Granted Patent B2

US 9,052,589 · App. 14/012,174 · Granted Jun 9, 2015

Abstract

Claims (39)

1. A polymer comprising the polymerized product of:

an acid-deprotectable monomer, a base-soluble monomer, a lactone-containing monomer, a photoacid-generating monomer, or a combination thereof; with

a chain transfer agent of formula (I);

 wherein in the formula (I):

Z is a y valent C 1-20 organic group,

L is a heteroatom or a single bond,

A 1 and A 2 are each independently ester containing or non-ester containing and are fluorinated or non-fluorinated, and are independently C 1-40 alkylene, C 3-40 cycloalkylene, C 6-40 arylene, or C 7-40 aralkylene, and A 1 contains a nitrile, ester, or aryl substituent group alpha to the point of attachment with sulfur,

X 1 is a single bond, —O—, —S—, —C(═O)—O—, —O—C(═O)—, —O—C(═O)—O—, —C(═O)—NR—, —NR—C(═O)—, —NR—C(═O)—NR—, —S(═O) 2 —O—, —O—S(═O) 2 —O—, —NR—S(═O) 2 —, or —S(═O) 2 —NR, wherein R is H, C 1-10 alkyl, C 3-10 cycloalkyl or C 6-10 aryl,

Y − is an anionic group,

G + is a metallic or non-metallic cation, and

y is an integer of 1 to 6, and

wherein the group

 of the chain transfer agent is included in the polymerized product as an end group.

2. The polymer of claim 1 , wherein the chain-transfer agent of formula (I) has formula (I-a):

wherein in the formula (I-a), L, A 1 , A 2 and G + are as defined in formula (I), and Z 1 is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl.

3. The polymer of claim 2 , wherein the chain-transfer agent of formula (I) has formula (I-b) or (I-c):

wherein in the formulae (I-b) and (I-c), L, A 1 , and G + are as defined in formula (I), Z 1 is a substituted or unsubstituted C 1-10 alkyl, C 3-10 cycloalkyl, C 6-10 aryl, or C 7-10 aralkyl, and R 1 , R 2 and R 3 are independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl, or C 3-10 fluorocycloalkyl, p is an integer of from 0 to 10, q is an integer of from 1 to 10, and r is an integer of 0 to 4.

4. The polymer of claim 1 , wherein G + is a cation of the formula (II):

wherein in the formula (II), X a is I or S, each R 6 and R 7 is independently substituted or unsubstituted and is a lone pair of electrons, C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 7-20 aralkyl, or C 7-20 fluoroaralkyl, wherein when X a is S, R 6 and R 7 are separate or connected to each other by a single bond, and when X a is I, one of R 6 or R 7 is a lone pair of electrons, and Ar is a C 5-30 aromatic-containing group.

5. The polymer of claim 1 , wherein the acid-deprotectable monomer comprises a monomer of formula (III), the base-soluble monomer comprises a monomer of formula (IV), the lactone-containing monomer comprises a monomer of formula (V), and the photoacid-generating monomer comprises a monomer of formula (VI):

wherein in the formulae (III), (IV), (V), and (VI), each R a is independently H, F, CN, C 1-10 alkyl, or C 1-10 fluoroalkyl,

each R b is independently C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl, and each R b is separate or at least one R b is bonded to another R b to form a cyclic structure,

Q 1 is an ester-containing or non-ester containing C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl,

W is a base-reactive group comprising —C(═O)—OH; —C(CF 3 ) 2 OH; —NH—SO 2 —Y 1 where Y 1 is F or C 1-4 perfluoroalkyl; an aromatic —OH; or an adduct of any of the foregoing with a vinyl ether,

a is an integer of 1 to 3,

T is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group,

Q 2 is ester-containing or non-ester containing and fluorinated or non-fluorinated and is C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl group,

A is ester-containing or non ester-containing and fluorinated or non-fluorinated, and is C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl,

Y − is an anionic moiety comprising sulfonate, an anion of a sulfonamide, or an anion of a sulfonimide, and

G + is a cation of formula (II).

6. The polymer of claim 5 , wherein the acid deprotectable monomer of formula (III) comprises:

or a combination comprising at least one of the foregoing, wherein R a is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl; and/or wherein the base-soluble monomer having the formula (IV) comprises:

or a combination comprising at least one of the foregoing, wherein R a is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl; and/or wherein the lactone-containing monomer of the formula (V) comprises:

or a combination comprising at least one of the foregoing, wherein R a is H, F, CN, C 1-6 alkyl, or C 1-6 fluoroalkyl.

7. The polymer of claim 5 , wherein in formula (VI), A is a —[(C(R c ) 2 ) x C(═O)O] c —(C(R d ) 2 ) y (CF 2 ) z — group, or an o-, m- or p-substituted —C 6 R e 4 — group, where each R c , R d , and R e are each independently H, F, CN, C 1-6 fluoro alkyl, or C 1-6 alkyl, c is 0 or 1, x is an integer of 1 to 10, y and z are independently integers of from 0 to 10, and the sum of y+z is at least 1.

8. A photoresist composition comprising the polymer of claim 1 .

9. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of the photoresist composition of claim 8 over the one or more layers to be patterned.

10. A method of forming an electronic device, comprising: (a) applying a layer of the photoresist composition of claim 8 on a substrate; (b) pattern-wise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image.

11. The method of claim 10 , wherein the radiation is extreme-ultraviolet or e-beam radiation.

Assignments (6)