CN101295143B - Photoresist Residue Cleaner - Google Patents

Abstract

The present invention discloses a cleaning agent for removing photoresist residues after dry etching and ashing processes, which has a simple preparation method, low corrosion rate to substrate materials and metal wiring, and no pollution to the environment. The cleaning agent raw materials and weight percentages are as follows: surfactant 1% to 15%, ammonium fluoride salt 0.01% to 5%, organic sulfonic acid 5% to 20%, organic solvent 5% to 20%, penetrant 1% to 5%, nitrogen-containing carboxylic acid 0.1% to 5%, corrosion inhibitor 0.01% to 5%, and pure water as the balance.

Description

Photoresist Residue Cleaner

Technical field:

The invention relates to a cleaning agent, especially a cleaning agent used in the manufacturing process of integrated circuits (IC) and ultra-large-scale integrated circuits (ULSI) to remove photoresist residues after dry etching and ashing processes .

Background technique:

In the manufacturing process of integrated circuits (ICs) and ultra-large-scale integrated circuits (ULSIs), it is a very important process to use photoresists to form conductive layer patterns on wafers. Generally, the photoresist is evenly applied on the insulating film or metal film, and after exposure and development, a conductive layer image is formed on the photoresist, and then the photoresist is used as a mask to etch the insulating film or metal film. To form a conductive layer on the wafer, and finally remove the photoresist. At present, plasma dry etching and ashing processes are usually used to process photoresist masks. However, during the dry etching and ashing processes, ions and free radicals in the etching gas undergo complex chemical reactions with the photoresist. , so that the photoresist is prone to curing and difficult to remove, and at the same time, the resist polymer formed in the chemically degraded sidewall region is also difficult to remove. Moreover, the degraded photoresist becomes residual patterns and particles due to the popping phenomenon to produce a surface cured layer, which also becomes a difficult-to-remove residue. In addition, metal ions that are difficult to remove will also be generated during the etching process of the metal conductive film. Therefore, there are photoresist residues, metal ions and other pollutants on the wafer surface after dry etching and ashing processes, which seriously affect the quality of integrated circuits.

Invention content:

The present invention aims to solve the above-mentioned problems in the prior art, and provides a photoresist residue cleaning agent with simple preparation method, low cost, low corrosion rate to substrate materials and metal wiring, and no pollution to the environment.

The technical solution of the present invention is: a kind of photoresist residue cleaning agent, it is characterized in that containing raw material and weight percent as follows:

Surfactant 1%～15%

Ammonium fluoride salt 0.01%～5%

Organic sulfonic acid 5%～20%

Organic solvent 5%～20%

Penetrant 1%～5%

Nitrogen-containing carboxylic acid 0.1%～5%

Corrosion inhibitor 0.01%～5%

Pure water balance.

The optimal scheme that contains raw material and weight percentage is as follows:

Surfactant 5%

Ammonium fluoride salt 0.5%

Organic sulfonic acid 10%

Organic solvents 10%

Penetrant 2%

Nitrogen-containing carboxylic acid 0.5%

Corrosion inhibitor 0.05%

Pure water balance.

Described surfactant is block copolymer of polyethylene oxide, polypropylene oxide, ethylene oxide, propylene oxide, in the hydrophilic polymer that adds alkyl to obtain in described block copolymer at least one of .

The ammonium fluoride salt is at least one of ammonium fluoride, ammonium difluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, triethanol ammonium fluoride, and methyldiethanol ammonium fluoride.

The organic sulfonic acid is at least one of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

The described penetrant is JFC penetrant.

Described organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol At least one of monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.

The nitrogen-containing carboxylic acid is at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid or nitrilotriacetic acid, ammonium salt, and sodium salt.

The corrosion inhibitor is at least one of ammonium polyacrylate, polyacrylic acid, polymaleic anhydride, mercaptosuccinic acid, citric acid, lactic acid, gallic acid, maleic acid, and maleic anhydride.

The pure water is water filtered by an ion exchange resin, and its resistivity is at least 18MΩ at 25°C.

The coordinated action of each component of the present invention has the following advantages:

1. The non-ionic surfactant contained in the present invention works synergistically with the JFC penetrant, which can quickly and evenly penetrate the wafer surface, has efficient degreasing ability, and can quickly remove photoresist and other residues on the wafer surface and substrate metal surface thing.

2. The nitrogen-containing carboxylic acid contained in the present invention can capture metal ions in pollutants and form complex ions with them, thereby removing metal ion pollutants.

3. The present invention does not produce residual impurity particles during the cleaning process;

4. The invention has low volatility, low corrosion rate to substrate materials and metal wiring, low toxicity, no health hazards to operators, and no pollution to the environment.

