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

Abstract

The present invention provides a photoresist cleaning solution composition comprising a compound represented by chemical formula 1 (see the detailed description of the invention). In addition, the present invention provides a method for forming a photoresist pattern, comprising the steps of: (a) forming a photoresist film on a substrate; (b) forming a photoresist pattern by exposing and developing the photoresist film; and (c) cleaning the photoresist pattern with a photoresist cleaning solution composition comprising a compound represented by chemical formula 1 (see the detailed description of the invention).

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 having improved cleaning power for removing residues of a developer by suppressing foam generation and improved line width roughness of a pattern, and a method for forming a photoresist pattern using the same.

[0008]

[0009] A photoresist cleaning composition according to the present invention comprises a compound represented by the following chemical formula 1.

[0010] [Chemical Formula 1]

[0011]

[0012] 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.

[0013] In one embodiment of the present invention, at least one of R1 and R2 and at least one of R3 and R4 may be a branched chain alkylene having 3 to 6 carbon atoms.

[0014] In one embodiment of the present invention, the branched chain alkylene having 3 to 6 carbon atoms may be isopropyl, isobutyl, sec-butyl, or tert-butyl.

[0015] In one embodiment of the present invention, R5 and R6 may be hydrogen.

[0016] In one embodiment of the present invention, the compound represented by the chemical formula 1 may be a compound represented by the following chemical formula 2.

[0017] [Chemical Formula 2]

[0018]

[0019] In the above chemical formula 2, R1 and R3 are each independently isopropyl, isobutyl, sec-butyl, or tert-butyl, and n and m are each independently integers from 1 to 6.

[0020] In one embodiment of the present invention, the content of the compound may be 0.01 wt% to 1.00 wt% based on the total weight of the photoresist cleaning solution composition.

[0021] In one embodiment of the present invention, the HLB (Hydrophile Lipophile Balance) value of the compound may be 6 to 10.

[0022] In one embodiment of the present invention, the photoresist cleaning composition may include water and an additive.

[0023] In one embodiment of the present invention, the additive may include an alcohol having 1 to 8 carbon atoms and a surfactant different from the compound represented by the chemical formula 1.

[0024] In one embodiment of the present invention, the photoresist cleaning composition may include 0.01 to 1.00 wt% of the compound represented by the chemical formula 1, 0.01 to 1.00 wt% of the alcohol having 1 to 8 carbon atoms, 0.0001 to 1.00 wt% of the surfactant, and water as a remainder.

[0025] In one embodiment of the present invention, the photoresist cleaning composition may have a surface tension of 35 dyne / cm to 50 dyne / cm at room temperature (25°C).

[0026] In one embodiment of the present invention, the photoresist cleaning solution composition may have a foaming amount of 3 ml or less according to the following measurement method.

[0027] [measurement method]

[0028] 1) According to KS M ISO 696, 50 ml of the above cleaning solution composition is dropped from a height of 450 mm.

[0029] 2) After leaving the above cleaning solution composition for 60 seconds, measure the volume of foam.

[0030] 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 solution composition containing a compound represented by the following chemical formula 1.

[0031] [Chemical Formula 1]

[0032]

[0033] 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.

[0034] In one embodiment of the present invention, the exposure in step (b) may be selected from the group consisting of KrF, ArF, and EUV.

[0035] In one embodiment of the present invention, step (c) may be performed at room temperature (25°C).

[0036] 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.

[0037] 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.

[0038]

[0039] A photoresist cleaning composition according to the present invention comprises a compound represented by chemical formula 1 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.

[0040] 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 compound of the present invention includes a structure having branched alkyl groups on both sides, the phenomenon in which the hydrophobic portion encapsulates air and generates foam can be significantly reduced.

[0041] Therefore, the photoresist cleaning solution composition according to the present invention can suppress foaming, thereby improving the cleaning power for removing residues of the developer, thereby improving the line width roughness of the photoresist pattern, thereby improving the consistency between the photomask pattern and the photoresist pattern, and also increasing the efficiency of the cleaning process.

[0042] In addition, the compound includes a linear ether group structure that can be imparted with hydrophilicity, thereby reducing the surface tension of the photoresist cleaning composition, thereby minimizing the phenomenon of the photoresist pattern collapsing that may occur during the cleaning process.

