Silicon material cleaning agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of silicon material cleaning, and particularly relates to a silicon material cleaning agent and a preparation method and application thereof. The silicon material cleaning agent provided by the invention comprises the following components in parts by mass: 50-60 parts of water; 15 to 30 parts of an acidic etching solution; 10 to 20 parts of a first chelating agent; 10 to 20 parts of a second chelating agent; 0.5 to 5 parts of a surfactant; 5 to 15 parts of a builder; wherein the first chelating agent is selected from at least one of 1-hydroxyethylidene-1, 1-diphosphonic acid or ethylenediaminetetraacetic acid; the second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid, malic acid, sodium citrate, sodium gluconate, potassium pyrophosphate and sodium pyrophosphate. The silicon material cleaning agent is used for silicon material cleaning, various metal ions can be cleaned at a time, the silicon material cleaning efficiency is improved, and the industrial cost is effectively reduced.

Description

Technical Field

[0001] The present application relates to the technical field of silicon material cleaning, and in particular to a silicon material cleaning agent, a preparation method thereof, and an application thereof. Background Art

[0002] Currently, silicon materials are primarily divided into P-type and N-type materials. Electronic devices made from N-type silicon have a longer lifespan and higher conductivity than P-type silicon, making it more widely used in the processing of solar silicon wafers. During the processing and production of solar silicon wafers, the cutting of the ingots produces a large amount of irregularly shaped scraps. However, these scraps are often contaminated with impurities such as silicon mud, ink, oil, oxidation color, silica gel, quartz, and metal ions. These impurity-laden ingots are often returned to the furnace for remanufacturing, resulting in numerous defects and unsuitable for continued use. Metal ions are the most difficult to remove.

[0003] Currently, the main cleaning agents for N-type silicon materials are acid, alkaline, and reagent cleaning. Acid cleaning formulas primarily use hydrofluoric acid and nitric acid to clean the silicon material surface through corrosion and oxidation. However, these methods pose significant risks to operators, generate waste gas and waste liquids that require cumbersome disposal, and cause significant environmental pollution. Improper handling of the corrosion process can also result in significant silicon material losses. Alkaline cleaning formulas primarily use sodium hydroxide and potassium hydroxide, but these can corrode the silicon material surface, creating a corroded microstructure that makes some impurities difficult to remove. Reagent cleaning, as a newer cleaning method, can remove metal ion impurities, but its single-pass efficiency is low, and it cannot simultaneously remove the diverse impurities introduced into complex production environments, such as oil, metal ions, and oxide layers. Therefore, research and development of more efficient and clean silicon material cleaning agents is of great significance. Summary of the Invention

[0004] The purpose of the present application is to provide a silicon material cleaning agent, which can be used for silicon material cleaning, clean multiple impurities at a single time, improve silicon material cleaning efficiency, and effectively reduce industrial costs.

[0005] In a first aspect of the present application, a silicon material cleaning agent is provided, wherein the silicon material cleaning agent comprises the following components in parts by mass:

[0006] Water: 50-60 parts;

[0007] Acidic etching solution: 15-30 parts;

[0008] First chelating agent: 10-20 parts;

[0009] Second chelating agent: 10-20 parts;

[0010] Surfactant: 0.5-5 parts;

[0011] Detergent: 5-15 parts;

[0012] Wherein, the first chelating agent is selected from at least one of hydroxyethylidene diphosphonic acid or ethylenediaminetetraacetic acid;

[0013] The second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid, malic acid, sodium citrate, sodium gluconate, potassium pyrophosphate, and sodium pyrophosphate.

[0014] A second aspect of the present application provides a method for preparing the silicon material cleaning agent described in the first aspect, comprising the following steps:

[0015] The first chelating agent and the second chelating agent are completely dissolved in water in sequence, and then an acidic etching solution is added and completely dissolved, and then a surfactant is added and completely dissolved, and then a builder is added and completely dispersed; finally, stirring is performed for 20 to 45 minutes to prepare the silicon material cleaning agent.

[0016] The third aspect of the present application provides the use of the silicon material cleaning agent described in the third aspect of the present application in silicon material cleaning.

[0017] Technical effects of this application:

[0018] The silicon material cleaning agent provided by this application is the first to adopt a two-component chelating agent, which realizes a single efficient cleaning of various complex impurities on the surface of the silicon material under acidic conditions. In the silicon material cleaning agent system protected by this application, the two-component chelating agent composed of the acidic etching liquid component and the first chelating agent and the second chelating agent achieves stable coexistence, which can replace the high-concentration strong acid (such as hydrofluoric acid and nitric acid) in the traditional pickling process, thereby avoiding the large amount of heat release, release of nitrogen oxides (such as yellow gas NO2), mixed acid volatilization and other environmental pollution caused by the traditional pickling process, and at the same time avoids the problem that the weak surface corrosion caused to the silicon material in the traditional alkaline washing environment cannot be completely removed. Among them, HEDP and EDTA are both polyacids. This application adopts two specific polyacids as the first chelating agent. First, the first chelating agent structure contains multiple hydroxyl groups and acyl groups, which greatly improves the hydrophilicity of the silicon material cleaning agent system; secondly, the hydroxyl and acyl fragments are conducive to faster capture of metal ions and the formation of a stable six-membered ring structure. At the same time, the silicon material cleaning agent of the present application is also combined with another small molecule polyacid or its salt as a second chelating agent. In the aqueous system, these substances are all small molecule compounds that can provide multiple oxygen anions and have multiple hydrophilic and chelating functional groups. When the second chelating agent chelates with the metal ions, the polar fragments in the first chelating agent that do not participate in the ring formation not only improve the hydrophilic properties of each substance in the system, but also promote the second chelating agent to chelate with the metal impurity ions faster.

