more than 160s), and the organic substance, the silicon powder and the like in the cleaning agent are easy to remain on the surface of a silicon wafer to form dirt, so that the quality of the silicon wafer is reduced, and the cleaning cost is increased.
CN108441353A discloses a silicon wafer cleaning liquid, cleaning equipment and a cleaning process, which comprise a potassium hydroxide solution with the concentration of 45% and a hydrogen peroxide solution with the concentration of 31%, wherein the volume ratio of the potassium hydroxide solution to the hydrogen peroxide solution is 1:1.05-1:7.25, and the silicon wafer cleaning equipment comprises an ultrasonic cleaning part and a cleaning part, wherein the ultrasonic cleaning part is used for removing granular silicon powder; a liquid medicine cleaning part for removing grease, metal ions and organic impurities; a first rinsing part for removing residual liquid medicine on the surface of the silicon wafer; a cleaning liquid cleaning part for removing organic matters by using the silicon wafer cleaning liquid; the second rinsing part is used for removing the cleaning liquid left on the surface of the silicon wafer; and the slow pulling part is used for removing the residual cleaning liquid on the surface of the silicon wafer. Although the patent can reduce the dirty rate of the silicon wafer to a certain extent, a large amount of deionized water, hydrogen peroxide and KOH are used in the cleaning process, and the defect of long cleaning time still exists. CN102952650A discloses a solar cell silicon wafer cleaning agent and a cleaning process thereof, which are composed of the following components: 0.5-3% of surfactant, 2.1-13% of inorganic salt, 1-5% of organic salt and the balance of deionized water, wherein the cleaning process comprises the steps of mixing the surfactant, the inorganic salt, the organic salt and the deionized water according to the weight percentage to prepare a solar cell silicon wafer cleaning agent, then adding deionized water with the volume of 20-25 times of that of the cleaning agent to obtain silicon wafer cleaning liquid, and placing the silicon wafer into the obtained silicon wafer cleaning liquid for cleaning at normal temperature. Although the patent does not corrode the surface of the silicon wafer, part of organic matters in the cleaning agent remain on the surface of the silicon wafer, which causes secondary pollution, and the cleaning time of the silicon wafer cannot be shortened by using the cleaning agent.
Therefore, it is necessary to develop a method for cleaning a silicon wafer which can reduce the rate of contamination and shorten the cleaning time.
Disclosure of Invention
The invention aims to provide a silicon wafer cleaning method. The silicon wafer cleaning method has the advantages of good cleaning effect, low dirty ratio of the finally cleaned silicon wafer and shortened cleaning time.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicon wafer cleaning method, including the steps of:
cleaning the silicon wafer by using a cleaning solution A, a cleaning solution B and a cleaning solution C in sequence;
the cleaning solution A comprises a silicon wafer cleaning agent; the cleaning solution B comprises a silicon wafer cleaning agent and KOH; the cleaning solution C comprises hydrogen peroxide and KOH.
In the invention, the cleaning liquid A, the cleaning liquid B and the cleaning liquid C are names of the cleaning liquid in the medicament tank used in the invention, and as can be seen from components in the cleaning liquid A and the cleaning liquid B, the cleaning liquid A and the cleaning liquid B are silicon wafer cleaning liquids commonly used in the prior art, and the components in the cleaning liquid C are hydrogen peroxide and KOH and can be interpreted as chemical cleaning liquids.
The cleaning liquid is divided into a silicon wafer cleaning liquid (silicon wafer cleaning liquid) and a chemical cleaning liquid (hydrogen peroxide and KOH), the silicon wafer cleaning liquid and the chemical cleaning liquid are matched together, the silicon wafer cleaning liquid can react with residues (silicon powder or cutting fluid and other impurities) on the surface of a silicon wafer to generate a complex, the complex has certain hydrophobicity, then the chemical cleaning liquid is used for removing the complex and organic matters and other impurities brought by the silicon wafer cleaning liquid, the purpose of cleaning the silicon wafer is finally achieved, and the dirty proportion is effectively reduced.
