PROCESS LIQUID COMPOSITION FOR PHOTOLITHOGRAPHY AND PATTERN FORMING METHOD USING SAME

Abstract

A process liquid composition for moving a lifting defect level of a photoresist pattern having hydrophobicity represented by a contact angle of 75° or larger of a photoresist surface with respect to water in a photoresist patterning process, and a preparation method thereof are proposed. The process liquid composition includes 0.00001% to 0.1% by weight of a fluorine-based surfactant, 0.00001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof, and the remaining proportion of water. The process liquid composition has a surface tension of 45 mN/m or less and a contact angle of 65° or smaller.

Claims

1. A process liquid composition for alleviating a lifting defect level of a photoresist pattern, the photoresist pattern having hydrophobicity represented by a contact angle of 75° or greater of a surface thereof with respect to water in a photoresist patterning process, the composition comprising a surfactant and having a surface tension of 45 mN/m or less and a contact angle of 65° or smaller.

2. The composition according to claim 1, comprising: 0.00001% to 0.1% by weight of a fluorine-based surfactant; 0.00001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof; and the remaining proportion of water.

3. The composition according to claim 2, comprising: 0.0001% to 0.1% by weight of a fluorine-based surfactant; 0.00001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof; and the remaining proportion of water.

4. The composition according to claim 3, comprising: 0.001% to 0.1% by weight of a fluorine-based surfactant; 0.00001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof; and the remaining proportion of water.

5. The composition according to claim 4, comprising: 0.001% to 0.1% by weight of the fluorine-based surfactant; 0.0001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof; and the remaining proportion of water.

6. The composition according to claim 5, comprising: 0.001% to 0.1% by weight of the fluorine-based surfactant; 0.001% to 1.0% by weight of a triol derivative, a tetraol derivative, or a mixture thereof; and the remaining proportion of water.

7. The composition according to claim 2, wherein the fluorine-based surfactant is selected from the group consisting of fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, perfluorianted sulfonate, and mixtures thereof.

8. The composition according to claim 2, wherein the triol derivative is a C3 to C10 triol derivative selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof, and wherein the tetraol derivative is a C4 to C14 tetraol derivative selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

9. A method of forming a photoresist pattern, the method comprising the steps of: (a) applying photoresist on a semiconductor substrate to form a photoresist film; (b) exposing the photoresist film to light and developing the photoresist film to form a photoresist pattern; and (c) cleaning the photoresist pattern with the composition of claim 1.

Description

MODE FOR CARRYING OUT THE INVENTION

Example 1

[0033] A process liquid composition for alleviating a collapse level of a photoresist pattern which contains 0.001% by weight of fluoroacryl carboxylate and 0.01% by weight of 1,2,3-propanetriol was prepared using the following method.

[0034] 0.001% By weight of fluoroacryl carboxylate and 0.01% by weight of 1,2,3-propanetriol were added into the remaining proportion of distilled water and stirred for 5 hours. Then, the resulting liquid was filtered through a 0.01 μm filter to remove fine solid impurities. In this manner, the process liquid composition for alleviating the collapse level of the photoresist pattern was prepared.

Example 2 to Example 80

[0035] Process liquid compositions for alleviating a defect level of the same photoresist pattern as in Example 1 were prepared according to composition components and ratios that were specified as shown in Tables 1 to 15.

Comparative Example 1

[0036] Distilled water that was used as a cleaning liquid in the last process among typical semiconductor manufacturing processes was prepared.

Comparative Example 2 to Comparative Example 13

[0037] For comparison with Examples, process liquid compositions were prepared in the same manner as in Example 1, according to the composition components and ratios that were specified as shown in Tables 1 to 15.

Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13

[0038] Measurements of pattern lifting defect levels were performed on silicon wafers on which patterns were formed using the compositions prepared in Examples 1 to 80 and Comparative Examples 1 to 13. The measurements are described as Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13. The results of the measurements are shown in Table 16.

[0039] (1) Verification of Pattern Lifting Prevention

[0040] After exposure energy and focus were split, among a total of 89 blocks, the number of blocks in which a pattern did not collapse was detected using a critical dimension-scanning electron microscope (CD-SEM, manufactured by Hitachi, Ltd).

