Rinse liquid composition for extreme ultraviolet lithography and pattern formation method using the same

Abstract

The present invention relates to a rinse composition for extreme ultraviolet photolithography and a pattern formation method using the same, and the rinse composition is characterized by comprising: 0.0001 to 0.01 wt % of a fluorine-based surfactant; 0.0001 to 0.5 wt % of a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5 wt % of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or mixtures thereof; and the balance: water.

Description

[Technical Field]

[0001] The present invention relates to a rinse composition for improving lifting defects in a photoresist pattern in photolithography using extreme ultraviolet light as an exposure source, and a method for forming a photoresist pattern using the same. [Background technology]

[0002] Generally, semiconductors are manufactured by a lithography process using ultraviolet light in wavelength bands such as 193 nm, 248 nm, or 365 nm as exposure light, and there is fierce competition among manufacturers to reduce the minimum line width (hereinafter referred to as CD: Critical Dimension). Therefore, to form finer patterns, a light source with a smaller wavelength band is required, but currently, lithography technology using extreme ultraviolet (EUV, extreme ultra violet, wavelength of 13.5 nm) light sources is widely used, and this has made it possible to realize finer wavelengths. However, since the etching resistance of extreme ultraviolet photoresists has not yet been improved, photoresist patterns with large aspect ratios are continuously required, which leads to the problem of pattern lifting defects easily occurring during development, significantly reducing the process margin in the manufacturing process. Therefore, there is a need for technological development to improve the level of lifting defects that occur during the formation of fine patterns. Although the best way to improve the level of pattern lifting defects would be to improve the performance of photoresists, the reality is that it is difficult to develop a new photoresist that satisfies all performance requirements. While the need for new photoresist development remains, efforts are continually being made to improve the level of pattern lifting in other ways. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Korean Patent Registration No. 10-2251232 [Patent Document 2] Korean Patent Registration No. 10-2100432 [Patent Document 3] Korean Patent Publication No. 10-2016-0117305 [Patent Document 4] Korean Patent Registration No. 10-2080780 [Patent Document 5] Korean Patent Registration No. 10-1771177 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a rinse composition for improving the level of lifting defects in a pattern that occur after developing a photoresist, and to provide a method for forming a photoresist pattern that can significantly reduce production costs by including a step of cleaning with such a rinse composition. [Means for solving the problem]

[0005] Various surfactants are used in aqueous process liquid compositions used in the development process, but in the present invention, an effective process liquid composition is prepared using a fluorine-based surfactant. The use of a hydrophobic hydrocarbon surfactant in an aqueous process solution composition that primarily uses ultrapure water can hydrophobize the photoresist wall, thereby reducing pattern melting and collapse. However, because hydrocarbon surfactants tend to aggregate, the properties of the rinse solution composition are not uniform, and the aggregated hydrocarbon surfactants can actually cause defects during use. In other words, when a hydrocarbon surfactant is used, the amount must be increased to improve melting, which can damage the photoresist. Furthermore, excessive use of an inappropriate surfactant in an attempt to lower the surface tension of the rinse solution composition to reduce capillary force can induce pattern melting and further lead to pattern collapse. In the present invention, it has been confirmed that the use of a fluorine-based surfactant, in addition to which a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof, a substance selected from the group consisting of triol derivatives, tetraol derivatives, or a mixture thereof, and water provides an excellent effect in improving the level of pattern lifting defects. Chemical formula (1) [ka] In chemical formula (1), X is fluorine, hydrogen, or C1-C5 alkyl; X forms a single bond, l is 1 to 4, and m and n are 1 to 3. Chemical formula (2) [ka] In chemical formula (2), X is fluorine, hydrogen, or C1-C5 alkyl; X forms a single bond, O is 0 to 2.

