Photoresist cleaning solution composition and method for forming photoresist pattern using same

Abstract

The present invention provides a photoresist cleaning solution composition and a method for forming a photoresist pattern using same, wherein the photoresist cleaning solution composition comprises: a first nonionic surfactant having a hydrophile-lipophile balance (HLB) value of 6 to 10 (both inclusive); and a second nonionic surfactant having an HLB value of 10 (exclusive) to 19 (inclusive), and the first nonionic surfactant and the second nonionic surfactant each possess a branched chain alkyl group, with the weight ratio of the first non-ionic surfactant to the second non-ionic surfactant ranging from 1:0.1 (inclusive) to less than 1:5.0.

Description

Photoresist cleaning solution composition and method for forming a photoresist pattern using the same

[0001] The present invention relates to a photoresist cleaning solution composition and a method for forming a photoresist pattern using the same.

[0002]

[0003] Photoresist is a chemical film that can form a pattern printed on a photomask onto a substrate by using a photochemical reaction caused by light.

[0004] As devices become increasingly miniaturized and refined, the need for fine patterning of photoresist is increasing. To achieve fine patterning using photoresist, any remaining residue on the substrate after the photoresist coating is exposed and developed must be removed. Conventionally, distilled water was used to remove this residue, but the high surface tension of distilled water caused the photoresist's fine pattern to collapse, or, if the pattern was linear, microbridge defects to occur.

[0005] To address these issues, Korean Patent No. 10-0429455 used a small amount of nonionic surfactant mixed with distilled water. While the nonionic surfactant reduced surface tension, it also generated excessive foam, reducing the cleaning power for removing developer residue. Furthermore, the insufficient cleaning power increased the pattern line width roughness, resulting in a mismatch between the photomask pattern and the photoresist pattern.

[0006]

[0007] The present invention provides a photoresist cleaning composition that suppresses foaming, thereby improving the cleaning power for removing residues of a developer, and suppresses melting and swelling of a pattern, thereby improving the phenomenon of pattern collapse, and a method for forming a photoresist pattern using the same.

[0008]

[0009] A photoresist cleaning composition according to the present invention comprises a first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less, and a second nonionic surfactant having an HLB value of more than 10 and 19 or less, wherein the first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, and a weight ratio of the first nonionic surfactant: the second nonionic surfactant is 1:0.1 or more and less than 1:5.0.

[0010] In one embodiment of the present invention, the HLB (Hydrophile Lipophile Balance) value of the first nonionic surfactant may be 7 or more and 9 or less.

[0011] In one embodiment of the present invention, the content of the first nonionic surfactant may be 0.01 wt% or more and 1.00 wt% or less based on the total weight of the photoresist cleaning solution composition.

[0012] In one embodiment of the present invention, the content of the second nonionic surfactant may be 0.001 wt% or more and less than 5.000 wt% based on the total weight of the photoresist cleaning solution composition.

[0013] In one embodiment of the present invention, the weight ratio of the first nonionic surfactant: the second nonionic surfactant may be 1:0.1 or more and 1:3.5 or less.

[0014] In one embodiment of the present invention, the second nonionic surfactant may include a second-first nonionic surfactant having an HLB value of more than 10 and less than or equal to 15, and a second-second nonionic surfactant having an HLB value of more than 15 and less than or equal to 19.

[0015] In one embodiment of the present invention, the weight ratio of the 2-1 nonionic surfactant: the 2-2 nonionic surfactant may be 1:0.2 or more and 1:3.5 or less.

[0016] In one embodiment of the present invention, the branched alkyl group may include a C3 to C6 branched alkyl group.

[0017] In one embodiment of the present invention, the C3 to C6 branched alkyl group may be isopropyl, isobutyl, sec-butyl, or tert-butyl.

[0018] In one embodiment of the present invention, the photoresist cleaning composition may include water and an additive.

[0019] In one embodiment of the present invention, the additive may include a surfactant different from the first and second nonionic surfactants and an alcohol having 1 to 8 carbon atoms.

[0020] In one embodiment of the present invention, the photoresist cleaning composition may include 0.01 wt% or more to 1.00 wt% or less of the first nonionic surfactant, 0.001 wt% or more to less than 5.000 wt% of the second nonionic surfactant, 0.0001 wt% or more to 1.0000 wt% or less of a surfactant different from the first and second nonionic surfactants, 0.01 wt% or more to 1.00 wt% or less of the alcohol having 1 to 8 carbon atoms, and water as a remainder.

[0021] In one embodiment of the present invention, the photoresist cleaning composition may have a surface tension of 30 dyne / cm to 50 dyne / cm at room temperature (25°C).

[0022] In one embodiment of the present invention, the photoresist cleaning solution composition may have a foaming amount of 4 ml or less according to the following measurement method.

[0023] [measurement method]

[0024] 1) According to KS M ISO 696, 50 ml of the above cleaning solution composition is dropped from a height of 450 mm.

[0025] 2) After leaving the above cleaning solution composition for 60 seconds, measure the volume of foam.

[0026] A method for forming a photoresist pattern according to the present invention comprises the steps of (a) forming a photoresist film on a substrate, (b) exposing and developing the photoresist film to form a photoresist pattern, and (c) cleaning the photoresist pattern with a photoresist cleaning composition, wherein the photoresist cleaning composition comprises a first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less, and a second nonionic surfactant having an HLB value of more than 10 and 19 or less, wherein the first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, and a weight ratio of the first nonionic surfactant:the second nonionic surfactant is 1:0.1 or more and less than 1:5.0.

[0027] In one embodiment of the present invention, the exposure in step (b) may be selected from the group consisting of KrF, ArF, and EUV.

[0028] In one embodiment of the present invention, step (c) may be performed at room temperature (25°C).

[0029] In one embodiment of the present invention, the step (c) may include a step of first cleaning the photoresist pattern using water and then second cleaning it with the cleaning solution composition, or a step of first cleaning the photoresist pattern using the cleaning solution composition and then second cleaning it with water.

[0030] In one embodiment of the present invention, after step (c), the minimum space size of the photoresist pattern in the circuit unit may be 1 nm to 30 nm.

[0031]

[0032] A photoresist cleaning composition according to the present invention comprises two types of nonionic surfactants having different hydrophilic-lipophilic ratios and including a branched-chain alkyl group in a specific content range.

