Single-source precursors for ternary chalcopyrite materials, and methods of making and using the same
View Patent ↗A single source precursor for depositing ternary I-III-VI 2 chalcopyrite materials useful as semiconductors. The single source precursor has the I-III-VI 2 stoichiometry “built into” a single precursor molecular structure which degrades on heating or pyrolysis to yield the desired I-III-VI 2 ternary chalcopyrite. The single source precursors effectively degrade to yield the ternary chalcopyrite at low temperature, e.g. below 500° C., and are useful to deposit thin film ternary chalcopyrite layers via a spray CVD technique. The ternary single source precursors according to the invention can be used to provide nanocrystallite structures useful as quantum dots. A method of making the ternary single source precursors is also provided.
1. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having a structural formula selected from the group consisting of
wherein L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups, said single source precursor excluding
[{P(C 6 H 5 ) 3 } 2 Cu(S—C 2 H 5 ) 2 In(S—C 2 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(Se—C 2 H 5 ) 2 In(Se—C 2 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(S(i-C 4 H 9 ) 2 In(S(i-C 4 H 9 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(Se(i-C 4 H 9 ) 2 In(Se(i-C 4 H 9 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(Cl)(SC{O}CH 3 )In(SC{O}CH 3 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(Cl)(SC{O}C 6 H 5 )In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 In(SC{O}CH 3 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ], and
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 Ga(SC{O}CH 3 ) 2 ].
2. A single source precursor according to claim 1 , said singles source precursor being a liquid at room temperature.
3. A single source precursor according to claim 2 , said single source precursor being soluble in polar organic solvents and in non-polar organic solvents.
4. A single source precursor according to claim 1 , of the formula [{P(n-C 4 H 9 ) 3 } 2 Cu(Se—C 6 H 5 ) 2 In(Se—C 6 H 5 ) 2 ].
5. A single source precursor according to claim 1 , of the formula [{P(n-C 4 H 9 ) 3 } 2 Ag(S—C 2 H 5 ) 2 In(S—C 2 H 5 ) 2 ].
6. A single source precursor according to claim 1 , of the formula [{P(n-C 4 H 9 ) 3 } 2 Cu(S—C 2 H 5 ) 2 In(S—C 2 H 5 ) 2 ].
7. A single source precursor according to claim 1 , of the formula [{P(n-C 4 H 9 ) 3 } 2 Cu(S—C 3 H 7 ) 2 In(S—C 3 H 7 ) 2 ].
8. A single source precursor according to claim 1 , of the formula [{P(C 6 H 5 ) 3 } 2 Ag(S—CH 3 ) 2 In(S—CH 3 ) 2 ].
9. A single source precursor according to claim 1 , said single source precursor being effective to yield a I-III-VI 2 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor at a temperature less than about 500° C.
10. A single source precursor according to claim 1 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 1.5 eV between a conduction band and a valence band thereof.
11. A single source precursor according to claim 10 , said ternary chalcopyrite material being CuInS 2 .
12. A single source precursor according to claim 1 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 2 eV between a conduction band and a valence band thereof.
13. A single source precursor according to claim 12 , said ternary chalcopyrite material being CuGaS 2 .
14. A single source precursor according to claim 1 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of 1.5–2 eV between a conduction band and a valence band thereof, said ternary chalcopyrite material being Cu(In:Ga)(S:Se) 2 .
15. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having a structural formula selected from the group consisting of
wherein L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups.
16. A single source precursor according to claim 15 , said single source precursor being effective to yield a I-III-VI 2 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor at a temperature less than about 500° C.
17. A single source precursor according to claim 15 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 1.5 eV between a conduction band and a valence band thereof.
18. A single source precursor according to claim 17 , said ternary chalcopyrite material being CuInS 2 .
19. A single source precursor according to claim 15 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 2 eV between a conduction band and a valence band thereof.
20. A single source precursor according to claim 19 , said ternary chalcopyrite material being CuGaS 2 .
21. A single source precursor according to claim 15 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of 1.5–2 eV between a conduction band and a valence band thereof, said ternary chalcopyrite material being Cu(In:Ga)(S:Se) 2 .
22. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having a structural formula selected from the group consisting of
wherein L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the soup consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups.
23. A single source precursor according to claim 22 , said single source precursor being effective to yield a I-III-VI 2 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor at a temperature less than about 500° C.
24. A single source precursor according to claim 22 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 1.5 eV between a conduction band and a valence band thereof.
25. A single source precursor according to claim 24 , said ternary chalcopyrite material being CuInS 2 .
26. A single source precursor according to claim 22 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 2 eV between a conduction band and a valence band thereof.
27. A single source precursor according to claim 26 , said ternary chalcopyrite material being CuGaS 2 .
28. A single source precursor according to claim 22 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of 1.5–2 eV between a conduction band and a valence band thereof, said ternary chalcopyrite material being Cu(In:Ga)(S:Se) 2 .
29. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having a structural formula selected from the group consisting of
wherein L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups.
30. A single source precursor according to claim 29 , said single source precursor being effective to yield a I-III-VI 2 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor at a temperature less than about 500° C.
31. A single source precursor according to claim 29 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 1.5 eV between a conduction band and a valence band thereof.
32. A single source precursor according to claim 31 , said ternary chalcopyrite material being CuInS 2 .
33. A single source precursor according to claim 29 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of about 2–2.4 eV between a conduction band and a valence band thereof.