[0006] Currently, the typical developer used in most photolithography development processes is based on pure water and diluted with tetramethylammonium hydroxide at a certain concentration (in most processes, a mixture of 2.38% by weight of tetramethylammonium hydroxide and 97.62% by weight of water is used). In addition, when a photoresist pattern is developed during a photolithography process and then rinsed with pure water alone, pattern lifting defects were observed. Furthermore, when a rinse solution composition containing tetramethylammonium hydroxide in pure water was applied either after development or after treatment with pure water, pattern collapse was also observed. It is presumed that the rinse solution composition containing tetramethylammonium hydroxide weakens the exposed fine pattern and destroys the pattern due to the large or uneven capillary force. Therefore, in order to improve the collapse of the exposed pattern and further improve the LWR (Line Width Roughness) and defects of the photoresist pattern required in the process, it is necessary to consider a substance that has a relatively weaker effect on the exposed pattern than tetramethylammonium hydroxide. In the present invention, it has been confirmed that when a fluorine-based surfactant is used in addition to this, a pattern strengthener which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof, and a substance selected from the group consisting of a triol derivative, a tetraol derivative, or a mixture thereof, is used, pattern collapse as well as LWR or defects are improved. Therefore, as a preferred first embodiment, the present invention provides a rinse solution composition for improving the level of lifting defects in a photoresist pattern that occur during photoresist development, characterized by comprising: 0.0001 to 0.01 wt % of a fluorine-based surfactant; 0.0001 to 0.5 wt % of a pattern strengthening agent that is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5 wt % of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or a mixture thereof; and the balance being water. In addition, as a more preferred second embodiment, the present invention provides a rinse solution composition for improving the level of lifting defects in a photoresist pattern that occur during photoresist development, characterized by comprising: 0.0001 to 0.01 wt % of a fluorine-based surfactant; 0.001 to 0.5 wt % of a pattern strengthening agent that is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5 wt % of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or a mixture thereof; and the balance being water.

[0007] In addition, as a third most preferred embodiment, the present invention provides a rinse solution composition for improving the level of lifting defects in a photoresist pattern that occur during photoresist development, characterized by comprising: 0.0001 to 0.01 wt % of a fluorine-based surfactant; 0.01 to 0.5 wt % of a pattern strengthening agent that is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5 wt % of a substance selected from the group consisting of triol derivatives, tetraol derivatives, or a mixture thereof; and the balance being water. The fluorosurfactant according to this embodiment may be selected from the group consisting of fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, or a mixture thereof. The triol derivative substance according to the embodiment is composed of C3 to C10, and is preferably 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-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-hydromethylbenzene-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.

[0008] The tetraol derivative material according to the embodiment is composed of C4 to C14, and includes 1,2,3,4-butanetetraol, 1,2,3,4-pentanetetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, and 1,2,6,7-heptanetetraol. octanetetraol, 2,3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or a mixture thereof. The present invention also provides a method for forming a photoresist pattern, comprising: (a) applying a photoresist to a semiconductor substrate to form a film; (b) exposing the photoresist film to light and developing it to form a pattern; and (c) rinsing the photoresist pattern with a rinse solution composition for improving lifting defects in the photoresist pattern. Pattern collapse is thought to be caused by capillary forces that occur between patterns when the patterns are washed with pure water after development, but numerous long-term studies have shown that simply reducing the capillary forces is not enough to completely improve pattern collapse and reduce the number of defects. If an inappropriate surfactant is used excessively in an attempt to lower the surface tension of the rinse composition to reduce the capillary force, it may induce pattern melting, further inducing pattern lifting defects. To improve the pattern lifting defect, it is important to select a surfactant that reduces the surface tension of the rinse liquid composition and prevents the melting of the photoresist pattern. The rinse liquid composition of the present invention exhibits excellent effects on photoresists, and is particularly effective in improving lifting defects in patterns that occur during photoresist development. [Effects of the Invention]