[0033] Accordingly, there was a problem in that the hydrophobic portion of a conventional nonionic surfactant encapsulates air and generates a large amount of foam, but since the hydrophobic portion of the nonionic surfactant of the present invention includes a branched alkyl group, the phenomenon in which the hydrophobic portion encapsulates air and generates foam can be significantly reduced.

[0034] In addition, by including one type of nonionic surfactant exhibiting relatively hydrophilicity and one type of nonionic surfactant exhibiting relatively lipophilicity in a specific content range, melting and swelling of the photoresist pattern can be suppressed, so that the phenomenon of pattern collapse can be improved, and the cleaning power for removing developer and photoresist residue can be improved.

[0035]

[0036] Figures 1 to 5 are cross-sectional views briefly illustrating a process for forming a photoresist pattern according to the present invention.

[0037]

[0038] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for the purpose of explaining embodiments according to the technical idea of ​​the present invention, and the embodiments according to the technical idea of ​​the present invention can be implemented in various forms other than the embodiments disclosed in this specification or application, and the technical idea of ​​the present invention is not construed as being limited to the embodiments described in this specification or application.

[0039] Additionally, when a component is referred to as "including" in this specification or application, unless otherwise specifically stated, this does not exclude other components, but rather implies the inclusion of additional components. Furthermore, all numerical ranges indicating physical property values, dimensions, etc. of the components described in this specification or application should be understood to be modified by the term "about" in all cases, unless otherwise specified.

[0040]

[0041] Hereinafter, a photoresist cleaning composition according to the present invention and a method for forming a photoresist pattern using the same will be described.

[0042]

[0043] <Composition for cleaning photoresist>

[0044] A photoresist cleaning composition according to the present invention comprises a first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less, and a second nonionic surfactant having an HLB value of more than 10 and 19 or less, wherein the first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, and a weight ratio of the first nonionic surfactant: the second nonionic surfactant is 1:0.1 or more and less than 1:5.0.

[0045] The above HLB refers to the hydrophilicity-lipophilicity value of the first nonionic surfactant and the second nonionic surfactant. The HLB can be measured using the Griffin equation, and specifically, can be measured using the following calculation formula 1.

[0046] [Calculation Formula 1]

[0047] HLB = 20 × [(M1 / M0)]

[0048] In the above calculation formula 1, the M0 refers to the molecular mass of the first nonionic surfactant (or the second nonionic surfactant), and the M1 refers to the molecular mass of the hydrophilic portion of the first nonionic surfactant (or the second nonionic surfactant). According to the above calculation formula 1, the HLB may have a value between 0 and 20, and the closer the HLB value is to 0, the more hydrophilic it is, and the closer the HLB value is to 20, the more lipophilic it is. The degree of hydrophilicity-lipophilicity of the first nonionic surfactant and the second nonionic surfactant can be estimated by the HLB value.

[0049] The photoresist cleaning composition according to the present invention comprises a first nonionic surfactant that is relatively hydrophilic and has an HLB value of 6 or more and 10 or less. The HLB value of the first nonionic surfactant may be 6 or more and 10 or less, 6 or more and 9 or less, 7 or more and 9 or less, or 8. When the above range is satisfied, sufficient solubility in water can be secured, and the cleaning power for removing a developer and photoresist residues can be improved.

[0050] Based on the total weight of the photoresist cleaning composition, the content of the first nonionic surfactant may be 0.01 wt% to 1.00 wt%, 0.01 wt% to 0.80 wt%, 0.01 wt% to 0.70 wt%, 0.01 wt% to 0.60 wt%, 0.01 wt% to 0.50 wt%, 0.01 wt% to 0.40 wt%, 0.01 wt% to 0.30 wt%, 0.01 wt% to 0.20 wt%, or 0.01 wt% to 0.10 wt%. When the above range is satisfied, the penetration power of the photoresist cleaning composition for photoresist residue and the cleaning power for removing the photoresist residue can be improved.

[0051] The weight average molecular weight (Mw) of the first nonionic surfactant may be 100 g / mol to 2,000 g / mol, 100 g / mol to 1,500 g / mol, 100 g / mol to 1,000 g / mol, 150 g / mol to 1,000 g / mol, 150 g / mol to 900 g / mol, 150 g / mol to 800 g / mol, 150 g / mol to 700 g / mol, 150 g / mol to 600 g / mol, 150 g / mol to 500 g / mol, 150 g / mol to 450 g / mol, or 150 g / mol to 400 g / mol. The weight average molecular weight can be measured by gel permeation chromatography (GPC). When the above range is satisfied, the solubility in water can be increased, and mixing with other components included in the photoresist cleaning solution composition can be facilitated.

[0052] The solubility of the first nonionic surfactant in water at 25°C may be 3,000 ppm or more, 3,500 ppm or more, 4,000 ppm or more, 4,500 ppm or more, 5,000 ppm or more, 5,500 ppm or more, or 6,000 ppm or more. The solubility refers to the mass (ppm) in which the compound is completely dissolved when added to water at 25°C, with respect to the total mass of the water and the compound. When the above range is satisfied, the phenomenon of the photoresist pattern collapsing that may occur during the cleaning process can be minimized, and the line width roughness of the photoresist pattern can be improved.

[0053] The photoresist cleaning composition according to the present invention is relatively lipophilic and includes a second nonionic surfactant having an HLB value of more than 10 and less than or equal to 19. The second nonionic surfactant may include a second-first nonionic surfactant having an HLB value of more than 10 and less than or equal to 15, and a second-second nonionic surfactant having an HLB value of more than 15 and less than or equal to 19. By including two or more types of nonionic surfactants having different HLB values, melting and swelling of a photoresist pattern can be suppressed, thereby improving a phenomenon of pattern collapse.

[0054] The HLB value of the above-mentioned 2-1 nonionic surfactant may be 11 or more and 14 or less, 12 or more and 14 or less, or 13. The HLB value of the above-mentioned 2-2 nonionic surfactant may be 16 or more and 19 or less, 17 or more and 19 or less, or 18. When the above ranges are satisfied, appropriate solubility in water can be secured, and the cleaning power for removing developer and photoresist residues can be improved.

