阅读说明：本技术 一种新型环保硅晶片清洗试剂及其制备方法及其应用 (Novel environment-friendly silicon wafer cleaning reagent and preparation method and application thereof ) 是由 骆祖文 王鲁艳 朱艳丽 于 2020-03-12 设计创作，主要内容包括：一种新型环保硅晶片清洗试剂及其制备方法及其应用,包括如下质量浓度的物质：氢氧化钾0.2-1.0g/L；硅酸钠0.1-0.8g/L；焦磷酸钾0.1-1.0g/L；络合剂0.01-0.1g/L；渗透剂0.05-0.5g/L；乳化剂0.05-0.5g/L；余量为蒸馏水。本发明的配方中不含有任何有机溶剂和氟离子表面活性剂,本发明所制备的清洗试剂特别适用于单晶硅、多晶硅等硅晶片的清洗,清洗表面均匀光洁,无任何花斑、砂粒、研磨料、金属离子及指纹等残留,通过滤纸擦拭,无任何硅粉等物质残留,能极好的满足客户生产需求,且该工艺环保,生产过程无任何有机溶剂添加,产品环保无污染。(The novel environment-friendly silicon wafer cleaning reagent comprises, by mass, 0.2-1.0 g/L of potassium hydroxide, 0.1-0.8 g/L of sodium silicate, 0.1-1.0 g/L of potassium pyrophosphate, 0.01-0.1 g/L of a complexing agent, 0.05-0.5 g/L of a penetrating agent, 0.05-0.5 g/L of an emulsifying agent and the balance of distilled water.)

1. A novel environment-friendly silicon wafer cleaning reagent is characterized in that: the material comprises the following substances by mass concentration:

0.2-1.0 g/L of potassium hydroxide;

0.1-0.8 g/L of sodium silicate;

potassium pyrophosphate 0.1-1.0 g/L;

0.01-0.1 g/L of complexing agent;

0.05-0.5 g/L of penetrant;

0.05-0.5 g/L of emulsifier;

the balance of distilled water.

2. The novel environmental silicon wafer cleaning reagent according to claim 1, characterized in that: the material comprises the following substances by mass concentration:

0.4-0.6 g/L of potassium hydroxide;

0.2-0.5 g/L of sodium silicate;

0.2-0.5 g/L of potassium pyrophosphate;

0.03-0.06 g/L of complexing agent;

0.1-0.3 g/L of penetrant;

0.1-0.3 g/L of emulsifier;

the balance of distilled water.

3. The novel environmental silicon wafer cleaning reagent according to claim 1, characterized in that: the complexing agent is one or a mixture of any two or more of disodium ethylene diamine tetraacetate, trisodium nitrilotriacetate, sodium aminotrimethylene phosphate, sodium hydroxyethylidene diphosphonate and sodium potassium tartrate in any proportion.

4. The novel environmental silicon wafer cleaning reagent according to claim 1, characterized in that: the penetrating agent is any one or a mixture of more than two of linear octyl polyoxyethylene ether, linear nonyl polyoxyethylene ether, linear decyl polyoxyethylene ether, linear octyl polyoxyethylene polyoxypropylene ether, linear nonyl polyoxyethylene polyoxypropylene ether, linear decyl polyoxyethylene polyoxypropylene ether, branched diethyl hexyl polyoxyethylene ether, diethyl hexyl polyoxyethylene polyoxypropylene ether, diethyl hexyl sodium sulfate and diethyl hexyl sodium phosphate in any proportion.

5. The novel environmental silicon wafer cleaning reagent according to claim 1, characterized in that: the emulsifier is any one or a mixture of more than two of sodium dodecyl benzene sulfonate, sodium decyl benzene sulfonate, sodium dodecyl sulfate, sodium oleate, sodium linoleate, polyoxyethylene lauryl ether, sodium polyoxyethylene lauryl ether phosphate, polyoxyethylene nonylphenol, polyoxyethylene octylphenol ether and octenyl succinic acid in any proportion.

6. The novel environmental silicon wafer cleaning reagent according to claim 1, characterized in that: the pH value is 10-13.

7. The novel environmental silicon wafer cleaning reagent according to claim 6, characterized in that: the pH value is 11-13.

8. A preparation method of a novel environment-friendly silicon wafer cleaning reagent is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: calculating and weighing potassium hydroxide, sodium silicate, potassium pyrophosphate, a complexing agent, a penetrating agent and an emulsifying agent;

step two: adding two thirds of distilled water with theoretical volume into a reaction kettle, starting stirring, adding the required potassium hydroxide, and stirring until the potassium hydroxide is completely dissolved;

step three: adding sodium silicate and potassium pyrophosphate into a reaction kettle, and stirring until the sodium silicate and the potassium pyrophosphate are completely dissolved;

step four: adding complexing agent, penetrating agent and emulsifier, stirring for 3-4h until the solution is clear and transparent;

step five: and (4) fixing the volume according to the required production volume, stirring for 0.5h until the components are fully and uniformly mixed, filtering and packaging to obtain the product.

