Bicyclic guanidines, metal complexes thereof and their use in vapor deposition

Patent metadata

Field	Value
Publication number	US-9029189-B2
Application number	US-91878509-A
Country	US
Kind code	B2
Filing date	Feb 20, 2009
Priority date	Nov 14, 2003
Publication date	May 12, 2015
Grant date	May 12, 2015

Abstract

Bicyclic guanidine compounds are described. Metal bicyclic guanidinate and its use in vapor deposition processes to deposit a metal-containing thin film are also described. Methods of making alkaline earth metal N,N′dialkylacetamidinates or bicyclic guanidinates including dissolution of alkaline earth metal into liquid ammonia followed by addition of a solution of an amidine or guanidine ligand in the free base from are provided.

First claim

What is claimed is:

1. A bicyclic guanidinate compound having the formula, M x G y L z , where
M is a metal or a semiconductor,
G is a bicyclic guanidinate anion having the structure

in which each of R 1 through R 8 are independently selected from the group consisting of hydrogen, hydrocarbon groups, substituted hydrocarbon groups, and other groups of nonmetallic atoms and at least one of the R 1 through R 8 is not hydrogen, and
L is a neutral or anionic ligand,
where x has a value of 1 or 2, with the proviso x is 1 when M is Mo(IV) in the +4 oxidation state,
where y and z are selected to satisfy the charge neutrality of the bicyclic guanidinate compound.

2. A compound as in claim 1 , wherein at least one of R 1 , R 2 , R 7 , and R 8 is not hydrogen.

3. A compound as in claim 1 , where the bicyclic guanidinate anion has the structure

4. A compound as in claim 3 , wherein x is 1, y is 3, and M is La.

5. A compound as in claim 1 , where the bicyclic guanidinate anion has the structure

6. A compound as in claim 5 , wherein x is 1, y is 2, and M is Ca, Sr, Ni, Co, or Ru.

7. A compound as in claim 6 , wherein M is Ru, z is 2 and L is CO.

8. A compound as in claim 5 , wherein x is 2, y is 2, and M is Cu.

9. A compound as in claim 5 , wherein x is 1, y is 4, and M is Zr.

10. A compound as in claim 9 , wherein z is 2 and L is methyl.

11. A compound as in claim 1 , where the bicyclic guanidinate anion has the structure

12. The compound as in claim 1 , wherein M is Cu(I), Ag(I), Au(I), Ir(I), In(I), Tl(I), Li(I), Na(I), K(I), Rb(I), Cs(I), Be(II), Ni(II), Co(II), Cr(II), Ge(II), Zn(II), Sn(II), Mg(II), Cu(II), Fe(II), V(II), Pt(II), Mn(II), Pd(II), Ti(II), Ru(II), Ag(II), Cd(II), Ca(II), Tm(II), Hg(II), Yb(II), Dy(II), Eu(II), Sr(II), Sm(II), Pb(II), Te(II), Ba(II), Al(III), As(III), Ni(III), Ga(III), Cr(III), Co(III), V(III), Fe(III), Mn(III), Ti(III), Rh(III), Ru(III), Ir(III), Mo(III), W(III), Nb(III), Ta(III), Sc(III), Sb(III), In(III), Lu(III), Yb(III), Tm(III), Er(III), TRIM, Y(III), Ho(III), Dy(III), Tb(III), Gd(III), Eu(III), Sm(III), Nd(III), Pr(III), Ce(III), La(III), U(III), Si(IV), Ge(IV), Co(IV), Fe(IV), Mn(IV), Cr(IV), V(IV), Rh(IV), Ti(IV), Ru(IV), Ir(IV), Os(IV), Re(IV), Mo(IV), W(IV), Nb(IV), Ta(IV), Sn(IV), Hf(IV), Zr(IV), Tb(IV), Pb(IV), Te(IV), Pr(IV), Ce(IV), U(IV), or Th(IV), and wherein M(I) is in the +1 oxidation state, M(II) is in the +2 oxidation state, M(III) is in the +3 oxidation state and M(IV) is in the +4 oxidation state.

