Photoresist cleaning liquid composition and photoresist pattern forming method using same

Abstract

The invention provides a photoresist cleaning liquid composition and a photoresist pattern forming method using the same. A photoresist cleaning liquid composition according to an embodiment of the present invention contains a monohydric alcohol solvent and a polyol compound. The content of the polyol compound is greater than 0 ppm and 150 ppm or less relative to the total weight of the composition. By using the photoresist cleaning liquid composition containing the monohydric alcohol solvent and the polyol compound, the photoresist pattern can be prevented from collapsing, the line width roughness can be improved, and the uniformity of the photoresist pattern can be improved.

Description

Technical Field

[0001] The present invention relates to a photoresist cleaning liquid composition and a photoresist patterning method using the same. Background Art

[0002] A photoresist is a chemical film that can use a photochemical reaction caused by light to draw a fine pattern printed on a photomask on a desired substrate. Both the photoresist and the photomask are polymer materials applied to exposure technology and are considered the main factors for the integration and resolution of components. In recent years, as semiconductor components have developed towards higher integration and miniaturization, it has been necessary to develop a photoresist capable of forming a fine pattern (patterning).

[0003] In the technology of forming a fine pattern using a photoresist, the field that has received the same attention as the development of a new photoresist is a cleaning liquid for a semiconductor substrate. In order to form a high-resolution pattern, after the exposure and development processes of the applied photoresist, it is necessary to remove the residues remaining on the semiconductor substrate through a cleaning process using a cleaning liquid.

[0004] For example, while rotating a semiconductor substrate, distilled water can be sprayed from the upper part of a rotating device to remove the remaining photoresist film. In this case, due to the large surface tension of distilled water, the pattern may collapse.

[0005] Therefore, there is a need for a cleaning liquid composition that has excellent removing power for residues generated after the exposure and development processes and can improve the resolution and uniformity of the pattern.

[0006] Korean Registered Patent Publication No. 10-1376340 discloses a composition for cleaning a semiconductor substrate. However, there is still a need for a cleaning liquid composition for improving the resolution and uniformity of the pattern. Summary of the Invention

[0007] Problems to be Solved

[0008] One problem of the present invention is to provide a photoresist cleaning liquid composition that can prevent the collapse of a photoresist pattern and improve line width roughness.

[0009] One problem of the present invention is to provide a photoresist patterning method using the above cleaning liquid composition.

[0010] Means for Solving the Problems

[0011] 1. A photoresist cleaning liquid composition comprising a monohydric alcohol-based solvent and a polyhydric alcohol-based compound, wherein the content of the polyhydric alcohol-based compound is greater than 0 ppm and 150 ppm or less in the total weight of the composition.

[0012] 2. In the photoresist cleaning liquid composition as described in 1 above, in the total weight of the composition, the content of the above-mentioned polyol compound is greater than 0 ppm and 100 ppm or less.

[0013] 3. In the photoresist cleaning liquid composition as described in 1 above, the above-mentioned monohydric alcohol solvent contains an alkyl alcohol having 2 to 5 carbon atoms.

[0014] 4. In the photoresist cleaning liquid composition as described in 1 above, the above-mentioned monohydric alcohol solvent contains an alkyl alcohol having a boiling point of 120°C or lower.

[0015] 5. In the photoresist cleaning liquid composition as described in 1 above, the above-mentioned polyol compound contains a diol compound having two hydroxyl groups.

[0016] 6. In the photoresist cleaning liquid composition as described in 5 above, the above-mentioned diol compound contains an alkyl diol compound having 2 to 5 carbon atoms.

[0017] 7. In the photoresist cleaning liquid composition as described in 5 above, the above-mentioned diol compound contains a diol compound having hydroxyl groups bonded to both ends.

[0018] 8. In the photoresist cleaning liquid composition as described in 5 above, the two hydroxyl groups of the above-mentioned diol compound are each bonded to adjacent carbons.

[0019] 9. In the photoresist cleaning liquid composition as described in 5 above, the two hydroxyl groups of the above-mentioned diol compound are bonded to the same carbon.

