TWI410758B - A barrier removal fluid composition, and a method of removing the barrier layer - Google Patents

Abstract

The present invention provides a resist layer removal liquid composite, which comprises: (A) inorganic base, and the inorganic base content is 0.5 to 5 wt% on the basis of total weight of the resist layer removal liquid composite; (B) polar solvent, and the polar solvent content is 5 to 70 wt% on the basis of total weight of the resist layer removal liquid composite; and (C) substituted alcohol, and the substituted alcohol content is 25 to 94 wt% on the basis of total weight of the resist layer removal liquid composite. The composition and component ratio of the composite according to the present invention may effective remove the resist layer, and prevent the metal oxidation and the solution of polyimide. The present invention further provides a method of removing the resist layer using the above-mentioned composite.

Description

Repellent layer removing liquid composition and method of removing resist layer

The present invention relates to a resist layer removing liquid composition and a method for removing the resist layer thereof; in particular, an inorganic base-containing resist layer removing liquid composition and a method of removing the resist layer.

Recently, the development of chip packaging technology is progressing toward the following trends: the ratio of wafer area to package area is close, the applicable frequency is increased, the heat resistance is improved, the number of wires is increased, the wire pitch is reduced, the weight is reduced, the reliability is improved, and the lead-free process is adopted. . In order to cope with the above trend, the use of polyimide (PI) as a dielectric layer in packaging process materials has become mainstream.

Photolithography is a commonly used technique in semiconductor process or printed circuit board processes. In lithography processes, photoresist or dry film is often used to define circuit patterns. After the lithography process, it is necessary to use a stripper to remove the photoresist or dry film.

In general, conventional strippers contain an organic base such as an aqueous solution of tetraalkylammonium hydroxide (TMAH). For example, Taiwan Patent No. I275904 discloses a composition of a stripping liquid containing organic alkali. However, the peeling liquid containing a caustic alkali has a poor ability to peel off the resist layer. In addition, since the stripping liquid contains organic alkali, it needs to exist in the form of an aqueous solution, and the presence of water tends to cause oxidation of the copper surface. Furthermore, this type of stripper also readily dissolves polyammonium.

Therefore, how to develop a stripping liquid which is excellent in peeling ability, low in metal oxidation ability, and low in dissolving power to polybenzamine has become a problem to be solved at present.

In view of the above, the present invention provides a resist layer removing liquid composition comprising: (A) an inorganic base having a content of 0.5 to 5 wt based on the total weight of the resist layer removing liquid composition (B) a polar solvent based on the total weight of the resist removal composition, the polar solvent being present in an amount of 5 to 70 wt%; and (C) a substituted alcohol removed by the barrier layer The substituted alcohol is present in an amount of from 25 to 94% by weight based on the total weight of the liquid composition.

In addition, the present invention also provides a method for removing a resist layer, comprising the steps of: providing a substrate formed with a patterned resist layer and a resist removal liquid composition according to the present invention; heating the resist removal liquid composition; And contacting the heated resist layer removal fluid composition with the patterned resist layer on the substrate to remove the patterned resist layer.

The resist layer removing liquid composition of the present invention has excellent peeling ability and does not cause residual layer of the resist layer; in particular, the resist layer removing liquid composition of the present invention is an inorganic alkali-free aqueous solution capable of preventing metal from coming into contact with water. Oxidizes and prevents the dissolution of polyamidamine.

The embodiments of the present invention are described by way of specific examples, and those skilled in the art can understand the advantages and advantages of the present invention as disclosed in the present disclosure. The present invention may be embodied or applied in various other specific embodiments. The details of the present invention can be variously modified and changed without departing from the spirit and scope of the invention.

In order to solve the conventional problems, the inventors of the present invention have found a resist layer removing liquid composition comprising: (A) an inorganic base; (B) a polar solvent; and (C) a substituted alcohol after conducting various experiments.

In the resist layer removing liquid composition of the present invention, the inorganic base is contained in an amount of 0.5 to 5 wt%, preferably 1 to 5 wt%, more preferably based on the total weight of the resist layer removing liquid composition. 1 to 3 wt%. An inorganic base may be an alkali metal hydroxide or an alkaline earth metal hydroxide; in one embodiment, the inorganic base is sodium hydroxide; in another embodiment, the inorganic base is potassium hydroxide.

