Method of producing zinc oxide thin film, method of producing photovoltaic device and method of producing semiconductor device

Abstract

The present invention provides a method of producing a zinc oxide thin film in which a current is passed between a conductive substrate immersed in an aqueous solution containing at least zinc ions, ammonium ions and zinc ammonia complex ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate. This method stabilizes formation of the zinc oxide thin film and improves adhesion between the thin film and the substrate.

1 - 15 . (Cancelled)  
     
     
         16 . A method of producing a zinc oxide thin film comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc ions, hydrogenzincate ions and zincate ions, and an electrode as a cathode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         17 . A method of producing a zinc oxide thin film according to  claim 16 , wherein the conductive substrate comprises a support and a transparent conductive layer deposited thereon.  
     
     
         18 . A method of producing a zinc oxide thin film according to  claim 16 , wherein the hydrogen ion concentration of the aqueous solution is controlled in the range of pH 8 to pH 12.5.  
     
     
         19 . A method of producing a zinc oxide thin film according to  claim 16 , wherein the hydrogen ion concentration of the aqueous solution near the uppermost surface in which the zinc oxide thin film is formed is controlled in the range of pH 6 to pH 8.  
     
     
         20 . A method of producing a zinc oxide thin film according to  claim 16 , wherein the aqueous solution contains a hydrocarbon.  
     
     
         21 . A method of producing a photovoltaic device comprising the steps of: 
 forming a zinc oxide thin film on a conductive substrate immersed in an aqueous solution containing at least zinc ions, hydrogenzincate ions and zincate ions by passing a current between the conductive substrate and an electrode as a cathode immersed in the aqueous solution; and    forming a semiconductor layer.    
     
     
         22 . A method of producing a photovoltaic device according to  claim 21 , wherein the conductive substrate comprises a support and a transparent conductive layer deposited thereon.  
     
     
         23 . A method of producing a photovoltaic device according to  claim 21 , wherein the hydrogen ion concentration of the aqueous solution is controlled in the range of pH 8 to pH 12.5.  
     
     
         24 . A method of producing a photovoltaic device according to  claim 21 , wherein the hydrogen ion concentration of the aqueous solution near the uppermost surface in which the zinc oxide thin film is formed is controlled in the range of pH 6 to pH 8.  
     
     
         25 . A method of producing a photovoltaic device according to  claim 21 , wherein the aqueous solution contains a hydrocarbon.  
     
     
         26 . A method of producing a semiconductor device substrate comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc ions, hydrogenzincate ions and zincate ions, and an electrode as a cathode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         27 . A method of producing a semiconductor device substrate according to  claim 26 , wherein the conductive substrate comprises a support and a transparent conductive layer deposited thereon.  
     
     
         28 . A method of producing a semiconductor device substrate according to  claim 26 , wherein the hydrogen ion concentration of the aqueous solution is controlled in the range of pH 8 to pH 12.5.  
     
     
         29 . A method of producing a semiconductor device substrate according to  claim 26 , wherein the hydrogen ion concentration of the aqueous solution near the uppermost surface in which the zinc oxide thin film is formed is controlled in the range of pH 6 to pH 8.  
     
     
         30 . A method of producing a semiconductor device substrate according to  claim 26 , wherein the aqueous solution contains a hydrocarbon.  
     
     
         31 - 45 . (Cancelled)  
     
     
         46 . A method of producing a zinc oxide film comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc acetate, zinc ions and acetate ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         47 . A method of producing a zinc oxide film comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc formate, zinc ions and formate ions and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         48 . A method of producing a zinc oxide film comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc benzoate, zinc ions and benzoate ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         49 . A method of producing a zinc oxide film comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least carboxylic acid ions and zinc ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate, wherein the aqueous solution is controlled in the range of pH 3.5 to pH to 5.5.  
     
     
         50 . A method of producing a photovoltaic device comprising the steps of: 
 forming a zinc oxide thin film on a conductive substrate immersed in an aqueous solution containing at least zinc acetate, zinc ions and acetate ions, by passing a current between the conductive substrate and an electrode as an anode immersed in the aqueous solution; and    forming a semiconductor layer on the top of the zinc oxide thin film.    
     
     
         51 . A method of producing a photovoltaic device comprising the steps of: 
 forming a zinc oxide thin film on a conductive substrate immersed in an aqueous solution containing at least zinc formate, zinc ions and formate ions, by passing a current between the conductive substrate and an electrode as an anode immersed in the aqueous solution; and    forming a semiconductor layer on the top of the zinc oxide thin film.    
     
     
         52 . A method of producing a photovoltaic device comprising the steps of: 
 forming a zinc oxide thin film on a conductive substrate immersed in an aqueous solution containing at least zinc benzoate, zinc ions and benzoate ions, by passing a current between the conductive substrate and an electrode as an anode immersed in the aqueous solution; and    forming a semiconductor layer on the top of the zinc oxide thin film.    
     
     
         53 . A method of producing a photovoltaic device comprising the steps of: 
 forming a zinc oxide thin film on a conductive substrate immersed in an aqueous solution controlled in the range of pH 3.5 to pH 5.5 containing at least zinc benzoate, zinc ions and benzoate ions, by passing a current between the conductive substrate and an electrode as an anode immersed in the aqueous solution; and    forming a semiconductor layer on the top of the zinc oxide thin film.    
     
     
         54 . A method of producing a semiconductor device substrate comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least zinc acetate, zinc ions and acetate ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         55 . A method of producing a semiconductor device substrate comprising passing a current between a conductive substrate immersed in an aqueous solution anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate.  
     
     
         57 . A method of producing a semiconductor device substrate comprising passing a current between a conductive substrate immersed in an aqueous solution containing at least carboxylic acid ions and zinc ions, and an electrode as an anode immersed in the aqueous solution to form a zinc oxide thin film on the conductive substrate, wherein the aqueous solution is controlled in the range of pH 3.5 to pH 5.5.