[0055] Based on the total weight of the photoresist cleaning composition, the content of the second nonionic surfactant may be 0.001 wt% to 5.000 wt%, 0.001 wt% to 3.000 wt%, 0.001 wt% to 2.000 wt%, 0.001 wt% to 1.000 wt%, 0.005 wt% to 1.000 wt%, 0.01 wt% to 1.00 wt%, 0.02 wt% to 1.00 wt%, 0.03 wt% to 1.00 wt%, or 0.05 wt% to 1.00 wt%. When the above range is satisfied, the penetration power of the photoresist cleaning composition for photoresist residue and the cleaning power for removing the photoresist residue can be improved.

[0056] The weight ratio of the above-mentioned 2-1 nonionic surfactant: the above-mentioned 2-2 nonionic surfactant may be 1:0.2 or more and 1:3.5 or less, 1:0.2 or more and 1:3.0 or less, 1:0.2 or more and 1:2.5 or less, or 1:0.2 or more and 1:2.0 or less. When the above range is satisfied, appropriate solubility in water can be secured, and the solubility and removal power for residues can be improved.

[0057] The weight average molecular weight (Mw) of the above-mentioned 2-1 nonionic surfactant may be 100 g / mol to 2,000 g / mol, 100 g / mol to 1,500 g / mol, 100 g / mol to 1,000 g / mol, 150 g / mol to 1,000 g / mol, 150 g / mol to 900 g / mol, 200 g / mol to 800 g / mol, 250 g / mol to 800 g / mol, 300 g / mol to 800 g / mol, 400 g / mol to 800 g / mol, 450 g / mol to 800 g / mol, or 500 g / mol to 800 g / mol. The weight average molecular weight (Mw) of the above-mentioned 2-2 nonionic surfactant may be 100 g / mol to 2,000 g / mol, 100 g / mol to 1,500 g / mol, 100 g / mol to 1,000 g / mol, 2000 g / mol to 1,000 g / mol, 300 g / mol to 1,000 g / mol, 400 g / mol to 1,000 g / mol, 500 g / mol to 1,000 g / mol, 600 g / mol to 1,000 g / mol, 700 g / mol to 1,000 g / mol, 750 g / mol to 1,000 g / mol, or 800 g / mol to 1,000 g / mol. The above weight average molecular weight can be measured by gel permeation chromatography (GPC). When the above range is satisfied, the solubility in water can be increased, and mixing with other components included in the photoresist cleaning solution composition can be facilitated.

[0058] The solubility of the above-mentioned 2-1 nonionic surfactant in water at 25°C may be 2,500 ppm or more, 3,000 ppm or more, 3,500 ppm or more, 4,000 ppm or more, 4,500 ppm or more, 5,000 ppm or more, or 5,500 ppm or more. The solubility of the above-mentioned 2-2 nonionic surfactant in water at 25°C may be 2,000 ppm or more, 2,500 ppm or more, 3,000 ppm or more, 3,500 ppm or more, 4,000 ppm or more, 4,500 ppm or more, or 5,000 ppm or more. When the above ranges are satisfied, the phenomenon of the photoresist pattern collapsing that may occur in the cleaning process may be minimized, and the line width roughness of the photoresist pattern may be improved.

[0059] The weight ratio of the first nonionic surfactant to the second nonionic surfactant may be 1:0.1 or more and less than 1:5.0, 1:0.1 or more and less than 1:4.5, 1:0.1 or more and less than 1:4.0, 1:0.1 or more and less than 1:3.5, or 1:0.1 or more and less than 1:3.0. When the above range is satisfied, appropriate solubility in water can be secured, and the surface tension of the cleaning solution composition can be lowered, thereby minimizing collapse of the pattern after cleaning.

[0060]

[0061] The first nonionic surfactant and the second nonionic surfactant have a branched alkyl group. The branched alkyl group may include a C3 to C6 branched alkyl group. The C3 to C6 branched alkyl group may be isopropyl, isobutyl, sec-butyl, or tert-butyl. There was a problem in that the hydrophobic portion of a conventional nonionic surfactant encapsulates air and a large amount of foam is generated. However, the hydrophobic portion of the first nonionic surfactant and the second nonionic surfactant of the present invention includes a branched alkyl group, so that the phenomenon of the hydrophobic portion encapsulating air and generating foam can be significantly reduced.

[0062] In addition, by including a first nonionic surfactant exhibiting relatively hydrophilicity and a second nonionic surfactant exhibiting relatively lipophilicity in a specific content range, the phenomenon of foaming is reduced, and melting and swelling of the photoresist pattern are suppressed, so that the phenomenon of pattern collapse can be improved, and the cleaning power for removing the developer and photoresist residue can be improved. Accordingly, the line width roughness of the photoresist pattern, which may be increased by the photoresist film or the developer residue, can be improved, so that the consistency between the photomask pattern and the photoresist pattern can be improved, and the efficiency of the cleaning process can also be increased.

[0063]

[0064] The above first nonionic surfactant, second-first nonionic surfactant and second-second nonionic surfactant may be compounds having a linear ether group structure capable of imparting hydrophilicity and an alkyl group branched around a triple bond capable of imparting hydrophobicity on both sides.

[0065] Specifically, the first nonionic surfactant may be a compound represented by the following chemical formula 1 (weight average molecular weight (Mw) 150 g / mol to 400 g / mol).

[0066] [Chemical Formula 1]

[0067]

[0068] In the above chemical formula 1, R1 to R4 are each independently substituted or unsubstituted alkyl having 1 to 8 carbon atoms, at least one of R1 and R2 and at least one of R3 and R4 has a tertiary carbon or a quaternary carbon, R5 and R6 are each independently hydrogen or methyl, and n and m are each independently integers of 1 to 8. The tertiary carbon refers to carbon bonded to three carbons. The quaternary carbon refers to carbon bonded to four carbons. The tertiary carbon and the quaternary carbon may refer to carbon having a branched alkyl group.

[0069] In addition, the above-mentioned 2-1 nonionic surfactant may be a compound represented by the above-mentioned chemical formula 1 (weight average molecular weight (Mw) 500 g / mol to 800 g / mol).

[0070] In addition, the above-mentioned 2-2 nonionic surfactant may be a compound represented by the above-mentioned chemical formula 1 (weight average molecular weight (Mw) 800 g / mol to 1,000 g / mol).

[0071]

[0072] At least one of the above R1 and R2, and at least one of the above R3 and R4 may be a branched chain alkylene having 3 to 6 carbon atoms. The branched chain alkylene having 3 to 6 carbon atoms may be isopropyl, isobutyl, sec-butyl, or tert-butyl.

