Inpria Corporation

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 pure composition comprises a monoalkyltin trialkoxide compound represented by the chemical formula RSn(OR′) 3 or a monoalkyl tin triamide compound represented by the chemical formula RSn(NR′ 2 ) 3 and no more than 4 mole % dialkyltin compounds relative to the total tin amount, where R is a hydrocarbyl group with 1-31 carbon atoms, and wherein R′ is a hydrocarbyl group with 1-10 carbon atoms. Methods are described for the formation of the pure compositions. A solid composition comprises a monoalkyl triamido tin compound represented by the chemical formula RSn—(NR′COR″) 3 , where R is a hydrocarbyl group with 1-31 carbon atoms, and where R′ and R″ are independently a hydrocarbyl group with 1-10 carbon atoms. The compositions are suitable for the formation of resist compositions suitable for EUV patterning in which the compositions have a high EUV absorption.

Organometallic patterning compositions are modified with iodine to improve radiation sensitivity and reduce radiation dose without significant loss of pattern quality. Iodine can be introduced as ligands to the metal ion and/or through introduction of iodide containing additives. Iodine is found to survive, at least in part, pre-irradiation processing. Thus, iodide ions are maintained in some form in the films being irradiated.

A pure composition comprises a monoalkyltin trialkoxide compound represented by the chemical formula RSn(OR′) 3 or a monoalkyl tin triamide compound represented by the chemical formula RSn(NR′ 2 ) 3 and no more than 4 mole % dialkyltin compounds relative to the total tin amount, where R is a hydrocarbyl group with 1-31 carbon atoms, and wherein R′ is a hydrocarbyl group with 1-10 carbon atoms. Methods are described for the formation of the pure compositions. A solid composition comprises a monoalkyl triamido tin compound represented by the chemical formula RSn—(NR′COR″) 3 , where R is a hydrocarbyl group with 1-31 carbon atoms, and where R′ and R″ are independently a hydrocarbyl group with 1-10 carbon atoms. The compositions are suitable for the formation of resist compositions suitable for EUV patterning in which the compositions have a high EUV absorption.

The purification of monoalkyl tin trialkoxides and monoalkyl tin triamides are described using fractional distillation and/or ultrafiltration. The purified compositions are useful as radiation sensitive patterning compositions or precursors thereof. The fractional distillation process has been found to be effective for the removal of metal impurities down to very low levels. The ultrafiltration processes have been found to be effective at removal of fine particulates. Commercially practical processing techniques are described.

Organotin compositions having the formula RSnL 3 and corresponding synthetic methods are described. R includes aromatic, cyclic and/or halogenated ether moieties, or polyethers, and L includes hydrolysable groups. The organotin compositions may be formed as radiation-patternable coatings on substrates. The coatings may have an average thickness from about 1 nm to about 75 nm and have the formula RSnO n (OH) 3-2n , forming an oxo-hydroxo network, where R is a hydrocarbyl ether group with 1 to 30 carbon atoms and 0<n<3/2, wherein regions of the coating are soluble in 2-heptanone in a puddle development step following a bake at 150° C. for 120 seconds. The coatings may be radiation-patternable using UV, EUV or ion beam radiation, and corresponding methods are described.

Patterning compositions are described based on organo tin dodecamers with hydrocarbyl ligands, oxo ligands, hydroxo ligands and carboxylato ligands. Alternative dodecamer embodiments have organo tin ligands in place of hydrocarbyl ligands. The organo tin ligands can be incorporated into the dodecamers from a monomer with the structure (RCC) 3 SnQ, where R is a hydrocarbyl group and Q is a alkyl tin moiety with a carbon bonded to the Sn atom of the monomer and with a Sn bonded as a replacement of a quaternary carbon atom with bonds to 4 carbon atoms. Some or all of the carboxylato and hydroxyl ligands can be replaced with fluoride ions. Good EUV patterning results are obtained with the dodecamer based patterning compositions.

Synthesis reactions are described to efficiently and specifically form compounds of the structure RSnL 3 , where R is an organic ligand to the tin, and L is hydrolysable ligand or a hydrolysis product thereof. The synthesis is effective for a broad range of R ligands. The synthesis is based on the use of alkali metal ions and optionally alkaline earth (pseudo-alkaline earth) metal ions. Compounds are formed of the structures represented by the formulas RSn(C≡CSiR′ 3 ) 3 , R′R″ACSnL 3 , where A is a halogen atom (F, Cl, Br or I) or an aromatic ring with at least one halogen substituent, R′R″ (R″O) CSnL 3 or R′R″ (N≡C) CSnZ 3 .

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.

Synthesis reactions are described to efficiently and specifically form compounds of the structure RSnL 3 , where R is an organic ligand to the tin, and L is hydrolysable ligand or a hydrolysis product thereof. The synthesis is effective for a broad range of R ligands. The synthesis is based on the use of alkali metal ions and optionally alkaline earth (pseudo-alkaline earth) metal ions. Compounds are formed of the structures represented by the formulas RSn(C≡CSiR′ 3 ) 3 , R′R″ACSnL 3 , where A is a halogen atom (F, Cl, Br or I) or an aromatic ring with at least one halogen substituent, R′R″(R″′O)CSnL 3 or R′R″(N≡C)CSnZ 3 .