# US 7,608,382 B2 · Method of controlling the differential dissolution rate of photoresist compositions, polycyclic olefin polymers and monomers used for making such polymers

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

- Number: US 7,608,382 B2
- Document ID: US7608382B2
- Status: Granted
- Kind: B2
- Application number: 11/981,617
- Filed: 2007-10-31
- Published: 2008-05-29
- Granted: 2009-10-27
- Earliest claimed: 2003-02-24
- Assignees: Promerus, LLC; International Business Machines Corporation
- Inventors: Larry F. Rhodes; Chun Chang; Leah J. Langsdorf; Howard A. Sidaway; Hiroshi Ito
- Web page: https://patentgrep.com/patent/US7608382B2

## CPC

- G03F 7/0395: {the macromolecular compound having a backbone with alicyclic moieties}
- G03F 7/30: Imagewise removal using liquid means
- Y10S 430/106: Binder containing
- Y10S 430/108: Polyolefin or halogen 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

A photoresist composition encompassing a polymer having at least one polycyclic olefin repeat unit having a desired exo mole percent is provided, where the repeat unit is derived from a polycyclic olefin monomer having the desired exo mole percent. Such polymers having such repeat units having a desired exo mole percent offer control of differential dissolution rate and hence provide enhanced imaging properties. Exemplary monomers having a desired exo mole percent are also provided.

## Claims

### Claim 1

A photoresist composition comprising a polymer having a desired dissolution rate, said polymer comprising at least one repeat unit derived from a polycyclic olefin monomer having a desired exo isomer mole percent, where the desired exo isomer mole percent is greater than or less than an expected exo isomer mole percent for the polycyclic olefin monomer from which the repeat unit is derived, such expected exo isomer mole percent based on the thermodynamic equilibrium of the isomers of such monomer that are obtained from a Diels-Alder reaction used to form such monomer,
wherein said polycyclic olefin monomer comprises at least one polycyclic olefin monomer represented by the following general formula:
wherein n is an integer from 0 to 5, and R′ is selected from hydrogen or an acid labile group, and
wherein said desired exo isomer mole percent of said polycyclic olefin monomer is selected from less than about 15 mole percent and greater than about 25 mole percent, based on total moles of exo isomer and endo isomer.

### Claim 2 (depends on 1)

The photoresist composition of claim 1, where the at least one repeat unit derived from a polycyclic olefin monomer has an exo isomer mole percent greater than the expected exo isomer mole percent for the at least one polycyclic olefin monomer.

### Claim 3 (depends on 1)

The photoresist composition of claim 1, where the at least one repeat unit derived from a polycyclic olefin monomer has an exo isomer mole percent less than the expected exo isomer mole percent for the at least one polycyclic olefin monomer.

### Claim 4

A photoresist composition comprising a polycyclic olefin based polymer having a desired dissolution rate, said polymer comprising at least one repeat unit derived from a polycyclic olefin monomer having a fluorinated carbinol pendent group as represented by Formula A:
where for Formula A m is an integer from 0 to 5; and Z represents —(CH2)p—, where p is equal to 1; and where one of R1 to R4 is a fluorinated carbinol pendent group represented by the following formula:
—(CH2)n—C(CF3)2—OR′
wherein n is an integer from 0 to 5, and R′ is selected from hydrogen or an acid labile group, and the remaining three of R1, R2, R3 and R4 are each hydrogen, and where such at least one type of repeat unit has an exo isomer mole percent for the fluorinated carbinol pendent group that is greater than or less than an expected exo isomer mole percent for the polycyclic olefin monomer, such expected exo isomer mole percent based on the thermodynamic equilibrium of the isomers of such polycyclic olefin monomer that are obtained from a Diels-Alder reaction used to form such monomer and
wherein said exo isomer mole percent for said fluorinated carbinol pendent group is selected from less than about 15 mole percent and greater than about 25 mole percent, based on total moles of exo isomer and endo isomer.

