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

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.dbd.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.dbd.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.dbd.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.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.8 cycloalkyl, C.sub.2 -C.sub.10 alkenyl, C.sub.2 -C.sub.15 cycloalkenyl, C.sub.6 -C.sub.10 aryl, and fluorinated derivatives thereof wherein at least one hydrogen substituent is replaced by fluorine.

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 .beta.-diketotiates and .beta.-ketoesters, and their sulfur and nitrogen analogs;
• R is selected from the group consisting of C.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.8 cycloalkyl, C.sub.2 -C.sub.10 alkenyl, C.sub.2 -C.sub.15 cycloalkenyl, C.sub.6 -C.sub.10 aryl, and fluorinated derivatives thereof, wherein hydrogen substituent(s) of the C.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.8 cycloalkyl, C.sub.2 -C.sub.10 alkenyl, C.sub.2 -C.sub.15, cycloalkenyl, or C.sub.6 -C.sub.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 .ltoreq.1;
• each of X, Y, and Z is independently .gtoreq.0;
• and A.sub.a (OR).sub.x B.sub.y Q.sub.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.

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 .beta.-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 .beta.-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:
• .dbd.NR.sub.b, wherein R.sub.b is H, C.sub.1 -C.sub.8 alkyl, or C.sub.1 -C.sub.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.sup.1 is C.sub.1 -C.sub.6 hydrocarbyl or fluoroalkyl;
• and
• R.sup.2 and R.sup.3 are independently selected from the group consisting of C.sub.1 -C.sub.14 hydrocarbyl, C.sub.1 -C.sub.6 alkoxy, and C.sub.2 -C.sub.6 fluoroalkyl groups.

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:
• .beta.-diketonates, .beta.-ketoiminates, .beta.-diiminates, C.sub.1 -C.sub.8 alkyl, C.sub.2 -C.sub.10 alkenyl, C.sub.2 -C.sub.15 cycloalkenyl, C.sub.6 -C.sub.10 aryl, C.sub.1 -C.sub.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.