Single-source precursors for ternary chalcopyrite materials, and methods of making and using the same

• US 6,992,202 B1
• Filed: 10/31/2003
• Issued: 01/31/2006
• Est. Priority Date: 10/31/2002
• Status: Expired due to Fees

• Current Assignee: The Ohio Aerospace Institute, United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Original Assignee: The Ohio Aerospace Institute, United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Inventors: Hepp, Aloysius F., Harris, Jerry D., Castro, Stephanie L., Banger, Kulbinder K., Jin, Michael Hyun-Chul
• Primary Examiner(s): NAZARIO GONZALEZ, PORFIRIO
• Application Number:
  US10/698,118
• Time in Patent Office: 823 Days
• Field of Search: 556/21, 556/28, 556/30, 556/31, 427/587, 427/593, 427/248.1, 117/3, 117/84
• US Class Current: 556/28
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C07F 5/003 without C-Metal linkages
• CPC Class Codes: C23C 16/305 Sulfides, selenides, or tellurides

Abstract

A single source precursor for depositing ternary I-III-VI₂ chalcopyrite materials useful as semiconductors. The single source precursor has the I-III-VI₂ stoichiometry “built into” a single precursor molecular structure which degrades on heating or pyrolysis to yield the desired I-III-VI₂ 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.

Claims

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(C₆H₅)₃}₂Cu(S—

C₂H₅)₂In(S—

C₂H₅)₂],

[{P(C₆H₅)₃}₂Cu(Se—

C₂H₅)₂In(Se—

C₂H₅)₂],

[{P(C₆H₅)₃}₂Cu(S(i-C₄H₉)₂In(S(i-C₄H₉)₂],

[{P(C₆H₅)₃}₂Cu(Se(i-C₄H₉)₂In(Se(i-C₄H₉)₂],

[{P(C₆H₅)₃}₂Ag(Cl)(SC{O}CH₃)In(SC{O}CH₃)₂],

[{P(C₆H₅)₃}₂Ag(Cl)(SC{O}C₆H₅)In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂In(SC{O}CH₃)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂], and

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂Ga(SC{O}CH₃)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-C₄H₉)₃}₂Cu(Se—

C₆H₅)₂In(Se—

C₆H₅)₂].

5. A single source precursor according to claim 1, of the formula [{P(n-C₄H₉)₃}₂Ag(S—

C₂H₅)₂In(S—

C₂H₅)₂].

6. A single source precursor according to claim 1, of the formula [{P(n-C₄H₉)₃}₂Cu(S—

C₂H₅)₂In(S—

C₂H₅)₂].

7. A single source precursor according to claim 1, of the formula [{P(n-C₄H₉)₃}₂Cu(S—

C₃H₇)₂In(S—

C₃H₇)₂].

8. A single source precursor according to claim 1, of the formula [{P(C₆H₅)₃}₂Ag(S—

CH₃)₂In(S—

CH₃)₂].

9. A single source precursor according to claim 1, said single source precursor being effective to yield a I-III-VI₂ 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 CuInS₂.

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 CuGaS₂.

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.

56. A single source precursor according to claim 1, said single source precursor being effective to yield a I-III₅-VI₈ ternary chalcopyrite material upon heating or pyrolysis of said single source precursor.

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.

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-VI₂ 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 CuInS₂.

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 CuGaS₂.

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.

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.

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-VI₂ 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 CuInS₂.

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 CuGaS₂.

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-VI₂ 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 CuInS₂.

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 CuGaS₂.

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.

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.

36. A single source precursor for the deposition of ternary chalcopyrite materials, said single source precursor having the empirical formula [{L}_nM′

(ER)_x(X)_y(R)_zM″

], 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(C₆H₅)₃}₂Cu (S—

C₂H₅)₂In(S—

C₂H₅)₂],

[{P(C₆H₅)₃}₂Cu (Se—

C₂H₅)₂In(Se—

C₂H₅)₂],

[{P(C₆H₅)₃}₂Cu (S(i-C₄H₉))₂In(S(i-C₄H₉))₂],

[{P(C₆H₅)₃}₂Cu (Se(i-C₄H₉))₂In(Se(i-C₄H₉))₂],

[{P(C₆H₅)₃}₂Ag(Cl)(SC{O}CH₃)In(SC{O}CH₃)₂],

[{P(C₆H₅)₃}₂Ag(Cl)(SC{O}C₆H₅)In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂In(SC{O}CH₃)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂], and

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂Ga(SC{O}CH₃)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-VI₂ 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}_nM′

(ER)_x(X)_y(R)_zM″

], 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(C₆H₅)₃}₂Cu(S—

C₂H₅)₂In(S—

C₂H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Cu(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂In(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}C₆H₅)₂Ga(SC{O}C₆H₅)₂],

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂In(SC{O}CH₃)₂], and

[{P(C₆H₅)₃}₂Ag(SC{O}CH₃)₂Ga(SC{O}CH₃)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_ALKER+M′

X₃+M″

X+nL→

[{L}_nM′

(ER)₂M″

(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″

(CH₃CN)_(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-VI₂ chalcopyrite material.

53. A method according to claim 51, said quantum dot made of a ternary I-III₅-VI₈ 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}_nM′

(ER)_x(X)_y(R)_zM″

], 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.