Photolithography process liquid composition and pattern forming method using the same

Abstract

The present invention relates to a process liquid composition for improving crack defects in a photoresist pattern during a photoresist patterning process, and a pattern forming method using the same. The photoresist pattern is hydrophobic, with a contact angle of water on the photoresist surface being 75° or greater. More specifically, the present invention relates to a process liquid composition comprising 0.00001 to 0.1% by weight of a fluorochemical surfactant, 0.00001 to 1.0% by weight of a substance selected from the group consisting of a triol derivative, a tetraol derivative, or a mixture thereof, and the balance being water, and having a surface tension of 45 mN / m or less and a contact angle of 65° or less.

Description

Technical Field

[0001] The present invention relates to a process liquid composition for improving crack defects in a photoresist pattern in a photoresist pattern process and a photoresist pattern forming method using the same, wherein the photoresist pattern has hydrophobicity with a contact angle of water on the photoresist surface being greater than 75°. Background Art

[0002] Typically, semiconductors are manufactured using a photolithography process that uses ultraviolet light in wavelengths such as 193nm, 248nm, or 365nm as an exposure light source. Companies are competing fiercely to reduce the critical dimension (CD).

[0003] Therefore, in order to form finer patterns, a light source with a smaller wavelength is required. Currently, photolithography technology using extreme ultraviolet (EUV) light sources with a wavelength of 13.5nm is widely used, which can achieve even finer wavelengths.

[0004] However, the etching resistance of EUV photoresists has not been improved, and thus photoresist patterns with large aspect ratios continue to be required. This easily leads to pattern crack defects during development, significantly reducing the process margin in the manufacturing process.

[0005] Therefore, it is necessary to develop a technology that can be used to improve the degree of crack defects generated during fine pattern formation. In order to improve the degree of pattern crack defects, the best way is to improve the performance of photoresists, but it cannot be ignored that it is currently difficult to develop new photoresists that meet all the requirements.

[0006] While the need for new photoresist development remains, efforts are ongoing to improve the degree of pattern cracking through other methods. Summary of the Invention

[0007] Technical problems to be solved

[0008] The purpose of the present invention is to develop a process liquid composition and a method for forming a photoresist pattern using the same, wherein the process liquid composition is used to improve the degree of crack defects in the pattern produced after photoresist development, wherein the photoresist pattern has a hydrophobicity with a contact angle of water on the photoresist surface of not less than 75°.

[0009] Solutions to the Problem

[0010] Although various surfactants are currently used in aqueous process liquid compositions used in development processes, in the present invention, an effective process liquid composition is prepared using a fluorine-based surfactant.

[0011] When using a hydrocarbon surfactant that tends to be hydrophobic in a process liquid composition of an aqueous type mainly using ultrapure water, the hydrophobization of the photoresist wall is induced, thereby being able to induce the dissolution (melting) of the pattern to be reduced and the collapse to be reduced. However, due to the strong tendency of hydrocarbon surfactants to aggregate with each other, the physical properties of the process liquid composition become uneven, so there is the possibility of inducing defects (defects) by the aggregated hydrocarbon surfactants during use. That is, when using hydrocarbon surfactants, it is necessary to increase the usage amount in order to improve dissolution, which has the concern of causing damage (Damage) to the photoresist. In addition, when using an unsuitable surfactant for the purpose of reducing the surface tension of the process liquid composition in order to reduce capillary force, it is possible to further induce pattern collapse due to the dissolution of the induced pattern.

[0012] In this invention, we have confirmed that the use of a fluorochemical surfactant, in addition to a substance selected from the group consisting of triol derivatives, tetraol derivatives, or mixtures thereof, significantly improves the degree of pattern crack defects. This is believed to be due to the fact that, compared to hydrocarbon-based surfactants, these surfactants reduce surface tension and contact angle, increase penetration and diffusivity, and thus facilitate the formation of fine patterns.

