Onium salts and the use therof as latent acids

A process for the preparation of a photoresist by

• (1) applying to a substrate a composition as described above;
• (2) post apply baking the composition at temperatures between 60° C. and 160° C.;
• (3) image-wise irradiating with light of wavelengths between 150 nm and 1500 nm;
• (4) optionally post exposure baking the composition at temperatures between 60° C. and 160° C.;
• and
• (5) developing with a solvent or with an aqueous alkaline developer.

A compound of the formula Ia, Ib, Ic, IIa, IIb or IIc

• wherein
• R1 is C2-C12alkyl which is interrupted by one or more —O— or —(CO)—, or is C3-C30cycloalkyl, or is C3-C30cycloalkyl which is interrupted by one or more —O—, —S—, —NR6—, —(CO)—, —O(CO)— or —NR6(CO)—, or is C2-C12alkenyl, or is C4-C8cycloalkenyl, or is C6-C12bicycloalkenyl,
• all of which are unsubstituted or substituted by one or more C1-C5alkyl, C1-C5haloalkyl;
• C3-C30cycloalkyl which optionally is interrupted by one or more —O—, —S—, —NR6—, —(CO)—, —O(CO)— or —NR6(CO)—;
• or are substituted by halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR5, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• or R1 is benzyl;
• or R1 is phenyl, or is naphthyl, or is anthracyl or is phenanthryl, or is a heteroaryl radical,
• all of which are unsubstituted or substituted by one or more C1-C5alkyl;
• C2-C12alkyl which is interrupted by one or more —O—;
• or are substituted by C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• optionally the substituents —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR5, —SOR2, —SO2R2 and/or —OSO2R2 form 5- or 6-membered rings, via the radicals R2, R3, R4 R5 and/or R6, with further substituents on the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring or with one of the carbon atoms of the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
• wherein all radicals R1 optionally additionally are substituted by a group having a —O—C-bond or a —O—Si-bond which cleaves upon the action of an acid;
• R′1 is C1-C12alkylene;
• or is C2-C12alkylene which is interrupted by one or more C3-C30cycloalkylene, —O—, —S—, —NR6—, —(CO)—, —O(CO)—, —S(CO)—, —NR6(CO)—, —SO—, —SO2—, or —OSO2—;
• optionally the radicals C1-C12alkylene and C2-C12alkylene are substituted by one or more C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• or R′1 is C1-C30cycloalkylene, optionally interrupted by one or more —O—, —S—, —NR6—, —(CO)—, —O(CO)—, or —NR6(CO)—, and which is unsubstituted or substituted by one or more C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• or R1 is phenylene, naphthylene,
• diphenylene, oxydiphenylene or
• wherein these radicals are unsubstituted or substituted by one or more C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• A is a direct bond, —O—, —S—, —NR6—, —O(CO)—, —S(CO)—, —NR6(CO)—, —SO—, —SO2— or —OSO2—;
• B is a direct bond, C1-C12alkylene or C2-C12alkylene which is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, —S(CO)—, —NR6(CO)—, —SO—, —SO2— or —OSO2—, and optionally the radicals C1-C12alkylene and C2-C12alkylene are substituted by one or more C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• R2 is phenyl, or is C3-C30cycloalkyl, or is C1-C5alkyl;
• or is C2-C5alkyl which is interrupted by one or more —O—, or is C3-C30cycloalkyl which is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, or —NR6(CO)—;
• all of which are unsubstituted or substituted by phenyl, OH, C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, C1-C4alkoxy, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, —NR4R5, C1-C4alkylthio, C2-C4alkoxycarbonyl, C2-C4haloalkanoyl, halobenzoyl, C1-C4alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, C1-C4alkylsulfonyloxy, phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy and/or by C1-C4alkanoyl;
• or R2 is hydrogen;
• R3 is phenyl, or is C3-C30cycloalkyl, or is C1-C5alkyl;
• or is C2-C5alkyl which is interrupted by one or more —O—;
• or is C3-C30cycloalkyl which is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, or —NR6(CO)—;
• or is C2-C18alkanoyl, or is benzoyl, or is C1-C18alkylsulfonyl, all of which are unsubstituted or substituted by phenyl, OH, C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, C1-C4alkoxy, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, —NR4R5, C1-C4alkylthio, C2-C4alkoxycarbonyl, C2-C4haloalkanoyl, halobenzoyl, C1-C4alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, C1-C4alkylsulfonyloxy, phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy and/or by C1-C4alkanoyl;
• or R3 is hydrogen, phenylsulfonyl, (4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;
• R4, R5 and R6 independently of each other are phenyl, or are C3-C30cycloalkyl, or are C1-C5alkyl;