[0073] The compound represented by the above chemical formula 1 may include a structure in which at least one of R1 and R2 and at least one of R3 and R4 are symmetrical. The compound has a branched chain alkylene having 3 to 6 carbon atoms, and at least one of R1 and R2 and at least one of R3 and R4 has a symmetrical structure, so that the phenomenon of bubbles forming by enveloping air can be significantly reduced.

[0074] The above R5 may be hydrogen or methyl. The above R6 may be hydrogen or methyl. Preferably, the above R5 and R6 may be hydrogen. When the above R5 and R6 are hydrogen, the hydrophilicity of the compound may be improved, and the effect of reducing the surface tension of the photoresist cleaning solution composition may be increased.

[0075]

[0076] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formulas 2 to 5.

[0077] [Chemical Formula 2]

[0078]

[0079] In the above chemical formula 2, n and m are each independently an integer from 1 to 6.

[0080] [Chemical Formula 3]

[0081]

[0082] In the above chemical formula 3, n and m are each independently integers from 1 to 6.

[0083] [Chemical Formula 4]

[0084]

[0085] In the above chemical formula 4, n and m are each independently an integer from 1 to 6.

[0086] [Chemical Formula 5]

[0087]

[0088] In the above chemical formula 5, n and m are each independently an integer from 1 to 6.

[0089]

[0090] The above photoresist cleaning composition may include water and additives.

[0091] The water may be distilled water or deionized water. The distilled water may refer to a colorless, odorless, and tasteless liquid purified by cooling the water vapor generated by heating the water. The deionized water may refer to distilled water from which ions have been removed.

[0092] Preferably, the water may be deionized water for semiconductor processes, and may have a maximum resistivity value of 18.0 MΩ·cm, 18.1 MΩ·cm, or 18.2 MΩ·cm at 25°C. When the above range is satisfied, the cleaning power is improved, wastewater treatment is facilitated, and manufacturing cost efficiency can be improved.

[0093] The above additive may include a surfactant different from the first and second nonionic surfactants and an alcohol having 1 to 8 carbon atoms.

[0094] The surfactant may reduce the surface tension of the photoresist cleaning composition. The surfactant may include at least one selected from the group consisting of cationic surfactants, anionic surfactants, nonionic surfactants, silicone-based surfactants, and fluorinated surfactants. Preferably, the surfactant may include a nonionic surfactant. The nonionic surfactant may have excellent wettability, thereby improving the cleaning power for a substrate. The nonionic surfactant may be a glycol ether derivative or an ester derivative of a glycol ether. Specifically, it may be polypropylene oxide or polyethylene oxide.

[0095] The above silicone-based surfactant may be at least one selected from the group consisting of poly(dimethylsiloxane) ethoxylate, poly(dimethylsiloxane) ethoxylate / propoxylate copolymer, trimethylsiloxane ethoxylate, and trimethylsiloxane ethoxylate / propoxylate copolymer.

[0096] The above fluorine-based surfactants are diethylene glycol perfluorohexyl ether, diethylene glycol perfluoropentyl ether, diethylene glycol perfluorobutyl ether, diethylene glycol perfluoropropyl ether, diethylene glycol perfluoroethyl ether, triethylene glycol perfluorohexyl ether, triethylene glycol perfluoropentyl ether, triethylene glycol perfluorobutyl ether, triethylene glycol perfluoropropyl ether, triethylene glycol perfluoroethyl ether, tetraethylene glycol perfluorohexyl ether, tetraethylene glycol perfluoropentyl ether, tetraethylene glycol perfluorobutyl ether, tetraethylene glycol perfluoropropyl ether, tetraethylene glycol perfluoroethyl ether, pentaethylene glycol perfluorohexyl ether, pentaethylene glycol perfluoropentyl ether, pentaethylene glycol perfluorobutyl ether, pentaethylene glycol perfluoropropyl ether, pentaethylene glycol It may be at least one selected from the group consisting of perfluoroethyl ether, hexaethylene glycol perfluorohexyl ether, hexaethylene glycol perfluoropentyl ether, hexaethylene glycol perfluorobutyl ether, hexaethylene glycol perfluoropropyl ether, hexaethylene glycol perfluoroethyl ether, octaethylene glycol perfluorohexyl ether, octaethylene glycol perfluoropentyl ether, octaethylene glycol perfluorobutyl ether, octaethylene glycol perfluoropropyl ether, and octaethylene glycol perfluoroethyl ether.

[0097]

[0098] The alcohol may be at least one selected from the group consisting of methanol, ethanol, butanol, butanediol, propanol, isopropanol, pentanol, hexanol, heptanol, and octanol. Preferably, the alcohol may include butanol.

[0099] Based on the total weight of the photoresist cleaning composition, the content of the alcohol having 1 to 8 carbon atoms may be 0.01 wt% to 1.00 wt%, 0.02 wt% to 1.00 wt%, 0.03 wt% to 1.00 wt%, 0.04 wt% to 1.00 wt%, 0.05 wt% to 1.00 wt%, 0.06 wt% to 1.00 wt%, 0.07 wt% to 1.00 wt%, 0.08 wt% to 1.00 wt%, or 0.10 wt% to 1.00 wt%. When the above range is satisfied, the efficiency of removing the photoresist cleaning composition after the cleaning process may be improved.

[0100] The above additive may include an acid or a base. The acid or base may be used to adjust the pH of the photoresist cleaning solution composition or to improve the solubility of the surfactants.

[0101] The acid or base may be a carboxylic acid, an amine, or an ammonium compound. Specifically, it may be formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, ethylenediamine, diethylenetriamine, pentaethylenehexamine, piperidine, piperazine, morpholine, or tetramethylammonium hydroxide.

[0102] Based on the total weight of the photoresist cleaning composition, the content of the acid or base may be 0.001 wt% to 0.100 wt%, 0.005 wt% to 0.100 wt%, 0.010 wt% to 0.100 wt%, or 0.010 wt% to 0.100 wt%.

[0103] The additive may include a hydrophilicity enhancing agent. The hydrophilicity enhancing agent can capture the hydrophobic portions of the surfactants included in the photoresist cleaning composition, thereby transforming the photoresist cleaning composition into a more hydrophilic state. Accordingly, the photoresist cleaning composition can be more easily removed after the cleaning process.

[0104] The above additive may include a surface treatment agent. The surface treatment agent may serve to improve the surface roughness of the sidewall of the photoresist pattern. For example, tetrabutylammonium hydroxide (TBAH) may be used as the surface treatment agent.

