Photosensitive resin composition and cured film

Abstract

A photosensitive resin composition including a polyamide-imide resin having a specific structure, a film comprising a cured product of the photosensitive resin composition, a method for preparing the film and a method for forming a resist pattern using the photosensitive resin composition.

Claims

1. A negative-type photosensitive resin composition comprising a polyamide-imide resin containing a repeating unit represented by Chemical Formula 11 and a repeating unit represented by Chemical Formula 12, and a photoacid generator: ##STR00010## wherein, in the Chemical Formulae 11 and 12, X is an aliphatic, alicyclic, or aromatic tetravalent organic group or a tetravalent organic group containing at least one heteroatom selected from the group consisting of N, O, and S, Y is an aliphatic, alicyclic, or aromatic divalent organic group, or a divalent organic group containing at least one heteroatom selected from the group consisting of N, O, and S, and n and m are each an integer of 1 or more, wherein Q.sub.1 and Q.sub.2 each include a divalent functional group represented by Chemical Formula 13, ##STR00011## wherein, in the Chemical Formula 13, L.sub.1 is a single bond, —O—, —CO—, —S—, —SO.sub.2—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, —CONH—, —COO—, —(CH.sub.2).sub.n1—, —O(CH.sub.2).sub.n2O—, —OCH.sub.2—C(CH.sub.3).sub.2—CH.sub.2O—, or —OCO(CH.sub.2).sub.n3OCO—, n1, n2, and n3 are each an integer of 1 to 10, R.sub.1 and R.sub.2 are the same as or different from each other, and are hydrogen, a halogen, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or a carboxyl group, p and q are an integer of 1 to 4, at least one of R.sub.1 and R.sub.2 is a hydroxyl group or a carboxyl group, and the remaining thereof is a functional group comprising a structure formed from a reaction of a hydroxyl group or a carboxyl group substituted in the aromatic ring with one of compounds represented by Chemical Formulae 15 to 16, ##STR00012##

2. The negative-type photosensitive resin composition according to claim 1, wherein X includes a tetravalent functional group of the following Chemical Formula 4: ##STR00013## wherein, in Chemical Formula 4, A is a single bond, —O—, —CO—, —S—, —SO.sub.2—, —C(CH.sub.3).sub.2—, —C(CF.sub.3).sub.2—, —CONH—, —COO—, —(CH.sub.2).sub.n1—, —O(CH.sub.2).sub.n2O—, or —OCO(CH.sub.2).sub.n3OCO—, and n1, n2, and n3 are each an integer of 1 to 10.

3. The negative-type photosensitive resin composition according to claim 1, further comprising a photo-curable polyfunctional acrylic compound.

4. A film comprising a cured product of the photosensitive resin composition of claim 1.

5. A method for preparing a film comprising a step of curing the photosensitive resin composition of claim 1 at a temperature of 250° C. or less.

6. A method for forming a resist pattern comprising the steps of: forming a resist film on a substrate using the photosensitive resin composition of claim 1; irradiating the resist film in a pattern using a high energy ray, and developing the resist film using an alkali developing solution.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The present invention will be described in more detail by way of the following examples. However, the following examples are provided only to illustrate the invention, and the scope of the invention is not limited by the following examples.

PREPARATION EXAMPLES

Preparation Example 1: Synthesis of Polyamide-Imide Resin (A1)

(2) 5 g (0.0156 mol) of 2,2′-bis(trifluoromethyl)benzidine; 1.904 g (0.0052 mol) of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; 3.226 g (0.0104 mol) of 4,4′-oxydiphthalic anhydride; 2.111 g (0.0104 mol) of isophthaloyl dichloride; and 30 g of N,N-dimethylacetamide were added to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the mixture was stirred in a nitrogen atmosphere for 3 hours to carry out a polymerization reaction.

(3) 2.34 g of acetic anhydride and 0.32 g of pyridine were added to the polyamic acid solution obtained by the polymerization reaction, and the mixture was stirred in an oil bath at 60° C. for 18 hours to carry out a chemical imidization reaction.

(4) After completion of the reaction, the solid content was precipitated with water and ethanol, and the precipitated solids were filtered and then dried under vacuum at 40° C. for 24 hours or more to obtain a polyamide-imide block copolymer having the following repeating units (weight average molecular weight: 120,000 g/mol).