Detailed ways:

Example 1:

Raw materials and weight percentages are as follows:

Surfactant 1%-15%, ammonium fluoride salt 0.01%-5%, organic sulfonic acid 5%-20%, organic solvent 5%-20%, penetrant 1%-5%, nitrogen-containing carboxylic acid 0.1% ～5%, corrosion inhibitor 0.01%～5%, pure water balance. Each raw material is selected within its weight range, and the total weight is 100%.

Described surfactant is block copolymer of polyethylene oxide, polypropylene oxide, ethylene oxide, propylene oxide, in the hydrophilic polymer that adds alkyl to obtain in described block copolymer at least one of .

The ammonium fluoride salt is at least one of ammonium fluoride, ammonium difluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, triethanol ammonium fluoride, and methyldiethanol ammonium fluoride.

The organic sulfonic acid is at least one of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

The described penetrant is JFC penetrant.

Described organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol At least one of monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.

The nitrogen-containing carboxylic acid is at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid or nitrilotriacetic acid, ammonium salt, and sodium salt.

The corrosion inhibitor is at least one of ammonium polyacrylate, polyacrylic acid, polymaleic anhydride, mercaptosuccinic acid, citric acid, lactic acid, gallic acid, maleic acid, and maleic anhydride.

The pure water is water filtered by an ion exchange resin, and its resistivity is at least 18MΩ at 25°C.

Mix the above ingredients evenly.

The specific cleaning method is: at room temperature to 65°C, immerse the dry-etched and ashed wafer in the cleaning agent of Example 1 of the present invention for 5-20 minutes, rinse with ultra-pure water for 3 minutes, and finally use high Dry with pure nitrogen.

Cleaning effect evaluation: the photoresist, metal ions and other residues on the wafer can be quickly peeled off with the cleaning agent of Example 1 of the present invention, and there is no residual impurity on the wafer surface, and the corrosion rate to the substrate material and metal wiring is small .

Example 2:

Raw materials and weight percentages are as follows:

Pluronic Surfactant 5%

Ammonium Fluoride 0.5%

p-toluenesulfonic acid 10%

Organic solvents 10%

JFC Penetrant 2%

EDTA 0.5%

Citric acid 0.05%

Pure water balance.

The total weight is 100%.

Cleaning method is the same as embodiment 1, and cleaning effect is better than embodiment 1.

Claims (8)

1. A photoresist residue cleaning agent, characterized in that it contains raw materials and weight percentages as follows: 1% to 15% of surfactant, 0.01% to 5% of ammonium fluoride salt, 5% to 20% of organic sulfonic acid, 5% to 20% of organic solvent, 1% to 5% of penetrant, 0.1% to 5% of nitrogen-containing carboxylic acid, 0.01% to 5% of corrosion inhibitor, and the balance of pure water. The surfactant is polyepoxide At least one of block copolymers of ethylene, polypropylene oxide, ethylene oxide, and propylene oxide, and hydrophilic polymers obtained by adding alkyl groups to the block copolymers, and the penetrating agent is JFC Penetrant. 2. photoresist residue cleaning agent according to claim 1, is characterized in that containing raw material and percentage by weight are as follows: Surfactant 5% Ammonium fluoride salt 0.5% Organic sulfonic acid 10% Organic solvents 10% Penetrant 2% Nitrogen-containing carboxylic acid 0.5% Corrosion inhibitor 0.05% Pure water balance. 3. photoresist residue cleaning agent according to claim 2, is characterized in that described ammonium fluoride salt is ammonium fluoride, ammonium difluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride , triethanol ammonium fluoride, methyldiethanol ammonium fluoride at least one. 4. photoresist residue cleaning agent according to claim 3 is characterized in that described organic sulfonic acid is methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid at least one of the acids. 5. photoresist residue cleaning agent according to claim 4 is characterized in that described organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono Phenyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether at least one of the 6. photoresist residue cleaning agent according to claim 5 is characterized in that described nitrogen-containing carboxylic acid is ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid or at least one of nitrilotriacetic acid. 7. photoresist residue cleaning agent according to claim 6 is characterized in that described corrosion inhibitor is ammonium polyacrylate, polyacrylic acid, polymaleic anhydride, mercaptosuccinic acid, citric acid, lactic acid, gallic acid , maleic acid, maleic anhydride at least one. 8. The photoresist residue cleaning agent according to claim 7, characterized in that the pure water is water filtered through an ion exchange resin, and its resistivity is at least 18 MΩ at 25°C.