[0020] 10. In the photoresist cleaning liquid composition as described in 1 above, the above-mentioned polyol compound does not contain a polyol compound having three or more hydroxyl groups.

[0021] 11. In the photoresist cleaning liquid composition as described in 1 above, it does not contain an acidic compound or a basic compound.

[0022] 12. A method for forming a photoresist pattern, which includes: a step of forming a photoresist film on a substrate; a step of partially removing the above-mentioned photoresist film to form a photoresist pattern; and a step of using the photoresist cleaning liquid composition as described in 1 above to clean the above-mentioned substrate on which the above-mentioned photoresist pattern is formed.

[0023] Advantages of the Invention

[0024] The photoresist cleaning liquid composition of the embodiments of the present invention may contain a monohydric alcohol-based solvent and a polyhydric alcohol-based compound. The content of the above polyhydric alcohol-based compound is adjusted to a predetermined range. Through the content of the above polyhydric alcohol-based compound, a photoresist pattern with improved uniformity can be achieved.

[0025] In some embodiments, the above polyhydric alcohol-based compound may include a diol-based compound having two hydroxyl groups. Through the above diol-based compound, the unexposed photoresist can be effectively removed without pattern collapse. Therefore, the yield reduction of semiconductor elements can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 ~ Figure 4 It is a schematic cross-sectional view for explaining a method of forming a photoresist pattern of an exemplary embodiment.

[0027] SYMBOL DESCRIPTION

[0028] 50: Exposure mask 100: Substrate

[0029] 110: Photoresist film 113: Unexposed portion

[0030] 115: Exposed portion 120: Photoresist pattern

[0031] 130: Development residue DETAILED DESCRIPTION

[0032] According to an exemplary embodiment of the present invention, a photoresist cleaning liquid composition includes a monohydric alcohol-based solvent and a polyhydric alcohol-based compound with a controlled content. In addition, a method of forming a photoresist pattern using the above cleaning liquid composition is provided.

[0033] In this specification, "alkyl" includes straight-chain hydrocarbons and branched-chain hydrocarbons. For example, an alkyl group having 4 carbon atoms may include n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0034] Hereinafter, embodiments of the present invention will be described in detail.

[0035] <Photoresist Cleaning Liquid Composition>

[0036] The photoresist cleaning liquid composition of an exemplary embodiment may contain a monohydric alcohol-based solvent and a polyhydric alcohol-based compound with a controlled content.

[0037] The above cleaning liquid composition can remove process residues such as unexposed photoresist or residual developer solution present on, for example, a semiconductor substrate. For example, a polyol compound having two or more hydroxyl groups can provide additional activity to organic and inorganic residues present between photoresist patterns after exposure and development, and effectively remove the residues from the semiconductor substrate.

[0038] The monohydric alcohol-based solvent may include an organic solvent having one hydroxyl group.

[0039] The above monohydric alcohol-based solvent can, for example, remove the developer solution and photoresist residues after the development process, and prevent the collapse of the photoresist pattern during the drying process.

[0040] For example, it may include: alkyl alcohols, including 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, etc.; alkenyl alcohols, including 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, etc.

[0041] According to an exemplary embodiment, the above monohydric alcohol-based solvent may include alkyl alcohols.

[0042] According to an exemplary embodiment, the above monohydric alcohol-based solvent may include alkyl alcohols having 2 to 5 carbon atoms.

[0043] For example, the above alkyl alcohols having 2 to 5 carbon atoms may include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, tert-pentanol, etc.

[0044] For example, an alcohol-based solvent such as 2-propanol derived from fossil resources such as coal, petroleum, and natural gas as raw materials before refining can be used, or 2-propanol derived from biomass (Bio-2-Propanol) can be used.

[0045] Examples of Bio-2-propanol include: 2-propanol obtained from biomass raw materials using bacteria that produce 2-propanol (see International Publication No. 2009 / 008377); 2-propanol obtained by hydrating propylene obtained from bio-methanol; 2-propanol obtained by reducing acetone obtained from bio-ethanol; 2-propanol obtained by hydrating propylene obtained from bio-ethanol, and the like.