13. A bicyclic guanidinate compound having the formula, M x G y L z , where
M is a metal or a semiconductor,
G is a bicyclic guanidinate anion having the structure

where x has a value of 1 or 2,
where y and z are selected to satisfy the charge neutrality of the compound, and
L is a neutral or anionic ligand, provided that M is not Mo or Au.

14. A compound as in claim 13 , wherein x is 2, y is 2, and M is Cu.

15. A compound as in claim 13 , wherein x is 1, y is 3, and M is Ti.

16. A compound as in claim 13 , wherein x is 1, y is 4, and M is Zr.

17. A compound as in claim 16 , wherein z is 2 and L is methyl.

18. A bicyclic guanidine compound having the structure

in which each of R 1 through R 8 are independently selected from the group consisting of non-aromatic hydrocarbon groups and substituted non-aromatic hydrocarbon groups.

19. A process for forming a thin film comprising a metal, comprising:
exposing a heated surface to the vapor of one or more volatile metal or semiconductor bicyclic guanidinate compounds of the formula, M x G y L z ,
where M is a metal or a semiconductor,
G is a bicyclic guanidinate anion having the structure

in which each of R 1 through R 8 are independently selected from the group consisting of hydrogen, hydrocarbon groups, substituted hydrocarbon groups, and other groups of nonmetallic atoms and at least one of R 1 through R 8 is not hydrogen, and
L is a neutral or anionic ligand,
where x has a value of 1 or 2, with the proviso x is 1 when M is Mo(IV) in the +4 oxidation state,
where y and z are selected to satisfy the charge neutrality of the bicyclic guanidinate compound.

20. The process as in claim 18 , wherein M is Cu(I), Ag(I), Au(I), Ir(I), In(I), Tl(I), Na(I), K(I), Rb(I), Cs(I), Be(II), Ni(II), Co(II), Cr(II), Ge(II), Zn(II), Sn(II), Mg(II), Cu(II), Fe(II), V(II), Pt(II), Mn(II), Pd(II), Ti(II), Ru(II), Ag(II), Cd(II), Ca(II), Tm(II), Hg(II), Yb(II), Dy(II), Eu(II), Sr(II), Sm(II), Pb(II), Te(II), Ba(II), Al(III), As(III), Ni(III), Ga(III), Cr(III), Co(III), V(III), Fe(III), Mn(III), Ti(III), Rh(III), Ru(III), Ir(III), Mo(III), W(III), Nb(III), Ta(III), Sc(III), Sb(III), In(III), Lu(III), Yb(III), Tm(III), Er(III), TOR), Y(III), Ho(III), Dy(III), Tb(III), Gd(III), Eu(III), Sm(III), Nd(III), Pr(III), Ce(III), La(III), U(III), Si(IV), Ge(IV), Co(IV), Fe(IV), Mn(IV), Cr(IV), V(IV), Rh(IV), Ti(IV), Ru(IV), Ir(IV), Os(IV), Re(IV), Mo(IV), W(IV), Nb(IV), Ta(IV), Sn(IV), Hf(IV), Zr(IV), Tb(IV), Pb(IV), Te(IV), Pr(IV), Ce(IV), U(IV), or Th(IV), and wherein M(I) is in the +1 oxidation state, M(II) is in the +2 oxidation state, M(III) is in the +3 oxidation state and M(IV) is in the +4 oxidation state.

21. A process for forming a thin film comprising a metal, comprising:
exposing a heated surface to the vapor of one or more volatile metal or semiconductor bicyclic guanidinate compounds of the formula, M x G y L z ,
where M is a metal or a semiconductor, provided that M is not Mo or Au,
G is a bicyclic guanidinate anion having the structure

and
L is a neutral or anionic ligand,
where x has a value of 1 or 2,
where y and z are selected to satisfy the charge neutrality of the compound.

Assignees

• Gordon Roy Gerald
• Rodriguez Leonard Neil Jacques
• Harvard College

Inventors

• Gordon Roy Gerald
• Rodriguez Leonard Neil Jacques

Classifications

• C23C16/18 Primary

  from metallo-organic compounds · CPC title

• C07D487/04

  Ortho-condensed systems · CPC title

• C07F15/0053

  without a metal-carbon linkage · CPC title

• C07F7/00

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title