TWI438585B - Photo resist stripper - Google Patents

Description

Photoresist cleaner

The present invention relates to semiconductor wafer cleaning, and more particularly to a photoresist cleaning agent.

In a general semiconductor process, a pattern is transferred by a wet etching method or a dry etching method after exposure to a photomask having a photoresist on a surface such as a metal such as cerium oxide or copper or a low-k material. In the process of photoresist cleaning on a semiconductor wafer, the cleaning agent often causes corrosion of the wafer substrate. Metal corrosion is a fairly common and very serious problem, especially when chemical cleaning agents are used to remove metal etch residues, often resulting in a significant reduction in wafer yield.

Therefore, reducing substrate corrosion during wafer cleaning is an urgent problem to be overcome. In the patent document WO03104901, the use of trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA) as a corrosion inhibitor, and the solution thereof is tetramethylammonium hydroxide (TMAH), cyclobutane (SFL). , water and trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA) and the like. However, it is slightly more corrosive to the semiconductor wafer substrate. In the patent document WO04059700, 2-mercaptobenzimidazole (MBI) is used as a corrosion inhibitor, and the solution is tetramethylammonium hydroxide (TMAH), N-methylmorpholine-N-oxide (MO). ), water and 2-mercaptobenzimidazole (MBI). However, its corrosion on semiconductor wafer substrates is high.

The present invention provides a photoresist cleaning agent to reduce metal corrosion generated during wafer cleaning of a semiconductor process.

The photoresist cleaning agent proposed by the present invention contains a corrosion inhibitor and a solvent. The corrosion inhibitor comprises two kinds of compounds: one is an alkyl alcohol monoaryl ether compound, and the other is selected from a phenol compound, a carboxylic acid, a polycarboxylic acid, a carboxylate, a polycarboxylate compound, an acid anhydride, A polyanhydride compound or a phosphonic acid or phosphonate compound.

In the present invention, the alkyl alcohol monoaryl ether compound is ethylene glycol monophenyl ether (EGMPE), propylene glycol monophenyl ether (PGMPE), isopropyl glycol monophenyl ether, diethylene glycol monophenyl ether Dipropylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobenzyl ether or isopropyl glycol monobenzyl ether. Among them, preferred examples are ethylene glycol monophenyl ether, propylene glycol monophenyl ether or isopropyl glycol monophenyl ether. The content of the alkyl alcohol monoaryl ether compound may be 0.05 to 30% by weight, and more preferably 1.0 to 15% by weight.

In the present invention, the phenolic compound may be 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol, of which the preferred choice is pyrogallol. The content of the phenolic compound may be 0.001 to 15% by weight, and more preferably 0.01 to 5.0% by weight.

In the present invention, the carboxylic acid, polycarboxylic acid, carboxylic acid ester, polycarboxylate compound may be benzoic acid, p-aminobenzoic acid (PABA), phthalic acid (PA), gallic acid (GA). , propyl gallate or carboxylated acrylate polymer. Among them, preferred choices are p-aminobenzoic acid, phthalic acid, and gallic acid. The content of the carboxylic acid, the polycarboxylic acid, the carboxylic acid ester, and the polycarboxylate compound may be 0.001 to 15% by weight, and more preferably 0.01 to 5.0% by weight.

In the present invention, the acid anhydride or polyanhydride compound may be acetic anhydride, propionic anhydride, hexanoic anhydride, maleic anhydride or polymaleic anhydride, with a preferred choice being polymaleic anhydride. The content of the acid anhydride or polyanhydride compound may be 0.001 to 15% by weight, more preferably 0.01 to 5.0% by weight.

In the present invention, the phosphonic acid, phosphonate compound is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid (HEDPA), aminotrimethylenephosphonic acid (ATMP) or 2-phosphine. Butane-1,2,4-tricarboxylic acid (PBTCA), of which the preferred choice is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid. The content of the phosphonic acid or phosphonate compound may be 0.001 to 15% by weight, more preferably 0.01 to 5.0% by weight.

In the present invention, the solvent may be selected from the group consisting of an anthraquinone, an anthracene, an imidazolidinone, and/or an alkyl glycol monoalkyl ether. The solvent may be present in an amount of from 55 to 99.90% by weight, more preferably from 60 to 95% by weight.

