Precursor compositions for chemical vapor deposition, and ligand exchange resistant metal-organic precursor solutions comprising same

Claim 2

A metal source reagent solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of: (i) at least one metal coordination complex including a metal selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Pb, Tm, Bi, and Yb, to which is coordinatively bound at least one ligand in a stable complex, wherein the ligand is selected from the group consisting of: β-diketonates, β-ketoiminiates, βdiiminates, C 1 -C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for said metal coordination complex, selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitriles, alkanols, organic amines, and polyamines.

Claim 3

A metal source reagent liquid solution according to claim 1, comprising a multi-component solution including at least two said metal source complexes.

Claim 4

A metal source reagent liquid solution according to claim 2, wherein the ligands of the metal source complexes are either (a) identical to result in degenerative ligand exchange, or (b) resistant to non-degenerative ligand exchange in relation to one another.

Claim 5

A metal source reagent liquid solution according to claim 1, wherein the solvent comprises at least one solvent species selected from the group consisting of: glymes, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, esters, nitrites, and alcohols.

Claim 6

A metal source reagent liquid solution according to claim 1, wherein the solvent comprises an organic ether selected from the group consisting of dialkyl, cyclic and crown ethers.

Claim 7

A metal source reagent liquid solution according to claim 1, wherein the solvent comprises an alkyl nitrile of the formula: C.tbd.NR b , wherein R b is H, C 1 -C 8 alkyl, or C 1 -C 8 perfluoroalkyl.

Claim 8

A metal source reagent liquid solution according to claim 1, wherein the solvent comprises at least one solvent species selected from the group consisting of: glyme solvents having from 1 to 20 ethoxy -(C 2 H 4 O)- repeat units; C 2 -C 12 alkanols, organic ethers selected from the group consisting of dialkyl ethers comprising C 1 -C 6 alkyl moieties, C 4 -C 8 cyclic ethers, and C 12 -C 60 crown O 4 -O 20 ethers wherein the prefixed C i range is the number i of carbon atoms in the ether compound and the suffixed O i range is the number i of oxygen atoms in the ether compound; C 6 -C 12 aliphatic hydrocarbons; and C 6 -C 18 aromatic hydrocarbons.

Claim 9

A metal source reagent liquid solution according to claim 1, wherein the solvent comprises a crown ether selected from the group consisting of 12-crown-4, 15- crown-5, 18-crown-6, and 24-crown-8 crown ethers.

Claim 10

A metal source reagent solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of (i) at least one metal coordination complex including a metal coordination atom selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Sn, Pb, Tm, Bi, and Yb, to which is coordinately bound in a stable complex at least two different ligands selected from the group consisting of: β-diketonates, β-ketoiminates, β-diiminates, C 1 -C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for said metal coordination complex selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitriles, alkanols, organic amines, and polyamines.

Claim 11

A metal source reagent solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of (i) at least one metal coordination complex including a metal coordination atom selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Sn, Pb, Tm, Bi, and Yb, to which is coordinately bound in a stable complex at least two different ligands selected from the group consisting of: β-diketonates, β-ketoiminates, β-diiminates, C 1 -C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for said metal coordination complex selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitriles, alkanols, organic amines, and polyamines.

Claim 12

A metal source reagent liquid solution according to claim 9, wherein the metal coordination atom comprises a metal selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Al, Tl, Er, Sn, Pb, Tm, Bi, and Yb.

Claim 13

A metal source reagent liquid solution according to claim 9, wherein the metal coordination atom is coordinated to at least one alkoxide ligand and at least one β-diketonate ligand.

Claim 14

A metal source reagent liquid solution according to claim 9, wherein the metal coordination atom is coordinated to a β-diketonate ligand selected from the group consisting of acac, thd, fod, hfod, tfacac, and hfacac.

Claim 15

A metal source reagent liquid solution according to claim 9, wherein the solvent comprises at least one solvent species selected from the group consisting of: glyme solvents having from 1 to 20 ethoxy -(C 2 H 4 O)- repeat units; C 2 -C 12 alkanols, organic ethers selected from the group consisting of dialkyl ethers comprising C 1 -C 6 alkyl moieties, C 4 -C 8 cyclic ethers; C 12 -C 60 crown O 4 -O 20 ethers wherein the prefixed C i range is the number i of carbon atoms in the ether compound and the suffixed O i range is the number i of oxygen atoms in the ether compound; C 6 -C 12 aliphatic hydrocarbons; C 6 -C 18 aromatic hydrocarbons; organic esters; organic amines; and polyamines.