[0013] As a representative developer used in most current photolithography development processes, pure water is used as a base, and tetramethylammonium hydroxide is diluted to a certain concentration (in most processes, 2.38 wt % tetramethylammonium hydroxide is mixed with 97.62 wt % water).

[0014] In the photolithography process, after developing a hydrophobic photoresist pattern with a water contact angle of 75° or greater on the photoresist surface, pattern cracking defects were observed when the pattern was continuously washed with pure water alone. Pattern collapse was also observed when a process liquid composition containing tetramethylammonium hydroxide in pure water was used continuously after development or after treatment with pure water.

[0015] In the case of the process liquid composition containing tetramethylammonium hydroxide, it is presumed that the exposed fine pattern is weakened and the pattern collapse occurs due to a large or uneven capillary force.

[0016] Therefore, in order to improve the collapse of the exposed pattern and further improve the line width roughness (LWR) and defects of the photoresist pattern required in the process, it is necessary to study a substance that imparts a relatively weaker force to the exposed pattern than tetramethylammonium hydroxide.

[0017] In the present invention, it was confirmed that LWR or defects including pattern collapse were improved by using a fluorine-based surfactant and, in addition thereto, utilizing a substance selected from the group consisting of triol derivatives, tetraol derivatives, and mixtures thereof.

[0018] Therefore, the present invention provides, as a preferred first embodiment, a process liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the process liquid composition is composed of 0.00001 to 0.1 weight percent of a fluorochemical surfactant, 0.00001 to 1.0 weight percent of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or mixtures thereof, and the remainder is water, and has a surface tension of 45 mN / m (millinewtons / meter, millinewtons / meter = 1 / 1000 Newtons / meter) or less and a contact angle of 65° or less.

[0019] In addition, the present invention, as a more preferred second embodiment, provides a process liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the process liquid composition is composed of 0.0001 to 0.1 weight % of a fluorochemical surfactant, 0.00001 to 1.0 weight % of a substance selected from the group consisting of a triol derivative, a tetraol derivative or a mixture thereof, and the remainder is water, and has a surface tension of less than 45 mN / m and a contact angle of less than 65°.

[0020] Furthermore, the present invention provides, as the most preferred third embodiment, a process liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the process liquid composition comprises 0.001 to 0.1 weight percent of a fluorochemical surfactant, 0.00001 to 1.0 weight percent of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or mixtures thereof, and the remainder is water, and has a surface tension of less than 45 mN / m and a contact angle of less than 65°.

[0021] Furthermore, the present invention, as the most preferred fourth embodiment, provides a process liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the process liquid composition is composed of 0.001 to 0.1 weight % of a fluorochemical surfactant, 0.0001 to 1.0 weight % of a substance selected from the group consisting of a triol derivative, a tetraol derivative or a mixture thereof, and the remainder is water, and has a surface tension of less than 45 mN / m and a contact angle of less than 65°.

[0022] In addition, the present invention, as the most preferred fifth embodiment, provides a process liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the process liquid composition is composed of 0.001 to 0.1 weight % of a fluorochemical surfactant, 0.001 to 1.0 weight % of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or mixtures thereof, and the remainder is water, and has a surface tension of less than 45 mN / m and a contact angle of less than 65°.

[0023] The fluorine-based surfactant according to the above embodiment can be selected from the group consisting of fluoroacrylcarboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkylphosphate, fluoroacryl co-polymer, fluoroco-polymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, or a mixture thereof.

[0024] The triol derivative substance according to the above embodiment is a substance composed of C3 to C10, which can be selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2,8-octantriol, 1,3,5-octantriol, 1,4,7-heptane ... -octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol or a mixture thereof.

[0025] The tetraol derivative substance according to the above embodiment is a substance composed of C4 to C14, selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4 ...4,6-hexanetetrol, 1,2,3,4,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,4 The group consisting of 6,7-heptetrol, 2,3,4,5-heptetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0026] In addition, the present invention also provides a method for forming a photoresist pattern, which is characterized in that it includes the following steps: (a) coating a photoresist on a semiconductor substrate to form a film; (b) exposing the photoresist film and then developing it to form a pattern; and (c) washing the photoresist pattern using a process liquid composition for improving crack defects in the photoresist pattern.

