TW201418913A - Slurry for removing residual photoresist - Google Patents

Abstract

The invention relates to photo-resist strippers. The photo-resist stripper includes hydramine, organic solvent, gallic acid and its ester, and 3-Amino-1, 2, 4-triazole. And the photo-resist stripper does not include water, hydroxylamine, and fluoride. The stripper could remove the photo-resist on the wafer, and inhibit the corrosion of substrates, such as aluminium, argentums, copper, tungsten, titanium, silica dioxide, and gallium nitride. The stripper possesses the potential application prospect in cleaning semiconductor wafer and LED wafer.

Description

Cleaning liquid for removing photoresist residue

The present invention relates to a cleaning solution, and more particularly to a cleaning solution for removing photoresist residues.

In the conventional LED and semiconductor manufacturing processes, patterning is performed after exposure by forming a photoresist on the surface of some materials, and after obtaining the desired pattern, it is necessary to remove the residual photoresist before performing the next process. In this process it is required to completely remove the unwanted photoresist while not corroding any substrate.

At present, the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid. One type is a photoresist cleaning solution containing water, which generally has a water content of more than 5%; as disclosed in JP1998239865, an aqueous cleaning solution is disclosed, which is composed of tetramethylammonium hydroxide (TMAH) and dimethylammonium (DMSO). ), 1,3'-dimethyl-2-imidazolidinone (DMI) and water. The wafer is immersed in the cleaning solution to remove photoresist of 20 μm or more on the metal and dielectric substrate at 50 to 100 ° C; the rot of the semiconductor wafer substrate The etch is slightly high, and the photoresist on the semiconductor wafer cannot be completely removed, and the cleaning ability is insufficient. Further, for example, US Pat. No. 5,529,887 discloses potassium hydroxide (KOH), alkyl glycol monoalkyl ether, water-soluble fluoride and water. An alkaline cleaning solution is formed, and the wafer is immersed in the cleaning solution to remove the photoresist on the metal and dielectric substrates at 40 to 90 °C. It has a high corrosion to the semiconductor wafer substrate. In such a cleaning liquid, since it contains a free strong basic group -OH and water is present, it tends to cause some corrosion to the metal substrate. The other type is a photoresist cleaning solution that is substantially free of water, typically having a water content of less than 5%, or even substantially no water. No. 5,480,585 discloses a cleaning solution comprising a non-aqueous system, the composition of which is ethanolamine, cyclobutyl hydrazine or dimethyl hydrazine and catechol, capable of removing light on metal and dielectric substrates at 40 to 120 ° C. Resistance, basically no corrosion to metal. Further, for example, US2005119142 discloses a non-aqueous cleaning solution comprising an alkoxy group-containing polymer, dipropylene glycol alkyl ether, N-methylpyrrolidone and methyl isobutyl ketone. The cleaning solution can be applied to both positive and negative photoresist cleaning. The non-aqueous photoresist cleaning liquid has no corrosion to the metal substrate because it does not contain water; however, when the cleaning liquid is mixed with a small amount of water in the operating system, the corrosion rate of the metal increases remarkably, resulting in a metal base. Corrosion of materials. Therefore, there is a problem that the operation space is small.

It can be seen that the search for a photoresist cleaning solution which is more effective in suppressing the metal corrosion suppression method and the larger operation blank is a priority direction for the improvement of the photoresist cleaning liquid.

The technical problem to be solved by the present invention is to provide a method for removing photoresist residues. The cleaning solution of the residue and its composition. The cleaning solution removes photoresist residue on the wafer and has substantially no corrosion to substrates such as metal aluminum, silver, copper, titanium, tungsten, and non-metal ceria, gallium nitride, etc., while at the same time for the metal in the LED process. The cleaning effect of the pad is better, and has a good application prospect in the fields of semiconductor and LED wafer cleaning.

In order to solve the above technical problems, the present invention provides a novel cleaning liquid comprising an alcohol amine, an organic solvent, gallic acid and its ester, and 3-amino-1,2,4-triazole.

Among them, the content of the alkanolamine is 5 to 50% by weight (% by mass), preferably 10 to 45% by weight.

Wherein the content of the organic solvent is 40-90% by weight, preferably 50-85% by weight.

