Resist compositions and patterning process

A chemical amplification type resist composition contains as a photoacid generator a sulfonyldiazomethane compound of the formula (1): ##STR1## wherein R.sup.1 is C.sub.1-10 alkyl or C.sub.6-14 aryl, R.sup.2 is C.sub.1-6 alkyl, G is SO.sub.2 or CO, R.sup.3 is C.sub.1-10 alkyl or C.sub.6-14 aryl, p is an integer of 0 to 4, q is an integer of 1 to 5, 1.ltoreq.p+q.ltoreq.5, n is 1 or 2, m is 0 or 1, and n+m=2. The composition is suited for microfabrication, especially by deep UV lithography because of many advantages including improved resolution, minimized line width variation or shape degradation even on long-term PED, minimized debris after coating, development and peeling, and improved pattern profile after development.

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What is claimed is:

1. A resist composition comprising as a photoacid generator a sulfonyldiazomethane compound of the following general formula (1): ##STR45##

wherein R.sup.1 is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or substituted or unsubstituted aryl group of 6 to 14 carbon atoms, R.sup.2 which may be the same or different is a straight,branched or cyclic alkyl group of 1 to 6 carbon atoms, G is SO.sub.2 or CO, R.sup.3 is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or substituted or unsubstituted aryl group of 6 to 14 carbon atoms, pis an integer of 0 to 4, q is an integer of 1 to 5, p+q is from 1 to 5, n is equal to 1 or 2, m is equal to 0 or 1, and n+m is equal to 2.

2. A resist composition comprising as a photoacid generator a bissulfonyldiazomethane compound of the following general formula (1a): ##STR46##

wherein R.sup.1 is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or substituted or unsubstituted aryl group of 6 to 14 carbon atoms.

3. A chemical amplification resist composition comprising

(A) a resin which changes its solubility in an alkaline developer under the action of an acid, and

(B) a sulfonyldiazomethane compound capable of generating an acid upon exposure to radiation represented by the general formula (1) or (1a) ##STR47##

wherein R.sub.1 is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or substituted or unsubstituted aryl group of 6 to 14 carbon atoms, R.sub.2 which may be the same or different is a straight,branched or cyclic alkyl group of 1 to 6 carbon atoms, G is SO.sub.2 or CO, R.sub.3 is a substituted or unsubstituted, straight, branched or cyclic alkyl group of 1 to 10 carbon atoms or substituted or unsubstituted aryl group of 6 to 14 carbon atoms, pis an integer of 0 to 4, q is an integer of 1 to 5, p+q is from 1 to 5, n is equal to 1 or 2, m is equal to 0 or 1, and n+m is equal to 2.

4. The resist composition of claim 3 further comprising (C) a compound capable of generating an acid upon exposure to radiation other than component (B).

5. The resist composition of claim 3 wherein the resin (A) has such substituent groups having C--O--C linkages that the solubility in an alkaline developer changes as a result of scission of the C--O--C linkages under the action of an acid.

6. The resist composition of claim 5 wherein the resin (A) is a polymer containing phenolic hydroxyl groups in which hydrogen atoms of the phenolic hydroxyl groups are replaced by acid labile groups of at least one type in a proportion of morethan 0 mol % to 80 mol %, on the average, of the entire hydrogen atoms of the phenolic hydroxyl groups, said polymer having a weight average molecular weight of 3,000 to 100,000.

7. The resist composition of claim 6 wherein the resin (A) is a polymer comprising recurring units represented by the following general formula (2): ##STR48##

wherein R.sup.4 is hydrogen or methyl, R.sup.5 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, x is 0 or a positive integer, y is a positive integer, and x+y is up to 5, in which hydrogen atoms of the phenolic hydroxylgroups are replaced by acid labile groups of at least one type in a proportion of more than 0 mol % to 80 mol %, on the average, of the entire hydrogen atoms of the phenolic hydroxyl groups, said polymer having a weight average molecular weight of 3,000to 100,000.

8. The resist composition of claim 7 wherein the resin (A) is the polymer of formula (2) in which some of the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid labile groups of at least one type, and the hydrogen atoms of theremaining phenolic hydroxyl groups are crosslinked within a molecule and/or between molecules, in a proportion of more than 0 mol % to 50 mol %, on the average, of the entire phenolic hydroxyl groups on the polymer, with crosslinking groups havingC--O--C linkages represented by the following general formula (3a) or (3b): ##STR49##

wherein each of R.sup.7 and R.sup.8 is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, or R.sup.7 and R.sup.8, taken together, may form a ring, and each of R.sup.7 and R.sup.8 is a straight or branched alkylenegroup of 1 to 8 carbon atoms when they form a ring, R.sup.9 is a straight, branched or cyclic alkylene group of 1 to 10 carbon atoms, "a" is an integer of 1 to 7, "b" is 0 or an integer of 1 to 10, A is an (a+1)-valent aliphatic or alicyclic saturatedhydrocarbon group, aromatic hydrocarbon group or heterocyclic group of 1 to 50 carbon atoms, which may be separated by a hetero atom and in which some of the hydrogen atom attached to carbon atoms may be replaced by hydroxyl, carboxyl, carbonyl orhalogen, and B is --CO--O--, --NHCO--O-- or --NHCONH--.

