Method for fabrication of copper-indium gallium oxide and chalcogenide thin films

Abstract

A composition of matter and method of forming copper indium gallium sulfide (CIGS), copper indium gallium selenide (CIGSe), or copper indium gallium telluride thin film via conversion of layer-by-layer (LbL) assembled Cu—In—Ga oxide (CIGO) nanoparticles and polyelectrolytes. CIGO nanoparticles are created via a flame-spray pyrolysis method using metal nitrate precursors, subsequently coated with polyallylamine (PAH), and dispersed in aqueous solution. Multilayer films are assembled by alternately dipping a substrate into a solution of either polydopamine (PDA) or polystyrenesulfonate (PSS) and then in the CIGO-PAH dispersion to fabricate films as thick as 1-2 microns. After LbL deposition, films are oxidized to remove polymer and sulfurized, selenized, or tellurinized to convert CIGO to CIGS, CIGSe, or copper indium gallium telluride.

What is claimed as new and desired to be protected by Letters Patent of the United States is: 
     
         1 . A copper indium gallium chalcogenide thin film made by the method comprising:
 producing copper-indium-gallium oxide (CIGO) nanoparticles via flame spray pyrolysis;   binding the CIGO nanoparticles to a polyamine and dispersing the polyamine-CIGO nanoparticles in an aqueous solution to form a polyamine-CIGO dispersion;   making a polyanion solution; and   dipping a substrate into the polyanion solution and then the polyamine-CIGO dispersion, wherein alternate dipping between the polyanion solution and the coated CIGO dispersion may be repeated multiple times to form a CIGO film.   
     
     
         2 . The copper indium gallium chalcogenide thin film of  claim 1 , additionally comprising oxidizing the CIGO film. 
     
     
         3 . The copper indium gallium chalcogenide thin film of  claim 1 , additionally comprising sulfurizing the film to convert the CIGO film to a copper indium gallium sulfide film. 
     
     
         4 . The copper indium gallium chalcogenide thin film of  claim 1 , additionally comprising selenizing the film to convert the CIGO film to a copper indium gallium selenide film. 
     
     
         5 . The copper indium gallium chalcogenide thin film of  claim 1 , additionally comprising tellurizing the film to convert the CIGO film to a copper indium gallium telluride film. 
     
     
         6 . The copper indium gallium chalcogenide thin film of  claim 1 , wherein the polyamine comprises polyallylamine (PAH). 
     
     
         7 . The copper indium gallium chalcogenide thin film of  claim 1 , wherein the polyanion comprises polystyrenesulfonate (PSS) or polydopamine (PDA). 
     
     
         8 . The copper indium gallium chalcogenide thin film of  claim 1 , wherein the substrate comprises silicon, quartz, or molybdenum. 
     
     
         9 . The copper indium gallium chalcogenide thin film of  claim 8 , wherein the silicon or quartz substrate has a coating comprising N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (EDA) and the molybdenum substrate remains uncoated or has a coating of polydopamine (PDA). 
     
     
         10 . A photovoltaic device comprising a copper indium gallium sulfide thin film made by the method comprising:
 producing copper-indium-gallium oxide (CIGO) nanoparticles via flame spray pyrolysis;   binding the CIGO nanoparticles to a polyamine and dispersing the polyamine-CIGO nanoparticles in an aqueous solution to form a polyamine-CIGO dispersion;   making a polyanion solution;   dipping a substrate into the polyanion solution and then the polyamine-CIGO dispersion, wherein alternate dipping between the polyanion solution and the coated CIGO dispersion may be repeated multiple times to form a CIGO film ;   oxidizing the CIGO film; and   sulfurizing the film to convert the CIGO film to a copper indium gallium sulfide film.   
     
     
         11 . The photovoltaic device of  claim 10 , wherein the polyamine comprises polyallylamine (PAH). 
     
     
         12 . The photovoltaic device of  claim 10 , wherein the polyanion comprises polystyrenesulfonate (PSS) or polydopamine (PDA). 
     
     
         13 . The photovoltaic device of  claim 10 , wherein the substrate comprises silicon, quartz, or molybdenum. 
     
     
         14 . The photovoltaic device of  claim 13 , wherein the silicon or quartz substrate has a coating comprising N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (EDA) and the molybdenum substrate remains uncoated or has a coating of polydopamine (PDA). 
     
     
         15 . A composition of matter, comprising:
 a silicon substrate coated with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (EDA);   multiple alternating layers of
 polydopamine (PDA) and 
 polyallylamine bound copper-indium-gallium oxide nanoparticles on the substrate. 
   
     
     
         16 . A composition of matter, comprising:
 copper-indium-gallium oxide (CIGO) nanoparticles prepared via flame spray pyrolysis; and   polyallylamine (PAH) bound to the CIGO nanoparticles and dispersing the PAH-CIGO nanoparticles to form PAH-coated CIGO nanoparticles.   
     
     
         17 . A copper indium gallium sulfide (CIGS) thin film made by the method comprising:
 coating a silicon substrate with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (EDA);   producing copper-indium-gallium oxide (CIGO) nanoparticles via flame spray pyrolysis;   binding the CIGO nanoparticles to polyallylamine (PAH) and dispersing the PAH-CIGO nanoparticles in an aqueous solution to form a PAH-CIGO dispersion;   making a polydopamine (PDA) solution; and   dipping the substrate into the PDA solution and then the PAH-CIGO dispersion, wherein alternate dipping between the PDA solution and the PAH-CIGO dispersion may be repeated multiple times to form a CIGO film;   oxidizing the CIGO film; and   sulfurizing the film to convert the CIGO film to a CIGS film;   wherein the CIGS film comprises fibrils on its surface.