Metal complex source reagents for MOCVD

• US 5,453,494 A
• Filed: 01/18/1994
• Issued: 09/26/1995
• Est. Priority Date: 07/06/1990
• Status: Expired due to Term

• Current Assignee: Entegris Incorporated
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Gardiner, Robin A., Kirlin, Peter S., Brown, Duncan W.
• Primary Examiner(s): WU, SHEAN CHIU
• Application Number:
  US08/181,800
• Time in Patent Office: 616 Days
• Field of Search: 505/100, 505/120, 505/121, 505/124, 505/125, 505/734, 546/256, 546/257, 546/259, 534/15
• US Class Current: 534/15
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/408 of copper or solid solutions thereof
• CPC Class Codes: C23C 16/409 of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
• CPC Class Codes: C23C 16/4481 by evaporation using carrier gas in contact with the source material C23C16/4486 takes precedence
• CPC Class Codes: C23C 16/4483 using a porous body
• CPC Class Codes: C23C 16/45561 Gas plumbing upstream of the reaction chamber
• CPC Class Codes: G02B 6/02 Optical fibres with cladding with or without a coating
• CPC Class Codes: H10N 60/0464 by metalloorganic chemical vapour deposition [MOCVD]

Abstract

Metal organic chemical vapor deposition (MOCVD) source reagents useful for formation of metal-containing films, such as thin film copper oxide high temperature superconductor (HTSC) materials. The source reagents have the formula MAyX wherein: M is a metal such as Cu, Ba, Sr, La, Nd, Ce, Pr, Sm, Eu, Th, Gd, Tb, Dy, Ho, Er, Tm Yb, Lu Bi, Tl, Y or Pb; A is a monodentate or multidentate organic ligand; y is 2 or 3; MAy is a stable sub-complex at STP conditions; and X is a monodentate or multidentate ligand coordinated to M and containing one or more atoms independently selected from the group consisting of atoms of the elements C, N, H, S, O, and F. The ligand A may for example be selected from beta-diketonates, cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases. The complexes of the invention utilize monodentate or multidentate ligands to provide additional coordination to the metal atom, so that the resulting complex is of enhanced volatility characteristics, and enhanced suitability for MOCVD applications.

Claims

1. A metalorganic complex of the formula:

space="preserve" listing-type="equation">MAyX

wherein;

M is a y-valent metal;

A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MAy with ligand X and which forms a stable STP sub-complex MAy with M;

y is 2 or 3;

each of the A ligands may be the same or different; and

X is a monodentate or multidentate ligand coordinated to M and containing one or more atoms independently selected from the group consisting of atoms of the elements C, N, H, S, O and F.

2. A complex according to claim 1, wherein M is selected from the group consisting of Cu, Ba, Sr, La, Nd, Ce, Pr, Sm, Eu, Th, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Bi, Tl, Y and Pb.

3. A complex according to claim 1, wherein A is selected from the group consisting of β

-diketonates, cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases.

4. A complex according to claim 1, wherein A is selected from the group consisting of β

-diketonates and cyclopentadienyls.

5. A complex according to claim 1, wherein A is a β

-diketonate.

6. A complex according to claim 1, wherein A is selected from the group consisting of:

(i) 2,2,6,6-tetramethyl-3,5-heptanedionate;

(ii) 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate;

(iii) 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate;

(iv) cyclopentadienyl;

(v) 4,4'"'"'-(ethane-1,2-diyldiimino)bis(3-pentene-2-one);

(vi) pentamethylcyclopentadienyl and other substituted cyclopentadienyls;

(vii) 2,4-pentadionate; and

(viii) 1,1,1-trifluoro-2,4-pentadionate.

7. A complex according to claim 1, wherein X is selected from the group consisting of:

(i) oxyhydrocarbyl ligands;

(ii) nitrogenous oxyhydrocarbyl ligands; and

(iii) fluorooxyhydrocarbyl ligands.

8. A complex according to claim 1, wherein X is selected from the group consisting of:

(a) amines and polyamines;

(b) bipyridines;

(c) ligands of the formula;

##STR24## wherein G is --O--, --S--, or --NR--, wherein R is H or hydrocarbyl;

(d) crown ethers; and

(e) ligands of the formula;

space="preserve" listing-type="equation">R.sup.0 (C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.n R.sup.0

wherein;

R⁰ =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl;

R¹ =H, F, or a sterically acceptable hydrocarbyl substituent;

R² =H, F, or a sterically acceptable hydrocarbyl substituent;

n=4, 5, or 6; and

each R⁰, R¹, and R² may be the same as or different from the other R⁰, R¹, and R², respectively.

9. A complex according to claim 1, wherein X is selected from the group consisting of tetraglyme, tetrahydrofuran, bipydridine, and 18 crown 6 ethers.

10. A complex according to claim 1, wherein X comprises a ligand of the formula;

space="preserve" listing-type="equation">R.sup.0 (C(R.sup.1).sub.2 (R.sup.2).sub.2 O).sub.n R.sup.o

wherein;

R⁰ =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl;

R¹ =H, F, or a sterically acceptable hydrocarbyl substituent;

R² =H, F, or a sterically acceptable hydrocarbyl substituent;

n=4, 5, or 6; and

each R⁰, R¹, and R² may be the same as or different from the other R⁰, R¹, and R², respectively.

11. A complex according to claim 1, wherein X comprises a ligand of the formula:

space="preserve" listing-type="equation">R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.4 R.sup.o

wherein;

each R⁰, R¹, and R² is selected independently, and

R⁰ =H, CH₃, or C₂ H₅ ;

R¹ and R² =H or F.

12. A complex according to claim 1, wherein:

A is a β

-diketonate; and

X is tetraglyme, 18 crown 6 ether, or bipyridine.

13. A complex according to claim 1, wherein each of the ligands A is a constituent moiety of a single group which is coordinatingly attached to M thereby.

14. A complex according to claim 1, wherein the ligand X and at least one of said ligands A is a constituent moiety of a single group which is coordinatingly attached to M thereby.

15. A composition comprising:

(i) a metalorganic complex of the formula;

space="preserve" listing-type="equation">MAyX

wherein;

M is a y-valent metal;

A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MAy with ligand X and which forms a stable STP sub-complex MAy with M;

y is 2 or 3;

each of the A ligands may be the same or different; and

X is a monodentate or multidentate ligand coordinated to M and containing one or more atoms independently selected from the group consisting of atoms of the elements C, N, H, S, O and F, or precursor or components thereof; and

(ii) a solvent or suspending agent therefor.