Flushing liquid composition for extreme ultraviolet lithography and pattern forming method using same

Abstract

The present invention relates to a rinse solution composition for extreme ultraviolet lithography and a pattern forming method using the same. The rinse liquid composition consists of 0.0001 to 0.01 wt% of a fluorine-based surfactant, 0.0001 to 0.5 wt% of a pattern enhancer 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 a balance of water.

Description

Technical Field

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

[0002] Generally, semiconductors are manufactured by photolithography using ultraviolet light in wavelengths such as 193nm, 248nm or 365nm as the exposure light source, and companies are competing fiercely to reduce the critical line width (hereinafter referred to as CD: Critical Dimension).

[0003] Therefore, in order to form finer patterns, a light source with a smaller wavelength band is required. Currently, photolithography technology using extreme ultraviolet (EUV, extreme ultra violet, wavelength of 13.5nm) light source is widely used, and by using it, a finer wavelength can be achieved.

[0004] However, the etching resistance of EUV photoresists has not been improved, and thus photoresist patterns with large aspect ratios continue to be required. Therefore, crack defects in the pattern are easily generated during development, resulting in a problem of 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 in 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 performance requirements.

[0006] Even though the need for newly developed photoresists remains, efforts are being made to improve the degree of pattern cracking by other methods.

[0007] (Prior art literature)

[0008] Patent document 1: 10-2251232B1

[0009] Patent Document 2: 10-2100432B1

[0010] Patent Document 3: 10-2016-0117305A

[0011] Patent Document 4: 10-2080780B1

[0012] Patent Document 5: 10-1771177B1 Summary of the invention

[0013] Technical issues to be solved

[0014] The object of the present invention is to provide a rinse liquid composition for improving the degree of crack defects in a pattern generated after photoresist development, and to provide a method for forming a photoresist pattern that can significantly reduce production costs by including a step of washing using the rinse liquid composition.

[0015] Solutions to the problem

[0016] Although various surfactants are being used in the aqueous type rinse liquid composition used in the development process, an effective rinse liquid composition is prepared by using a fluorine-based surfactant in the present invention.

[0017] When a hydrocarbon surfactant tending to be hydrophobic is used in a rinse liquid composition of an aqueous type mainly using ultrapure water, the hydrophobicization of the photoresist wall is induced, thereby being able to induce the reduction of dissolution (melting) and collapse of the pattern. However, due to the strong tendency of hydrocarbon surfactants to aggregate with each other, the physical properties of the rinse liquid composition become uneven, so there is the possibility of inducing defects (defects) by the aggregated hydrocarbon surfactants during use. That is, when a hydrocarbon surfactant is used, it is necessary to increase the amount used in order to improve dissolution, which has concerns about damage to the photoresist. In addition, when an unsuitable surfactant is used excessively for the purpose of reducing the surface tension of the rinse liquid composition in order to reduce capillary force, it is possible to further induce pattern collapse due to the dissolution of the induced pattern.

[0018] In the present invention, it is confirmed that the effect of improving the degree of pattern crack defects is excellent by using a fluorine-based surfactant and, on this basis, using a pattern enhancer which is a compound of chemical formula (1), a compound of chemical formula (2) or a mixture thereof, using a substance selected from the group consisting of a triol derivative, a tetraol derivative or a mixture thereof, and using water.

[0019] Chemical formula (1)

[0020]

[0021] In the above chemical formula (1),

[0022] X is fluorine, hydrogen or C1-C5 alkyl,

[0023] X forms a single bond,

[0024] l is 1~4, m and n are 1~3.

[0025] Chemical formula (2)

[0026]

[0027] In the above chemical formula (2),

[0028] X is fluorine, hydrogen or C1-C5 alkyl,

[0029] X forms a single bond,

[0030] o is 0~2.

[0031] 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).

[0032] In the photolithography process, pattern crack defects were observed when the photoresist pattern was continuously washed with pure water alone after development. Pattern collapse was also observed when a rinse liquid composition containing tetramethylammonium hydroxide in pure water was continuously used after development or after being treated with pure water.

[0033] In the case of the rinse liquid composition containing tetramethylammonium hydroxide, it is presumed that the exposed fine pattern is weakened and the pattern collapses due to a large or uneven capillary force.

