KR20120036030A - Composition for removing a negative photoresist residue and cleaning method using the same - Google Patents

Abstract

PURPOSE: A composition for eliminating negative photoresist residues and a cleaning method using the same are provided to prevent the generation of pollutants such as metal impurities and to improve the eliminating force of negative photoresist during a semiconductor manufacturing process. CONSTITUTION: A composition for eliminating negative photoresist residues includes 4-40 weight% of alkylbenzene sulfonic acid, 50-95 weight% of water-soluble organic solvent, and 0.5-10 weight% of hydrogen peroxide. The alkylbenzene sulfonic acid is one or more selected from dodecyl benzenesulfonic acid, toluene sulfonic acid, o-cresol sulfonic acid(2-methyl phenol sulfonic acid), cresol sulfonic acid(methyl phenol sulfonic acid), cumene sulfonic acid, xylene sulfonic acid, 2,5-xylene sulfonic acid, 2,4-xylene sulfonic acid, camphor sulfonic acid, and salts of the same. The water-soluble organic solvent is one or more selected from N-methylpyrolidone, dimethyl sulfuroxide, ethyl-3-ethoxypropionate, methyl 3-methoxypropionate, dimethylacetamide, and N,N-dimethylformamide.

Description

Composition For Removing A Negative Photoresist Residue And Cleaning Method Using The Same}

The present invention relates to a composition for removing negative photoresist residue and a cleaning method using the same.

In general, the manufacture of semiconductor devices and flat panel display devices includes a process of forming a metal film or an insulating film, a process of forming a photoresist, an exposure process of transferring a mask pattern to the photoresist, a developing process of developing the exposed photoresist, It proceeds to the etching process of etching a film along a pattern, and the peeling process of removing a photoresist. In the said peeling process, the photoresist apply | coated on the wafer or the board | substrate is removed by ashing. After this ashing process, there are some altered and / or cured photoresist residues and the like. If the deteriorated and / or cured photoresist is not completely removed, the photoresist residue may cause short circuit and disconnection of the wiring in the subsequent process, which may cause a decrease in production yield.

Photoresist is a photosensitive film used to transfer an image to a substrate, where the photoresist may be positive- or negative-functional. For most negative-functional photoresists, portions of the coating layer exposed to activating radiation polymerize or crosslink by the reaction of the photoactive compounds with the polymerizable reagents of the photoresist composition. As a result, the exposed coating portion is less soluble in the developer than the unexposed portion. At this time, a bulk photoresist residue may be present even after the development process as described above, and a decrease in production yield may also exist due to the photoresist residue.

As a method for removing photoresist residues, for example, Korean Patent No. 10-0714951 discloses a cleaning composition composed of a water-soluble organic solvent, sulfonic acid or salt thereof, and water. However, the composition is excellent in the removal power of the positive photoresist, but the negative power of the negative photoresist has a weak problem.

In addition, Korean Patent No. 10-0301680 discloses a composition containing an alkylbenzene sulfonic acid, a light aromatic solvent naphtha, a chlorine-containing organic compound, a polyoxy ethyleneoctylphenyl ether derivative, and hydroxy benzenes. The composition has a problem in that the negative photoresist removal ability is good, but it is not environmentally friendly by using a material having a harmful effect on the human body, such as a hard aromatic naphtha.

In addition, Korean Patent No. 10-0718527 discloses a stripper composition for a negative chemically amplified resist composed of hydrazine, a polar organic solvent, a basic compound and water, wherein the composition is not excellent in removing negative photoresist, and KOH in the basic compound. In the case of using NaOH, it is difficult to use the semiconductor process due to the inclusion of metal ions.

The present invention is to solve the above problems, an object of the present invention is to provide a new negative photoresist residue removal composition that is environmentally friendly, excellent in removing power of the negative photoresist, easy to use water in the pore process It is.

Another object of the present invention is to provide a negative photoresist residue cleaning method using the composition for removing the negative photoresist residue.

In order to achieve the above object, the present invention provides a composition for removing negative photoresist residue comprising alkylbenzene sulfonic acid, a water-soluble organic solvent and hydrogen peroxide.

In addition, the present invention is a method for cleaning a negative photoresist residue using a composition for removing a negative photoresist residue,

i) providing a composition for removing photoresist residues to a substrate or semiconductor device structure in which the photoresist residues are present; And

ii) cleaning the negative photoresist residue comprising contacting and cleaning the composition on the surface of the substrate or semiconductor device structure where the photoresist residue is present.

The composition for removing the negative photoresist residue of the present invention is excellent in removing power of the negative photoresist during the semiconductor manufacturing process, and water is easily used in the cleaning process using a water-soluble organic solvent. In addition, it does not generate pollutants such as metal impurities because it does not use components containing metal ions, and it is relatively environmentally friendly because it does not use environmental regulation target materials.

