Patterning process and chemically amplified negative resist composition

1. A pattern forming process comprising the steps of:

applying a resist composition onto a substrate,

prebaking the composition to form a resist film,

exposing a selected region of the resist film to high-energy radiation,

baking, and

developing the exposed resist film in an organic solvent-based developer different from a solvent used to apply the resist composition onto the substrate to form a negative pattern wherein the unexposed region of resist film is dissolved away and the exposed region of resist film is not dissolved,

said resist composition comprising a polymer comprising recurring units having a carboxyl group which may or may not be substituted with an acid labile group and/or a hydroxyl group which may or may not be substituted with an acid labile group excluding α-trifluoromethylhydroxy, and an acid generator capable of generating fluorinated tetraphenylborate;

wherein the acid generator capable of generating fluorinated tetraphenylborate has the general formula (1)-1 or (1)-2:

wherein R 101a , R 101b , and R 101c are each independently a straight, branched or cyclic C 1 -C 12 alkyl, alkenyl, oxoalkyl or oxoalkenyl, C 6 -C 20 aryl, or C 7 -C 20 aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by alkyl, halo-alkyl, halogen, hydroxy, carboxyl, alkoxycarbonyl, alkoxy, acyl, acyloxy, nitro or amino, or which may contain ether, ester, lactone ring, amide, lactam or sultone ring, or R 101b and R 101c may form a ring, each of R 101b and R 101c is a C 1 -C 14 alkylene or arylene group when they form a ring, R 102 to R 105 are fluorine or trifluoromethyl, p, q, r and s are an integer of 1 to 5.

2. The process of claim 1 wherein the acid generator has the general formula (3)-1 or (3)-2:

wherein R 102 to R 105 , p, q, r and s are as defined above, R 8 to R 11 are each independently hydrogen, halogen, a straight, branched or cyclic C 1 -C 12 alkyl, alkenyl, oxoalkyl or oxoalkenyl, C 6 -C 20 aryl, or C 7 -C 20 aralkyl or aryloxoalkyl group, in which some or all hydrogen atoms may be substituted by halogen, hydroxy, carboxyl, alkoxycarbonyl, alkoxy, acyl, acyloxy, nitro or amino, Y 1 is a linking group selected from a single bond, methylene, ethylene, —O—, —S—, —NR 12 —, —C(═O)—, and —S(═O 2 )—, R 12 is hydrogen or C 1 -C 4 alkyl, Y 2 is a single bond, methylene or ethylene, e is an integer of 1 to 5, f and g each are an integer of 1 to 4, and h is an integer of 1 to 7.

3. A pattern forming process comprising the steps of:

applying a resist composition onto a substrate,

prebaking the composition to form a resist film,

exposing a selected region of the resist film to high-energy radiation,

baking, and

developing the exposed resist film in an organic solvent-based developer different from a solvent used to apply the resist composition onto the substrate to form a negative pattern wherein the unexposed region of resist film is dissolved away and the exposed region of resist film is not dissolved,

said resist composition comprising a polymer comprising recurring units having a carboxyl group which may or may not be substituted with an acid labile group and/or a hydroxyl group which may or may not be substituted with an acid labile group excluding α-trifluoromethylhydroxy, and an acid generator capable of generating fluorinated tetraphenylborate;

wherein the recurring units having a carboxyl group which may or may not be substituted with an acid labile group and/or a hydroxyl group which may or may not be substituted with an acid labile group excluding α-trifluoromethylhydroxy are recurring units (a1) or (a2) having the general formula (2):

wherein R 1 and R 3 are hydrogen or methyl,

R 2 and R 5 are hydrogen or an acid labile group,

X 1 is a single bond, phenylene, naphthylene or —C(═O)—O—R 6 —, R 6 is a straight, branched or cyclic C 1 -C 10 alkylene group which may have ether, ester, lactone ring or hydroxyl, or phenylene or naphthylene group,

X 2 is a single bond, phenylene or naphthylene group which may contain nitro, cyano or halogen, or —C(═O)—O—R 7 —, —C(═O)—NH—R 7 —, —O—R 7 —, or —S—R 7 —, R 7 is a straight, branched or cyclic C 1 -C 10 alkylene group which may have ether, ester, lactone ring or hydroxyl, or a phenylene or naphthylene group which may have a straight, branched or cyclic C 1 -C 6 alkyl, alkoxy, acyl, acyloxy, C 2 -C 6 alkenyl, alkoxycarbonyl, C 6 -C 10 aryl, nitro, cyano, or halogen,

R 4 is a single bond, a straight, branched or cyclic C 1 -C 16 di or tri-valent aliphatic hydrocarbon group, or a phenylene group which may have ether or ester, 0≦a1≦1.0, 0≦a2≦1.0, 0<a1+a2≦1.0, and m is 1 or 2.

4. The process of claim 1 wherein the developer comprises at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.

5. The process of claim 1 wherein the step of exposing the resist film to high-energy radiation includes lithography using i-line of wavelength 365 nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV of wavelength 13.5 nm or EB.

6. The process of claim 3 wherein the developer comprises at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.

7. The process of claim 3 wherein the step of exposing the resist film to high-energy radiation includes lithography using i-line of wavelength 365 nm, KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, EUV of wavelength 13.5 nm or EB.