Wherein the content of gallic acid and its ester is 0.05-5 wt%, preferably 0.1-3 wt%

Wherein the content of 3-amino-1,2,4-triazole is 0.01-5 wt%, preferably 0.05-3 wt%

The above content is a mass percentage content; and in the cleaning liquid for removing photoresist residues disclosed in the present invention, it is preferable that water, hydroxylamine and/or fluoride are not contained.

In the present invention, the alcoholamine is preferably monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N,N-diethylethanolamine, N-(2-amino group Ethyl)ethanolamine and diglycolamine. Preference is given to monoethanolamine, diglycolamine and mixtures thereof.

In the present invention, the organic solvent is preferably one or more of anthraquinone, anthracene, imidazolidinone, pyrrolidone, imidazolidinone, decylamine and an alcohol ether; One or more of dimethyl hydrazine and methyl ethyl hydrazine; hydrazine is preferably one or more of methyl hydrazine and cyclobutyl hydrazine; imidazolidinone is preferably 2-imidazolidinone and 1 One or more of 3-dimethyl-2-imidazolidinone; pyrrolidone is preferably one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; imidazolinone Preferably, the 1,3-dimethyl-2-imidazolidinone amide is preferably one or more of dimethylformamide and dimethylacetamide; the alcohol ether is preferably ethylene. One or more of an alcohol alkyl ether and a propylene glycol alkyl ether. The ethylene glycol alkyl ether is preferably one or more of ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monobutyl ether; the propylene glycol alkyl ether is preferably propylene glycol monomethyl ether, One or more of propylene glycol monobutyl ether and dipropylene glycol monomethyl ether.

In the present invention, gallic acid and its ester are preferably gallic acid, methyl gallate, ethyl gallate, butyl gallate, octyl gallate, gallic acid One or more of lauryl acid ester and 1-gallate glyceride.

In the cleaning liquid of the present invention, the photoresist residue on the wafer can be cleaned at 50 ° C to 90 ° C. The specific method is as follows: the wafer containing the photoresist residue is immersed in the cleaning liquid in the present invention, immersed at 50 ° C to 90 ° C for 10-30 min, taken out and rinsed, and then dried with high-purity nitrogen gas.

The positive progress of the present invention is as follows: 1) The cleaning solution of the present invention removes photoresist residues on the wafer while simultaneously treating substrates such as aluminum, silver, copper, titanium, tungsten and non-metal cerium oxide, nitrogen. Gallium and other basic non-corrosive; 2) The cleaning effect of the metal pad Pad in the LED process is better. The reagents and starting materials used in the present invention are commercially available. The cleaning liquid of the present invention is simple and uniform from the above components It can be prepared by mixing well.

The advantages of the present invention are further illustrated by the following specific examples, but the scope of the present invention is not limited only to the following examples.

The polishing liquid was prepared in accordance with the ingredients of the respective examples in Tables 1 and 2 and the comparative examples, and the ratio thereof was uniformly mixed.

Effect Example 1

In order to further investigate the cleaning of the cleaning liquid, the present invention adopts the following technical means: immersing the LED metal pad (Pad) wafer containing the photoresist residue in the cleaning liquid, and oscillating at 50 ° C to 90 ° C with constant temperature. The device was shaken at a vibration frequency of about 60 rpm for 10 to 30 minutes, then rinsed and then dried with high purity nitrogen. The cleaning effect of the photoresist residue and the corrosion of the cleaning solution on the wafer are shown in Table 3.

As can be seen from Table 3, the cleaning liquid of the present invention has a good cleaning effect on a wafer metal pad (Pad) wafer containing a photoresist residue, and has a wide temperature range. It can be seen from Comparative Example 1 and Example 13 that under the conditions of the same components and the same operating conditions, no gallic acid and its ester are added, and the cleaning of the LED metal pad remains, and the metal aluminum is slightly corroded; It can be seen from Comparative Example 2 and Example 13 that under the conditions of the same components and the same operating conditions, 3-amino-1,2,4-triazole is not added, and the cleaning of the LED metal pad is clean but metal. A slight corrosion of aluminum indicates that there is a synergistic effect of gallic acid and its esters and 3-amino-1,2,4-triazole on the corrosion inhibition of metallic aluminum in this system. It can be seen from Comparative Example 3 and Example 13 that 5-amino-1,2,4-triazole is substituted for 3-amino-1,2,4- under the same conditions of other components and the same operating conditions. Triazole did not show the same synergistic effect.