Preparation Examples 2 to 4: Synthesis of Polyamide-Imide Resin (A2 to A4)

(5) A polyamide-imide block copolymer was obtained in the same manner as in Preparation Example 1, except that the proportions of the monomers used were changed as shown in Table 1 below.

Preparation Examples 5 to 8: Synthesis of Polyamide-Imide Resin (B1 to B4)

(6) A photo-curable group was introduced into the polyamide-imide resin obtained in Preparation Examples 1 to 4. Specifically, 4 g of the polyamide-imide resin of A1 to A4 was added to 16 g of N,N-dimethylacetamide in a 250 ml round flask, and the mixture was stirred to completely dissolve it. Then, 0.4 g (0.0026 mol) of 2-isocyanatoethyl methacrylate was added to the reaction solution and stirred at 50° C. for 4 hours to obtain a polyamide-imide resin of B1 to B4.

Comparative Preparation Example 1: Synthesis of Polyimide Resin (C1)

(7) 7.618 g (0.0208 mol) of 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; 9.24 g (0.0208 mol) of 4,4′-(hexafluoropropylidene)diphthalic anhydride; 0.131 g (0.0008 mol) of nadic anhydride, and 40 g of N,N-dimethylacetamide were added to a 250 mL round flask equipped with a Dean-Stark apparatus and a condenser, and the mixture was stirred in a nitrogen atmosphere for 4 hours to carry out a polymerization reaction.

(8) 2.34 g of acetic anhydride and 0.32 g of pyridine were added to the polyamic acid solution obtained by the polymerization reaction, and the mixture was stirred in an oil bath at 60° C. for 18 hours to carry out a chemical imidization reaction.

(9) After completion of the reaction, the solid content was precipitated with water and ethanol, and the precipitated solids were filtered and then dried under vacuum at 40° C. for 24 hours or more to obtain a polyimide resin having the following repeating units (weight average molecular weight: 55,000 g/mol).

Comparative Preparation Example 2: Synthesis of Polyimide Resin (C2)

(10) A polyimide resin was obtained in the same manner as in Preparation Example 5 by using the polyimide resin obtained in Comparative Preparation Example 1.

Comparative Preparation Example 3: Synthesis of Polyamide-Imide Resin (C3)

(11) A polyamide-imide resin was obtained in the same manner as in Preparation Example 1, except that the proportions of the monomers used were changed as shown in Table 1 below.

Comparative Preparation Example 4: Synthesis of Polyamide-Imide Resin (C4)

(12) A polyamide-imide resin was obtained in the same manner as in Preparation Example 5 by using the polyamide-imide resin obtained in Comparative Preparation Example 3.

(13) TABLE-US-00001 TABLE 1 Amine Amine Acid Acid Photo- Preparation component component dianhydride dianhydride End sealing polymerizable Example Resin {circle around (1)} {circle around (2)} {circle around (1)} {circle around (2)} material group 1 A1 TFMB BisAPAF ODPA IPDC — — (0.0156 mol) (0.0052 mol) (0.0104 mol) (0.0104 mol) 2 A2 TFMB BisAPAF ODPA IPDC — — (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0104 mol) 3 A3 TFMB HAB ODPA IPDC — — (0.0156 mol) (0.0052 mol) (0.0104 mol) (0.0104 mol) 4 A4 TFMB HAB ODPA IPDC — — (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0104 mol) 5 B1 TFMB BisAPAF ODPA IPDC — MOI (0.0156 mol) (0.0052 mol) (0.0104 mol) (0.0104 mol) (0.0021 mol) 6 B2 TFMB BisAPAF ODPA IPDC — MOI (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0021 mol) 7 B3 TFMB HAB ODPA IPDC — MOI (0.0156 mol) (0.0052 mol) (0.0104 mol) (0.0104 mol) (0.0021 mol) 8 B4 TFMB HAB ODPA IPDC — MOI (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0104 mol) (0.0021 mol) Comparative C1 — BisAPAF 6FDA — NDA — Preparation (0.0208 mol) (0.0208 mol) (0.0008 mol) Example 1 Comparative C2 — BisAPAF 6FDA — NDA MOI Preparation (0.0208 mol) (0.0208 mol) (0.0008 mol) (0.0021 mol) Example 2 Comparative C3 TFMB — ODPA IPDC — — Preparation (0.02068) (0.0104 mol) (0.0104 mol) Example 3 Comparative C4 TFMB — ODPA IPDC — MOI Preparation (0.02068) (0.0104 mol) (0.0104 mol) (0.0021 mol) Example 4 TFMB: 2,2′-bis(trifluoromethyl)benzidine BisAPAF: 2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane HAB: 3,3′-dihydroxy-4,4′-diaminobiphenyl ODPA: 4,4′-oxydiphthalic anhydride IPDC: isophthaloyl dichloride MOI: Karenz MOI ™ NDA: Nadic anhydride

