Homogeneous precursor formation method and device thereof

Patent metadata

Field	Value
Publication number	US-9738799-B2
Application number	US-201514824913-A
Country	US
Kind code	B2
Filing date	Aug 12, 2015
Priority date	Aug 12, 2014
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

A direct solution method based on a versatile amine-thiol solvent mixture which dissolves elemental metals, metal salts, organometallic complexes, metal chalcogenides, and metal oxides is described. The metal containing and metal chalcogenide precursors can be prepared by dissolving single or multiple metal sources, chalcogens, and/or metal chalcogenide compounds separately, simultaneously, or stepwise. Multinary metal chalcogenides containing at least one of copper, zinc, tin, indium, gallium, cadmium, germanium, and lead, with at least one of sulfur, selenium, or both are obtained from the above-mentioned metal chalcogenide precursors in the form of thin films, nanoparticles, inks, etc. Furthermore, infiltration of metal containing compounds into a porous structure can be achieved using the amine-thiol based precursors. In addition, due to the appreciable solubility of metal sources, metal chalcogenides, and metal oxides in the mixture of amine(s) and thiol(s), this solvent mixture can be used to remove these materials from a system.

First claim

The invention claimed is:

1. A method of dissolving at least one metal source to prepare a homogeneous solution of said at least one metal source, comprising contacting a starting material comprising said at least one metal source with a mixture of at least one amine and at least one thiol, wherein said at least one metal source comprises at least one elemental metal, a metal alloy, a metal chalcogenide, or an organometallic complex, and wherein said metal in said metal source is selected from the group consisting of Cu, Zn, Sn, In, Ga, Cd, Ge, Pb, and any combination thereof.

2. The method of claim 1 , wherein the amine is a primary, secondary, tertiary amine, or polyamine, and wherein the carbon chain ranges from C2 to C24.

3. The method of claim 1 , wherein the thiol has the structure of R5-SH, or HS-R6-SH, with the carbon chain ranging in size from C2 to C16; R5 represents any alkyl, aryl group, alcohol group —R′OH (R′=alkyl), or carboxylic acid group —R″COOH (R″=alkyl and/or aryl), and R6 represents an alkyl or aryl group.

4. A method of preparing a homogeneous solution of a metal chalcogenide precursor, comprising mixing at least one metal chalcogenide homogeneous solution, wherein the at least one metal chalcogenide homogeneous solution is prepared by:
contacting a metal chalcogenide with a solvent mixture comprising amine and dithiol, wherein the metal chalcogenide comprises at least one of Cu, Zn, Sn, In, Ga, Cd, Ge, or Pb, and at least one of S or Se, to provide a homogeneous solution of the metal chalcogenide;
wherein the amine comprises a primary, secondary, tertiary amine, or polyamine,
the amine's carbon chain ranges from C2 to C24; and
wherein the dithiol has the structure of HS-R6-SH and R6 represents an alkyl or an aryl group.

5. A method of depositing a thin film of a homogeneous solution of a metal chalcogenide precursor on a substrate, wherein the deposition of the thin film comprising:
preparing the homogeneous solution of the metal chalcogenide precursor;
applying the homogeneous solution of the metal chalcogenide precursor on the substrate using a printing/coating technique; and performing proper heat treatment under a suitable condition to form the thin film wherein the metal chalcogenide precursor comprises an elemental metal, a metal alloy, a metal chalcogenide or an organometallic complex; and wherein the homogenous solution comprises a mixture of at least one amine and at least one thiol.

6. The method in claim 5 , wherein the thin film can be at least one of CuS, CuSe, Cu 2 S, Cu 2 Se, SnS, SnSe, ZnS, ZnSe, SnS 2 , SnSe 2 , In 2 S 3 , In 2 Se 3 , CuInS 2 , CuInSe 2 , CdS, CdSe, PbS, PbSe, CuInS 2 , CuInSe 2 , Cu 2 SnS 3 , Cu 2 SnSe 3 , Cu x (In 1-y Ga y )(S 1-z Se z ) 2+q (0≦x≦1, 0≦y≦1, 0≦z≦1, and −1≦q≦1), and Cu 2-x Zn 1+y Sn(S 1-z Se z ) 4+q (0≦x≦1, 0≦y≦1, 0≦z≦1, and −1≦q≦1).