[0046] For example, when the number of carbon atoms of the above-mentioned alkyl alcohol is less than 2, the stability may be reduced due to high volatility, and unexposed photoresist residues cannot be removed. When the number of carbon atoms of the above-mentioned alkyl alcohol is greater than 5, the photoresist pattern may be dissolved and damaged due to the high boiling point and the remaining monohydric alcohol-based solvent on the substrate.

[0047] For example, the above-mentioned monohydric alcohol-based solvent may include a single solvent or a mixed solvent of the above-mentioned solvents.

[0048] In some embodiments, the above-mentioned monohydric alcohol-based solvent may include one or more selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol.

[0049] In some embodiments, the above-mentioned monohydric alcohol-based solvent may also include two or more selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol.

[0050] For example, based on the total weight of the above-mentioned monohydric alcohol-based solvent, the above-mentioned monohydric alcohol-based solvent may include 30 wt% to 70 wt% of one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol, and may include another selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, and 1-pentanol. For example, based on the total weight of the above-mentioned monohydric alcohol-based solvent, the above-mentioned monohydric alcohol-based solvent may include 50 wt% of 2-propanol and may include the balance of 1-butanol.

[0051] The content of the above-mentioned monohydric alcohol-based solvent may be the remainder or the balance. The terms "remainder" or "balance" used in the present application may refer to a variable amount that changes according to the addition of components or formulations.

[0052] In some embodiments, the above-mentioned monohydric alcohol-based solvent may include an alkyl alcohol having a boiling point of 120 °C or lower. For example, the boiling point of the above-mentioned monohydric alcohol-based solvent may be 110 °C or lower.

[0053] For example, the vapor pressure of the above-mentioned monohydric alcohol-based solvent at 25°C can be 0.3 kPa or more. For example, the vapor pressure of the above-mentioned monohydric alcohol-based solvent at 25°C can be 0.5 kPa or more.

[0054] For example, the above-mentioned monohydric alcohol-based solvent may contain one or more of 1-propanol, 2-propanol, and 1-butanol. When the boiling point and the vapor pressure at normal temperature satisfy the above ranges, the solvent will not remain on the substrate after the cleaning process.

[0055] The polyhydric alcohol-based compound may contain an organic solvent having two or more hydroxyl groups.

[0056] The polyhydric alcohol-based compound can selectively remove, for example, photoresist residues or developer. Therefore, the uniformity of the photoresist pattern can be improved.

[0057] For example, it may include: diol series, including 1,1-dihydroxyethane, 1,2-dihydroxyethane, 1,1-dihydroxypropane, 1,2-dihydroxypropane, 1,3-dihydroxypropane, 1,1-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,1-dihydroxypentane, 1,2-dihydroxypentane, 1,3-dihydroxypentane, 1,4-dihydroxypentane, 1,5-dihydroxypentane, 1,1-dihydroxyhexane, 1,2-dihydroxyhexane, etc.; triol series, including 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, trimethylolpropane, glycerin, etc.; tetraol series, including diglycerin, pentaerythritol, etc.; and so on.

[0058] According to the exemplary embodiment, the above polyol series compounds may include diol series compounds having two hydroxyl groups.

[0059] According to the exemplary embodiment, the above polyol series compounds may include alkyl diol series compounds having 2 to 5 carbon atoms.

[0060] For example, when the number of carbon atoms in the above alkyl diol compound is less than 2, the residue removal ability of the photoresist may be reduced and a uniform pattern may not be achieved. For example, when the number of carbon atoms in the above alkyl diol compound is greater than 5, the solubility of the photoresist may increase, resulting in damage to the photoresist pattern or an increase in line width roughness.

[0061] The residue removal ability of the cleaning liquid composition may vary depending on the hydroxyl binding position, binding structure, etc. of the diol compound.