[0105] The above additive may include a dissolution inhibitor. The dissolution inhibitor may prevent the surfactants in the photoresist cleaning composition from reacting with the surface of the photoresist pattern and penetrating into the interior of the photoresist pattern, thereby preventing the pattern from melting or collapsing. For example, an amine may be used as the dissolution inhibitor, and specifically, monoethanolamine, diethanolamine, or triethanolamine may be used.

[0106] The additive may include a dispersant. The dispersant may improve the solubility of the surfactants in the photoresist cleaning composition, thereby improving the dispersion stability of the surfactants in the photoresist cleaning composition. For example, the dispersant may be ammonia water.

[0107] The above additive may include a nitrogen-containing compound. The nitrogen-containing compound may prevent the collapse of the micropattern and the melting of the pattern due to extreme ultraviolet rays. The nitrogen-containing compound may include a tertiary amine. In addition, the nitrogen-containing compound may include two or more tertiary amines. The tertiary amine refers to an amine bonded to three alkyl groups. For example, the nitrogen-containing compound may be at least one selected from the group consisting of N,N,N',N'-tetrabutylethylenediamine, N,N,N',N'-tetrapropyl-1,2-propylenediamine, N,N,N',N'-tetrapropyl-1,2-butylenediamine, N,N,N',N'-tetraisobutyl-1,3-butylenediamine, N,N,N',N'-tetraisobutyl-1,4-butylenediamine, N,N,N',N'-tetramethyl-1,5-pentylenediamine, N,N,N',N'-tetraethyl-1,5-pentylenediamine, and N,N,N',N'-tetraethyl-1,3-butylenediamine.

[0108]

[0109] The photoresist cleaning composition may include 0.01 wt% or more and 1.00 wt% or less of the first nonionic surfactant, 0.001 wt% or more and 5.000 wt% or less of the second nonionic surfactant, 0.0001 wt% or more and 1.0000 wt% or less of a surfactant different from the first and second nonionic surfactants, 0.01 wt% or more and 1.00 wt% or less of the alcohol having 1 to 8 carbon atoms, and water as a balance. The balance refers to a variable amount that changes depending on the addition of components or agents of the photoresist cleaning composition. For example, the content of the water as the balance may refer to the remaining amount after excluding the first and second nonionic surfactants and the additive from the total amount of the photoresist cleaning composition.

[0110]

[0111] The photoresist cleaning composition may have a surface tension at room temperature (25° C.) of 10 dyne / cm to 80 dyne / cm, 10 dyne / cm to 75 dyne / cm, 15 dyne / cm to 75 dyne / cm, 20 dyne / cm to 65 dyne / cm, 30 dyne / cm to 60 dyne / cm, or 30 dyne / cm to 50 dyne / cm. When the above range is satisfied, the collapse of the photoresist micro-pattern can be minimized, and the cleaning power for residues between the micro-patterns can be improved.

[0112] The above photoresist cleaning solution composition may have a contact angle with water at room temperature (25°C) of 40° to 75°, 40° to 70°, 40° to 65°, 40° to 60°, or 40° to 55°. When the above range is satisfied, the melting of the fine pattern can be minimized while suppressing lifting defects of the photoresist pattern that occur during photoresist development.

[0113] The photoresist cleaning solution composition may have a foaming amount of 4 ml or less, 3.5 ml or less, 3 ml or less, 2.5 ml or less, 2.0 ml or less, 1.5 ml or less, or 1 ml or less according to the following measurement method. When the above range is satisfied, the cleaning power for removing developer residues may be improved, and as a result, the line width roughness of the photoresist pattern may be improved, thereby improving the consistency between the photomask pattern and the photoresist pattern, and the efficiency of the cleaning process may also be increased.

[0114] [measurement method]

[0115] 1) According to KS M ISO 696, 50 ml of the above cleaning solution composition is dropped from a height of 450 mm.

[0116] 2) After leaving the above cleaning solution composition for 60 seconds, measure the volume of foam.

[0117]

[0118] <Method for forming a photoresist pattern>

[0119] A method for forming a photoresist pattern according to the present invention comprises the steps of (a) forming a photoresist film on a substrate, (b) exposing and developing the photoresist film to form a photoresist pattern, and (c) cleaning the photoresist pattern with a photoresist cleaning composition, wherein the photoresist cleaning composition comprises a first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less, and a second nonionic surfactant having an HLB value of more than 10 and 19 or less, wherein the first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, and a weight ratio of the first nonionic surfactant:the second nonionic surfactant is 1:0.1 or more and less than 1:5.0.

[0120] The types and contents of the first nonionic surfactant and the second nonionic surfactant may be the same as the types and contents of the first nonionic surfactant and the second nonionic surfactant in the photoresist cleaning solution composition described above.

[0121]

[0122] Figures 1 to 5 are cross-sectional views schematically illustrating a process for forming a photoresist pattern according to the present invention. In addition, Figures 1 to 5 only illustrate an example of a pattern forming process using a positive photoresist, and the method for forming a photoresist pattern according to the present invention can also be applied to a pattern forming process using a negative photoresist.

[0123] Referring to FIG. 1, a photoresist film (20) may be formed by applying a photoresist material on a substrate (10). The substrate (10) may be formed of a semiconductor substrate. The substrate (10) may include a semiconductor material such as silicon or germanium. The substrate (10) may include a compound semiconductor such as SiGe, SiC, GaAs, InAs, or InP. The substrate (10) may have a silicon on insulator (SOI) structure. The substrate (10) may include a well doped with an impurity or a structure doped with an impurity. The substrate (10) may have various device isolation structures such as a shallow trench isolation (STI) structure.

[0124] The photoresist film (20) may be formed on the substrate (10) by spraying, spin coating, or dipping. The photoresist film (20) may include a polymer whose polarity can be changed by the action of an acid. The photoresist film (20) may be formed to a thickness of about 300 Å to 2,000 Å. After the photoresist film (20) is formed, a soft baking process may be performed for about 30 seconds to 90 seconds. The solvent included in the photoresist film (20) may be evaporated by the soft baking process.

[0125] Referring to FIGS. 2 and 3, a photoresist pattern (23) can be formed by exposing and developing the photoresist film (20).