[0019] At the same time, the silicon material cleaning agent system of the present application uses water as the medium and combines with acidic etching solution to effectively peel off the oxide layer of the silicon material coating layer to remove the oxidation color on the silicon material surface, promote the chelation of metal ions on the silicon material surface and the two-component chelating agent, and make the chelation structure of the first chelating agent, the second chelating agent and the metal ions more stable, thereby achieving the removal efficiency of ionic impurities on the basis of removing the oxidation color on the silicon material surface.

[0020] Furthermore, the surfactant in the system is selected to be a fluorocarbon surfactant, which can not only effectively clean the silicon mud and oil stains on the silicon material, but also promote the removal of metal ions in the silicon material. This is because fluorocarbon surfactants are more acid-resistant when cleaning the silicon material, making the stability and shelf life of the silicon material cleaning agent system of the present application more prominent. In addition, the introduction of fluorocarbon surfactants can greatly reduce the interfacial tension of the cleaning agent, accelerate the rapid dispersion of impurities on the surface of the silicon material in the silicon material cleaning agent, and quickly combine the impurities with the surfactant, greatly improving the cleaning efficiency.

[0021] Therefore, the silicon material cleaning agent of the present application can effectively clean various impurities on the surface of the silicon material with only a single cleaning under mild conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a comparison chart of the cleaning test results of Example 1 of the present application. DETAILED DESCRIPTION

[0023] The following describes the exemplary embodiments in more detail. However, the exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided to make this application more comprehensive and complete and to fully convey the concepts of the exemplary embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, numerous specific details are provided to provide a full understanding of the embodiments of the present application.

[0024] In a first aspect, the present application provides a silicon material cleaning agent, which comprises the following components in parts by mass:

[0025] Water: 50-60 parts;

[0026] Acid etching solution: 15-30 parts;

[0027] First chelating agent: 10-20 parts;

[0028] Second chelating agent: 10-20 parts;

[0029] Surfactant: 0.5-5 parts;

[0030] Detergent: 5-15 parts;

[0031] wherein the first chelating agent is selected from at least one of hydroxyethylidene diphosphonic acid (HEDP) or ethylenediaminetetraacetic acid (EDTA);

[0032] The second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid, malic acid, sodium citrate, sodium gluconate, potassium pyrophosphate, and sodium pyrophosphate.

[0033] In some embodiments, the acidic etching solution is selected from at least three of fluorosilicic acid, trifluoroacetic acid, benzenesulfonic acid, and aminosulfonic acid.

[0034] In some preferred embodiments, the first chelating agent is selected from hydroxyethylidene diphosphonic acid.

[0035] When hydroxyethylidene diphosphonic acid is used as the first chelating agent, the phosphate group and / or carboxylic acid group and the hydroxyl group fragment in its structure are all conducive to faster capture of metal ions and formation of a stable six-membered ring structure.

[0036] In some preferred embodiments, the second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid, and malic acid.

[0037] Among them, when at least one of citric acid, gluconic acid, tartaric acid, and malic acid is used as the second chelating agent, it ensures that the system is free from interference from external sodium ions and potassium ions, and the number of effective hydroxyl / carboxyl groups in the molecule that can participate in chelation is greater, which is beneficial to the chelation system against impurities.

[0038] Among them, at least one of citric acid, gluconic acid, tartaric acid, malic acid, sodium citrate, and sodium gluconate is used as the second chelating agent and is combined with the first chelating agent as a two-component chelating agent. The second chelating agent has a large number of carboxylic acid groups and hydroxyl groups on its carbon skeleton that can form hydrogen bonds with water, thereby making the silicon material cleaning agent more hydrophilic and the system stable.

[0039] In some embodiments, the surfactant is a fluorocarbon surfactant.

[0040] In some preferred embodiments, the fluorocarbon surfactant is selected from at least one of FS-3100, FS-30, FC327, FS-3000, FCF-204, or FCF-206.

[0041] In some embodiments, the builder is selected from ketone solvents having 5 to 10 carbon atoms.

[0042] In some preferred embodiments, the builder is selected from at least one of N-methylpyrrolidone and methyl isobutyl ketone.