9. The application of the novel environment-friendly silicon wafer cleaning reagent is characterized in that: the temperature of the cleaning reagent is 30-70 ℃ when the silicon wafer is cleaned; the cleaning time of the cleaning reagent is 20-30 min.

10. The method for preparing the novel environment-friendly silicon wafer cleaning reagent according to claim 9, characterized in that: the cleaning reagent is cleaned in a mode of cleaning reagent soaking ultrasonic oscillation or cleaning reagent spraying when the silicon wafer is cleaned.

Technical Field

The invention belongs to the field of silicon wafer cleaning, and particularly relates to a novel environment-friendly silicon wafer cleaning reagent and a preparation method and application thereof.

Background

With the development of large-scale integrated circuits, the integration level is continuously improved, the line width is continuously reduced, the quality requirement on silicon wafers is higher and higher, and particularly the surface quality requirement on silicon polished wafers is tighter and tighter. This is mainly because particles and metal impurity contamination on the surface of the polishing sheet can seriously affect the quality and yield of the device. In the production of silicon transistors and integrated circuits, almost every procedure has the problem of cleaning silicon wafers, the quality of the silicon wafers has serious influence on the performance of devices, the silicon wafers are not properly processed, the silicon wafers are completely scrapped, qualified products cannot be produced, or the produced products have poor performance and poor stability and reliability.

The silicon material to the usable silicon wafer is subjected to different procedures of slicing, chamfering, grinding, surface treatment, polishing, epitaxy and the like, the silicon wafer processing adopts a multi-line cutting technology, and in the process, the silicon carbide abrasive material cuts the silicon wafer, and sand grains, residual cutting abrasive material, fingerprints and metal ion pollution are formed on the surface of the silicon wafer. The purpose of cleaning is to remove the pollution of particles, metal ions, organic matters and the like on the surface of the silicon wafer, so that the surface of the silicon wafer reaches the technical indexes of no corrosion, no oxidation, no residue and the like. The quality of a grid film generated by subsequent oxidation on the surface of a silicon wafer can be influenced by metal ion pollution such as residues of copper, iron, zinc and the like, so that the component is easy to leak electricity, low in yield and poor in reliability. Surface oxidation of the silicon wafer, fingerprint contamination also affect the photoelectric conversion efficiency.

Traditional washing liquid adopts hydrochloric acid to wash mostly, and hydrochloric acid is strong corrosive substance and smell is big, and the waste liquid after the use is difficult to handle, leads to environmental pollution, and only has certain effect to the metal ion and the oxide layer on silicon wafer surface, and it is poor to get rid of the effect to particulate matter and organic component.

At present, the cleaning agent is a strong alkali liquid cleaning agent in the market, the cleaning effect is obviously improved compared with hydrochloric acid, the cleaning agent has a good removing effect on particulate matters and organic components, but the overall removing effect still cannot completely meet the requirements of customers, the using amount is too large, the cleaning efficiency is low, and the wastewater discharge is increased. In addition, in order to enable the surfactant to be well dispersed in the alkali liquor, a large amount of organic solvent such as ethanol, ethylene glycol butyl ether, diethylene glycol butyl ether and the like is introduced to assist dissolution and assist cleaning, so that a large odor is generated in the production process, and the emission of the organic solvent pollutes the environment.

Disclosure of Invention

The invention provides a novel environment-friendly silicon wafer cleaning reagent, a preparation method and application thereof, which are used for overcoming the defects in the prior art.

The invention is realized by the following technical scheme:

a novel environment-friendly silicon wafer cleaning reagent comprises the following substances in mass concentration:

0.2-1.0 g/L of potassium hydroxide;

0.1-0.8 g/L of sodium silicate;

potassium pyrophosphate 0.1-1.0 g/L;

0.01-0.1 g/L of complexing agent;

0.05-0.5 g/L of penetrant;

0.05-0.5 g/L of emulsifier;

the balance of distilled water.

The novel environment-friendly silicon wafer cleaning reagent comprises the following substances in mass concentration:

0.4-0.6 g/L of potassium hydroxide;

0.2-0.5 g/L of sodium silicate;

0.2-0.5 g/L of potassium pyrophosphate;

0.03-0.06 g/L of complexing agent;

0.1-0.3 g/L of penetrant;

0.1-0.3 g/L of emulsifier;

the balance of distilled water.

The novel environment-friendly silicon wafer cleaning reagent is characterized in that the complexing agent is any one or a mixture of any two or more of ethylene diamine tetraacetic acid, trisodium nitrilotriacetate, aminotrimethylene sodium phosphate, sodium hydroxyethylidene diphosphonate and potassium sodium tartrate in any proportion.

