Zinc oxide film method and structure for CIGS cell

• US 8,168,463 B2
• Filed: 10/09/2009
• Issued: 05/01/2012
• Est. Priority Date: 10/17/2008
• Status: Expired due to Fees

• Current Assignee: Stion Corporation
• Original Assignee: Stion Corporation
• Inventors: Wieting, Robert D.
• Primary Examiner(s): Linday, Jr., Walter L
• Assistant Examiner(s): MUSTAPHA, ABDULFATTAH B
• Application Number:
  US12/577,132
• Publication Number:
  US 20110263064A1
• Time in Patent Office: 935 Days
• Field of Search: 438/61, 136/224, 136/244, 136/261, 257/751, 257/763, 257/E21.168
• US Class Current: 438/61
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: H01L 21/02422 Non-crystalline insulating materials, e.g. glass, polymers
• CPC Class Codes: H01L 21/02474 Sulfides
• CPC Class Codes: H01L 21/02485 Other chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
• CPC Class Codes: H01L 21/02491 Conductive materials
• CPC Class Codes: H01L 21/02505 consisting of more than two layers
• CPC Class Codes: H01L 21/02554 Oxides
• CPC Class Codes: H01L 21/02576 N-type
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: H01L 31/1884 Manufacture of transparent electrodes, e.g. TCO, ITO
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells
• CPC Class Codes: Y02E 10/548 Amorphous silicon PV cells

Abstract

A method for fabricating a thin film photovoltaic device. The method includes providing a substrate comprising an absorber layer and an overlying window layer. The substrate is loaded into a chamber and subjected to a vacuum environment. The vacuum environment is at a pressure ranging from 0.1 Torr to about 0.02 Torr. In a specific embodiment, a mixture of reactant species derived from diethylzinc species, water species and a carrier gas is introduced into the chamber. The method further introduces a diborane species using a selected flow rate into the mixture of reactant species. A zinc oxide film is formed overlying the window layer to define a transparent conductive oxide using the selected flow rate to provide a resistivity of about 2.5 milliohm-cm and less and an average grain size of about 3000 to 5000 Angstroms.

Claims

1. A method for fabricating a thin film of zinc oxide for a photovoltaic device comprising:

providing a substrate having an absorber layer and an overlying window layer;

loading the substrate into a chamber;

subjecting the substrate to a vacuum environment ranging from 0.1 Torr to about 0.02 Torr while maintaining it at a temperature of between about 130 degrees Celsius to about 190 degrees Celsius;

introducing a mixture of reactant species derived from diethylzinc species, water species, and a carrier gas;

introducing a diborane species using a flow rate of less than five percent of the diethylzinc species into the mixture of reactant species;

forming a zinc oxide film overlying the window layer to define a transparent conductive zinc oxide having a resistivity of less than about 2.5 milliohm-cm and an average grain size between about 3000 Angstroms and about 5000 Angstroms.

2. The method of claim 1 wherein the diethylzinc species comprises dielethyl vapor.

3. The method of claim 1 wherein the water species comprises water vapor.

4. The method of claim 1 wherein the carrier gas comprises nitrogen gas or argon gas.

5. The method of claim 1 wherein the water to diethylzinc ratio is than about 1 to about 4.

6. The method of claim 1 wherein the water to diethylzinc ratio is about 1.

7. The method of claim 1 wherein the diborane to diethylzinc ratio is one percent.

8. The method of claim 1 wherein the substrate is maintained at a temperature greater than about 200 Degrees Celsius.

9. The method of claim 1 wherein the zinc oxide film is hazy.

10. The method of claim 1 wherein the zinc oxide film has an optical transmission rate of 90 percent and greater.

11. The method of claim 1 wherein the zinc oxide film has a transmission rate of 80 percent and greater for electromagnetic radiation having a wavelength of about 800 nanometers to about 1200 nanometers.

12. The method of claim 1 wherein the step of introducing a mixture of reactant species increases pressure of the chamber to about 0.5 to 1 Torr.

13. The method of claim 1 wherein the diethylzinc is semiconductor grade.

14. The method of claim 1 wherein the diethlyzinc is catalyst grade.

15. The method of claim 1 wherein the absorber layer comprises a CIGS material or a CIG material.

16. The method of claim 1 wherein the window layer comprises a cadmium sulfide material.

17. A method for forming a thin film photovoltaic device comprising:

providing a substrate having a surface region;

forming a first electrode layer overlying the surface region;

forming an absorber material comprising a copper species, an indium species, and a selenide species overlying the first electrode layer;

forming a window layer comprising a cadmium selenide species overlying the absorber material;

subjecting the substrate to a vacuum environment ranging from 0.1 Torr to about 0.02 Torr; and

forming a zinc oxide layer characterized by grain size ranging from about 3000 Angstroms to about 5000 Angstroms overlying the window layer using precursor gases including a zinc species, an oxygen species, and a carrier gas including at least a nitrogen species at a temperature greater than about 200 degrees Celsius to form a transparent zinc oxide layer having a resistivity of less than about 2.5 milliohm-cm.

18. The method of claim 17 wherein the oxygen bearing species is derived from water vapor.

19. The method of claim 17 wherein the zinc species is derived from diethyl zinc.

20. The method of claim 17 wherein the nitrogen species is nitrogen gas.

21. The method of claim 17 wherein the zinc oxide layer is characterized by an optical transmission rate of 99% and greater.