[0126] The above exposure may be selected from the group consisting of KrF (248 nm), ArF (193 nm), and EUV (13.5 nm). The exposure may be performed using an exposure mask (30). For example, light emitted from the KrF, ArF, or EUV may be irradiated to a portion of the photoresist film (20) where the exposure mask (30) is not positioned, and through the exposure, an exposed portion (21) and a non-exposed portion (22) may be formed on the substrate (10).

[0127] Through the above development, the photoresist pattern (23) can be formed on the substrate (10). For example, the exposed portion (21) can be removed on the substrate (10) using a developer, and the photoresist pattern (23) composed of the non-exposed portion (22) can be formed. The developer can be an alkaline developer, and for example, the developer can be a tetramethylammonium hydroxide (TMAH) aqueous solution of 0.01 wt% to 3.00 wt%.

[0128] The above drawings 2 and 3 only illustrate a pattern forming process using a positive photoresist, and in the case of a pattern forming process using a negative photoresist, the non-exposed portion (22) can be removed, and the photoresist pattern (23) composed of the exposed portion (21) can be formed.

[0129] A post-baking process may be performed after the above exposure process or after the above development process, as needed.

[0130] After the photoresist pattern (23) is formed, a development residue (40) may exist on the substrate (10). The development residue (40) may be a residue of the developer or photoresist of an undeveloped exposed portion (21). As the development residue (40) exists on the substrate (10) or the photoresist pattern (23), the line width roughness of the photoresist pattern (23) may increase.

[0131] Referring to FIGS. 4 and 5, the photoresist pattern (23) can be cleaned with the aforementioned photoresist cleaning composition (50). The cleaning can be performed by applying or immersing the photoresist cleaning composition (50) on the substrate (10). By the cleaning, the developing residue (40) present on the substrate (10) or the photoresist pattern (23) can be removed. The cleaning can be performed at room temperature (25°C) to 70°C, room temperature (25°C) to 60°C, room temperature (25°C) to 50°C, room temperature (25°C) to 40°C, and preferably room temperature (25°C). When the above cleaning is an immersion process, the immersion time of the substrate (10) in the photoresist cleaning composition (50) may be 10 to 600 seconds, 20 to 600 seconds, 30 to 600 seconds, or 30 to 300 seconds. When the above range is satisfied, the surface tension of the photoresist cleaning composition can be reduced, and melting of the photoresist pattern can be minimized.

[0132] The above cleaning may be performed by first cleaning the photoresist pattern (23) using water and then second cleaning with the photoresist cleaning solution composition (50), or by first cleaning the photoresist pattern (23) using the photoresist cleaning solution composition (50) and then second cleaning with water.

[0133] The photoresist cleaning composition (50) above can significantly reduce the phenomenon of bubble generation, so that only the developer residue (40) can be effectively removed while minimizing damage to structures such as the photoresist pattern (23).

[0134] After the above cleaning, the minimum space size of the photoresist pattern (23) in the circuit unit may be 1 nm to 30 nm, 2 nm to 30 nm, 3 nm to 30 nm, 3 nm to 25 nm, or 3 nm to 23 nm. When the above range is satisfied, micro bridge defects in the grooves (trench) between the photoresist patterns (23) can be suppressed.

[0135]

[0136] <Method of manufacturing semiconductors>

[0137] The method for manufacturing a semiconductor according to the present invention can pattern a substrate using a photoresist pattern manufactured by the method for forming a photoresist pattern described above. If a film layer, hard mask layer, or the like (hereinafter referred to as a modified layer) other than the photoresist pattern exists on the substrate, the modified layer can also be patterned using the photoresist pattern.

[0138] The above patterning method is not particularly limited, and for example, a pattern can be formed on the substrate by etching the modified layer using the photoresist pattern as an etching mask, and then etching the substrate using the modified layer pattern as an etching mask.

[0139] If a layer lower than the above-mentioned modified layer exists, the substrate can be etched using the photoresist pattern as an etching mask while etching the lower layer. Using the formed pattern, wiring can be formed on the substrate.

[0140] The above patterning may be performed using dry etching, wet etching, or a combination of dry and wet etching. The dry etching may utilize O2, CF4, CHF3, Cl2, or BCl3. The substrate on which the pattern has been formed may be cut into chips of any size and then connected to a lead frame. Thereafter, the chips may be packaged using resin and manufactured into semiconductors.

[0141]

[0142] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited to the following examples and comparative examples.

[0143]

[0144] Example

[0145] The components listed in Table 1 below were mixed in the corresponding amounts, and a photoresist cleaning solution composition was prepared by including the remainder of deionized water (DI water) so that the sum of the contents of the components satisfies 100 wt%.

[0146]

[0147] Deionized water A with nonionic surfactant additives 1) B-1 2) B-2 3) C 4) D 5) E 6)Unit weight % Example 10.05 0.005--0.0020.6 Remainder Example 20.05 0.025--0.0020.6 Remainder Example 30.05 0.05--0.0020.6 Remainder Example 40.05 0.15--0.0020.6 Remainder Example 50.05-0.05-0.0020.6 Remainder Example 60.05-0.15-0.0020.6 Remainder Example 70.06 0.03 0.10-0.0020.6 Remainder Example 80.06 0.10 0.10-0.0020.6 Remainder Example 90.06 0.15 0.10-0.0020.6 Remainder Example 100.050.007--0.0020.6 Residue Example 110.050.02--0.0020.6 Residue Example 120.050.10--0.0020.6 Residue Example 130.050.20--0.0020.6 Residue Example 140.05-0.005-0.0020.6 Residue Example 150.05-0.025-0.0020.6 Residue Example 160.05-0.10-0.0020.6 Residue Example 170.05-0.20-0.0020.6 Residue Example 180.060.100.03-0.0020.6 Residue Example 190.060.050.10-0.0020.6 Residue Example 200.060.100.15-0.0020.6 Residue Comparison Example 10.050.25--0.0020.6 Residue Comparison Example 20.050.35--0.0020.6 Residue Comparison Example 30.050.50--0.0020.6 Residue Comparison Example 40.05-0.25-0.0020.6 Residue Comparison Example 50.05-0.35-0.0020.6 Residue Comparison Example 60.05-0.50-0.0020.6 Residue Comparison Example 70.060.030.50-0.0020.6 Residue Comparison Example 80.060.031.00-0.0020.6 Residue comparison example 90.060.100.50-0.0020.6 Residue comparison example 100.060.101.00-0.0020.6 Residue comparison example 110.060.150.50-0.0020.6 Residue comparison example 120.060.151.00-0.0020.6 Residue comparison example 130.060.700.10-0.0020.6 Residue comparison example 140.060.700.50-0.0020.6 Residue comparison example 150.060.701.00-0.0020.6 Residue comparison example 160.050.050.50-0.0020.6 Residual Comparison Example 170.050.250.50-0.0020.6 Residue Comparison Example 180.050.350.50-0.0020.6 Residue Comparison Example 19---0.010.0020.6 Residue Comparison Example 20---0.100.0020.6 Residue 1) A: Ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, HLB = 8 2) B-1: Ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, HLB = 13 3) B-2: Ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol, HLB = 18)4) C: Polyoxyethylene alkylether (HLB = 10)5) D: Polypropylene glycol6) E: tert-Butanol.