Wherein, the fluorene may be dimethyl hydrazine, diethyl hydrazine or methyl ethyl hydrazine, of which the preferred choice is dimethyl hydrazine; the hydrazine may be methyl hydrazine, ethyl hydrazine or cyclobutyl hydrazine. The preferred choice is cyclobutyl hydrazine; the imidazolidinone may be 2-imidazolidinone (MI), 1,3-dimethyl-2-imidazolidinone (DMI) or 1,3-diethyl-2 - imidazolidinone, wherein preferred is 1,3-dimethyl-2-imidazolidinone; alkyl diol monoalkyl ether can be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether or dipropylene glycol monobutyl ether, of which the preferred choice is ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether.

In the present invention, the photoresist cleaning agent may further comprise a quaternary ammonium hydroxide, a surfactant, and/or water. The quaternary ammonium hydroxide may be tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide or benzyltrimethylammonium hydroxide. The preferred choice is tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide, and a more preferred choice is tetramethylammonium hydroxide. The surfactant may be polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene ether (POE) or polyoxyalkylene (PSOA), preferably polyvinylpyrrolidone or polyoxyethylene ether. The content of the quaternary ammonium hydroxide may be from 0 to 15% by weight, more preferably from 0.5 to 5.0% by weight. The surfactant may be present in an amount of from 0 to 15% by weight, more preferably from 0.05 to 5.0% by weight. The water content may be 0 to 40% by weight, and more preferably 0.5 to 25% by weight.

The photoresist cleaning agent of the present invention can be obtained by simple mixing of the above components. The photoresist cleaning agent can be used by immersing a photoresist-containing semiconductor wafer in the cleaning agent, and slowly shaking it for 15 to 30 minutes using a constant temperature oscillator at room temperature to 85 ° C, passing through deionized water. After washing, it was dried by high-purity nitrogen gas. It is worth noting that if the cleaning temperature is higher than 45 ° C, the wafer should be washed first with isopropyl alcohol and then with deionized water.

The positive effect produced by the invention is that the corrosion inhibitor in the photoresist cleaning agent can penetrate the intermolecular interaction with the surface material of the wafer substrate to form a dense protective film on the surface of the wafer substrate to block halogen atoms and hydroxide ions. Etc. Corrosion of the wafer substrate. The photoresist cleaner can be used at room temperature to 85 °C. The photoresist cleaning agent has good corrosion resistance to metals such as cerium oxide, copper and low-k materials, and therefore has a good development prospect in the field of microelectronics such as semiconductor wafer cleaning.

The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

In order to achieve the above-described aspects of the present invention, the present invention is to be construed as being limited to the scope of the embodiments described herein.

Example 1~21 :

Table 1 shows photoresist cleaner Examples 1-21.

Effect Example 1

The blank copper wafer was cleaned using the comparative cleaning agent 1 and the cleaning agents 1 to 7 in Table 2, and the etching rate of the above cleaning agent for metallic copper was measured. The test methods and conditions are as follows: a blank copper wafer is immersed in the cleaning agent, and slowly shaken at 25 to 85 ° C for 15 to 30 minutes using a constant temperature oscillator, then washed with deionized water and dried with high purity nitrogen (if the cleaning temperature Above 45 ° C, the wafer should be washed first with isopropyl alcohol and then with deionized water). Thereafter, the change in surface resistance of the blank copper wafer before and after etching was measured by a quadrupole probe instrument, and the calculation results are shown in Table 3.

Table 3 Comparison of etching rate of cleaning agent 1 and cleaning agent 1~7 on blank Cu wafer

It can be seen from Table 3 that the cleaning agents 1 to 7 exhibit lower etching properties for metallic copper than the comparative cleaning agent 1, indicating that the corrosion inhibitors in the cleaning agents 1 to 7 have good properties for metallic copper. Corrosion resistance.

The raw materials and reagents used in the present invention are all commercially available products.