[0041] (2) Transparency

[0042] Transparency of each of the prepared process liquid composition was checked with the naked eye and was marked as a transparent or opaque process liquid composition.

[0043] (3) Surface Tension and Contact Angle

[0044] The surface tension and contact angle of each of the process liquid compositions were measured using a surface tension measuring instrument [the K-100 Force Tensiometer manufactured by KRÜSS GmbH] and a contact angle measuring instrument [the DSA-100 Drop Shape Analyzer manufactured by KRÜSS GmbH].

TABLE-US-00001 TABLE 1 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 1 Fluoroacrylic 0.001 1,2,3- 0.01 Distilled 99.9890 carboxylate propanetriol water Example 2 Fluoroalkyl ether 0.001 1,2,3- 0.01 Distilled 99.9890 propanetriol water Example 3 Fluoroalkylene ether 0.001 1,2,3- 0.01 Distilled 99.9890 propanetriol water Example 4 Fluoroalkyl sulfate 0.001 1,2,3- 0.01 Distilled 99.9890 propanetriol water Example 5 Fluoroalkyl 0.001 1,2,3- 0.01 Distilled 99.9890 phosphate propanetriol water Example 6 Fluoroacrylic 0.001 1,2,3- 0.01 Distilled 99.9890 copolymer propanetriol water Example 7 Fluorine copolymer 0.001 1,2,3- 0.01 Distilled 99.9890 propanetriol water Example 8 Perfluoric acid 0.001 1,2,3- 0.01 Distilled 99.9890 propanetriol water Example 9 Perfluorinated 0.001 1,2,3- 0.01 Distilled 99.9890 carboxyl salts propanetriol water Example 10 Perfluorinated 0.001 1,2,3- 0.01 Distilled 99.9890 sulfonate propanetriol water Comparative — — — — Distilled 100 Example 1 water

TABLE-US-00002 TABLE 2 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 11 Fluoroacrylic 0.001 1,2,3,4- 0.01 Distilled 99.9890 carboxylate Butanetetraol water Example 12 Fluoroalkyl ether 0.001 1,2,3,4- 0.01 Distilled 99.9890 Butanetetraol water Example 13 Fluoroalkylene ether 0.001 1,2,3,4- 0.01 Distilled 99.9890 Butanetetraol water Example 14 Fluoroalkyl sulfate 0.001 1,2,3,4- 0.01 Distilled 99.9890 Butanetetraol water Example 15 Fluoroalkyl 0.001 1,2,3,4- 0.01 Distilled 99.9890 phosphate Butanetetraol water Example 16 Fluoroacrylic 0.001 1,2,3,4- 0.01 Distilled 99.9890 copolymer Butanetetraol water Example 17 Fluorine copolymer 0.001 1,2,3,4- 0.01 Distilled 99.9890 Butanetetraol water Example 18 Perfluoric acid 0.001 1,2,3,4- 0.01 Distilled 99.9890 Butanetetraol water Example 19 Perfluorinated 0.001 1,2,3,4- 0.01 Distilled 99.9890 carboxyl salts Butanetetraol water Example 20 Perfluorinated 0.001 1,2,3,4- 0.01 Distilled 99.9890 sulfonate Butanetetraol water

TABLE-US-00003 TABLE 3 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 21 Fluoroacrylic 0.00001 1,2,3- 0.01 Distilled 99.98999 carboxylate propanetriol water Example 22 Fluoroacrylic 0.0001 1,2,3- 0.01 Distilled 99.9899 carboxylate propanetriol water Example 1 Fluoroacrylic 0.001 1,2,3- 0.01 Distilled 99.9890 carboxylate propanetriol water Example 23 Fluoroacrylic 0.01 1,2,3- 0.01 Distilled 99.9800 carboxylate propanetriol water Example 24 Fluoroacrylic 0.1 1,2,3- 0.01 Distilled 99.8900 carboxylate propanetriol water Comparative Fluoroacrylic 1 1,2,3- 0.01 Distilled 98.9900 Example 2 carboxylate propanetriol water

