Polyimide degumming agent composition for wafers and preparation method thereof

文档序号：1916627 发布日期：2021-12-03 浏览：28次中文

阅读说明：本技术 一种晶圆用聚酰亚胺除胶剂组合物及其制备方法 (Polyimide degumming agent composition for wafers and preparation method thereof ) 是由刘亮亮陈修宁黄志齐李晨庆王立中王淑萍于 2021-09-07 设计创作，主要内容包括：本发明公开了一种晶圆用聚酰亚胺除胶剂组合物及其制备方法,涉及聚酰亚胺胶层除胶剂技术领域。本发明提供的晶圆用聚酰亚胺除胶剂组合物通过采用碱类、有机溶剂、醇胺类渗透剂、碳氮杂环缓蚀剂及挥发抑制剂的复配,共同起到协同增效的除胶作用。其中碱优选采用了pKa>12的强碱,以提高除胶剂的质子化能力,而醇胺类渗透剂能够增强除胶剂的渗透性,碳氮杂环缓蚀剂能够与金属发生耦合作用,抑制碱对金属的腐蚀；使用挥发抑制剂在除胶剂表层形成一层隔离膜,降低除胶剂中有效组分的挥发损失。本发明具有反应活性强、处理条件温和、可用于半导体、光伏、显示面板等技术领域中聚酰亚胺胶层的去除。(The invention discloses a polyimide degumming agent composition for a wafer and a preparation method thereof, and relates to the technical field of polyimide degumming agent. The polyimide degumming agent composition for the wafer provided by the invention has a synergistic degumming effect by compounding alkalis, organic solvents, alcamines penetrants, carbon nitrogen heterocyclic corrosion inhibitors and volatilization inhibitors. The alkali preferably adopts strong alkali with pKa greater than 12 to improve the protonation capacity of the degumming agent, the alcohol amine penetrant can enhance the permeability of the degumming agent, and the carbon nitrogen heterocyclic corrosion inhibitor can generate coupling effect with metal to inhibit the corrosion of the alkali to the metal; a layer of isolating film is formed on the surface layer of the degumming agent by using the volatilization inhibitor, so that the volatilization loss of effective components in the degumming agent is reduced. The method has the advantages of strong reactivity and mild treatment conditions, and can be used for removing the polyimide adhesive layer in the technical fields of semiconductors, photovoltaics, display panels and the like.)

1. The polyimide degumming agent composition for the wafer is characterized by comprising the following components in percentage by weight:

40-90% of an aprotic polar solvent;

9-70% of an alcamines penetrant;

0.1-15% of alkalis;

0.01-5% of carbon nitrogen heterocyclic corrosion inhibitor;

0.01-5% of volatilization inhibitor.

2. The polyimide degumming composition according to claim 1, wherein the aprotic polar solvent is selected from one or more of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

3. The polyimide degumming composition according to claim 1, wherein the alkanolamine penetrant is selected from one or more of diglycolamine, diethanolamine, monoethanolamine and triethanolamine.

4. The polyimide resist remover composition for wafers according to claim 1, wherein the alkali is at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and (2-hydroxyethyl) trimethylammonium hydroxide.

5. The polyimide degumming composition according to claim 1, wherein said carbo-nitrogen heterocyclic corrosion inhibitor is at least one selected from the group consisting of imidazoline and benzimidazole.

6. The polyimide degumming composition for wafers according to claim 1, wherein said volatilization inhibitor is at least one selected from the group consisting of liquid paraffin, glycerol, and propylene glycol.

7. The method for preparing the polyimide degumming composition for wafers according to any of the claims 1 to 6, wherein the components are mixed uniformly in proportion.

8. A method for removing glue from a wafer polyimide is characterized in that the wafer to be subjected to glue removal is placed in the polyimide glue removing agent composition for the wafer obtained in the claim 7 for glue removal reaction; and taking out the wafer after the reaction is finished, cleaning the wafer by using isopropanol and pure water, and drying the wafer.

9. The wafer polyimide degumming method according to claim 8, wherein the reaction temperature is 80-95 ℃ and the reaction time is 0.5-2h during degumming.