[0062] In some embodiments, the above diol compound may include a diol compound having hydroxyl groups bonded to both ends.

[0063] For example, the above diol compound may include a compound having hydroxyl groups bonded to both ends of a straight-chain or branched hydrocarbon chain. For example, the above diol compound may include 1,2-dihydroxyethane, 1,3-dihydroxypropane, etc.

[0064] The diol compound having hydroxyl groups bonded to both ends can reduce the collapse phenomenon of the photoresist pattern.

[0065] In some embodiments, the above alkyl diol compound may not include an alkyl diol compound having 4 or more or 5 or more carbon atoms and having hydroxyl groups bonded to both ends.

[0066] The removal selectivity of the residue of the alkyl diol compound having hydroxyl groups bonded to both ends and having a carbon number in the above range or more of the developing solution may be reduced due to the compound structure, resulting in damage to the photoresist pattern or a decrease in line width uniformity.

[0067] In some embodiments, the above diol compound may include an alkyl diol compound in which two hydroxyl groups are each bonded to an adjacent carbon.

[0068] For example, the alkyl diol compound in which two hydroxyl groups are each bonded to an adjacent carbon may include one or more of 1,2-dihydroxyethane, 1,2-dihydroxypropane, 1,2-dihydroxybutane, and 1,2-dihydroxypentane.

[0069] In some embodiments, the above diol compound may include an alkyl diol compound in which two hydroxyl groups are bonded to the same carbon.

[0070] For example, the alkyl diol compound in which two hydroxyl groups are bonded to a shared carbon may include one or more of 1,1-dihydroxyethane, 1,1-dihydroxypropane, 1,1-dihydroxybutane, and 1,1-dihydroxypentane.

[0071] When each of the two hydroxyl groups is bonded to carbons adjacent to each other or to the same common carbon, the diol compound can reduce line width roughness. Thus, the uniformity of the photoresist film can be improved.

[0072] In some embodiments, the above diol compound may include an alkyl diol compound having 4 to 5 carbon atoms, or may include an alkyl diol compound in which each of the two hydroxyl groups is bonded to a non-adjacent carbon.

[0073] For example, the alkyl diol compound in which each of the two hydroxyl groups is bonded to a non-adjacent carbon may include one or more of 1,3-dihydroxybutane, 1,3-dihydroxypentane, and 1,4-dihydroxypentane. Among them, the two hydroxyl groups may not be bonded to the two ends.

[0074] In some embodiments, the above polyol compound may not include a polyol compound having three or more hydroxyl groups.

[0075] When there are three or more hydroxyl groups, the capture ability of the undeveloped photoresist residue or the developer residue may decrease, resulting in an increase in the line width roughness of the fine pattern.

[0076] According to an exemplary embodiment, in the total weight of the above composition, the content of the above polyol compound may be greater than 0 ppm and 150 ppm or less.

[0077] In some embodiments, in the total weight of the above composition, the content of the above polyol compound may be greater than 0 ppm and 100 ppm or less, 0.01 ppm or more and 100 ppm or less, or 0.01 ppm or more and 50 ppm or less.

[0078] When within the above content range, the undeveloped photoresist residue can be removed without pattern collapse, and the line width roughness of the photoresist pattern can be improved.

[0079] For example, when the content of the polyol compound is lower than the above range, the amount of the undeveloped photoresist residue removed may be reduced, resulting in residues remaining on the cleaned substrate. For example, when the content of the polyol compound is higher than the above range, the fine pattern may dissolve, and thus pattern collapse may occur.

[0080] According to an exemplary embodiment, the above cleaning liquid composition may also include water. For example, the content of the above water may be 0.01 ppm or more and 50 ppm or less, or 0.1 ppm or more and 30 ppm or less.

[0081] According to an exemplary embodiment, the above-described cleaning liquid composition may not contain an acidic compound or a basic compound. The above-described acidic compound or basic compound may be substantially not contained. For example, the content of the acidic compound or basic compound may be 0.001 ppm or less.