TABLE-US-00004 TABLE 4 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 25 Fluoroalkyl 0.00001 1,2,3- 0.01 Distilled 99.98999 ether propanetriol water Example 26 Fluoroalkyl 0.0001 1,2,3- 0.01 Distilled 99.9899 ether propanetriol water Example 2 Fluoroalkyl 0.001 1,2,3- 0.01 Distilled 99.9890 ether propanetriol water Example 27 Fluoroalkyl 0.01 1,2,3- 0.01 Distilled 99.9800 ether propanetriol water Example 28 Fluoroalkyl 0.1 1,2,3- 0.01 Distilled 99.8900 ether propanetriol water Comparative Fluoroalkyl 1 1,2,3- 0.01 Distilled 98.9900 Example 3 ether propanetriol water

TABLE-US-00005 TABLE 5 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 29 Fluoroalkylene 0.00001 1,2,3- 0.01 Distilled 99.98999 ether propanetriol water Example 30 Fluoroalkylene 0.0001 1,2,3- 0.01 Distilled 99.9899 ether propanetriol water Example 3 Fluoroalkylene 0.001 1,2,3- 0.01 Distilled 99.9890 ether propanetriol water Example 31 Fluoroalkylene 0.01 1,2,3- 0.01 Distilled 99.9800 ether propanetriol water Example 32 Fluoroalkylene 0.1 1,2,3- 0.01 Distilled 99.8900 ether propanetriol water Comparative Fluoroalkylene 1 1,2,3- 0.01 Distilled 98.9900 Example 4 ether propanetriol water

TABLE-US-00006 TABLE 6 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 33 Fluoroalkyl 0.00001 1,2,3- 0.01 Distilled 99.98999 sulfate propanetriol water Example 34 Fluoroalkyl 0.0001 1,2,3- 0.01 Distilled 99.9899 sulfate propanetriol water Example 4 Fluoroalkyl 0.001 1,2,3- 0.01 Distilled 99.9890 sulfate propanetriol water Example 35 Fluoroalkyl 0.01 1,2,3- 0.01 Distilled 99.9800 sulfate propanetriol water Example 36 Fluoroalkyl 0.1 1,2,3- 0.01 Distilled 99.8900 sulfate propanetriol water Comparative Fluoroalkyl 1 1,2,3- 0.01 Distilled 98.9900 Example 5 sulfate propanetriol water

TABLE-US-00007 TABLE 7 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 37 Fluoroalkyl 0.00001 1,2,3- 0.01 Distilled 99.98999 phosphate propanetriol water Example 38 Fluoroalkyl 0.0001 1,2,3- 0.01 Distilled 99.9899 phosphate propanetriol water Example 5 Fluoroalkyl 0.001 1,2,3- 0.01 Distilled 99.9890 phosphate propanetriol water Example 39 Fluoroalkyl 0.01 1,2,3- 0.01 Distilled 99.9800 phosphate propanetriol water Example 40 Fluoroalkyl 0.1 1,2,3- 0.01 Distilled 99.8900 phosphate propanetriol water Comparative Fluoroalkyl 1 1,2,3- 0.01 Distilled 98.9900 Example 6 phosphate propanetriol water

TABLE-US-00008 TABLE 8 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 41 Fluoroacrylic 0.00001 1,2,3- 0.01 Distilled 99.98999 copolymer propanetriol water Example 42 Fluoroacrylic 0.0001 1,2,3- 0.01 Distilled 99.9899 copolymer propanetriol water Example 6 Fluoroacrylic 0.001 1,2,3- 0.01 Distilled 99.9890 copolymer propanetriol water Example 43 Fluoroacrylic 0.01 1,2,3- 0.01 Distilled 99.9800 copolymer propanetriol water Example 44 Fluoroacrylic 0.1 1,2,3- 0.01 Distilled 99.8900 copolymer propanetriol water Comparative Fluoroacrylic 1 1,2,3- 0.01 Distilled 98.9900 Example 7 copolymer propanetriol water

TABLE-US-00009 TABLE 9 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 45 Fluorine 0.00001 1,2,3- 0.01 Distilled 99.98999 copolymer propanetriol water Example 46 Fluorine 0.0001 1,2,3- 0.01 Distilled 99.9899 copolymer propanetriol water Example 7 Fluorine 0.001 1,2,3- 0.01 Distilled 99.9890 copolymer propanetriol water Example 47 Fluorine 0.01 1,2,3- 0.01 Distilled 99.9800 copolymer propanetriol water Example 48 Fluorine 0.1 1,2,3- 0.01 Distilled 99.8900 copolymer propanetriol water Comparative Fluorine 1 1,2,3- 0.01 Distilled 98.9900 Example 8 copolymer propanetriol water