In the resist layer removing liquid composition of the present invention, the polar solvent is contained in an amount of 5 to 70% by weight, preferably 6 to 60% by weight, more preferably 8 based on the total mass of the resist layer removing liquid composition. Up to 55 wt%. Examples of the polar solvent may be dimethyl hydrazine, diethylene glycol monobutyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrole a ketone, γ-butyrolactone, and N,N-dimethylimidazole, and may be selected from one or more polar solvents of the group, for example, dimethyl hydrazine, diethylene glycol monobutyl ether, and N are selected. , N-dimethylacetamide three polar solvents. In one embodiment, the polar solvent is N-methyl-2-pyrrolidone; in another embodiment, the polar solvent is N,N-dimethylformamide.

In the resist layer removing liquid composition of the present invention, the substituted alcohol is contained in an amount of 25 to 94% by weight, preferably 35 to 92% by weight, based on the total weight of the resist layer removing liquid composition. Good for 45 to 90 wt%. Further, the substituted alcohol may be a substituted C ₁ -C ₁₀ alcohol, that is, the C ₁ -C ₁₀ alcohol may be further substituted with a substituent. Preferred is a substituted C ₂ -C ₈ alcohol, more preferably a substituted C ₂ -C ₆ alcohol. Further, the substituent of the substituted alcohol may be a methyl group, an ethyl group, a methoxy group or an ethoxy group. Meanwhile, examples of the substituted alcohol may be 1-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxybutanol, 3-methoxy-3-methyl 1-butanol, 3-methyl-3-methoxy-2-butanol, and 3-methyl-3-methoxy-4-butanol, and one or more selected from the group consisting of Substituted alcohols, for example, selected substituted alcohols include 3-methoxy-3-methyl-1-butanol, 3-methyl-3-methoxy-2-butanol, and 3-methyl- 3-methoxy-4-butanol. In one embodiment, the substituted alcohol is 3-methoxy-3-methyl-1-butanol; in another embodiment, the substituted alcohol is 2-methoxyethanol.

In addition, the resist layer removing liquid composition of the present invention is used for removing the resist layer, and in terms of material, the resist layer may be a polymer film. In terms of morphology, in one embodiment, the resist layer refers to the photoresist; in another embodiment, the resist layer is a dry film.

In another aspect, in the method of removing a resist layer of the present invention, the step of removing the patterned resist layer may be performed by soaking or spraying to bring the resist layer removing liquid composition into contact with the patterned resist layer. In one embodiment, the step of removing the patterned resist layer is performed in a immersion manner.

In the method of removing the resist layer of the present invention, the resist layer removing liquid composition is heated to 40 to 110 ° C, preferably 60 to 100 ° C, more preferably 80 to 97 ° C.

The features and effects of the present invention are further illustrated by the following specific examples, but are not intended to limit the scope of the invention.

Example (Preparation of resist layer removal liquid composition)

According to the components and ratios shown in Tables 1 and 2, after uniformly mixing the various components, 21 kinds of resist removal liquid compositions were obtained, wherein Examples 1 to 18 are the barrier removal liquids prepared according to the present invention. The composition, Comparative Examples 1 to 3, was prepared by using an organic base to form a resist removal liquid composition.

In an embodiment, the resist layer removing liquid composition prepared mainly contains (A) 0.5 to 5 wt% of an inorganic base; (B) 5 to 70 wt% of a polar solvent; and (C) 25 to 94 wt% % of the substituted alcohol.

In a comparative example, the resist layer removing liquid composition prepared mainly contains (A) an aqueous solution of 1 to 2.7 wt% of an organic alkali; and (B) 92 to 99 wt% of a polar solvent, wherein the organic base is The content is one-third of the weight of the water.

(Test sample resist removal ability, antioxidant capacity and test for preventing polyimine solvency)

Under the treatment conditions listed in Table 3, the sample to be tested (polyimine substrate) having a size of 3 cm x 3 cm was immersed in the resist removal liquid composition prepared according to Tables 1 and 2, and the results were recorded. In Table 3.