34. A single source precursor according to claim 33 , said ternary chalcopyrite material being CuGaS 2 .
35. A single source precursor according to claim 29 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of 1.5–2 eV between a conduction band and a valence band thereof, said ternary chalcopyrite material being Cu(In:Ga)(S: Se) 2 .
36. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having the empirical formula [{L} n M′(ER) x (X) y (R) z M″], wherein x is 3, x+y+z=4, n is greater than or equal to 1, L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alky, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups, said single source precursor excluding
[{P(C 6 H 5 ) 3 } 2 Cu (S—C 2 H 5 ) 2 In(S—C 2 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu (Se—C 2 H 5 ) 2 In(Se—C 2 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu (S(i-C 4 H 9 )) 2 In(S(i-C 4 H 9 )) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu (Se(i-C 4 H 9 )) 2 In(Se(i-C 4 H 9 )) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(Cl)(SC{O}CH 3 )In(SC{O}CH 3 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(Cl)(SC{O}C 6 H 5 )In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 In(SC{O}CH 3 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ], and
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 Ga(SC{O}CH 3 ) 2 ].
37. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor being a liquid at room temperature and being effective to yield a ternary chalcopyrite material upon heating or pyrolysis thereof.
38. A single source precursor according to claim 37 , said single source precursor being effective to yield a I-III-VI 2 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor at a temperature less than about 500° C.
39. A method of depositing ternary chalcopyrite materials comprising the steps of:
a) providing a first single source precursor for said ternary chalcopyrite material, said first single source precursor having the empirical formula [{L} n M′(ER) x (X) y (R) z M″], wherein x is 1–4, x+y+z=4, n is greater than or equal to 1, L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups, said single source precursor excluding
[{P(C 6 H 5 ) 3 } 2 Cu(S—C 2 H 5 ) 2 In(S—C 2 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Cu(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 In(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}C 6 H 5 ) 2 Ga(SC{O}C 6 H 5 ) 2 ],
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 In(SC{O}CH 3 ) 2 ], and
[{P(C 6 H 5 ) 3 } 2 Ag(SC{O}CH 3 ) 2 Ga(SC{O}CH 3 ) 2 ];
and
b) depositing the single source precursor on a substrate using a spray CVD technique.
40. A method according to claim 39 , said single source precursor having a structural formula selected from the group consisting of
41. A method according to claim 39 , said single source precursor having a structural formula selected from the group consisting of
42. A method according to claim 39 , said single source precursor having a structural formula selected from the group consisting of
43. A method according to claim 39 , said single source precursor having a structural formula selected from the group consisting of
44. A method according to claim 39 , said single source precursor having three E-R groups.
45. A method according to claim 39 , comprising the steps of providing a second single source precursor, and applying said first and second single source precursors on said substrate via said spray CVD technique.
46. A method of making a single source precursor for the deposition of ternary chalcopyrite materials comprising the step of carrying out the following reaction:
4M ALK ER+M′X 3 +M″X+ n L→[{L} n M′(ER) 2 M″(ER) 2 ]
wherein
M ALK is an alkali metal element,
E is a Group VI-A element,
R is selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane and carbamato groups,
M′ is a Group I-B element,
M″ is a Group III-A element,
X is a Group VII-A element, and
n is greater than or equal to 1.
47. A method according to claim 46 , wherein said single source precursor is made in a single step consisting essentially of said reaction.
48. A method according to claim 46 , wherein the ionic complex [L (n) M″(CH 3 CN) (4-n) ] + is formed in situ as said reaction proceeds.
49. A method according to claim 46 , said reaction being carried out under anaerobic conditions.
50. A method according to claim 46 , said reaction being carried out under non-anaerobic conditions.
51. A method of making a quantum dot comprising the steps of:
a) providing a single source precursor for a ternary chalcopyrite material; and
b) pyrolyzing said single source precursor to yield a quantum dot made of ternary chalcopyrite material having dimensions less than 100 nanometers.
52. A method according to claim 51 , said quantum dot made of a ternary I-III-VI 2 chalcopyrite material.
53. A method according to claim 51 , said quantum dot made of a ternary I-III 5 -VI 8 chalcopyrite material.
54. A method according to claim 51 , said pyrolyzing step being carried out at a temperature less than about 500° C.
55. A method according to claim 51 , said single source precursor having the empirical formula [{L} n M′(ER) x (X) y (R) z M″], wherein x is 1–4, x+y+z=4, n is greater than or equal to 1, L is a Lewis base that is coordinated to M′ via a dative bond, M′ is a Group I-B atom, M″ is a Group III-A atom, E is a Group VI-A atom, X is a Group VII-A atom, and each R is individually selected from the group consisting of alkyl, aryl, vinyl, perfluoro alkyl, perfluoro aryl, silane, and carbamato groups.
56. A single source precursor according to claim 1 , said single source precursor being effective to yield a I-III 5 -VI 8 ternary chalcopyrite material upon heating or pyrolysis of said single source precursor.
57. A single source precursor according to claim 29 , said single source precursor being effective to yield a ternary chalcopyrite material having a band gap of 0.5–3.5 eV between a conduction band and a valence band thereof, said ternary chalcopyrite material being (Cu:Ag:Au) 1 (Al:In:Ga) 1 (S:Se:Te) 2 .
58. A single source precursor according to claim 1 , said Group VI-A atom being selected from the group consisting of S, Se and Te.
59. A single source precursor according to claim 15 , said Group VI-A atom being selected from the group consisting of S, Se and Te.