In the invention, after the silicon wafer is cleaned by the cleaning liquid A, most residual silicon powder on the surface of the silicon wafer is removed, and the concentration of a reactant (silicon powder, cutting fluid or other impurities) is reduced, therefore, the invention increases the alkali concentration of the cleaning liquid B by adding potassium hydroxide into the cleaning liquid B, so that the concentration of the reactant (alkali liquor) can be increased to improve the reaction rate, and more reactant is removed.
In the invention, after the silicon wafer is cleaned by the cleaning liquid A and the cleaning liquid B, partial organic matters remain on the surface of the silicon wafer, and if deionized water is directly used for rinsing, the organic matters can be firmly adhered to the surface of the silicon wafer.
In the invention, the silicon wafer is cleaned by using the cleaning liquid A and the cleaning liquid B and then using the chemical cleaning liquid (cleaning liquid C), the sequence can not be changed, if the silicon wafer is cleaned by using the chemical cleaning liquid, hydrogen peroxide has strong oxidizing property and can rapidly carry out oxidation reaction with chemical agents or impurities and the like remained on the surface of the silicon wafer to generate inorganic salt which is difficult to clean, and the inorganic salt is difficult to remove by the silicon wafer cleaning liquid; on the other hand, part of hydrogen peroxide enters the silicon wafer cleaning liquid along with the silicon wafer, and the silicon wafer cleaning liquid is invalid due to the reaction of the hydrogen peroxide and part of substances in the silicon wafer cleaning liquid.
In the present invention, the silicon wafer cleaning agent has a mass concentration of 4 to 6%, for example, 4.2%, 4.5%, 4.8%, 5.0%, 5.2%, 5.5%, 5.8%, etc., and the KOH has a mass concentration of 0.4 to 0.5%, for example, 0.42%, 0.44%, 0.45%, 0.46%, 0.48%, etc., in the cleaning solution B.
In the cleaning liquid B provided by the invention, when the concentration of KOH is within the range of 0.4-0.5%, the effect is best, if the concentration of KOH is higher, pits can be generated on the surface of a silicon wafer by corrosion, and the silicon wafer is damaged and simultaneously the dirty residue is easily caused; if the concentration of KOH is low, the effect of removing impurities on the surface of the silicon wafer cannot be expected.
Preferably, a KOH solution is prepared and then mixed with the wafer cleaner to finally form cleaner B.
Preferably, the silicon wafer cleaning agent is a conventional silicon wafer cleaning agent in the prior art, such as a santa clar cleaning agent (model: DY-100), a Junhe cleaning agent (model: Junhe 1020) and the like.
Preferably, the cleaning liquid C comprises hydrogen peroxide with the mass concentration of 1-3% and KOH with the mass concentration of 0.1-0.3%.
In the present invention, the preparation methods of the cleaning solution a, the cleaning solution B and the cleaning solution C are commonly used in the prior art, and any preparation method that can obtain the cleaning solution of the present invention can be applied to the present invention.
In the invention, the concentration of hydrogen peroxide is not suitable to be too high, which may be caused by the too high concentration of hydrogen peroxide, on one hand, the high concentration of hydrogen peroxide can form a layer of compact silicon dioxide film on the surface of the silicon chip, and the silicon dioxide film has strong hydrophilicity and is easy to cause water stain and dirt; on the other hand, if the concentration of the hydrogen peroxide is too high, a large amount of foam is easily generated in the cleaning process, so that the silicon wafer floats, and more fragments appear; if the content is too small, the oxidation effect is not obvious, and the degradation effect on long-chain organic matters is poor; when the concentration of KOH is too low, the cleaning effect is poor, and when the concentration of KOH is too high, the morphology of the silicon wafer can be damaged.
In the cleaning liquid C of the present invention, the mass concentration of the hydrogen peroxide is 1 to 3%, for example, 1.5%, 2%, 2.5%, or the like.
In the cleaning liquid C of the present invention, the mass concentration of KOH is 0.1 to 0.3%, for example, 0.15%, 0.20%, 0.25%, or the like.
Preferably, the preparation method further comprises the step of cleaning the silicon wafer by using the cleaning liquid C and then cleaning the silicon wafer once again by using the cleaning liquid C.