The evaluation results shown in Table 3 are the barrier removal ability of the barrier removal solution, the ability to prevent the copper layer from oxidizing, and the ability to prevent the dissolution of polyamidamine. The evaluation criteria are as follows:

◎: good;

○: Good;

△: OK;

╳: Poor

The sample to be tested is immersed in each resist removal liquid at the operating temperature, and taken out after the soaking time listed in Table 3, and the experimental results are observed by a scanning electron microscope and evaluated. Fig. 1 to Fig. 4 show the observation results, and Fig. 1 and Fig. 3 are observation results of copper oxidation degree of the comparative sample and the sample of the examples, respectively. Fig. 2 and Fig. 4 are observation results of the degree of dissolution of polyamines of the comparative sample and the sample of the examples, respectively.

It can be clearly seen from Fig. 1 that the outer surface of the dot has a black shadow band, which is the copper oxide region; the third image has no black shadow band. Therefore, the ability of the resist layer removing liquid composition of the present invention to prevent oxidation of the metal layer is preferred.

Furthermore, in Fig. 2, it is apparent that there is a halo in the outermost layer of the dot, and in addition, the halo region is caused by the dissolution of polyamine, and the fourth graph has no halo. The resist layer removing liquid composition of the present invention preferably has a better ability to prevent dissolution of polyamidamine.

As is apparent from the results shown in Table 3, the barrier layer pipetting composition of the present invention uses an inorganic base, the peeling ability to the resist layer, the oxidation resistance of the copper layer, and the prevention of the polyamidamine compared to the stripping liquid using the organic base. The solvency has been significantly improved.

The above examples are merely illustrative of the compositions and preparation methods of the present invention and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the claims of the present invention should be as set forth in the appended claims.

Fig. 1 is a view showing the results of copper oxidation degree of a sample to be tested after using the resist layer removing liquid composition of the comparative example;

Fig. 2 is a view showing the degree of dissolution of polyamines of the sample to be tested after using the composition of the resist layer removing liquid of the comparative example;

Figure 3 is a graph showing the degree of copper oxidation of a sample to be tested after using the resist layer removing liquid composition of the present invention;

Figure 4 is a view showing the degree of dissolution of polyamines of the sample to be tested after using the resist layer removing liquid composition of the present invention;

Claims (10)

A resist layer removing liquid composition comprising: (A) an inorganic base having a content of 0.5 to 5 wt% based on the total weight of the resist layer removing liquid composition, wherein the inorganic base is An alkali metal hydroxide; (B) a polar solvent having a content of the polar solvent of from 5 to 70% by weight based on the total weight of the resist removal composition; and (C) a substituted alcohol The substituted alcohol is present in an amount of from 25 to 94% by weight based on the total weight of the resist removal liquid composition, wherein the substituted alcohol is a substituted C ₁ -C ₁₀ alcohol. The resist layer removing liquid composition according to claim 1, wherein the inorganic base is sodium hydroxide, potassium hydroxide or a mixture thereof. The resist removal liquid composition according to claim 1, wherein the polar solvent is selected from the group consisting of dimethyl hydrazine, diethylene glycol monobutyl ether, N, N-dimethyl acetamide, N One or more groups consisting of N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and N,N-dimethylimidazole. The resist removal liquid composition of claim 1, wherein the substituted alcohol is an alcohol substituted with a substituent selected from the group consisting of methyl, ethyl, methoxy or ethoxy. The resist removal liquid composition according to claim 4, wherein the substituted alcohol is selected from the group consisting of 1-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, and 3- Methoxybutanol, 3-methoxy-3-methyl-1-butanol, 3-methyl-3-methoxy-2-butanol and 3-methyl-3-methoxy-4 One or more of the groups consisting of butanol. The resist layer removing liquid composition according to claim 1, wherein the resist layer is a polymer film. The resist layer removing liquid composition according to claim 1 or 6, wherein the resist layer is a photoresist or a dry film. A method of removing a resist layer, comprising the steps of: providing a substrate on which a patterned resist layer is formed; and providing a resist removal liquid composition according to any one of claims 1 to 7; heating the resist removal liquid a composition; and contacting the heated resist layer removing liquid composition with the patterned resist layer to remove the patterned resist layer. The method for removing the resist layer as described in claim 8 is to contact the patterned resist layer with a patterning resist layer by dipping or spraying. The method of removing the resist layer as described in claim 8 of the patent application is to heat the resist layer removing liquid composition to 40 to 110 °C.