阅读说明：本技术 一种碳化硅单晶片清洗剂及其制备方法和应用 (Silicon carbide single crystal wafer cleaning agent and preparation method and application thereof ) 是由 包亚群 罗壮东 刘长海 于 2019-10-18 设计创作，主要内容包括：本发明提供一种碳化硅单晶片清洗剂及其制备方法和应用,所述碳化硅单晶片清洗剂按质量百分比包括：螯合剂20-30％、聚乙二醇1-5％、异辛醇聚氧乙烯醚1-5％、聚氧乙烯聚氧丙烯嵌段聚醚1-5％和增溶剂1-10％,余量为水；所述螯合剂为柠檬酸钾和葡萄糖酸钾的混合物。本发明所述碳化硅单晶片清洗剂呈弱碱性,对晶片无腐蚀现象,操作安全性能高,且对于清洗碳化硅单晶片各加工工段的不同脏污都具有良好的清洗效果。(The invention provides a silicon carbide single crystal wafer cleaning agent and a preparation method and application thereof, wherein the silicon carbide single crystal wafer cleaning agent comprises the following components in percentage by mass: 20-30% of chelating agent, 1-5% of polyethylene glycol, 1-5% of isooctanol polyoxyethylene ether, 1-5% of polyoxyethylene polyoxypropylene block polyether, 1-10% of solubilizer and the balance of water; the chelating agent is a mixture of potassium citrate and potassium gluconate. The silicon carbide single crystal wafer cleaning agent disclosed by the invention is weakly alkaline, has no corrosion phenomenon on wafers, is high in operation safety performance, and has a good cleaning effect on different stains at each processing section of the silicon carbide single crystal wafer.)

1. The silicon carbide single crystal wafer cleaning agent is characterized by comprising the following components in percentage by mass: 20-30% of chelating agent, 1-5% of polyethylene glycol, 1-5% of isooctanol polyoxyethylene ether, 1-5% of polyoxyethylene polyoxypropylene block polyether, 1-10% of solubilizer and the balance of water;

the chelating agent is a mixture of potassium citrate and potassium gluconate.

2. The silicon carbide single-crystal wafer cleaning agent as claimed in claim 1, wherein the cleaning agent comprises, by mass: 20-24% of chelating agent, 2-3% of polyethylene glycol, 3-5% of isooctanol polyoxyethylene ether, 1-2% of polyoxyethylene polyoxypropylene block polyether, 5-8% of solubilizer and the balance of water;

the chelating agent is a mixture of potassium citrate and potassium gluconate.

3. The silicon carbide single-crystal wafer cleaning agent according to claim 1 or 2, wherein the chelating agent contains potassium citrate and potassium gluconate in a mass ratio of (1.2-2): 1.

4. The cleaning agent for silicon carbide single crystal wafer as set forth in any one of claims 1 to 3, wherein the polyethylene glycol has a number average molecular weight of 400-.

5. The silicon carbide single-crystal wafer cleaning agent according to any one of claims 1 to 4, wherein the isooctanol polyoxyethylene ether has an EO number of 7 to 10, preferably 7.

6. The silicon carbide single-crystal wafer cleaning agent as set forth in any one of claims 1 to 5, wherein the polyoxyethylene polyoxypropylene block polyether has a number average molecular weight of 2000-3000;

preferably, the polyoxyethylene polyoxypropylene block polyether has a relative HBL value of 3-13;

preferably, the polyoxyethylene polyoxypropylene block polyether is selected from any one of polyether L61, polyether L62, polyether L63 or polyether L64 or a combination of at least two of the polyether L62 and/or polyether L64.

7. The silicon carbide single crystal wafer cleaning agent according to any one of claims 1 to 6, wherein the solubilizer is selected from any one or a combination of at least two of ethylene glycol, propylene glycol, glycerol, isopropyl alcohol or diethylene glycol monobutyl ether, preferably glycerol.

8. The silicon carbide single crystal wafer cleaning agent according to any one of claims 1 to 7, wherein the cleaning agent further comprises coconut alcohol polyoxyethylene ether;

preferably, the coconut oil alcohol polyoxyethylene ether has an EO number of 8 to 12, preferably 10;

preferably, the mass percentage content of the coconut oil alcohol polyoxyethylene ether in the cleaning agent is 0.05-1.0%.

9. The preparation method of the silicon carbide single-crystal wafer cleaning agent according to any one of claims 1 to 8, characterized in that the preparation method comprises: adding a chelating agent, polyethylene glycol, isooctanol polyoxyethylene ether, polyoxyethylene polyoxypropylene block polyether and a solubilizer into water according to the formula ratio, and stirring and mixing to obtain the silicon carbide single-chip cleaning agent;

preferably, the temperature of the stirring is 40-60 ℃.

