TW201426206A - Photo-resist stripper - Google Patents

Abstract

The present invention discloses a photo-resist stripper with a low etching property for cleaning thick-film photo-resist patterns. The photo-resist stripper includes (a)quaternary ammonium hydroxide, (b)alkylol amine, (c)sugar and/or sugar alcohol, (d)surfactant, and (e)solvent. The photo-resist stripper can effectively remove the photo-resist on the semiconductor wafer. Meanwhile the photo-resist stripper doesn't attack substrate such as alumina and copper, thereby having a prospect in semiconductor wafer cleaning.

Description

Photoresist remover

The present invention relates to a photoresist removal agent.

In a conventional semiconductor manufacturing process, by forming a photoresist mask on the surface of some materials, pattern transfer after exposure, after obtaining the desired pattern, it is necessary to remove the residual photoresist before proceeding to the next process. In this process it is required to completely remove the unwanted photoresist while not corroding any substrate. For example, in the wafer microsphere implantation technology, a photoresist is required to form a mask, which needs to be removed after the microsphere is successfully implanted, but since the photoresist is thick, it is often difficult to completely remove it. . A more common method for improving the removal effect is to extend the soaking time, increase the soaking temperature, and use a more aggressive solution, but this often results in corrosion of the wafer substrate and corrosion of the microspheres, resulting in a significant reduction in wafer yield.

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. For example, WO2006/056298A1 utilizes tetramethylammonium hydroxide (TMAH), dimethyl amide An alkaline cleaning solution consisting of hydrazine (DMSO), ethylene glycol (EG) and water is used to clean the photoresist of the copper substrate while being substantially non-corrosive to metallic copper, but it is corrosive to metallic aluminum; for example, US 5529887 is oxidized by water. An alkaline cleaning solution consisting of potassium (KOH), alkyl glycol monoalkyl ether, water-soluble fluoride and water, immersing the wafer in the cleaning solution, and removing the thickness of the metal and the dielectric substrate at 40 to 90 ° C Membrane photoresist. It has a high corrosion to the semiconductor wafer substrate. With the rapid development of semiconductors, especially in the field of bump ball packaging, the requirements for the cleaning of photoresist residues have also increased accordingly; mainly with the increasing number of pins (I/O) per unit area, light The removal of resistance has also become more and more difficult.

It can be seen that finding a more effective method for suppressing metal corrosion suppression and high efficiency of photoresist removal is a priority for the improvement of such photoresist cleaning liquids.

The technical problem to be solved by the present invention is to provide a thick film photoresist cleaning capability and a countermeasure against the defects of the existing thick film photoresist cleaning liquid which have insufficient cleaning ability or strong corrosion to the semiconductor wafer pattern and the substrate. A semiconductor wafer pattern and a photoresist that is less corrosive to the substrate.

The invention discloses a low etching property suitable for cleaning with a thick photoresist and a cleaning method thereof. The low-etching photoresist cleaning liquid contains (a) a quaternary ammonium hydroxide, (b) an alcohol amine, (c) a sugar and/or a sugar alcohol, (d) a surfactant, and (e) a solvent. The low-etching photoresist cleaning agent can effectively remove the photoresist on the semiconductor wafer, and has no attack on the substrate, such as metal aluminum, copper, etc., and has a good application prospect in the field of semiconductor wafer cleaning.

In the present invention, the concentration of the quaternary ammonium hydroxide is 0.1 to 10% by weight, excellent 1~5wt%; the concentration of the alkanolamine is 0.1-30wt%, preferably 0.1-15wt%; the concentration of the sugar and/or sugar alcohol is 0.1~5wt%, preferably 0.1~3wt%; the concentration of the surfactant is 0.01~ 3 wt%, preferably 0.1 to 1 wt%; the balance is a solvent.

The mass of component a and component b described in the present invention is preferably between 6:1 and 1:2.5. When the ratio of component a to component b is greater than 6:1, the system may not form a homogeneous solution or form a homogeneous solution for a long time; on the other hand, when the ratio of component a to component b is less than 1 At 2.5, too much alcohol amine will cause the removal efficiency of the photoresist to decrease.

The quaternary ammonium hydroxides described in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, and hydroxy group. One or more of ethyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, and benzyltrimethylammonium hydroxide.

The alcohol amine described in the present invention is one of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanolamine and diglycolamine or Several. The presence of an alkanolamine is advantageous for increasing the solubility of the quaternary ammonium hydroxide.

The sugar or sugar alcohol described in the present invention is selected from the group consisting of threose, arabinose, xylose, ribose, ribulose, xylulose, glucose, mannose, galactose, tagatose, allose, a Sugar, idose, talose, sorbose, psicose, fructose, threitol, erythritol, ribitol, arabitol, xylitol, talitol, sorbitol, mannitol One or more of iditol and galactitol.

The surfactant described in the present invention is selected from the group consisting of polyvinylpyrrolidone. The addition of a surfactant facilitates the removal of the photoresist.

The solvent described in the present invention may be selected from an organic solvent or a mixture of an organic solvent and water. The organic solvent is preferably one or more of an anthracene, an anthracene, an imidazolidinone, a pyrrolidone, an imidazolidinone, a guanamine and an alcohol ether; the amidoxime is preferably a dimethyl hydrazine and One or more of methyl ethyl hydrazine; the hydrazine is preferably one or more of methyl hydrazine and cyclobutyl hydrazine; the imidazolidinone is preferably 2-imidazolidinone and 1,3 Or one or more of dimethyl-2-imidazolidinone; preferably, the pyrrolidone is one or more of N-methylpyrrolidone, N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; The imidazolinone is preferably 1,3-dimethyl-2-imidazolidinone; the guanamine is preferably one or more of dimethylformamide and dimethylacetamide; The alcohol ether is preferably one or more of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether. When the solvent described in the present invention is selected from a mixture of an organic solvent and water, the content of water in the mixture does not exceed 10% by weight.

