Compound, photoresist composition comprising same, photoresist pattern comprising same, and method for manufacturing photoresist pattern

Abstract

A compound represented by Chemical Formula 1, a photoresist composition comprising the same, a photoresist pattern comprising the same, and a method for preparing a photoresist pattern ##STR00001##

Claims

1. A compound represented by Chemical Formula 1: ##STR00042## wherein, in the Chemical Formula 1, R.sub.1 and R.sub.2 are the same as or different from each other, and each independently hydrogen; a halogen group; a nitrile group; a hydroxyl group; an ester group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; R.sub.3 to R.sub.6 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; and Ar.sub.1 and Ar.sub.2 are the same as or different from each other, and each independently hydrogen; a halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group.

2. The compound of claim 1, wherein R.sub.1 and R.sub.2 are the same as or different from each other, and each independently hydrogen; a halogen group; an ester group; a substituted or unsubstituted C.sub.1 to C.sub.60 alkyl group; a substituted or unsubstituted C.sub.6 to C.sub.60 aryl group; or a substituted or unsubstituted C.sub.2 to C.sub.60 heteroaryl group.

3. The compound of claim 1, wherein R.sub.4 to R.sub.6 are the same as or different from each other, and each independently a substituted or unsubstituted C.sub.6 to C.sub.60 aryl group.

4. The compound of claim 1, wherein Ar.sub.1 and Ar.sub.2 are the same as or different from each other, and each independently hydrogen; or a halogen group, and at least one of Ar.sub.1 and Ar.sub.2 is a halogen group.

5. The compound of claim 1, wherein R.sub.3 is a substituted or unsubstituted C.sub.1 to C.sub.60 alkyl group.

6. The compound of claim 1, wherein the compound is represented by any one of the following Chemical Formulae: ##STR00043##

7. A photoresist composition comprising: a resin; the compound of claim 1; a photoacid generator (PAG); an acid diffusion control agent; and a quencher.

8. The photoresist composition of claim 7, wherein the resin comprises at least one resin selected from a (meth)acrylate-based resin; a norbornene resin; a styrene-based resin; and an epoxy resin.

9. The photoresist composition of claim 7, comprising the compound in an amount of from 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the resin.

10. The photoresist composition of claim 7, comprising the photoacid generator in an amount of from 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the resin.

11. The photoresist composition of claim 7, comprising the acid diffusion control agent in an amount of from 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the resin.

12. The photoresist composition of claim 7, further comprising at least one material selected from a surfactant; a photosensitizer; and a photobase generator.

13. A photoresist layer comprising the photoresist composition of claim 7.

14. A method for preparing a photoresist pattern, the method comprising: forming a photoresist layer by coating the photoresist composition of claim 7 on a semiconductor substrate; selectively exposing the photoresist layer to ultraviolet rays; and developing the exposed photoresist layer in a developing solution.

15. The method for preparing a photoresist pattern of claim 14, wherein the selectively exposing of the photoresist layer is aligning a mask on the photoresist layer, and exposing an area of the photoresist layer not covered by the mask to the ultraviolet rays.

16. The method for preparing a photoresist pattern of claim 14, wherein the developing of the exposed photoresist layer is removing the exposed portion in the photoresist layer by immersing in the developing solution.

Description

PREPARATION EXAMPLE

Synthesis of Compounds

(1) ##STR00022##

(2) In the syntheses of the compounds, the compounds were synthesized using substituents described in the following Table 1.

(3) TABLE-US-00001 TABLE 1 R.sub.1 R.sub.2 Yield (%) Preparation Example 1 H H 95 Preparation Example 2 CH.sub.3 H 93 Preparation Example 3 Ph H 94 Preparation Example 4 CH.sub.3 CH.sub.3 93 Preparation Example 5 CH.sub.3 4-CO.sub.2CH.sub.3P—C.sub.6H.sub.4 90 Preparation Example 6 Ph 2-Pyridinyl 91

Preparation of Intermediate 1

(4) ##STR00023##

(5) Cyclopentadiene (132.2 g, 2.0 mol), 2-carboxyethyl acrylate (130.1 g, 1.0 mol) and 4-methoxyphenol (2.4 g, 0.02 mol) were introduced to a high pressure reactor, and the result was reacted for 18 hours at 180° C., and then vacuum distilled to obtain Intermediate 1 (190 g, 97%).

