Patterning process and resist composition

A process for forming a pattern comprising the steps of applying a resist composition onto a substrate to form a resist film, baking, exposure to radiation at a dose, post-exposure baking, and developing with an alkaline developer,

• said resist composition comprising a polymer comprising recurring units having an acid labile group, recurring units (e1), (e2) or (e3) having a sulfonium salt represented by the general formula (10) and recurring units (a1), (a2), (a3) or (a4) in the general formula (1) as a photobase generator capable of generating an amino group and substantially insoluble in an alkaline developer, a quencher having an amino group for neutralizing an acid released from the sulfonium salt-bearing units in the polymer and the acid released from the photoacid generator for inactivation, and an organic solvent, the sum of a total molar amount of amino groups in the quencher and a total molar amount of amino groups released from the photobase generator is greater than the sum of a total molar amount of the acid released from the sulfonium salt-bearing units and a total molar amount of the acid released from the photoacid generator,
• whereby a pattern of the resist film is formed including an unexposed region at a low exposure dose and an over-exposed region at an excess exposure dose which are not dissolved in the developer, and an exposed region at an intermediate exposure dose which is dissolved in the developer,
• wherein R120, R124, and R128 each are hydrogen or methyl, R121 is a single bond, phenylene group, —O—R— or —C(═O)—Y—R— wherein Y is an oxygen atom or NH, and R is a straight, branched or cyclic C1-C6 alkylene, phenylene, or C3-C10 alkenylene group, which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl radical, R122, R123, R125, R126, R127, R129, R130 and R131 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether radical, or a C6-C12 alkyl group which may contain a carbonyl, ester, or ether radical, or a C6-C12 aryl group, C7-C20 aralkyl group or thiophenyl group, Z is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R132—, or —C(═O)—Z1—R132— wherein Z1 is an oxygen atom or NH, and R132 is a straight, branched or cyclic C1-C6 alkylene group, phenylene group or alkenylene group, which may contain a carbonyl, ester, ether or hydroxy radical, M− is a non-nucleophilic counter ion, and the subscripts e1, e2, and e3 are numbers in the range:
• 0≦e1≦0.3, 0≦e2≦0.3, 0≦e3≦0.3, and 0<e1+e2+e3≦0.3,
• wherein R1, R7, R12, and R17 each are hydrogen or methyl,
• R2, R8, R13, and R18 each are a single bond, methylene, ethylene, phenylene, phenylmethylene, phenylethylene, phenylpropylene, or —C(═O)—O—R21— wherein R21 is a straight, branched or cyclic C1-C10 alkylene, C6-C10 arylene, or C7-C12 alkenylene group,
• R3, R9, and R14 each are hydrogen, a straight, branched or cyclic C1-C10 alkyl or C6-C10 aryl group, or may bond with R21 to form a ring with the nitrogen atom to which they are attached,
• R4, R5, and R6 each are hydrogen, a straight, branched or cyclic C1-C10 alkyl group, or a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, cyano or trifluoromethyl group, R4 and R5, R5 and R6, or R4 and R6 may bond together to form a ring with the carbon atom to which they are attached, with the proviso that not all R4, R5, and R6 are hydrogen, or not all R4, R5, and R6 are alkyl,
• R10 and R11 each are a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, cyano, trifluoromethyl or carbonyl group,
• R15 and R16 each are a straight or branched C1-C6 alkyl group, R15 and R16 may bond together to form a ring with the carbon and nitrogen atoms to which they are attached, the ring optionally containing a benzene ring, naphthalene ring, double bond or ether bond,
• R19 and R20 each are hydrogen, a straight, branched or cyclic C1-C8 alkyl group or a C6-C14 aryl group which may have a substituent group as described for R4, R5 and R6, at least one or both of R19 and R20 are aryl groups, or R19 and R20 may bond together to form a ring with the carbon atom to which they are attached,
• a1, a2, a3, a4 are numbers in the range:
• 0≦a1<1.0, 0≦a2<1.0, 0≦a3<1.0, 0≦a4<1.0, and 0<a1+a2+a3+a4<1.0.

