Photoresist compositions for deep UV image reversal

Claim 2

A photosensitive composition capable of alternatively producing positive or negative images upon imagewise exposure to activating energy, which comprises: (a) a non-crosslinked, aqueous alkali soluble or swellable resin in an amount sufficient to bind the composition components into a uniform film when the composition is coated onto a substrate; and (b) an oxime sulfonate ester which liberates a sulfonic acid upon exposure to sufficient activating energy, said oxime sulfonate ester being present in the composition in an amount sufficient to cause an imagewise differentiation upon imagewise exposure to sufficient activating energy; and (c) a photospeed enhancing crosslinking agent which is present in the composition in sufficient amount to crosslink said resin in the presence of sufficient acid and heat; said composition being substantially free of ethylenically unsaturated materials which are polymerizable by free radical initiation.

Claim 3

The composition of claim 1 wherein said resin comprises one or more components selected from the group consisting of novolaks, poly(hydroxystyrene)homopolymers, and copolymers of hydroxystyrene and C₁ to C₄ alkyl substituted hydroxystyrene.

Claim 4

The composition of claim 1 wherein the oxime sulfonate ester component comprises one or more compounds selected from the group consisting of wherein n is 1 or 2, R₁ is -COO alkyl, -COO aryl or -CN, and R₂ is alkyl or aryl, or phenyl substituted by C₁ to C₆ alkyl, -OH, -CN, C₁ to C₄ alkoxy, aryloxy, -COO alkyl, -COO aryl or NO₂; or R₂ and R₁ together with the atom to which they are bound form a C₅-C₁₀ carbocyclic or heterocyclic ring; and X and Y are independently selected from the group consisting of a direct bond, -CH₂-, or unsubstituted or substituted C₂-C₅ alkylene, and R₃ is, when n=1, C₁-C₁₈-alkyl or phenyl which may be unsubstituted or substituted by -OH, -CN, halogen, C₁-­C₁₂-alkyl, C₁-C₄-alkoxy, or NO₂; or naphthyl which is unsubstituted or substituted, or R₃ and R₂ or R₃ and R₁ together with the atoms to which they are bonded form a C₅-C₁₂ heterocyclic ring, and R₃ is, when n=2, a (CH₂) m group, wherein m is 2 to 8, or phenylene or naphthylene which are unsubstituted or substituted; and R₄ is arylene, substituted arylene, methylene, C₂-C₆ straight, branched, or cyclic alkylene; and R₅ is cyano, or a -COO-alkyl or -COO-aryl group; and R₆ is, when n=1, a hydrogen atom, or C₁-C₈ alkyl, or phenyl, phenyl substituted with -OH, -CN, C₁ to C₄-alkoxy, aryloxy, -COO-alkyl, -COO-aryl, NO₂, or halogen; or R₅ and R₆ together with the atoms to which they are bound form a C₆-C₁₂ carbocyclic or heterocyclic ring; and R₇ is phenyl, unsubstituted or substituted by -OH, -CN, alkoxy, halogen, or C₁-C₅ alkyl, or C₁-C₁₈ straight or branched alkyl which may be substituted or unsubstituted; or is C₆-C₁₂ aryl, unsubstituted or substituted, or R₇ and R₆ or R₅ and R₇, together with the atoms to which they are bound, form a C₆-C₁₂ heterocyclic ring.

Claim 5

The composition of claim 1 wherein component (c) comprises a compound which has the formula (R₁O - CHR₃) n - A - (CHR₄ - OR₂) m wherein A has the formula B or B-Y-B, wherein B is a substituted or unsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or an oxygen or sulfur containing heterocyclic compound, Y is a single bond, C₁-C₄-alkylene or -alkylenedioxy, the chains of which may be interrupted by oxygen atoms, -O-, -S-, -SO₂-, -CO-, CO₂, -O-CO₂-, -CONH- or phenylenedioxy, R₁ and R₂ are H, C₁-C₆-alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄ are independently H, C₁-C₄-alkyl or substituted or unsubstituted phenyl and n ranges from 1 to 3 and m ranges from 0 to 3, provided that n + m is greater than 1.

Claim 6

The composition of claim 1 wherein the component (c) has the formula wherein R₁, R₄, R₅, R₆ are independently H, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, aryl, arylalkyl or OR₂; and R₂, R₃ are independently H, (C₁-C₆) alkyl, (C₃-C₆) cycloalkyl, aryl or arylalkyl.

Claim 7

The composition of claim 1 wherein said component (c) is dimethylol paracresol or methyl methoxy diphenyl ether.

Claim 8

The composition of claim 1 wherein said component (c) is one or more compounds selected from the group consisting of benzene, 1-methoxy-2,6-bis(hydroxymethyl)-4-methyl-; phenol, 2,6-bis(methoxymethyl)-4-methyl-; and benzene, 1-methoxy-2,6-bis(methoxymethyl)-4-methyl-.

