Process solution composition for extreme ultraviolet lithography, and method for forming pattern by using same

Abstract

A processing solution composition for reducing collapse of a polyhydroxystyrene-containing photoresist pattern defined by an extreme-ultraviolet exposure source and a method of forming a pattern using the same are proposed. The processing solution composition includes 0.0001 to 1 wt % of a nonionic surfactant having an HLB (Hydrophilic-Lipophilic Balance) value of 9 to 16, 0.0001 to 1 wt % of an alkaline material selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and mixtures thereof, and 98 to 99.9998 wt % of water, and is effective at reducing the collapse of a polyhydroxystyrene-containing photoresist pattern defined by an extreme-ultraviolet exposure source.

Claims

1. A processing solution composition for reducing collapse of a polyhydroxystyrene-containing photoresist pattern defined by an extreme-ultraviolet exposure source, comprising: 0.0001 to 1 wt % of a nonionic surfactant having Hydrophilic-Lipophilic Balance value of 9 to 13, wherein the nonionic surfactant is a polyoxyethylene alkyl ether; 0.0001 to 1 wt % of tetrabutylammonium hydroxide; and 98 to 99.9998 wt % of water.

2. A method of forming a photoresist pattern, comprising: (a) forming a photoresist film by applying a photoresist on a semiconductor substrate; (b) forming a photoresist pattern by exposing and developing the photoresist film; and (c) cleaning the photoresist pattern with the processing solution composition of claim 1.

3. The method of claim 2, wherein the exposing is performed using an extreme-ultraviolet exposure source.

Description

BEST MODE

(1) Hereinafter, a detailed description will be given of the present disclosure.

(2) The present disclosure pertains to a processing solution for reducing the incidence of pattern collapse during photoresist development, including 0.0001 to 1 wt % of an alkaline material selected from the group consisting of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and mixtures thereof, 0.0001 to 1 wt % of a nonionic surfactant having an HLB (Hydrophilic-Lipophilic Balance) value of 9 to 16, and 98 to 99.9998 wt % of water.

(3) A better understanding of the present disclosure will be given through the following examples and comparative examples. These examples are merely set forth to illustrate the present disclosure, and are not to be construed as limiting the scope of the present disclosure.

MODE FOR DISCLOSURE

Examples and Comparative Examples

Example 1

(4) A processing solution for reducing the incidence of collapse of a photoresist pattern, including 0.01 wt % of polyoxyethylene alkyl ether having an HLB value of 9 and 0.01 wt % of tetrabutylammonium hydroxide, was prepared as follows.

(5) 0.01 wt % of polyoxyethylene alkyl ether having an HLB value of 9 and 0.01 wt % of tetrabutylammonium hydroxide were added to 99.98 wt % of deionized (DI) water, stirred for 5 hr, and passed through a 0.01 μm filter to remove fine solid impurities, thereby preparing a processing solution for reducing the incidence of collapse of a photoresist pattern.

Example 2 to Example 20

(6) Respective processing solutions for reducing the incidence of collapse of a photoresist pattern were prepared in the same manner as in Example 1 using components in the amounts shown in Tables 1 to 5 below.

Comparative Example 1

(7) Pure water (DI water), which is typically used as the final processing solution of the development process in a process of manufacturing a semiconductor device, was prepared.

Comparative Example 2 to Comparative Example 9

(8) For comparison with Examples, respective processing solutions were prepared in the same manner as in Example 1, using components in the amounts shown in Tables 1 to 5 below.

(9) TABLE-US-00001 TABLE 1 Surfactant Alkaline material DI water Amount Amount Amount Name HLB (wt %) Name (wt %) Name (wt %) Example 1 Polyoxyethylene 9 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 2 Polyoxyethylene 10 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 3 Polyoxyethylene 11 0.01 Tetrabutylammonium 0.01 DI 98.9800 alkyl ether hydroxide water Example 4 Polyoxyethylene 12 0.01 Tetrabutylammonium 0.01 DI 98.9800 alkyl ether hydroxide water Example 5 Polyoxyethylene 13 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 6 Polyoxyethylene 14 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 7 Polyoxyethylene 15 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 8 Polyoxyethylene 16 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Comparative — — — — — DI 100 Example 1 water Comparative Polyoxyethylene 8 0.01 Tetrabutylammonium 0.01 DI 99.9800 Example 2 alkyl ether hydroxide water Comparative Polyoxyethylene 17 0.01 Tetrabutylammonium 0.01 DI 99.9800 Example 3 alkyl ether hydroxide water

