Organometallic compounds

Abstract

Organometallic compounds containing an electron donating group-substituted alkenyl ligand are provided. Such compounds are particularly suitable for use as vapor deposition precursors. Also provided are methods of depositing thin films, such as by ALD and CVD, using such compounds.

Description

EXAMPLE 1

(1-Dimethylamino)allyl(η6-p-cymene)ruthenium diisopropylacetamidinate is expected to be synthesized as follows:

Dichloro(η6-p-cymene)ruthenium dimer is reacted with lithium diisopropylacetamidinate in THF at room temperature (approximately 25° C.) in a 3-neck round bottom flask which is equipped with magnetic or mechanical stirring and effective heating/cooling system to control the rate of reaction. After the mixture is stirred overnight at room temperature, (1-dimethylamino)allyl magnesium bromide is added at low temperature (approximately −30° C.). The resulting mixture is then stirred overnight under an inert atmosphere of nitrogen. The reagents are added in continuous and dropwise manner, and are allowed to mix slowly to control the exothermicity of the reaction. The crude product is then expected to separate from the reaction mass after filtration with a high yield expected. The target product is expected to be substantially free of organic solvents (<0.5 ppm) as determined by FT-NMR and also substantially free of metallic impurities (<10 ppb) as determined by ICP-MS/ICP-OES.

EXAMPLE 2

Bis(1-dimethylaminoallyl)bis(cyclopentadienyl)zirconium(IV) is expected to be synthesized as:

Dichloro bis(cyclopentadiene)zirconium is reacted with (1-dimethylamino)allyl magnesium bromide in THF at a low temperature (approximately −30° C.) in a 3-neck round bottom flask which is equipped with magnetic or mechanical stirring and effective heating/cooling system to control the rate of reaction. The mixture is stirred overnight at room temperature. The crude product is then expected to separate from the reaction mass after filtration with a high yield expected. The target product is expected to be substantially free of organic solvents (<0.5 ppm) as determined by FT-NMR and also substantially free of metallic impurities (<10 ppb) as determined by ICP-MS/ICP-OES.

EXAMPLE 3

Organometallic compounds of the formula (EDG-(CR¹R²)_y′—CR³═CR⁴—(CR⁵R⁶)_y″)_nM^+mL¹_(m-n)L²_p listed in the following table are expected to be prepared according to the procedures described in Examples 1 or 2.

Sample	M	n	EDG	y′/y″	R1/R2	R3/R4	R5/R6	L1	L2
A	Mg	1	NMe2	0/1	—	H/H	H/H	OEt	—
B	Ga	1	N(Et)Me	0/1	—	H/H	H/H	H, H	—
C	Si	2	N(i-Pr)Me	0/1	—	H/H	H/H	AMD,	—
								AMD
D	Se	2	Py	0/1	—	H/H	H/H	BDK	—
E	Cu	1	N(i-Pr)2	0/1	—	Me/H	H/H	PAMD	VTMS
F	Sc	1	NH(Allyl)	1/1	H/H	Me/H	H/H	N(Et)Me	—
G	La	1	NMe2	1/1	H/H	Me2NCH2/H	H/H	DMAP	—
H	Zr	2	NEt2	2/0	H/Me	H/Me	—	Cp, Cp	—
I	Hf	3	NMe2	1/1	H/H	H/H	H/H	DMAE	—
J	Nb	2	NMe2	1/1	H/H	H/Me	H/Me	Allyl, H, H	—
K	Ta	1	PhNH2	0/2	—	H/H	H/H	KIM	—
L	W	2	Ph-NMe2	1/1	H/H	H/H	H/H	t-Bu	—
M	Ni	1	N(i-Pr)2	1/1	H/H	H/Et	H/H	Pyrazo	Bz,
									CO
N	Ru	2	N(c-Hx)2	2/1	H/H	H/H	H/Et	NO3	—
O	Pt	1	PhOMe	0/0	—	H/Me	—	Me, Me, H	—
P	Pt	2	EtO	2/1	H/H,	H/Et	H/H	Cp, Me	—
					H/Me
AMD = N,N′-dimethyl-methyl-amidinate;
PAMD = N,P-dimethyl-methylphosphoamidinate;
KIM = β-diketiminate;
BDK = β-diketonate;
DMAE = dimethylaminoethyl;
DMAP = dimethylaminopropyl.

