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