10. Use of the silicon carbide single-crystal wafer cleaning agent according to any one of claims 1 to 8 for cleaning semiconductor chips.

Technical Field

The invention belongs to the technical field of cleaning agents, particularly relates to a cleaning agent, and a preparation method and application thereof, and particularly relates to a silicon carbide single crystal wafer cleaning agent, and a preparation method and application thereof.

Background

In the application of semiconductor devices, along with the reduction of the production cost of silicon carbide, the silicon carbide can replace silicon as a chip due to the excellent performance of the silicon carbide, the bottleneck of the performance of the silicon chip due to the material is broken, and revolutionary revolution is brought to the electronic industry. In the production and processing processes of silicon carbide wafers, processes such as cutting, grinding, polishing and the like are required, and different dirt residues are generated in different processing processes, so that the invention of a cleaning agent for the silicon carbide wafers is necessary to solve the technical problems. As a cleaning agent for a polished silicon carbide single crystal substrate, a chemical solution having a high concentration of a strong acid (sulfuric acid, hydrochloric acid) or an alkali (ammonia water) and hydrofluoric acid added to hydrogen peroxide as a base is generally used. However, the use of highly concentrated hydrogen peroxide of strong acid or strong basicity or highly toxic hydrofluoric acid at high temperature has problems not only in workability but also in corrosion resistance around the cleaning apparatus and exhaust equipment.

CN102449745A discloses a method for cleaning a substrate for a silicon carbide semiconductor, comprising a first cleaning step of cleaning a substrate for a semiconductor using a cleaning agent composition, and a second cleaning step of cleaning the substrate for a semiconductor cleaned in the first cleaning step using an acidic solution containing a chelating agent, the cleaning agent composition containing: comprises a water-soluble salt of a transition metal, a polycarboxylic acid compound and a peroxide. Although the composition for the cleaning agent can clean different dirt residues generated in a processing process, the composition has strong acidity and low operation safety, and a large amount of pure water is required to be used for a washing process after cleaning treatment, so that the load of the treated wastewater on the environment is large.

CN104928060A discloses a silicon chip anticorrosion cleaning agent, which is composed of the following raw materials in percentage by weight: 0.5-2.5% of potassium hydroxide, 4-8% of fatty alcohol polyoxyethylene (7) ether, 0.4-0.8% of ethylene glycol butyl ether, 0.4-0.8% of perfluoroalkyl ethoxy ether alcohol, 0.2-1% of complex, 2-4% of tetramethyl ammonium hydroxide, 0.1-0.3% of sodium carboxymethyl cellulose and the balance of deionized water. Although the anticorrosive cleaning agent has strong decontamination capability, the anticorrosive cleaning agent contains potassium hydroxide and tetramethyl ammonium hydroxide, has strong alkalinity and strong corrosivity to silicon wafers, and is not suitable for cleaning photovoltaic and semiconductor silicon wafers.

Therefore, it is very necessary to develop a green and environment-friendly silicon carbide single crystal wafer cleaning agent with good cleaning effect and high safety performance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a cleaning agent, a preparation method and application thereof, and particularly provides a cleaning agent for a silicon carbide single crystal wafer, a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a silicon carbide single crystal wafer cleaning agent, which comprises the following components in percentage by mass: 20-30% of chelating agent, 1-5% of polyethylene glycol, 1-5% of isooctanol polyoxyethylene ether, 1-5% of polyoxyethylene polyoxypropylene block polyether, 1-10% of solubilizer and the balance of water;

the chelating agent is a mixture of potassium citrate and potassium gluconate.

In the present invention, the content of the chelating agent is 20 to 30%, and may be, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.

In the present invention, the content of the polyethylene glycol is 1 to 5%, and for example, may be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

In the present invention, the isooctanol polyoxyethylene ether content is 1 to 5%, and may be, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

In the present invention, the polyoxyethylene polyoxypropylene block polyether content is 1-5%, and may be, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

In the present invention, the content of the solubilizer is 1 to 10%, and may be, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

In the invention, the mixture of potassium citrate and potassium gluconate is used as a chelating agent, the solubility is good, the potassium citrate and potassium gluconate are matched with each other, the synergistic effect is realized, the potassium citrate and potassium gluconate can be quickly complexed with metal ions such as calcium ions, magnesium ions and the like in water at a lower temperature to generate good flocculation and quick sedimentation, the difficulty of the metal ions in the water on cleaning is eliminated, and the potassium citrate and the potassium gluconate are both alkalescent, have high safety and do not corrode a wafer.