A resist composition comprising

• a sulfonium or iodonium salt photoacid generator adapted to generate a sulfonic acid, imidic acid or methide acid which is fluorinated at α-position upon light exposure,
• a quencher having an amino group, and
• a polymer comprising at least recurring units having a photobase generator group of the general formula (1) and recurring units having an acid labile group,
• wherein the sum of a total molar amount of amino groups in the quencher and a total molar amount of amino groups released from the photobase generator-bearing units is greater than a total molar amount of the acid released from the photoacid generator,
• wherein R1, R7, R12, and R17 each are hydrogen or methyl,
• R2, R8, R13, and R18 each are a single bond, methylene, ethylene, phenylene, phenylmethylene, phenylethylene, phenylpropylene, or —C(═O)—O—R21— wherein R21 is a straight, branched or cyclic C1-C10 alkylene, C6-C10 arylene, or C2-C12 alkenylene group,
• R3, R9, and R14 each are hydrogen, a straight, branched or cyclic C1-C10 alkyl or C6-C10 aryl group, or may bond with R21 to form a ring with the nitrogen atom to which they are attached,
• R4, R5, and R6 each are hydrogen, a straight, branched or cyclic C1-C10 alkyl group, or a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, cyano or trifluoromethyl group, R4 and R5, R5 and R6, or R4 and R6 may bond together to form a ring with the carbon atom to which they are attached, with the proviso that not all R4, R5, and R6 are hydrogen, or not all R4, R5, and R6 are alkyl,
• R10 and R11 each are a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl, C1-C6 alkoxy, nitro, halogen, cyano, trifluoromethyl or carbonyl group,
• R15 and R16 each are a straight or branched C1-C6 alkyl group, R15 and R16 may bond together to form a ring with the carbon and nitrogen atoms to which they are attached, the ring optionally containing a benzene ring, naphthalene ring, double bond or ether bond,
• R19 and R20 each are hydrogen, a straight, branched or cyclic C1-C8 alkyl group or a C6-C14 aryl group which may have a substituent group as described for R4, R5 and R6, at least one or both of R19 and R20 are aryl groups, or R19 and R20 may bond together to form a ring with the carbon atom to which they are attached,
• a1, a2, a3, a4 are numbers in the range:
• 0≦a1<1.0, 0≦a2<1.0, 0≦a3<1.0, 0≦a4<1.0, and 0<a1+a2+a3+a4<1.0.

A resist composition comprising

• a polymer comprising recurring units having an acid labile group and recurring units having an adhesive group selected from the class consisting of hydroxyl-containing groups derived from the following monomers:
• a sulfonium or iodonium salt photoacid generator adapted to generate a sulfonic acid, imidic acid or methide acid which is fluorinated at α-position upon light exposure,
• a quencher having an amino group, and
• at least one photobase generator selected from compounds of the general formulae (2) to (9),
• wherein the sum of a total molar amount of amino groups in the quencher and a total molar amount of amino groups released from the photobase generator is greater than a total molar amount of the acid released from the photoacid generator,
• wherein R21, R22, R23, R26, R27, R28, R32, R33, R34, R35, R36, R37, R40, R41, R42, R46, R47, and R48 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, or a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl or alkoxy, nitro, halogen, cyano or trifluoromethyl group, at least one of R21 to R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 is an aryl group and at least one is hydrogen, or at least two of R21 to R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 may bond together to form a ring,
• R24, R25, R29, R31, R38, R39, R43, R45, R51, R52, R55, and R57 each are hydrogen or a straight, branched or cyclic C1-C12 alkyl group which may have a double bond, ether, amino, carbonyl, hydroxyl or ester group, R24 and R25, R29 and R31, R29 and R30, R31 and R30, R38 and R39, R43 and R44, R44 and R45, R43 and R45, R51 and R52, R55 and R56, R55 and R57, or R56 and R57 may bond together to form a ring,
• R30, R44, and R56 each are a single bond, straight, branched or cyclic C1-C20 alkylene group, alkyne group, C6-C20 arylene group, C2-C12 alkenylene group, or C2-C12 alkynylene group, which groups may have a double bond, ether, amino, carbonyl, hydroxyl or ester group,
• R49, R50, R53, R54, R58, and R59 each are a straight or branched C1-C6 alkyl group, R49 and R50, R53 and R54, or R58 and R59 may bond together to form a ring, the ring optionally containing a benzene ring, naphthalene ring, double bond or ether bond,
• R60 is a straight, branched or cyclic C1-C16 alkyl, C6-C20 aryl or C2-C20 alkenyl group,
• R61 is a C6-C20 aryl group,
• R62 is hydrogen, a straight, branched or cyclic C1-C16 alkyl group or C6-C20 aryl group,
• R63, R64, and R65 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, C6-C14 aryl group, C2-C10 alkenyl or alkoxycarbonyl group, or cyano group, the alkyl, aryl and alkenyl groups optionally having a straight, branched or cyclic C1-C6 alkyl or alkoxy, alkoxycarbonyl, nitro, halogen, cyano, trifluoromethyl, sulfide, amino or ether group,
• m, n and r each are 1 or 2.

