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US20090087561: METAL AND METALLOID SILYLAMIDES, KETIMATES, TETRAALKYLGUANIDINATES AND DIANIONIC GUANIDINATES USEFUL FOR CVD/ALD OF THIN FILMS
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Patent Family
20 Claims, 16 Drawings
Abstract
Metal and metalloid precursors useful for forming metal-containing films on substrates, including amide precursors, tetraalkylguanidinate precursors, ketimate and dianionic guanidinate precursors. The precursors of the invention are readily formed and conveniently used to carry out chemical vapor deposition or atomic layer deposition at low temperature, e.g., at temperature below 400° C.
- 1. A metal precursor selected from the group consisting of:
(a) metal silylamide precursors with one or more disilylazacycloalkyl ligand(s), of the formula
RnM{N[(R1R2)Si(CR5R6)mSi(R3R4)]}ox-n;
(b) metal amides including silylamido ligand(s), of the formula
RnM(N(R1R2))ox-n;
(c) metal amides including silylamido ligand(s), of the formula
RnM{[Si(R3R4R5)NSi(R1R2R3)]}ox-n;
(d) metal precursors including a tetraalkylguanidine ligand, of the formula
(R)nM{N═C[(NR1R2)(NR3R4)]}ox-n;
(e) guanidinate complexes of the formula
RnM{R.NC{N═C[(NR1R2)(NR3R4)]}NR..}ox-n;
(f) ketimates of the formula
(R)nM{N═C(R1R2)}ox;
(g) guanidinate complexes of the formula
RnM{(R.NC[N═C(R1R2)]NR..}ox-n;
(h) alkylchalcogenide complexes of the formula
(R1R2R3)M′(ER4);
(i) aminochalcogenide complexes of the formula
{(NR2)(NR2)(R3)}M′(ER4); and
(j) dianionic guanidinate complexes of the formula
and corresponding complexes comprising singly deprotonated guanidinate ligands;
wherein:
M is a metal or metalloid;
M′ is a Group IV element selected from among C, Si, Ge, Sn and Pb;
OX is the oxidation state of M and M′;
E is a Group VI element selected from among O, S, Se and Te;
n is an integer having a value of from 0 to OX; and
m is an integer having a value of from 0 to 8;
wherein each R (R1, R2, R3, R4, R5, R6, R7, R′, R″ and R) is independently selected from among H, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 fluoroalkyl, amine, aryloxyalkyl, imidoalkyl, acetylalkyl, —NRaRb, C(Rc)3, —Si(R8)3, Ge(R8)3 and Cp-C(RIRIIRIIIRIVRV), wherein each of Ra, Rb and Rc is independently selected from C1-C6 alkyl; each R8 is independently selected from among H, C1-C6 alkyl, C5-C10 cycloalkyl, C6-C10 aryl, and —Si(R9)3 wherein each R9 is independently selected from C1-C6 alkyl;
Cp is cyclopentadienyl;
each of cyclopentadienyl substituents RI, RII, RIII, RIV, and RV can be the same as or different from the others, and is independently selected from among C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, silyl, C3-C18 alkylsilyl, C1-C6 fluoroalkyl, amide, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, hydrogen and acetylalkyl;
optionally with pendant ligands attached to one or more of said R1, R2, R3, R4, R5, R6, R7, R′, R″ and R comprising functional group(s) providing further coordination to the metal center, and selected from among aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, having the following formulae:
wherein: the methylene (—CH2—) moiety could alternatively be another divalent hydrocarbyl moiety; each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl and C6-C10 aryl; each of R5 and R6 is the same as or different from the other, with each being independently selected from among hydrogen, C1-C6 alkyl; n and m are each selected independently as having a value of from 0 to 4, with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;
wherein each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; R5 is selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; and n and m are selected independently as having a value of from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
wherein each of R1, R2, R3, R4, R5 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6alkyl, and C6-C10 aryl; each of R1′, R2′ is the same as or different from one another, with each being independently selected from hydrogen, C1-C6 alkyl, and C6-C10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;
wherein each of R1-R4 is the same as or different from one another, with each being independently selected from among hydrogen, C1-C6 alkyl, and C6-C10 aryl; R5 is selected from among hydrogen, hydroxyl, acetoxy, C1-C6 alkyl, C1-C12 alkylamino, C6-C10 aryl, and C1-C5 alkoxy; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time.
- 13. A method of making bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentanide)germanium (II), comprising:
(a) reacting butyllithium and a disilylamide of the formula:
in a solvent medium comprising tetrahydrofuran, to yield a bis(disilylaminolithium)(thf) complex of the formula:
(b) reacting said bis(disilylaminolithium)(thf) complex in the presence of germanium dichloride and dioxane to produce said bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentanide)germanium (II).
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