That is, in the present invention, it is preferable to clean the silicon wafer four times, and the cleaning liquids are cleaning liquid A, cleaning liquid B, cleaning liquid C, and cleaning liquid C in this order.
And the cleaning liquid C is repeatedly utilized to clean the silicon wafer for two times, so that the cleaning effect of the silicon wafer can be further improved, and the contamination rate is reduced.
The present invention selects KOH for one reason because silicon powder can react with KOH, and for the other reason, potassium ions are more easily removed than sodium ions for cleaning purposes, and KOH is selected for cost and subsequent cell processing considerations.
Preferably, the preparation method further comprises repeating the cleaning process by using the cleaning solution B once between the cleaning solution B and the cleaning solution C.
That is, in the present invention, it is also preferable to wash the silicon wafer four times, and the washing liquids are, in this order, the washing liquid a, the washing liquid B, and the washing liquid C. The method can further reduce the silicon wafer contamination rate.
Preferably, the temperature of the cleaning solution A is 50-60 ℃, such as 52 ℃, 54 ℃, 56 ℃, 58 ℃ and the like, preferably 50 ℃.
Preferably, the temperature of the cleaning solution B is 50-60 ℃, such as 52 ℃, 54 ℃, 56 ℃, 58 ℃ and the like, preferably 50 ℃.
Preferably, the temperature of the cleaning solution C is 55-65 ℃, such as 57 ℃, 59 ℃, 61 ℃, 64 ℃ and the like, preferably 55 ℃.
Preferably, when the silicon wafer is cleaned for the first time by the cleaning liquid C for the second time, the cleaning temperature is 55-65 ℃, such as 57 ℃, 59 ℃, 61 ℃, 64 ℃ and the like, and preferably 60 ℃.
Because the silicon wafer moves backwards from groove to groove, the residue on the surface of the silicon wafer is less and less, and accordingly the silicon wafer is more difficult to clean (the concentration of the reactant is reduced), the temperature needs to be gradually increased, the activity of the medicament (reactant) is gradually improved, and the residue (dirt) on the surface is effectively removed.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the silicon wafer cleaning liquid and the chemical cleaning liquid are matched together, the silicon wafer cleaning liquid can react with residues (silicon powder or cutting fluid and other impurities) on the surface of the silicon wafer to generate a complex, the complex has certain hydrophobicity, then the chemical cleaning liquid is utilized to remove the complex and organic matters and other impurities brought by the silicon wafer cleaning liquid, the purpose of cleaning the silicon wafer is finally achieved, and the dirty proportion is effectively reduced;
(2) in the invention, the cleaning liquid A and the cleaning liquid B are firstly utilized, and then the cleaning liquid C is utilized to clean the silicon wafer, the sequence can not be changed, if the sequence is changed, the cleaning efficiency of the silicon wafer is reduced, and the contamination rate of the silicon wafer is increased;
(3) the silicon wafer cleaning method provided by the invention is used for cleaning the silicon wafer, the decontamination effect on the silicon wafer is good, and the cleaning time can be shortened; wherein the dirt ratio is less than 0.8 percent and can be as low as less than 0.3 percent.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a silicon wafer cleaning method, which comprises the following steps:
the cleaning solution A is filled in the agent tank 1, 10L of silicon wafer cleaning agent is added firstly, and then 190L of deionized water is added to prepare the cleaning solution A containing 5 wt% of silicon wafer cleaning agent; the temperature was 50 ℃.
The agent tank 2 is filled with cleaning solution B, 190L of deionized water is firstly added, then 1.005kg of potassium hydroxide solid (or KOH solution with the amount of corresponding substances) is added, and after the potassium hydroxide solid is dissolved, 10L of silicon wafer cleaning agent is added to prepare the cleaning solution B containing 5 wt% of silicon wafer cleaning agent and 0.5 wt% of KOH; the temperature was 50 ℃.
Wherein the silicon wafer cleaning agent is a Junhe cleaning agent (Junhe 1020).