A process for forming a pattern comprising the steps of:

• exposing a resist film through a mask having a one-pair line-and-space pattern, the pattern being a dark pattern in which a peripheral region outside the line pattern is light-shielded,
• PEB and development to form a two-pair line-and-space pattern as being split from the mask pattern,
• exchanging the mask with a second mask,
• exposing the peripheral region outside the line pattern through the second mask,
• PEB and development to dissolve away the peripheral region.

A process for forming a pattern comprising the steps of applying a resist composition onto a substrate to form a resist film, baking exposure to radiation at a dose, post-exposure baking, and developing with an alkaline developer,

• said resist composition comprising a polymer comprising recurring units having an acid labile group and recurring units having an adhesive group selected from the class consisting of hydroxyl-containing groups derived from monomers shown below and substantially insoluble in the alkaline developer, a photoacid generator capable of generating an acid, a photobase generator capable of generating an amino group selected from compounds having the general formulae (2) to (9), a quencher having an amino group for neutralizing the acid released from the photoacid generator for inactivation, and an organic solvent, the sum of a total molar amount of amino groups in the quencher and a total molar amount of amino groups released from the photobase generator is greater than a total molar amount of the acid released from the photoacid generator,
• whereby a pattern of the resist film is formed including an unexposed region at a low exposure dose and an over-exposed region at an excess exposure dose which are not dissolved in the developer, and an exposed region at an intermediate exposure dose which is dissolved in the developer,
• wherein R21, R22, R23, R26, R27, R28, R32, R33, R34, R35, R36, R37, R40, R41, R42, R46, R47, and R48 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, or a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl or alkoxy, nitro, halogen, cyano or trifluoromethyl group, at least one of R21 or R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 is an aryl group and at least one is hydrogen, or at least two of R21 to R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 may bond together to form a ring,
• R24, R25, R29, R31, R38, R39, R43, R45, R51, R52, R55, and R57 each are hydrogen or a straight, branched or cyclic C1-C12 alkyl group which may have a double bond, ether, amino, carbonyl, hydroxyl or ester group, R24 and R25, R29 and R31, R29 and R30, R31 and R30, R35 and R39, R43 and R44, R44 and R45, R43 and R45, R51 and R52, R55 and R56, R55 and R57, or R56 and R57 may bond together to form a ring,
• R30, R44, and R56 each are a single bond, straight, branched or cyclic C1-C20 alkylene group, alkyne group, C6-C20 arylene group, C2-C12 alkenylene group, or C2-C12 alkynylene group, which groups may have a double bond, ether, amino, carbonyl, hydroxyl or ester group,
• R49, R50, R53, R54, R58, and R59 each are a straight or branched C1-C6 alkyl group, R49 and R50, R53 and R54, or R58 and R59 may bond together to form a ring, the ring optionally containing a benzene ring, naphthalene ring, double bond or ether bond,
• R60 is a straight, branched or cyclic C1-C16 alkyl, C6-C20 aryl or C2-C20 alkenyl group,
• R61 is a C6-C20 aryl group,
• R62 is hydrogen, a straight, branched or cyclic C1-C16 alkyl group of C6-C20 aryl group,
• R63, R64, and R65 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, C6-C14 aryl group, C2-C10 alkenyl or alkoxycarbonyl group, or cyano group, the alkyl, aryl and alkenyl groups optionally having a straight, branched or cyclic C1-C6 alkyl or alkoxy, alkoxycarbonyl, nitro, halogen, cyano, trifluoromethyl, sulfide, amino or ether group,
• m, n and r each are 1 or 2.

