Metal chalcogenide composite nano-particles and layers therewith

• US 7,468,146 B2
• Filed: 09/11/2003
• Issued: 12/23/2008
• Est. Priority Date: 09/12/2002
• Status: Expired due to Fees

• Current Assignee: Agfa-Gevaert N.V.
• Original Assignee: Agfa-Gevaert N.V.
• Inventors: Andriessen, Hieronymus
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US10/659,926
• Publication Number:
  US 20040103936A1
• Time in Patent Office: 1,930 Days
• Field of Search: 423/508, 423/509, 423/561.1, 423/562, 423/566.1, 252/301.4 R, 252/301.4 S, 252/301.6 R, 252/301.6 S, 977/826, 977/824, 977/783, 977/778, 977/834, 977/948, 438/95, 136/264, 136/265, 136/260, 136/243
• US Class Current: 252/301.40R
• CPC Class Codes: H01L 31/0324 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
• CPC Class Codes: H01L 31/0352 characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
• CPC Class Codes: Y10S 977/778 within specified host or matrix material, e.g. nanocomposite films
• CPC Class Codes: Y10S 977/783 Organic host/matrix, e.g. lipid
• CPC Class Codes: Y10S 977/824 Group II-VI nonoxide compounds, e.g. CdxMnyTe
• CPC Class Codes: Y10S 977/826 Nonstoichiometric semiconductor compounds, e.g. IIIxVy; x does not equal y
• CPC Class Codes: Y10S 977/834 Optical properties of nanomaterial, e.g. specified transparency, opacity, or index of refraction
• CPC Class Codes: Y10S 977/948 Energy storage/generating using nanostructure, e.g. fuel cell, battery

Abstract

A metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of the metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of the metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of the metal and is less than 50 atomic percent of the metal; a dispersion thereof; a layer comprising the nano-particles; and a photovoltaic device comprising the layer.

Claims

1. A metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal, wherein said metal capable of forming n-type semiconducting chalcogenide nano-particles is selected from the group consisting of zinc, bismuth, indium, tin, tantalum and titanium, and wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

2. A metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal, and wherein a stoichiometric deficit of the chalcogenide in said metal chalcogenide composite nano-particle is present.

3. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal chalcogenide composite nano-particle comprises a p-type semiconducting metal chalcogenide phase and a n-type semiconducting chalcogenide phase, and wherein the concentration of said p-type semiconducting metal chalcogenide in said metal chalcogenide composite nano-particle is at least 5 mole percent and is less than 50 mole percent.

4. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal chalcogenide composite particle is a coprecipitated particle.

5. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal chalcogenide composite particle is a metal sulphide composite particle.

6. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal capable of forming n-type semiconducting chalcogenide nano-particles is selected from the group consisting of zinc, bismuth, cadmium, mercury, indium, tin, tantalum and titanium.

7. The metal chalcogenide composite nano-particle according to claim 6, wherein said metal capable of forming p-type semiconducting chalcogenide nano-particles is selected from the group consisting of copper, chromium, iron, lead and nickel.

8. The metal chalcogenide composite nano-particle according to claim 7, wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV, and wherein said metal capable of forming spectrally sensitizing chalcogenide nano-particles is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

9. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal capable of forming p-type semiconducting chalcogenide nano-particles is selected from the group consisting of copper, chromium, iron, lead and nickel.

10. The metal chalcogenide composite nano-particle according to claim 2, wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV.

11. The metal chalcogenide composite nano-particle according to claim 10, wherein said metal capable of forming spectrally sensitizing chalcogenide nano-particles is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

12. A metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal, and wherein said metal capable of forming p-type semiconducting chalcogenide nano-particles is selected from the group consisting of copper, chromium, iron and nickel.

13. The metal chalcogenide composite nano-particle according to claim 12, wherein said metal chalcogenide composite nano-particle comprises a p-type semiconducting metal chalcogenide phase and a n-type semiconducting chalcogenide phase, and wherein the concentration of said p-type semiconducting metal chalcogenide in said metal chalcogenide composite nano-particle is at least 5 mole percent and is less than 50 mole percent.

14. The metal chalcogenide composite nano-particle according to claim 12, wherein said metal chalcogenide composite particle is a coprecipitated particle.

15. The metal chalcogenide composite nano-particle according to claim 12, wherein said metal chalcogenide composite particle is a metal sulphide composite particle.

16. The metal chalcogenide composite nano-particle according to claim 12, wherein said metal capable of forming n-type semiconducting chalcogenide nano-particles is selected from the group consisting of zinc, bismuth, cadmium, mercury, indium, tin, tantalum and titanium.

17. The metal chalcogenide composite nano-particle according to claim 16, wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV, and wherein said metal capable of forming spectrally sensitizing chalcogenide nano-particles is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

18. The metal chalcogenide composite nano-particle according to claim 12, wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV.

19. The metal chalcogenide composite nano-particle according to claim 18, wherein said metal capable of forming spectrally sensitizing chalcogenide nano-particles is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

20. A metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal, wherein said metal capable of forming n-type semiconducting chalcogenide nano-particles is selected from the group consisting of zinc, bismuth, indium, tin, tantalum and titanium, wherein said metal capable of forming p-type semiconducting chalcogenide nano-particles is selected from the group consisting of copper, chromium, iron, lead and nickel, wherein said metal chalcogenide composite particle further comprises a metal capable of forming spectrally sensitizing chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV, and wherein said metal capable of forming spectrally sensitizing chalcogenide nano-particles is selected from the group consisting of silver, lead, copper, bismuth, vanadium and cadmium.

21. A dispersion comprising a metal chalcogenide composite nano-particle comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal.

22. A layer comprising metal chalcogenide composite nano-particles comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal.

23. The layer according to claim 22, wherein said layer further contains at least one spectral sensitizer for said metal chalcogenide composite nano-particles.

24. The layer according to claim 23, wherein said at least one spectral sensitizer is selected from the group consisting of metal chalcogenide nano-particles with a band-gap between 1.0 and 2.9 eV, organic dyes, and metallo-organic dyes.

25. The layer according to claim 22, wherein said layer further comprises a binder.

26. The layer according to claim 25, wherein said binder is poly(vinyl pyrrolidone).

27. A photovoltaic device comprising a layer comprising metal chalcogenide composite nano-particles comprising a metal capable of forming p-type semiconducting chalcogenide nano-particles and a metal capable of forming n-type semiconducting chalcogenide nano-particles, wherein at least one of said metal chalcogenides has a band-gap between 1.0 and 2.9 eV and the concentration of said metal capable of forming p-type semiconducting chalcogenide nano-particles is at least 5 atomic percent of said metal and is less than 50 atomic percent of said metal.