[0043]

[0044] Figures 1 to 5 are cross-sectional views briefly illustrating a process for forming a photoresist pattern according to the present invention.

[0045]

[0046] 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.

[0047] 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.

[0048]

[0049] Hereinafter, a photoresist cleaning composition according to the present invention and a method for forming a photoresist pattern using the same will be described.

[0050]

[0051] <Composition for cleaning photoresist>

[0052] A photoresist cleaning composition according to the present invention comprises a compound represented by the following chemical formula 1.

[0053] [Chemical Formula 1]

[0054]

[0055] 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.

[0056] The above n:m may be 1:8 to 8:1, 1:7 to 7:1, 1:6 to 6:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1, or 1:1.

[0057] The above tertiary carbon refers to carbon bonded to three carbons. The above quaternary carbon refers to carbon bonded to four carbons. The above tertiary carbon and quaternary carbon may refer to carbon having a branched alkyl group. The compound represented by the above chemical formula 1 may be a surfactant. The compound represented by the above chemical formula 1 may be a nonionic surfactant.

[0058] The compound represented by the above chemical formula 1 may have a linear ether group structure that can be imparted with hydrophilicity and an alkyl group branched around a triple bond that can be imparted with hydrophobicity on both sides.

[0059] Accordingly, conventional nonionic surfactants had a problem in that the hydrophobic portion envelops the air and generates a large amount of foam, but since the hydrophobic portion of the compound includes a structure having branched alkyl groups on both sides, the phenomenon in which the hydrophobic portion envelops the air and generates foam can be reduced.

[0060] Accordingly, the photoresist cleaning composition containing the compound can suppress foaming, thereby improving the cleaning power for removing residues of a photoresist film or developer that may be generated during a photoresist exposure and development process.

[0061] Accordingly, the line width roughness of the photoresist pattern, which may be increased by the residue of the photoresist film or developer, 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.

[0062] In addition, the compound includes not only a hydrophobic portion having branched alkyl groups on both sides, but also a linear ether group structure that can be imparted with hydrophilicity, thereby reducing the surface tension of the photoresist cleaning solution composition, thereby minimizing the phenomenon of the photoresist pattern collapsing due to the high surface tension of the cleaning solution during the cleaning process.

[0063]

[0064] 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.

[0065] 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.

[0066] 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.

[0067]

[0068] The compound represented by the above chemical formula 1 may have at least one of R1 and R2 and at least one of R3 and R4 as tertiary carbon. R5 and R6 may be hydrogen.

[0069] Specifically, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 2.

[0070] [Chemical Formula 2]

[0071]

[0072] In the above chemical formula 2, R1 and R3 are each independently isopropyl, isobutyl, sec-butyl, or tert-butyl, and n and m are each independently integers from 1 to 6.

[0073] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 3.

[0074] [Chemical Formula 3]

[0075]

[0076] In the above chemical formula 3, n and m are each independently integers from 1 to 6.

[0077] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 4.

[0078] [Chemical Formula 4]

[0079]

[0080] In the above chemical formula 4, n and m are each independently an integer from 1 to 6.

[0081]

[0082] The compound represented by the above chemical formula 1 may have at least one of R1 and R2 and at least one of R3 and R4 as quaternary carbon. R5 and R6 may be hydrogen.

[0083] Specifically, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 5.

[0084] [Chemical Formula 5]

[0085]

[0086] In the above chemical formula 5, n and m are each independently an integer from 1 to 6.

[0087] The compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 6.

[0088] [Chemical Formula 6]

[0089]

[0090] In the above chemical formula 6, n and m are each independently an integer from 1 to 6.

[0091]

[0092] Based on the total weight of the photoresist cleaning composition, the content of the compound 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.

[0093] The HLB (Hydrophile Lipophile Balance) value of the compound represented by the above chemical formula 1 may be 6 to 10, 6 to 9.5, 6 to 9, 6.5 to 9, 7 to 9, 7.5 to 9, or 7.5 to 8.5. The HLB refers to the value of the degree of hydrophilicity-lipophilicity of the compound. The HLB can be measured using the Griffin formula, and specifically, can be measured using the following calculation formula 1.