[0082] For example, in the case of containing an acidic compound or a basic compound, the photoresist may become active due to hydrogen ions or hydroxide ions, resulting in melting of the photoresist pattern.

[0083] According to an exemplary embodiment, the above-described cleaning liquid composition may further contain an additional organic solvent. For example, it may further contain ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, ethylene glycol phenyl ether, propylene glycol monomethyl ether acetate, etc., and they may be added alone or in combination of two or more.

[0084] The above-described cleaning liquid composition may also contain an additive as needed. The above-described additive may be added within a range that does not impair the selective removal function of the photoresist residue or developer residue of the above-described polyol-based compound. For example, a preservative, etc., may be contained.

[0085] <Photoresist Pattern Formation Method>

[0086] Figure 1 ~ Figure 4 is a schematic cross-sectional view for explaining the pattern formation method of an exemplary embodiment. For example, Figure 1 ~ Figure 4 the pattern formation process using a negative photoresist is described.

[0087] However, the cleaning liquid composition of the exemplary embodiment is not limited to Figure 1 ~ Figure 4 the process, and a pattern formation process using a positive photoresist may also be employed.

[0088] Referring to Figure 1 , a photoresist film 110 can be formed by coating a photoresist material on a substrate 100.

[0089] The substrate 100 may contain a semiconductor material such as single crystal silicon or single crystal germanium, or may be formed in a manner containing polysilicon.

[0090] In some embodiments, after forming the above-described photoresist film 110, a soft baking process may be performed. Thereby, the organic solvent that may be contained in the above-described photoresist film 110 can be evaporated.

[0091] Refer to Figure 2 , through the exposure process, the non-exposed portion 113 and the exposed portion 115 can be formed on the substrate 100. The above exposure process can be carried out by using a light source (for example, an EUV light source) and an exposure mask 50.

[0092] The light (for example, EUV) passing through the above exposure mask 50 can irradiate the above photoresist film 110. Therefore, the above photoresist film 110 can have a non-exposed portion 113 and an exposed portion 115.

[0093] Refer to Figure 3 , through the development process, a photoresist pattern 120 can be formed on the substrate 100. For example, the non-exposed portion 113 can be removed from the substrate 100 by using a developer, thereby forming a photoresist pattern 120 composed of the exposed portion 115. The above developer can be an aqueous solution of tetramethylammonium hydroxide (TMAH).

[0094] Figure 3 The pattern formation process using a negative photoresist is described in

[0095] , but it is not limited thereto. For example, a positive photoresist can be used to implement the pattern formation process. In this case, the exposed portion 115 can be removed to form a photoresist pattern composed of the non-exposed portion 113.

[0096] In some embodiments, after the above exposure process or after the above development process, a post baking process can be further implemented.

[0096] After the above formation process, development residues 130 may exist on the substrate 100. The above development residues 130 can be undeveloped photoresist or developer residues. Since the development residues 130 remain on the substrate 100 or the photoresist pattern 120, it may cause seams to appear in the photoresist pattern 120, and the line width roughness of the pattern may increase.

[0097] Refer to Figure 4 , the cleaning liquid composition of the above exemplary embodiment can be coated or impregnated on the above substrate 100. Thereby, the development residues 130 formed on the substrate 100 or the photoresist pattern 120 can be removed.

[0098] The above cleaning step can be implemented by coating the cleaning liquid composition of the above exemplary embodiment on the substrate 100 under generally known cleaning conditions.

[0099] In some embodiments, the temperature during cleaning can be 25°C to 70°C or 25°C to 50°C. When immersed in the cleaning liquid composition, the residence time of the substrate 100 can be about 5 seconds to 10 minutes or 10 seconds to 5 minutes.

[0100] In some embodiments, the above cleaning step can use deionized water for the primary cleaning to remove the development residues, and then use the cleaning liquid composition of the above exemplary embodiments for the secondary cleaning.

[0101] As described above, the above cleaning liquid composition contains a monohydric alcohol-based solvent and a polyhydric alcohol-based compound, and thus can remove the undeveloped photoresist and can improve the profile of the photoresist pattern 120.