Claim 16

A metal source reagent liquid solution according to claim 9, wherein the solvent is selected from the group consisting of tetrahydrofuran, alkyl acetate, tetraglyme and C 3 -C 8 alkanols.

Claim 17

A metal source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of metal source reagent(s) and solvent medium selected from the group consisting of: ______________________________________ Metal Source Reagent(s) Solvent Medium ______________________________________ Al(thd).sub.3 80-98% tetrahydrofuran and 2-20% tetraglyme Al(OR).sub.3 80-98% tetrahydrofuran and 2-20% tetraglyme Ba(thd).sub.2 (tetraglyme) 85-99% butyl acetate and 1-15% tetraglyme Ca(thd).sub.2 (tetraglyme) Cu(thd).sub.2 Ba(thd).sub.2 (tetraglyme) 85-98% butyl acetate and 1-15% tetraglyme Sr(thd).sub.2 (tetraglyme) Ti(OiPr).sub.2 (thd).sub.2 Sr(thd).sub.2 (tetraglyme) 75-95% isopropanol with 5-25% tetraglyme Ca(thd).sub.2 (tetraglyme) Cr(thd).sub.3 80-98% tetrahydrofuran with 2-20% tetraglyme Er(thd).sub.3 85-99% butyl acetate and 1-15% tetraglyme Ir(acac).sub.3 butyl acetate or Ir(thd).sub.3 La(thd).sub.3 tetrahydrofuran (MeO).sub.3 P═O MgAl.sub.2 (OiPr).sub.8 isopropanol Nb(OiPr).sub.4 thd 45-88% tetrahydrofuran 10-35% isopropanol 2-20% tetraglyme Pb(thd).sub.2 80-98% tetrahydrofuran with 2-20% tetraglyme La(thd).sub.3 Ti(OiPr).sub.2 (thd).sub.2 Pb(thd).sub.2 80-98% tetrahydrofuran with 2-20% tetraglyme Ti(OiPr).sub.2 thd.sub.2 Pb(thd).sub.2 45-88% tetrahydrofuran Zr(thd).sub.4 10-35% isopropanol 2-20% tetraglyme Pb(thd).sub.2 45-88% tetrahydrofuran Zr(thd).sub.4 10-35% isopropanol Ti(OiPr).sub.2 (thd).sub.2 2-20% tetraglyme Ru(acac).sub.3 butyl acetate or Ru(thd).sub.3 Sn(alkyl).sub.2 (J-diketonate).sub.2 butyl acetate wherein alkyl = C.sub.1 -C.sub.18 alkyl Sn(acetate).sub.2 butyl acetate or 85-99% butyl acetate/ 1-15% tetraglyme Sr(thd).sub.2 (tetraglyme) 45-88% tetrahydrofuran BiPh.sub.3 10-35% isopropanol Ta(OiPr).sub.4 (thd) 2-20% tetraglyme Ta(OEt).sub.5 1% ethanol solution O═Ti(thd).sub.2 !.sub.n butyl acetate wherein n is 1 or 2 Y(thd).sub.3 isopropanol Y(thd).sub.3 butyl acetate/tetraglyme Ba(thd).sub.2 Cu(thd).sub.2 Zr(thd).sub.4 80-98% tetrahydrofuran and 2-20% tetraglyme Y(thd).sub.3 O═Zr(thd).sub.2 !.sub.n butyl acetate wherein n is 1 or 2 or butyl acetate/tetraglyme ______________________________________ wherein when the solvent medium contains multiple solvent components, the percentages specified are percentages by weight, based on the weight of the total solvent medium, and with the total percentage of all solvent compositions being 100% and wherein R is selected from the group consisting of C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, and fluorinated derivatives thereof wherein at least one hydrogen substituent is replaced by fluorine.