[0094] [Calculation Formula 1]

[0095] HLB = 20 × [(M1 / M0)]

[0096] In the above calculation formula 1, M0 means the molecular mass of the compound represented by the above chemical formula 1, and M1 means the molecular mass of the hydrophilic portion of the compound represented by the above chemical formula 1.

[0097] According to the above calculation formula 1, the HLB can 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 compound represented by the above chemical formula 1 can be estimated by the HLB value.

[0098] When the HLB value of the compound represented by the above chemical formula 1 satisfies the above range, collapse of the photoresist pattern can be minimized, and the line width roughness of the photoresist pattern can be improved.

[0099] The weight average molecular weight (Mw) of the compound represented by the above chemical formula 1 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.

[0100] The compound represented by the above chemical formula 1 may have a solubility in water at 25°C of 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.

[0101]

[0102] The above photoresist cleaning composition may include water and additives.

[0103] 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.

[0104] 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.

[0105] The above additive may include an alcohol having 1 to 8 carbon atoms and a surfactant different from the compound represented by the above chemical formula 1.

[0106] Specifically, 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.

[0107] 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.

[0108] A surfactant different from the compound represented by the above chemical formula 1 can reduce the surface tension of the photoresist cleaning composition. The surfactant may include at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, a nonionic surfactant, a silicone-based surfactant, and a fluorinated surfactant. Preferably, the surfactant may include a nonionic surfactant. The nonionic surfactant may have excellent wettability, thereby improving the cleaning power for the 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.

[0109] 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.

[0110] 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.

[0111] 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 compound represented by the above chemical formula 1.

[0112] 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.

[0113] 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%.

[0114] The additive may include a hydrophilicity enhancer. The hydrophilicity enhancer can capture the hydrophobic portion of the compound represented by Chemical Formula 1 included in the photoresist cleaning composition and the hydrophobic portion of a surfactant different from the compound represented by Chemical Formula 1, thereby changing the photoresist cleaning composition to a more hydrophilic state, so that the photoresist cleaning composition can be more easily removed after the cleaning process.

[0115] 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.

[0116] The above additive may include a dissolution inhibitor. The dissolution inhibitor may prevent the compound represented by the above chemical formula 1 and a surfactant different from the compound represented by the above chemical formula 1 from reacting with the surface of the photoresist pattern in the photoresist cleaning solution composition, thereby penetrating into the interior of the photoresist pattern and causing the pattern to melt or collapse. For example, an amine may be used as the dissolution inhibitor, and specifically, monoethanolamine, diethanolamine, or triethanolamine may be used.

[0117] The additive may include a dispersant. The dispersant may improve the solubility of the compound represented by the chemical formula 1 and a surfactant different from the compound represented by the chemical formula 1 in the photoresist cleaning composition, thereby improving the dispersion stability of the compound and the surfactant in the photoresist cleaning composition. For example, ammonia water may be used as the dispersant.

[0118] 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.

[0119]

[0120] The photoresist cleaning composition may include 0.01 to 1.00 wt% of the compound represented by the chemical formula 1, 0.01 to 1.00 wt% of the alcohol having 1 to 8 carbon atoms, 0.0001 to 1.00 wt% of the surfactant, 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 water as the balance may refer to the remaining amount after excluding the compound represented by the chemical formula 1 and the additive from the total amount of the photoresist cleaning composition.

[0121]

[0122] 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 35 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.

[0123] 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.

[0124] The photoresist cleaning solution composition may have a foaming amount of 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.

[0125] [measurement method]

[0126] 1) According to KS M ISO 696, 50 ml of the above cleaning solution composition is dropped from a height of 450 mm.

[0127] 2) After leaving the above cleaning solution composition for 60 seconds, measure the volume of foam.

[0128]

[0129] <Method for forming a photoresist pattern>

[0130] 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 solution composition containing a compound represented by the following chemical formula 1.

[0131] [Chemical Formula 1]

[0132]

[0133] 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.

[0134] The above R1 to R6, n and m may be the same as R1 to R6, n and m of the compound represented by chemical formula 1 in the photoresist cleaning solution composition described above.

