Precursor compositions for chemical vapor deposition, and ligand exchange resistant metal-organic precursor solutions comprising same
First Claim
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1. 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, β
diiminates, C1 -C8 alkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, C1 -C8 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.
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Abstract
A metal source reagent liquid solution, comprising: (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, C1 -C8 alkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, C1 -C8 alkoxy, and fluorinated derivatives thereof; and (ii) a solvent for the metal coordination complex. The solutions are usefully employed for chemical vapor deposition of metals from the metal coordination complexes, such as 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/or Yb. The solvent may comprise glyme solvents, alkanols, organic ethers, aliphatic hydrocarbons, and/or aromatic hydrocarbons. Solutions of the invention having two or more metal coordination complexes are resistant to detrimental ligand exchange reactions which adversely affect the stability and/or volatilizability of the metal complex for CVD applications.
259 Citations
19 Claims
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1. 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:
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(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, β
diiminates, C1 -C8 alkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, C1 -C8 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. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8)
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9. 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, C1 -C8 alkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, C1 -C8 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. - View Dependent Claims (10, 11, 12, 13, 14)
- β
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15. 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:
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space="preserve" listing-type="tabular">______________________________________ 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 C1 -C8 alkyl, C2 -C8 cycloalkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, and fluorinated derivatives thereof wherein at least one hydrogen substituent is replaced by fluorine.
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16. 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:
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(i) at least one metal coordination complex of the formula;
space="preserve" listing-type="equation">M.sup.i A.sub.n (OR).sub.x B.sub.y Q.sub.zwherein; 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 C1 -C8 alkyl, C2 -C8 cycloalkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, and fluorinated derivatives thereof, wherein hydrogen substituent(s) of the C1 -C8 alkyl, C2 -C8 cycloalkyl, C2 -C10 alkenyl, C2 -C15, cycloalkenyl, or C6 -C10 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
Aa (OR)x By Qz 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.
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17. 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;
space="preserve" listing-type="equation">M(OR.sup.1).sub.x (R.sup.2 --C(G)--CH--C(G)--R.sup.3).sub.ywherein; G is oxygen, sulfur, or imide of the formula;
═
NRb, wherein Rb is H, C1 -C8 alkyl, or C1 -C8 perfluoroalkyl;x+Y=p where p is the valence of metal M; x=2y=q where q is the coordination number of metal M; R1 is C1 -C6 hydrocarbyl or fluoroalkyl; and R2 and R3 are independently selected from the group consisting of C1 -C14 hydrocarbyl, C1 -C6 alkoxy, and C2 -C6 fluoroalkyl groups. - View Dependent Claims (18)
- -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
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19. 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:
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(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, C1 -C8 alkyl, C2 -C10 alkenyl, C2 -C15 cycloalkenyl, C6 -C10 aryl, C1 -C8 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.
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Specification
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- Resources
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Litigation Data
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Current AssigneeEntegris Incorporated
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Original AssigneeAdvanced Technology Materials, Inc. (Entegris Incorporated)
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InventorsVaartstra, Brian A., Gordon, Douglas, Baum, Thomas H., Glassman, Timothy E., Gardiner, Robin A., Kirlin, Peter S., Pombrik, Sofia
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Primary Examiner(s)Lovering, Richard D.
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Application NumberUS08/414,504Time in Patent Office1,292 DaysField of Search252/182.23, 106/287.17, 106/287.19, 423/DIG. 14, 556/44, 556/55, 556/114, 556/175, 562/607US Class Current106/287.17CPC Class CodesC23C 16/18 from metallo-organic compoundsC23C 16/40 OxidesC23C 16/408 of copper or solid solution...C23C 16/409 of the type ABO3 with A rep...C23C 16/4481 by evaporation using carrie...C23C 16/45561 Gas plumbing upstream of th...H10N 60/0464 by metalloorganic chemical ...Y10S 423/14 Ion exchange; chelation or ...
