Organometallic precursors are described for the formation of high resolution lithography patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands readily hydrolysable by water vapor or other OH source composition under modest conditions. The organometallic precursors generally comprise a radiation sensitive organo ligand to tin that can result in a coating that can be effective for high resolution patterning at relatively low radiation doses and is particularly useful for EUV patterning. The precursors compositions are readily processable under commercially suitable conditions. Solution phase processing with in situ hydrolysis or vapor based deposition can be used to form the coatings.

Organometallic precursors are described for the formation of high resolution lithography patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands readily hydrolysable by water vapor or other OH source composition under modest conditions. The organometallic precursors generally comprise a radiation sensitive organo ligand to tin that can result in a coating that can be effective for high resolution patterning at relatively low radiation doses and is particularly useful for EUV patterning. The precursors compositions are readily processable under commercially suitable conditions. Solution phase processing with in situ hydrolysis or vapor based deposition can be used to form the coatings.

A photosensitive resin composition is also provided that includes a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor; a photo-radical polymerization initiator; and a solvent, in which an acid value of an acid group contained in the polymer precursor and having a neutralization point in a pH range of 7.0 to 12.0 is in a range of 2.5 to 34.0 mgKOH/g, and either the polymer precursor contains a radically polymerizable group or the photosensitive resin composition includes a radically polymerizable compound other than the polymer precursor.

A positive resist composition comprising a base polymer comprising recurring units (a) having the structure of an ammonium salt of an iodized or brominated phenol, and recurring units (b1) having an acid labile group-substituted carboxyl group and/or recurring units (b2) having an acid labile group-substituted phenolic hydroxyl group exhibits a high sensitivity, high resolution, low edge roughness and dimensional uniformity, and forms a pattern of good profile after exposure and development.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer: ##STR00001##
A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer: ##STR00001##
A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

A radiation sensitive composition including a siloxane polymer exhibiting phenoplast crosslinking reactivity as a base resin, which is excellent in resolution and can be used as a radiation sensitive composition capable of allowing a pattern having a desired-shape to be formed with sufficient precision. A radiation sensitive composition including as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof; and a photoacid generator, in which the hydrolyzable silane includes hydrolyzable silanes of Formula (1)
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b)  Formula (1)
wherein R.sup.1 is an organic group of Formula (1-2) ##STR00001##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.3 is a hydrolyzable group; and Formula (2)
R.sup.7.sub.cR.sup.8.sub.dSi(R.sup.9).sub.4-(c+d)  Formula (2)
wherein R.sup.7 is an organic group of Formula (2-1) ##STR00002##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.9 is a hydrolyzable group.

A radiation sensitive composition including a siloxane polymer exhibiting phenoplast crosslinking reactivity as a base resin, which is excellent in resolution and can be used as a radiation sensitive composition capable of allowing a pattern having a desired-shape to be formed with sufficient precision. A radiation sensitive composition including as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof; and a photoacid generator, in which the hydrolyzable silane includes hydrolyzable silanes of Formula (1)
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b)  Formula (1)
wherein R.sup.1 is an organic group of Formula (1-2) ##STR00001##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.3 is a hydrolyzable group; and Formula (2)
R.sup.7.sub.cR.sup.8.sub.dSi(R.sup.9).sub.4-(c+d)  Formula (2)
wherein R.sup.7 is an organic group of Formula (2-1) ##STR00002##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.9 is a hydrolyzable group.

A photoresist composition comprising: a resin which has a structural unit represented by formula (I): ##STR00001##
wherein R.sup.1 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which optionally has a halogen atom, and R.sup.2 represents a C1 to C42 hydrocarbon group which optionally has a substituent; an alkali-soluble resin; an acid generator; and a solvent.

A photoresist composition comprising: a resin which has a structural unit represented by formula (I): ##STR00001##
wherein R.sup.1 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which optionally has a halogen atom, and R.sup.2 represents a C1 to C42 hydrocarbon group which optionally has a substituent; an alkali-soluble resin; an acid generator; and a solvent.