Examples 1 to 4: Preparation of Positive-Type Photosensitive Resin Composition

(14) To 3 g of each polyamide-imide resin synthesized in Preparation Examples 1 to 4, 0.3 g of diazonaphthoquinone ester compound (TPD 520) and 4.5 g of solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Examples 5 to 8: Preparation of Positive-Type Photosensitive Resin Composition

(15) To 3 g of each polyamide-imide resin synthesized in Preparation Examples 1 to 4, 0.6 g of a diazonaphthoquinone ester compound (TPD 520) and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Comparative Examples 1 and 2: Preparation of Positive-Type Photosensitive Resin Composition

(16) To 3 g of each of the polyimide resin synthesized in Comparative Preparation Example 1 and the polyamide-imide resin synthesized in Comparative Preparation Example 3, 0.3 g of a diazonaphthoquinone ester compound (TPD 520) and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Comparative Examples 3 and 4: Preparation of Positive-Type Photosensitive Resin Composition

(17) To 3 g of each of the polyimide resin synthesized in Comparative Preparation Example 1 and the polyamide-imide resin synthesized in Comparative Preparation Example 3, 0.6 g of a diazonaphthoquinone ester compound (TPD 520) and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Examples 9 to 12: Preparation of Negative-Type Photosensitive Resin Composition

(18) To 3 g of each polyamide-imide resin synthesized in Preparation Examples 5 to 8, 0.03 g of an oxime ester-based photo-polymerization initiator OXE-01, 0.45 g of polyethylene glycol di(meth)acrylate, 0.3 g of propylene glycol diglycidyl ether, and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours, and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Examples 13 to 16: Preparation of Negative-Type Photosensitive Resin Composition

(19) To 3 g of each polyamide-imide resin synthesized in Preparation Examples 5 to 8, 0.03 g of an oxime ester-based photo-polymerization initiator OXE-01, 0.9 g of polyethylene glycol di(meth)acrylate, 0.3 g of propylene glycol diglycidyl ether, and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours, and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Comparative Examples 5 to 6: Preparation of Negative-Type Photosensitive Resin Composition

(20) To 3 g of each of the polyimide resin synthesized in Comparative Preparation Example 2 and the polyamide-imide resin synthesized in Comparative Preparation Example 4, 0.03 g of an oxime ester-based photo-polymerization initiator OXE-01, 0.45 g of polyethylene glycol di(meth)acrylate, 0.3 g of propylene glycol diglycidyl ether, and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours, and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Comparative Examples 7 and 8: Preparation of Negative-Type Photosensitive Resin Composition

(21) To 3 g of each of the polyimide resin synthesized in Comparative Preparation Example 2 and the polyamide-imide resin synthesized in Comparative Preparation Example 4, 0.03 g of an oxime ester-based photo-polymerization initiator OXE-01, 0.9 g of polyethylene glycol di(meth)acrylate, 0.3 g of propylene glycol diglycidyl ether, and 4.5 g of a solvent N-methyl-2-pyrrolidone (NMP) were added, and the mixture was stirred at room temperature for 4 hours, and then filtered through a filter having a pore size of 5 μm to prepare a photosensitive resin composition.

Test Example 1: Evaluation Method of Sensitivity

(22) The photosensitive resin composition prepared in the Examples and Comparative Examples was spin-coated onto a 4-inch silicon wafer, and then heated on a hot plate at 120° C. for 2 minutes, thereby forming a photosensitive resin film having a thickness of 15 μm. The silicon wafer in which the photosensitive resin film was formed was sequentially exposed with an i-line stepper (Nikon NSR 1505 i5A) up to 990 mJ/cm.sup.2 at an interval from 30 mJ/cm.sup.2 to 40 mJ/cm.sup.2. After developing in a 2.38 wt % tetramethylammonium aqueous solution (NEPES, CPD-18) at 23° C. for 90 seconds, it was washed with ultrapure water for 60 seconds and dried in air.

