Monomer, polymer, positive resist composition, and patterning process

Patent metadata

Field	Value
Publication number	US-9829792-B2
Application number	US-201615204145-A
Country	US
Kind code	B2
Filing date	Jul 7, 2016
Priority date	Jul 9, 2015
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

A polymer comprising recurring units derived from a polymerizable monomer having two structures of hydroxyphenyl methacrylate having a hydroxy group substituted with an acid labile group is used as base resin in a positive resist composition, especially chemically amplified positive resist composition. The resist composition forms a resist film which is processed by lithography into a pattern of good profile having a high resolution, minimal edge roughness, and etch resistance.

First claim

The invention claimed is:

1. A polymer comprising recurring units (a) having the formula (A):

wherein R 1 is hydrogen or methyl, R 2 is hydrogen or a straight, branched or cyclic C 1 -C 15 monovalent hydrocarbon group in which any constituent —CH 2 — may be replaced by —O—, —C(═O)—, —C(═O)—O— or —O—C(═O)—, R 3 is each independently hydrogen, cyano, nitro, or a straight, branched or cyclic C 1 -C 6 monovalent hydrocarbon group in which any constituent —CH 2 — may be replaced by —O—, —C(═O)—, —C(═O)—O— or —O—C(═O)—, R 4 is each independently hydrogen or an acid labile group, X 1 is a single bond, a C 1 -C 12 linking group having an ester moiety, ether moiety or lactone ring, a phenylene group or naphthylene group, m is an integer of 1 to 4, and a is a positive number in the range: 0<a≦1.0.

2. The polymer of claim 1 wherein the acid labile group is t-butyl, t-pentyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, ethyladamantyl, t-butoxycarbonyl, t-pentyloxycarbonyl, or —CR 5 R 6 —O—R 7 , wherein R 5 and R 6 are each independently hydrogen or a straight or branched C 1 -C 4 alkyl group, R 1 is a straight, branched or cyclic C 1 -C 12 alkyl group or straight, branched or cyclic C 2 -C 12 alkenyl group.

3. The polymer of claim 1 , further comprising recurring units (b) containing an adhesive group selected from the group consisting of hydroxyl, carboxyl, lactone ring, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonic acid ester, cyano, amide, and —O—C(═O)-G- wherein G is sulfur or NH.

4. The polymer of claim 3 wherein the recurring unit (b) is a unit containing a phenolic hydroxyl group.

5. The polymer of claim 4 wherein the recurring unit containing a phenolic hydroxyl group is selected from recurring units (b1) to (b9) having the formulae (B1) to (B9):

wherein R 8 is hydrogen or methyl, R 9 is C 1 -C 4 alkyl, —C(═O)—R 9a , —O—C(═O)—R 9a , —C(O)—O—R 9a , cyano or nitro group, X 11 and X 22 are each independently a single bond or —C(═O)—O—R 10a —, X 33 and X 44 each are —C(═O)—O—R 10a —, R 9a is C 1 -C 4 alkyl or C 2 -C 4 alkenyl, R 10a is a single bond or a straight, branched or cyclic C 1 -C 10 alkylene group, Y 1 and Y 2 are each independently methylene or ethylene, Z is methylene, oxygen or sulfur, p is 1 or 2, b1 to b9 are numbers in the range: 0≦b1<1.0, 0≦b2<1.0, 0≦b3<1.0, 0≦b4<1.0, 0≦b5<1.0, 0≦b6<1.0, 0≦b7<1.0, 0≦b8<1.0, 0≦b9<1.0, and 0<b1+b2+b3+b4+b5+b6+b7+b8+b9<1.0.

6. The polymer of claim 1 , further comprising recurring units of at least one type selected from recurring units (c1) to (c5) having the formulae (C1) to (C5):

wherein R 11 to R 15 are each independently hydrogen, C 1 -C 30 alkyl, C 1 -C 30 alkyl in which one or more or all carbon-bonded hydrogen atoms are substituted by halogen, C 1 -C 5 alkoxy, C 1 -C 8 alkanoyl, C 2 -C 8 alkoxycarbonyl, C 6 -C 10 aryl, halogen, or 1,1,1,3,3,3-hexafluoro-2-propanol group,
Z is methylene, oxygen or sulfur, c1 to c5 are numbers in the range: 0≦c1 <1.0, 0≦c2<1.0, 0≦c3<1.0, 0≦c4<1.0, 0≦c5<1.0, and 0<c1+c2+c3+c4+c5<1.0.

7. The polymer of claim 1 , further comprising recurring units of at least one type selected from sulfonium salt-containing recurring units (d1) to (d3) having the formulae (D1) to (D3):

wherein R 112 is hydrogen or methyl, R 113 is a single bond, phenylene, —O—R 122 —, or —C(═O)—Z 22 —R 122 —, Z 22 is oxygen or NH, R 122 is a straight, branched or cyclic C 1 -C 6 alkylene, C 2 -C 6 alkenylene or phenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, L is a single bond or —Z 33 —C(═O)—O—, Z 33 is a straight, branched or cyclic C 1 -C 20 divalent hydrocarbon group which may be substituted with a heteroatom, Z 11 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R 123 —, or —C(═O)—Z 44 —R 123 —, Z 44 is oxygen or NH, R 123 is a straight, branched or cyclic C 1 -C 6 alkylene, C 2 -C 6 alkenylene or phenylene group, which may contain a carbonyl, ester, ether or hydroxyl moiety, M − is a non-nucleophilic counter ion, R 114 , R 115 , R 116 , R 117 , R 118 , R 119 , R 120 , and R 121 are each independently a straight, branched or cyclic C 1 -C 20 monovalent hydrocarbon group which may contain a heteroatom, d1, d2 and d3 are numbers in the range:
0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and
0<d1+d2+d3≦0.5.

8. A positive resist composition comprising the polymer of claim 1 , and an organic solvent.

9. The resist composition of claim 8 , further comprising a photoacid generator.

10. The resist composition of claim 8 , further comprising a dissolution regulator.

11. The resist composition of claim 8 , further comprising a basic compound and/or surfactant.

12. A pattern forming process comprising the steps of coating the positive resist composition of claim 8 onto a substrate, baking the coating to form a resist film, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.

Assignees

• Shinetsu Chemical Co

Inventors

• Hasegawa Koji
• Hatakeyama Jun
• Adachi Teppei

Classifications

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C07C2601/08

  the ring being saturated · CPC title

• C07C69/86

  with esterified hydroxyl groups · CPC title

• G03F7/168

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• C07C2603/74

  Adamantanes · CPC title