Chemically amplified photoresist composition and photoresist film using the same

Abstract

A chemically amplified photoresist composition comprising a triazole-based plasticizer and an alkali developable resin, which is capable of minimizing cracking of a photoresist obtained from the composition and improving adhesion to a substrate and sensitivity, and a photoresist film comprising a cured product of the chemically amplified photoresists composition.

Claims

1. A chemically amplified photoresist composition comprising: a triazole-based plasticizer represented by the following Chemical Formula 1; and an alkali developable resin, ##STR00020## wherein, in Chemical Formula 1, (i) A.sub.1 is a C.sub.1 to C.sub.5 alkylene group, and X.sub.1 is a carboxyl group, (ii) A.sub.1 is a polyalkyleneoxy group represented by the following Chemical Formula 2-1, and X.sub.1 is a C.sub.1 to C.sub.5 alkyl group, or (iii) A.sub.1 is a polyalkyleneoxy group represented by the following Chemical Formula 2-1, and X.sub.1 is a hydroxyl group, R.sub.1 is an organic functional group having a valence of 1 to 5, R.sub.2 is hydrogen, a C1 to C5 alkyl group, a hydroxy group, or a carboxyl group, and p is an integer of 1 to 5, ##STR00021## wherein, in Chemical Formula 2-1, R.sub.3 is a C1 to C3 alkylene group, and q is an integer of 1 to 50.

2. The chemically amplified photoresist composition according to claim 1, wherein, in Chemical Formula 1, R.sub.1 is a monovalent organic functional group represented by the following Chemical Formula 3 or a C1 to C20 alkyl group, and p is 1, ##STR00022## wherein, in Chemical Formula 3, X.sub.2 is a C1 to C5 alkyl group, a hydroxy group, or a carboxyl group, R.sub.4 and R.sub.5 are each independently a C1 to C5 alkylene group, and r is an integer of 1 to 10.

3. The chemically amplified photoresist composition according to claim 1, wherein, in Chemical Formula 1, R.sub.1 is a divalent organic functional group represented by the following Chemical Formula 4, and p is 2, ##STR00023## wherein, in Chemical Formula 4, Y.sub.1 and Y.sub.2 are each independently a direct bond, —O—, —CO—, —S—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, —CONH—, —COO—, —(CH.sub.2).sub.z—, —O(CH.sub.2).sub.zO—, or —COO—(CH.sub.2).sub.z—OCO—, z is an integer of 1 to 10, R.sub.6 and R.sub.7 are each independently a C1 to C5 alkylene group, and s is an integer of 1 to 50.

4. The chemically amplified photoresist composition according to claim 1, wherein the triazole-based plasticizer is a compound represented by the following Chemical Formula 1-1: ##STR00024## wherein, in Chemical Formula 1-1, A.sub.1 is a C1 to C5 alkylene group or a polyalkyleneoxy group represented by the following Chemical Formula 2-1, X.sub.1 is a C1 to C5 alkyl group, a hydroxy group, or a carboxyl group, X.sub.2 is a carboxyl group, and R.sub.4 and R.sub.5 are each independently a C1 to C3 alkylene group, and r is an integer of 3 to 7, ##STR00025## wherein, in Chemical Formula 2-1, R.sub.3 is a C1 to C3 alkylene group, and q is an integer of 1 to 50.

5. The chemically amplified photoresist composition according to claim 1, wherein the triazole-based plasticizer is a compound represented by the following Chemical Formula 1-2: ##STR00026## wherein, in Chemical Formula 1-2, A.sub.1 is a C1 to C5 alkylene group or a polyalkyleneoxy group represented by the following Chemical Formula 2-1, X.sub.1 is a C1 to C5 alkyl group, a hydroxy group, or a carboxyl group, X.sub.2 is a carboxyl group, Y.sub.1 and Y.sub.2 are each independently —COO—, R.sub.6 and R.sub.7 are each independently a C1 to C3 alkylene group, and s is an integer of 1 to 50, ##STR00027## wherein, in Chemical Formula 2-1, R.sub.3 is a C1 to C3 alkylene group, and q is an integer of 1 to 50.

6. The chemically amplified photoresist composition according to claim 1, wherein 0.1 to 10 parts by weight of the triazole-based plasticizer is included based on 100 parts by weight of the alkali developable resin.

7. The chemically amplified photoresist composition according to claim 1, wherein the alkali developable resin comprises at least two selected from the group of a novolac resin, a hydroxystyrene resin, and an acrylic resin.

8. The chemically amplified photoresist composition according to claim 7, wherein the acrylic resin is represented by the following Chemical Formula 5: ##STR00028## wherein, in Chemical Formula 5, a molar ratio of a:b:c:d is 3 to 6:1 to 5:0.5 to 2:1 to 5.

9. The chemically amplified photoresist composition according to claim 7, the alkali developable resin comprises the acrylic resin and at least one selected from the group of the novolac resin and the hydroxystyrene resin.