TABLE-US-00010 TABLE 10 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 49 Perfluoric 0.00001 1,2,3- 0.01 Distilled 99.98999 acid propanetriol water Example 50 Perfluoric 0.0001 1,2,3- 0.01 Distilled 99.9899 acid propanetriol water Example 8 Perfluoric 0.001 1,2,3- 0.01 Distilled 99.9890 acid propanetriol water Example 51 Perfluoric 0.01 1,2,3- 0.01 Distilled 99.9800 acid propanetriol water Example 52 Perfluoric 0.1 1,2,3- 0.01 Distilled 99.8900 acid propanetriol water Comparative Perfluoric 1 1,2,3- 0.01 Distilled 98.9900 Example 9 acid propanetriol water

TABLE-US-00011 TABLE 11 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 53 Perfluorinated 0.00001 1,2,3- 0.01 Distilled 99.98999 carboxyl salts propanetriol water Example 54 Perfluorinated 0.0001 1,2,3- 0.01 Distilled 99.9899 carboxyl salts propanetriol water Example 9 Perfluorinated 0.001 1,2,3- 0.01 Distilled 99.9890 carboxyl salts propanetriol water Example 55 Perfluorinated 0.01 1,2,3- 0.01 Distilled 99.9800 carboxyl salts propanetriol water Example 56 Perfluorinated 0.1 1,2,3- 0.01 Distilled 99.8900 carboxyl salts propanetriol water Comparative Perfluorinated 1 1,2,3- 0.01 Distilled 98.9900 Example 10 carboxyl salts propanetriol water

TABLE-US-00012 TABLE 12 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 57 Perfluorinated 0.00001 1,2,3- 0.01 Distilled 99.98999 sulfonate propanetriol water Example 58 Perfluorinated 0.0001 1,2,3- 0.01 Distilled 99.9899 sulfonate propanetriol water Example 10 Perfluorinated 0.001 1,2,3- 0.01 Distilled 99.9890 sulfonate propanetriol water Example 59 Perfluorinated 0.01 1,2,3- 0.01 Distilled 99.9800 sulfonate propanetriol water Example 60 Perfluorinated 0.1 1,2,3- 0.01 Distilled 99.8900 sulfonate propanetriol water Comparative Perfluorinated 1 1,2,3- 0.01 Distilled 98.9900 Example 11 sulfonate propanetriol water

TABLE-US-00013 TABLE 13 Surfactant Additive Additive Content Content Content Distilled Content (% by (% by (% by water (% by Name weight) Name weight) Name weight) Name weight) Example 61 Fluoroacrylic 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 carboxylate propanetriol Butanetetraol water Example 62 Fluoroalkyl 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 ether propanetriol Butanetetraol water Example 63 Fluoroalkylene 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 ether propanetriol Butanetetraol water Example 64 Fluoroalkyl 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 sulfate propanetriol Butanetetraol water Example 65 Fluoroalkyl 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 phosphate propanetriol Butanetetraol water Example 66 Fluoroacrylic 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 copolymer propanetriol Butanetetraol water Example 67 Fluorine 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 copolymer propanetriol Butanetetraol water Example 68 Perfluoric acid 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 propanetriol Butanetetraol water Example 69 Perfluorinated 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 carboxyl salts propanetriol Butanetetraol water Example 70 Perfluorinated 0.001 1,2,3- 0.005 1,2,3,4- 0.005 Distilled 99.9890 sulfonate propanetriol Butanetetraol water