[0043] Among them, N-methylpyrrolidone or methyl isobutyl ketone is used as the co-solvent of the system. Since the ketone substances used have high polarity, they promote the rapid dissolution of the cleaning agent and increase the preparation speed of the cleaning agent. At the same time, ketone substances have excellent solubility in oils and fats, so they can play a role in cleaning metal ions and oils on the surface of silicon wafers, which is beneficial to the cleaning of impurities such as oil, water and silicon mud on the surface of silicon materials, and accelerates the removal of various impurities.

[0044] In some embodiments, the silicon material cleaning agent comprises 50 to 60 parts by weight of water. For example, the amount is 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 parts by weight, or any value therebetween. In some preferred embodiments, the amount of water is 50, 54, 55, 56, 58, or 60 parts by weight.

[0045] In some embodiments, the silicon material cleaning agent comprises 15 to 30 parts by mass of the acidic etching solution. For example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 parts, or any value therebetween. In some preferred embodiments, the acidic etching solution comprises 15, 18, 22, 23, 24, 25, or 30 parts.

[0046] In some embodiments, the first chelating agent is present in the silicon material cleaning agent in an amount of 10 to 20 parts by weight. For example, the amount is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts by weight, or any value therebetween. In some preferred embodiments, the amount of the first chelating agent is 10, 12, 14, 15, 16, 18, or 20 parts by weight.

[0047] In some embodiments, the second chelating agent is present in the silicon material cleaning agent in an amount of 10 to 20 parts by weight. For example, the amount is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts by weight, or any value therebetween. In some preferred embodiments, the amount of the second chelating agent is 10, 12, 13, 15, 16, 17, or 20 parts by weight.

[0048] In some embodiments, the surfactant is present in the silicon material cleaning agent in an amount of 0.5 to 5 parts by mass. For example, the surfactant is present in an amount of 0.5, 0.6, 0.8, 1, 1.2, 1.5, 1.7, 2.1, 2.2, 2.4, 2.9, 3, 3.3, 3.6, 4, 4.2, 4.5, 4.8, or 5 parts by mass, or any value therebetween. In some preferred embodiments, the surfactant is present in an amount of 0.5, 1, 1.5, 2, 3, or 5 parts by mass.

[0049] In some embodiments, the silicon material cleaning agent comprises 5 to 15 parts by weight of the builder, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts, or any value therebetween. In some preferred embodiments, the builder comprises 5, 6, 8, 10, 12, 13, or 15 parts.

[0050] A second aspect of the present application provides a method for preparing the above-mentioned silicon material cleaning agent, comprising the following steps:

[0051] The first chelating agent and the second chelating agent are completely dissolved in water in sequence, and then an acidic etching solution is added and completely dissolved, and then a surfactant is added and completely dissolved, and then a builder is added and completely dispersed; finally, stirring is performed for 20 to 45 minutes to prepare the silicon material cleaning agent.

[0052] The conditions for adding each component are as follows: when adding the subsequent component, it is necessary to ensure that the component added in the previous step has been completely dissolved or dispersed. Specifically, each component is completely dissolved or dispersed in sequence by sufficient stirring.

[0053] In some embodiments, the specific steps of adding the acidic etching solution and dissolving it completely are: adding each component substance in the acidic etching solution one by one and dissolving them one by one.

[0054] In some preferred embodiments, the stirring speed is 80 rpm to 300 rpm.

[0055] In some preferred embodiments, the stirring temperature is 20°C to 24°C.

[0056] In a third aspect, the present application provides a use of the silicon material cleaning agent described in the second aspect in silicon material cleaning.

[0057] Specifically, the silicon material cleaning agent of the present application is used for silicon material cleaning. Experimental verification shows that the silicon material cleaning agent of the present application can wash away multiple metal ions at one time and can effectively reduce the residual ions to below 200 ppbw.

[0058] Preparation Example

[0059] The technical solution of the present application is further illustrated below through specific examples. The embodiments described in this application are only some of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application. The raw materials and substances used in the following preparation examples and comparative examples of this application are all commercially purchased. Among them, deionized water is used for water, and electronic grade fluorosilicic acid with a mass concentration of 33% is used for fluorosilicic acid. Fluorocarbon surfactants are purchased from FS-3100 (Capstone TM FS-3100, Chemours Chemical (Shanghai) Co., Ltd.), FS-30 (Capstone TM FS-30, Chemours Chemical (Shanghai) Co., Ltd.), FS-3000 (Capstone TM FS-3000, Chemours Chemical (Shanghai) Co., Ltd.), FC327, FCF-204 (Guangzhou Shunrun New Material Technology Co., Ltd.), FCF-206 (Guangdong Tianren Technology Co., Ltd.).

[0060] Preparation Example 1

[0061] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0062]

[0063] The specific preparation steps are as follows: at a speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and completely dissolved, followed by adding 10 g of citric acid and completely dissolved, then adding 7 g of aminosulfonic acid and completely dissolved, 8 g of fluorosilicic acid and completely dissolved, 8 g of trifluoroacetic acid and completely dissolved, then adding 1 g of FS-3100 and completely dissolved, and finally adding 5 g of N-methylpyrrolidone and completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-1.

