Positive resist composition and pattern forming process
A positive resist composition is provided comprising a base polymer comprising repeat units having a carboxy group whose hydrogen is substituted by a nitrobenzene ring-containing tertiary hydrocarbyl group. The resist composition has a high sensitivity and resolution and forms a pattern of good profile with reduced edge roughness and size variation after exposure.
1. A positive resist composition comprising a base polymer comprising repeat units represented by the formula (a):
wherein R A is hydrogen or methyl,
X 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing at least one moiety selected from an ester bond, ether bond and lactone ring, and
R is a tertiary hydrocarbyl group consisting of R 1 , R 2 and a nitrobenzene ring, which is represented by the formula (a1):
wherein R 1 and R 2 are each independently a C 1 -C 6 aliphatic hydrocarbyl group which may contain a heteroatom, R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached in which the nitrobenzene ring in the formula (a1) is separate from the ring formed of R 1 and R 2 , R 3 is hydrogen, halogen, a C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group or C 1 -C 6 acyloxy group, m is an integer of 1 to 4, n is 1 or 2, and the broken line designates a valence bond.
2. The resist composition of claim 1 wherein the repeat units have the formula (a):
wherein R A is hydrogen or methyl,
X 1 is a single bond, phenylene, naphthylene, or a C 1 -C 12 linking group containing at least one moiety selected from an ester bond, ether bond and lactone ring, and
R is a group having the formula (a1):
wherein R 1 and R 2 are each independently a C 1 -C 6 aliphatic hydrocarbyl group which may contain a heteroatom, R 1 and R 2 may bond together to form a ring with the carbon atom to which they are attached, R 3 is hydrogen, halogen, a C 1 -C 6 alkyl group, C 1 -C 6 alkoxy group or C 1 -C 6 acyloxy group, m is an integer of 1 to 4, n is 1 or 2, and the broken line designates a valence bond.
3. The resist composition of claim 1 wherein the base polymer further comprises repeat units of at least one type selected from repeat units having a carboxy group whose hydrogen is substituted by an acid labile group other than the nitrobenzene ring-containing tertiary hydrocarbyl group, and repeat units having a phenolic hydroxy group whose hydrogen is substituted by an acid labile group.
4. The resist composition of claim 3 wherein the repeat units having a carboxy group whose hydrogen is substituted by an acid labile group other than the nitrobenzene ring-containing tertiary hydrocarbyl group have the formula (b1), and the repeat units having a phenolic hydroxy group whose hydrogen is substituted by an acid labile group have the formula (b2):
wherein R A is each independently hydrogen or methyl,
Y 1 is a single bond, phenylene group, naphthylene group, or a C 1 -C 12 linking group containing at least one moiety selected from an ester bond, ether bond and lactone ring,
Y 2 is a single bond, ester bond or amide bond,
Y 3 is a single bond, ether bond or ester bond,
R 11 is an acid labile group other than the nitrobenzene ring-containing tertiary hydrocarbyl group,
R 12 is an acid labile group,
R 13 is fluorine, trifluoromethyl, cyano or a C 1 -C 6 saturated hydrocarbyl group,
R 14 is a single bond or a C 1 -C 6 alkanediyl group in which some constituent —CH 2 — may be replaced by an ether bond or ester bond,
a is 1 or 2, b is an integer of 0 to 4, and the sum of a+b is from 1 to 5.
5. The resist composition of claim 1 wherein the base polymer further comprises repeat units having an adhesive group which is selected from among hydroxy, carboxy, lactone ring, carbonate bond, thiocarbonate bond, carbonyl, cyclic acetal, ether bond, ester bond, sulfonic ester bond, cyano, amide bond, —O—C(═O)—S—, and —O—C(═O)—NH—.
6. The resist composition of claim 1 wherein the base polymer further comprises repeat units of at least one type selected from repeat units having the formulae (d1) to (d3):
wherein R A is each independently hydrogen or methyl,
Z 1 is a single bond, a C 1 -C 6 aliphatic hydrocarbylene group, phenylene, naphthylene, or a C 7 -C 18 group obtained by combining the foregoing, or —O—Z 11 —, —C(═O)—O—Z 11 — or —C(═O)—NH—Z 11 —, Z 11 is a C 1 -C 6 aliphatic hydrocarbylene group, phenylene, naphthylene, or a C 7 -C 18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety,
Z 2 is a single bond or ester bond,
Z 3 is a single bond, —Z 31 —C(═O)—O—, —Z 31 —O— or —Z 31 —O—C(═O)—, 731 is a C 1 -C 12 aliphatic hydrocarbylene group, phenylene group, or a C 7 -C 18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond, iodine or bromine,
Z 4 is a methylene, 2,2,2-trifluoro-1,1-ethanediyl or carbonyl group,
Z 5 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, —O—Z 51 —, —C(—O)—O—Z 51 — or —C(═O)—NH—Z 51 —, Z 51 is a C 1 -C 6 aliphatic hydrocarbylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxy moiety,
R 21 to R 28 are each independently halogen or a C 1 -C 20 hydrocarbyl group which may contain a heteroatom, R 23 and R 24 , or R 26 and R 27 may bond together to form a ring with the sulfur atom to which they are attached, and
M is a non-nucleophilic counter ion.
7. The resist composition of claim 1 , further comprising an acid generator.
8. The resist composition of claim 1 , further comprising an organic solvent.
9. The resist composition of claim 1 , further comprising a quencher.
10. The resist composition of claim 1 , further comprising a surfactant.
11. A pattern forming process comprising the steps of applying the positive resist composition of claim 1 onto a substrate to form a resist film thereon, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.
12. The pattern forming process of claim 11 wherein the high-energy radiation is i-line, ArF excimer laser, KrF excimer laser, EB, or EUV of wavelength 3 to 15 nm.