TABLE-US-00014 TABLE 14 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 71 Fluoroacrylic 0.001 1,2,3- 0.00001 Distilled 99.99899 carboxylate propanetriol water Example 72 Fluoroacrylic 0.001 1,2,3- 0.0001 Distilled 99.9989 carboxylate propanetriol water Example 73 Fluoroacrylic 0.001 1,2,3- 0.001 Distilled 99.9980 carboxylate propanetriol water Example 1 Fluoroacrylic 0.001 1,2,3- 0.01 Distilled 99.9890 carboxylate propanetriol water Example 74 Fluoroacrylic 0.001 1,2,3- 0.1 Distilled 99.8990 carboxylate propanetriol water Example 75 Fluoroacrylic 0.001 1,2,3- 1.0 Distilled 98.9990 carboxylate propanetriol water Comparative Fluoroacrylic 0.001 1,2,3- 2.0 Distilled 97.9990 Example 12 carboxylate propanetriol water

TABLE-US-00015 TABLE 15 Surfactant Additive Distilled water Content (% Content (% Content (% Name by weight) Name by weight) Name by weight) Example 76 Fluoroacrylic 0.001 1,2,3,4- 0.00001 Distilled 99.99899 carboxylate Butanetetraol water Example 77 Fluoroacrylic 0.001 1,2,3,4- 0.0001 Distilled 99.9989 carboxylate Butanetetraol water Example 78 Fluoroacrylic 0.001 1,2,3,4- 0.001 Distilled 99.9980 carboxylate Butanetetraol water Example 11 Fluoroacrylic 0.001 1,2,3,4- 0.01 Distilled 99.9890 carboxylate Butanetetraol water Example 79 Fluoroacrylic 0.001 1,2,3,4- 0.1 Distilled 99.8990 carboxylate Butanetetraol water Example 80 Fluoroacrylic 0.001 1,2,3,4- 1.0 Distilled 98.9990 carboxylate Butanetetraol water Comparative Fluoroacrylic 0.001 1,2,3,4- 2.0 Distilled 97.9990 Example 13 carboxylate Butanetetraol water

[0045] [Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13] Measurements of pattern lifting defect levels, transparency values, contact angles, and surface tension values were performed on silicon wafers on which patterns are formed using the compositions prepared in Examples 1 to 80 and Comparative Examples 1 to 13. The measurements are described as Experimental Examples 1 to 80 and Comparative Experimental Examples 1 to 13. The results of the measurements are shown in Table 16.

[0046] (1) Verification of Pattern Lifting Prevention

[0047] After exposure energy and focus were split, among a total of 89 blocks, the number of blocks in which a pattern did not collapse was detected using a critical dimension-scanning electron microscope (CD-SEM, manufactured by Hitachi, Ltd).

[0048] (2) Transparency

[0049] Transparency of each of the prepared process liquid composition was checked with the naked eye and was marked as a transparent or opaque process liquid composition.

[0050] (3) Contact Angle and Surface Tension

[0051] The surface tension and contact angle of each of the process liquid compositions were measured using a surface tension measuring instrument [K-100, manufactured by KRÜSS GmbH] and a contact angle measuring instrument [DSA-100, manufactured by KRÜSS GmbH].