A process for forming a pattern comprising the steps of applying a resist composition onto a substrate to form a resist film, baking, exposure to radiation at a dose, post-exposure baking, and developing with an alkaline developer,

• said resist composition comprising a polymer comprising recurring units having an acid labile group and recurring units (e1), (e2) or (e3) having a sulfonium salt represented by the general formula (10) and substantially insoluble in an alkaline developer, a photobase generator capable of generating an amino group selected from compounds having the general formulae (2) to (9), a quencher having an amino group for neutralizing an acid released from the sulfonium salt-bearing units in the polymer and the acid released from the photoacid generator for inactivation, and an organic solvent, the sum of a total molar amount of amino groups in the quencher and a total molar amount of amino groups released from the photobase generator is greater than the sum of a total molar amount of the acid released from the sulfonium salt-bearing units and a total molar amount of the acid released from the photoacid generator,
• whereby a pattern of the resist film is formed including an unexposed region at a low exposure dose and an over-exposed region at an excess exposure dose which are not dissolved in the developer, and an exposed region at an intermediate exposure dose which is dissolved in the developer,
• wherein R120, R124, and R128 each are hydrogen or methyl, R121 is a single bond, phenylene group, —O—R— or —C(═O)—Y—R— wherein Y is an oxygen atom or NH, and R is a straight, branched or cyclic C1-C6 alkylene, phenylene, or C3-C10 alkenylene group which may contain a carbonyl (—CO—), ester (—COO—), ether (—O—) or hydroxyl radical, R122, R123, R125, R126, R127, R129, R130, and R131 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether radical, or a C6-C12 aryl group, C7-C20 aralkyl group or thiophenyl group, Z is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R132—, or —C(═O)—Z1—R132— wherein Z1 is an oxygen atom or NH, and R132 is a straight, branched or cyclic C1-C6 alkylene group, phenylene group or alkenylene group, which may contain a carbonyl, ester, ether or hydroxy radical, M− is a non-nucleophilic counter ion, and the subscripts e1, e2 and e3 are numbers in the range:
• 0≦e1≦0.3, 0≦e2≦0.3, 0≦e3≦0.3, and 0<e1+e2+e3≦0.3,
• wherein R21, R22, R23, R26, R27, R28, R32, R33, R34, R35, R36, R37, R40, R41, R42, R46, R47, and R48 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, or a C6-C14 aryl group which may have a straight, branched or cyclic C1-C6 alkyl or alkoxy, nitro, halogen, cyano or trifluoromethyl group, at least one of R21 to R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 is an aryl group and at least one is hydrogen, or at least two of R21 to R23, R26 to R28, R32 to R34, R35 to R37, R40 to R42, and R46 to R48 may bond together to form a ring,
• R24, R25, R29, R31, R38, R39, R43, R45, R51, R52, R55, and R57 each are hydrogen or a straight, branched or cyclic C1-C12 alkyl group which may have a double bond, ether, amino, carbonyl, hydroxyl or ester group, R24 and R25, R29 and R31, R29 and R30, R31 and R30, R38 and R39, R43 and R44, R44 and R45, R43 and R45, R51 and R52, R55 and R56, R55 and R57, or R56 and R57 may bond together to form a ring,
• R30, R44, and R56 each are a single bond, straight, branched or cyclic C1-C20 alkylene group, alkyne group, C6-C20 arylene group, C2-C12 alkenylene group, or C2-C12 alkynylene group, which groups may have a double bond, ether, amino, carbonyl, hydroxyl or ester group,
• R49, R50, R53, R54, R58, and R59 each are a straight or branched C1-C6 alkyl group, R49 and R50, R53 and R54, or R58 and R59 may bond together to form a ring, the ring optionally containing a benzene ring, naphthalene ring, double bond or ether bond,
• R60 is a straight, branched or cyclic C1-C16 alkyl, C6-C20 aryl or C2-C20 alkenyl group,
• R61 is a C6-C20 aryl group,
• R62 is hydrogen, a straight, branched or cyclic C1-C16 alkyl group or C6-C20 aryl group,
• R63, R64, and R65 each are hydrogen, a straight, branched or cyclic C1-C6 alkyl group, C6-C14 aryl group, C2-C10 alkenyl or alkoxycarbonyl group, or cyano group, the alkyl, aryl and alkenyl groups optionally having a straight, branched or cyclic C1-C6 alkyl or alkoxy, alkoxycarbonyl, nitro, halogen, cyano, trifluoromethyl, sulfide, amino or ether group,
• m, n and r each are 1 or 2.