CN101295143B

CN101295143B - Photoresist leftover cleaning agent

Info

Publication number: CN101295143B
Application number: CN2008100119068A
Authority: CN
Inventors: 侯军; 吕冬
Original assignee: Dalian Sandaaoke Chemistry Co Ltd
Current assignee: Dalian Sandaaoke Chemistry Co Ltd
Priority date: 2008-06-19
Filing date: 2008-06-19
Publication date: 2011-11-23
Anticipated expiration: 2028-06-19
Also published as: CN101295143A

Abstract

The invention discloses a cleaning agent which has simple preparation method, low corrosion rate on substrate material and metallic wiring, and no pollution on environment and is used for removing the residues of photoresist after processes of dry corrosion and cineration. According to the weight percentage, the cleaning agent comprises the following the raw materials: 1%-15% of surfactant, 0.01%-5% of ammonium salt fluoride, 5%-20% of organic sulfonic acid, 5%-20% of organic solvent, 1%-5% of penetrant, 0.1%-5% of carboxylic acids containing nitrogen, 0.01%-5% of corrosion inhibitor and residual quantity of pure water.

Description

The photoetching glue residue clean-out system

Technical field:

The present invention relates to a kind of clean-out system, especially a kind of being applied in integrated circuit (IC), VLSI (very large scale integrated circuit) (ULSI) manufacturing process is in order to remove the photoetching glue residue clean-out system behind dry corrosion, cineration technics.

Background technology:

In the manufacturing process of integrated circuit (IC), VLSI (very large scale integrated circuit) (ULSI), making and forming conductive layer pattern with photoresist on wafer is a very important procedure.Generally be evenly to spread upon with photoresist on dielectric film or the metal film, after exposure, development, on photoresist, form the conductive layer image, and then utilize photoresist, dielectric film or metal film are carried out etching as mask, on wafer, to form conductive layer, remove photoresist at last again.At present, usually using plasma dry corrosion, cineration technics are handled the photoresist mask, but, because in dry corrosion, cineration technics process, complicated chemical reaction takes place in ion in the etching gas and free radical and photoresist, make photoresist take place easily to solidify and be difficult to and remove, simultaneously, the resist polymkeric substance that forms in the sidewall areas of chemical degradation also is difficult to remove.And because the explosion phenomenon produces the surface cure layer, the photoresist of degeneration promptly becomes remaining pattern and particle, also becomes the residue that is difficult to remove.In addition, metal conductive film also can produce the metallic ion that is difficult to remove in etching process.Therefore, there are pollutants such as photoresist is residual, metallic ion in the crystal column surface behind dry corrosion, the cineration technics, has had a strong impact on the quality of integrated circuit.

Summary of the invention:

The present invention is in order to solve existing in prior technology the problems referred to above, provides that a kind of preparation method is simple, cost is low, the photoetching glue residue clean-out system of, environmentally safe low to backing material and metal wiring rate of corrosion.

Technical solution of the present invention is: a kind of photoetching glue residue clean-out system is characterized in that containing raw material and percentage by weight is as follows:

Surfactant 1%～15%

Ammonium fluoride 0.01%～5%

Organic sulfonic acid 5%～20%

Organic solvent 5%～20%

Bleeding agent 1%～5%

Contain nitronic acid 0.1%～5%

Corrosion inhibiter 0.01%～5%

The pure water surplus.

The preferred plan that contains raw material and percentage by weight is as follows:

Surfactant 5%

Ammonium fluoride 0.5%

Organic sulfonic acid 10%

Organic solvent 10%

Bleeding agent 2%

Contain nitronic acid 0.5%

Corrosion inhibiter 0.05%

The pure water surplus.

Described surfactant is the segmented copolymer of polyethylene oxide, polypropyleneoxide, oxirane, epoxypropane, add at least a in the hydrophilic polymer that alkyl obtains in described segmented copolymer.

Described ammonium fluoride is at least a in ammonium fluoride, fluoram, Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, three ethanol ammonium fluorides, the methyl diethanol ammonium fluoride.

Described organic sulfonic acid is at least a in methane-sulforic acid, ethyl sulfonic acid, propane sulfonic acid, p-toluenesulfonic acid, the dodecylbenzene sulfonic acid.

Described bleeding agent is the JFC bleeding agent.

Described organic solvent is at least a in the single ether of glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, the propylene glycol monobutyl ether.

The described nitronic acid that contains is at least a in ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, triethylenetetraaminehexaacetic acid or nitrilotriacetic acid(NTA), ammonium salt, the sodium salt.

Described corrosion inhibiter is at least a in ammonium polyacrylate, polyacrylic acid, HPMA, mercapto succinic acid, citric acid, lactic acid, gallic acid, maleic acid, the maleic anhydride.