TABLE-US-00016 TABLE 16 Number of blocks without pattern Contact Surface lifting defects Transparency angle tension Experimental 82 Transparent 50 28 Example 1 Experimental 80 Transparent 58 32 Example 2 Experimental 79 Transparent 54 30 Example 3 Experimental 78 Transparent 60 32 Example 4 Experimental 74 Transparent 59 31 Example 5 Experimental 75 Transparent 61 33 Example 6 Experimental 71 Transparent 63 41 Example 7 Experimental 71 Transparent 57 40 Example 8 Experimental 72 Transparent 59 38 Example 9 Experimental 73 Transparent 58 35 Example 10 Experimental 81 Transparent 56 32 Example 11 Experimental 79 Transparent 59 34 Example 12 Experimental 79 Transparent 57 30 Example 13 Experimental 77 Transparent 62 33 Example 14 Experimental 74 Transparent 61 31 Example 15 Experimental 74 Transparent 63 34 Example 16 Experimental 71 Transparent 64 38 Example 17 Experimental 70 Transparent 57 36 Example 18 Experimental 71 Transparent 58 35 Example 19 Experimental 72 Transparent 58 33 Example 20 Experimental 67 Transparent 63 43 Example 21 Experimental 69 Transparent 59 34 Example 22 Experimental 75 Transparent 45 26 Example 23 Experimental 74 Transparent 40 23 Example 24 Experimental 55 Transparent 62 45 Example 25 Experimental 67 Transparent 60 28 Example 26 Experimental 74 Transparent 55 29 Example 27 Experimental 72 Transparent 54 27 Example 28 Experimental 62 Transparent 63 41 Example 29 Experimental 66 Transparent 57 34 Example 30 Experimental 74 Transparent 54 26 Example 31 Experimental 71 Transparent 50 23 Example 32 Experimental 64 Transparent 64 41 Example 33 Experimental 67 Transparent 60 35 Example 34 Experimental 76 Transparent 59 28 Example 35 Experimental 74 Transparent 52 24 Example 36 Experimental 62 Transparent 62 40 Example 37 Experimental 66 Transparent 60 35 Example 38 Experimental 71 Transparent 57 27 Example 39 Experimental 70 Transparent 56 23 Example 40 Experimental 61 Transparent 64 41 Example 41 Experimental 69 Transparent 61 34 Example 42 Experimental 72 Transparent 58 25 Example 43 Experimental 71 Transparent 57 25 Example 44 Experimental 54 Transparent 63 45 Example 45 Experimental 62 Transparent 62 39 Example 46 Experimental 70 Transparent 59 31 Example 47 Experimental 67 Transparent 57 30 Example 48 Experimental 60 Transparent 60 43 Example 49 Experimental 68 Transparent 58 40 Example 50 Experimental 70 Transparent 54 30 Example 51 Experimental 72 Transparent 52 27 Example 52 Experimental 66 Transparent 62 43 Example 53 Experimental 71 Transparent 60 37 Example 54 Experimental 76 Transparent 57 30 Example 55 Experimental 74 Transparent 52 28 Example 56 Experimental 64 Transparent 63 43 Example 57 Experimental 70 Transparent 57 34 Example 58 Experimental 73 Transparent 56 25 Example 59 Experimental 72 Transparent 53 23 Example 60 Experimental 81 Transparent 53 33 Example 61 Experimental 79 Transparent 58 33 Example 62 Experimental 79 Transparent 55 34 Example 63 Experimental 77 Transparent 61 33 Example 64 Experimental 74 Transparent 60 31 Example 65 Experimental 74 Transparent 61 34 Example 66 Experimental 72 Transparent 63 40 Example 67 Experimental 70 Transparent 55 39 Example 68 Experimental 70 Transparent 56 37 Example 69 Experimental 73 Transparent 58 34 Example 70 Experimental 64 Transparent 44 21 Example 71 Experimental 71 Transparent 45 23 Example 72 Experimental 78 Transparent 48 26 Example 73 Experimental 77 Transparent 52 31 Example 74 Experimental 71 Transparent 55 33 Example 75 Experimental 61 Transparent 49 25 Example 76 Experimental 70 Transparent 50 28 Example 77 Experimental 78 Transparent 52 30 Example 78 Experimental 77 Transparent 54 34 Example 79 Experimental 70 Transparent 58 35 Example 80 Comparative Test 45 Transparent 87 71 Example 1 Comparative Test 55 Opaque 40 18 Example 2 Comparative Test 52 Opaque 54 22 Example 3 Comparative Test 50 Opaque 49 20 Example 4 Comparative Test 49 Opaque 53 19 Example 5 Comparative Test 51 Opaque 52 21 Example 6 Comparative Test 52 Opaque 57 23 Example 7 Comparative Test 49 Opaque 59 26 Example 8 Comparative Test 48 Opaque 51 41 Example 9 Comparative Test 50 Opaque 54 27 Example 10 Comparative Test 53 Opaque 53 24 Example 11 Comparative Test 60 Opaque 59 37 Example 12 Comparative Test 59 Opaque 60 38 Example 13