7. A method of depositing a Cu 2 ZnSn(S,Se) 4 film containing a compound formula: Cu 2-x Zn 1+y Sn(S 1-z Se z ) 4+q , wherein 0≦x≦1, 0≦y≦1, 0≦z≦1, and −1≦q≦1; the preparation of the solution comprises:
dissolving a source of Cu, a source of Zn, a source of Sn in an amine-thiol mixture to form a homogeneous solution A;
dissolving a source of at least one of S or Se in an amine-thiol mixture to form a homogeneous solution B;
combining solution A and solution B at sufficient conditions to form a stable precursor, wherein the stable precursor is a homogeneous solution;
applying the stable precursor on a substrate to form a Cu 2-x Zn 1+y Sn(S 1-z Se z ) 4+q thin film;
performing proper drying processes and heat treatment; and
fabricating photovoltaic devices using the resulting thin film,
wherein the source of Cu, source of Zn, source of Sn comprises an elemental metal, a metal alloy, a metal chalcogenide, or an organometallic complex.

8. The method of claim 7 , wherein the amine is a primary, secondary, tertiary amine, or polyamine, and wherein the amine carbon chain ranges from C2 to C24.

9. The metal of claim 7 , wherein the thiol can have the structure of R5-SH or HS-R6-SH, with a carbon chain ranging in size from C2 to C16; wherein R5 represents any alkyl, aryl group, alcohol group —R′OH (R′=alkyl), or carboxylic acid group —R″COOH (R″=alkyl or aryl), and R6 represents any alkyl or an aryl group.

10. The method of claim 7 , wherein the Zn source is elemental Zn and the thiol comprises at least one dithiol.

11. A method of preparing a homogeneous solution of a metal chalcogenide precursor, comprising contacting at least one elemental metal, metal alloy, organometallic complex, or metal chalcogenide, and at least one chalcogen with a mixture of amine and thiol, wherein said metal is selected from the group consisting of Cu, Zn, Sn, In, Ga, Cd, Ge, Pb, and any combination thereof.

12. The method of claim 11 , wherein the amine comprises a primary, secondary, tertiary amine, or polyamine, and the amine carbon chain ranges from C2 to C24.

13. The method of claim 11 , wherein the thiol has the structure of R5-SH or HS-R6-SH with a carbon chain ranging in size from C2 to C16; wherein R5 represents an alkyl, aryl group, alcohol group —R′OH (R′=alkyl), or carboxylic acid group —R″COOH (R″=alkyl and/or aryl), and R6 represents an alkyl or an aryl group.

14. A homogeneous solution of a metal source, comprising a mixture of at least one amine and at least one thiol, wherein said metal source comprises at least one elemental metal, a metal alloy, a metal chalcogenide, or an organometallic complex, wherein said metal in said metal source is selected from the group consisting of Cu, Zn, Sn, In, Ga, Cd, Ge, Pb, and any combination thereof, wherein the amine is a primary, secondary, tertiary amine, or polyamine, and the amine carbon chain ranges from C2 to C24, wherein the thiol has the structure of R5-SH or HS-R6-SH with a carbon chain ranging in size from C2 to C16, wherein R5 represents an alkyl, aryl group, alcohol group —R′OH (R′=alkyl), or carboxylic acid group —R″COOH (R″=alkyl and/or aryl), and R6 represents an alkyl or an aryl group.

Assignees

• Purdue Research Foundation

Inventors

• Agrawal Rakesh
• Zhang Ruihong
• Walker Bryce Chryst
• Handwerker Carol

Classifications

• H10P14/3461

  Nanoparticles · CPC title

• H10P14/3436

  being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds · CPC title

• H10P14/3431

  Selenides · CPC title

• H10P14/3428

  Sulfides · CPC title

• H10P14/265

  using solutions · CPC title