[0034] 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 has a relatively weaker effect on the exposed pattern than tetramethylammonium hydroxide.

[0035] In the present invention, it is confirmed that when a fluorine-based surfactant is used and, on this basis, a pattern enhancer which is a compound of the chemical formula (1), a compound of the 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, LWR or defects including pattern collapse are improved.

[0036] Therefore, as a preferred first specific example, the present invention provides a rinse liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the rinse liquid composition is composed of 0.0001 to 0.01 weight % of a fluorine-based surfactant, 0.0001 to 0.5 weight % of a pattern enhancer which is a compound of formula (1), a compound of formula (2) or a mixture thereof, 0.0001 to 0.5 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.

[0037] In addition, as a more preferred second specific example, the present invention provides a rinse liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the rinse liquid composition is composed of 0.0001 to 0.01 weight % of a fluorine-based surfactant, 0.001 to 0.5 weight % of a pattern enhancer which is a compound of chemical formula (1), a compound of chemical formula (2) or a mixture thereof, 0.0001 to 0.5 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.

[0038] Furthermore, as the most preferred third specific example, the present invention provides a rinse liquid composition for improving the degree of crack defects in a photoresist pattern occurring during photoresist development, characterized in that the rinse liquid composition is composed of 0.0001 to 0.01 weight % of a fluorine-based surfactant, 0.01 to 0.5 weight % of a pattern enhancer which is a compound of formula (1), a compound of formula (2) or a mixture thereof, 0.0001 to 0.5 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.

[0039] The fluorine-based surfactant according to the above specific example 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.

[0040] The triol derivative substance according to the above specific example is a substance composed of C3 to C10, and 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 -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.

[0041] The tetraol derivative substance according to the above specific example 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, 2,3,4,5-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.

[0042] 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 rinsing liquid composition for improving crack defects in the photoresist pattern.

[0043] 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 perfectly improve pattern collapse and reduce the number of defects.

[0044] When an inappropriate surfactant is used excessively for the purpose of reducing the surface tension of the rinse liquid composition in order to reduce the capillary force, dissolution of the pattern may be induced, thereby further inducing pattern crack defects.

[0045] In order to improve the pattern crack defect, it is important to select a surfactant that can reduce the surface tension of the rinse composition while preventing the dissolution of the photoresist pattern.

[0046] The rinse liquid composition of the present invention exhibits an excellent effect on a photoresist, and in particular has an effect of improving crack defects in a pattern generated during development of a photoresist.

[0047] Effects of the Invention

[0048] The rinsing liquid composition of the present invention has the effect of improving the degree of crack defects in the pattern, which is an effect that cannot be achieved by using photoresist alone when forming a pattern using photoresist. In particular, the photoresist pattern forming method including the use of such a rinsing liquid composition for a washing step shows the effect of significantly reducing production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 The crack evaluation results of the photoresist pattern according to Example 1 are shown.

[0050] Figure 2 The crack evaluation results of the photoresist pattern according to Comparative Example 1 are shown. DETAILED DESCRIPTION

[0051] Best Mode for Carrying Out the Invention

[0052] Hereinafter, the present invention will be described in more detail.

[0053] The present invention, which has been developed after a long period of extensive research, relates to a rinse liquid composition for improving crack defects in a photoresist pattern, wherein the rinse liquid composition comprises 0.0001 to 0.01 wt % of a fluorine-based surfactant, 0.0001 to 0.5 wt % of a pattern enhancer which is a compound of formula (1), a compound of formula (2) or a mixture thereof, 0.0001 to 0.5 wt % of a triol derivative or a tetraol derivative alone or in combination, and the remainder is water, wherein 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, acid), perfluorocarboxylate, perfluorosulfonate sulfonate) or a mixture thereof, wherein the triol derivative or the tetraol derivative 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-octan ... triol, 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-trimethyl Benzene-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, 1,2,3-triol as tetrahydric alcohol derivative substances composed of C4 to C143,4-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-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 a mixture thereof. The components and composition ratios of the rinsing liquid composition of the present invention are set as Examples 1 to 100, and the components and composition ratios for comparison are set as Comparative Examples 1 to 21. ,

[0054] Hereinafter, preferred embodiments of the present invention and comparative examples for comparison therewith will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

[0055] Specific ways to implement the invention

[0056] [Example 1]

[0057] A rinse liquid composition for extreme ultraviolet lithography for improving the collapse degree of a photoresist pattern was prepared by the following method, comprising 0.001 wt % of fluoropropylene carboxylate, 0.001 wt % of a fluoroimide compound having a chemical formula (1) where l=1, m=1, n=1, and 0.001 wt % of 1,2,3-propanetriol.