(23) At this time, in the case of the positive composition, the amount of exposure (also referred to as the minimum amount of exposure Eth) in which the exposed portion was not completely eluted and lost was taken as sensitivity.

(24) On the other hand, in the case of the negative composition, the amount of exposure in which the unexposed portion was completely eluted and lost was taken as sensitivity. The results are shown in Tables 2 and 3 below.

Test Example 2: Measurement Method of Alkali Development Speed

(25) The photosensitive resin compositions prepared in the examples and comparative examples were spin-coated onto a 4 inch silicon wafer, and then heated on a hot plate at 120° C. for 2 minutes, thereby forming a photosensitive resin film having a thickness of 15 μm. The number of revolutions of the spin coating was adjusted so that the thickness of the resin film became 15 μm. The resin film was developed in a 2.38 wt % tetramethylammonium aqueous solution (NEPES, CPD-18) at 23° C. for 1 minute, then washed with ultrapure water for 60 seconds and dried in air. The film thickness after drying was measured, and the decrease in film thickness per minute was calculated. These results are shown in Tables 2 and 3 below.

Test Example 3: Measurement Method of Physical Properties of Resin Cured Film

(26) The photosensitive resin compositions prepared in the examples and comparative examples were spin-coated onto a 4 inch silicon wafer, and then heated on a hot plate at 120° C. for 2 minutes, thereby forming a photosensitive resin film having a thickness of 15 μm. The number of revolutions of the spin coating was adjusted so that the thickness of the resin film became 15 μm. The silicon wafer coated with the resin film was heated at a temperature from 25° C. to 200° C. for 1 hour in a nitrogen atmosphere, and then the temperature was maintained at 200° C. for 1 hour to obtain a cured film. Then, the cured film was peeled off using a hydrofluoric acid aqueous solution, washed with water, and dried. The peeled film was cut to a size of 1 cm in width and 8 cm in length, and then tensile properties were measured. The results are shown in Tables 2 and 3 below.

(27) TABLE-US-00002 TABLE 2 Alkali development Tensile Elongation Sensitivity speed strength Modulus rate (mJ/cm.sup.2) (nm/min) (MPa) (GPa) (%) Example 1 470 4000 125 3.4 11.2 Example 2 430 6000 133 3.4 15.8 Example 3 630 1800 137 3.6 28.5 Example 4 590 2300 135 3.6 22.3 Example 5 430 4700 127 3.3 14.7 Example 6 390 7200 131 3.5 17.1 Example 7 590 2000 143 3.7 27.4 Example 8 510 2500 148 3.7 25.3 Comparative 270 >50000 122 3.2 3.8 Example 1 Comparative 870 200 143 3.7 29.8 Example 2 Comparative 190 >50000 130 3.3 6.1 Example 3 Comparative 830 200 141 3.8 32.1 Example 4

(28) TABLE-US-00003 TABLE 3 Alkali development Tensile Elongation Sensitivity speed strength Modulus rate (mJ/cm.sup.2) (nm/min) (MPa) (GPa) (%) Example 9 630 3500 126 3.4 13.5 Example 10 710 4700 129 3.4 18.2 Example 11 830 1500 127 3.6 28.1 Example 12 790 2000 135 3.6 23.8 Example 13 550 3300 129 3.3 13.7 Example 14 670 4200 125 3.5 18.0 Example 15 790 1900 140 3.7 25.1 Example 16 790 1500 139 3.7 26.6 Comparative 230 15000 128 3.2 4.7 Example 5 Comparative 870 100 141 3.7 30.5 Example 6 Comparative 150 17000 133 3.3 6.8 Example 7 Comparative 910 100 147 3.8 29.7 Example 8

(29) (Compound used)

(30) Diazonaphthoquinone compound: TPD 520/Miwon Specialty Chemical Co., Ltd.

(31) Photo-initiator compound: OXE-01/BASF

(32) Photo-curable acrylic compound: polyethylene glycol di(meth)acrylate/Sigma-Aldrich

(33) Curing agent: propylene glycol diglycidyl ether (trade name, Epolight-70P)/Kyoeisha Chemical Co., Ltd.

(34) Solvent: N-methyl-2-pyrrolidone/Sigma-Aldrich

(35) As shown in Tables 2 and 3, it was confirmed that when the compositions of the examples were used, high sensitivity and alkali development speed could be achieved together, and a high elongation rate could be secured while maintaining the tensile strength and modulus of the finally obtained cured film at a high level.