The present invention relates to a composition for removing negative photoresist residue comprising alkylbenzene sulfonic acid, a water soluble organic solvent and hydrogen peroxide. More specifically, the composition of the present invention, based on the total weight of the composition, 4 to 40% by weight of alkylbenzene sulfonic acid; 50 to 95 wt% of a water-soluble organic solvent; And 0.5 to 10% by weight of hydrogen peroxide.

As used herein, "photoresist residue" refers to photoresist residues (side polymers, side protections), including photoresist and / or incompletely ashed resists, organometallic polymers, metal oxides, and the like remaining after the developer treatment. Film).

The alkylbenzene sulfonic acid is preferably 4 to 40% by weight of alkylbenzene sulfonic acid based on the total weight of the composition. If the alkylbenzene sulfonic acid is included in less than 4% by weight can not implement a sufficient cleaning effect, if it contains more than 40% by weight may be difficult to increase the viscosity and mixing when mixed with the solvent effective removal of the negative photoresist Can't expect it.

In this case, the alkylbenzene sulfonic acid preferably includes a straight or branched chain alkyl group having 1 to 20 carbon atoms. The alkylbenzene sulfonic acid is not particularly limited, but specific examples include dodecylbenzenesulfonic acid, toluenesulfonic acid, 0-cresolsulfonic acid (2-methylphenolsulfonic acid), cresolsulfonic acid (methylphenolsulfonic acid), cumenesulfonic acid, xylenesulfonic acid, 2 , 5-xylenesulfonic acid, 2,4-xylenesulfonic acid, camphorsulfonic acid and salts thereof. In the composition of this invention, the said alkylbenzene sulfonic acid can be used individually or in combination of 2 or more types.

The water-soluble organic solvent is preferably included in 50 to 95% by weight relative to the total weight of the composition. If the water-soluble organic solvent is included in less than 50% by weight relative to the total weight of the composition, it is difficult to effectively mix with alkylbenzene sulfonic acid, and when contained in excess of 95% by weight, the content of alkylbenzene sulfonic acid may be reduced, making it difficult to effectively remove the negative photoresist. have.

Specific examples of the water-soluble organic solvent include N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethyl 3-ethoxypropionate (EEP), 1 type selected from the group consisting of methyl 3-methoxypropionate (MMP), dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF) Or two or more kinds, but is not limited thereto.

In addition, the use of a hydrophilic solvent such as a water-soluble organic solvent has the advantage that the water washing process is easy.

The composition for removing the negative photoresist residue includes hydrogen peroxide as another component. The hydrogen peroxide is preferably included in 0.5 to 10% by weight based on the total weight of the composition. When the hydrogen peroxide is added in less than 0.5% by weight relative to the total weight of the composition, it is difficult to expect effective oxidizing power, when contained in more than 10% by weight it is difficult to effectively expect the removal power of the negative photoresist is contained in excess, aluminum It is easy to cause corrosion.

Here, the hydrogen peroxide is preferably 25 to 35% aqueous solution, more preferably 29 to 32% hydrogen peroxide aqueous solution, and more preferably hydrogen peroxide is 31% aqueous solution.

In the case of photoresist that is cured and deteriorated due to energy during the process of using negative photoresist, the surface of the photoresist has many carbon (C) components by removing oxygen (O) and hydrogen (H) ions. There will be a negative photoresist having an existing structure. After changing the surface of the negative photoresist using an oxidizing agent, an acidic group of sulfonic acid may act to remove the negative photoresist.

At this time, the hydrogen peroxide reacts with sulfonic acid to form a strong oxidizing agent, which is effective for removing residual photoresist residue.

In addition, the composition for removing the negative photoresist residue may further include at least one known additive, such as an alkaline compound, a surfactant, and the like within a range that does not impair the object and effect of the present invention.

The alkaline compound is methylamine, ethylamine, propylamine, butylamine, ethanolamine, N-methylethanolamine, N-ethylethanolamine, diethanolamine, isopropanolamine, 2- (2-aminoethoxy) ethanol, ethylene It is preferably one or two or more selected from the group consisting of diamine, propylenediamine, butylenediamine, diethylenetriamine, piperazine and morpholine, but is not necessarily limited thereto.

The surfactant may be any known cationic, anionic, nonionic or zwitterionic type without limitation.

The negative photoresist residue removing composition prepared by the present invention may be prepared by mixing the above-mentioned compounds in an advantageous amount in an advantageous amount, and the mixing method is not particularly limited, and various known methods may be applied.

In addition, the present invention is a method for cleaning a negative photoresist residue using a composition for removing a negative photoresist residue,

i) providing a composition for removing the negative photoresist residue of the present invention to a substrate or semiconductor device structure in which the photoresist residue is present; And

ii) cleaning the negative photoresist residue comprising contacting and cleaning the composition on the surface of the substrate or semiconductor device structure where the photoresist residue is present.

In the present cleaning method, the substrate or semiconductor device structure includes at least one layer selected from the group consisting of an exposed metal layer, a silicon oxide layer, a polycrystalline silicon surface layer and a silicon nitride film layer.