(6) 1H-NMR (CDCl3): (ppm) δ=6.3 (dd, H), 6.2 (dd, H), 3.6 (s, 3H), 3.34 (dd, H), 3.29 (dd, H), 3.2-3.1 (m, 2H), 1.5 (m, H), 1.4-1.3 (br, H)

Preparation of Intermediate 2

(7) ##STR00024##

(8) Intermediate 1 (196 g, 1.0 mol), sodium 1,1-difluoro-2-hydroxyethane-1-sulfonate (220.9 g, 1.2 mol) and H.sub.2SO.sub.4 (19.6 g, 0.2 mol) were introduced and reacted for 6 hours at 60° C. After the reaction was finished, H.sub.2O (1 L) was introduced thereto, the result was extracted 3 times with ethyl acetate (1 L), and the solvent was removed. The obtained result was recrystallized with EtOH to obtain Intermediate 2 (330 g, 91%).

(9) 1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 4.9 (m, 2H), 3.7-3.5 (m, 5H), 3.1-2.9 (m, 2H), 1.8-1.5 (m, 2H)

Preparation of Intermediate 3

(10) ##STR00025##

(11) Intermediate 2 (181 g, 0.5 mol) and triphenylsulfonium bromide (172 g, 0.5 mol) were introduced to a H.sub.2O:dichloro-methane=1:1 solution (1 L), and reacted for 12 hours at room temperature (25° C.). After the reaction was finished, the organic layer was washed 3 times with H.sub.2O (1 L), and then diethyl ether was introduced thereto to form precipitates. The precipitates were filtered and then dried to obtain Intermediate 3 (compound B1) (280 g, 93%).

(12) 1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 6.1-6.0 (m, 2H), 4.5 (m, 2H), 3.7-3.5 (m, 5H), 3.1-2.9 (m, 2H), 1.8-1.5 (m, 2H)

Preparation of Intermediate 4

(13) ##STR00026##

(14) Intermediate 1 (196.0 g, 1.0 mol), cyclopentadiene (132.2 g, 2.0 mol) and 4-methoxyphenol (2.4 g, 0.02 mol) were introduced to a high pressure reactor, reacted for 18 hours at 180° C., and then vacuum distilled to obtain Intermediate 4 (250 g, 95%).

(15) 1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 3.6 (s, 3H), 2.8 (m, H), 2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m, 2H), 1.0-0.7 (m, 2H)

Preparation of Intermediate 5

(16) ##STR00027##

(17) Intermediate 4 (131.0 g, 0.5 mol), sodium 1,1-difluoro-2-hydroxyethane-1-sulfonate (110.5 g, 0.6 mol) and H.sub.2SO.sub.4 (9.8 g, 0.1 mol) were introduced and reacted for 6 hours at 60° C. After the reaction was finished, H.sub.2O (1 L) was introduced thereto, the result was extracted 3 times with ethyl acetate (1 L), and the solvent was removed. The obtained result was recrystallized with EtOH to obtain Intermediate 5 (196.9 g, 92%).

(18) 1H-NMR (DMSO-D6): (ppm) δ=6.1-6.0 (m, 2H), 4.9 (dd, 2H), 3.7 (s, 3H), 2.85 (m, H), 2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m, 2H), 1.1-0.7 (m, 2H)

Preparation of Intermediate 6

(19) ##STR00028##

(20) Intermediate 5 (214.0 g, 0.5 mol) and triphenylsulfonium bromide (172 g, 0.5 mol) were introduced to a H.sub.2O:dichloro-methane=1:1 solution (1 L), and reacted for 12 hours at room temperature (25° C.). After the reaction was finished, the organic layer was washed 3 times with H.sub.2O (1 L), and then diethyl ether was introduced thereto to form precipitates. The precipitates were filtered and then dried to obtain Intermediate 6 (compound B2) (314.0 g, 94%).

(21) 1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 6.2-6.0 (m, 2H), 4.9 (dd, 2H), 3.7 (s, 3H), 2.85 (m, H), 2.6-2.4 (m, 3H), 2.2-1.6 (m, 4H), 1.2 (m, 2H), 1.1-0.7 (m, 2H)

(22) Specific syntheses of Preparation Example 1 to Preparation Example 6 described in Table 1 are as follows.

Preparation Example 1

(23) ##STR00029##

(24) 1,2,4,5-Tetrazine (4.5 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane (1 L), and the result was reacted for 12 hours at room temperature. After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A1 (31.2 g, 95%).

(25) 1H-NMR (DMSO-D6): (ppm) δ=7.5 (d, H), 7.4-7.1 (m, 15H), 5.7 (s, H), 4.5 (m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.3-2.2 (m, H), 2.1-2.0 (m, H), 1.7-1.4 (m, 2H)

Preparation Example 2

(26) ##STR00030##

(27) 3-Methyl-1,2,4,5-tetrazine (5.2 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane (1 L), and the result was reacted for 12 hours at room temperature (25° C.). After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A2 (31.2 g, 93%).