The agent tank 3 is a cleaning solution C, 12L of hydrogen peroxide (with the mass concentration of 30%) is added, 188L of deionized water is added, and 0.402kg of potassium hydroxide solid (or KOH solution of the corresponding substance) is added to prepare the cleaning solution C containing 2 wt% of hydrogen peroxide and 0.2 wt% of KOH; the temperature was 55 ℃.
The agent tank 4 is a cleaning solution C, 12L of hydrogen peroxide (with the mass concentration of 30%) is added, 188L of deionized water is added, and 0.402kg of potassium hydroxide solid (or KOH solution of the corresponding substance) is added to prepare the cleaning solution C containing 2 wt% of hydrogen peroxide and 0.2 wt% of KOH; the temperature was 60 ℃.
And sequentially cleaning the silicon wafers in the reagent tanks 1-4 for 120 s.
Examples 2 to 4
The difference from example 1 is that the amount of KOH added to the chemical tank 2 was adjusted so that the KOH concentration was 0.4 wt% (example 2), 0.2 wt% (example 3), and 0.7 wt% (example 4).
Examples 5 to 8
The difference from example 1 is that the amount of KOH added in the chemical tank 3 was adjusted to 0.1 wt% (example 5), 0.3 wt% (example 6), 0.05 wt% (example 7), and 0.5 wt% (example 8).
Examples 9 to 12
The difference from example 1 is that the amount of hydrogen peroxide added to the chemical tank 3 was adjusted so that the amount of hydrogen peroxide added was 1 wt% (example 9), 3 wt% (example 10), 0.5 wt% (example 11), and 5 wt% (example 12).
Example 13
The embodiment provides a silicon wafer cleaning method, which comprises the following steps:
the agent tank 1 is filled with cleaning solution A which contains 5 wt% of silicon wafer cleaning agent; the temperature was 50 ℃.
The agent groove 2 is filled with cleaning solution B which contains 5 wt% of silicon wafer cleaning agent and 0.5 wt% of KOH; the temperature was 50 ℃.
The agent tank 3 is filled with cleaning solution B which contains 5 wt% of silicon wafer cleaning agent and 0.5 wt% of KOH; the temperature was 50 ℃.
Wherein the silicon wafer cleaning agent is a Junhe cleaning agent (Junhe 1020).
The agent groove 4 is filled with cleaning solution C which contains 2 wt% of hydrogen peroxide and 0.2 wt% of KOH; the temperature was 60 ℃.
And sequentially cleaning the silicon wafers in the reagent tanks 1-4 for 120 s.
Example 14
The embodiment provides a silicon wafer cleaning method, which comprises the following steps:
the agent tank 1 is filled with cleaning solution A which contains 4 wt% of silicon wafer cleaning agent and the balance of deionized water; the temperature was 60 ℃.
The agent tank 2 is filled with cleaning solution B which contains 4 wt% of silicon wafer cleaning agent and 0.5 wt% of KOH, and the balance is deionized water; the temperature was 60 ℃.
Wherein the silicon wafer cleaning agent is a Santa Claus cleaning agent (model: DY-100).
The agent tank 3 is filled with cleaning solution C which contains 1 wt% of hydrogen peroxide and 0.3 wt% of KOH, and the balance is deionized water; the temperature was 65 ℃.
The agent tank 4 is filled with cleaning solution C which contains 3 wt% of hydrogen peroxide and 0.1 wt% of KOH, and the balance is deionized water; the temperature was 65 ℃.
And sequentially cleaning the silicon wafers in the reagent tanks 1-4 for 120 s.
Example 15
The embodiment provides a silicon wafer cleaning method, which comprises the following steps:
the agent tank 1 is filled with cleaning solution A, which contains 6 wt% of silicon wafer cleaning agent and the balance of deionized water; the temperature was 50 ℃.
The agent tank 2 is filled with cleaning solution B which contains 6 wt% of silicon wafer cleaning agent and 0.4 wt% of KOH, and the balance is deionized water; the temperature was 50 ℃.
Wherein the silicon wafer cleaning agent is a Santa Claus cleaning agent (model: DY-100).