[0009] The rinse solution composition of the present invention has the effect of improving the level of lifting defects in a pattern, which is an effect that cannot be achieved by using a photoresist alone when forming a pattern using a photoresist. In particular, a method for forming a photoresist pattern, which includes a step of cleaning with such a rinse solution composition, has the effect of significantly reducing production costs. [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows the results of evaluation of lifting of the photoresist pattern according to Example 1. [Figure 2] 1 shows the results of evaluation of lifting of the photoresist pattern according to Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will now be described in more detail. The present invention, which was developed through numerous long-term studies, provides a wide range of compounds including "fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro copolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, and the like. 0.0001 to 0.01% by weight of a fluorine-based surfactant selected from the group consisting of a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5% by weight of a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; and 0.0001 to 0.5% by weight of a triol derivative substance consisting of C3 to C10, such as 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-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-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, and 1,2,3,4-butanetetraol and 1,2,3,4-pentanetetraol as tetraol derivative substances consisting of C4 to C14. hexanetetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, 1,2,6,7-heptanetetraol, 2, 3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetraol, anthracene The present invention relates to a rinse solution composition for improving lifting defects in a photoresist pattern, which comprises 0.0001 to 0.5% by weight of a triol derivative or tetraol derivative alone or in a mixture selected from the group consisting of benzophenone-1,4,9,10-tetraol, or a mixture thereof; and the balance being water. The components and composition ratios of the rinse solution compositions of the present invention are set as Examples 1 to 100, and the components and composition ratios to be compared are set as Comparative Examples 1 to 21. Preferred examples of the present invention and comparative examples for comparison are described below. However, the following examples are merely preferred examples of the present invention and are not intended to limit the present invention. [Example]

[0012] [Example 1] A rinse solution composition for extreme ultraviolet photolithography for improving the degradation level of a photoresist pattern was prepared by the following method, which contained 0.001 wt % of a fluorinated acrylic carboxylate, 0.001 wt % of a fluorinated imide compound having a structure of chemical formula (1) where l=1, m=1, n=1, and 0.001 wt % of 1,2,3-propanetriol. A rinse solution composition for improving the defect level of a photoresist pattern was prepared by adding 0.001 wt % of a fluorine-containing acrylic carboxylate, 0.001 wt % of a fluorine-containing imide compound having a structure of formula (1) l=1, m=1, n=1, and 0.001 wt % of 1,2,3-propanetriol to the remaining amount of distilled water, stirring for 6 hours, and then passing the mixture through a 0.01 μm filter to remove fine solid impurities. [Examples 2 to 50] Using the compositions shown in Tables 1 to 12, rinse liquid compositions for improving the defect level of a photoresist pattern were prepared in the same manner as in Example 1. [Example 51] A rinse solution composition for extreme ultraviolet photolithography for improving the degradation level of a photoresist pattern was prepared by the following method, which contained 0.001 wt % of a fluorinated acrylic carboxylate, 0.001 wt % of a fluorinated imide compound having a structure of chemical formula (2) o=1, and 0.001 wt % of 1,2,3-propanetriol. 0.001 wt% of fluorine acrylic carboxylate, 0.001 wt% of a fluorine imide compound having the structure of formula (2) o=1, and 0.001 wt% of 1,2,3-propanetriol were added to the remaining amount of distilled water, stirred for 6 hours, and then passed through a 0.01 μm filter to remove fine solid impurities, thereby preparing a rinse composition for improving the defect level of a photoresist pattern. [Examples 52 to 100] Using the compositions shown in Tables 13 to 24, rinse liquid compositions for improving the defect level of a photoresist pattern were prepared in the same manner as in Example 51. [Comparative Example 1] Distilled water, which is generally used as a final cleaning solution in the development step in the manufacturing process of semiconductor devices, was prepared. [Comparative Examples 2 to 11] Rinse liquid compositions were prepared using the compositions shown in Tables 1 to 12 in the same manner as in Example 1 for comparison with the examples. [Comparative Examples 12 to 21] Rinse liquid compositions were prepared using the compositions shown in Tables 13 to 24 in the same manner as in Example 51 for comparison with the examples. [Experimental Examples 1 to 100, Comparative Experimental Examples 1 to 21] A chemically amplified PHS acrylate hydrate hybrid EUV resist was spin-coated onto a 12-inch silicon wafer (SK Siltron) and soft-baked at 110°C for 60 seconds to form a 40-nm-thick resist film. The resist film on the wafer was exposed to EUV light using an EUV exposure tool through an 18-nm (1:1 line:space) mask, and the wafer was then post-exposed (PEB) at 110°C for 60 seconds. The resist film was then puddle-developed with a 2.38% tetramethylammonium hydroxide (TMAH) solution for 40 seconds. Deionized water (DI water) was poured into the developer puddle on the wafer, and the wafer was rotated while the water was poured to replace the developer. The wafer rotation was stopped in the puddled state with DI water. Subsequently, the rinse liquid compositions of Examples 1 to 100 and Comparative Examples 2 to 21 were introduced into the puddle of deionized water on the wafer, and the wafer was spun at high speed to dry it. At this time, using the rinse solutions manufactured in Examples 1 to 100 and Comparative Examples 1 to 21, pattern lifting defects were measured for silicon wafers on which patterns were formed, and the results are shown as Experimental Examples 1 to 100 and Comparative Experimental Examples 1 to 21, and the results are shown in Tables 25 and 26.

