Organotin oxide hydroxide patterning compositions, precursors, and patterning
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.
1. A radiation sensitive coating comprising an organotin composition having a blend of different hydrocarbyl ligands, wherein the organotin composition is represented by the formula ((R and/or R′) a R″ b )SnO 2−((a+b/2)−(w/2) (OH) w , where 0<(a+b)≤2 and 0<(a+b+w)<4, and R, R′, R″ are independently hydrocarbyl ligands with 1-31 carbon atoms, wherein R, R′, and R″ are different hydrocarbyl ligands.
2. The radiation sensitive coating of claim 1 wherein the hydrocarbyl ligands comprise a linear group, a branched group, a cyclic group, an aryl group, an alkenyl group, a benzyl group, an alkynyl group, a hydrocarbyl group substituted with heteroatom functional groups, or a combination thereof.
3. The radiation sensitive coating of claim 2 wherein the heteroatom functional groups comprise cyano, thio, silyl, ether, keto, ester, halogenated groups, or combinations thereof.
4. The radiation sensitive coating of claim 1 wherein the hydrocarbyl ligands comprise methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, sec-butyl, tert-amyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, 1-adamantyl, 2-adamantyl, or combinations thereof.
5. The radiation sensitive coating of claim 1 wherein the hydrocarbyl ligands comprise t-butyl, i-propyl, and/or methyl.
6. The radiation sensitive coating of claim 1 wherein the organotin composition is formed through hydrolysis of a precursor composition comprising two or more organotin compounds having different hydrocarbyl ligands.
7. The radiation sensitive coating of claim 6 wherein the precursor composition comprises at least about 5 mole percent of each organotin compound.
8. The radiation sensitive coating of claim 6 wherein the precursor composition comprises at least about 20 mole percent of each organotin compound.
9. The radiation sensitive coating of claim 6 wherein the precursor composition comprises three organotin compounds having different hydrocarbyl ligands.
10. The radiation sensitive coating of claim 6 wherein the precursor composition comprises an organotin compound represented by the formula R n SnX 4−n and an organotin compound represented by the formula R′ m SnX′ 4−m , wherein R and R′ are bound to Sn with a metal-carbon bond, n=1-3, m=1-3, and X and X′ are independently a ligand having a hydrolysable bond with Sn.
11. The radiation sensitive coating of claim 10 wherein X and X′ are the same.
12. The radiation sensitive coating of claim 10 further comprising an organotin compound represented by the formula R″ p SnX“ 4−p , wherein R” is bound to Sn with a metal-carbon bond, p=1-3, and X, X′, and X″ are independently a ligand having a hydrolysable bond with Sn.
13. The radiation sensitive coating of claim 10 wherein X and/or X′ independently comprise an alkylamido, a chloro, alkynido, an alkoxo, a siloxo, a silylamido, a disilylamido, an aryloxo, an azido, a carboxylate, a halide, a dialkylamide, amidato, amidinato, or fluorinated analogues thereof.
14. The radiation sensitive coating of claim 6 wherein hydrolysis of the precursor composition comprises contacting the precursor composition with water from the ambient atmosphere.
15. The radiation sensitive coating of claim 6 wherein hydrolysis of the precursor composition comprises contacting the precursor composition with water from the ambient atmosphere during and/or after vapor deposition of the organotin compounds.
16. The radiation sensitive coating of claim 6 wherein hydrolysis of the precursor composition comprises contacting the precursor composition with an organic solvent having a controlled amount of water.