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. Therefore, the scope of the patented scope of the invention should be construed as broadly construed in the

Claims (26)

A photoresist cleaning agent comprising a corrosion inhibitor and a solvent, wherein the corrosion inhibitor comprises two kinds of compounds, one is an alkyl alcohol monoaryl ether compound, and the other is selected from a phenol compound, a carboxylic acid, a polycarboxylate An acid, a carboxylic acid ester, a polycarboxylate compound, an acid anhydride, a polyanhydride compound or a phosphonic acid or phosphonate compound, wherein the alkyl alcohol monoaryl ether compound is contained in an amount of 0.05 to 30% by weight, the phenol The content of the compound is 0.001 to 15% by weight, the content of the carboxylic acid, the polycarboxylic acid, the carboxylic acid ester, and the polycarboxylate compound is 0.001 to 15% by weight, and the content of the acid anhydride and the polyanhydride compound is 0.001 to 15% by weight. The content of the phosphonic acid or phosphonate compound is 0.001 to 15% by weight, and the content of the solvent is 55 to 99.90% by weight. The photoresist cleaning agent according to claim 1, wherein the alkyl alcohol monoaryl ether compound is ethylene glycol monophenyl ether, propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, and diethyl Glycol monophenyl ether, dipropylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monobenzyl ether or isopropyl glycol monobenzyl ether. The photoresist cleaning agent according to claim 1, wherein the alkyl alcohol monoaryl ether compound is contained in an amount of 1.0 to 15% by weight. The photoresist cleaning agent of claim 1, wherein the phenolic compound is 1,2-dihydroxyphenol, p-hydroxyphenol or pyrogallol. The photoresist cleaning agent according to claim 1, wherein the phenolic compound is contained in an amount of 0.01 to 5.0% by weight. The photoresist cleaning agent according to claim 1, wherein the carboxylic acid, the polycarboxylic acid, the carboxylic acid ester, and the polycarboxylate compound are benzoic acid, p-aminobenzoic acid, phthalic acid, and no food. An acid, a propyl gallate or a carboxyl group-containing acrylate polymer. The photoresist cleaning agent according to claim 1, wherein the content of the carboxylic acid, the polycarboxylic acid, the carboxylic acid ester, and the polycarboxylate compound is 0.01 to 5.0% by weight. The photoresist cleaning agent according to claim 1, wherein the acid anhydride or polyanhydride compound is acetic anhydride, propionic anhydride, hexanoic anhydride, maleic anhydride or polymaleic anhydride. The photoresist cleaning agent according to claim 1, wherein the content of the acid anhydride and the polyanhydride compound is 0.01 to 5.0% by weight. The photoresist cleaning agent according to claim 1, wherein the phosphonic acid or phosphonate compound is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid or aminotrimethylene. Phosphonic acid or 2-phosphonic acid butane-1,2,4-tricarboxylic acid. The photoresist cleaning agent according to claim 1, wherein the content of the phosphonic acid or phosphonate compound is 0.01 to 5.0% by weight. The photoresist cleaning agent of claim 1, wherein the solvent is an anthracene, an anthracene, an imidazolidinone, and/or an alkyl glycol monoalkyl ether. The photoresist cleaning agent according to claim 1, wherein the solvent is contained in an amount of 60 to 95% by weight. The photoresist cleaning agent according to claim 12, wherein the hydrazine is dimethyl hydrazine, diethyl hydrazine or methyl ethyl hydrazine. The photoresist cleaning agent of claim 12, wherein the hydrazine is methyl hydrazine, ethyl hydrazine or cyclobutyl hydrazine. The photoresist cleaning agent of claim 12, wherein the imidazolidinone is 2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone or 1,3-diethyl-2 - Imidazolidinone. The photoresist cleaning agent of claim 12, wherein the alkyl group The diol monoalkyl ether is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or dipropylene glycol monobutyl ether. The photoresist cleaning agent of claim 1, wherein the photoresist cleaning agent further comprises a quaternary ammonium hydroxide, a surfactant, and/or water. The photoresist cleaning agent of claim 18, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Or benzyltrimethylammonium hydroxide. The photoresist cleaning agent of claim 18, wherein the surfactant is polyvinyl alcohol, polyvinylpyrrolidone, polyoxyethylene ether or polyoxyalkylene. The photoresist cleaning agent of claim 18, wherein the quaternary ammonium hydroxide is present in an amount of from 0 to 15% by weight. The photoresist cleaning agent according to claim 18, wherein the quaternary ammonium hydroxide is contained in an amount of from 0.5 to 5.0% by weight. The photoresist cleaning agent according to claim 18, wherein the surfactant is contained in an amount of from 0 to 15% by weight. The photoresist cleaning agent according to claim 23, wherein the surfactant is contained in an amount of 0.05 to 5.0% by weight. The photoresist cleaning agent according to claim 18, wherein the water content is 0 to 40% by weight. The photoresist cleaning agent according to claim 25, wherein the water content is 0.5 to 25 wt%.