[0027] The cause of pattern collapse is believed to be the capillary force generated between patterns when the patterns are washed with pure water after development. However, after long-term and numerous studies, it has been found that simply reducing the capillary force cannot completely improve pattern collapse and reduce the number of defects.

[0028] When an inappropriate surfactant is used in excess for the purpose of reducing the surface tension of the process liquid composition in order to reduce capillary force, dissolution of the pattern may be induced, thereby further inducing pattern crack defects.

[0029] In order to improve pattern crack defects, it is important to select a surfactant that can reduce the surface tension of the process liquid composition while preventing the dissolution of the photoresist pattern.

[0030] The process liquid composition of the present invention has an excellent effect on photoresist, in particular, has an effect of improving pattern crack defects occurring during the development of the photoresist, wherein the photoresist pattern has hydrophobicity with a contact angle of water on the photoresist surface of 75° or more.

[0031] Effects of the Invention

[0032] The process liquid composition of the present invention has the effect of improving pattern crack defects when forming a pattern using a hydrophobic photoresist having a water contact angle of 75° or more on the photoresist surface. This effect cannot be achieved when using the photoresist alone. In particular, the photoresist pattern forming method including a washing step using such a process liquid composition shows the effect of significantly reducing production costs.

[0033] Best Practice

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

[0035] The present invention, developed after extensive research over a long period of time, relates to a process liquid composition for improving crack defects in a photoresist pattern. The composition comprises 0.00001 to 0.1 wt % of a fluorine-based surfactant, 0.00001 to 1.0 wt % of a triol derivative or a tetraol derivative, either singly or in combination, and the remainder being water. The fluorine-based surfactant is selected from the group consisting of fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl co-polymer, fluoroco-polymer, perfluorinated acid, and perfluorinated carboxylate. carboxylate), perfluorinated sulfonate or a mixture thereof, wherein the triol derivative is a triol derivative substance composed of C3 to C10 and is selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6 ... alcohol, 1,2,8-octantriol, 1,3,5-octantriol, 1,4,7-octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1, The group consisting of 2,3-triol, 2,4,6-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol or mixtures thereof;The tetraol derivative substance is a tetraol derivative substance composed of C4 to C14 and is selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,4 ... The group consisting of 6,7-heptetrol, 2,3,4,5-heptetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octen-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol, or mixtures thereof. The components and composition ratios of the process liquid compositions of the present invention are set as Examples 1 to 80, and the components and composition ratios for comparison are set as Comparative Examples 1 to 13.

[0036] Hereinafter, preferred embodiments of the present invention and comparative examples for comparison will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto. DETAILED DESCRIPTION

[0037] [Example 1]

[0038] A process liquid composition for improving the collapse degree of a photoresist pattern, comprising 0.001 wt % of fluoropropylene carboxylate and 0.01 wt % of 1,2,3-propanetriol, was prepared by the following method.

[0039] 0.001 wt % of fluoropropylene carboxylate and 0.01 wt % of 1,2,3-propanetriol were added to the remaining amount of distilled water, stirred for 5 hours, and then passed through a 0.01 μm filter to remove fine solid impurities, thereby preparing a process liquid composition for improving the collapse degree of a photoresist pattern.

[0040] [Example 2 to Example 80]

[0041] According to the compositions described in Tables 1 to 15, the same process liquid compositions as those in Example 1 for improving the degree of defects in a photoresist pattern were prepared.

[0042] [Comparative Example 1]

[0043] Distilled water, which is generally used as a final washing solution in a development process in a semiconductor device manufacturing process, was prepared.

[0044] [Comparative Examples 2 to 13]

[0045] For comparison with the examples, process liquid compositions were prepared according to the compositions described in Tables 1 to 15 in the same manner as in Example 1.