[0064] Preparation Example 2

[0065] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0066]

[0067] The specific preparation steps are as follows: at a speed of 200 rpm, 54 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 16 g of HEDP is added thereto and completely dissolved, followed by adding 12 g of gluconic acid and completely dissolved, 5 g of aminomethanesulfonic acid and completely dissolved, 10 g of fluorosilicic acid and completely dissolved, 10 g of trifluoroacetic acid and completely dissolved, then 3 g of FCF-206 is added and completely dissolved, and finally 10 g of N-methylpyrrolidone is added and completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 30 ° C and a speed of 200 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-2.

[0068] Preparation Example 3

[0069] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0070]

[0071]

[0072] The specific preparation steps are as follows: at a speed of 100 rpm, 60 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 10 g of HEDP is added thereto and it is completely dissolved, followed by adding 20 g of tartaric acid and waiting for it to be completely dissolved, and then adding 9 g of benzenesulfonic acid and waiting for it to be completely dissolved, 2 g of fluorosilicic acid and waiting for it to be completely dissolved, 4 g of trifluoroethylamine and waiting for it to be completely dissolved, and then adding 5 g of FS-30 and waiting for it to be completely dissolved, and finally adding 8 g of N-methylpyrrolidone and waiting for it to be completely dispersed. After the preparation is completed, cover with plastic wrap and stir in a constant temperature water bath at 25 ° C and a speed of 100 rpm for 40 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-3.

[0073] Preparation Example 4

[0074] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0075]

[0076] The specific preparation steps are as follows: at a speed of 80 rpm, 56 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 20 g of HEDP is added thereto and it is completely dissolved, followed by adding 15 g of malic acid and waiting for it to be completely dissolved, and then adding 10 g of benzenesulfonic acid and waiting for it to be completely dissolved, 10 g of fluorosilicic acid and waiting for it to be completely dissolved, 10 g of trifluoroacetic acid and waiting for it to be completely dissolved, and then adding 0.5 g of FS-3000 and waiting for it to be completely dissolved, and finally adding 15 g of methyl isobutyl ketone and waiting for it to be completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 20 ° C and a speed of 80 rpm for 40 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-4.

[0077] Preparation Example 5

[0078] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0079]

[0080] The specific preparation steps are as follows: at a speed of 210 rpm, 60 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 12 g of HEDP is added thereto and it is completely dissolved, followed by adding 12 g of potassium pyrophosphate and it is completely dissolved, and then 12 g of benzenesulfonic acid is added and it is completely dissolved, 16 g of fluorosilicic acid is added and it is completely dissolved, 2 g of trifluoroacetic acid is added and it is completely dissolved, and then 0.5 g of FC327 is added and it is completely dissolved, and finally 13 g of methyl isobutyl ketone is added and it is completely dispersed. After the preparation is completed, the plastic wrap is covered and the temperature is controlled in a constant temperature water bath at 25 ° C and a speed of 210 rpm for 20 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-5.

[0081] Preparation Example 6

[0082] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0083]

[0084] The specific preparation steps are as follows: at a speed of 200 rpm, 54 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 15 g of HEDP is added thereto and it is completely dissolved, followed by adding 17 g of sodium pyrophosphate and waiting for it to be completely dissolved, and then adding 5 g of benzenesulfonic acid and waiting for it to be completely dissolved, 5 g of fluorosilicic acid and waiting for it to be completely dissolved, and 5 g of trifluoroacetic acid and waiting for it to be completely dissolved, followed by adding 2 g of FCF-204 and waiting for it to be completely dissolved, and finally adding 5 g of methyl isobutyl ketone and waiting for it to be completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25 ° C and a speed of 200 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-6.

[0085] Preparation Example 7

[0086] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0087]

[0088] The specific preparation steps are as follows: at a speed of 150 rpm, 58 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and completely dissolved, followed by adding 20 g of sodium citrate and completely dissolved, 5 g of aminosulfonic acid and completely dissolved, 8 g of fluorosilicic acid and completely dissolved, 8 g of trifluoroacetic acid and completely dissolved, then 1 g of FCF-204 is added and completely dissolved, and finally 15 g of methylpyrrolidone is added and completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 40 ° C and a speed of 150 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-7.

[0089] Preparation Example 8

[0090] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0091]

[0092] The specific preparation steps are as follows: at a speed of 200 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and it is completely dissolved, followed by adding 10 g of sodium gluconate and it is completely dissolved, and then 6 g of aminosulfonic acid is added and it is completely dissolved, 4 g of benzenesulfonic acid is added and it is completely dissolved, 8 g of fluorosilicic acid is added and it is completely dissolved, and then 1 g of FS-30 is added and it is completely dissolved, and finally 6 g of N-methylpyrrolidone is added and it is completely dispersed. After the preparation is completed, the plastic wrap is covered and the temperature is controlled in a constant temperature water bath at 20 ° C and a speed of 200 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-8.