[0148]

[0149] Experimental example

[0150] Experimental Example 1 - Measurement of Foam Volume

[0151] The amount of foam generated from the photoresist cleaning compositions of Examples 1 to 20 and Comparative Examples 1 to 20 was measured according to KS M ISO 696. Specifically, 50 ml of each of the photoresist cleaning compositions of Examples 1 to 20 and Comparative Examples 1 to 20 was dropped from a 450 mm high test device onto a measuring device and left for 60 seconds. Thereafter, the volume of foam generated from the cleaning compositions was measured, and the results are shown in Table 2 below.

[0152]

[0153] Experimental Example 2 - Surface Tension Measurement

[0154] The surface tension of the photoresist cleaning solution compositions of Examples 1 to 20 and Comparative Examples 1 to 20 was measured at room temperature (25°C) using a K100 (KRUSS) surface tension meter, and the results are shown in Table 2 below.

[0155]

[0156] Experimental Example 3 - Contact Angle Measurement

[0157] The contact angles of the photoresist cleaning solution compositions of Examples 1 to 20 and Comparative Examples 1 to 20 were measured at room temperature (25°C) using a Phoenix 300 analyzer, and the results are shown in Table 2 below.

[0158]

[0159] Experimental Example 4 - Photoresist Residue Evaluation

[0160] For a substrate on which photoresist micropattern development was completed, each of the photoresist cleaning solution compositions of Examples 1 to 20 and Comparative Examples 1 to 20 was dipped for 30 seconds, and then rinsed with deionized water for 15 seconds. Thereafter, the presence of residue on the substrate was evaluated using FE-SEM (Hitachi) equipment based on the following criteria, and the results are shown in Table 2 below.

[0161] - ○: No residue from photoresist pattern

[0162] - ×: Residue of photoresist pattern exists

[0163]

[0164] Experimental Example 5 - Line Width Roughness Evaluation

[0165] For the substrate on which the photoresist micro-pattern development and cleaning in Experimental Example 4 above were completed, the difference between the widest and narrowest parts of the pattern on the substrate was measured using CD-SEM (Hitachi) equipment, and the difference was evaluated based on the following criteria, and the results are shown in Table 2 below.

[0166] - ◎: ​​less than 4 nm

[0167] - ○: 4 nm or more ~ ​​less than 4.5 nm

[0168] - △: 4.5 nm or more ~ ​​less than 6 nm

[0169] - ×: 6 nm or more

[0170]

[0171] Experimental Example 6 - Evaluation of Photoresist Pattern Residual Rate

[0172] For the substrate on which the photoresist micro-pattern development and cleaning in the above Experimental Example 4 was completed, the degree of collapse of the photoresist pattern was measured using CD-SEM (Hitachi) equipment, and the pattern survival rate was calculated using Equation 1 below, and the results are shown in Table 2 below.

[0173] [Formula 1]

[0174] Pattern survival rate (%) = (PR-1 / 55) × 100

[0175] In the above equation 1, PR-1 is the number of non-collapsed pattern sections among the total 55 pattern evaluation sections.

[0176]

[0177] Experimental Example 7 - Evaluation of Photoresist Pattern Thickness Changes

[0178] The difference in the thickness of the photoresist micro-pattern after the photoresist micro-pattern development was completed and the thickness of the photoresist micro-pattern on the substrate on which the photoresist micro-pattern development and cleaning in Experimental Example 4 was completed was measured and evaluated based on the following criteria, and the results are shown in Table 2 below.

[0179] - ◎: ​​No melting or swelling

[0180] - ○: Thickness change less than ±5Å

[0181] - △: Thickness change exceeding ±5Å ~ less than ±20Å

[0182] - ×: Thickness change exceeding ±20Å

[0183]

[0184] Classification 1 Nonionic surfactants 1) :Second nonionic surfactant 2)Weight ratio, foam volume, surface tension, contact angle, photoresist residue, evaluation, line width, roughness, evaluation, pattern residual ratio, evaluation, thickness change, evaluation, unit - ml dyne / cm ° -- % - Example 11: 0.11.04 7.27 73.04 ○ ◎ 45.45 ◎ Example 21: 0.52.04 2.51 66.04 ○ ◎ 47.27 ◎ Example 31: 12.04 0.39 61.41 ○ ◎ 45.45 ◎ Example 41: 33.83 5.48 53.23 ○ ◎ 50.91 ◎ Example 51: 11.74 7.14 69.75 ○ ◎ 52.73 ○ Example 61: 33.04 3.70 64.03 ○ ◎ 50.91 ○ Example 71:2.172.044.1765.94○◎47.27○Example 81:3.3-39.1258.98○◎52.73○Example 91:4.173.333.3040.82○○52.73◎Example 101:0.141.245.3270.12○◎50.91◎Example 111:0.41.244.4169.61○◎50.91◎Example 121:22.538.2658.32○◎52.73○Example 131:43.934.6450.23○○50.91◎Example 141:0.11.047.8970.14○◎45.45○Example 151:0.51.347.5669.89○◎52.73◎Example 161:22.545.1865.63○◎50.91◎Example 171:43.342.3558.12○○52.73◎Example 181:2.172.044.0564.96○◎47.27○Example 191:2.50.538.5654.23○◎52.73○Example 201:4.173.231.2338.15○○52.73◎Comparative Example 11:54.233.2247.66×△45.45△Comparative example 21:74.331.1942.23×△47.27△Comparative example 31:104.330.3741.43×△50.91△Comparative example 41:54.341.3461.20×△45.45△Comparative example 51:75.740.5660.92×△47.27△Comparative example 61:105.039.6754.24×△52.73△Comparative example 71:8.335.340.0958.04×△50.91△Comparative example 81:17.175.338.6356.04×△54.55△Comparative example 91:107.038.6154.13××50.91△Comparative example 101:18.336.336.2449.37××54.55△Comparative Example 111: 10.835.732.4339.81×△45.45×Comparative Example 121: 19.177.231.3437.84××54.55×Comparative Example 131: 13.336.032.0334.51××52.73×Comparative Example 141: 205.731.3837.74×△54.55×Comparative Example 151: 13.335.729.3736.63×△54.55×Comparative Example 161: 115.732.4339.81×△50.91×Comparative Example 171: 157.231.3437.84××52.73×Comparative Example 181:176.032.0334.51××54.55×Comparative example 19-9.231.1233.28××54.55×Comparative example 20-11.330.2231.58××58.18×1) First nonionic surfactant: A2 in [Table 1]) Second nonionic surfactant: B-1 + B-2 in [Table 1].