[0046] In Examples 1 to 80 and Comparative Examples 1 to 13, pattern crack defects were measured on silicon wafers having patterns formed thereon. The results are shown in Table 16 as Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13.

[0047] (1) Confirmation of preventing pattern cracks

[0048] After splitting the exposure energy and focus, a critical dimension scanning electron microscope (CD-SEM, Hitachi) was used to measure the number of blocks without pattern collapse among all 89 blocks.

[0049] (2) Transparency

[0050] The transparency of the prepared process liquid composition was confirmed with the naked eye and expressed as transparent or opaque.

[0051] (3) Surface tension and contact angle

[0052] The surface tension and contact angle of the prepared process liquid composition were measured using a surface tension meter (K-100, a product of Kruss Company) and a contact angle meter (DSA-100, a product of Kruss Company).

[0053]

Table 1

[0054]

[0055]

Table 2

[0056]

[0057]

[0058]

Table 3

[0059]

[0060]

Table 4

[0061]

[0062]

[0063]

Table 5

[0064]

[0065]

Table 6

[0066]

[0067]

[0068]

Table 7

[0069]

[0070]

Table 8

[0071]

[0072]

[0073]

Table 9

[0074]

[0075]

Table 10

[0076]

[0077]

Table 11

[0078]

[0079]

[0080]

Table 12

[0081]

[0082]

Table 13

[0083]

[0084]

[0085]

Table 14

[0086]

[0087]

Table 15

[0088]

[0089]

[0090] [Examples 1 to 80 and Comparative Examples 1 to 13] In Examples 1 to 80 and Comparative Examples 1 to 13, the degree of pattern crack defects and the transparency, contact angle, and surface tension of the patterned silicon wafers were measured, as shown in Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13, and the results are recorded in Table 16.

[0091] (1) Confirmation of preventing pattern cracks

[0092] After separating the exposure energy from the focus, a critical dimension scanning electron microscope (CD-SEM, Hitachi) was used to measure the number of blocks without pattern collapse among all 89 blocks.

[0093] (2) Transparency

[0094] The transparency of the prepared process liquid composition was confirmed with the naked eye and expressed as transparent or opaque.

[0095] (3) Contact angle and surface tension

[0096] The surface tension and contact angle of the prepared process liquid composition were measured using a surface tension meter (K-100, a product of Kruss Company) and a contact angle meter (DSA-100, a product of Kruss Company), respectively.

[0097] Table 16

[0098]

[0099]

[0100]

[0101]

