Polymer composition and photoresist comprising same

Patent metadata

Field	Value
Publication number	US-10025181-B2
Application number	US-201213529541-A
Country	US
Kind code	B2
Filing date	Jun 21, 2012
Priority date	Jun 27, 2011
Publication date	Jul 17, 2018
Grant date	Jul 17, 2018

Abstract

A polymer comprises the polymerized product of monomers comprising an acid-deprotectable monomer, a base-soluble monomer, a lactone-containing monomer, and a photoacid-generating monomer; a chain transfer agent of the formula;

wherein Z is a y valent C 1-20 organic group, x is 0 or 1, R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl; and optionally, an initiator.

First claim

The invention claimed is:

1. A polymer, comprising the reversible addition-fragmentation chain-transfer polymerized product of monomers comprising:
an acid-deprotectable monomer having the formula (I), a base-soluble monomer having the formula (II), a lactone-containing monomer of the formula (III), and a photoacid-generating monomer of the formula (IV):

wherein each R a is independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl,
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 an adjacent 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,
L 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,
wherein when Q 2 is ester-containing, (i) the ester forms a connective link between Q 2 and the point of attachment to the double bond of the formula (IV), and (ii) A is non-ester-containing,
Z is an anionic moiety comprising sulfonate, an anion of a sulfonamide, or an anion of a sulfonimide,
G has formula (V):

wherein X is S or I,
each R c is halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group, wherein when X is S, one of the R c groups is optionally attached to one adjacent R c group by a single bond, and
z is 2 or 3, provided that when X is I, z is 2, or when X is S, z is 3;
a chain transfer agent of formula (IX);

wherein in formula (IX):
Z is a y valent C 1-20 organic group, wherein y is an integer of from 1 to 3, x is 0 or 1,
R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl; and
optionally, an initiator.

2. The polymer of claim 1 , wherein the acid deprotectable monomer of formula (I) 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.

3. The polymer of claim 1 , wherein the base-soluble monomer having the formula (II) comprises:

or a combination comprising at least one of the foregoing, and wherein the lactone-containing monomer of the 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.

4. The polymer of claim 1 , wherein A is a —[(C(R e ) 2 ) x1 C(═O)O] c —(C(R f ) 2 ) y1 (CF 2 ) z1 — group, or an o-, m- or p-substituted —C 6 R g 4 — group, where each R e , R f , and R g are each independently H, F, C 1-6 fluoroalkyl, or C 1-6 alkyl, c is 0 or 1, x1 is an integer of 1 to 10, y1 and z1 are independently integers of from 0 to 10, and the sum of y1+z1 is at least 1.

5. The polymer of claim 1 , wherein the photoacid-generating monomer of formula (IV) is:

or a combination comprising at least one of the foregoing, where each R a is independently H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl, k is an integer of 0 to 4, l is an integer of 0 to 3, and G is a cation of formula (V).

6. The polymer of claim 1 , wherein G has the formula (VI), (VII), or (VIII):

wherein X is I or S, R h , R i , R j , and R k are each independently hydroxy, nitrile, halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, or C 6-20 fluoroaryloxy, Ar 1 and Ar 2 are independently C 10-30 fused or singly bonded polycyclic aryl groups; R 1 is a lone pair of electrons where X is I, or a C 6-20 aryl group where X is S; p is an integer of 2 or 3, wherein when X is I, p is 2, and where X is S, p is 3, q and r are each independently an integer from 0 to 5, and s and t are each independently an integer from 0 to 4.

7. The polymer of claim 1 , wherein the photoacid-generating monomer of formula (IV) has the formula:

wherein R a is H, F, C 1-6 alkyl, or C 1-6 fluoroalkyl.

8. The polymer of claim 1 , wherein the chain transfer agent of formula (IX) has the structure of formula (X):

wherein R m is a C 1-10 alkyl, C 1-10 alkoxy, C 3-10 cycloalkyl, C 6-10 aryl, or C 7-10 aralkyl group, and R c is substituted or unsubstituted and is a C 1-10 alkyl or C 6-10 aryl group.

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

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

11. A method of forming a reversible addition-fragmentation chain-transfer polymerized product, comprising radically or thermally initiating the monomers of claim 1 in the presence of the chain transfer agent.

12. A method of forming an electronic device, comprising:
(a) applying a layer of the photoresist composition of claim 9 on a surface of a substrate;
(b) patternwise exposing the photoresist composition layer to activating radiation; and
(c) developing the exposed photoresist composition layer to provide a resist relief image.

Assignees

• Kramer John W
• Dow Global Technologies Llc

Inventors

• Kramer John W

Classifications

• G03F7/0045

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F20/10

  Esters · CPC title

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title

• G03F7/0046 Primary

  with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence) · CPC title