[0093] Preparation Example 9

[0094] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0095]

[0096] The specific preparation steps are as follows: at a speed of 300 rpm, 56 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 12 g of EDTA is added thereto and it is completely dissolved, followed by adding 10 g of citric acid and waiting for it to be completely dissolved, and then adding 4 g of benzenesulfonic acid and waiting for it to be completely dissolved, 6 g of fluorosilicic acid and waiting for it to be completely dissolved, 10 g of trifluoroacetic acid and waiting for it to be completely dissolved, and then adding 2 g of FCF-204 and waiting for it to be completely dissolved, and finally adding 10 g of N-methylpyrrolidone and waiting for it to be completely dispersed. After the preparation is completed, the plastic wrap is covered and the mixture is stirred and temperature controlled in a constant temperature water bath at 25 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-9.

[0097] Preparation Example 10

[0098] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0099]

[0100] The specific preparation steps are as follows: at a speed of 260 rpm, 60 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 12 g of EDTA is added thereto and it is completely dissolved, followed by adding 20 g of gluconic acid and waiting for it to be completely dissolved, and then adding 7 g of aminosulfonic acid and waiting for it to be completely dissolved, 8 g of fluorosilicic acid and waiting for it to be completely dissolved, and 8 g of trifluoroacetic acid and waiting for it to be completely dissolved, followed by adding 0.5 g of FS-3100 and waiting for it to be completely dissolved, and finally adding 5 g of N-methylpyrrolidone and waiting for it to be completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25 ° C and a speed of 260 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-10.

[0101] Preparation Example 11

[0102] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0103]

[0104] The specific preparation steps are as follows: at a speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 10 g of EDTA is added thereto and it is completely dissolved, followed by adding 13 g of tartaric acid and waiting for it to be completely dissolved, and then adding 6 g of aminosulfonic acid and waiting for it to be completely dissolved, 12 g of fluorosilicic acid and waiting for it to be completely dissolved, 12 g of trifluoroacetic acid and waiting for it to be completely dissolved, and then adding 1.5 g of FS-3000 and waiting for it to be completely dissolved, and finally adding 12 g of N-methylpyrrolidone and waiting for it to be completely dispersed. After the preparation is completed, cover with plastic wrap and stir in a constant temperature water bath at 20 ° C and a speed of 300 rpm for 20 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-11.

[0105] Preparation Example 12

[0106] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0107]

[0108] The specific preparation steps are as follows: at a speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 18 g of EDTA is added thereto and it is completely dissolved, followed by adding 15 g of malic acid and waiting for it to be completely dissolved, then adding 8 g of aminosulfonic acid and waiting for it to be completely dissolved, 4 g of fluorosilicic acid and waiting for it to be completely dissolved, 6 g of benzenesulfonic acid and waiting for it to be completely dissolved, then adding 3 g of FS-30 and waiting for it to be completely dissolved, and finally adding 5 g of methyl isobutyl ketone and waiting for it to be completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 20 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-12.

[0109] Preparation Example 13

[0110] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0111]

[0112] The specific preparation steps are as follows: at a speed of 300 rpm, 54 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of EDTA is added thereto and it is completely dissolved, followed by adding 10 g of potassium pyrophosphate and it is completely dissolved, and then 5 g of benzenesulfonic acid is added and it is completely dissolved, 5 g of fluorosilicic acid is added and it is completely dissolved, 5 g of fluoroboric acid is added and it is completely dissolved, and then 5 g of FC327 is added and it is completely dissolved, and finally 15 g of methyl isobutyl ketone is added and it is completely dispersed. After the preparation is completed, the plastic wrap is covered and the temperature is controlled in a constant temperature water bath at 25 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-13.

[0113] Preparation Example 14

[0114] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0115]

[0116]

[0117] The specific preparation steps are as follows: at a speed of 300 rpm, 60 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 12 g of EDTA is added thereto and it is completely dissolved, followed by adding 13 g of sodium pyrophosphate and waiting for it to be completely dissolved, and then adding 8 g of aminosulfonic acid and waiting for it to be completely dissolved, 12 g of fluorosilicic acid and waiting for it to be completely dissolved, 4 g of trifluoroacetic acid and waiting for it to be completely dissolved, and then adding 0.5 g of FCF-206 and waiting for it to be completely dissolved, and finally adding 10 g of N-methylpyrrolidone and waiting for it to be completely dispersed. After the preparation is completed, the plastic wrap is covered and the temperature is controlled in a constant temperature water bath at 25 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-14.

[0118] Preparation Example 15

[0119] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0120]

[0121] The specific preparation steps are as follows: at a speed of 200 rpm, 56 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 20 g of EDTA is added thereto and it is completely dissolved, followed by adding 17 g of sodium citrate and waiting for it to be completely dissolved, and then adding 6 g of aminosulfonic acid and waiting for it to be completely dissolved, 6 g of fluorosilicic acid and waiting for it to be completely dissolved, 10 g of trifluoroacetic acid and waiting for it to be completely dissolved, and then adding 3 g of FS-30 and waiting for it to be completely dissolved, and finally adding 12 g of methyl isobutyl ketone and waiting for it to be completely dispersed. After the preparation is completed, the plastic wrap is covered and the mixture is stirred and temperature controlled in a constant temperature water bath at 25 ° C and a speed of 200 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-15.