Claim 18

A metal source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of metal source reagent(s) and solvent medium selected from the group consisting of: ______________________________________ Metal Source Reagent(s) Solvent Medium ______________________________________ Al(thd).sub.3 80-98% tetrahydrofuran and 2-20% tetraglyme Al(OR).sub.3 80-98% tetrahydrofuran and 2-20% tetraglyme Ba(thd).sub.2 (tetraglyme) 85-99% butyl acetate and 1-15% tetraglyme Ca(thd).sub.2 (tetraglyme) Cu(thd).sub.2 Ba(thd).sub.2 (tetraglyme) 85-98% butyl acetate and 1-15% tetraglyme Sr(thd).sub.2 (tetraglyme) Ti(OiPr).sub.2 (thd).sub.2 Sr(thd).sub.2 (tetraglyme) 75-95% isopropanol with 5-25% tetraglyme Ca(thd).sub.2 (tetraglyme) Cr(thd).sub.3 80-98% tetrahydrofuran with 2-20% tetraglyme Er(thd).sub.3 85-99% butyl acetate and 1-15% tetraglyme Ir(acac).sub.3 butyl acetate or Ir(thd).sub.3 La(thd).sub.3 tetrahydrofuran (MeO).sub.3 P═O MgAl.sub.2 (OiPr).sub.8 isopropanol Nb(OiPr).sub.4 thd 45-88% tetrahydrofuran 10-35% isopropanol 2-20% tetraglyme Pb(thd).sub.2 80-98% tetrahydrofuran with 2-20% tetraglyme La(thd).sub.3 Ti(OiPr).sub.2 (thd).sub.2 Pb(thd).sub.2 80-98% tetrahydrofuran with 2-20% tetraglyme Ti(OiPr).sub.2 thd.sub.2 Pb(thd).sub.2 45-88% tetrahydrofuran Zr(thd).sub.4 10-35% isopropanol 2-20% tetraglyme Pb(thd).sub.2 45-88% tetrahydrofuran Zr(thd).sub.4 10-35% isopropanol Ti(OiPr).sub.2 (thd).sub.2 2-20% tetraglyme Ru(acac).sub.3 butyl acetate or Ru(thd).sub.3 Sn(alkyl).sub.2 (J-diketonate).sub.2 butyl acetate wherein alkyl = C.sub.1 -C.sub.18 alkyl Sn(acetate).sub.2 butyl acetate or 85-99% butyl acetate/ 1-15% tetraglyme Sr(thd).sub.2 (tetraglyme) 45-88% tetrahydrofuran BiPh.sub.3 10-35% isopropanol Ta(OiPr).sub.4 (thd) 2-20% tetraglyme Ta(OEt).sub.5 1% ethanol solution O═Ti(thd).sub.2 !.sub.n butyl acetate wherein n is 1 or 2 Y(thd).sub.3 isopropanol Y(thd).sub.3 butyl acetate/tetraglyme Ba(thd).sub.2 Cu(thd).sub.2 Zr(thd).sub.4 80-98% tetrahydrofuran and 2-20% tetraglyme Y(thd).sub.3 O═Zr(thd).sub.2 !.sub.n butyl acetate wherein n is 1 or 2 or butyl acetate/tetraglyme ______________________________________ wherein when the solvent medium contains multiple solvent components, the percentages specified are percentages by weight, based on the weight of the total solvent medium, and with the total percentage of all solvent compositions being 100% and wherein R is selected from the group consisting of C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, and fluorinated derivatives thereof wherein at least one hydrogen substituent is replaced by fluorine.

Claim 19

A source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of: (i) at least one metal coordination complex of the formula: M.sup.i A.sub.n (OR).sub.x B.sub.y Q.sub.z wherein: M is a metal selected from the group consisting of Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, Nb, Cr, W, Pm, Mn, Re, Sm, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Pb, Tm, Bi, and Yb; A is selected from the group consisting of β-diketotiates and β-ketoesters, and their sulfur and nitrogen analogs; R is selected from the group consisting of C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, and fluorinated derivatives thereof, wherein hydrogen substituent(s) of the C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 , cycloalkenyl, or C 6 -C 10 aryl ligand is/are replaced by fluorine substituent(s); B is selected from the group consisting of polyethers, polyamines, polythiols, bipyridines, glymes, alcohols, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, arylthiols, and aliphatic thiols (mercaptans); Q is hydrocarbyl or halohydrocarbyl; A, x, y and z are stoichiometric coefficients for the ligands A, OR, B and Q, respectively, wherein A is ≦1; each of X, Y, and Z is independently ≧0; and A a (OR) x B y Q z is in stoichiometric relationship to metal M; and (ii) a solvent for the metal coordination complexes selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitrites, alkanols, organic amines, and polyamines.

Claim 20

A source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of: (i) at least one metal coordination complex of the formula: M.sup.i A.sub.n (OR).sub.x B.sub.y Q.sub.z wherein: M is a metal selected from the group consisting of Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, Nb, Cr, W, Pm, Mn, Re, Sm, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Pb, Tm, Bi, and Yb; A is selected from the group consisting of β-diketotiates and β-ketoesters, and their sulfur and nitrogen analogs; R is selected from the group consisting of C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, and fluorinated derivatives thereof, wherein hydrogen substituent(s) of the C 1 -C 8 alkyl, C 2 -C 8 cycloalkyl, C 2 -C 10 alkenyl, C 2 -C 15 , cycloalkenyl, or C 6 -C 10 aryl ligand is/are replaced by fluorine substituent(s); B is selected from the group consisting of polyethers, polyamines, polythiols, bipyridines, glymes, alcohols, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, arylthiols, and aliphatic thiols (mercaptans); Q is hydrocarbyl or halohydrocarbyl; A, x, y and z are stoichiometric coefficients for the ligands A, OR, B and Q, respectively, wherein A is ≦1; each of X, Y, and Z is independently ≧0; and A a (OR) x B y Q z is in stoichiometric relationship to metal M; and (ii) a solvent for the metal coordination complexes selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitrites, alkanols, organic amines, and polyamines.