(10) TABLE-US-00002 TABLE 2 Surfactant Alkaline material DI water Amount Amount Amount Name HLB (wt %) Name (wt %) Name (wt %) Example 9 Polyoxyethylene 10 0.0001 Tetrabutylammonium 0.01 DI 99.9899 alkyl ether hydroxide water Example 10 Polyoxyethylene 10 0.001 Tetrabutylammonium 0.01 DI 99.9890 alkyl ether hydroxide water Example 11 Polyoxyethylene 10 0.1 Tetrabutylammonium 0.01 DI 99.8900 alkyl ether hydroxide water Example 12 Polyoxyethylene 10 1 Tetrabutylammonium 0.01 DI 98.9900 alkyl ether hydroxide water Comparative — — — Tetrabutylammonium 0.01 DI 99.9900 Example 4 hydroxide water Comparative Polyoxyethylene 10 2 Tetrabutylammonium 0.01 DI 97.9900 Example 5 alkyl ether hydroxide water

(11) TABLE-US-00003 TABLE 3 Surfactant Alkaline material DI water Amount Amount Amount Name HLB (wt %) Name (wt %) Name (wt %) Example 13 Polyoxyethylene 10 0.01 Tetrabutylammonium 0.0001 DI 99.9899 alkyl ether hydroxide water Example 14 Polyoxyethylene 10 0.01 Tetrabutylammonium 0.001 DI 99.9890 alkyl ether hydroxide water Example 15 Polyoxyethylene 10 0.01 Tetrabutylammonium 0.1 DI 99.8900 alkyl ether hydroxide water Example 16 Polyoxyethylene 10 0.01 Tetrabutylammonium 1 DI 98.9900 alkyl ether hydroxide water Comparative Polyoxyethylene 10 0.01 — — DI 99.9900 Example 6 alkyl ether water Comparative Polyoxyethylene 10 0.01 Tetrabutylammonium 2 DI 97.9900 Example 7 alkyl ether hydroxide water

(12) TABLE-US-00004 TABLE 4 Surfactant Alkaline material DI water Amount Amount Amount Name HLB (wt %) Name (wt %) Name (wt %) Example 17 Polyoxypropylene 10 0.01 Tetrabutylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 18 Polyoxyethylene 10 0.01 Tetrabutylammonium 0.01 DI 99.9800 oxypropylene alkyl ether hydroxide water

(13) TABLE-US-00005 TABLE 5 Surfactant Alkaline material DI water Amount Amount Amount Name HLB (wt %) Name (wt %) Name (wt %) Example 19 Polyoxyethylene 10 0.01 Tetraethylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Example 20 Polyoxyethylene 10 0.01 Tetrapropylammonium 0.01 DI 99.9800 alkyl ether hydroxide water Comparative Polyoxyethylene 10 0.01 Tetramethylammonium 0.01 DI 99.9800 Example 8 alkyl ether hydroxide water Comparative Polyoxyethylene 10 0.01 Tetrapentylammonium 0.01 DI 99.9800 Example 9 alkyl ether hydroxide water

Test Examples and Comparative Test Examples

(14) The pattern, formed by applying a photoresist on a semiconductor substrate to form a photoresist film and exposing and developing the photoresist film to form a pattern, was cleaned using the processing solution composition of each of Example 1 to Example 20 and Comparative Example 1 to Comparative Example 9, after which the silicon wafer having the pattern formed thereon was measured for pattern collapse and a defect number reduction ratio. The results thereof are shown as Test Example 1 to Test Example 20 and Comparative Test Example 1 to Comparative Test Example 9 in Table 6 below.

(1) Prevention of Pattern Collapse

(15) After exposure and focus splitting, the number of blocks in which the pattern did not collapse out of the total of 89 blocks was measured using a critical dimension scanning electron microscope (CD-SEM, Hitachi).