### Claim 5 (depends on 4)

The photoresist composition of claim 4, where R′ is a group selected from hydrogen, dimethyl ether, methyl ethyl ether, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), dimethylcyclopropylmethyl (Dmcp) and —C(O)OR″ where R″ is a t-butyl, trimethylsilyl, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, Dcpm, or Dmcp group, or combinations thereof.

### Claim 6 (depends on 5)

The photoresist composition of claim 5, where the exo isomer mole percent for the fluorinated carbinol pendent group containing repeat units is greater than the expected exo isomer mole percent for the polycyclic olefin monomer from which it is derived.

### Claim 7 (depends on 5)

The photoresist composition of claim 5, where the exo isomer mole percent for the fluorinated carbinol pendent group containing repeat units is less than the expected exo isomer mole percent for the polycyclic olefin monomer from which it is derived.

### Claim 8 (depends on 7)

The photoresist composition of claim 7, where the polycyclic olefin based polymer further comprises repeat units derived from polycyclic olefins monomers represented by one or more of Formulae A2, B and C:
where for Formula A2, n′ is an integer from 0 to 5 and Ra, Rb, and Rc, independently, represent linear or branched C1 to C20 hydrocarbyl groups or Ra and Rb taken together along with the common carbon to which they are attached represent a saturated cyclic group containing 4 to 12 carbon atoms; and where for Formula B, m is an integer from 0 to 5 and Z represents —(CH2)p— wherein p is equal to 1 or 2 and each of R5, R6, R7 and R8, independently, are H, a fluorine, a linear, branched or cyclic C1 to C30 alkyl, alkylol, aryl, aralkyl, alkaryl, alkenyl or alkynyl; with the proviso that at least one of R5, R6, R7 and R8 is a functional group that is capable of crosslinking and where for Formula C, m is an integer from 0 to 5 and Z represents —(CH2)p— wherein p is equal to 1 or 2 and each of R9, R10, R11 and R12 are each an independently selected neutral substituents selected from the group of substituents consisting of fluorines, —(CH2)n—C(O)OR21, —(CH2)n—(CM2)n—OR18, —(CM2)n—OC(O)R17, —(CH2)n—OC(O)OR17, —(CH2)n—C(O)R18, —(CH2)nC(R19)2CH(R19)(C(O)OR20), —(CH2)n—NH—(SO2)—CF3, —(CH2)nC(R19)2CH(C(O)OR20)2, —C(O)O—(CH2)n—OR18, —(CH2)n—O—(CH2)n—OR18 and —(CH2)n—(O—(CH2)n)n—C(CF3)2OR21 where each occurrence of n is independently an integer from 0 to 5, M can be hydrogen or fluorine, R19 can independently be hydrogen, fluorine, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 fluorinated alkyl cycloalkyl group, R18 can independently be hydrogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 fluorinated alkyl or cycloalkyl group, R20 is not readily cleavable by an acid from a photoacid generator and can independently be a linear or branched C1 to C10 alkyl group or cycloalkyl group, or a linear or branched C1 to C10 fluorinated alkyl or cycloalkyl group, R17 is not readily cleavable by a photoacid generator and can independently be linear or branched C1 to C10 alkyls or fluorinated alkyls, a monocyclic or polycyclic C4 to C20 cycloaliphatic or fluorinated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester (lactone), where each of the cyclic ether, ketone and ester can be fluorinated or not and R21 is defined as R17 plus hydrogen.

### Claim 9 (depends on 4)

The photoresist composition of claim 4, where the exo isomer mole percent for the fluorinated carbinol pendent group is less than the expected exo isomer mole percent for the polycyclic olefin monomer.