Effect Example 2

In order to further investigate the corrosion inhibition of metal by such cleaning liquid, the present invention adopts the following technical means: immersing various metal wafers (aluminum, silver, copper, titanium, tungsten) without pattern in the cleaning liquid, respectively, at 85 The mixture was shaken at a vibration frequency of about 60 rpm for 60 minutes using a constant temperature oscillator at ° C, and then rinsed and then dried with high purity nitrogen gas. The resistance change before and after immersion was tested by a four-point probe instrument, and the corrosion rate was calculated, and the surface metallic luster was visually inspected for change. The results are shown in Table 4.

Table 4 Part of the example of the lower metal corrosion rate of 85 ° C, A / min

It can be seen from Table 4 that the cleaning liquid of the present invention has a small metal corrosion rate, and the apparent metallic luster of the metal remains good before and after washing.

In summary, the positive progress of the present invention is: 1) the cleaning solution of the present invention is used to remove photoresist residue on the wafer while simultaneously oxidizing the substrate such as metal aluminum, silver, copper, titanium, tungsten and non-metal. Niobium, gallium nitride and the like are basically non-corrosive; 2) the cleaning effect of the Pad in the LED process is better.

It should be understood that the wt% of the present invention refers to the mass percentage content. .

The specific embodiments of the present invention have been described in detail above, but are merely exemplary, and the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions to the invention are also within the scope of the invention. Accordingly, equivalents and modifications may be made without departing from the spirit and scope of the invention.

Claims (16)

A cleaning solution for removing photoresist residues, comprising an alcohol amine, an organic solvent, gallic acid and its ester, and 3-amino-1,2,4-triazole. The cleaning solution according to claim 1, wherein the content of the alcoholamine is 5 to 50% by weight. The cleaning solution according to claim 2, wherein the content of the alcoholamine is from 10 to 45% by weight. The cleaning liquid according to claim 1, wherein the organic solvent is contained in an amount of 40 to 90% by weight. The cleaning liquid according to claim 4, wherein the organic solvent is contained in an amount of 50 to 85 wt%. The cleaning solution according to claim 1, wherein the gallic acid and an ester thereof are contained in an amount of from 0.05 to 5% by weight. The cleaning solution according to claim 6, wherein the gallic acid and its ester are contained in an amount of from 0.1 to 3% by weight. The cleaning solution according to claim 1, wherein the 3-amino-1,2,4-triazole is contained in an amount of from 0.01 to 5% by weight. The cleaning solution according to claim 8, wherein the 3-amino-1,2,4-triazole is contained in an amount of from 0.05 to 3% by weight. The cleaning solution according to claim 1, wherein the alcohol amine is selected from the group consisting of monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, and N,N-diethylethanolamine. One or more of N-(2-aminoethyl)ethanolamine and diglycolamine. The cleaning solution of claim 10, wherein the alcohol amine is selected from the group consisting of ethanolamine, diglycolamine, and mixtures thereof. The cleaning solution according to claim 1, wherein the organic solvent is one or more selected from the group consisting of anthraquinone, anthracene, imidazolidinone, pyrrolidone, imidazolidinone, decylamine and an alcohol ether. The cleaning solution according to claim 12, wherein the hydrazine is selected from one or more of dimethyl hydrazine and methyl ethyl hydrazine; and the hydrazine is one or more selected from the group consisting of methyl hydrazine and cyclobutyl hydrazine. The imidazolidinone is selected from one or more of 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; the pyrrolidone is selected from the group consisting of N-methylpyrrolidone, N-cyclohexylpyrrolidone, and One or more of N-hydroxyethylpyrrolidone; the imidazolidinone is selected from the group consisting of 1,3-dimethyl-2-imidazolidinone; the guanamine is selected from the group consisting of dimethylformamide and dimethylamine One or more of guanamine; the alcohol ether is selected from one or more of ethylene glycol alkyl ether and propylene glycol alkyl ether. The cleaning solution according to claim 13, wherein the ethylene glycol alkyl ether is one or more of ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and diethylene glycol monobutyl ether; the propylene glycol The alkyl ether is one or more of propylene glycol monomethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. The cleaning solution according to claim 1, wherein the gallic acid and its ester are selected from the group consisting of gallic acid, methyl gallate, ethyl gallate, butyl gallate, and no food. One or more of octyl octanoate, lauryl gallate, and 1-gallate glyceride. The cleaning solution of claim 1, wherein the cleaning solution does not contain water, hydroxylamine and/or fluoride.