# US 9,519,216 B2 · Positive photosensitive resin compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,519,216 B2 - Document ID: US9519216B2 - Status: Granted - Kind: B2 - Application number: 12/363,492 - Filed: 2009-01-30 - Published: 2009-08-06 - Granted: 2016-12-13 - Earliest claimed: 2008-02-04 - Assignees: Fujifilm Electronic Materials U.S.A., Inc. - Applicants: Ahmad A. Naiini; Il'ya Rushkin; William D. Weber; Donald W. Racicot - Inventors: Ahmad A. Naiini; Il'ya Rushkin; William D. Weber; Donald W. Racicot - Web page: https://patentgrep.com/patent/US9519216B2 ## CPC - G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition} - G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors} - G03F 7/40: Treatment after imagewise removal, e.g. baking - Y10T 428/265: 1 mil or less - 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) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract The present disclosure relates to compositions that include at least one polybenzoxazole precursor polymer, at least one photoacid generator, and at least one basic compound. Articles, films, and methods related to these compositions are also disclosed. ## Claims ### Claim 1 A composition, comprising: (a) at least one polybenzoxazole precursor polymer, the polybenzoxazole precursor polymer has Structure I, II, or II*: in which Ar1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof; Ar2 is a divalent aromatic or a divalent heterocyclic; Ar3 is a divalent aromatic group, a divalent heterocyclic group, or mixtures thereof; Ar4 is Ar1(OB)k3(OH)k4 or Ar2; x is an integer from about 4 to about 1000, y is an integer from 0 to about 500, provided that (x+y)≦1000; B is an acid sensitive group R1 or a moiety E-O—R2 containing an acid sensitive group R2, E is a divalent group which is not acid labile and makes an -E-OH moiety an aqueous base solubilizing group, E being selected from the group consisting of an aromatic group, and a heterocyclic group, provided that R1, in combination with the O atom attached to the Ar1 group, is not a carbonate group; k3 is a fractional number between 0.1 and 2, k4 is a fractional number between 0 and 1.9 provided that (k3+k4)=2; G is a substituted or unsubstituted monovalent organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, and G* is a substituted or unsubstituted divalent organic group having at least one carbonyl or sulfonyl group attached directly to the terminal N of the polymer; (b) at least one photoacid generator; and (c) at least a first basic compound selected from the group consisting of tertiary amines of Structure XIV: in which R30, R31, and R32 are independently selected from the group consisting of a C1-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least one of R30, R31, and R32 is selected from the group consisting of a C1-C30 substituted or unsubstituted cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, and not all of R30, R31, and R32 are a C6-C30 substituted or unsubstituted aryl; wherein the acid sensitive group R1 or R2 is a group capable of reacting with an acid to form an aqueous base solubilizing group and the first basic compound is from about 0.001 wt % to about 3 wt % of the composition. ### Claim 2 (depends on 1) The composition of claim 1, wherein the first basic compound is selected from the group consisting of tertiary amines of Structure XIV, in which R30, R31, and R32 are independently selected from the group consisting of a C1-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least one of R30, R31, and R32 is selected from the group consisting of a C1-C30 substituted or unsubstituted cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, and not all of R30, R31, and R32 are a C6-C30 substituted or unsubstituted aryl. ### Claim 3 (depends on 2) The composition of claim 2, wherein the first basic compound comprises a tertiary amine of Structure XIV, in which R30, R31, and R32 are independently selected from the group consisting of a C3-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C15 tertiary aminoalkyl, a C3-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least two of R30, R31, and R32 have at least two substituents on the carbon atom bonded to the tertiary nitrogen atom or at least one of R30, R31, and R32 has a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage. ### Claim 4 (depends on 3) The composition of claim 3, wherein the first basic compound comprises a tertiary amine of Structure XIV, in which R30, R31, and R32 are independently selected from the group consisting of a C3-C15 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C10 tertiary aminoalkyl, a C3-C15 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, and a C3-C15 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least two of R30, R31, and R32 have at least two substituents on the carbon atom bonded to the tertiary nitrogen atom or at least one of R30, R31, and R32 has a C3-C15 substituted or unsubstituted alkyl group containing at least one ether linkage. ### Claim 5 (depends on 2) The composition of claim 2, further comprising an adhesion promoter. ### Claim 6 (depends on 5) The composition of claim 5, wherein the adhesion promoter comprises a compound selected from the group consisting of vinylalkoxysilanes, methacryloxalkoxysilanes, mercaptoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes. ### Claim 