Technical Field

The invention relates to the technical field of polyimide glue layer removers, in particular to a polyimide glue layer remover composition for a wafer and a preparation method thereof.

Background

With the rapid development of 5G communication technology, the terminal applications thereof are becoming more and more abundant, and the requirements for high signal transmission speed, no delay and low loss are required, and the requirements for the technical performance of the used semiconductor materials will become higher and higher. At present, domestic semiconductor materials are restricted to foreign countries in the application of various electronic chemicals, and the requirements of the semiconductor processing process for improving the corresponding electronic chemicals are becoming more and more severe. However, at present, domestic electronic chemicals generally have various problems of unstable performance, harsh reaction conditions, use of harmful components and the like, and the formula optimization of corresponding electronic chemicals is urgently needed. As a key raw material of semiconductors, polyimide plays a role in protecting metal on the surface layer of a wafer in a wafer manufacturing process, and can avoid the defects of disconnection, short circuit, dark injury and the like in the manufacturing process.

Polyimide is a relatively stable high molecular polymer, is chemically inactive at high temperature, can resist strong acid and strong alkali environments, and becomes an excellent passivation layer to protect metal below the layer due to the characteristics. However, in the rework process, the removal of the polyimide glue layer has great difficulty, the line width required for high performance of the semiconductor is smaller and smaller, and a thicker polyimide protective layer with more stable chemical performance is required, so that the traditional method for removing the polyimide is more and more limited in practical use. For a polyimide adhesive remover with excellent performance, the requirements are that the removing effect is good, the operation condition is mild, and the polyimide adhesive remover has no corrosion effect on metals under a film, and in addition, in the wafer manufacturing process, the safety, the environmental pollution, the economic benefit and the timeliness of the adhesive remover are also the key points of attention of developers.

The hydroxylamine in the adhesive remover component of the polyimide adhesive layer is combined with organic base or inorganic base and is matched with different solvent auxiliaries for mixed use in many cases. The strong electrolysis of organic or inorganic alkali promotes the protonation of amido bond, the polyimide macromolecular chain amide loses electron bond breaking, and the polyimide macromolecular film layer is decomposed by strong alkali under the action of solvent. At present, organic strong base is mostly quaternary ammonium tetraalkyl hydroxide, such as tetramethyl ammonium hydroxide, the alkalinity of the quaternary ammonium tetraalkyl hydroxide is equivalent to that of inorganic strong base, such as sodium hydroxide, the quaternary ammonium tetraalkyl hydroxide has excellent glue line removing effect, and the quaternary ammonium tetraalkyl hydroxide is widely used in various patents (such as Japanese patent JP 7201704A; U.S. Pat. No. 3, 4518765A; Chinese patent CN 1224864C; U.S. Pat. No. 5091103A). However, the organic alkali often contains more than 50% of moisture by mass fraction, the moisture has strong corrosivity on metals under a film, particularly aluminum, and in addition, the tetraalkyl quaternary ammonium hydroxide has strong volatility, components begin to decompose at room temperature, the decomposition speed is accelerated along with the temperature rise, the glue removing performance is unstable, and the organic alkali is not suitable for removing glue for many times. Inorganic base such as sodium hydroxide is also commonly used as a key component for degumming, which can prevent the existence of moisture in a reaction system, but the inorganic base has poor solubility in an organic solvent, has a very serious corrosion effect on bottom layer metal, and even if a special solvent is used for dissolving, the removal effect is also poor.

Hydroxylamine plays a role of a penetrating agent on one hand, promotes the separation of the protonated glue layer from the base layer, and on the other hand, due to the existence of hydroxyl, the hydroxylamine is very easy to form the coupling of hydrogen bonds, and plays a certain protection role for metal below the film. Currently, hydroxylamine aids commonly used include diethanolamine, triethanolamine, monoethanolamine, diglycolamine, and the like. Hydroxylamine is often used in combination with aprotic solvents such as dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like for polyimide resist removal, and patents such as japanese patent JP63231343A, japanese patent JP5281753A, US5334332A, japanese patent JP4124668A, and the like. Although the method can remove the polyimide glue layer and has wide action range, the operation temperature is over 160 ℃, and even the operation temperature of some glue removing processes needs to be over 200 ℃. The new polyimide glue layer is polymerized at low temperature, the glue layer is thick, the glue layer cannot be effectively removed by using alcohol amine-solvent only, and the addition of alkalies is essential.

