Enhanced EUV photoresist materials, formulations and processes

1. A method of forming a patterned resist comprising:

a. providing a substrate,

b. applying a multiple trigger resist composition comprising:

i. at least one polymer comprising two or more crosslinkable functionalities, wherein essentially all the functionalities are attached to acid labile protecting groups,

ii. at least one acid activatable crosslinker,

iii. at least one photoacid generator,

iv. at least one solvent, and

v. at least one xMT ester comprising a compound of one of the following structures:

wherein at least one of X or Y comprises

-(alkyl)j-(aryl)k-(O) p —(COO) q -LG

wherein j, k, p, and q take the values in the following table:

-alkyl-

-aryl-

—O—

—COO—

j

k

p

q

1

1

1

1

1

1

0

1

1

1

1

0

1

0

0

1

1

0

1

0

0

1

1

1

0

1

0

1

0

1

1

0

0

0

0

1

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1-16 carbon atoms having 0-16 heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, divalent heteroaromatic group, or divalent fused aromatic or fused heteroaromatic group, and wherein LG is a tertiary alkyl or tertiary cycloalkyl group, an alicyclic group, a ketal or cyclic aliphatic ketal, or an acetal is a leaving group,

c. heating the coated substrate to form a substantially dried coating to obtain a desired thickness,

d. imagewise exposing the coated substrate to actinic radiation,

e. removing the unexposed areas of the coating using an aqueous developer, a solvent developer or a combination aqueous-solvent developer composition, wherein the remaining photoimaged pattern is optionally heated and wherein the exposed resist may be selectively heated prior to development and wherein the composition is free of any additional acid diffusion control components.

2. The method of claim 1 , wherein the xMT ester comprises a compound one of the following structures:

wherein at least one of X or Y comprises -(alkyl)j-(aryl)k-(O) p -(COO) q -LG wherein j, k, p, and q take the values in the following table:

-alkyl-

-aryl-

—O—

—COO—

j

k

p

q

1

1

1

1

1

1

0

1

1

1

1

0

1

0

0

1

1

0

1

0

0

1

1

1

0

1

0

1

0

1

1

0

0

0

0

1

wherein alkyl is a branched or unbranched, substituted or unsubstituted divalent alkyl chain of 1-16 carbon atoms having 0-16 heteroatoms substituted into the chain, aryl is a substituted or unsubstituted divalent phenyl group, divalent heteroaromatic group, or divalent fused aromatic or fused heteroaromatic group, and wherein LG is a tertiary alkyl or tertiary cycloalkyl group, an alicyclic group, a ketal or cyclic aliphatic ketal, or an acetal is a leaving group.

3. The method of claim 1 wherein the at least one photoacid generator comprises an onium salt compound, a sulfonium salt, a triphenylsulphonium salt, a sulfonimide, a halogen-containing compound, a sulfone, a sulfone imide, a sulfonate ester, a quinone-diazide, a diazomethane, an iodonium salt, an oxime sulfonate, a dicarboxyimidyl sulfate ester, an ylideneaminooxy sulfonic acid ester, a sulfonyldiazomethane, or a mixture thereof which are capable of generating an acid when exposed to at least one of UV, deep UV, extreme UV, x-ray, or e-beam actinic radiation.

4. The method of claim 3 , wherein the at least one acid activatable crosslinker comprises an aliphatic, aromatic or aralkyl monomer, oligomer, a resin or polymer, comprising at least one of a glycidyl ether, glycidyl ester, an oxetane, a glycidyl amine, a methoxymethy 1 group, an ethoxy methyl group, a butoxymethy 1 group, a benzyloxymethyl group, dimethylamino methyl group, diethylamino methyl amino group, a dialkylolmethyl amino group, a dibutoxymethyl amino group, a dimethylolmethyl amino group, diethylolmethyl amino group, a dibutylolmethyl amino group, a morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, formyl group, acetyl group, vinyl group or an isopropenyl group.

5. The method of claim 1 , wherein the composition further comprises at least one metal component wherein the metal component exhibits high EUV photoabsorption cross-section, median to high inelastic electron scattering and low to median elastic scattering coefficients.

6. The method of claim 5 , wherein the at least one metal is chosen from the periodic table of elements of columns 3 through 17 and rows 3 through 6, which includes Scandium, Titanium, Vanadium, Chromium, Manganese, Iron, Cobalt, Nickel, Copper, Zinc, Gallium, Germanium, Arsenic, Selenium, Bromine, Yttrium, Zirconium, Niobium, Molybdenum, Technetium, Ruthenium, Rhodium, Palladium, Silver, Cadmium, Indium, Tin, Antimony, Tellurium, Iodine, the Lanthanides, Hafnium, Tantalum, Tungsten, Rhenium, Osmium, Iridium, Platinum, Gold, Mercury, Lead, Bismuth, Polonium, and columns 13-17 row 3 which includes Aluminum, Silicon, Phosphorus, Sulfur and Chlorine or a salt, coordinated complex, a metal containing a monomeric, oligomeric or polymeric ligand.

7. The method of claim 6 , wherein the at least one acid activatable crosslinker comprises an aliphatic, aromatic or aralkyl monomer, oligomer, a resin or polymer, comprising at least one of a glycidyl ether, glycidyl ester, an oxetane, a glycidyl amine, a methoxymethy 1 group, an ethoxy methyl group, a butoxymethy 1 group, a benzyloxymethyl group, dimethylamino methyl group, diethylamino methylamino group, a dialkylolmethyl amino group, a dibutoxymethyl amino group, a dimethylolmethyl amino group, diethylolmethyl amino group, a dibutylolmethyl amino group, a morpholinomethyl group, acetoxymethyl group, benzyloxymethyl group, formyl group, acetyl group, vinyl group or an isopropenyl group.