Claim 9

The composition of claim 1 further comprising a solvent.

Claim 10

The composition of claim 8 wherein said solvent component comprises one or more components selected from the group consisting of propylene glycol monoalkyl ether and propylene glycol monoalkyl ether acetate.

Claim 11

The composition of claim 1 further comprising one or more components selected from the group consisting of colorants, dyes, anti-striation agents, leveling agents, plasticizers, adhesion promoters, speed enhancers, solvents and surfactants.

Claim 12

A photosensitive article which comprises a substrate, and the composition of claim 1 coated on said substrate.

Claim 13

The article of claim 11 wherein the surface of said substrate on which the composition is coated has been treated with an adhesion promoter.

Claim 14

The article of claim 12 wherein the adhesion promoter comprises hexamethyl disilazane.

Claim 15

The article of claim 11 wherein said substrate is selected from the group consisting of silicon, aluminum, polymeric resins, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics and aluminum/copper mixtures.

Claim 18

The method of claim 15 wherein said resin comprises one or more components selected from the group consisting of novolaks, poly(hydroxystyrene)homopolymers, and copolymers of hydroxystyrene and C₁ to C₄ alkyl substituted hydroxystyrene.

Claim 19

The method of claim 15 wherein the oxime sulfonate ester component comprises one or more compounds selected from the group consisting of wherein n is 1 or 2, R₁ is -COO alkyl, -COO aryl or -CN, and R₂ is alkyl or aryl, phenyl substituted by -OH, -CN, C₁ to C₆ alkyl, C₁ to C₄ alkoxy, aryloxy, COO-aryl, -COO-­alkyl or NO₂,or R₂ and R₁ together with the atom to which they are bound form a C₅-C₁₀ carbocyclic or heterocyclic ring; and X and Y are independently selected from the group consisting of a direct bond, -CH₂-, or unsubstituted or substituted C₂-C₅ alkylene, and R₃ is, when n=1, C₁-C₁₈-alkyl or phenyl which may be unsubstituted or substituted by -OH, -CN, halogen, C₁-­C₁₂-alkyl, C₁-C₄-alkoxy, or NO₂; or naphthyl which is unsubstituted or substituted, or R₃ and R₂ or R₃ and R₁ together with the atoms to which they are bonded form a C₅-C₁₂ heterocyclic ring, and R₃ is, when n=2, a (CH₂) m group, wherein m is 2 to 8, or phenylene or naphthylene which are unsubstituted or substituted; and R₄ is arylene, substituted arylene, methylene, C₂-C₆ straight, branched, or cyclic alkylene; and R₅ is cyano, or a -COO alkyl or -COO aryl group; and R₆ is, when n=1, a hydrogen atom, or C₁-C₈ alkyl, or phenyl, phenyl substituted with -OH, -CN, C₁ to C₄ alkoxy, aryloxy, -COO-alkyl, -COO-aryl, NO₂, or halogen; or R₅ and R₆ together with the atoms to which they are bound form a C₆-C₁₂ with the atoms to which they are bound form a C₆-C₁₂ carbocyclic or heterocyclic ring; and R₇ is phenyl, unsubstituted or substituted by -OH, -CN, alkoxy, halogen, or C₁-C₅ alkyl, or C₁-C₁₈ straight or branched alkyl which may be substituted or unsubstituted; or is C₆-C₁₂ aryl, unsubstituted or substituted, or R₇ and R₆ or R₅ and R₇, together with the atoms to which they are bound, form a C₆-C₁₂ heterocyclic ring.

Claim 20

The method of claim 15 wherein component (c) comprises a compound which has the formula (R₁O - CHR₃) n - A - (CHR₄ - OR₂) m wherein A has the formula B or B-Y-B, wherein B is a substituted or unsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or an oxygen or sulfur containing heterocyclic compound, Y is a single bond, C₁-C₄-alkylene or -alkylenedioxy, the chains of which may be interrupted by oxygen atoms, -O-, -S-, -SO₂-, -CO-, CO₂, -O-CO₂-, -CONH- or phenylenedioxy, R₁ and R₂ are H, C₁-C₆-alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄ are independently H, C₁-C₄-alkyl or substituted or unsubstituted phenyl and n ranges from 1 to 3 and m ranges from 0 to 3, provided that n + m is greater than 1.

Claim 21

The method of claim 15 further comprising one or more components selected from the group consisting of colorants, dyes, anti-striation agents, leveling agents, plasticizers, adhesion promoters, speed enhancers, solvents and surfactants.

Claim 22

The method of claim 15 wherein said substrate is selected from the group consisting of silicon, aluminum, polymeric resins, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics and aluminum/copper mixtures.

Claim 23

The method of claim 15 wherein step II is conducted with actinic, electron beam, ion beam or x-radiation.