The current general method uses organic alkali solution with higher water content to remove the glue layer, however, the water content greatly weakens the stripping force of the glue removing agent to the glue layer, and the glue removing agent also has strong corrosivity to the metal under the film. The technical problem to be overcome in the field is how to reduce the water content in the degumming agent and inhibit the corrosion of alkalis to the metal below the film.

Disclosure of Invention

The technical problems to be solved by the invention are that the existing polyimide degumming agent has high water content, weak stripping force to an adhesive layer and certain corrosivity to metal under the film.

In order to solve the above problems, the present invention proposes the following technical solutions:

the invention provides a polyimide degumming agent composition for wafers, which comprises the following components in percentage by weight:

40-90% of an aprotic polar solvent;

9-70% of an alcamines penetrant;

0.1-15% of alkalis;

0.01-5% of carbon nitrogen heterocyclic corrosion inhibitor;

0.01-5% of volatilization inhibitor.

Preferably, the polyimide degumming agent composition for wafers comprises the following components in percentage by weight:

50-65% of an aprotic polar solvent;

15-50% of alcohol amine penetrant;

1-10% of alkalies;

0.1-3% of carbon nitrogen heterocyclic corrosion inhibitor;

0.1-3% of volatilization inhibitor.

Further, the aprotic polar solvent mainly promotes the dissolution of the polyimide polymer branch and promotes the functions of components such as an auxiliary agent, alkali and the like, and is selected from one or more of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; dimethyl sulfoxide and N-methylpyrrolidone are preferred, and N-methylpyrrolidone is particularly preferred.

Further, the alcohol amine penetrant mainly plays a role in penetration, promotes separation of the adhesive layer from the base material, and is selected from one or more of diglycolamine, diethanolamine, monoethanolamine and triethanolamine; diglycolamine and diethanolamine are preferred, and diglycolamine is particularly preferred.

Further, the alkali is used for promoting the bond breaking of the polymer chain segment of the polyimide composition to promote the peeling of the adhesive layer, and is at least one selected from the group consisting of lithium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and (2-hydroxyethyl) trimethylammonium hydroxide; strong bases with pKa >12 are preferred, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium hydroxide being particularly preferred.

Further, the carbon nitrogen heterocyclic corrosion inhibitor is used for reducing the corrosion effect of organic alkali on metal, and is selected from at least one of imidazoline and benzimidazole, preferably benzimidazole.

Further, the volatilization inhibitor is used for increasing the viscosity of the components, forming a protective film layer on the surface layer of the composition and inhibiting the volatilization of the solvent, and is selected from at least one of liquid paraffin, glycerol and propylene glycol; liquid paraffin is preferred.

The invention also provides a preparation method of the polyimide degumming agent composition for the wafer, which is characterized in that the components are uniformly mixed according to a proportion.

The invention also provides a method for removing the glue of the wafer polyimide, which comprises the steps of placing the wafer to be subjected to glue removal in the obtained polyimide glue removing agent composition for the wafer, and performing glue removal reaction; and taking out the wafer after the reaction is finished, cleaning the wafer by using isopropanol and pure water, and drying the wafer.

Further, the reaction temperature is 80-95 ℃ and the reaction time is 0.5-2h during the degumming. The preferred reaction temperature is 90 ℃ and the reaction time is 1.5 h.

Specifically, the polyimide degelling agent composition for wafers can be heated to 80-95 ℃ by using oil bath heating, microwave heating and the like.

Further, Plasma (Plasma) or ultrasound may be employed to assist in the removal of the glue.