[0135]

[0136] 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.

[0137] 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.

[0138] 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.

[0139] Referring to FIGS. 2 and 3, a photoresist pattern (23) can be formed by exposing and developing the photoresist film (20).

[0140] 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).

[0141] 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%.

[0142] 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.

[0143] A post-baking process may be performed after the above exposure process or after the above development process, as needed.

[0144] 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.

[0145] Referring to FIGS. 4 and 5, the photoresist pattern (23) can be cleaned with a photoresist cleaning composition (50) containing a compound represented by the aforementioned chemical formula 1. 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.

[0146] 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.

[0147] 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).

[0148] 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.

[0149]

[0150] <Method of manufacturing semiconductors>

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155]

[0156] 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.

[0157]

[0158] Example

[0159] 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%.

[0160]

[0161] Classification Chemical formula 1 Compound Additive Deionized water Surfactant Alcohol Unit weight % Example 10.05 (A-1) 0.002 (B-1 1) )0.6 (C-1 2)) Residue Example 20.25 (A-1) 0.002 (B-1) 0.6 (C-1) Residue Example 30.35 (A-1) 0.002 (B-1) 0.6 (C-1) Residue Example 40.50 (A-1) 0.002 (B-1) 0.6 (C-1) Residue Example 51.00 (A-1) 0.002 (B-1) Residue Example 60.05 (A-2) 0.002 (B-1) 0.6 (C-1) Residue Example 70.25 (A-2) 0.002 (B-1) 0.6 (C-1) Residue Example 80.35 (A-2) 0.002 (B-1) 0.6 (C-1) Residue Example 90.50 (A-2) 0.002 (B-1) 0.6 (C-1) Residue Example 101.00 (A-2) 0.002 (B-1) - Residue Example 110.05 (A-3) 0.002 (B-1) 0.6 (C-1) Residue Example 120.25 (A-3) 0.002 (B-1) 0.6 (C-1) Residue Example 130.35 (A-3) 0.002 (B-1) 0.6 (C-1) Residue Example 140.50 (A-3) 0.002 (B-1) 0.6 (C-1) Residue Example 151.00 (A-3) 0.002 (B-1) - Residue Example 160.05 (A-4) 0.002 (B-1) 0.6 (C-1) Residue Example 170.25 (A-4) 0.002 (B-1) 0.6 (C-1) Residue Example 180.35 (A-4) 0.002 (B-1) 0.6 (C-1) Residue Example 190.50 (A-4) 0.002 (B-1) 0.6 (C-1) Residue Example 201.00 (A-4) 0.002 (B-1) Residue Example 210.05 (A-5) 0.002 (B-1) 0.6 (C-1) Residue Example 220.25 (A-5) 0.002 (B-1) 0.6 (C-1) Residue Example 230.35 (A-5)0.002 (B-1)0.6 (C-1) Residue Example 240.50 (A-5)0.002 (B-1)0.6 (C-1) Residue Example 251.00 (A-5)0.002 (B-1)- Residue Example 260.05 (A-6)0.002 (B-1)0.6 (C-1) Residue Example 270.25 (A-6)0.002 (B-1)0.6 (C-1) Residue Example 280.35 (A-6)0.002 (B-1)0.6 (C-1) Residue Example 290.50 (A-6)0.002 (B-1) 0.6 (C-1) Residue Example 301.00 (A-6) 0.002 (B-1) - Residue Comparison Example 1 - 0.05 (A`-1) 0.002 (B-1) 0.6 (C-1) Residue Comparison Example 2 - 0.05 (A`-2) 0.002 (B-1) 0.6 (C-1) Residue Comparison Example 3 - 0.05 (A`-3) 0.002 (B-1) 0.6 (C-1) Residue Comparison Example 4 - 0.05 (A`-4) 0.002 (B-1) 0.6 (C-1) Residue Comparison Example 5 - 0.05 (A`-5) 0.002 (B-1) 0.6 (C-1) Residue Comparison Example 6 - 0.05 (A`-6)0.002 (B-1)0.6 (C-1)Residue Comparison Example 7-0.05 (A`-7)0.002 (B-1)0.6 (C-1)Residue 1) B-1: Polypropylene glycol 2) C-1: tert-Butanol.