7 (depends on 6) The composition of claim 6, wherein the adhesion promoter comprises a compound selected from the group consisting of epoxyalkoxysilanes and glycidoxyalkoxysilanes. ### Claim 8 (depends on 2) The composition of claim 2, further comprising a solvent. ### Claim 9 (depends on 2) The composition of claim 2, wherein the first basic compound is from about 0.01 wt % to about 1.5 wt % of the composition. ### Claim 10 (depends on 1) The composition of claim 1, further comprising an adhesion promoter. ### Claim 11 (depends on 10) The composition of claim 10, wherein the adhesion promoter comprises a compound selected from the group consisting of vinylalkoxysilanes, methacryloxalkoxysilanes, mercaptoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes. ### Claim 12 (depends on 11) The composition of claim 11, wherein the adhesion promoter comprises a compound selected from the group consisting of epoxyalkoxysilanes and glycidoxyalkoxysilanes. ### Claim 13 (depends on 1) The composition of claim 1, further comprising a solvent. ### Claim 14 (depends on 1) The composition of claim 1, wherein the first basic compound is from about 0.01 wt % to about 1.5 wt % of the composition. ### Claim 15 (depends on 1) The composition of claim 1, further comprising a second basic compound different from the first basic compound, the second basic compound being a tertiary amine of Structure XIV, in which R30, R31, and R32 are C6-C30 substituted or unsubstituted aryl. ### Claim 16 (depends on 15) The composition of claim 15, wherein R30, R31, and R32 in the second basic compound are substituted or unsubstituted phenyl. ### Claim 17 (depends on 1) A film comprising a composition of claim 1. ### Claim 18 (depends on 17) The film of claim 17, wherein the film has a thickness of at least about 5 μm. ### Claim 19 (depends on 17) The film of claim 17, wherein the film has a thickness of at least about 8 μm. ### Claim 20 (depends on 17) The film of claim 17, wherein the film has a thickness of at least about 10 μm. ### Claim 21 (depends on 17) An article, comprising: a substrate; and a film of claim 17 supported by the substrate. ### Claim 22 (depends on 21) The article of claim 21, wherein the substrate comprises a wafer. ### Claim 23 (depends on 22) The article of claim 22, wherein the wafer is a silicon wafer, a ceramic wafer, a glass wafer, a metal wafer, or a plastic wafer. ### Claim 24 (depends on 22) The article of claim 22, wherein the wafer is a copper coated wafer. ### Claim 25 (depends on 1) A method, comprising treating a composition of claim 1 on a substrate to form a relief pattern on the substrate. ### Claim 26 (depends on 25) The method of claim 25, further comprising applying the composition to the substrate prior to treating the composition. ### Claim 27 (depends on 26) The method of claim 26, wherein treating the composition comprises baking the composition to form a baked composition. ### Claim 28 (depends on 27) The method of claim 27, wherein treating the composition further comprises exposing the baked composition to actinic radiation to form an exposed composition. ### Claim 29 (depends on 28) The method of claim 28, wherein treating the composition further comprises developing the exposed composition with an aqueous developer, thereby forming an uncured relief image on the substrate. ### Claim 30 (depends on 29) The method of claim 29, wherein treating composition further comprises curing the relief image. ### Claim 31 (depends on 25) An article prepared by the method of claim 25. ### Claim 32 (depends on 1) The composition of claim 1, wherein R1, in combination with the O atom attached to the Ar1 group, is an acetal group, a ketal group, an ether group, or a silyl ether group. ### Claim 33 (depends on 1) The composition of claim 1, wherein R1 is ### Claim 34 (depends on 1) The composition of claim 1, wherein R1 is ### Claim 35 (depends on 1) The composition of claim 1, wherein R2, in combination with E-O, comprises an acetal group, a ketal group, an ether group, a silyl ether group, an acid sensitive methylene ester groups, an acid sensitive ester group, or a carbonate. ### Claim 36 (depends on 1) The composition of claim 1, wherein E-O—R2 is ### Claim 37 (depends on 1) The composition of claim 1, wherein E-O—R2 is ### Claim 38 A composition, comprising: (a) at least one polybenzoxazole precursor polymer, the polybenzoxazole precursor polymer has Structure I, II, or II*: in which Ar1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof; Ar2 is a divalent aromatic or a divalent heterocyclic; Ar3 is a divalent aromatic group, a divalent heterocyclic group, or mixtures thereof; Ar4 is Ar1(OB)k3(OH)k4 or Ar2; x is an integer from about 4 to about 1000, y is an integer from 0 to about 500, provided that (x+y)≦1000; B is an acid sensitive group R1 or a moiety E-O—R2 containing an acid sensitive group R2, E is a divalent group which is not acid labile and makes an -E-OH moiety an aqueous base solubilizing group, E being selected from the group consisting of provided that R1, in combination with the O atom attached to the Ar1 group, is not a carbonate group; k3 is a fractional number between 0.1 and 2, k4 is a fractional number between 0 and 1.9 provided that (k3+k4)=2; G is a substituted or unsubstituted monovalent organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, and