### Claim 10 (depends on 9)

The photoresist composition of claim 9, where the polycyclic olefin based polymer further comprises repeat units derived from polycyclic olefins monomers represented by one or more of Formulae A2, B and C:
where for Formula A2, n′ is an integer from 0 to 5 and Ra, Rb, and Rc, independently, represent linear or branched C1 to C20 hydrocarbyl groups or Ra and Rb taken together along with the common carbon to which they are attached represent a saturated cyclic group containing 4 to 12 carbon atoms; and where for Formula B, m is an integer from 0 to 5 and Z represents —(CH2)p— wherein p is equal to 1 or 2 and each of R5, R6, R7 and R8, independently, are H, a fluorine, a linear, branched or cyclic C1 to C30 alkyl, alkylol, aryl, aralkyl, alkaryl, alkenyl or alkynyl; with the proviso that at least one of R5, R6, R7 and R8 is a functional group that is capable of crosslinking and where for Formula C, m is an integer from 0 to 5 and Z represents —(CH2)p— wherein p is equal to 1 or 2 and each of R9, R10, R11 and R12, are each an independently selected neutral substituent selected from the group of substituents consisting of fluorines, —(CH2)n—C(O)OR21, —(CH2)n—(CM2)n—OR18, —(CM2)n—OC(O)R17, —(CH2)n—OC(O)OR17, —(CH2)n—C(O)R18, —(CH2)nC(R19)2CH(R19)(C(O)OR20), —(CH2)n—NH—(SO2)—CF3, —(CH2)nC(R19)2CH(C(O)OR20)2, —C(O)O—(CH2)n—OR18, —(CH2)n—O—(CH2)n—OR18 and —(CH2)n—(O—(CH2)n)n—C(CF3)2OR21 where each occurrence of n is independently an integer from 0 to 5, M can be hydrogen or fluorine, R19 can independently be hydrogen, fluorine, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 fluorinated alkyl cycloalkyl group, R18 can independently be hydrogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 fluorinated alkyl or cycloalkyl group, R20 not readily cleavable by an acid from a photoacid generator and can independently be a linear or branched C1 to C10 alkyl group or cycloalkyl group, or a linear or branched C1 to C10 fluorinated alkyl or cycloalkyl group, R17 is not readily cleavable by a photoacid generator and can independently be linear or branched C1 to C10 alkyls or fluorinated alkyls, a monocyclic or polycyclic C4 to C20 cycloaliphatic or fluorinated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester (lactone), where each of the cyclic ether, ketone and ester can be fluorinated or not and R21 is defined as R17 plus hydrogen.