[0122] Preparation Example 16

[0123] The specific components and preparation method of the silicon material cleaning agent of this embodiment are as follows:

[0124]

[0125] The specific preparation steps are as follows: at a speed of 300 rpm, 55 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 18 g of EDTA is added thereto and it is completely dissolved, followed by adding 16 g of sodium gluconate and it is completely dissolved, and then 12 g of aminosulfonic acid is added and it is completely dissolved, 10 g of benzenesulfonic acid is added and it is completely dissolved, 8 g of trifluoroacetic acid is added and it is completely dissolved, and then 3 g of FCF-204 is added and it is completely dissolved, and finally 10 g of N-methylpyrrolidone is added and it is completely dispersed. After the preparation is completed, the plastic wrap is covered and the temperature is controlled in a constant temperature water bath at 25 ° C and a speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this embodiment, which is recorded as S-16.

[0126] Preparation Comparative Example 1

[0127] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0128]

[0129]

[0130] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP·Na is added thereto and the mixture is completely dissolved, 10 g of citric acid is added thereto and the mixture is completely dissolved, 7 g of aminosulfonic acid is added thereto and the mixture is completely dissolved, 8 g of fluorosilicic acid is added thereto and the mixture is completely dissolved, 8 g of trifluoroacetic acid is added thereto and the mixture is completely dissolved, 1 g of FS-3100 is added thereto and the mixture is completely dissolved, and finally 2 g of N-methylpyrrolidone is added thereto and the mixture is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25° C. and a rotation speed of 300 rpm for 30 minutes to prepare the silicon material cleaning agent of this comparative example, which is recorded as D-1.

[0131] Preparation Comparative Example 2

[0132] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0133]

[0134] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP·Na is added thereto and the mixture is completely dissolved, 10 g of sodium citrate is added thereto and the mixture is completely dissolved, 7 g of aminosulfonic acid is added thereto and the mixture is completely dissolved, 8 g of fluorosilicic acid is added thereto and the mixture is completely dissolved, 8 g of trifluoroacetic acid is added thereto and the mixture is completely dissolved, 1 g of FS-3100 is added thereto and the mixture is completely dissolved, and finally 5 g of N-methylpyrrolidone is added thereto and the mixture is completely dispersed, and then 5 g of diethanolamine is added thereto and the mixture is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25° C. and a rotation speed of 300 rpm for 30 minutes to prepare the silicon material cleaning agent of this comparative example, which is recorded as D-2.

[0135] Preparation Comparative Example 3

[0136] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0137]

[0138] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 10 g of citric acid is added thereto and is completely dissolved, followed by adding 7 g of aminosulfonic acid and being completely dissolved, 8 g of fluorosilicic acid and being completely dissolved, 8 g of trifluoroacetic acid and being completely dissolved, and then 1 g of FS-3100 is added and is completely dissolved, and finally 5 g of N-methylpyrrolidone is added and is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25 ° C and a rotation speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this comparative example, which is recorded as D-3.

[0139] Preparation Comparative Example 4

[0140] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0141]

[0142] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and is completely dissolved, followed by the addition of 7 g of aminosulfonic acid and the complete dissolution thereof, 8 g of fluorosilicic acid and the complete dissolution thereof, 8 g of trifluoroacetic acid and the complete dissolution thereof, and then 1 g of FS-3100 is added and is completely dissolved, and finally 5 g of N-methylpyrrolidone is added and is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25° C. and a rotation speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this comparative example, which is recorded as D-4.

[0143] Preparation Comparative Example 5

[0144] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0145]

[0146] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and it is completely dissolved, then 10 g of citric acid is added and it is completely dissolved, then 1 g of FS-3100 is added and it is completely dissolved, and finally 5 g of N-methylpyrrolidone is added and it is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25 ° C and a rotation speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this comparative example, which is recorded as D-5.

[0147] Preparation Comparative Example 6

[0148] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0149]

[0150] The specific preparation steps are as follows: at a rotation speed of 300 rpm, 50 g of deionized water is added to a 500 mL polytetrafluoroethylene beaker, 14 g of HEDP is added thereto and is completely dissolved, followed by the addition of 10 g of citric acid and the complete dissolution thereof, followed by the addition of 7 g of aminosulfonic acid and the complete dissolution thereof, 8 g of fluorosilicic acid and the complete dissolution thereof, and 8 g of trifluoroacetic acid and the complete dissolution thereof, followed by the addition of 1 g of OP-10 and the complete dissolution thereof, and finally, 5 g of N-methylpyrrolidone is added and is completely dispersed. After the preparation is completed, the mixture is covered with plastic wrap and stirred in a constant temperature water bath at 25° C. and a rotation speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this comparative example, which is recorded as D-6.