Claim 24

The method of claim 21 wherein step II is conducted with ultraviolet radiation of from about 180 nm to about 300 nm.

Claim 25

The method of claim 15 wherein said solution comprises one or more components selected from the group consisting of N-methylmorpholine, an alkali metal hydroxide, carbonate or bicarbonate or tetra-alkylammonium hydroxide.

Claim 28

The method of claim 24 wherein said resin comprises one or more components selected from the group consisting of novolaks, poly(hydroxystyrene)homopolymers, and copolymers of hydroxystyrene and C₁ to C₄ alkyl substituted hydroxystyrene.

Claim 29

The method of claim 24 wherein the oxime sulfonate ester component comprises one or more compounds selected from the group consisting of wherein n is 1 or 2, R₁ is -COO alkyl, -COO aryl or -CN, and R₂ is alkyl or aryl, or phenyl substituted by -OH, -CN, C₁ to C₆ alkyl, C₁ to C₄ alkoxy, aryloxy, COO-aryl, -COO-­alkyl or NO₂,or R₂ and R₁ together with the atom to which they are bound form a C₅-C₁₀ carbocyclic or heterocyclic ring; and X and Y are independently selected from the group consisting of a direct bond, -CH₂-, or unsubstituted or substituted C₂-C₅ alkylene, and R₃ is, when n=1, C₁-C₁₈-alkyl or phenyl which may be unsubstituted or substituted by -OH, -CN, halogen, C₁-­C₁₂-alkyl, C₁-C₄-alkoxy, or NO₂; or naphthyl which is unsubstituted or substituted, or R₃ and R₂ or R₃ and R₁ together with the atoms to which they are bonded form a C₅-C₁₂ heterocyclic ring, and R₃ is, when n=2, a (CH₂) m group, wherein m is 2 to 8, or phenylene or naphthylene which are unsubstituted or substituted; and R₄ is arylene, substituted arylene, methylene, C₂-C₆ straight, branched, or cyclic alkylene; and R₅ is cyano, or a -COO alkyl or -COO aryl group; and R₆ is, when n=1, a hydrogen atom, or C₁-C₈ alkyl, or phenyl, phenyl substituted with -OH, -CN, C₁ to C₄ alkoxy, aryloxy, COO-alkyl, -COO-aryl, NO₂, or halogen; or R₅ and R₆ together with the atoms to which they are bound form a C₆-C₁₂ carbocyclic or heterocyclic ring; and R₇ is phenyl, unsubstituted or substituted by -OH, -CN, alkoxy, halogen, or C₁-C₅ alkyl, or C₁-C₁₈ straight or branched alkyl which may be substituted or unsubstituted; or is C₆-C₁₂ aryl, unsubstituted or substituted, or R₇ and R₆ or R₅ and R₇, together with the atoms to which they are bound, form a C₆-C₁₂ heterocyclic ring.

Claim 30

The method of claim 24 wherein component (c) comprises a compound which has the formula (R₁O - CHR₃) n - A - (CHR₄ - OR₂) m wherein A has the formula B or B-Y-B, wherein B is a substituted or unsubstituted mononuclear or fused polynuclear aromatic hydrocarbon or an oxygen or sulfur containing heterocyclic compound, Y is a single bond, C₁-C₄-alkylene or -alkylenedioxy, the chains of which may be interrupted by oxygen atoms, -O-, -S-, -SO₂-, -­CO-, CO₂, -O-CO₂-, -CONH- or phenylenedioxy, R₁ and R₂ are H, C₁-C₆-alkyl, cycloalkyl, substituted or unsubstituted aryl, alkaryl or acyl; R₃, R₄ are independently H, C₁-­C₄-alkyl or substituted or unsubstituted phenyl and n ranges from 1 to 3 and m ranges from 0 to 3, provided that n + m is greater than 1.

Claim 31

The method of claim 24 further comprising one or more components selected from the group consisting of colorants, dyes, anti-striation agents, leveling agents, plasticizers, adhesion promoters, speed enhancers, solvents and surfactants.

Claim 32

The method of claim 24 wherein said substrate is selected from the group consisting of silicon, aluminum, polymeric resins, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramics and aluminum/copper mixtures.

Claim 33

The method of claim 24 wherein steps II and IV are independently conducted with actinic, electron beam, ion beam or x-radiation.

Claim 34

The method of claim 30 wherein steps II and IV are independently conducted with ultraviolet radiation of from about 180 nm to about 300 nm.

Claim 35

The method of claim 24 wherein said solution comprises one or more components selected from the group consisting of N-methylmorpholine, an alkali metal hydroxide, carbonate or bicarbonate or tetra-alkylammonium hydroxide.

Claim 36

The method of claim 24 wherein said heating step III is conducted at a temperature of from about 95°C to about 160°C for from about 10 to about 90 seconds.