### Claim 11

A photoresist composition comprising a polymer consisting essentially of norbomene-type repeat units where such repeat units are derived from one or more types of norbomene-type monomers each having a reactive pendent group, where at least one such norbomene-type monomer is represented by Formula A and other norbomene-type monomers are represented by Forumlae B and/or C:
where for Formula A, m is an integer from 0 to 5; and Z represents —(CH2)p—, where p is equal to 1; and where one of R1 to R4 is independently a fluorinated carbinol pendent group represented by the following formula:
—(CH2)n—C(CF3)2—OR′
wherein n is an integer from 0 to 5, and R′ is selected from hydrogen or an acid labile group, and the remaining three of R1, R2, R3 and R4 are each hydrogen, and where such at least one type of repeat unit has an exo isomer mole percent for the fluorinated carbinol pendent group that is greater than or less than an expected exo isomer mole percent for the polycyclic olefin monomer, such expected exo isomer mole percent based on the thermodynamic equilibrium of the isomers of such polycyclic olefin monomer that are obtained from a Diels-Alder reaction used to form such monomer, and wherein said exo isomer mole percent for the fluorinated carbinol pendent group is selected from less than about 15 mole percent and greater than about 25 mole percent, based on total moles of exo isomer and endo isomer;
where for Formula B, m is an integer from 0 to 5, and Z represents —(CH2)p— wherein p is equal to 1 or 2, and where each of R5, R6, R7 and R8, independently, are H, a halogen, a linear, branched or cyclic C1 to C30 alkyl, an alkylol, an aryl, an aralkyl, an alkaryl, an alkenyl or an alkynyl; with the proviso that at least one of R5, R6, R7 and R8 is a crosslinkable functional group represented by Formulae B1, B2, B3 or B4:
-A—O—[—(CR**2)q—O—]p—(CR**2)q—OH Formula B1
—R***-Q Formula B2
—(CH2)nC(O)OR# Formula B3
—(CH2)t—C(CF3)2—O—(CH2)t—CO—(OR##) Formula B4
where for Formula B 1, A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R** is independently selected from H, methyl and ethyl, q is independently an integer from 1 to 5 and p is an integer from 0 to 3;
where for Formula B2, R*** is a linear, branched or cyclic C1 to C30 alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group that is partially or completely halogenated, and Q is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy;
where for Formula B3, n is an integer from 1 to 5 and R# represents an acid labile group cleavable by a photoacid generator;
where for Formula B4, each occurrence of t is independently an integer from 1 to 6 and R## is a C1-C8 linear or branched alkyl moiety;
where for Formula C, m is an integer from 0 to 5, and Z represents —(CH2)p— wherein p is equal to 1 or 2, and where each of R9, R10, R11 and R12, is independently a neutral substituent selected from halogens, —(CH2)n—C(O)OR21, —(CH2)n—(CM2)n—OR18, —(CM2)n—OC(O)R17, —(CH2)n—OC(O)OR17, —(CH2)n—C(O)R18, —(CH2)nC(R19)2CH(R19)(C(O)OR20), —(CH2)n—NH—(SO2)—CF3, —(CH2)nC(R19)2CH(C(O)OR20)2, —C(O)O—(CH2)n—OR18 and —(CH2)n—O—(CH2)n—OR18, —(CH2)n—(O—(CH2)n)n—C(CF3)2OR21 where each occurrence of n is independently an integer from 0 to 5, M is hydrogen or a halogen, R18 and R19 are independently a hydrogen, a halogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R20 is not readily cleavable by a photoacid generator and is independently a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R17 is not readily cleavable by a photoacid generator and is a linear or branched C1 to C10 alkyl or halogenated alkyl, a monocyclic or polycyclic C4 to C20 cycloaliphatic or halogenated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester, where each of the cyclic ether, ketone and ester is halogenated or not and R21 is defined as R17 plus hydrogen.

### Claim 12 (depends on 1)

The photoresist composition of claim 1 wherein said desired exo isomer mole percent of said polycyclic olefin monomer is selected from the group consisting of 10 mole percent, 30 mole percent, 42 mole percent, 52 mole percent, 56 mole percent, and combinations thereof, based on in each case total moles of exo isomer and endo isomer.

### Claim 13 (depends on 1)

The photoresist composition of claim 1 wherein R′ is a group selected from hydrogen, dimethyl ether, methyl ethyl ether, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), dimethylcyclopropylmethyl (Dmcp) and —C(O)OR″ where R″ is a t-butyl, trimethylsilyl, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, Dcpm, or Dmcp group, or combinations thereof.

### Claim 14 (depends on 4)

The photoresist composition of claim 4 wherein said exo isomer mole percent for said fluorinated carbinol pendent group is selected from the group consisting of 10 mole percent, 30 mole percent, 42 mole percent, 52 mole percent, 56 mole percent, and combinations thereof, based on in each case total moles of exo isomer and endo isomer.

### Claim 15 (depends on 11)

The photoresist composition of claim 11 wherein said exo isomer mole percent for said fluorinated carbinol pendent group is selected from the group consisting of 10 mole percent, 30 mole percent, 42 mole percent, 52 mole percent, 56 mole percent, and combinations thereof, based on in each case total moles of exo isomer and endo isomer.

### Claim 16 (depends on 11)

The photoresist composition of claim 11 wherein R′ is a group selected from hydrogen, dimethyl ether, methyl ethyl ether, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3oxocyclohexanonyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), dimethylcyclopropylmethyl (Dmcp) and —C(O)OR″ where R″ is a t-butyl, trimethylsilyl, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, Dcpm, or Dmcp group, or combinations thereof.