# US 5,344,742 A · Benzyl-substituted photoactive compounds and photoresist compositions comprising same

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 5,344,742 A
- Document ID: US5344742A
- Status: Granted
- Kind: A
- Application number: 08/050,920
- Filed: 1993-04-21
- Granted: 1994-09-06
- Earliest claimed: 1993-04-21
- Assignees: Shipley Company, L.L.C.
- Inventors: Roger F. Sinta; George Barclay; Martha M. Rajaratnam
- Web page: https://patentgrep.com/patent/US5344742A

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- Y10S 430/122: Sulfur compound containing
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention comprises certain benzyl-substituted photoactive compounds and photoresist compositions comprising such photoactive compounds. The benzyl-substituted photoactive compounds of the invention are particularly suitable as the photoactive component in chemically amplified positive-acting and negative-acting compositions.

## Claims

### Claim 1

A photoresist comprising a resin binder and at least one photoactive compound of the following formula: ##STR5## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl;
each R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently selected from the group consisting of hydrogen, halo, hydroxy, cyano, alkanoyl, carboxyl, sulfonyl, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl, wherein at least one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is other than hydrogen.

### Claim 2 (depends on 1)

The photoresist of claim 1 wherein the composition is a positive-acting photoresist.

### Claim 3 (depends on 1)

The photoresist composition of claim 1 where the composition is a chemically amplified positive-acting composition.

### Claim 4 (depends on 3)

The photoresist composition of claim 3 where the resin binder comprises a polymer having acid labile groups.

### Claim 5 (depends on 4)

The photoresist composition of claim 4 where the polymer has pendant acid labile groups and contains phenolic and nonaromatic cyclic alcohol units.

### Claim 6 (depends on 1)

The photoresist composition of claim 1 where the composition is a negative-acting composition.

### Claim 7 (depends on 1)

The photoresist composition of claim 1 where the composition is a negative acting acid-hardening composition comprising an amine-based crosslinker and a phenolic resin.

### Claim 8 (depends on 1)

The photoresist composition of claim 1 where at least one of R.sup.1 and R.sup.2 is hydrogen.

### Claim 9 (depends on 1)

The photoresist composition of claim 1 where one or more of the groups R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is an electron-withdrawing group.

### Claim 10 (depends on 1)

The photoresist composition of claim 1 where one or more of the groups R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is fluoro.

### Claim 11 (depends on 1)

The photoresist composition of claim 1 where the photoactive compound is selected from the group consisting of pentaflurobenzyl-4-methylbenzene sulfonate, pentaflurobenzyl-4-fluorobenzene sulfonate, pentafluorobenzyl-4,5-dimethozybenzene sulfonate, pentafluorobenzyl-2,4,6-trimethylbenzene sulfonate, pentafluorobenzyl-2,3,6-trimethyl-4-methoxybenzene sulfonate and pentafluorobenzyl-ethane sulfonate.

### Claim 12 (depends on 1)

The photoresist composition of claim 1 further comprising a sensitizer compound.

### Claim 13 (depends on 12)

The photoresist composition of claim 12 where the sensitizer compound is a phenyl-based compound.

### Claim 14 (depends on 13)

The photoresist compositions of claim 13 where the phenyl-based compound is substituted with one or more electron-donating groups.

### Claim 15 (depends on 1)

An article of manufacture comprising a substrate having on at least one surface a coating layer of the photoresist of claim 1.

### Claim 16 (depends on 1)

The photoresist composition of claim 1 where the substituents R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen or an electron-withdrawing group, and at least one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is an electron-withdrawing group.

### Claim 17 (depends on 16)

The photoresist composition of claim 16 where the one or more electron-withdrawing R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 groups are halo.

### Claim 18 (depends on 16)

The photoresist composition of claim 16 where the one or more electron-withdrawing R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 groups are fluoro.

### Claim 19 (depends on 16)

The photoresist composition of claim 16 where the photoresist is a chemically-amplified resist.

### Claim 20

A photoresist composition comprising a resin binder and one or more photoactive compounds of of the following formula I: ##STR6## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
each R.sup.3 phenol ring substituent is independently selected from the group consisting of hydrogen, halo, hydroxy, cyano, alkanoyl, carboxyl, sulfonyl, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted aryl, and substituted and unsubstituted aralkyl; and n is an integer of from 1 to 6.

### Claim 21 (depends on 20)

The photoresist composition of claim 20 further comprising one or more photoactive compounds of the following formula II: ##STR7## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl;
each R.sup.3 phenyl ring substituent is independently selected from the group consisting of hydrogen, halo, hydroxy, cyano, alkanoyl, carboxyl, sulfonyl, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted aryl, and substituted and unsubstituted aralkyl; n is an integer of from 1 to 5; and m is an integer of from 2 to 6.

### Claim 22

A photoresist composition comprising a resin binder and one or more photoactive compounds of of the following formula II: ##STR8## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl;
each R.sup.3 phenyl ring substituent is independently selected from the group consisting of hydrogen, halo hydroxy, cyano, alkanoyl, carboxyl, sulfonyl, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted aryl, and substituted and unsubstituted aralkyl; n is an integer of from 1 to 5; and m is an integer of from 2 to 6.

### Claim 23

A photoresist comprising a resin binder and at least one photoactive compound of the following formula: ##STR9## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, and substituted and unsubstituted aryl;
each R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently selected from the group consisting of hydrogen, an electron-withdrawing group, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl.

### Claim 24 (depends on 23)

The photoresist composition of claim 23 where R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen and substituted and unsubstituted aryl.

### Claim 25 (depends on 23)

The photoresist composition of claim 23 where one or more of the groups R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is an electron withdrawing group.

### Claim 26 (depends on 25)

The photoresist of claim 25 where said one or more electron-withdrawing groups is halo, sulfonyl, cyano or acyl.

### Claim 27

A photoresist comprising a resin binder and at least one photoactive compound of the following formula: ##STR10## wherein R is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted aralkyl, and substituted and unsubstituted aryl;
R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halo, cyano, substituted and unsubstituted alkyl, substituted and unsubstituted alkoxy, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl;
each R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is independently selected from the group consisting of hydrogen, an electron-withdrawing group, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aralkyl and substituted and unsubstituted aryl, wherein at least one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is other than hydrogen.

### Claim 28 (depends on 27)

The photoresist composition of claim 27 where one or more of the groups R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is an electron withdrawing group selected from the group consisting of halo, sulfonyl, cyano or acyl.