[0052] From the comparison of Experimental examples 1 to 80 with Comparative Experimental Examples 1 to 13 on the basis of the result of conducting much research over a long period of time, it could be seen that, when the number of blocks in which a pattern did not collapse was 50 or greater and the composition exhibited a transparent property, a more improved result was obtained. That is, it was verified that when the compositions as in Experimental Examples 1 to 80 described below were used, the effect of reducing the pattern lifting defects was improved compared to the cases where the compositions as in Comparative Experimental Examples 1 to 13 were used. Each of the compositions as in Experimental Examples 1 to 80 included: 0.00001% to 0.1% by weight of a fluorine-based surfactant selected from the following, 0.00001% to 1.0% by weight of a C3 to C10 triol derivative alone selected from the following, a C4 to C14 tetraol alone selected from the following, or a mixture thereof; and 98.9% to 99.99998% of water, in which the fluorine-based surfactant were selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, and perfluorianted sulfonate; the C3 to C10 triol derivative was selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof, and the C4 to C14 tetraol derivative is selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

[0053] In addition, among the compositions corresponding to Experimental Examples 1 to 80, the composition containing 0.0001% to 0.1% by weight of a fluorine-based surfactant selected from the following, 0.00001% to 1.0% by weight of a C3 to C10 triol derivative alone selected from the following, a C4 to C14 tetraol alone selected from the following, or a mixture thereof; and the remaining proportion of water improved the effect of reducing the pattern lifting defects compared to Comparative Experimental Examples 1 to 13, in which the fluorine-based surfactant was selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, and perfluorianted sulfonate; the C3 to C10 triol derivative was selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof; and the C4 to C14 tetraol derivative was selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

[0054] Among the compositions as in Experimental Examples 1 to 80, the composition including 0.001% to 0.1% by weight of a fluorine-based surfactant selected from the following, 0.00001% to 1.0% by weight of a C3 to C10 triol derivative alone selected from the following, a C4 to C14 tetraol alone selected from the following, or a mixture thereof, and the remaining proportion of water improved the effect of reducing the pattern lifting defects compared to Comparative Experimental Examples 1 to 13, in which the fluorine-based surfactant were selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, and perfluorianted sulfonate; the C3 to C10 triol derivative was selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof, and the C4 to C14 tetraol derivative is selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

[0055] In addition, among the compositions corresponding to Experimental Examples 1 to 80, the composition containing 0.001% to 0.1% by weight of a fluorine-based surfactant selected from the following, 0.0001% to 1.0% by weight of a C3 to C10 triol derivative alone selected from the following, a C4 to C14 tetraol alone selected from the following, or a mixture thereof; and the remaining proportion of water improved the effect of reducing the pattern lifting defects compared to Comparative Experimental Examples 1 to 13, in which the fluorine-based surfactant was selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, and perfluorianted sulfonate; the C3 to C10 triol derivative was selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof; and the C4 to C14 tetraol derivative was selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

[0056] In addition, among the compositions corresponding to Experimental Examples 1 to 80, the composition containing 0.001% to 0.1% by weight of a fluorine-based surfactant selected from the following, 0.001% to 1.0% by weight of a C3 to C10 triol derivative alone selected from the following, a C4 to C14 tetraol alone selected from the following, or a mixture thereof; and the remaining proportion of water improved the effect of reducing the pattern lifting defects compared to Comparative Experimental Examples 1 to 13, in which the fluorine-based surfactant was selected from fluoroacryl carboxylate, fluoroalkyl ether, fluoroalkylene ether, fluoroalkyl sulfate, fluoroalkyl phosphate, fluoroacryl copolymer, fluoro co-polymer, perfluorinated acid, perfluorinated carboxylate, and perfluorianted sulfonate; the C3 to C10 triol derivative was selected from the group consisting of 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-tetrahydro naphthalene-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 mixtures thereof; and the C4 to C14 tetraol derivative was selected from the group consisting of 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, 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-1,4,9,10-tetraol, and mixtures thereof.

[0057] the result of measuring the collapse level of the photoresist pattern formed in Example 1 for evaluation was that the number of blocks in which the pattern did not collapse was 82, thereby having exhibited the best effect.

[0058] the result of measuring the collapse level of the photoresist pattern as in *Comparative Experimental Example 1 for evaluation was that the number of blocks in which the pattern did not collapse was 45.

[0059] The specific aspects of the present invention are described in detail above. It would be apparent to a person of ordinary skill in the art to which the present invention pertains that this specific description is only for the desired embodiments and do not impose any limitation on the scope of the present invention. Therefore, a substantial scope and a scope equivalent thereto must be defined by the following claims.