[0102] In addition, by controlling the type, content, etc. of the above polyhydric alcohol-based compound, the residues can be effectively removed only without damaging the structures (e.g., photoresist patterns) included in the semiconductor element.

[0103] Thereby, it is possible to prevent scum, pattern collapse, etc. generated during the formation of fine patterns, improve the line width roughness of the pattern, and can be effectively used for the formation of fine patterns using extreme ultraviolet lithography (EUVL) technology.

[0104] Hereinafter, experimental examples including specific examples and comparative examples are provided to help the understanding of the present invention. However, it is obvious to those skilled in the art that this is only an illustration of the present invention and does not limit the scope of the appended claims. Various changes and modifications can be made to the embodiments within the scope and technical idea of the present invention, and of course such changes and modifications also belong to the scope of the appended claims.

[0105] Examples and Comparative Examples

[0106] Mix the components described in Table 1 below according to the corresponding contents to manufacture a cleaning liquid composition with a total content of each component of 100% by weight.

[0107] [Table 1]

[0108]

[0109] The specific component names of the polyhydric alcohol and the organic solvent described in Table 1 above are as follows.

[0110] Polyol

[0111] A-1: 1,2-dihydroxyethane

[0112] A-2: 1,2-dihydroxypropane

[0113] A-3: 1,3-dihydroxyethane

[0114] A-4: 1,2-dihydroxybutane

[0115] A-5: 1,2-dihydroxypentane

[0116] A-6: 1,2-dihydroxyheptane

[0117] A-7: glycerol

[0118] Organic Solvent

[0119] B-1: 2-propanol

[0120] B-2: 1-propanol

[0121] B-3: ethanol

[0122] B-4: 1-butanol

[0123] B-5: 1-pentanol

[0124] B-6: 1-heptanol

[0125] Experimental Example

[0126] The lower antireflection film (DUV42P-6, manufactured by Nissan Chemical Industries, Ltd.) was spin-coated on a silicon wafer and then heated at 215 °C for 90 seconds to form a film with a thickness of 600 Å. The PHS-type photosensitive agent (KTF-5664, manufactured by Dongwoo Fine-Chem Co., Ltd.) was spin-coated on the upper part of the silicon wafer with the film formed thereon to fabricate a photoresist film, and then soft baked in an oven at 100 °C for 60 seconds. Next, exposure was performed using a scanner device equipped with a KrF laser, and then post baked in an oven at 110 °C for 60 seconds. Thereafter, development was carried out by immersing in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds.

[0127] Then, the developing residues on the upper part of the above silicon wafer were removed using deionized water. After coating 30 ml of the cleaning liquid composition of the example on the surface of the silicon wafer after water washing for 10 seconds, it was dried by high-speed spinning, thereby obtaining an 180 nm L / S pattern.

[0128] (1) Pattern Collapse Evaluation

[0129] A Critical Dimension Scanning Electron Microscope (CD-SEM, Hitachi, Ltd.) was used to observe the phenomenon of pattern collapse of the above 180 nm L / S pattern. The phenomenon of pattern collapse was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0130] <Evaluation Criteria>

[0131] ○: No pattern collapse

[0132] △: Only the edge pattern shows a collapse phenomenon

[0133] ×: The edge and central part patterns show a collapse phenomenon

[0134] (2) Line Width Roughness Evaluation

[0135] A CD-SEM (Hitachi, Ltd.) was used to measure the difference between the widest part and the narrowest part of the above 180 nm L / S pattern to confirm the line width roughness value, and the results are shown in Table 2 below. The smaller the line width roughness value, the more uniform the pattern.

[0136] (3) Photoresist Thickness Reduction Evaluation

[0137] An FE-SEM (Hitachi, Ltd.) was used to measure the difference in photoresist thickness before and after treatment with the photoresist cleaning liquid composition to confirm the degree of photoresist thickness reduction. The photoresist thickness reduction was evaluated according to the following criteria, and the results are shown in Table 2 below. The smaller the difference in photoresist thickness, the less damage the photoresist pattern suffers.