In the above table, ligands separated by a comma denote that each ligand is present in that compound.

EXAMPLE 4

Compositions suitable for use in ALD or direct liquid injection processes are prepared by combining certain of the compounds of Example 3 with certain organic solvents. The particular compositions are shown in the following table. The organometallic compounds are typically present in a concentration of 0.1 M for direct liquid injection.

	Composition	Organometallic
	Sample	Compound Sample	Solvent
	1	C	1,4-Dioxane
	2	D	THF
	3	D	2-Methoxyethyl acetate
	4	E	Diglyme
	5	F	THF
	6	G	n-Butyl acetate
	7	H	Diglyme
	8	H	Octane
	9	H	Diglyme/THF
	10	I	n-Butyl acetate
	11	I	Octane
	12	I	2-Methoxyethoxy acetate
	13	J	THF
	14	K	Octane
	15	K	Diglyme
	16	L	n-Butyl acetate
	17	M	2-Methoxyethoxy acetate
	18	N	Octane
	19	N	THF
	20	P	2-Methoxyethoxy acetate
	21	P	Octane

Claims

1. An organometallic compound having the formula (EDG-(CR1R2)y′—CR3═CR4—(CR5R6)y″)nM+mL1(m-n)L2p, wherein each R1 and R2 is independently chosen from H, (C1-C6)alkyl and EDG; R3═H, (C1-C6)alkyl, EDG or EDG-(CR1R2)y′; R4═H or (C1-C6)alkyl; each R5 and R6 is independently chosen from H and (C1-C6)alkyl; EDG is an electron donating group; M=a metal; L1=an anionic ligand; L2 is a neutral ligand; y′=0-6; y″=0-6; m=the valence of M; n=1-7; and p=0-3.

2. The compound of claim 1 wherein L1 is chosen from hydride, halide, azide, alkyls, alkenyl, alkynyl, carbonyl, dialkylaminoalkyl, imino, hydrazido, phosphido, nitrosyl, nitryl, nitrate, nitrile, alkoxy, dialkylaminoalkoxy, siloxy, diketonates, ketoiminates, cyclopentadienyls, silyls, pyrazolates, guanidinates, phosphoguanidinates, amidinates, phosphoamidinates, amino, alkylamino, dialkylamino and alkoxyalkyldialkylamino.

3. The compound of claim 1 wherein EDG comprises one or more of oxygen, phosphorus, sulfur, nitrogen, alkenes, alkynes and aryl groups.

4. The compound of claim 1 wherein M is chosen from a Group 2 to Group 16 metal.

5. A method of depositing a film comprising the steps of: providing a substrate in a vapor deposition reactor; conveying as a precursor the organometallic compound of claim 1 in a gaseous form to the reactor; and depositing a film comprising the metal on the substrate.

6. A composition comprising the compound of claim 1 and an organic solvent.

7. A method of depositing a film comprising the steps of: providing a substrate in a reactor; conveying the composition of claim 6 into the reactor using direct liquid injection; and depositing a film comprising the metal on the substrate.

8. A method of depositing a film comprising the steps of: providing a substrate in a vapor deposition reactor; conveying as a first precursor the organometallic compound of claim 1 in a gaseous form to the reactor; chemisorbing the first precursor compound on the surface of the substrate; removing any non-chemisorbed first precursor compound from the reactor; conveying a second precursor in a gaseous form to the reactor; reacting the first and second precursors to form a film on the substrate; and removing any unreacted second precursor.

9. The method of claim 8 wherein the second precursor is chosen from oxygen, ozone, water, peroxide, alcohols, nitrous oxide and ammonia.

10. A delivery device for delivering a precursor in the vapor phase to a vapor deposition reaction comprising the compound of claim 1.