The novel environment-friendly silicon wafer cleaning agent is characterized in that the penetrating agent is any one of linear octyl polyoxyethylene ether, linear nonyl polyoxyethylene ether, linear decyl polyoxyethylene ether, linear octyl polyoxyethylene polyoxypropylene ether, linear nonyl polyoxyethylene polyoxypropylene ether, linear decyl polyoxyethylene polyoxypropylene ether, branched diethyl hexyl polyoxyethylene ether, diethyl hexyl polyoxyethylene polyoxypropylene ether, sodium diethyl hexyl sulfate and sodium diethyl hexyl phosphate, or a mixture of any two or more of the above in any proportion.

The novel environment-friendly silicon wafer cleaning reagent is characterized in that the emulsifier is any one or a mixture of any two or more of sodium dodecyl benzene sulfonate, sodium decyl benzene sulfonate, sodium dodecyl sulfate, sodium oleate, sodium linoleate, polyoxyethylene lauryl ether, sodium polyoxyethylene lauryl ether phosphate, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether and octenyl succinic acid in any proportion.

The novel environment-friendly silicon wafer cleaning agent has the pH value of 10-13.

The novel environment-friendly silicon wafer cleaning agent has the pH value of 11-13.

A preparation method of a novel environment-friendly silicon wafer cleaning reagent comprises the following steps:

the method comprises the following steps: calculating and weighing potassium hydroxide, sodium silicate, potassium pyrophosphate, a complexing agent, a penetrating agent and an emulsifying agent;

step two: adding two thirds of distilled water with theoretical volume into a reaction kettle, starting stirring, adding the required potassium hydroxide, and stirring until the potassium hydroxide is completely dissolved;

step three: adding sodium silicate and potassium pyrophosphate into a reaction kettle, and stirring until the sodium silicate and the potassium pyrophosphate are completely dissolved;

step four: adding complexing agent, penetrating agent and emulsifier, stirring for 3-4h until the solution is clear and transparent;

step five: and (4) fixing the volume according to the required production volume, stirring for 0.5h until the components are fully and uniformly mixed, filtering and packaging to obtain the product.

The application of a novel environment-friendly silicon wafer cleaning reagent is characterized in that the temperature of the cleaning reagent is 30-70 ℃ when the silicon wafer is cleaned; the cleaning time of the cleaning reagent is 20-30 min.

According to the preparation method of the novel environment-friendly silicon wafer cleaning reagent, the cleaning reagent is cleaned in a mode of soaking the cleaning reagent in ultrasonic oscillation or spraying the cleaning reagent when the silicon wafer is cleaned.

The invention has the advantages that:

1. the formula of the cleaning agent does not contain any organic solvent and fluoride ion surfactant, the cleaning agent prepared by the invention is particularly suitable for cleaning silicon wafers such as monocrystalline silicon, polycrystalline silicon and the like, the cleaning surface is uniform and smooth, no specks, sand grains, abrasive, metal ions, fingerprints and other residues exist, the cleaning agent is wiped by filter paper, no silicon powder and other substance residues exist, the production requirements of customers can be met well, the process is environment-friendly, no organic solvent is added in the production process, and the product is environment-friendly and pollution-free;

2. the penetrant used in the invention has excellent dispersion and penetration effects, can be quickly immersed into oil stains and base materials, achieves the effect of quick stripping and a certain emulsification effect, and is low-foam and environment-friendly;

3. the emulsifier used in the invention has excellent emulsifying effect under extremely low concentration, can well emulsify particles and organic matters on the surface of the silicon wafer, and does not damage the substrate;

4. the complexing agent used in the invention can effectively complex the residual metal ions such as copper, iron, zinc and the like in the cutting of the silicon wafer, and meanwhile, the complexing agent is environment-friendly, easy to degrade and free from environmental pollution;

5. the potassium hydroxide used by the invention can provide a good alkaline environment for the cleaning environment, and can ensure the efficient cleaning of the silicon wafer;

6. the sodium silicate used in the invention has good emulsification effect on oil stains, and in the process of cleaning the silicon wafer, one end of oxygen atoms of the sodium silicate is hydrophobic and faces oil when being adsorbed, and the other end of the oxygen atoms of the sodium silicate is hydrophilic and faces aqueous solution when being adsorbed. As a result of this adsorption at the oil-water solution interface, the interfacial tension between the oil and the water solution is reduced compared to when no emulsifier is added. Because of the reduction of the interfacial tension, the contact surface between the oil and the water is increased, and the oil is changed into a small oil drop to be dispersed in the water solution and then removed;

7. the potassium pyrophosphate used in the invention can generate chelation with alkaline earth metal and heavy metal ions and can react with Ca in hard water²⁺、Mg²⁺Pyrophosphate ion (P) forms stable complex to soften hard water, improve washing ability, remove dirt₂O₇ ^4-) Has strong dispersing ability for finely dispersed solid, can promote the uniform mixing of fine and trace substances, and has better auxiliary cleaning effect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a comparison of the effects of metallographic examination 100X and 1000X times in example 1 of the invention;

FIG. 2 is a comparison of the effects of metallographic examination 100X and 1000X times in example 2 of the invention;

FIG. 3 is a graph showing comparison of the effects of metallographic examination by a factor of 100X and 1000X in comparative example 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.