Silicon resist for photolithography at short exposure wavelengths and process for making photoresists

1. A chemically amplified photo-resist, comprising:

a polymer having a polar group, acid-labile radicals attached to said polar group to be eliminated for increasing solubility of the polymer in polar developers, and anchor groups for attaching to a linking group of a consolidating agent, the polymer including first repeating units having a structure according to Formula I

where

A is selected from the group consisting of a single bond, —O—, and —C(O)—O—;

B is selected from the group consisting of —(CR 5 R 6 ) n —, —(O—(CR 5 R 6 )) n —, a cyclo-alkylene group having from 5 to 20 carbon atoms, and an arylene group having from 6 to 22 carbon atoms;

R 1 is selected from the group consisting of —H, an alkyl group having from 1 to 10 carbon atoms, —CN, and —CF 3 ;

R 2 , R 3 , and R 4 are each selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 20 carbon atoms, an aryl group having from 6 to 22 carbon atoms, and a siloxane group;

R 5 and R 6 are selected from the group consisting of —H and an alkyl group having from 1 to 10 carbon atoms; and

n is an integer from 0 to 6; and

if A is a single bond, then B is a —CH 2 — group, R 1 is —H, R 2 , R 3 , and R 4 may not simultaneously be a CH 3 group, and A and B are chosen so that no Si—O—C group is formed;

second repeating units derived from unsaturated carboxylic acid anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride, cyclohexenedicarboxylic anhydride, norbornenedicarboxylic anhydride, and methacrylic anhydride;

third repeating units derived from the acidic methyl or ethyl monoesters of an unsaturated dicarboxylic acid selected from the group consisting of maleic acid, itaconic acid, cyclohexenedicarboxylic acid and norbornenedicarboxylic acid;

and fourth repeating units derived from an unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, cyclohexenecarboxylic acid, and norbornenecarboxylic acid, wherein said carboxyl groups of said fourth repeating units are esterified with an acid-labile radical;

a photoacid generator; and

a solvent.

2. The chemically amplified photoresist according to claim 1 , wherein at least one of R 2 , R 3 , and R 4 is an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 20 carbon atoms or an aryl group having from 6 to 22 carbon atoms carrying an acid-eliminable group attached by an ether linkage.

3. The chemically amplified photoresist according to claim 1 , wherein at least one of R 2 , R 3 , and R 4 is an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 20 carbon atoms or an aryl group having from 6 to 22 carbon atoms carrying an acid-eliminable group attached by an ester linkage.

4. The chemically amplified photoresist according to claim 1 , wherein at least one of R 2 , R 3 , and R 4 is an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 20 carbon atoms or an aryl group having from 6 to 22 carbon atoms carrying an acid-eliminable group attached by an acetal.

5. The chemically amplified photoresist according to claim 1 , wherein the siloxane group has a structure according to Formula II

in which

R 7 and R 8 are selected from the group consisting of —CH 3 and

p is an integer from 0 to 10; and

q is an integer from 0 to 5.

6. A process for producing structured resists, which comprises the steps of:

(a) applying a photoresist to a substrate, the photoresist including:

a polymer having a polar group, acid-labile radicals attached to the polar group to be eliminated for increasing solubility of the polymer in polar developers, and anchor groups for attaching to a linking group of a consolidating agent, the polymer including first repeating units having a structure according to Formula I

where

A is selected from the group consisting of a single bond, —O—, and —C(O)—O—;

B is selected from the group consisting of —(CR 5 R 6 ) n —, —(O—(CR 5 R 6 )) n —, a cyclo-alkylene group having from 5 to 20 carbon atoms, and an arylene group having from 6 to 22 carbon atoms;

R 1 is selected from the group consisting of —H, an alkyl group having from 1 to 10 carbon atoms, —CN, and —CF 3 ;

R 2 , R 3 , and R 4 are each selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 20 carbon atoms, an aryl group having from 6 to 22 carbon atoms, and a siloxane group;

R 5 and R 6 are selected from the group consisting of —H and an alkyl group having from 1 to 10 carbon atoms; and

n is an integer from 0 to 6; and

if A is a single bond, B is a —CH 2 — group and R 1 is —H, R 2 , R 3 , and R 4 may not simultaneously be a CH 3 group, and, A and B are chosen so that no Si—O—C group is formed,

second repeating units derived from unsaturated carboxylic acid anhydrides selected from the group consisting of maleic anhydride, itaconic anhydride, cyclohexenedicarboxylic anhydride, norbornenedicarboxylic anhydride, and methacrylic anhydride;

third repeating units derived from the acidic methyl or ethyl monoesters of an unsaturated dicarboxylic acid selected from the group consisting of maleic acid, itaconic acid, cyclohexenedicarboxylic acid, and norbornenedicarboxylic acid;

and fourth repeating units derived from an unsaturated carboxylic acid selected from the group consisting of crylic acid, methacrylic acid, cyclohexenecarboxylic acid, and norbornenecarboxylic acid, wherein said carboxyl groups of said fourth repeating units are esterified with an acid-labile radical;

a photoacid generator, and

a solvent;

(b) removing the solvent to give a photosensitive resist film;

(c) sectionally exposing sections of the resist film to liberate an acid from the photoacid generator in the exposed sections of the resist film;

(d) contrasting the exposed resist film by eliminating the acid-labile groups of the polymer with the acid in the exposed sections of the resist film;

(e) developing the exposed and contrasted resist film in a developer to remove the exposed sections of the resist film to give a structured resist;

(f) applying a consolidating agent to give a consolidated structured resist; and

(g) removing excess consolidating agent.

7. The process according to claim 6 , which further comprises the step of liberating the anchor groups after the developing step.

8. The process of claim 6 , wherein the exposing step (c) includes exposing with radiation having a wavelength less than 200 nm.

9. The process of claim 8 , wherein the consolidating agent in the applying step (f) is applied in solution.