[0151] Preparation Comparative Example 7

[0152] The specific components and preparation method of the silicon material cleaning agent of this comparative example are as follows:

[0153] 15g of 48% hydrofluoric acid

[0154] 85g of 69% concentrated nitric acid

[0155] The specific preparation steps are as follows: 15 g of 48% hydrofluoric acid and 85 g of 69% concentrated nitric acid were added to a 500 mL polytetrafluoroethylene beaker at a rotation speed of 300 rpm. After the preparation was completed, the mixture was covered with plastic wrap and stirred in a constant temperature water bath at 40° C. and a rotation speed of 300 rpm for 30 minutes to obtain the silicon material cleaning agent of this comparative example, which was recorded as D-7.

[0156] Performance and index testing

[0157] Test Method

[0158] The silicon material cleaning agents prepared in the above examples and comparative examples of the present application were used to clean silicon materials and their performance was tested.

[0159] 1. Silicon material cleaning method: Take a 500mL polytetrafluoroethylene cleaning tank and completely immerse the silicon material in the newly prepared silicon material cleaning agent; let it stand in a constant temperature water bath at 25℃ for 30 minutes; pick up the cleaned silicon material with polytetrafluoroethylene tweezers and place it in a polytetrafluoroethylene funnel. Spray and rinse the residual cleaning agent on the surface of the silicon material with deionized water for 2 minutes; purge the silicon material surface with nitrogen for 2 minutes to clean it.

[0160] 2. Performance testing:

[0161] 2.1 Detection of metal ions on silicon material surface

[0162] Test method: GB / T 24582-2009 "Determination of metallic impurities on the surface of polycrystalline silicon by acid leaching-inductively coupled plasma mass spectrometry";

[0163] Testing instrument: ICP-MS (Agilent 7700s);

[0164] Test environment: ISO Class 5 cleanroom requirements as defined in GB / T 25915.1-2010 “Cleanrooms and associated controlled environments — Part 1: Grades of air cleanliness”.

[0165] 2.2 Cleaning power W:

[0166] The calculation formula of cleaning force W is:

[0167] Wherein, A represents the metal ion content on the surface of the silicon material before cleaning; B represents the metal ion content on the surface of the silicon material after cleaning.

[0168] 2.3 Oil stains and oxidation color

[0169] Test method: visual.

[0170] 1) When the silicone surface is contaminated with oil, the surface will be visually stained with oily liquids such as lubricants and engine oil, and the surface will be dull. After cleaning with silicone cleaning agent, the surface will be visually free of visible oily liquid residue and will have a metallic luster.

[0171] 2) When the silicon material surface has an oxidized color, the visual state is that the surface has a rainbow-colored reflective band. After cleaning with a silicon material cleaning agent, the visual state is that the silicon material surface has a silvery white metallic luster.

[0172] Test results

[0173] According to the above test method, the silicon material cleaning agents of Examples 1 to 16 of the present application and the silicon material cleaning agents of Comparative Examples 1 to 7 were used to clean silicon material. The results of the total metal ion content on the silicon material surface before and after cleaning are shown in Table 1. The cleaning power of the corresponding silicon material cleaning agents, the oxidation color and oil stain status of the silicon material surface after cleaning, and whether gas is generated and heat is released during the cleaning process are shown in Table 2.

[0174] Table 1

[0175]

[0176]

[0177] According to Table 1, the silicon material cleaning agents of the present invention and the comparative example were used to clean silicon material. Surface metal ion detection results show that the silicon material cleaning agents prepared in Examples 1 to 16 of the present invention achieved a total metal ion content on the silicon material surface of less than 200 ppbw, specifically 26.92 ppbw to 197.12 ppbw. In contrast, the total metal ion content on the silicon material surface after cleaning in the comparative example ranged from 226.02 ppbw to 3154.28 ppbw.

[0178] Table 2

[0179] Silicon material cleaning agent Cleaning power / % Oxidation color Oil pollution Whether gas is generated Is it exothermic? S-1 99.22％ no no no no S-2 98.25％ no no no no S-3 98.24％ no no no no S-4 98.57％ no no no no S-5 96.71％ no no no no S-6 97.02％ no no no no S-7 96.87％ no no no no S-8 96.57％ no no no no S-9 98.27％ no no no no S-10 98.23％ no no no no S-11 98.24％ no no no no S-12 98.12％ no no no no S-13 95.89％ no no no no S-14 96.45％ no no no no S-15 96.20％ no no no no S-16 96.41％ no no no no D-1 69.80％ no no no no D-2 68.19％ no no no no D-3 73.74％ no no no no D-4 66.06％ no no no no D-5 46.75％ have no no no D-6 75.44％ no no no no D-7 96.20％ no no yes yes

[0180] Combining the test results in Table 1 and Table 2, it can be seen that the silicon material cleaning agents prepared in Examples 1 to 16 of the present application are used to clean the silicon material. Compared with Comparative Examples 1 to 7, under the conditions of a single cleaning test, the silicon material cleaning agents prepared in the examples of the present application have a stronger cleaning effect.