The metal layer is made of at least one metal selected from the group consisting of aluminum, tungsten, copper, and titanium nitride, and the silicon oxide layer is made of tetraethoxysilane (TEOS), borophospho silicate glass (BPSG), and silicon oxide film of low dielectric constant. At least one silicon oxide selected from the group.

In the present invention, contacting the substrate or the semiconductor device structure and the composition in step ii) may be performed by a method known in the art. Preferably it is carried out by a batch type immersing the substrate or semiconductor device structure in the composition, or by a single type of supplying the cleaning composition to the surface while rotating the substrate or semiconductor structure. The contact between the substrate or the semiconductor device structure and the composition is not limited, but is preferably performed for 0.1 to 40 minutes at a temperature of 10 ℃ to 90 ℃.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following Examples and Comparative Examples are intended to illustrate the present invention, the present invention is not limited to the following Examples and Comparative Examples can be variously modified and changed.

Example  1 to 9 and Comparative example  1 to 5

A composition for removing photoresist residues was prepared by mixing and stirring with the ingredients and compositions shown in Table 1.

 (Unit: wt%) Alkylbenzene sulfonic acid Water soluble organic solvent 31%
Hydrogen peroxide
Aqueous solution water ABS-1 AQ-1 AQ-2 AQ-3 Example 1 4 93 - - 3 - Example 2 10 89 - - One - Example 3 30 - - 67 3 - Example 4 30 67 - - 3 - Example 5 20 77 - - 3 - Example 6 20 - 77 - 3 - Example 7 30 - - 67 3 - Example 8 10 - 87 - 3 - Example 9 30 60 - - 10 - Comparative Example 1 3 97 - - - Comparative Example 2 - 95 - - 5 - Comparative Example 3 20 - 80 - - - Comparative Example 4 30 69.9 - - 0.1 - Comparative Example 5 30 - - 67 - 3 ABS-1: dodecylbenzenesulfonic acid
AQ-1: Dimethyl sulfoxide (DMSO)
AQ-2: N-methylpyrrolidone (NMP)
AQ-3: Dimethylacetamide (DMAc)

Test Example  One. Negative Photoresist Removal  evaluation

After the photoresist is applied on the silicon substrate, the photoresist is cured through an exposure machine to prepare a specimen. The negative photoresist substrate thus prepared was immersed in the negative photoresist removing composition of the present invention at 85 ° C. for 20 minutes. Subsequently, the deposited substrate was taken out and washed with water, and then observed by SEM to evaluate the photoresist removal force on the substrate. The results are shown in Table 2. In the following Table 2, when the photoresist was removed,?, Slightly remaining?, And when the removal force was lowered, X was indicated.

Negative Photoresist Removal Example 1 ○ Example 2 ○ Example 3 ◎ Example 4 ◎ Example 5 ◎ Example 6 ◎ Example 7 ◎ Example 8 ◎ Example 9 ◎ Comparative Example 1 X Comparative Example 2 X Comparative Example 3 X Comparative Example 4 X Comparative Example 5 X

As shown in Table 2, Examples 1 to 9 containing all of the alkylbenzene sulfonic acid, the water-soluble organic solvent, and hydrogen peroxide of the present invention were excellent in removing negative photoresist residues. However, the compositions of Comparative Examples 1-4 containing only some of the above components showed poor results. On the other hand, in the case of Comparative Example 5 using water instead of hydrogen peroxide, the removal of the negative photoresist residue was not easy.

Claims (6)

A composition for removing negative photoresist residue comprising an alkylbenzene sulfonic acid, a water soluble organic solvent and hydrogen peroxide. The method according to claim 1, wherein the total weight of the composition
4-40% by weight of alkylbenzene sulfonic acid,
50 to 95% by weight of a water-soluble organic solvent; And
A composition for removing negative photoresist residues, comprising 0.5 to 10% by weight of hydrogen peroxide. The method of claim 1, wherein the alkyl benzene sulfonic acid is dodecylbenzene sulfonic acid, toluene sulfonic acid, 0- cresol sulfonic acid (2-methylphenol sulfonic acid), cresol sulfonic acid (methylphenol sulfonic acid), cumene sulfonic acid, xylene sulfonic acid, 2,5- xylene sulfonic acid , 2,4-xylenesulfonic acid, camphorsulfonic acid, and salts thereof. The composition for removing negative photoresist, characterized in that one or two or more selected from the group consisting of. The method of claim 1, wherein the water-soluble organic solvent is N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethyl 3-ethoxypropionate (Ethyl 3-ethoxypropionate; EEP ), Methyl 3-methoxypropionate (MMP), dimethylacetamide (DMAc) and N, N-dimethylformamide (NMF) A composition for removing negative photoresist residues, characterized in that the species or two or more. The composition of claim 1, wherein the composition further comprises one or two or more selected from the group consisting of an alkaline compound and a surfactant. i) providing a composition for removing negative photoresist residues as defined in any one of claims 1 to 5 to a substrate or semiconductor device structure in which the photoresist residues are present; And
ii) cleaning the negative photoresist residue by contacting the composition with a surface of the substrate or semiconductor device structure where the photoresist residue is present.