[0058] 0.001 wt % of fluoropropylene carboxylate, 0.001 wt % of a fluoroimide compound having the chemical formula (1) wherein l=1, m=1, n=1, and 0.001 wt % of 1,2,3-propanetriol are added to the remaining amount of distilled water, stirred for 6 hours, and then passed through a 0.01 um filter to remove fine solid impurities, thereby preparing a rinse liquid composition for improving the degree of defects in a photoresist pattern.

[0059] [Example 2 to Example 50]

[0060] According to the compositions described in Tables 1 to 12, a rinse liquid composition for improving the degree of defects in a photoresist pattern was prepared in the same manner as in Example 1.

[0061] [Example 51]

[0062] A rinse solution composition for EUV lithography for improving the collapse of a photoresist pattern was prepared by the following method, comprising 0.001 wt % of fluoropropylene carboxylate, 0.001 wt % of a fluoroimide compound having a chemical formula (2) o=1, and 0.001 wt % of 1,2,3-propanetriol.

[0063] 0.001 wt % of fluoropropylene carboxylate, 0.001 wt % of a fluoroimide compound having the chemical formula (2) o=1, and 0.001 wt % of 1,2,3-propanetriol are added to the remaining amount of distilled water, stirred for 6 hours, and then passed through a 0.01 um filter to remove fine solid impurities, thereby preparing a rinse liquid composition for improving the degree of defects in a photoresist pattern.

[0064] [Example 52 to Example 100]

[0065] According to the compositions described in Tables 13 to 24, a rinsing liquid composition for improving the degree of defects in a photoresist pattern was prepared in the same manner as in Example 51.

[0066] [Comparative Example 1]

[0067] Distilled water, which is generally used as a final washing solution in a development process in a semiconductor device manufacturing process, was prepared.

[0068] [Comparative Example 2 to Comparative Example 11]

[0069] For comparison with the examples, rinse liquid compositions were prepared according to the compositions described in Tables 1 to 12 in the same manner as in Example 1.

[0070] [Comparative Example 12 to Comparative Example 21]

[0071] For comparison with the examples, rinse liquid compositions were prepared according to the compositions described in Tables 13 to 24 in the same manner as in Example 51.

[0072] [Experimental Examples 1 to 100, Comparative Experimental Examples 1 to 21]

[0073] A chemically amplified PHS acrylate hydrate mixed EUV resist was spin-coated on a 12-inch silicon wafer (SK siltron) and soft-baked at 110°C for 60 seconds to form a resist film with a thickness of 40nm. The resist film on the wafer was exposed in an EUV exposure device through an 18nm size (line: spacing = 1:1) mask, and the wafer was baked (Post Exposure Bake, PEB) at 110°C for 60 seconds. Then, the resist film was puddle-developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 40 seconds. Deionized water (DI water) was poured into the puddle of the developer on the wafer, and the wafer was rotated while continuing to pour, and the developer was replaced with deionized water, and the rotation of the wafer was stopped in the puddled state by the deionized water. Next, the rinsing compositions of Experimental Examples 1 to 100 and Comparative Examples 2 to 21 were introduced into a puddle of deionized water on the wafer, and the wafer was rotated at a high speed to be dried.

[0074] At this time, the pattern crack defects on the patterned silicon wafer were measured using the rinsing liquid prepared in Examples 1 to 100 and Comparative Examples 1 to 21, and were expressed as Experimental Examples 1 to 100 and Comparative Experimental Examples 1 to 21, and the results were recorded in Tables 25 to 26.

[0075] (1) Confirmation of preventing pattern cracks

[0076] After the exposure energy was split, the number of blocks without pattern collapse among all 89 blocks was measured using a feature size measurement scanning electron microscope (CD-SEM, Hitachi).

[0077] (2) Transparency

[0078] The transparency of the prepared rinse solution composition was confirmed with the naked eye and indicated as transparent or opaque.