• or are C2-C5alkyl which is interrupted by one or more —O—;
• or are C3-C30cycloalkyl which is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, or —NR6(CO)—;
• or are C2-C18alkanoyl, or are benzoyl, or are C1-C18alkylsulfonyl,
• all of which are unsubstituted or substituted by phenyl, OH, C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, C1-C4alkoxy, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, C1-C4alkylthio, C2-C4alkoxycarbonyl, C2-C4haloalkanoyl, halobenzoyl, C1-C4alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, C1-C4alkylsulfonyloxy, phenylsulfonyloxy, (4-methylphenyl)sulfonyloxy and/or by C1-C4alkanoyl;
• or R4, R5 and R6 independently of each other are hydrogen, phenylsulfonyl, (4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;
• or R4 and R5, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring which optionally is interrupted by —O— or by —NR6—;
• Ar1 and Ar2 independently of each other are phenyl, or are naphthyl, or are anthracyl, or are phenanthryl, or are heteroaryl,
• all of which are unsubstituted or are substituted by one or more C1-C12alkyl, C1-C5haloalkyl, C3-C30cycloalkyl;
• C3-C30cycloalkyl which is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, or —NR6(CO)—;
• or are substituted by halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)R3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2, optionally the substituents —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2 form 5- or 6-membered rings, via the radicals R2, R3, R4, R5 and/or R6, with further substituents on the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring or with one of the carbon atoms of the phenyl, naphthyl, anthracyl, phenanthryl, or heteroaryl ring;
• or Ar1 and Ar2, if appropriate together with C1-C2alkylene, —O—, —S—, —NR6—, or —(CO)—, form a fused ring;
• wherein all radicals Ar1 and Ar2 optionally additionally are substituted by a group having a —O—C-bond or a —O—Si-bond which cleaves upon the action of an acid;
• Ar3, Ar4 and Ar5 have one of the meanings given for Ar1 and Ar2 or are
• or Ar3, Ar4 and Ar5 independently of each other are C1-C12alkyl;
• or are C2-C12alkyl which is interrupted by one or more —O—;
• or are C1-C5haloalkyl;
• or are C3-C30cycloalkyl which optionally is interrupted by one or more —O—, —S—, —NR6—, —O(CO)—, -or —NR6(CO)—;
• all of which are unsubstituted or substituted by one or more C1-C12alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR9, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• or Ar3 and Ar4, if appropriate together with C1-C2alkylene, —O—, —S—, —NR6—, —(CO)—, form a fused ring;
• or Ar3 and Ar4, if appropriate together with C1-C2alkylene, —O—, —S—, —NR6—, —(CO)—, form a 5-, 6-, or 7-membered ring;
• wherein all radicals Ar3, Ar4 and Ar5 optionally additionally are substituted by a group having a —O—C-bond or a —O—Si-bond which cleaves upon the action of an acid;
• Ar6 is phenyl, or is naphthyl, or is anthracyl, or is phenanthryl or is heteroaryl,
• all of which are unsubstituted or substituted by one or more C1-C5alkyl;
• C2-C12alkyl which is interrupted by one or more —O—;
• or by C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, phenyl, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R6, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2, optionally the substituents —(CO)R2, —(CO)OR3, (CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2 form 5- or 6-membered rings, via the radicals R2, R3, R4 R5 and/or R6, with further substituents on the phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl ring or with one of the carbon atoms of the phenyl, naphthyl, anthracyl, phenanthryl or heteroaryl ring;
• X is phenylene, or is naphthylene, or is
• or is diphenylene, or is oxydiphenylene or is
• all of which are unsubstituted or substituted by one or more C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• Y has one of the menaings given for X,
• or is C1-C12alkylene;
• or C2-C12alkylene which is interrupted by one or more C3-C30cycloalkylene, —O—, —S—, —NR6—, —(CO)—, —O(CO)—, —S(CO)—, —NR6(CO)—, —SO—, —SO2—, or —OSO2—;
• wherein the C1-C12alkylene and C2-C12alkylene are unsubstituted or substituted by one or more C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5, —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2;
• or Y is C3-C30cycloalkylene which optionally is interrupted by one or more —O—, —S—, —NR6—, —(CO)—, —O(CO)—, or —NR6(CO)—, and which is unsubstituted or substituted by one or more C1-C5alkyl, C1-C5haloalkyl, C3-C30cycloalkyl, halogen, —NO2, —CN, —Ar6, —(CO)R2, —(CO)OR3, —(CO)NR4R5;
• —O(CO)R2, —O(CO)OR3, —O(CO)NR4R5, —NR6(CO)R2, —NR6(CO)OR3, —OR3, —NR4R5, —SR6, —SOR2, —SO2R2 and/or —OSO2R2.