The agent tank 3 is filled with cleaning solution C which contains 3 wt% of hydrogen peroxide and 0.1 wt% of KOH, and the balance is deionized water; the temperature was 55 ℃.
The agent tank 4 is filled with cleaning solution C which contains 1 wt% of hydrogen peroxide and 0.3 wt% of KOH, and the balance is deionized water; the temperature was 55 ℃.
And sequentially cleaning the silicon wafers in the reagent tanks 1-4 for 120 s.
Example 16
The embodiment provides a silicon wafer cleaning method, which comprises the following steps:
the agent tank 1 is filled with cleaning solution A which contains 5 wt% of silicon wafer cleaning agent; the temperature was 50 ℃.
The agent groove 2 is filled with cleaning solution B which contains 5 wt% of silicon wafer cleaning agent and 0.5 wt% of KOH; the temperature was 50 ℃.
Wherein the silicon wafer cleaning agent is a Junhe cleaning agent (Junhe 1020).
The agent tank 3 is filled with cleaning solution C which contains 2 wt% of hydrogen peroxide and 0.2 wt% of KOH; the temperature was 55 ℃.
And sequentially cleaning the silicon wafers in the reagent tanks 1-3 for 120 s.
Comparative example 1
The difference from example 16 is that the silicon wafer was washed in the chemical tank 3 → 1 → 2 in this order, and the washing time was 120 seconds each.
Comparative example 2
The difference from example 16 is that the silicon wafer was washed in the chemical tank 3 → 2 → 1 in this order, and the washing time was 120 seconds each.
Comparative example 3
The cleaning solution A provided in example 1 was added to all of the four chemical tanks, and the cleaning time was 160 seconds.
Comparative example 4
The difference from example 1 is that KOH was not added to the chemical tank 2.
Comparative example 5
All of the four chemical tanks were filled with the cleaning solution C provided in example 1.
Comparative example 6
The silicon wafer is cleaned by the cleaning process disclosed in CN108441353A, the cleaning time of each groove is 120s, and the method comprises the following steps:
the tank 1 is an ultrasonic cleaning part, pure water is filled in the ultrasonic cleaning tank, and the cleaning temperature is 45 ℃.
The tank 2-4 is a liquid medicine cleaning part, and the tank 2-3 is a mixed liquid of a Junhe cleaning agent A and a Junhe cleaning agent B, wherein the volume fraction of the Junhe cleaning agent A is 0.96%, the volume fraction of the Junhe cleaning agent B is 0.48%, and the cleaning temperature is 50 ℃.
The 5-tank is a first rinsing part, pure water is filled in the first rinsing part, and the temperature is 55 ℃.
The 6 tank is a cleaning liquid cleaning part and is composed of KOH with the concentration of 45 percent and hydrogen peroxide solution with the concentration of 31 percent, wherein the volume ratio of potassium hydroxide to the hydrogen peroxide solution is 1:4.75, and the temperature is 55 ℃.
The 7-10 tank is a second cleaning part, pure water is filled in the tank, and the temperature is 55 ℃.
The 11 tank is a slow pulling part, and pure water with a temperature of 55 ℃ is filled in the tank.
The silicon wafers are sequentially cleaned in the reagent tanks 1-11 for 120 s.
Performance testing
The silicon wafers cleaned by the silicon wafer cleaning methods provided in examples 1 to 16 and comparative examples 1 to 4 were subjected to a performance test by the following method:
(1) the fouling rate: and (3) classifying the silicon wafers by using a full-automatic silicon wafer sorting machine (semilab), and calculating the contamination ratio.
The test results are shown in table 1:
TABLE 1
According to the embodiment and the performance test, the silicon wafer cleaning method has the advantages of good cleaning effect and capability of shortening the cleaning time; the silicon wafer obtained by the silicon wafer cleaning method provided by the invention has a low contamination rate, wherein the contamination rate is less than 0.8% and can be as low as below 0.3%.
