US5344948A
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Single-source molecular organic chemical vapor deposition agents and use
Assignee: Iowa State University Research Foundation Inc
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Filing: 1992-07-10
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Granted: 1994-09-06
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Expires: 2012-07-10
Abstract
Abstract Neutral single-source molecular organic precursors containing tetradentate tripodal chelating ligands are provided that are useful for the preparation of films using chemical vapor deposition. These complexes can be generally represented by the formula ##STR1## wherein "M" is selected from the group consisting of a lanthanide, an actinide, a Group IIIA metal, a Group IIIA metalloid, a Group IVA metal, a Group IVA metalloid, a Group VA metal, a Group VA metalloid, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and a Group VIIIB metal. The ligand "Z" can be present or absent, i.e., k=0-1, and is selected from the group consisting of hydrogen, halide, and a group bonded to "M" through N, O, P, S, As, Si, or C. In the tetradentate tripodal chelating ligand "E c " is N, P, or As, and m=0-1. When "E t " is N, P, or As, m=1, and when "E t " is O, S, or Se, m=0. Each "R 1 " is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl. In --[C(R 2 ) 2 ] n --, n=1-4, and each "R 2 " is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, and a heterocycle.
Inventors
- 👤 John G. Verkade
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 02:19
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/025; C07F5/00; C07F5/02; C07F5/022; C07F5/06; C07F5/069; C07F7/003; C07F7/08; C07F7/10; C07F7/22; C07F7/2284; C07F9/00; C07F9/005; C23; C23C; C23C16/00; C23C16/06; C23C16/18
Claims Analysis
Total Claims: 25
Claim 1
Independent Claim
195 words
A compound of the formula ##STR87## wherein: (a) M is selected from the group consisting of a lanthanide, an actinide, a Group IIIA metal, a Group IIIA metalloid, a Group IVA metal, a Group IVA metalloid, a Group VA metal, a Group VA metalloid, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and a Group VIIIB metal; (b) k=0-1; (c) Z is a nitrogen-bound, silicon-bound, or sulfur-bound ligand; (d) E c and each E t are independently selected from the group consisting of N, P, and As; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 2 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 2
Dependent Claim
195 words
A compound of the formula ##STR87## wherein: (a) M is selected from the group consisting of a lanthanide, an actinide, a Group IIIA metal, a Group IIIA metalloid, a Group IVA metal, a Group IVA metalloid, a Group VA metal, a Group VA metalloid, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and a Group VIIIB metal; (b) k=0-1; (c) Z is a nitrogen-bound, silicon-bound, or sulfur-bound ligand; (d) E c and each E t are independently selected from the group consisting of N, P, and As; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 2 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 3
Dependent Claim
43 words
The compound of claim 1 wherein k=0 and M is selected from the group consisting of B, Al, Ga, In, Tl, Ge, Si, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, and Ir.
Claim 4
Dependent Claim
30 words
The compound of claim 2 wherein a molecule of the compound is bound to another molecule of the compound through two E t --M bonds to form a dimeric species.
Claim 5
Dependent Claim
29 words
The compound of claim 1 wherein k=1 and M is selected from the group consisting of Si, Ge, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W.
Claim 6
Dependent Claim
30 words
The compound of claim 4 wherein a molecule of the compound is bound to another molecule of the compound through two E t --M bonds to form a dimeric species.
Claim 7
Dependent Claim
27 words
The compound of claim 4 wherein Z is selected from the group consisting of --NH 2 , --N(CH 3 ) 2 , --NCS, and --N 3 .
Claim 8
Dependent Claim
11 words
The compound of claim 4 wherein E c =E t =N.
Claim 9
Dependent Claim
173 words
A compound of the formula ##STR88## wherein: (a) M is selected from the group consisting of a Group IVA metal, a Group IVA metalloid, a Group IVB metal, a Group VB metal, and a Group VIB metal; (b) k=0-1; (c) Z is a nitrogen-bound, silicon-bound, or sulfur-bound ligand; (d) E c is selected from the group consisting of N, P, and As; (e) each E t is independently selected from the group consisting of N, P, As, and m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 10
Dependent Claim
173 words
A compound of the formula ##STR88## wherein: (a) M is selected from the group consisting of a Group IVA metal, a Group IVA metalloid, a Group IVB metal, a Group VB metal, and a Group VIB metal; (b) k=0-1; (c) Z is a nitrogen-bound, silicon-bound, or sulfur-bound ligand; (d) E c is selected from the group consisting of N, P, and As; (e) each E t is independently selected from the group consisting of N, P, As, and m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 11
Dependent Claim
41 words
The compound of claim 8 wherein each E t is independently selected from the group consisting of N, P, and As, and each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 4 )alkyl, and triorganosilyl.