[0079]

Table 1

[0080]

[0081]

[0082]

[0083]

Table 2

[0084]

[0085]

[0086]

Table 3

[0087]

[0088]

[0089]

Table 4

[0090]

[0091]

[0092]

Table 5

[0093]

[0094]

[0095]

Table 6

[0096]

[0097]

[0098]

Table 7

[0099]

[0100]

[0101]

Table 8

[0102]

[0103]

Table 9

[0104]

[0105]

[0106]

Table 10

[0107]

[0108]

[0109]

Table 11

[0110]

[0111]

[0112]

Table 12

[0113]

[0114]

[0115]

Table 13

[0116]

[0117]

[0118]

Table 14

[0119]

[0120]

[0121]

Table 15

[0122]

[0123]

[0124]

Table 16

[0125]

[0126]

[0127]

Table 17

[0128]

[0129]

Table 18

[0130]

[0131]

Table 19

[0132]

[0133]

[0134]

Table 20

[0135]

[0136]

[0137]

Table 21

[0138]

[0139]

Table 22

[0140]

[0141]

[0142]

Table 23

[0143]

[0144]

[0145]

Table 24

[0146]

[0147] [Experimental Examples 1 to 100, Comparative Experimental Examples 1 to 21]

[0148] In Examples 1 to 100 and Comparative Examples 1 to 21, the pattern crack defect degree and transparency of the silicon wafer formed with the pattern were measured respectively, represented by Experimental Examples 1 to 100 and Comparative Experimental Examples 1 to 21, and the results are recorded in Tables 25 and 26.

[0149] (1) Measuring the degree of pattern crack defects

[0150] After dividing the exposure energy, the number of blocks without pattern collapse among all 89 blocks was measured using a scanning electron microscope for feature size measurement (CD-SEM, Hitachi).

[0151] (2) Measurement transparency

[0152] The transparency of the prepared rinse solution composition was confirmed with the naked eye and indicated as transparent or opaque.

[0153]

Table 25

[0154]

[0155]

[0156]

[0157]

Table 26

[0158]

[0159]

[0160]

[0161]

[0162] Based on the results of a long-term study, the results of comparing Experimental Examples 1 to 100 with Comparative Experimental Examples 1 to 21 show that if the number of blocks without pattern collapse is 50 or more among all 89 blocks, excellent results are shown.

[0163] When the rinsing liquid composition corresponding to Experimental Examples 1 to 100 is composed of 0.0001 to 0.01 wt % of a fluorine-based surfactant, 0.0001 to 0.5 wt % of a pattern enhancer 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 triol derivative and a tetraol derivative alone or in combination, and 98.99 to 99.9997 wt % of water, it can be confirmed that the pattern crack defect is preferably improved when compared with Comparative Experimental Examples 1 to 21. The fluorinated 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, sulfonate), the triol derivative and the tetraol derivative substance are 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, alcohol, 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-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,1,2,3,4-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- The group consisting of 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.

[0164] In addition, in the rinsing liquid compositions corresponding to Experimental Examples 1 to 100, when the rinsing liquid compositions consist of 0.0001 to 0.01 weight % of a fluorine-based surfactant, 0.001 to 0.5 weight % of a pattern enhancer which is a compound of Chemical Formula (1), a compound of Chemical Formula (2) or a mixture thereof, 0.0001 to 0.5 weight % of a triol derivative and a tetraol derivative substance which are either singly or in mixture, and 98.99 to 99.9988 weight % of water, when compared with Comparative Experimental Examples 1 to 21, it can be confirmed that the pattern crack defect improvement effect is more preferably increased. The fluorine-based surfactant is selected from fluorinated acrylic acid ester (Fluoroacryl carboxylate), fluorinated alkyl ether (Fluoroalkyl ether), fluorinated alkylene ether (Fluoroalkylene ether), fluorinated alkyl sulfate (Fluoroalkyl sulfate), fluorinated alkyl phosphate (Fluoroalkyl phosphate), fluorinated acrylic acid copolymer (Fluoroacryl co-polymer), fluorinated copolymer (Fluoro co-polymer), perfluorinated acid (perfluorinated acid), perfluorinated carboxylate (perfluorinated carboxylate), perfluorinated sulfonate, the triol derivative and the tetraol derivative are 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-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,1,2,3,4-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- The group consisting of 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.