(28) 1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 5.6 (s, H), 4.4 (m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.4-1.9 (m, 5H), 1.7-1.4 (m, 2H)

Preparation Example 3

(29) ##STR00031##

(30) 3-Phenyl-1,2,4,5-tetrazine (8.7 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane (1 L), and the result was reacted for 12 hours at room temperature (25° C.). After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A3 (34.4 g, 94%).

(31) 1H-NMR (DMSO-D6): (ppm) δ=7.9 (m, 2H), 7.5-7.1 (m, 18H), 5.6 (s, H), 4.4 (m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.2-1.9 (m, 2H), 1.7-1.4 (m, 2H)

Preparation Example 4

(32) ##STR00032##

(33) 3,6-Dimethyl-1,2,4,5-tetrazine (6.1 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane (1 L), and the result was reacted for 12 hours at room temperature (25° C.). After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A4 (31.8 g, 94%).

(34) 1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 15H), 4.4 (m, 2H), 3.7 (s, 3H), 3.2-2.8 (m, 3H), 2.5-1.9 (m, 8H), 1.7-1.4 (m, 2H)

Preparation Example 5

(35) ##STR00033##

(36) Methyl 4-(6-methyl-1,2,4,5-tetrazin-3-yl)benzoate (12.7 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloromethane (1 L), and the result was reacted for 12 hours at mom temperature (25° C.). After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A5 (36.2 g, 90%).

(37) 1H-NMR (DMSO-D6): (ppm) δ=7.4-7.1 (m, 19H), 4.4 (m, 2H), 3.9 (s, 3H), 3.7 (s, 3H), 3.2-2.8 (m, 3H), 2.5-1.9 (m, 5H), 1.7-1.4 (m, 2H)

Preparation Example 6

(38) ##STR00034##

(39) 3-Phenyl-6-(pyridin-2-yl)-1,2,4,5-tetrazine (12.9 g, 0.055 mol) and Intermediate 3 (30 g, 0.05 mol) were introduced to dichloro-methane (1 L), and the result was reacted for 12 hours at room temperature (25° C.). After the reaction was finished, diethyl ether was introduced thereto to form precipitates, and the precipitates were filtered and then dried to obtain A6 (36.9 g, 91%).

(40) 1H-NMR (DMSO-D6): (ppm) δ=8.5 (d, H), 7.9 (m, 2H), 7.4-7.1 (m, 21H), 4.4 (m, 2H), 3.7 (s, 3H), 3.1-2.8 (m, 3H), 2.2-1.9 (m, 2H), 1.7-1.4 (m, 2H)

Synthesis of Resin

Polymer R1

(41) ##STR00035##

(42) Composition A:B:C:D=50:20:20:10 Mw 6,000

(43) 2-methoxyethyl methacrylate (72 g, 0.5 mol), 2-methyl-2-adamantyl methacrylate (46.8 g, 0.2 mol), tert-butyl methacrylate (28.4 g, 0.2 mol), methacrylic acid (8.6 g, 0.1 mol) and tetrahydrofuran (THF) (150 g) were introduced to a flask, and stirred for 20 minutes under the nitrogen atmosphere.

(44) AIBN (11.5 g, 0.07 mol) was dissolved in THF (10 g) to prepare an initiator solution. After heating the reaction solution to 65° C., the initiator solution was introduced thereto, and the result was stirred for 18 hours. After the reaction was finished, the reaction solution was diluted with acetone, and precipitates were formed using an excess amount of hexane. The precipitates were filtered, and then dried for 18 hours in a 30° C. oven to collect a polymer. A weight average molecular weight of Polymer R1 measured using gel permeation chromatography (GPC) was 6,000 g/mol.

Polymer R2

(45) ##STR00036##

(46) Norbomene Monomer 1 (17.1 g, 0.06 mol), Norbomene Monomer 2 (11.5 g, 0.04 mol) and anisole (28.6 g) was introduced to a flask, and stirred for 20 minutes under the nitrogen atmosphere. A palladium catalyst was dissolved in anisole (1 g) under the argon atmosphere to prepare a palladium catalyst solution. After heating the reaction solution to 80° C., the palladium catalyst solution was introduced thereto, and the result was stirred for 18 hours. After the reaction was finished, the reaction solution was diluted with THF, and precipitates were formed using an excess amount of hexane. The precipitates were filtered, and then dried for 18 hours in a 30° C. oven to collect a polymer. A weight average molecular weight of Polymer R2 measured using gel permeation chromatography (GPC) was 5,000 g/mol.