[0181] Specifically, compared with its corresponding salt system (Comparative Example 1), alkaline environment (Comparative Example 2) or single chelating agent (Comparative Example 3, Comparative Example 4), the two-component chelating agent under acidic conditions of the present application has stronger chelation and stability for impurity ions. This may be because HEDP or EDTA both have a polyacid structure and have better hydrophilicity and chelation stability. However, the alkaline environment maintained by HEDP·Na or diethanolamine changes the system environment or introduces additional sodium ions, which destroys the chelation stability. In addition, when a salt chelating agent is selected as a formula cleaning agent, the potassium and sodium ion content on the surface of the silicon material after cleaning is significantly higher.

[0182] The silicon material cleaning agent system of the present application is also used in conjunction with an acidic etching solution. Compared with the case where no acidic etching solution is used (Comparative Example 5), the use of the acidic etching solution can strip off the metal ions on the surface of the silicon material, promote the rapid complexation of the chelating agent and the metal ions on the surface of the silicon material, and effectively remove the oxidation color of the silicon material.

[0183] The silicon material cleaning agent system of the present application also uses a fluorocarbon surfactant. Compared with the conventional non-ionic surfactant OP-10 (Comparative Example 6), the silicon material cleaning agent of the present application has a better cleaning effect. This may be because the introduction of the fluorocarbon surfactant effectively reduces the surface tension of the solution, greatly increasing the silicon material cleaning agent's ability to coat and remove various impurities on the silicon material surface. At the same time, the fluorocarbon surfactant used in the present application is more stable in the acidic system of the silicon material cleaning agent.

[0184] In order to better illustrate the test results of the acidic silicon material cleaning agent of the present application and the traditional acid cleaning (HF+HNO3), that is, compared with Comparative Example 7, it can be seen that the silicon material cleaning agent of the present application will not produce a large amount of toxic yellow smoke exhaust gas during the cleaning process, nor will it release a large amount of heat. The silicon material cleaning agent of the present application is a silicon material cleaning agent suitable for use in a mild process environment. It is safe for operators to use and has high cleaning efficiency, which is conducive to simplifying and reducing the cost of silicon material cleaning.

[0185] Specifically, Figure 1 The surface state of the silicon material before and after cleaning is compared using the silicon material cleaning agent S-1 prepared in Example 1 of the present application. Figure 1 -(a) shows a dark background with a distinct rainbow-like color band area on it. This is due to the formation of oil, various metal ions and surface oxide layer attached to the surface of the silicon material during the cutting process. The surface state of the silicon material after cleaning is shown in Figure 2. Figure 1 -(b), the surface of the silicon material after cleaning is bright silver-white and presents a metallic luster. Therefore, it can be seen that the silicon material cleaning agent of the present application can achieve an efficient cleaning state of the silicon material surface after a single cleaning.

[0186] The preferred embodiments of the present invention are described in detail above. However, the present application is not limited to the specific details in the above embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

Claims

1. A silicon material cleaning agent, characterized in that: The silicon material cleaning agent comprises the following components in parts by mass: Water: 50-60 parts; Acidic etching solution: 15-30 parts; First chelating agent: 10-20 parts; Second chelating agent: 10-20 parts; Surfactant: 0.5-5 parts; Detergent: 5-15 parts; Wherein, the first chelating agent is selected from at least one of hydroxyethylidene diphosphonic acid or ethylenediaminetetraacetic acid; The second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid, malic acid, sodium citrate, sodium gluconate, potassium pyrophosphate, and sodium pyrophosphate.

2. The silicon material cleaning agent according to claim 1, characterized in that The first chelating agent is selected from hydroxyethylidene diphosphonic acid.

3. The silicon material cleaning agent according to claim 1, characterized in that The second chelating agent is selected from at least one of citric acid, gluconic acid, tartaric acid and malic acid.

4. The silicon material cleaning agent according to claim 1, characterized in that The surfactant is a fluorocarbon surfactant.

5. The silicon material cleaning agent according to claim 4, characterized in that: The fluorocarbon surfactant is selected from at least one of FS-3100, FS-30, FC327, FS-3000, FCF-204 and FCF-206.

6. The silicon material cleaning agent according to claim 1, characterized in that The acidic etching solution is selected from at least three of fluorosilicic acid, trifluoroacetic acid, benzenesulfonic acid and aminosulfonic acid.

7. The silicon material cleaning agent according to claim 1, characterized in that The builder is selected from ketone solvents having 5 to 10 carbon atoms.

8. The method for preparing the silicon material cleaning agent according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: completely dissolving a first chelating agent and a second chelating agent in water in sequence, then adding an acidic etching solution and completely dissolving the etching solution, then adding a surfactant and completely dissolving the etching solution, then adding a builder and completely dispersing the builder, and finally stirring the builder for 20 to 45 minutes to obtain the silicon material cleaning agent.

9. Use of the silicon material cleaning agent according to claim 8 in cleaning silicon materials.

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