# US 5,344,948 A · Single-source molecular organic chemical vapor deposition agents and use

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- Number: US 5,344,948 A
- Document ID: US5344948A
- Status: Granted
- Kind: A
- Application number: 07/911,923
- Filed: 1992-07-10
- Granted: 1994-09-06
- Earliest claimed: 1992-02-25
- Assignees: Iowa State University Research Foundation, Inc.
- Inventors: John G. Verkade
- Web page: https://patentgrep.com/patent/US5344948A

## CPC

- C07F 7/025: {without C-silicon linkages}
- C07F 5/022: {without C-boron linkages}
- C07F 5/069: {without C-aluminium linkages}
- C07F 7/003: {without C-Metal linkages}
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C07F 7/2284: {Compounds with one or more Sn-N linkages}
- C07F 9/005: {Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages}
- C23C 16/18: from metallo-organic compounds
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## 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.sub.c " is N, P, or As, and m=0-1. When "E.sub.t " is N, P, or As, m=1, and when "E.sub.t " is O, S, or Se, m=0. Each "R.sup.1 " is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18)heterocycle, and triorganosilyl. In --[C(R.sup.2).sub.2 ].sub.n --, n=1-4, and each "R.sup.2 " is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, and a heterocycle.

## Claims

### Claim 1

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.sub.c and each E.sub.t are independently selected from the group consisting of N, P, and As;
(e) m=1;
(f) each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.2 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18)heterocycle, and triorganosilyl;
(g) n=1-4; and
(h) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 2 (depends on 1)

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 3 (depends on 2)

The compound of claim 2 wherein a molecule of the compound is bound to another molecule of the compound through two E.sub.t --M bonds to form a dimeric species.

### Claim 4 (depends on 1)

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 5 (depends on 4)

The compound of claim 4 wherein a molecule of the compound is bound to another molecule of the compound through two E.sub.t --M bonds to form a dimeric species.

### Claim 6 (depends on 4)

The compound of claim 4 wherein Z is selected from the group consisting of --NH.sub.2, --N(CH.sub.3).sub.2, --NCS, and --N.sub.3.

### Claim 7 (depends on 4)

The compound of claim 4 wherein E.sub.c =E.sub.t =N.

### Claim 8

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.sub.c is selected from the group consisting of N, P, and As;
(e) each E.sub.t is independently selected from the group consisting of N, P, As, and m=1;
(f) each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18)heterocycle, and triorganosilyl;
(g) n=1-4; and
(h) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 9 (depends on 8)

The compound of claim 8 wherein each E.sub.t is independently selected from the group consisting of N, P, and As, and each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.4)alkyl, and triorganosilyl.

### Claim 10 (depends on 8)

The compound of claim 8 wherein n=2 and each R.sup.2 in --[C(R.sup.2).sub.2 ].sub.n -- is hydrogen.

### Claim 11

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.sub.c is N;
(e) each E.sub.t is N or O, wherein at least one E.sub.t is N and at least one E.sub.t is O, with the proviso that
(i) when E.sub.t is N, m=1; and
(ii) when E.sub.t is O, m=0;
(f) each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18)heterocycle, and triorganosilyl;
(g) n=1-4; and
(h) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 12 (depends on 11)

The compound of claim 11 wherein a molecule of the compound combines with another molecule of the compound through two E.sub.t --M bonds to form a dimeric species.

### Claim 13

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.sub.c =E.sub.t =N;
(e) m=1;
(f) each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18)heterocycle, and a triorganosilyl;
(g) n=1-4; and
(h) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 14 (depends on 13)

The compound of claim 13 wherein "M--Z" is V.dbd.O.

### Claim 15 (depends on 13)

The compound of claim 13 wherein "M--Z" is V.dbd.NR.sup.7 wherein R.sup.7 is selected from the group consisting of (C.sub.1 -C.sub.4)alkyl and triorganosilyl.

### Claim 16 (depends on 13)

The compound of claim 13 wherein "M-Z" is Mo.tbd.N.

### Claim 17

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.sub.c =E.sub.t =N;
(e) m=1;
(f) each R.sup.1 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, a (C.sub.5 -C.sub.18 heterocycle, and triorganosilyl;
(g) n=1-4; and
(h) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.7 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 18

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.sup.5).sub.2 wherein each R.sup.5 is independently selected from the group consisting of hydrogen and (C.sub.1 -C.sub.4)alkyl; and
(ii) --SR.sup.6 wherein R.sup.6 is selected from the group consisting of (C.sub.1 -C.sub.10)alkyl, (C.sub.2 -C.sub.10)alkenyl, (C.sub.6 -C.sub.18)aryl, and (C.sub.7 -C.sub.20)aralkyl;
(d) E.sub.c is N;
(e) each E.sub.t is O, and m=0;
(f) n=1-4; and
(g) each R.sup.2 is independently selected from the group consisting of hydrogen, (C.sub.1 -C.sub.20)alkyl, (C.sub.2 -C.sub.20)alkenyl, (C.sub.2 -C.sub.20)alkynyl, (C.sub.6 -C.sub.18)aryl, (C.sub.6 -C.sub.20)aralkyl, and a (C.sub.5 -C.sub.18)heterocycle.

### Claim 19 (depends on 18)

The compound of claim 18 wherein a molecule of the compound is combined with another molecule of the compound through two E.sub.t --M bonds to form a dimeric species.