US5225561A
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Source reagent compounds for MOCVD of refractory films containing group IIA elements
Assignee: Entegris Inc
•
Filing: 1990-09-12
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Granted: 1993-07-06
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Expires: 2010-09-12
Abstract
Abstract Metal organic chemical vapor deposition (MOCVD) formation of copper oxide superconductor materials. Various source reagents of Group II elements suitable for high temperature superconductor (HTSC) material formation are described, including beta-diketonates, cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases, as well as complexes of such Group II compounds, utilizing monodentate or multidentate ligands to provide additional coordination to the Group IIA atom, so that the resulting complex is of enhanced volatility characteristics, and enhanced suitability for MOCVD applications. Also disclosed are methods of synthesizing such compounds and complexes, including a method of making Group II metal beta-diketonate compounds having enhanced thermal stability characteristics. Further disclosed are a vertical inverted reactor for chemical vapor deposition, and various methods of processing applied metal oxide films for enhanced HTSC character.
Inventors
- 👤 Peter S. Kirlin
- 👤 Duncan W. Brown
- 👤 Robin A. Gardiner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 21:35
CPC Classifications
G; G02; G02B; G02B6/00; G02B6/02; C; C23; C23C; C23C16/00; C23C16/06; C23C16/18; C23C16/22; C23C16/30; C23C16/40; C23C16/408; C23C16/409; C23C16/44; C23C16/448; C23C16/4481; C23C16/4483; C23C16/455; C23C16/45561; H; H10; H10N; H10N60/00; H10N60/01; H10N60/0268; H10N60/0296; H10N60/0436; H10N60/0464
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
159 words
A Group II metalorganic complex of the formula: MA.sub.2 X wherein M is barium, calcium, or strontium; A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MA 2 with ligand X and which forms a stable STP sub-complex MA 2 with M; 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, X being selected such that the metalorganic complex MA 2 X: (a) is of higher volatility than the sub-complex MA 2 ; (b) has a vapor pressure of at least 100 microns of mercury at a temperature in the range of from 120° C. to 250° C.; (c) is thermally stable below about 250° C.; and (d) thermally decomposes at a temperature of ≧400° C.
Claim 2
Dependent Claim
159 words
A Group II metalorganic complex of the formula: MA.sub.2 X wherein M is barium, calcium, or strontium; A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MA 2 with ligand X and which forms a stable STP sub-complex MA 2 with M; 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, X being selected such that the metalorganic complex MA 2 X: (a) is of higher volatility than the sub-complex MA 2 ; (b) has a vapor pressure of at least 100 microns of mercury at a temperature in the range of from 120° C. to 250° C.; (c) is thermally stable below about 250° C.; and (d) thermally decomposes at a temperature of ≧400° C.
Claim 3
Dependent Claim
24 words
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.
Claim 4
Dependent Claim
18 words
A complex according to claim 1, wherein A is selected from the group consisting of β-diketonates and cyclopentadienyls.
Claim 5
Dependent Claim
11 words
A complex according to claim 1, wherein A is a β-diketonate.
Claim 6
Dependent Claim
35 words
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) 4,4'-(ethane-1, 2-diyldiimino) bis (pent-3-ene-2-one); (v) cyclopentadienyl; (vi) pentamethylcyclopentadienyl; (vii) 2,4-pentadionate; and (viii) 1,1,1-trifluoro-2,4-pentadionate.
Claim 7
Dependent Claim
26 words
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.
Claim 8
Dependent Claim
122 words
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: ##STR35## wherein G is --O--, --S--, or --NR--, wherein R is H or hydrocarbyl; (d) crown ethers; and (e) ligands of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.n R.sup.0 wherein: R 0 =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl; R 1 =H, F, or a sterically acceptable hydrocarbyl substituent; R 2 =H, F, or a sterically acceptable hydrocarbyl substituent; n=4, 5, or 6; and each R 0 , R 1 , and R 2 may be the same as or different from the other R 0 , R 1 , and R 2 , respectively.
Claim 9
Dependent Claim
23 words
A complex according to claim 1, wherein X is selected from the group consisting of tetraglyme, tetrahydrofuran, bipydridine, and 18 crown 6 ethers.