[0162]

[0163] Specific compounds A-1 to A-6 described in Table 1 above are shown in Table 2 below.

[0164]

[0165] A-1 A-2 A-3 A-4 A-5 A-6

[0166]

[0167] Specific compounds of the surfactants A`-1 to A`-7 described in Table 1 above are shown in Table 3 below.

[0168]

[0169] A`-1 A`-2 A`-3 A`-4 A`-5 A`-6 A`-7

[0170]

[0171] Experimental example

[0172] Experimental Example 1 - Measurement of Foam Volume

[0173] The amount of foam generated from the photoresist cleaning compositions of Examples 1 to 30 and Comparative Examples 1 to 7 was measured according to KS M ISO 696. Specifically, 50 ml of each of the photoresist cleaning compositions of Examples 1 to 30 and Comparative Examples 1 to 7 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 4 below.

[0174]

[0175] Experimental Example 2 - Evaluation of the time it takes for bubbles to burst

[0176] After placing 50 ml of each of the photoresist cleaning compositions of Examples 1 to 30 and Comparative Examples 1 to 7 in a flask, shaking was performed at a speed of 150 rpm for 3 minutes, and the time for the bubbles generated from the cleaning composition to break was evaluated based on the following criteria, and the results are shown in Table 4 below.

[0177] - ◎: ​​Less than 5 seconds

[0178] - ○: 5 seconds or more but less than 10 seconds

[0179] - △: 10 seconds or more but less than 30 seconds

[0180] - ×: 30 seconds or more

[0181]

[0182] Experimental Example 3 - Surface Tension Measurement

[0183] The surface tension of the photoresist cleaning solution compositions of Examples 1 to 30 and Comparative Examples 1 to 7 was measured at room temperature (25°C) using a K100 (KRUSS) surface tension meter, and the results are shown in Table 4 below.

[0184]

[0185] Experimental Example 4 - Contact Angle Measurement

[0186] The contact angles of the photoresist cleaning solution compositions of Examples 1 to 30 and Comparative Examples 1 to 7 were measured at room temperature (25°C) using a Phoenix 300 analyzer, and the results are shown in Table 4 below.

[0187]

[0188] Experimental Example 5 - Photoresist Residue Evaluation

[0189] For each of the photoresist cleaning compositions of Examples 1 to 30 and Comparative Examples 1 to 7, a substrate on which photoresist micropattern development was completed 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 4 below.

[0190] - ○: No residue from photoresist pattern

[0191] - ×: Residue of photoresist pattern exists

[0192]

[0193] Experimental Example 6 - Line Width Roughness Evaluation

[0194] For the substrate on which the photoresist micro-pattern development and cleaning in Experimental Example 5 above was 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 4 below.

[0195] - ◎: ​​Less than 4 nm

[0196] - ○: 4 nm or more and less than 4.5 nm

[0197] - △: 4.5 nm or more and less than 6 nm

[0198] - ×: 6 nm or more

[0199]

[0200] Classification Bubble volume Bubble bursting time Evaluation Surface tension Contact angle Photoresist residue Evaluation Line width Roughness Evaluation unit ml-dyne / cm°--Example 11.0◎47.8074.01○◎Example 21.0◎39.2655.68○◎Example 3-◎36.1451.60○◎Example 4-◎35.4844.79○◎Example 51.0◎48.1174.05○◎Example 60.8◎47.8574.03○◎Example 70.7◎39.3555.78○◎Example 8-◎36.1751.63○◎Example 9-◎35.4944.82○◎Example 100.8◎48.2375.23○◎Example 110.5◎47.9074.11○◎Example 120.5◎39.3855.79○◎Example 13-◎36.1952.01○◎Example 14-◎35.5144.86○◎Example 150.5◎48.9075.55○◎Example 160.5◎47.9274.12○◎Example 170.5◎39.4055.81○◎Example 18-◎36.2152.11○◎Example 19-◎35.5344.92○◎Example 200.5◎48.9575.65○◎Example 210.5◎48.8075.01○◎Example 220.4◎39.4155.83○◎Example 23-◎36.3252.21○◎Example 24-◎35.5544.98○◎Example 250.5◎49.8075.70○◎Example 260.5◎47.8275.13○◎Example 270.5◎39.4455.85○◎Example 28-◎36.5252.26○◎Example 29-◎35.5945.02○◎Example 300.5◎49.8275.73○◎Comparative Example 18.7×31.6458.16××Comparative Example 28.7×31.3124.46×△Comparative example 310.7×28.988.90×△Comparative example 48.3×49.9363.67××Comparative example 58.0×34.3638.80××Comparative example 67.5△50.1075.33××Comparative example 77.0△55.6478.35××