[0165] Furthermore, in the rinsing liquid compositions corresponding to Experimental Examples 1 to 100, when the rinsing liquid compositions consist of 0.0001 to 0.01 weight % of a fluorine-based surfactant, 0.01 to 0.5 weight % of a pattern enhancer which is a compound of formula (1), a compound of formula (2) or a mixture thereof, 0.0001 to 0.5 weight % of a triol derivative and a tetraol derivative alone or in combination, and 98.99 to 99.9898 weight % of water, when compared with Comparative Experimental Examples 1 to 21, it can be confirmed that the pattern crack defect improvement effect is further preferably increased. The fluorine-based surfactant is selected from fluorinated acrylic acid ester (Fluoroacryl carboxylate), fluorinated alkyl ether (Fluoroalkyl ether), fluorinated alkylene ether (Fluoroalkylene ether), fluorinated alkyl sulfate (Fluoroalkyl sulfate), fluorinated alkyl phosphate (Fluoroalkyl phosphate), fluorinated acrylic acid copolymer (Fluoroacryl co-polymer), fluorinated copolymer (Fluoro co-polymer), perfluorinated acid (perfluorinated acid), perfluorinated carboxylate (perfluorinated carboxylate), perfluorinated sulfonate, the triol derivative and the tetraol derivative are 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 alcohol, 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-1,2,1,2,3,4-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- The group consisting of 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.

[0166] The results of evaluating the collapse degree of the photoresist pattern according to Example 1 are as follows: Figure 1 As shown, the number of blocks (bolcks) without pattern collapse was measured to be 58, showing the most excellent effect.

[0167] The results of evaluating the collapse degree of the photoresist pattern according to Comparative Experimental Example 1 are as follows: Figure 2 As shown, the number of blocks (bolcks) without pattern collapse was measured to be 31.

[0168] The specific parts of the present invention are described in detail above, so it is obvious to those skilled in the art that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto. Therefore, the essential scope of the present invention will be limited by the appended claims and their equivalents.

Claims

1. A rinse liquid composition for extreme ultraviolet lithography, characterized in that: The rinse liquid composition comprises a fluorine-based surfactant, a pattern enhancer as a compound of formula (1), a compound of formula (2) or a mixture thereof, a substance selected from the group consisting of a triol derivative, a tetraol derivative or a mixture thereof, and the balance water. Chemical formula (1) In the above chemical formula (1), X is fluorine, hydrogen or C1-C5 alkyl, X forms a single bond, l is 1 to 4, m and n are 1 to 3; Chemical formula (2) In the above chemical formula (2), X is fluorine, hydrogen or C1-C5 alkyl, X forms a single bond, o is 0~2.

2. The EUV lithography rinsing liquid composition according to claim 1, characterized in that: The rinse liquid composition comprises 0.0001 to 0.01 wt % of the fluorine-based surfactant, 0.0001 to 0.5 wt % of a pattern enhancer which is the compound of the chemical formula (1), the compound of the chemical formula (2) or a mixture thereof, 0.0001 to 0.5 wt % of a substance selected from the group consisting of the triol derivative, the tetraol derivative or a mixture thereof, and the balance water.

3. The EUV lithography rinsing liquid composition according to claim 2, characterized in that: The rinse liquid composition comprises 0.0001 to 0.01 wt % of the fluorine-based surfactant, 0.001 to 0.5 wt % of a pattern enhancer which is the compound of the chemical formula (1), the compound of the chemical formula (2) or a mixture thereof, 0.0001 to 0.5 wt % of a substance selected from the group consisting of the triol derivative, the tetraol derivative or a mixture thereof, and the balance water.

4. The EUV lithography rinsing liquid composition according to claim 2, characterized in that: 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, perfluorosulfonates or mixtures thereof.

5. The EUV rinsing liquid composition according to claim 2, characterized in that: The triol derivative and the tetraol derivative are 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 triol, 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, 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-heptanetrol as tetrahydric alcohol derivative substances composed of C4 to C14 The present invention is a group consisting of 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 a mixture thereof.

6. A method for forming a photoresist pattern, characterized in that: The steps include: (a) coating a photoresist on a semiconductor substrate and forming a film; (b) exposing the photoresist film and then developing it to form a pattern; and (c) washing the photoresist pattern using the EUV lithography rinse composition according to any one of claims 1 to 5.

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