Polymer R3

(47) ##STR00037##

(48) Composition A:B:C:D=50:20:20:10 Mw 6,500

(49) Polymerization was conducted in the same manner as with Polymer R1. A weight average molecular weight of Polymer R3 measured using gel permeation chromatography (GPC) was 6,500 g/mol.

Polymer R4

(50) ##STR00038##

(51) Composition A:B:C=60:30:10 Mw 5,500

(52) Polymerization was conducted in the same manner as with Polymer R2. A weight average molecular weight of Polymer R4 measured using gel permeation chromatography (GPC) was 5,500 g/mol.

(53) With each of the compounds and the polymers according to Preparation Examples 1 to 6, a photoresist composition comprising a content and a material of the following Table 2 was prepared.

(54) TABLE-US-00002 TABLE 2 Photoacid Dose Generator Quencher Compound mJ/c LWR Resin (Mass %) (Mass %) (Mass %) m.sup.2 Evaluation nm Evaluation Example 1 R1 R3 5.0 0.5 A1 0.5  75 Δ  7.7 ○ (60%) (40%) Example 2 R1 R3 5.0 0.5 A3 0.5  64 ○  8.3 ○ (60%) (40%) Example 3 R1 R4 5.0 0.5 A2 0.5  58 ○  8.4 ○ (60%) (40%) Example 4 R1 R4 5.0 0.5 A4 0.5  52 ○  8.0 ○ (60%) (40%) Example 5 R2 R3 2.0 0.5 A1 0.5  47 ⊚  8.1 ○ (60%) (40%) Example 6 R2 R4 2.0 0.5 A4 0.5  44 ⊚  6.5 ⊚ (60%) (40%) Comparative R1 R3 5.0 1.0 — 112 X 13.8 X Example 1 (60%) (40%) Comparative R1 R4 5.0 1.0 —  98 X 11.5 Δ Example 2 (60%) (40%) Comparative R2 R3 2.0 1.0 —  78 Δ  9.2 ○ Example 3 (60%) (40%) Comparative R2 R4 2.0 1.0 —  81 Δ  8.6 ○ Example 4 (60%) (40%) Comparative R1 R3 2.0 1.0 B1 0.5  73 Δ  8.2 ○ Example 5 (60%) (40%) Comparative R1 R3 2.0 1.0 B2 0.5  76 Δ 10.2 ○ Example 6 (60%) (40%) 0

(55) In Table 2, the mass % of the photoacid generator, the quencher and the compound are based on 4% of the total resin solid content.

(56) In Table 2, the photoresist evaluation condition was 120° C./60 s for SOB, 110° C./90 s for PEB, and 50 nm to 60 nm for the photoresist layer thickness.

(57) Optimum exposure (dose): based on 32 nm pitch, it was described as 50 mJ/cm.sup.2 or less (⊚), 70 mJ/cm.sup.2 or less (◯), 90 mJ/cm.sup.2 or less (Δ), and greater than 90 mJ/cm.sup.2 (X).

(58) LWR (line width roughness): it was described as 7 nm or less (⊚), 10 nm or less (◯), 13 nm or less (Δ), and greater than 13 nm (X).

(59) As seen from Table 2, it was identified that the compound according to one embodiment of the present application was capable of, by having the structure of Chemical Formula 1, further enhancing contrast of an exposed portion and an unexposed portion in the photoresist process afterward, and was also capable of improving line width roughness (LWR) without reducing sensitivity.

(60) According to Table 2, it was seen that Examples 1 to 6 were more useful for micropattern preparation compared to Comparative Examples 1 to 6 due to low dose. This is due to the fact that the photoresist composition used a photo-degradable base represented by Chemical Formula 1 having no sensitivity decrease caused by an increase in the base concentration, and as a result, a high resolution pattern was able to be obtained even with small exposure by having higher sensitivity compared to existing photoresist compositions.

(61) In addition, according to Table 2, it was seen that Examples 1 to 6 were more useful for micropattern preparation compared to Comparative Examples 1 to 6 due to low line width roughness (LWR). It was due to high compatibility of the photo-degradable base, and it was identified that the compound was uniformly distributed into the photoresist composition improving LWR.

(62) Furthermore, as seen in Examples 1 to 6, the compound according to one embodiment of the present application comprises a compound having SO.sub.3.sup.− and S.sup.+ ionic groups, and the photoresist layer was not able to be formed when the compound was not included since the function as a photoacid generator was not fulfilled.