Chemical vapor deposition of metal oxide films through ester elimination reactions

Claim 1

A method of depositing a thin film on a semiconductor substrate, said method comprising: (a) supplying first and second precursors in a dehydrated mixed stable phase, said first precursor of the formula A(O 2 CR) 2 , and said second precursor of the formula BR' x R" 4-x , wherein: (i) A is a metal selected from the group consisting of barium, strotium, calcium, and combinations thereof; (ii) B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof; (iiii) R is selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (iv) R' is an alkoxyl organic substituent; (V) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; and (vi) x has a value selected between 1 and 4, inclusive; and (b) contacting said first and second precursors in said mixed stable phase with said substrate while holding said substrate at a temperature sufficient to produce a surface-mediated ester elimination reaction between said first and second precursors without substantial thermal decomposition of said first precursor, said reaction forming a volatile ester R'O 2 CR and depositing an intermediate compound film comprising A, B, and O on said substrate.

Claim 2

A method of depositing a thin film on a semiconductor substrate, said method comprising: (a) supplying first and second precursors in a dehydrated mixed stable phase, said first precursor of the formula A(O 2 CR) 2 , and said second precursor of the formula BR' x R" 4-x , wherein: (i) A is a metal selected from the group consisting of barium, strotium, calcium, and combinations thereof; (ii) B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof; (iiii) R is selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (iv) R' is an alkoxyl organic substituent; (V) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; and (vi) x has a value selected between 1 and 4, inclusive; and (b) contacting said first and second precursors in said mixed stable phase with said substrate while holding said substrate at a temperature sufficient to produce a surface-mediated ester elimination reaction between said first and second precursors without substantial thermal decomposition of said first precursor, said reaction forming a volatile ester R'O 2 CR and depositing an intermediate compound film comprising A, B, and O on said substrate.

Claim 15

A method of forming a thin film of insulating material on a semiconductor substrate, said insulating material having an empirical formula ABO 3 , where A is a divalent metal selected from the group consisting of barium, strontium, calcium, and combinations thereof, where B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof, said method comprising: (a) supplying a gas stream comprising a dry carrier gas and first and second precursors in a dehydrated mixed stable vapor phase, said first precursor having an empirical formula A(O 2 CR) 2 ·L and said second precursor having an empirical formula BR' x R" 4-x , wherein: (i) R is a first organic substituent selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (ii) L is a multidentate ligand coordinated to A; (iii) R' is an alkoxyl organic substituent; (iv) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; and (v) x has a value selected between 1 and 4, inclusive; and (b) contacting said gas stream with said substrate; (c) controlling the temperature of said substrate, thereby producing a surface-mediated ester elimination reaction between said first and second precursors, said reaction forming a volatile ester and forming an intermediate compound film comprising A, B, and O on said substrate; and (d) annealing said intermediate compound film in an oxygen-containing atmosphere, thereby converting said intermediate compound film into said film of insulating material.

Claim 16

A method of forming a thin film of insulating material on a semiconductor substrate, said insulating material having an empirical formula ABO 3 , where A is a divalent metal selected from the group consisting of barium, strontium, calcium, and combinations thereof, where B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof, said method comprising: (a) supplying a gas stream comprising a dry carrier gas and first and second precursors in a dehydrated mixed stable vapor phase, said first precursor having an empirical formula A(O 2 CR) 2 ·L and said second precursor having an empirical formula BR' x R" 4-x , wherein: (i) R is a first organic substituent selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (ii) L is a multidentate ligand coordinated to A; (iii) R' is an alkoxyl organic substituent; (iv) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; and (v) x has a value selected between 1 and 4, inclusive; and (b) contacting said gas stream with said substrate; (c) controlling the temperature of said substrate, thereby producing a surface-mediated ester elimination reaction between said first and second precursors, said reaction forming a volatile ester and forming an intermediate compound film comprising A, B, and O on said substrate; and (d) annealing said intermediate compound film in an oxygen-containing atmosphere, thereby converting said intermediate compound film into said film of insulating material.

Claim 25

A method of forming a thin film of insulating material on a semiconductor substrate, said insulating material having an empirical formula ABO 3 , where A is a divalent metal selected from the group consisting of barium, strontium, calcium, and combinations thereof, where B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof, said method comprising: (a) injecting droplets of a dehydrated liquid precursor mixture into a dry carrier gas stream, said liquid precursor mixture comprising first and second liquid precursors in a molar ratio of substantially 1:1, said first precursor having a formula A(O 2 CR) 2 ·L and said second precursor having a formula BR' 2 R" 2 , wherein: (i) R is a first organic substituent selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (ii) L is a multidentate ligand coordinated to A; (iii) R' is an alkoxyl organic substituent; and (iv) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; (b) heating said carrier gas stream containing said droplets such that substantially all of said droplets are vaporized, thereby forming first and second vapor precursors corresponding to said first and second liquid precursors; (c) contacting said carrier gas stream with said substrate; (c) controlling the temperature of said substrate, thereby producing a surface-mediated ester elimination reaction between said first and second vapor precursors, said reaction forming a volatile ester and forming an intermediate compound film comprising A, B, and O on said substrate; and (d) annealing said intermediate compound film in an oxygen-containing atmosphere, thereby converting said intermediate compound film into said film of insulating material.

Claim 26

A method of forming a thin film of insulating material on a semiconductor substrate, said insulating material having an empirical formula ABO 3 , where A is a divalent metal selected from the group consisting of barium, strontium, calcium, and combinations thereof, where B is a metal selected from the group consisting of titanium, niobium, zirconium, and combinations thereof, said method comprising: (a) injecting droplets of a dehydrated liquid precursor mixture into a dry carrier gas stream, said liquid precursor mixture comprising first and second liquid precursors in a molar ratio of substantially 1:1, said first precursor having a formula A(O 2 CR) 2 ·L and said second precursor having a formula BR' 2 R" 2 , wherein: (i) R is a first organic substituent selected from the group consisting of alkyl, aryl, and halogenated hydrocarbon substituents; (ii) L is a multidentate ligand coordinated to A; (iii) R' is an alkoxyl organic substituent; and (iv) R" is a third organic substituent selected from the group consisting of alkoxyls, β-diketonates, β-ketoiminates, Schiff bases, and combinations thereof; (b) heating said carrier gas stream containing said droplets such that substantially all of said droplets are vaporized, thereby forming first and second vapor precursors corresponding to said first and second liquid precursors; (c) contacting said carrier gas stream with said substrate; (c) controlling the temperature of said substrate, thereby producing a surface-mediated ester elimination reaction between said first and second vapor precursors, said reaction forming a volatile ester and forming an intermediate compound film comprising A, B, and O on said substrate; and (d) annealing said intermediate compound film in an oxygen-containing atmosphere, thereby converting said intermediate compound film into said film of insulating material.