| CPC G03F 7/0382 (2013.01) [G03F 7/0048 (2013.01); G03F 7/029 (2013.01); G03F 7/2006 (2013.01)] | 12 Claims |
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1. A negative resist composition comprising
a base polymer,
a quencher in the form of a first sulfonium salt of a weaker acid than a sulfonic acid which is fluorinated at α- and/or β-position of the sulfo group, and
an acid generator capable of generating a sulfonic acid which is fluorinated at α- and/or β-position of the sulfo group,
wherein the first sulfonium salt has the formula (A):
 wherein k1 is an integer of 0 to 4, m1 is an integer of 1 to 3, n1 is an integer of 0 to 2, meeting 2≤k1+m1≤7 and m1+n1=3, p1 is 1 or 2, q1 is an integer of 0 to 4, meeting 1≤p1+q1≤5, r1 is an integer of 0 to 5,
X− is —CO2−, —N−—SO2—RF or —O−, RF is fluorine or a C1-C30 fluorinated hydrocarbyl group which may contain at least one moiety selected from hydroxy, carboxy, carbonyl, ether bond, ester bond, and amide bond,
X1 is a single bond, ester bond, ether bond, amide bond or urethane bond,
X2 is fluorine or a C1-C40 hydrocarbyl group which contains a heteroatom when k1 is 0 and X− is —CO2−, a C1-C40 hydrocarbyl group which contains a heteroatom when k1 is 1 to 4, hydrogen or a C1-C40 hydrocarbyl group which may contain a heteroatom when k1 is 0 and X− is —N−—SO2—RF, a C1-C40 hydrocarbyl group which may contain a heteroatom when k1 is 0 and X− is —O−, a single bond or a C1-C40 hydrocarbylene group which may contain a heteroatom when k1 is 1, and a C1-C40 (k1+1)-valent hydrocarbon group which may contain a heteroatom when k1 is 2, 3 or 4, with the proviso that when X− is —O−, the carbon atom to which —O is attached is not a carbon atom on an aromatic ring,
X3 is a single bond, ester bond, ether bond, amide bond, urethane bond, or a C1-C10 alkanediyl group in which some constituent —CH2— may be replaced by an ester bond, ether bond, amide bond or urethane bond,
R1 to R3 are each independently hydrogen, halogen, or a C1-C40 saturated hydrocarbyl group, in the saturated hydrocarbyl group, some or all of the hydrogen atoms may be substituted by fluorine or hydroxy, some constituent —CH2— may be replaced by an ether bond or ester bond, and some carbon-carbon bond may be a double bond,
R4 and R5 are each independently halogen, cyano, nitro, mercapto, sulfo, a C1-C10 saturated hydrocarbyl group, or a C7-C20 aralkyl group, the saturated hydrocarbyl group and aralkyl group may contain oxygen, sulfur, nitrogen or halogen, two R4 or two R5 may bond together to form a ring with the benzene ring to which they are attached, and R4 and R5 may bond together to form a ring with the benzene rings to which they are attached and the sulfur therebetween.
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