9. The resist composition of claim 5 wherein the resin (A) is a polymer comprising recurring units represented by the following general formula (2a'): ##STR50##

wherein R.sup.4 is hydrogen or methyl, R.sup.5 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms, R.sup.6 is an acid labile group, R.sup.6a is hydrogen or an acid labile group, R.sup.6a being at least partially an acid labilegroup, x is 0 or a positive integer, y is a positive integer, satisfying x+y.ltoreq.5, M and N are positive integers, L is 0 or a positive integer, satisfying 0<N/(M+N).ltoreq.0.5 and 0<(N+L)/(M+N+L).ltoreq.0.8.

10. The resist composition of claim 6 wherein said acid labile groups are groups of the following general formulae (4) to (7), tertiary alkyl groups of 4 to 20 carbon atoms, trialkylsilyl groups whose alkyl groups each have 1 to 6 carbon atoms,oxoalkyl groups of 4 to 20 carbon atoms, or aryl-substituted alkyl groups of 7 to 20 carbon atoms, ##STR51##

wherein R.sup.10 and R.sup.11 are independently hydrogen or straight, branched or cyclic alkyl groups of 1 to 18 carbon atoms, R.sup.12 is a monovalent hydrocarbon group of 1 to 18 carbon atoms which may have a hetero atom, or R.sup.10 andR.sup.11, R.sup.10 and R.sup.12, or R.sup.11 and R.sup.12, taken together, may form a ring, with the proviso that each of R.sup.10, R.sup.11 and R.sup.12 is a straight or branched alkylene group of 1 to 18 carbon atoms when they form a ring,

R.sup.13 is a tertiary alkyl group of 4 to 20 carbon atoms, a trialkylsilyl group whose alkyl groups each have 1 to 6 carbon atoms, an oxoalkyl group of 4 to 20 carbon atoms or a group of formula (4), and letter z is an integer of 0 to 6,

R.sup.14 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms or substituted or unsubstituted aryl group of 6 to 20 carbon atoms, h' is equal to 0 or 1, i is equal to 0, 1, 2 or 3, satisfying 2h'+i=2 or 3,

R.sup.15 is a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms or substituted or unsubstituted aryl group of 6 to 20 carbon atoms, R.sup.16 to R.sup.25 are independently hydrogen or monovalent hydrocarbon groups of 1 to 15 carbonatoms which may contain a hetero atom, or R.sup.16 to R.sup.25, taken together, may form a ring, with the proviso that they are divalent hydrocarbon groups of 1 to 15 carbon atoms which may contain a hetero atom when they form a ring, or two of R.sup.16to R.sup.25 which are attached to adjacent carbon atoms may directly bond together to form a double bond.

11. The resist composition of claim 3 further comprising (D) a basic compound.

12. The resist composition of claim 3 further comprising (E) an organic acid derivative.

13. The resist composition of claim 3 further comprising a propylene glycol alkyl ether acetate, an alkyl lactate or a mixture thereof as a solvent.

14. A process for forming a pattern, comprising the steps of:

applying the resist composition of claim 1 onto a substrate to form a coating,

heat treating the coating and exposing the coating to high energy radiation with a wavelength of up to 300 nm or electron beam through a photo-mask,

optionally heat treating the exposed coating, and developing the coating with a developer.

15. A process for forming a pattern, comprising

applying the resist composition of claim 2 onto a substrate to form a coating,

heat treating the coating and exposing the coating to high energy radiation with a wavelength of up to 300 nm or electron beam through a photo-mask,

optionally heat treating the exposed coating and developing the coating with a developer.

16. A process for forming a pattern, comprising

applying the resist composition of claim 3 onto a substrate to form a coating,

heat treating the coating and exposing the coating to high energy radiation with a wavelength of up to 300 nm or electron beam through a photo-mask,

optionally heat treating the exposed coating and developing the coating with a developer.

17. A resist composition of claim 6, wherein the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid labile groups of at least one type in a proportion of on the average 2 to 50 mol% of the hydrogen atoms of the phenolic hydroxylgroups.

18. A resist composition of claim 8, wherein the hydrogen atoms of the phenolic hydroxyl groups, which are not replaced by acid labile groups, are cross-linked within a molecule and/or between molecules, in a proportion of on the average 0.2 to20 mol% of the phenolic hydroxyl groups on the polymer.

19. A resist composition according to claim 9, wherein the polymer comprises units of p-hydroxystyrene and/or .alpha.-methyl-p-hydroxystyrene in which some hydrogen atoms of phenolic hydroxyl groups are replaced by acid labile groups of at leastone type, and units of acrylate and/or methacrylate, wherein the acrylate and/or methacrylate is an ester protected with an acid labile group, the units of acrylate and methacrylate are contained in the polymer in a proportion of more than 0 mol% to 50mol% on the average, the acid labile groups are present in a proportion of more than 0 mol% to 80 mol%, on the average, based on the entire polymer, and the polymer has a weight average molecular weight of 3,000 to 100,000.