[0138] <Evaluation Criteria>

[0139] ○: The difference in photoresist thickness is 20 Å or less

[0140] △: The difference in photoresist thickness is greater than 20 Å and 50 Å or less

[0141] ×: The difference in photoresist thickness is greater than 50 Å

[0142] [Table 2]

[0143]

[0144] Referring to Table 2 above, in the case of using the cleaning liquid composition of the example, as compared with the case of the cleaning liquid composition of the comparative example, the line width roughness and the difference in photoresist thickness are reduced, and no pattern collapse phenomenon is observed.

[0145] In the case of using the cleaning liquid composition of Example 17 containing an organic solvent having more than 5 carbon atoms, the difference in photoresist thickness is more than 20 Å and 50 Å or less.

[0146] In the case of using the cleaning liquid composition of Example 18 containing a polyol having more than 5 carbon atoms, the difference in photoresist thickness is more than 20 Å and 50 Å or less.

[0147] In the case of using the cleaning liquid composition of Example 19 containing a polyol having more than 2 hydroxyl groups, a collapse phenomenon occurs in the edge pattern.

[0148] In the case of using the cleaning liquid compositions of Comparative Examples 1 and 2 in which a polyol is used as a solvent and the above-mentioned organic solvent is not contained, a collapse phenomenon occurs in the edge pattern and the central pattern, and the line width roughness is more than 5 nm.

[0149] In the case of using the cleaning liquid compositions of Comparative Examples 3 and 4 not containing a polyol, the line width roughness is more than 5 nm.

[0150] In the case of using the cleaning liquid composition of Comparative Example 5 in which the content of the polyol is 200 ppm or more, a collapse phenomenon occurs in the edge pattern, and the line width roughness is more than 3 nm.

Claims

1. A photoresist cleaning liquid composition comprising a monohydric alcohol-based solvent and a polyhydric alcohol-based compound, In the total weight of the composition, the content of the polyhydric alcohol-based compound is greater than 0 ppm and 150 ppm or less.

2. The photoresist cleaning liquid composition according to claim 1, wherein in the total weight of the composition, the content of the polyhydric alcohol-based compound is greater than 0 ppm and 100 ppm or less.

3. The photoresist cleaning liquid composition according to claim 1, wherein the monohydric alcohol-based solvent comprises an alkyl alcohol having 2 to 5 carbon atoms.

4. The photoresist cleaning liquid composition according to claim 1, wherein the monohydric alcohol-based solvent comprises an alkyl alcohol having a boiling point of 120°C or less.

5. The photoresist cleaning liquid composition according to claim 1, wherein the polyhydric alcohol-based compound comprises a diol-based compound having two hydroxyl groups.

6. The photoresist cleaning liquid composition according to claim 5, wherein the diol-based compound comprises an alkyl diol-based compound having 2 to 5 carbon atoms.

7. The photoresist cleaning liquid composition according to claim 5, wherein the diol-based compound comprises a diol-based compound having hydroxyl groups bonded to both ends.

8. The photoresist cleaning liquid composition according to claim 5, wherein the two hydroxyl groups of the diol-based compound are each bonded to adjacent carbons.

9. The photoresist cleaning liquid composition according to claim 5, wherein the two hydroxyl groups of the diol-based compound are bonded to the same carbon.

10. The photoresist cleaning liquid composition according to claim 1, wherein the polyhydric alcohol-based compound does not comprise a polyhydric alcohol-based compound having three or more hydroxyl groups.

11. The photoresist cleaning liquid composition according to claim 1, which does not comprise an acidic compound or a basic compound.

12. A photoresist pattern forming method, comprising: A step of forming a photoresist film on a substrate; A step of partially removing the photoresist film to form a photoresist pattern; And A step of using the photoresist cleaning liquid composition according to claim 1 to clean the substrate on which the photoresist pattern is formed.

Images