Claim 10
Dependent Claim
87 words
A complex according to claim 1, wherein X comprises a ligand of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.n R.sup.0 wherein: R 0 =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl; R 1 =H, F, or a sterically acceptable hydrocarbyl substituent; R 2 =H, F, or a sterically acceptable hydrocarbyl substituent; n=4, 5, or 6; and each R 0 , R 1 , and R 2 may be the same as or different from the other R 0 , R 1 , and R 2 , respectively.
Claim 11
Dependent Claim
53 words
A complex according to claim 1, wherein X comprises a ligand of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.4 R.sup.0 wherein: each R 0 , R 1 and R 2 is selected independently, and R 0 =H, CH 3 , or C 2 H 5 ; R 1 and R 2 =H or F.
Claim 12
Dependent Claim
24 words
A complex according to claim 1, wherein: M is barium; A is a β-diketonate; and X is tetraglyme, 18 crown 6 ether, or bipyridine.
Claim 13
Dependent Claim
24 words
A complex according to claim 1, wherein both ligands A are constituent moieties of a single group which is coordinatingly attached to M thereby.
Claim 14
Dependent Claim
32 words
A complex according to claim 1, wherein the ligand X and at least one of said ligands A are constituent moieties of a single group which is coordinatingly attached to M thereby.
Claim 15
Independent Claim
30 words
A method of making a Group II β-diketonate compound, comprising reacting a hydride of the Group II metal with a dione corresponding to the β-diketonate, in a non-aqueous solvent medium.
Claim 16
Independent Claim
30 words
A method of making a Group II β-diketonate compound, comprising reacting a hydride of the Group II metal with a dione corresponding to the β-diketonate, in a non-aqueous solvent medium.
Claim 17
Dependent Claim
50 words
A method according to claim 14, wherein the non-aqueous solvent medium comprises a solvent selected from the group consisting of (i) compounds of the formula ##STR36## wherein G is selected from the group consisting of --S--, --O--, and --NR-- wherein R is H or hydrocarbyl, and (ii) straight chain ethers.
Claim 18
Dependent Claim
10 words
A method according to claim 15, wherein G is --O--.
Claim 19
Dependent Claim
27 words
A method according to claim 14, wherein the dione has the formula ##STR37## wherein R a is fluoroalkyl, R b is akylene, and R c is alkyl.
Claim 20
Dependent Claim
20 words
A method according to claim 17, wherein R a is perfluoropropyl, R b is methylene, and R c is t-butyl.
Claim 21
Dependent Claim
176 words
A Group II metalorganic complex of the formula: MA.sub.2 X wherein: M is barium, calcium, or strontium; A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MA 2 with ligand X and which forms a stable STP sub-complex MA 2 with M wherein A is selected from the group consisting of cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases; 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, X being selected such that the metalorganic complex MA 2 X: (a) is of higher volatility than the sub-complex MA 2 ; (b) has a vapor pressure of at least 100 microns of mercury at a temperature in the range of from 120° C. to 250° C.; (c) is thermally stable below about 250° C.; and (d) thermally decomposes at a temperature of ≧400° C.
Claim 22
Dependent Claim
176 words
A Group II metalorganic complex of the formula: MA.sub.2 X wherein: M is barium, calcium, or strontium; A is a monodentate or multidentate organic ligand coordinated to M which allows complexing of MA 2 with ligand X and which forms a stable STP sub-complex MA 2 with M wherein A is selected from the group consisting of cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases; 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, X being selected such that the metalorganic complex MA 2 X: (a) is of higher volatility than the sub-complex MA 2 ; (b) has a vapor pressure of at least 100 microns of mercury at a temperature in the range of from 120° C. to 250° C.; (c) is thermally stable below about 250° C.; and (d) thermally decomposes at a temperature of ≧400° C.
Claim 23
Dependent Claim
18 words
A complex according to claim 19, wherein A is selected from the group consisting of β-diketonates and cyclopentadienyls.
Claim 24
Dependent Claim
18 words
A complex according to claim 14, wherein A is selected from the group consisting of cyclopentadienyl and pentamethylcyclopentadienyl.