10. The chemically amplified photoresist composition according to claim 9, wherein the alkali developable resin comprises 50 to 90 parts by weight of an acrylic resin, and 10 to 50 parts by weight of a novolac resin or a hydroxystyrene resin, based on 100 parts by weight of the alkali developable resin.

11. The chemically amplified photoresist composition according to claim 1, wherein the alkali developable resin comprises 50 to 90 parts by weight of an acrylic resin, and 10 to 50 parts by weight of a novolac resin or a hydroxystyrene resin, based on 100 parts by weight of the alkali developable resin.

12. The chemically amplified photoresist composition according to claim 1, wherein the alkali developable resin has a weight average molecular weight (measured by GPC) of 10,000 g/mol to 300,000 g/mol.

13. A photoresist film comprising a cured product of the chemically amplified photoresist composition according to claim 1.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The invention will be described in more detail in the following examples. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples.

SYNTHESIS EXAMPLES: SYNTHESIS OF PLASTICIZER

(2) Synthesis Example 1

(3) ##STR00013##

(4) Compound A-1 was obtained by a click reaction between Compound a1 and Compound b1.

(5) Specifically, 1.0 equiv. of Compound a1 and 1.0 equiv. of Compound b1 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound A-1 (60% yield).

(6) Synthesis Example 2

(7) ##STR00014##

(8) Compound A-2 was obtained by a click reaction between Compound a2 and Compound b1.

(9) Specifically, 1.0 equiv. of Compound a2 and 1.0 equiv. of Compound b1 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound A-2 (60% yield).

(10) Synthesis Example 3

(11) ##STR00015##

(12) Compound A-3 was obtained by a click reaction between Compound a3 and Compound b1.

(13) Specifically, 1.0 equiv. of Compound a3 and 1.0 equiv. of Compound b1 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound A-3 (60% yield).

(14) Synthesis Example 4

(15) ##STR00016##

(16) Compound B-1 was obtained by a click reaction between Compound a′1 and Compound b2.

(17) Specifically, 1.0 equiv. of Compound a′1 and 1.0 equiv. of Compound b2 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound B-1 (60% yield).

(18) Synthesis Example 5

(19) ##STR00017##

(20) Compound B-2 was obtained by a click reaction between Compound a′2 and Compound b2.

(21) Specifically, 1.0 equiv. of Compound a′2 and 1.0 equiv. of Compound b2 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound B-2 (60% yield).

(22) Synthesis Example 6

(23) ##STR00018##

(24) Compound B-3 was obtained by a click reaction between Compound a3 and Compound b2.

(25) Specifically, 1.0 equiv. of Compound a3 and 1.0 equiv. of Compound b2 were dissolved in chloroform, and then a preliminarily prepared catalyst solution (CuBr/PMDETA=1/1 mol/mol, wherein PMDETA is N,N,N′,N″,N-pentamethyldiethylenetriamine) was added thereto in an amount of 0.05 equiv. based on CuBr at room temperature, followed by stirring for 12 hours. The reaction mixture was washed with water and HCl (1 N), and then an organic layer was concentrated and purified by column chromatography to obtain 21 g of Compound B-3 (60% yield).

EXAMPLES AND COMPARATIVE EXAMPLES: PREPARATION OF CHEMICALLY AMPLIFIED PHOTORESIST COMPOSITION

(26) Examples 1 to 8

(27) The components shown in Table 1 below were mixed to prepare chemically amplified photoresist compositions of Examples 1 to 8, respectively.

(28) Specifically, the photoresist composition was prepared by mixing 100 g of an alkali developable resin (R1-R3), 5 g of a plasticizer (A-1, A-2, A-3, B-1, B-2, B-3), and 10 g of an organic solvent (PGMEA).

(29) In the following Table 1, the components applied to the above examples are as follows.

(30) [R1] m,p-cresol novolac resin (Mw 12,000 g/mol, ADR 500 Å/s)

(31) [R2] Acetal protected polyhydroxystyrene (PHS) resin (Mw 15,300 g/mol, substitution rate 40%)

(32) [R3] Acrylic resin (Mw 50,000 g/mol)

(33) ##STR00019##

(34) [A-1] Plasticizer (Compound A-1 according to Synthesis Example 1)

(35) [A-2] Plasticizer (Compound A-2 according to Synthesis Example 2)

(36) [A-3] Plasticizer (Compound A-3 according to Synthesis Example 3)

(37) [B-1] Plasticizer (Compound B-1 according to Synthesis Example 4)

(38) [B-2] Plasticizer (Compound B-2 according to Synthesis Example 5)

(39) [A-3] Plasticizer (Compound B-3 according to Synthesis Example 6)

(40) Comparative Examples 1 to 3

(41) The components shown in Table 1 below were mixed to prepare chemically amplified photoresist compositions of Comparative Examples 1 to 3, respectively.

(42) Specifically, a photoresist composition was prepared by mixing 100 g of an alkali developable resin (R1-R3), 1 g of a corrosion inhibitor (benzotriazole, BTA), and 10 g of an organic solvent (PGMEA).

