Chemically amplified positive resist composition and resist pattern forming process

Abstract

The invention relates to a chemically amplified positive resist composition and a resist pattern forming process. A positive resist composition comprising a polymer adapted to be decomposed under theaction of acid to increase its solubility in alkaline developer and a sulfonium compound of formula (A) has a high resolution. When the resist composition is processed by lithography, a pattern with minimal LER can be formed.

Description

[0001] Cross References to Related Applications

[0002] This non-provisional application claims priority under 35 U.S.C. §119(a) to Patent Application No. 2016-255018 filed in Japan on December 28, 2016, the entire contents of which are hereby incorporated herein by reference. technical field

[0003] The present invention relates to a chemically amplified positive resist composition and a resist pattern forming method using the same. Background technique

[0004] In order to meet recent demands for higher integration in integrated circuits, patterning is required to be finer in feature size. Acid-catalyzed chemically amplified resist compositions are most often used in forming resist patterns having a feature size of 0.2 μm or less. High energy rays such as UV, far UV or electron beam (EB) are used as exposure light sources for these resist compositions. In particular, when EB lithography is used as an ultrafine microfabrication technique, it is also indispensable in pr...

Examples

Embodiment

[0192] Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation "pbw" means parts by weight. THF is tetrahydrofuran. The copolymer composition is represented by molar ratio. Mw was determined by GPC against polystyrene standards. Analytical instruments are shown below.

[0193] IR: NICOLET 6700 manufactured by Thermo Fisher Scientific Inc.

[0194] 1 H-NMR: ECA-500 manufactured by JEOL Ltd.

[0195] 19 F-NMR: ECA-500 manufactured by JEOL Ltd.

[0196] LC-MS: ACQUITY UPLC H-Class System and ACQUITY QDa manufactured by Waters.

[0197] 1) Synthesis of sulfonium compounds

Synthetic example 1

[0199] Synthesis of 2-(diphenylsulfonium)phenoxide Q-1

Synthetic example 1-1

[0201] Synthesis of (2-tert-butoxyphenyl)diphenylsulfonium chloride (intermediate A)

[0202]

[0203] The Grignard reagent was prepared using standard methods in THF using 2.6 g of magnesium and 16 g of 2-tert-butoxychlorobenzene. 6.1 g of diphenylsulfoxide and 27 g of THF were added to the Grignard reagent. Then, 9.8 g of chlorotrimethylsilane was added dropwise to this solution at room temperature, and aged for 3 hours. After aging, a saturated aqueous ammonium chloride solution was added to quench the reaction, and 100 g of water was added to the reaction solution, washed with diisopropyl ether to obtain the target compound (2-tert-butoxyphenyl) di Aqueous solution of phenylsulfonium chloride (designated as Intermediate A). This compound was fed to the next step without isolation.

[0001] Cross References to Related Applications

[0002] This non-provisional application claims priority under 35 U.S.C. §119(a) to Patent Application No. 2016-255018 filed in Japan on December 28, 2016, the entire contents of which are hereby incorporated herein by reference. technical field

[0003] The present invention relates to a chemically amplified positive resist composition and a resist pattern forming method using the same. Background technique

[0004] In order to meet recent demands for higher integration in integrated circuits, patterning is required to be finer in feature size. Acid-catalyzed chemically amplified resist compositions are most often used in forming resist patterns having a feature size of 0.2 μm or less. High energy rays such as UV, far UV or electron beam (EB) are used as exposure light sources for these resist compositions. In particular, when EB lithography is used as an ultrafine microfabrication technique, it is also indispensable in pr...

Examples

Embodiment

[0192] Examples of the invention are given below by way of illustration and not by way of limitation. The abbreviation "pbw" means parts by weight. THF is tetrahydrofuran. The copolymer composition is represented by molar ratio. Mw was determined by GPC against polystyrene standards. Analytical instruments are shown below.

[0193] IR: NICOLET 6700 manufactured by Thermo Fisher Scientific Inc.

[0194] 1 H-NMR: ECA-500 manufactured by JEOL Ltd.

[0195] 19 F-NMR: ECA-500 manufactured by JEOL Ltd.

[0196] LC-MS: ACQUITY UPLC H-Class System and ACQUITY QDa manufactured by Waters.

[0197] 1) Synthesis of sulfonium compounds

Synthetic example 1

[0199] Synthesis of 2-(diphenylsulfonium)phenoxide Q-1

Synthetic example 1-1

[0201] Synthesis of (2-tert-butoxyphenyl)diphenylsulfonium chloride (intermediate A)

[0202]

[0203] The Grignard reagent was prepared using standard methods in THF using 2.6 g of magnesium and 16 g of 2-tert-butoxychlorobenzene. 6.1 g of diphenylsulfoxide and 27 g of THF were added to the Grignard reagent. Then, 9.8 g of chlorotrimethylsilane was added dropwise to this solution at room temperature, and aged for 3 hours. After aging, a saturated aqueous ammonium chloride solution was added to quench the reaction, and 100 g of water was added to the reaction solution, washed with diisopropyl ether to obtain the target compound (2-tert-butoxyphenyl) di Aqueous solution of phenylsulfonium chloride (designated as Intermediate A). This compound was fed to the next step without isolation.

Images