Claim 25
Dependent Claim
26 words
A complex according to claim 14, wherein X is selected from the group consisting of: (i) oxyhydrocarbyl ligands; (ii) nitrogenous oxyhydrocarbyl ligands; and (iii) fluorooxyhydrocarbyl ligands.
Claim 26
Dependent Claim
122 words
A complex according to claim 14, wherein X is selected form the group consisting of: (a) amines and polyamines; (b) bipyridines; (c) ligands of the formula: ##STR38## wherein G is --O--, --S--, or --NR--, wherein R is H or hydrocarbyl; (d) crown ethers; and (e) ligands of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.n R.sup.0 wherein: R 0 =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl; R 1 =H, F, or a sterically acceptable hydrocarbyl substituent; R 2 =H, F, or a sterically acceptable hydrocarbyl substituent; n=4, 5, or 6; and each R 0 , R 1 , and R 2 may be the same as or different from the other R 0 , R 1 , and R 2 , respectively.
Claim 27
Dependent Claim
23 words
A complex according to claim 19, wherein X is selected from the group consisting of tetraglyme, tetrahydrofuran, bipydridine, and 18 crown 6 ethers.
Claim 28
Dependent Claim
87 words
A complex according to claim 19, wherein X comprises a ligand of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.n R.sup.0 wherein: R 0 =H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl; R 1 =H, F, or a sterically acceptable hydrocarbyl substituent; R 2 =H, F, or a sterically acceptable hydrocarbyl substituent; n=4, 5, or 6; and each R 0 , R 1 , and R 2 may be the same as or different from the other R 0 , R 1 , and R 2 , respectively.
Claim 29
Dependent Claim
54 words
A complex according to claim 19, wherein X comprises a ligand of the formula: R.sup.0 O(C(R.sup.1).sub.2 C(R.sup.2).sub.2 O).sub.4 R.sup.0 wherein: each R 0 , R 1 and R 2 is selected independently, and R 0 =H, CH 3 , or C 2 H 5 ; and R 1 and R 2 =H or F.
Claim 30
Dependent Claim
36 words
A complex according to claim 19, wherein: M is barium; A is selected form the group consisting of cyclopentadienyls, alkyls, perfluoroalkyls, alkoxides, perfluoroalkoxides, and Schiff bases; and X is tetraglyme, 18 crown 6 ether, or bipyridine.
Claim 31
Dependent Claim
24 words
A complex according to claim 19, wherein both ligands A are constituent moieties of a single group which is coordinatingly attached to M thereby.
Claim 32
Dependent Claim
32 words
A complex according to claim 19, wherein the ligand X and at least one of said ligands A are constituent moieties of a single group which is coordinatingly attached to M thereby.
Claim 33
Independent Claim
40 words
A method of making a Group II β-diketonate compound, comprising reacting a hydride of a Group II metal selected form the group consisting of barium, calcium, and strontium with a dione corresponding to the β-diketonate, in a non-aqueous solvent medium.
Claim 34
Independent Claim
40 words
A method of making a Group II β-diketonate compound, comprising reacting a hydride of a Group II metal selected form the group consisting of barium, calcium, and strontium with a dione corresponding to the β-diketonate, in a non-aqueous solvent medium.
Claim 35
Dependent Claim
50 words
A method according to claim 30, wherein the non-aqueous solvent medium comprises a solvent selected form the group consisting of (i) compounds of the formula ##STR39## wherein G is selected from the group consisting of --S--, --O--, and --NR-- wherein R is H or hydrocarbyl, and (ii) straight chain ethers.
Claim 36
Dependent Claim
10 words
A method according to claim 31, wherein G is --O--.
Claim 37
Dependent Claim
27 words
A method according to claim 30, wherein the dione has the formula ##STR40## wherein R a is fluoroalkyl, R b is alkylene, and R c is alkyl.
Claim 38
Dependent Claim
20 words
A method according to claim 33, wherein R a is perfluoropropyl, R b is methylene, and R c is t-butyl.
Claim 39
Dependent Claim
39 words
A complex according to claim 1, wherein X is selected from the group consisting of tetraglyme, tetrahydrofuran, amines, polyamines, bipyridine, and bipyridine analogs of the formula ZWZ wherein Z is pyridinyl and W is a divalent organic linking group.
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