(43) TABLE-US-00001 TABLE 1 A- A- A- B- B- B- R1 R2 R3 1 2 3 1 2 3 BTA Ex. 1 30 — 70 5 — — — — — — Ex. 2 30 — 70 — 5 — — — — — Ex. 3 30 — 70 — — 5 — — — — Ex. 4 30 — 70 — — — 5 — — — Ex. 5 30 — 70 — — — — 5 — — Ex. 6 30 — 70 — — — — — 5 — Ex. 7 — 30 70 5 — — — — — — Ex. 8 — 30 70 — — — 5 — — — Comp. 30 — 70 — — — — — — 1 Ex. 1 Comp. — 30 70 — — — — — — 1 Ex. 2 Comp. — — 100 — — — — — — 1 Ex. 3

(44) The content of the components listed in the Table 1 is based on the solid content. The sum of the alkali developable resin is 100 parts by weight, and the photoacid generator and the corrosion inhibitor are based on 100 parts by weight of the alkali developable resin.

(45) Experimental Examples

(46) Physical properties of the photoresist composition were evaluated in the following manner by using the respective photoresist compositions according to the examples and comparative examples, and the results are shown in Table 2 below.

(47) (1) Sensitivity (Exposure Dose, mJ/cm.sup.2)

(48) The photoresist compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on a glass substrate and dried on a hot plate at 120° C. for 2 minutes. Then, it was exposed using a step mask, further dried on the hot plate at 100° C. for 2 minutes, and then developed in an aqueous solution of tetramethylammonium hydroxide (TMAH). The exposure dose of the step mask pattern and the photoresist (PR) pattern with the same CD (Critical Dimension) size was evaluated as sensitivity.

(49) (2) Occurrence of Footing at Lower Part of Pattern

(50) The photoresist compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on a glass substrate and dried on a hot plate at 120° C. for 2 minutes. Then, they were exposed using a step mask, further dried on the hot plate at 100° C. for 2 minutes, and then developed in an aqueous solution of tetramethylammonium hydroxide (TMAH). A reduced value of the hole diameter from the top to the bottom of the thick film resist pattern was evaluated as a footing length. The footing property of PR was evaluated based on the following criteria.

(51) ⊚: The footing length of more than 0 nm and below 200 nm

(52) ∘: The footing length of more than 200 nm and below 500 nm

(53) Δ: The footing length of more than 500 nm and below 1 μm

(54) X: The footing length of more than 1 μm

(55) (3) Adhesion

(56) The photoresist compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on a glass substrate and dried on a hot plate at 120° C. for 2 minutes. Then, they were exposed using a step mask, further dried on the hot plate at 100° C. for 2 minutes, and then developed in an aqueous solution of tetramethylammonium hydroxide (TMAH) to prepare a resist pattern. Herein, whether the resist pattern was scratched or not was observed and used as an index of the adhesion. The adhesion was evaluated based on the following criteria.

(57) ⊚: a 5B rating on ASTM D3359-97 Cross-Cut Tape test

(58) ∘: a 4B rating on ASTM D3359-97 Cross-Cut Tape test

(59) Δ: a 3B rating on ASTM D3359-97 Cross-Cut Tape test

(60) X: a 2B rating on ASTM D3359-97 Cross-Cut Tape test

(61) (4) Crack Resistance

(62) The photoresist compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were spin-coated on a glass substrate to a thickness of 6 μm and dried on a hot plate at 120° C. for 2 minutes. Then, they were exposed using a step mask, further dried on the hot plate at 100° C. for 2 minutes, and then developed in an aqueous solution of tetramethylammonium hydroxide (TMAH) to prepare a resist pattern. Herein, whether or not cracks were generated in the resist pattern was observed and used as an index of the crack resistance. The crack resistance was evaluated based on the following criteria.

(63) ⊚: When left in yellow room after development, cracks occurred after 3 weeks.

(64) ∘: When left in yellow room after development, cracks occurred after 2 weeks.

(65) Δ: When left in yellow room after development, cracks occurred after 1 week.

(66) X: When left in yellow room after development, cracks occurred after 3 days.

(67) TABLE-US-00002 TABLE 2 Sensitivity Crack (mJ/cm.sup.2) Footing Adhesion resistance Ex. 1 340 ◯ ◯ ◯ Ex. 2 280 ◯ ⊚ ◯ Ex. 3 210 ◯ ◯ ◯ Ex. 4 260 ◯ ⊚ ◯ Ex. 5 310 ⊚ ⊚ ⊚ Ex. 6 180 ⊚ ⊚ ⊚ Ex. 7 330 ⊚ ⊚ ◯ Ex. 8 310 ⊚ ⊚ ◯ Comp. Ex. 1 870 X ◯ X Comp. Ex. 2 790 Δ Δ X Comp. Ex. 3 990 Δ X X

(68) Referring to Table 2 above, the photoresist compositions according to the examples showed excellent sensitivity, developability, and adhesion at a low exposure dose, and were confirmed to exhibit excellent crack resistance even without a separate corrosion inhibitor.