[0102] Based on extensive and extensive research, comparing Experimental Examples 1 to 80 with Comparative Examples 1 to 13, it was found that excellent results were achieved when 50 or more of the 89 blocks showed no pattern collapse and transparency was achieved. When a process liquid composition equivalent to that of Experimental Examples 1 to 80, consisting of 0.00001 to 0.1% by weight of a fluorine-based surfactant, 0.00001 to 1.0% by weight of a triol derivative or tetraol derivative, either singly or in combination, and 98.9 to 99.99998% by weight of water, was used, compared to Comparative Examples 1 to 13, it was confirmed that pattern crack defects were improved. The fluorine-based surfactant is selected from fluoropropylene carboxylates, fluoroalkyl ethers, fluoroalkylene ethers, fluoroalkyl sulfates, fluoroalkyl phosphates, fluoroacrylic acid copolymers, fluoro copolymers, perfluorinated acids, perfluorinated carboxylates, perfluorinated sulfonates, and the like. sulfonate), the triol derivative as a triol derivative substance composed of C3 to C10 is selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2 ,8-octantriol, 1,3,5-octantriol, 1,4,7-octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6,-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6,-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,The tetraol derivative substance is a tetraol derivative substance composed of C4 to C14, selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, tetraol, 2,3,4,5-hexane tetraol, 1,2,6,7-heptetrol, 2,3,4,5-heptetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0103] In addition, in the process liquid compositions corresponding to Experimental Examples 1 to 80, when the process liquid compositions are composed of 0.0001 to 0.1 wt % of a fluorine-based surfactant, 0.00001 to 1.0 wt % of a triol derivative and a tetraol derivative alone or in combination, and the remainder of water, when compared with Comparative Experimental Examples 1 to 13, it can be confirmed that the pattern crack defect improvement effect is preferably increased. Wherein, the fluorine-based surfactant is selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl co-polymer, fluoroco-polymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, and the like. sulfonate), the triol derivative is a triol derivative substance composed of C3 to C10, selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5 -Hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2,8-octantriol, 1,3,5-octantriol, 1,4,7-octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol Triol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6,-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6,-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol or a mixture thereof, wherein the tetraol derivative substance is a tetraol derivative substance composed of C4 to C14 and is selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,6,7-heptanetetrol, 2,3,4,5-heptanetetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0104] Moreover, in the process liquid compositions corresponding to Experimental Examples 1 to 80, when the process liquid compositions are composed of 0.001 to 0.1 wt % of a fluorine-based surfactant, 0.00001 to 1.0 wt % of a triol derivative and a tetraol derivative alone or in combination, and the remainder of water, when compared with Comparative Experimental Examples 1 to 13, it can be confirmed that the pattern crack defect improvement effect is more preferably increased. Wherein, the fluorine-based surfactant is selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl co-polymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, sulfonate), the triol derivative is a triol derivative substance composed of C3 to C10, selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5 -Hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2,8-octantriol, 1,3,5-octantriol, 1,4,7-octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol Triol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6,-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6,-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol or a mixture thereof, wherein the tetraol derivative substance is a tetraol derivative substance composed of C4 to C14 and is selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,6,7-heptanetetrol, 2,3,4,5-heptanetetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0105] On the one hand, in the process liquid composition corresponding to Experimental Examples 1 to 80, when the process liquid composition is composed of 0.001 to 0.1 wt% of a fluorine-based surfactant, 0.0001 to 1.0 wt% of a triol derivative and a tetraol derivative alone or in combination, and the balance of water, when compared with Comparative Experimental Examples 1 to 13, it can be confirmed that the pattern crack defect improvement effect is further preferably increased. Wherein, the fluorine-based surfactant is selected from fluoropropylene carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacrylic copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, sulfonate), the triol derivative is a triol derivative substance composed of C3 to C10, selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4, 5-Hexanetriol, 2,3,4-Hexanetriol, 1,2,3-Heptanetriol, 1,2,4-Heptanetriol, 1,2,6-Heptanetriol, 1,3,5-Heptanetriol, 1,4,7-Heptanetriol, 2,3,4-Heptanetriol, 2,4,6-Heptanetriol, 1,2,8-Octanetriol, 1,3,5-Octanetriol, 1,4,7-Octanetriol, butane-1,1,1-triol, 2-methyl-1,2,3 -propylene glycol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6,-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6,-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7- The tetraol derivative substance is a tetraol derivative substance composed of C4 to C14 and is selected from the group consisting of 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,3,4-tetramethylene ...2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,6,7-heptanetetrol, 2,3,4,5-heptanetetrol, 1,1,1,2-octanetrol The group consisting of: alcohol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0106] On the other hand, in the process liquid compositions corresponding to Experimental Examples 1 to 80, when the process liquid compositions are composed of 0.001 to 0.1 wt % of a fluorine-based surfactant, 0.001 to 1.0 wt % of a triol derivative and a tetraol derivative alone or in combination, and the remainder of water, when compared with Comparative Experimental Examples 1 to 13, it can be confirmed that the pattern crack defect improvement effect is most preferably increased. Wherein, the fluorine-based surfactant is selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl co-polymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, sulfonate), the triol derivative is a triol derivative substance composed of C3 to C10, selected from 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,4,5 -Hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2,8-octantriol, 1,3,5-octantriol, 1,4,7-octantriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol Triol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6,-triol, benzene-1,3,5-triol, 2-methyl-benzene-1,2,3-triol, 5-methyl-benzene-1,2,3-triol, 2,4,6,-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydroxymethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol or a mixture thereof, wherein the tetraol derivative substance is a tetraol derivative substance composed of C4 to C14 and is selected from 1,2,3,4-butanetetrol, 1,2,3,4-pentanetetrol, 1,2,4,5-pentanetetrol, 1,2,3,4-hexanetetrol, 1,2,3,5-hexanetetrol, 1,2,3,6-hexanetetrol, 1,2,4,5-hexanetetrol, 1,2,4,6-hexanetetrol, 1,2,5,6-hexanetetrol, 1,3,4,5-hexanetetrol, 1,3,4,6-hexanetetrol, 2,3,4,5-hexanetetrol, 1,2,6,7-heptanetetrol, 2,3,4,5-heptanetetrol, 1,1,1,2-octanetrol, 1,2,7,8-octanetrol, 1,2,3,8-octanetrol, 1,3,5,7-octanetrol, 2,3,5,7-octanetrol, 4,5,6,7-octanetrol, 3,7-dimethyl-3-octene-1,2,6,7-tetrol, 3-hexyne-1,2,5,6-tetrol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetrol, anthracene-1,4,9,10-tetrol or mixtures thereof.