(2) Defect Number Ratio

(16) For the photoresist pattern rinsed with each rinse solution sample using a surface defect observation device [KLA, Tencor], the number of defects (A) was measured and expressed as a percentage (%) of the number of defects (B) observed upon rinsing with pure water alone, that is, (A/B)×100.

(17) The number of defects after treatment with pure water alone was set to 100% as a standard, and the extent of decrease or increase is expressed as a percentage compared to 100%, as the number of defects when treated with pure water alone, which is referred to as the defect number ratio (decrease or increase ratio). Here, a lower value is judged to be better.

(3) Transparency

(18) The transparency of the prepared cleaning solution was observed with the naked eye and indicated as transparent or opaque.

(19) TABLE-US-00006 TABLE 6 Number of Defect number blocks without reduction ratio pattern collapse (%) Transparency Example 1 75 50 Transparent Example 2 77 30 Transparent Example 3 71 38 Transparent Example 4 70 43 Transparent Example 5 65 50 Transparent Example 6 61 65 Transparent Example 7 52 79 Transparent Example 8 50 83 Transparent Example 9 55 53 Transparent Example 10 63 46 Transparent Example 11 64 35 Transparent Example 12 68 80 Transparent Example 13 70 81 Transparent Example 14 72 53 Transparent Example 15 75 38 Transparent Example 16 66 96 Transparent Example 17 70 42 Transparent Example 18 68 47 Transparent Example 19 57 69 Transparent Example 20 63 51 Transparent Comparative 46 100 Transparent Example 1 Comparative 78 151 Opaque Example 2 Comparative 42 90 Transparent Example 3 Comparative 40 95 Transparent Example 4 Comparative 41 327 Opaque Example 5 Comparative 65 118 Transparent Example 6 Comparative 40 126 Transparent Example 7 Comparative 38 149 Transparent Example 8 Comparative 43 97 Transparent Example 9

(20) Based on the results of comparison of Test Examples 1 to 8 with Comparative Test Examples 1 to 3, when the HLB value of the surfactant was 9 to 16, the number of blocks that did not exhibit pattern collapse was increased, the number of defects was reduced, and all of the cleaning solutions thereof were transparent. In particular, when the HLB value was 9 to 13, vastly superior effects were exhibited.

(21) Based on the results of comparison of Test Examples 2 and 9 to 12 with Comparative Test Examples 4 and 5, when the amount of the surfactant was 0.0001 to 1 wt %, the number of blocks not exhibiting pattern collapse was increased, the number of defects was reduced, and all of the cleaning solutions thereof were transparent.

(22) Based on the results of comparison of Test Examples 2 and 13 to 16 with Comparative Test Examples 6 and 7, when the amount of the alkaline material was 0.0001 to 1 wt %, the number of blocks not exhibiting pattern collapse was increased, the number of defects was reduced, and all of the cleaning solutions thereof were transparent.

(23) Based on the results of comparison of Test Examples 2, 17 and 18 with Comparative Test Example 1, when the surfactant was polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, or polyoxyethylene oxypropylene alkyl ether, the number of blocks not exhibiting pattern collapse was increased, the number of defects was reduced, and all of the cleaning solutions thereof were transparent. In particular, when the surfactant was polyoxyethylene alkyl ether, vastly superior effects were exhibited.

(24) Based on the results of a comparison of Test Examples 2, 19 and 20 with Comparative Test Examples 8 and 9, when the alkaline material was tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or tetrabutylammonium hydroxide, the number of blocks not exhibiting pattern collapse was increased, the number of defects was reduced, and all of the cleaning solutions thereof were transparent. In particular, when the alkaline material was tetrabutylammonium hydroxide, vastly superior effects were exhibited.

(25) Meanwhile, based on the results of evaluation of the pattern collapse of Example 2, it was confirmed that the number of blocks in which pattern collapse did not occur was 77, indicative of vastly superior effects.

(26) In contrast, based on the results of evaluation of the pattern collapse of Comparative Example 1, it was confirmed that the number of blocks in which pattern collapse did not occur was 46, indicative of poor effects.

(27) Although specific embodiments of the present disclosure have been disclosed in detail above, it will be obvious to those skilled in the art that the description is merely of preferable exemplary embodiments and is not to be construed to limit the scope of the present disclosure. Therefore, the substantial scope of the present disclosure will be defined by the appended claims and equivalents thereof.