Claim 12
Dependent Claim
21 words
The compound of claim 8 wherein n=2 and each R 2 in --[C(R 2 ) 2 ] n -- is hydrogen.
Claim 13
Dependent Claim
240 words
A compound of the formula ##STR89## wherein: (a) M is selected from the group consisting of a lanthanide, an actinide, a Group IIIA metal, a Group IIIA metalloid, a Group IVA metal, a Group IVA metalloid, a Group VA metal, a Group VA metalloid, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and a Group VIIIB metal; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c is N; (e) each E t is N or O, wherein at least one E t is N and at least one E t is O, with the proviso that (i) when E t is N, m=1; and (ii) when E t is O, m=0; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 14
Dependent Claim
240 words
A compound of the formula ##STR89## wherein: (a) M is selected from the group consisting of a lanthanide, an actinide, a Group IIIA metal, a Group IIIA metalloid, a Group IVA metal, a Group IVA metalloid, a Group VA metal, a Group VA metalloid, a Group IIIB metal, a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, and a Group VIIIB metal; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c is N; (e) each E t is N or O, wherein at least one E t is N and at least one E t is O, with the proviso that (i) when E t is N, m=1; and (ii) when E t is O, m=0; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 15
Dependent Claim
29 words
The compound of claim 11 wherein a molecule of the compound combines with another molecule of the compound through two E t --M bonds to form a dimeric species.
Claim 16
Dependent Claim
177 words
A compound of the formula ##STR90## wherein: (a) M is selected from the group consisting of a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, a Group VIIIB iron group metal, and a Group VIIIB cobalt group metal; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c =E t =N; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and a triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 17
Dependent Claim
177 words
A compound of the formula ##STR90## wherein: (a) M is selected from the group consisting of a Group IVB metal, a Group VB metal, a Group VIB metal, a Group VIIB metal, a Group VIIIB iron group metal, and a Group VIIIB cobalt group metal; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c =E t =N; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 )heterocycle, and a triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 18
Dependent Claim
9 words
The compound of claim 13 wherein "M--Z" is V═O.
Claim 19
Dependent Claim
27 words
The compound of claim 13 wherein "M--Z" is V═NR 7 wherein R 7 is selected from the group consisting of (C 1 -C 4 )alkyl and triorganosilyl.
Claim 20
Dependent Claim
9 words
The compound of claim 13 wherein "M-Z" is Mo.tbd.N.
Claim 21
Dependent Claim
150 words
A compound of the formula ##STR91## wherein: (a) M is selected from the group consisting of Ge and Sn; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c =E t =N; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 22
Dependent Claim
150 words
A compound of the formula ##STR91## wherein: (a) M is selected from the group consisting of Ge and Sn; (b) k=0-1; (c) Z is selected from the group consisting of hydrogen, halide, and a ligand which bonds to M through N, O, P, S, As, Si, or C; (d) E c =E t =N; (e) m=1; (f) each R 1 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, a (C 5 -C 18 heterocycle, and triorganosilyl; (g) n=1-4; and (h) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 7 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 23
Dependent Claim
142 words
A compound of the formula ##STR92## wherein: (a) M is Ti; (b) k=1; (c) Z is selected from the group consisting of: (i) --N(R 5 ) 2 wherein each R 5 is independently selected from the group consisting of hydrogen and (C 1 -C 4 )alkyl; and (ii) --SR 6 wherein R 6 is selected from the group consisting of (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 6 -C 18 )aryl, and (C 7 -C 20 )aralkyl; (d) E c is N; (e) each E t is O, and m=0; (f) n=1-4; and (g) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 6 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 24
Dependent Claim
142 words
A compound of the formula ##STR92## wherein: (a) M is Ti; (b) k=1; (c) Z is selected from the group consisting of: (i) --N(R 5 ) 2 wherein each R 5 is independently selected from the group consisting of hydrogen and (C 1 -C 4 )alkyl; and (ii) --SR 6 wherein R 6 is selected from the group consisting of (C 1 -C 10 )alkyl, (C 2 -C 10 )alkenyl, (C 6 -C 18 )aryl, and (C 7 -C 20 )aralkyl; (d) E c is N; (e) each E t is O, and m=0; (f) n=1-4; and (g) each R 2 is independently selected from the group consisting of hydrogen, (C 1 -C 20 )alkyl, (C 2 -C 20 )alkenyl, (C 2 -C 20 )alkynyl, (C 6 -C 18 )aryl, (C 6 -C 20 )aralkyl, and a (C 5 -C 18 )heterocycle.
Claim 25
Dependent Claim
30 words
The compound of claim 18 wherein a molecule of the compound is combined with another molecule of the compound through two E t --M bonds to form a dimeric species.
References Cited (Backward Citations)
US5051533A
Cited
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