G* is a substituted or unsubstituted divalent organic group having at least one carbonyl or sulfonyl group attached directly to the terminal N of the polymer; (b) at least one photoacid generator; and (c) at least a first basic compound selected from the group consisting of tertiary amines of Structure XIV: in which R30, R31, and R32 are independently selected from the group consisting of a C1-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least one of R30, R31, and R32 is selected from the group consisting of a C1-C30 substituted or unsubstituted cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, and not all of R30, R31, and R32 are a C6-C30 substituted or unsubstituted aryl; wherein the acid sensitive group R1 or R2 is a group capable of reacting with an acid to form an aqueous base solubilizing group and the first basic compound is from about 0.001 wt % to about 3 wt % of the composition. ### Claim 39 A composition, comprising: (a) at least one polybenzoxazole precursor polymer, the polybenzoxazole precursor polymer has Structure I, II, or II*: in which Ar1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof; Ar2 is a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that optionally contains silicon; Ar3 is a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, or mixtures thereof; Ar4 is Ar1(OB)k3(OH)k4 or Ar2; x is an integer from about 10 to about 1000, y is an integer from 0 to about 500, provided that (x+y)≦1000; B is an acid sensitive group R1 or a moiety E-O—R2 containing an acid sensitive group R2, E is a divalent group which is not acid labile and makes an -E-OH moiety an aqueous base solubilizing group, E being selected from the group consisting of an aromatic group, an aliphatic group, and a heterocyclic group, provided that R1, in combination with the O atom attached to the Ar1 group, is not a carbonate group; k3 is a fractional number between 0.1 and 2, k4 is a fractional number between 0 and 1.9 provided that (k3+k4)=2; G is a substituted or unsubstituted monovalent organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, and G* is a substituted or unsubstituted divalent organic group having at least one carbonyl or sulfonyl group attached directly to the terminal N of the polymer; (b) at least one photoacid generator; and (c) at least a first basic compound selected from the group consisting of tertiary amines of Structure XIV: in which R30, R31, and R32 are independently selected from the group consisting of a C1-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least one of R30, R31, and R32 is selected from the group consisting of a C1-C30 substituted or unsubstituted cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, and not all of R30, R31, and R32 are a C6-C30 substituted or unsubstituted aryl; wherein the acid sensitive group R1 or R2 is a group capable of reacting with an acid to form an aqueous base solubilizing group and the first basic compound is from about 0.001 wt % to about 3 wt % of the composition. ### Claim 40 A composition, comprising: (a) at least one polybenzoxazole precursor polymer, the polybenzoxazole precursor polymer has Structure I, II, or II*: in which Ar1 is a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof; Ar2 is a divalent aromatic, or a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that optionally contains silicon; Ar3 is a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, or mixtures thereof; Ar4 is Ar1(OB)k3(OH)k4 or Ar2; x is an integer from about 10 to about 1000, y is an integer from 0 to about 500, provided that (x+y)≦1000; B is an acid sensitive group R1 or a moiety E-O—R2 containing an acid sensitive group R2, E is a divalent group which is not acid labile and makes an -E-OH moiety an aqueous base solubilizing group, E being selected from the group consisting of provided that R1, in combination with the O atom attached to the Ar1 group, is not a carbonate group; k3 is a fractional number between 0.1 and 2, k4 is a fractional number between 0 and 1.9 provided that (k3+k4)=2; G is a substituted or unsubstituted monovalent organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, and G* is a substituted or unsubstituted divalent organic group having at least one carbonyl or sulfonyl group attached directly to the terminal N of the polymer; (b) at least one photoacid generator; and (c) at least a first basic compound selected from the group consisting of tertiary amines of Structure XIV: in which R30, R31, and R32 are independently selected from the group consisting of a C1-C30 substituted or unsubstituted linear, branched, or cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, in which at least one of R30, R31, and R32 is selected from the group consisting of a C1-C30 substituted or unsubstituted cyclic alkyl, a C3-C30 tertiary aminoalkyl, a C2-C30 substituted or unsubstituted linear, branched, or cyclic hydroxyalkyl, a C6-C30 substituted or unsubstituted aryl, and a C1-C30 substituted or unsubstituted alkyl group containing at least one ether linkage, and not all of R30, R31, and R32 are a C6-C30 substituted or unsubstituted aryl; wherein the acid sensitive group R1 or R2 is a group capable of reacting with an acid to form an aqueous base solubilizing group and the first basic compound is from about 0.001 wt % to about 3 wt % of the composition.