[0201]

[0202] As can be confirmed in Tables 1 to 4 above, it was confirmed that Examples 1 to 30 including the compound represented by Chemical Formula 1 had a significantly reduced amount of bubble generation compared to Comparative Examples 1 to 7. In addition, Examples 1 to 30 did not generate bubbles or the time for bubbles to burst was significantly shorter than Comparative Examples 1 to 7, so it was confirmed that there was no residue in the photoresist pattern and that the line width roughness of the pattern that could be generated by the residue was significantly improved.

[0203]

[0204] 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 photoresist cleaning solution composition comprising a compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, The above R1 to R4 are each independently substituted or unsubstituted alkyl having 1 to 8 carbon atoms, At least one of the above R1 and R2, and at least one of the above R3 and R4 has a tertiary carbon or a quaternary carbon, The above R5 and R6 are each independently hydrogen or methyl, The above n and m are each independently integers from 1 to 8.

2. In paragraph 1, A photoresist cleaning composition wherein at least one of the above R1 and R2 and at least one of the above R3 and R4 is a branched-chain alkylene having 3 to 6 carbon atoms.

3. In paragraph 2, A photoresist cleaning composition wherein the branched chain alkylene having 3 to 6 carbon atoms is isopropyl, isobutyl, sec-butyl, or tert-butyl.

4. In paragraph 1, A photoresist cleaning composition wherein the above R5 and R6 are hydrogen.

5. In paragraph 1, A photoresist cleaning solution composition wherein the compound represented by the above chemical formula 1 is a compound represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, The above R1 and R3 are each independently isopropyl, isobutyl, sec-butyl, or tert-butyl, The above n and m are each independently integers from 1 to 6.

6. In paragraph 1, A photoresist cleaning composition, wherein the content of the compound is 0.01 wt% to 1.00 wt% based on the total weight of the photoresist cleaning composition.

7. In paragraph 1, A photoresist cleaning solution composition wherein the HLB (Hydrophile Lipophile Balance) value of the above compound is 6 to 10.

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

9. In paragraph 8, A photoresist cleaning composition wherein the additive comprises an alcohol having 1 to 8 carbon atoms and a surfactant different from the compound represented by the chemical formula 1.

10. In paragraph 9, The above photoresist cleaning composition, 0.01 wt% to 1.00 wt% of the compound represented by the above chemical formula 1; 0.01 to 1.00 wt% of the alcohol having 1 to 8 carbon atoms; 0.0001 wt% to 1.00 wt% of the above surfactant; and A photoresist cleaning composition comprising water as a residue.

11. In paragraph 1, The photoresist cleaning composition above is a photoresist cleaning composition having a surface tension of 35 dyne / cm to 50 dyne / cm at room temperature (25°C).

12. In paragraph 1, The photoresist cleaning solution composition above is a photoresist cleaning solution composition having a foaming amount of 3 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. 13.(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 containing a compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, The above R1 to R4 are each independently substituted or unsubstituted alkyl having 1 to 8 carbon atoms, At least one of the above R1 and R2, and at least one of the above R3 and R4 has a tertiary carbon or a quaternary carbon, The above R5 and R6 are each independently hydrogen or methyl, The above n and m are each independently integers from 1 to 8.

14. In paragraph 13, 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.

15. In paragraph 13, A method for forming a photoresist pattern, wherein the above step (c) is performed at room temperature (25°C).

16. In paragraph 13, 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.

17. In paragraph 13, 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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