Claim 21

A metal source reagent composition having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of (i) a metal source reagent in (ii) solvent medium selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitriles, alkanols, organic amines, and polyamines, wherein the metal source reagent comprises at least one β-diketonate alkoxide compound including a metal M selected from the group consisting of Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Sn, Pb, Tm, B, and Yb, coordinated to at least one alkoxide ligand and at least one β-diketonate ligand, and having the formula; M(OR.sup.1).sub.x (R.sup.2 --C(G)--CH--C(G)--R.sup.3).sub.y wherein; G is oxygen, sulfur, or imide of the formula: ═NR b , wherein R b is H, C 1 -C 8 alkyl, or C 1 -C 8 perfluoroalkyl; x+Y=p where p is the valence of metal M; x=2y=q where q is the coordination number of metal M; R 1 is C 1 -C 6 hydrocarbyl or fluoroalkyl; and R 2 and R 3 are independently selected from the group consisting of C 1 -C 14 hydrocarbyl, C 1 -C 6 alkoxy, and C 2 -C 6 fluoroalkyl groups.

Claim 22

A metal source reagent composition having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of (i) a metal source reagent in (ii) solvent medium selected from the group consisting of glymes, aliphatic hydrocarbons, aromatic hydrocarbons, organic ethers, organic esters, alkyl nitriles, alkanols, organic amines, and polyamines, wherein the metal source reagent comprises at least one β-diketonate alkoxide compound including a metal M selected from the group consisting of Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Zr, Hf, Pr, V, Nb, Ta, Nd, Cr, W, Pm, Mn, Re, Sm, Fe, Ru, Eu, Co, Rh, Ir, Gd, Ni, Tb, Cu, Dy, Ho, Tl, Er, Sn, Pb, Tm, B, and Yb, coordinated to at least one alkoxide ligand and at least one β-diketonate ligand, and having the formula; M(OR.sup.1).sub.x (R.sup.2 --C(G)--CH--C(G)--R.sup.3).sub.y wherein; G is oxygen, sulfur, or imide of the formula: ═NR b , wherein R b is H, C 1 -C 8 alkyl, or C 1 -C 8 perfluoroalkyl; x+Y=p where p is the valence of metal M; x=2y=q where q is the coordination number of metal M; R 1 is C 1 -C 6 hydrocarbyl or fluoroalkyl; and R 2 and R 3 are independently selected from the group consisting of C 1 -C 14 hydrocarbyl, C 1 -C 6 alkoxy, and C 2 -C 6 fluoroalkyl groups.

Claim 23

A solution according to claim 17, wherein hydrocarbyl is selected from the group consisting of the group consisting of C 1 -C 8 alkyl, C 6 -C 10 cycloalkyl, C 2 -C 12 alkenyl and C 6 -C 14 aryl groups, and C 2 -C 6 fluoroalkyl groups is selected from perfluoroalkyls of 2 through 6 carbons.

Claim 24

A metal source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of: (i) at least one metal coordination complex including a metal to which is coordinatively bound at least one ligand in a stable complex, wherein the ligand is selected from the group consisting of: β-diketonates, β-ketoiminates, β-diiminates, C 1 -C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for said metal coordination complex, selected from the group consisting of: (A) 9:1 tetrahydrofuran/tetraglyme; (B) 8:2:1 tetrahydrofuran/isopropanol/tetraglyme; and (C) 25:1 butyl acetate/tetraglyme.

Claim 25

A metal source reagent liquid solution having utility for chemical vapor deposition in the manufacture of semiconductor device structures, said metal source reagent solution consisting essentially of: (i) at least one metal coordination complex including a metal to which is coordinatively bound at least one ligand in a stable complex, wherein the ligand is selected from the group consisting of: β-diketonates, β-ketoiminates, β-diiminates, C 1 -C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 15 cycloalkenyl, C 6 -C 10 aryl, C 1 -C 8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for said metal coordination complex, selected from the group consisting of: (A) 9:1 tetrahydrofuran/tetraglyme; (B) 8:2:1 tetrahydrofuran/isopropanol/tetraglyme; and (C) 25:1 butyl acetate/tetraglyme.