[0013] (1) Checking for pattern lifting prevention After splitting the exposure energy, the number of blocks in which the pattern was not destroyed out of a total of 89 blocks was counted using a CD-SEM (critical dimension scanning electron microscope, manufactured by Hitachi, Ltd.). (2) Transparency The transparency of the prepared process liquid composition was checked with the naked eye and was marked as transparent or opaque. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24]

[0014] [Experimental Examples 1 to 100, Comparative Experimental Examples 1 to 21] The pattern lifting defect level and transparency of the silicon wafers on which patterns were formed in Examples 1 to 100 and Comparative Examples 1 to 21 were measured, and the results are shown as Experimental Examples 1 to 100 and Comparative Experimental Examples 1 to 21. The results are shown in Tables 25 and 26. (1) Check the pattern lifting defect level After splitting the exposure energy, the number of blocks in which the pattern was not destroyed out of the total 89 blocks was measured using a CD-SEM (manufactured by Hitachi, Ltd.). (2) Transparency measurement The transparency of the prepared process liquid composition was checked with the naked eye and was marked as transparent or opaque. [Table 25a] [Table 25b] [Table 26a] [Table 26b]

[0015] Based on the results of long-term research, a comparison of Experimental Examples 1 to 100 with Comparative Experimental Examples 1 to 21 revealed that excellent results were obtained if the number of blocks without pattern collapse out of a total of 89 blocks was 50 or more. The process liquid compositions corresponding to Experimental Examples 1 to 100 are "fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate, and the like." 0.0001 to 0.01% by weight of a fluorine-based surfactant selected from the group consisting of a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.0001 to 0.5% by weight of a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; and 0.0001 to 0.5% by weight of a triol derivative substance consisting of C3 to C10, such as 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-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-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, and tetraol derivative substances consisting of C4 to C14, such as 1,2,3,4-butanetetraol and 1,2,3,4-pentanetetraol. Tetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, 1,2,6,7-heptanetetraol Tanetetrol, 2,3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3- In the case of a rinse solution composition comprising 0.0001 to 0.5 wt % of a triol derivative or tetraol derivative material selected from the group consisting of hexyne-1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or a mixture thereof, and 98.99 to 99.9997 wt % of water, it was confirmed that pattern lifting defects were significantly improved compared to Comparative Experimental Examples 1 to 21.

[0016] In addition, among the rinse liquid compositions corresponding to Experimental Examples 1 to 100, "0.0001 to 0.01 wt % of a fluorosurfactant selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, and perfluorinated sulfonate; 0.001 to 0.5% by weight of a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; and 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, hexanetriol, 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-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-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, and tetraol derivative substances consisting of C4 to C14, such as 1,2,3,4-butanetetraol and 1,2,3,4-pentanetetraol. tetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, 1,2,6,7-heptanetetraol tetraol, 2,3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyne- In the case of a rinse solution composition comprising 0.0001 to 0.5 wt % of a triol derivative or tetraol derivative material selected from the group consisting of 1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or a mixture thereof, and 98.99 to 99.9988 wt % of water, it was confirmed that the pattern lifting defect improvement effect was further improved compared to Comparative Experimental Examples 1 to 21.