In the invention, the polyethylene glycol has good compatibility, and can reduce the freezing point of an aqueous solution, so that the cleaning agent still has no icing phenomenon at a lower temperature.

In the invention, the isooctanol polyoxyethylene ether is used as a nonionic surfactant, has no toxicity and small irritation, has good wetting, emulsifying, decontaminating, descaling, solubilizing, foaming, dispersing and lubricating performances, and is easy to be compatible with various active ingredients for use so as to improve the dynamic surface tension. The polyoxyethylene polyoxypropylene block polyether is specifically a Polyoxyethylene (PEO) -polyoxypropylene (PPO) block copolymer, and a high-molecular polyether type nonionic surfactant which takes polyoxypropylene as a hydrophobic group and polyoxyethylene as a hydrophilic group has the characteristics of no toxicity, no irritation and good stability, is matched with isooctanol polyoxyethylene ether, has the function of coordination and synergism, greatly improves the water solubility (cloud point rise) of the cleaning agent, maintains the permeability, and greatly improves the emulsification rate, thereby improving the washing performance.

In the invention, the solubilizer can increase the solubility of the cleaning agent, improve the contents of isooctanol polyoxyethylene ether and oxyethylene polyoxypropylene block polyether in the cleaning agent and improve the cleaning capability.

Preferably, the cleaning agent comprises the following components in percentage by mass: 20-24% of chelating agent, 2-3% of polyethylene glycol, 3-5% of isooctanol polyoxyethylene ether, 1-2% of polyoxyethylene polyoxypropylene block polyether, 5-8% of solubilizer and the balance of water;

the chelating agent is a mixture of potassium citrate and potassium gluconate.

Preferably, the mass ratio of potassium citrate to potassium gluconate in the chelating agent is (1.2-2):1, and may be, for example, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2: 1.

Preferably, the number average molecular weight of the polyethylene glycol is 400-.

Preferably, the isooctanol polyoxyethylene ether has an EO number of 7 to 10, and may be, for example, 7, 8, 9, 10, preferably 7.

Preferably, the polyoxyethylene polyoxypropylene block polyether has a number average molecular weight of 2000-.

Preferably, the polyoxyethylene polyoxypropylene block polyether has a relative HBL value of 3-13, which may be, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13.

Preferably, the polyoxyethylene polyoxypropylene block polyether is selected from any one of polyether L61, polyether L62, polyether L63 or polyether L64 or a combination of at least two of the polyether L62 and/or polyether L64.

Preferably, the solubilizer is selected from any one or a combination of at least two of ethylene glycol, propylene glycol, glycerol, isopropanol or diethylene glycol monobutyl ether, preferably glycerol.

Preferably, the cleaning agent further comprises coconut oil alcohol polyoxyethylene ether.

Preferably, the coconut oil alcohol polyoxyethylene ether has an EO number of 8 to 12, which may be, for example, 8, 9, 10, 11, 12, preferably 10.

Preferably, the content of the coconut oil alcohol polyoxyethylene ether in the cleaning agent is 0.05-1.0% by mass, and may be, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.

In a second aspect, the invention provides a preparation method of the silicon carbide single-crystal wafer cleaning agent, which comprises the following steps: adding chelating agent, polyethylene glycol, isooctanol polyoxyethylene ether, polyoxyethylene polyoxypropylene block polyether and solubilizer into water according to the formula ratio, and stirring and mixing to obtain the silicon carbide single crystal wafer cleaning agent.

Preferably, the stirring temperature is 40-60 ℃, for example, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃.

In a third aspect, the invention provides the use of the silicon carbide single crystal wafer cleaning agent as described in the first aspect for cleaning semiconductor chips.

Compared with the prior art, the invention has the following beneficial effects:

(1) the silicon carbide single crystal wafer cleaning agent disclosed by the invention is mild in components, free of stimulation, alkalescent after compatibility, free of corrosion phenomenon on a silicon carbide single crystal wafer and high in operation safety.

(2) The silicon carbide single crystal wafer cleaning agent is suitable for cleaning silicon carbide single crystal wafers after cutting, grinding and polishing processes, has a good cleaning effect on cleaning different stains of each processing section, and can effectively improve the yield of the silicon carbide single crystal wafers. The yield of the cleaned and cut silicon carbide single crystal wafer reaches more than 98%, the yield of the cleaned and ground silicon carbide single crystal wafer reaches more than 97%, and the yield of the cleaned and polished silicon carbide single crystal wafer reaches more than 95%.

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.