[0107] The results of evaluating the degree of collapse of the photoresist pattern according to Example 1 are shown in Table 16. The number of blocks (bolts) without pattern collapse was measured to be 82, indicating the most excellent effect.

[0108] The results of evaluating the degree of collapse of the photoresist pattern according to Comparative Experimental Example 1 are shown in Table 16. The number of blocks (bolts) where no pattern collapse occurred was measured to be 45.

[0109] While specific aspects of the present invention have been described in detail above, it will be apparent to those skilled in the art that these specific techniques are merely preferred embodiments and that the scope of the present invention is not limited thereto. Therefore, the true scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A process liquid composition for improving crack defects in a photoresist pattern, the process liquid composition comprising a surfactant, characterized in that: The process liquid composition is a process liquid composition for improving crack defects in a photoresist pattern in a photoresist pattern process, wherein the photoresist pattern has a hydrophobicity with a contact angle of water on the photoresist surface of 75° or more. The surface tension of the process liquid composition is below 45 mN / m, and the contact angle is below 65°. The process liquid composition for improving crack defects in a photoresist pattern comprises 0.0001 to 0.1 weight percent of a fluorine-based surfactant, 0.0001 to 1.0 weight percent of a substance selected from the group consisting of 1,2,3-propanetriol, 1,2,3,4-butanetetrol, or a mixture thereof, and the balance water. The fluorine-based surfactant is selected from the group consisting of fluoropropylene carboxylates, fluoroalkyl ethers, fluoroalkylene ethers, fluoroalkyl sulfates, fluoroalkyl phosphates, fluoroacrylic acid copolymers, fluoro copolymers, perfluoro acids, perfluorocarboxylates, or mixtures thereof.

2. The process liquid composition for improving crack defects in a photoresist pattern according to claim 1, wherein The process liquid composition consists of 0.001 to 0.1 wt% of a fluorine-based surfactant, 0.0001 to 1.0 wt% of a substance selected from the group consisting of 1,2,3-propanetriol, 1,2,3,4-butanetetrol or a mixture thereof, and the balance water.

3. The process liquid composition for improving crack defects in a photoresist pattern according to claim 2, wherein: The process liquid composition consists of 0.001 to 0.1 wt% of a fluorine-based surfactant, 0.001 to 1.0 wt% of a substance selected from the group consisting of 1,2,3-propanetriol, 1,2,3,4-butanetetrol or a mixture thereof, and the balance water.

4. A method for forming a photoresist pattern, characterized in that: The steps include: (a) coating a photoresist on a semiconductor substrate to form a film; (b) exposing the photoresist film and then developing it to form a pattern; and (c) washing the photoresist pattern using the process liquid composition for improving crack defects of a photoresist pattern according to any one of claims 1 to 3.

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