[0185]

[0186] As can be seen in Tables 1 and 2 above, it was confirmed that Examples 1 to 20, which included a nonionic surfactant having a branched alkyl group and exhibiting relative hydrophilicity and a nonionic surfactant exhibiting relative lipophilicity in a specific content range, showed a significantly reduced amount of foaming compared to Comparative Examples 1 to 20. In addition, it was confirmed that Examples 1 to 20 showed a significantly improved line width roughness of the pattern as compared to Comparative Examples 1 to 20 because no residue existed on the photoresist pattern, and that the change in the thickness of the photoresist pattern after cleaning was small and the pattern retention rate was equal to or higher.

[0187]

[0188] The embodiment can be applied to a photoresist cleaning solution composition and a method for forming a photoresist pattern using the same.

Claims

1. A first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less; and A second nonionic surfactant having an HLB value of more than 10 and less than or equal to 19 is included, The first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, A photoresist cleaning composition wherein the weight ratio of the first nonionic surfactant to the second nonionic surfactant is 1:0.1 or more and less than 1:5.

0.

2. In paragraph 1, A photoresist cleaning composition wherein the HLB (Hydrophile Lipophile Balance) value of the first nonionic surfactant is 7 or more and 9 or less.

3. In paragraph 1, A photoresist cleaning composition, wherein the content of the first nonionic surfactant is 0.01 wt% or more and 1.00 wt% or less, based on the total weight of the photoresist cleaning composition.

4. In paragraph 1, A photoresist cleaning composition, wherein the content of the second nonionic surfactant is 0.001 wt% or more and less than 5.000 wt% based on the total weight of the photoresist cleaning composition.

5. In paragraph 1, A photoresist cleaning composition wherein the weight ratio of the first nonionic surfactant to the second nonionic surfactant is 1:0.1 or more and 1:3.5 or less.

6. In paragraph 1, The second nonionic surfactant is, A second-1 nonionic surfactant having an HLB value of more than 10 and less than or equal to 15; and A photoresist cleaning composition comprising a second-second nonionic surfactant having an HLB value of more than 15 and less than or equal to 19.

7. In paragraph 6, A photoresist cleaning composition wherein the weight ratio of the above-mentioned 2-1 nonionic surfactant: the above-mentioned 2-2 nonionic surfactant is 1:0.2 or more and 1:3.5 or less.

8. In paragraph 1, A photoresist cleaning composition wherein the branched alkyl group comprises a C3 to C6 branched alkyl group.

9. In paragraph 8, A photoresist cleaning composition wherein the branched alkyl group of C3 to C6 is isopropyl, isobutyl, sec-butyl, or tert-butyl.

10. In paragraph 1, The photoresist cleaning composition above comprises water and an additive.

11. In paragraph 10, A photoresist cleaning composition wherein the additive comprises a surfactant different from the first and second nonionic surfactants and an alcohol having 1 to 8 carbon atoms.

12. In paragraph 11, The above photoresist cleaning composition, 0.01 wt% or more and 1.00 wt% or less of the first nonionic surfactant; 0.001 wt% or more and less than 5.000 wt% of the second nonionic surfactant; 0.0001 wt% or more to 1.0000 wt% or less of a surfactant different from the first and second nonionic surfactants; 0.01 wt% or more and 1.00 wt% or less of the alcohol having 1 to 8 carbon atoms; and A photoresist cleaning composition comprising water as a residue.

13. In paragraph 1, The photoresist cleaning composition above is a photoresist cleaning composition having a surface tension of 30 dyne / cm to 50 dyne / cm at room temperature (25°C).

14. In paragraph 1, The photoresist cleaning solution composition above is a photoresist cleaning solution composition having a foaming amount of 4 ml or less according to the following measurement method: [measurement method] 1) According to KS M ISO 696, 50 ml of the above cleaning solution composition is dropped from a height of 450 mm. 2) After leaving the above cleaning solution composition for 60 seconds, measure the volume of foam. 15.(a) A step of forming a photoresist film on a substrate; (b) a step of forming a photoresist pattern by exposing and developing the photoresist film; and (c) A method for forming a photoresist pattern, comprising the step of cleaning the photoresist pattern with a photoresist cleaning solution composition, The above photoresist cleaning composition, A first nonionic surfactant having an HLB (Hydrophile Lipophile Balance) value of 6 or more and 10 or less; and A second nonionic surfactant having an HLB value of more than 10 and less than or equal to 19 is included, The first nonionic surfactant and the second nonionic surfactant have a branched alkyl group, A method for forming a photoresist pattern, wherein the weight ratio of the first nonionic surfactant: the second nonionic surfactant is 1:0.1 or more and less than 1:5.

0.

16. In paragraph 15, A method for forming a photoresist pattern, wherein the exposure in the above step (b) is selected from the group consisting of KrF, ArF, and EUV.

17. In paragraph 15, A method for forming a photoresist pattern, wherein the above step (c) is performed at room temperature (25 ℃).

18. In paragraph 15, Step (c) above, A step of first cleaning the photoresist pattern using water, and then second cleaning it with the cleaning solution composition; or A method for forming a photoresist pattern, comprising the step of first cleaning the photoresist pattern with the above cleaning solution composition and then second cleaning it using water.

19. In paragraph 15, A method for forming a photoresist pattern, wherein after the above step (c), the minimum space size of the photoresist pattern in the circuit unit is 1 nm to 30 nm.

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