Described pure water is the water that filters through ion exchange resin, and 25 ℃ of its resistivity are at least 18M Ω.

Each component coordinative role of the present invention has the following advantages:

1. the non-ionic surfactant that contains of the present invention and JFC bleeding agent synergy, uniformly penetrating has degreasing power efficiently to crystal column surface fast, can remove the residues such as photoresist of crystal column surface and substrate metal surfaces rapidly.

2. the present invention contains contains nitronic acid, can catch in the pollutant metallic ion and with its formation complex ion, thereby remove contaminant metal ions.

3. the present invention does not produce the residual impurity particulate in cleaning process;

4. volatility of the present invention is little, and low to the rate of corrosion of backing material and metal wiring, toxicity is low, and operating personnel are not caused health hazard, environmentally safe.

Embodiment:

Embodiment 1:

Raw material and percentage by weight are as follows:

Surfactant 1%～15%, ammonium fluoride 0.01%～5%, organic sulfonic acid 5%～20%, organic solvent 5%～20%, bleeding agent 1%～5% contains nitronic acid 0.1%～5%, corrosion inhibiter 0.01%～5%, pure water surplus.Each raw material is selected in its weight range, and general assembly (TW) is 100%.

Described bleeding agent is the JFC bleeding agent.

Mentioned component mixed get final product.

Concrete cleaning method is: under the room temperature to 65 ℃, will immerse soaking and washing 5～20min in the clean-out system of the embodiment of the invention 1 through the wafer after dry corrosion, the ashing treatment, and with ultrapure water rinsing 3min, use the high pure nitrogen drying at last.

Cleaning performance is estimated: can peel off residues such as photoresist on the wafer, metallic ion fast with the clean-out system of the embodiment of the invention 1, at crystal column surface noresidue impurity, little to the rate of corrosion of backing material and metal wiring.

Embodiment 2:

Raw material and percentage by weight are as follows:

Pluronic surfactant 5%

Ammonium fluoride 0.5%

P-toluenesulfonic acid 10%

Organic solvent 10%

JFC bleeding agent 2%

Ethylenediamine tetraacetic acid 0.5%

Citric acid 0.05%

The pure water surplus.

General assembly (TW) is 100%.

Cleaning method is with embodiment 1, and cleaning performance more is better than embodiment 1.

Claims

1. photoetching glue residue clean-out system, it is characterized in that containing raw material and percentage by weight is as follows: surfactant 1%～15%, ammonium fluoride 0.01%～5%, organic sulfonic acid 5%～20%, organic solvent 5%～20%, bleeding agent 1%～5%, contain nitronic acid 0.1%～5%, corrosion inhibiter 0.01%～5%, the pure water surplus, described surfactant is a polyethylene oxide, polypropyleneoxide, oxirane, the segmented copolymer of epoxypropane, add at least a in the hydrophilic polymer that alkyl obtains in described segmented copolymer, described bleeding agent is the JFC bleeding agent.

2. photoetching glue residue clean-out system according to claim 1 is characterized in that containing raw material and percentage by weight is as follows:

Surfactant 5%

Ammonium fluoride 0.5%

Organic sulfonic acid 10%

Organic solvent 10%

Bleeding agent 2%

Contain nitronic acid 0.5%

Corrosion inhibiter 0.05%

The pure water surplus.

3. photoetching glue residue clean-out system according to claim 2 is characterized in that described ammonium fluoride is at least a in ammonium fluoride, fluoram, Methanaminium, N,N,N-trimethyl-, fluoride, tetrabutyl ammonium fluoride, three ethanol ammonium fluorides, the methyl diethanol ammonium fluoride.

4. photoetching glue residue clean-out system according to claim 3 is characterized in that described organic sulfonic acid is at least a in methane-sulforic acid, ethyl sulfonic acid, propane sulfonic acid, p-toluenesulfonic acid, the dodecylbenzene sulfonic acid.

5. photoetching glue residue clean-out system according to claim 4 is characterized in that described organic solvent is at least a in the single ether of glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, the propylene glycol monobutyl ether.

6. photoetching glue residue clean-out system according to claim 5 is characterized in that the described nitronic acid that contains is at least a in ethylenediamine tetraacetic acid, diethylene-triamine pentaacetic acid, triethylenetetraaminehexaacetic acid or the nitrilotriacetic acid(NTA).

7. photoetching glue residue clean-out system according to claim 6 is characterized in that described corrosion inhibiter is at least a in ammonium polyacrylate, polyacrylic acid, HPMA, mercapto succinic acid, citric acid, lactic acid, gallic acid, maleic acid, the maleic anhydride.

8. photoetching glue residue clean-out system according to claim 7 is characterized in that described pure water is the water that filters through ion exchange resin, and 25 ℃ of its resistivity are at least 18M Ω.