In the cleaning liquid of the present invention, the photoresist residue on the wafer can be cleaned at 25 ° C to 85 ° C. The specific method is as follows: the wafer containing the photoresist residue is immersed in the cleaning liquid in the present invention, and after being immersed at 25 ° C to 85 ° C for a suitable period of time, it is taken out and rinsed, and then dried by high-purity nitrogen gas.

The technical effect of the invention is that: a) selecting a suitable ratio of quaternary ammonium hydroxide/alcoholamine is advantageous for coordinating photoresist removal ability and corrosion prevention of metal microspheres; b) presence of sugar or sugar alcohol is beneficial for inhibiting metal Corrosion of copper, aluminum, tin, lead, and silver; and c) the addition of polyvinylpyrrolidone facilitates the removal of photoresist.

The reagents and starting materials used in the present invention are commercially available. The cleaning liquid of the present invention can be obtained by simply and uniformly mixing the above components.

Advantages of the present invention are further illustrated by the following detailed description. However, the invention includes, but is not limited to, the specific compositions of the following examples.

Preparation example

Table 1 shows the cleaning solution formulations of the present invention. The percentages described below are all percentage by mass.

In order to further investigate the cleaning condition of the cleaning liquid, the present invention adopts the following technical means: immersing the wafer containing the photoresist in the cleaning agent, and using a constant temperature oscillator at a vibration frequency of about 60 rpm at 25 ° C to 85 ° C Shake for 30 to 90 minutes, then wash with deionized water and dry with high purity nitrogen. The cleaning effect of the photoresist and the corrosion of the cleaning solution on the wafer are shown in Table 2.

As can be seen from Table 2, the cleaning liquid of the present invention has a good cleaning effect on the photoresist and has a wide temperature range. In addition, the comparison between Example 5 and Comparative Example 1 shows that the addition of polyvinylpyrrolidone facilitates the removal of the photoresist; the comparison of Example 22 with Comparative Example 2 shows that the presence of sugar or sugar alcohol is beneficial to inhibit the metal. Corrosion of aluminum.

In summary, the cleaning liquid of the invention has strong photoresist removal ability; strong corrosion inhibition ability to metal and non-metal; and large operation space.

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 only As an example, 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 (12)

A photoresist remover comprising a quaternary ammonium hydroxide, an alcohol amine, a sugar and/or a sugar alcohol, a surfactant, and a solvent. The photoresist removing agent according to claim 1, wherein the concentration of the quaternary ammonium hydroxide is 0.1 to 10% by weight, the concentration of the alcohol amine is 0.1 to 30% by weight, and the concentration of the sugar and/or sugar alcohol The concentration of the surfactant is from 0.01 to 5% by weight, and the concentration of the solvent is the balance. The photoresist remover according to claim 2, wherein the concentration of the quaternary ammonium hydroxide is 1 to 5 wt%, the concentration of the alkanolamine is 0.1 to 15 wt%, and the concentration of the sugar and/or sugar alcohol The concentration of the surfactant is 0.1 to 1% by weight, and the concentration of the surfactant is 0.1 to 1% by weight. The photoresist cleaning agent according to claim 2, wherein the mass ratio of the quaternary ammonium hydroxide to the alcohol amine is between 6 and 1 and between 1.5 and 2.5. The photoresist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. One or more of methyltriethylammonium hydroxide, hydroxyethyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, and benzyltrimethylammonium hydroxide. The photoresist cleaning agent according to claim 1, wherein the alcohol amine described in the present invention is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol. One or more of ethyl diethanolamine and diglycolamine. The photoresist cleaning agent of claim 1, wherein the sugar and/or The sugar alcohol is selected from the group consisting of threose, arabinose, xylose, ribose, ribulose, xylulose, glucose, mannose, galactose, tagatose, allose, altrose, idose, tarot Sugar, sorbose, psicose, fructose, threitol, erythritol, ribitol, arabitol, xylitol, talitol, sorbitol, mannitol, iditol and galactitol One or several. The photoresist cleaning agent of claim 1, wherein the surfactant is polyvinylpyrrolidone. The photoresist cleaning agent of claim 1, wherein the solvent is selected from the group consisting of an organic solvent or a mixture of an organic solvent and water. The photoresist cleaning agent according to claim 9, wherein the organic solvent is one or more selected from the group consisting of an anthraquinone, an anthracene, an imidazolidinone, a pyrrolidone, an imidazolidinone, a guanamine, and an alcohol ether. The photoresist cleaning agent according to claim 10, wherein the hydrazine is selected from one or more of dimethyl hydrazine and methyl ethyl hydrazine; and the hydrazine is selected from the group consisting of methyl hydrazine and cyclobutyl hydrazine. One or more; the imidazolidinone is selected from one or more of 2-imidazolidinone and 1,3-dimethyl-2-imidazolidinone; the pyrrolidone is selected from N-methylpyrrolidone, One or more of N-cyclohexylpyrrolidone and N-hydroxyethylpyrrolidone; the imidazolinone is 1,3-dimethyl-2-imidazolidinone; the guanamine is selected from the group consisting of dimethyl One or more of guanamine and dimethylacetamide; the alcohol ether is selected from one or more of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether. The photoresist cleaner according to claim 9, wherein the solvent is selected from the mixture of an organic solvent and water, and the water content of the mixture does not exceed 10% by weight.