As can be seen from the comparison between the example 1 and the examples 2 to 4, in the silicon wafer cleaning method provided by the invention, the concentration of KOH in the cleaning liquid B is optimally 0.4 to 0.5 percent; as is clear from comparison between examples 1 and 5 to 12, in the cleaning liquid C, the silicon wafer cleaning effect was good when the concentrations of hydrogen peroxide and KOH were in the ranges of 1 to 3% and 0.1 to 0.3%, respectively. When the concentration of KOH in the cleaning liquid B is 0.4-0.5%, and the concentrations of hydrogen peroxide and KOH in the cleaning liquid C are respectively 1-3% and 0.1-0.3%, the cleaning effect on the silicon wafer is optimal, and at the moment, the proportion of dirt is below 0.3%, even can reach below 0.2%; as can be seen from the comparison between example 1 and example 16, the silicon wafer cleaning method provided by the present invention can further reduce the contamination rate of the cleaned silicon wafer by adding a chemical cleaning step (cleaning solution C) to the cleaning method; as is clear from comparison between example 13 and example 16, the cleaning effect on the silicon wafer can be further improved and the contamination ratio can be reduced by adding the cleaning liquid B between the cleaning liquid B and the cleaning liquid C and cleaning again.
As is clear from the comparison between example 16 and comparative examples 1 to 2, in the present invention, the cleaning sequence cannot be changed and the technical effect of the present invention cannot be achieved; as can be seen from the comparison between example 1 and comparative example 3, the present invention can reduce the silicon wafer fouling rate at a shorter cleaning time than the prior art (comparative example 1). As is clear from the comparison between example 1 and comparative example 4, the addition of KOH to the chemical bath 2 reduced the silicon wafer contamination rate. As can be seen from the comparison between example 1 and comparative example 5, the silicon wafer cannot be cleaned by using only the chemical cleaning agent. As can be seen from the comparison of example 1 and comparative example 6, the cleaning method provided by the present invention has a shorter cleaning time and a lower fouling rate.
The applicant states that the present invention is illustrated by the above examples to describe the silicon wafer cleaning method of the present invention, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be implemented by relying on the above detailed methods. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A silicon wafer cleaning method is characterized by comprising the following steps:
cleaning the silicon wafer by using a cleaning solution A, a cleaning solution B and a cleaning solution C in sequence;
the cleaning solution A comprises a silicon wafer cleaning agent; the cleaning solution B comprises a silicon wafer cleaning agent and KOH; the cleaning solution C comprises hydrogen peroxide and KOH.
2. The silicon wafer cleaning method according to claim 1, wherein in the cleaning solution B, the mass concentration of the silicon wafer cleaning agent is 4 to 6%, and the mass concentration of KOH is 0.4 to 0.5%.
3. The silicon wafer cleaning method according to claim 1 or 2, characterized in that the cleaning solution C comprises 1 to 3% by mass of hydrogen peroxide and 0.1 to 0.3% by mass of KOH.
4. The silicon wafer cleaning method according to any one of claims 1 to 3, wherein the production method further comprises cleaning the silicon wafer with the cleaning liquid C and then cleaning the silicon wafer with the cleaning liquid C again.
5. The silicon wafer cleaning method according to any one of claims 1 to 3, wherein the production method further comprises repeating the cleaning process with the cleaning liquid B once between the cleaning liquid B and the cleaning liquid C.
6. The silicon wafer cleaning method according to any one of claims 1 to 5, wherein the silicon wafer cleaning agent has a mass concentration of 4 to 6% in the cleaning liquid A.
7. The silicon wafer cleaning method according to any one of claims 1 to 6, wherein the temperature of the cleaning liquid A is 50 to 60 ℃, preferably 50 ℃.
8. The silicon wafer cleaning method according to any one of claims 1 to 7, wherein the temperature of the cleaning liquid B is 50 to 60 ℃, preferably 50 ℃.
9. The silicon wafer cleaning method according to any one of claims 1 to 8, wherein the temperature of the cleaning liquid C is 55 to 65 ℃, preferably 55 ℃.
10. The silicon wafer cleaning method according to any one of claim 4, wherein the temperature for cleaning the silicon wafer for the second time by using the cleaning solution C is 55-65 ℃, preferably 60 ℃.
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