[0017] Among the process liquid compositions corresponding to Experimental Examples 1 to 100, "fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, perfluorinated sulfonate" is not included. 0.0001 to 0.01% by weight of a fluorine-based surfactant selected from the group consisting of a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; 0.01 to 0.5% by weight of a pattern strengthening agent which is a compound of chemical formula (1), a compound of chemical formula (2), or a mixture thereof; and 0.01 to 0.5% by weight of a triol derivative substance consisting of C3 to C10, such as 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-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-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, and tetraol derivative substances consisting of C4 to C14, such as 1,2,3,4-butanetetraol and 1,2,3,4-pentanetetraol. tetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, 1,2,6,7-heptanetetraol tetraol, 2,3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyne- In the case of a rinse solution composition comprising 0.0001 to 0.5 wt % of a triol derivative or tetraol derivative material selected from the group consisting of 1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or a mixture thereof, and 98.99 to 99.9898 wt % of water, it was confirmed that the pattern lifting defect improvement effect was further improved compared to Comparative Experimental Examples 1 to 21. The result of evaluating the level of photoresist pattern collapse in Example 1 was shown in FIG. 1, with the number of blocks where pattern collapse did not occur being 58, indicating the most excellent effect. The result of evaluating the level of photoresist pattern collapse in Comparative Experimental Example 1 was that the number of blocks where pattern collapse did not occur was measured as 31, as shown in FIG.

[0018] Although certain 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 are not intended to limit the scope of the present invention. Therefore, the true scope of the present invention should be defined by the claims and their equivalents.

Claims

1. Fluorosurfactants; a pattern enhancing agent which is a compound of formula (1), a compound of formula (2), or a mixture thereof; a material selected from the group consisting of a triol derivative, a tetraol derivative, or a mixture thereof; and A rinse solution composition for extreme ultraviolet photolithography, comprising: a balance of water. Chemical formula (1) 【Chemical 1】 (In chemical formula (1), X is fluorine, hydrogen or C1-C5 alkyl; X forms a single bond, l is 1 to 4, and n and m are 1 to 3. Chemical formula (2) 【Chemistry 2】 (In chemical formula (2), X is fluorine, hydrogen or C1-C5 alkyl; X forms a single bond, O is 0 to 2.)

2. 0.0001 to 0.01% by weight of the fluorochemical surfactant; 0.0001 to 0.5 wt % of a pattern strengthening agent which is the compound of formula (1), the compound of formula (2), or a mixture thereof; 0.0001 to 0.5% by weight of a material selected from the group consisting of the triol derivatives, tetraol derivatives, or mixtures thereof; and The rinse liquid composition for extreme ultraviolet photolithography according to claim 1, characterized in that it consists essentially of: water; and the balance.

3. 0.0001 to 0.01% by weight of the fluorochemical surfactant; 0.001 to 0.5 wt % of a pattern strengthening agent which is the compound of formula (1), the compound of formula (2), or a mixture thereof; 0.0001 to 0.5% by weight of a material selected from the group consisting of the triol derivatives, tetraol derivatives, or mixtures thereof; and The rinse liquid composition for extreme ultraviolet photolithography according to claim 2, characterized in that it consists essentially of: water; and the balance.

4. The fluorine-based surfactants include fluoroacrylic carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacrylic copolymer, fluorocopolymer, perfluorinated acid, perfluorinated carboxylate, and perfluorinated sulfonate.

3. The rinse composition for extreme ultraviolet photolithography according to claim 2, wherein the compound is selected from the group consisting of methyl methyl acrylate, methyl methyl acrylate, methyl meth ...

5. The triol derivative and tetraol derivative substances include, as triol derivative substances consisting of C3 to C10, 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, and 1,2,4-heptanetriol. triol, 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-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-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, and as tetraol derivative substances consisting of C4 to C14, 1,2,3,4-butanetetraol, 1, 2,3,4-pentane tetraol, 1,2,4,5-pentane tetraol, 1,2,3,4-hexane tetraol, 1,2,3,5-hexane tetraol, 1,2,3,6-hexane tetraol, 1,2,4,5-hexane tetraol, 1,2,4,6-hexane tetraol, 1,2,5,6-hexane tetraol, 1,3,4,5-hexane tetraol, 1,3,4,6-hexane tetraol, 2,3,4,5-hexane tetraol, 1,2,6,7-heptane tetraol, 2,3,4,5-heptane tetraol, 1,1,1,The rinse liquid composition for extreme ultraviolet photolithography according to claim 2, characterized in that the rinsing agent is selected from the group consisting of 2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyne-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyne-1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or a mixture thereof.

6. (a) applying a photoresist to a semiconductor substrate to form a film; (b) exposing the photoresist film to light and then developing it to form a pattern; (c) cleaning the photoresist pattern with the rinse liquid composition for extreme ultraviolet photolithography according to any one of claims 1 to 5.

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