Compared with the prior art, the invention can achieve the following technical effects:

the polyimide degumming agent composition for the wafer provided by the invention has a synergistic effect by compounding alkalies, organic solvents, alcamines penetrants, carbon nitrogen heterocyclic corrosion inhibitors and volatilization inhibitors. The alkali preferably adopts strong alkali with pKa greater than 12 to improve the protonation capacity of the gel remover, the alcohol amine penetrant can enhance the permeability of the gel remover, and the carbon nitrogen heterocyclic corrosion inhibitor can generate coupling effect with metal to inhibit the corrosion of the alkali on the metal; a layer of isolating film is formed on the surface layer of the degumming agent by using the volatilization inhibitor, so that the volatilization loss of effective components in the degumming agent is reduced.

Because the moisture is not beneficial to the stripping of the glue line and is easy to cause metal corrosion, the glue remover composition is an anhydrous system, and the moisture content of the system is reduced by using high-purity alkalis.

The polyimide degumming agent for the wafer has the characteristics of strong reactivity, mild treatment conditions, wide polyimide removal variety and strong selectivity, can be used for removing a thick glue layer and a new polyimide glue layer, and has extremely high technical threshold and product competitiveness.

The polyimide degumming agent composition for the wafer can remove the glue at a lower temperature, and has high degumming speed and no glue residue.

Drawings

FIG. 1 is a diagram showing the effect of removing polyimide resist composition for wafers according to example 1 of the present invention;

FIG. 2 is a diagram showing the effect of removing the polyimide resist remover composition for wafers according to example 2 of the present invention;

FIG. 3 is a diagram showing the effect of removing polyimide resist remover composition for wafers according to example 3 of the present invention;

FIG. 4 is a graph showing the effect of removing the polyimide resist remover composition for wafers according to example 4 of the present invention;

FIG. 5 is a graph showing the effect of removing the polyimide resist remover composition for wafers according to example 5 of the present invention;

FIG. 6 is a graph showing the effect of removing the polyimide resist remover composition for wafers according to example 6 of the present invention;

FIG. 7 is a graph showing the effect of removing the polyimide resist remover composition for wafers according to example 7 of the present invention;

FIG. 8 is a graph showing the effect of removing polyimide resist remover composition for wafers according to example 8 of the present invention;

FIG. 9 is a graph showing the effect of removing the polyimide resist remover composition for wafers according to comparative example 1 of the present invention;

FIG. 10 is a graph showing the effect of removing the polyimide resist composition for wafers according to comparative example 2 of the present invention;

FIG. 11 is a graph showing the effect of removing the polyimide resist composition for wafers according to comparative example 3 of the present invention;

FIG. 12 is a graph showing the effect of removing the polyimide resist composition for wafers according to comparative example 4 of the present invention.

Detailed Description

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. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. 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.

It is to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Example 1

The embodiment of the invention provides a polyimide degumming agent composition for wafers and a preparation method thereof, wherein the polyimide degumming agent composition comprises the following components in parts by mass:

60 parts of N-methylpyrrolidone, 35 parts of diglycolamine, 4 parts of tetramethylammonium hydroxide (with the purity of 95%), 0.1 part of benzimidazole and 0.9 part of liquid paraffin.

And (3) putting the components into a stirring kettle, and fully stirring and uniformly mixing the components by using a glass rod to prepare the degumming agent.

The embodiment also provides a method for removing the glue of the wafer polyimide, which comprises the steps of placing the wafer to be subjected to glue removal in a glue removing agent for glue removing reaction; the reaction temperature is 80-95 ℃ and the reaction time is 0.5-2 h. And taking out the wafer after the reaction is finished, cleaning the wafer by using isopropanol and pure water, and drying the wafer.

Specifically, the degumming agent is placed in an oil bath at 90 ℃ for heating, after the temperature is raised to a set temperature, the wafer to be degummed is placed in the degumming agent, and the reaction time is 1.5 h. And after the reaction is finished, taking out the wafer, repeatedly rinsing the wafer for 3 minutes by using isopropanol and pure water respectively, and drying the surface of the wafer by using a hot air blower.

Example 2