Durable sputtered metal oxide coating

Abstract

A method and resultant product are disclosed wherein a metal film is deposited by sputtering a metal cathode target in an essentially nonreactive atmosphere comprising inert gas and a reactive gas, wherein the concentration of reactive gas is sufficiently low that the sputtering is accomplished in the metallic mode, i.e. the film is deposited as metal. The metal film of the present invention is harder than a metal film sputtered in an atmosphere consisting of only inert gas. The method and resultant product may further comprise thermal oxidation of the metal film, which proceeds more efficiently than oxidation of a metal film sputtered in an atmosphere consisting of only inert gas.

1 - 20 . (canceled)  
     
     
         21 . A coated article made by the process of: 
 placing a substrate in an evacuated chamber having an atmosphere comprising an inert gas and a reactive gas;    sputtering a metal cathode target below its switch point in the chamber, wherein the atmosphere is sufficiently inert that the metals sputtered to deposit a metal film and sufficiently reactive that the metal film deposited is substantially amorphous; and    oxidizing the metal film after the sputtering step.    
     
     
         22 . The article according to  claim 21 , wherein the metal of the metal cathode target comprises at least one metal selected from the group consisting of titanium, zirconium, tantalum, hafnium, niobium, vanadium and mixtures thereof.  
     
     
         23 . The article according to  claim 21 , wherein the reactive gas is selected from the group consisting of oxygen, nitrogen and mixtures thereof.  
     
     
         24 . The article according to  claim 21 , wherein the inert gas is argon.  
     
     
         25 . The article according to  claim 21 , wherein the atmosphere comprises argon and up to 30 percent oxygen.  
     
     
         26 . The article according to  claim 21 , further including a metal oxide layer deposited over the amorphous metal film prior to the oxidizing step, wherein the amorphous metal film is thermally oxidized.  
     
     
         27 . A coated product comprising: 
 a substrate;    a film sputtered from a metal cathode target in an atmosphere comprising inert gas and reactive gas, the metal in the metal cathode target having a reactive gas switch point, wherein the concentration of the reactive gas during sputtering is below the reactive gas switch point such that the metal target is sputtered in a metallic mode to deposit a metal film having an amorphous structure defined as an amorphous metal film; and    a second metal oxide film over the amorphous metal film, wherein the amorphous metal film is oxidized to form a first metal oxide film in the coated product.    
     
     
         28 . The article in accordance with  claim 27 , wherein the metal of the metal cathode target comprises at least one metal selected from the group consisting of titanium, zirconium, tantalum, hafnium, niobium, vanadium and mixtures thereof.  
     
     
         29 . The article in accordance with  claim 27 , wherein the deposited amorphous metal film has a thickness ranging from 200 Å to 1500 Å.  
     
     
         30 . The article in accordance with  claim 27 , wherein the reactive gas is selected from oxygen, nitrogen and mixtures thereof.  
     
     
         31 . The article in accordance with  claim 27 , wherein the inert gas is argon.  
     
     
         32 . The article in accordance with  claim 31 , wherein the substrate is glass and the metal in the metal film is titanium.  
     
     
         33 . A coated article, comprising: 
 a substrate; and    a crystalline metal oxide film from oxidation of an essentially amorphous metal film sputtered from a metal cathode target in an atmosphere comprising inert gas and reactive gas, the metal in the metal cathode target having a reactive gas switch point, wherein the concentration of the reactive gas during sputtering is below the reactive gas switch point such that the metal target is sputtered in a metallic mode to deposit a metal film having an amorphous structure.    
     
     
         34 . The article according to  claim 33 , further comprising another metal oxide film directly over the crystalline metal oxide film, where the other metal oxide film is deposited by reactive sputtering of amorphous metal oxide.  
     
     
         35 . The article according to  claim 33 , wherein: 
 the crystalline metal film has a predetermined property value and the amorphous reacted metal film has a predetermined property value different than the predetermined property value of the crystalline metal film;    the predetermined property value of the crystalline metal film defines a first limit and the predetermined property value of the amorphous reacted metal film defines a second limit wherein the first limit and second limit define a predetermined value range, and    the crystalline metal film has a predetermined property value different than the predetermined property value of at least one of the crystalline metal films and the amorphous metal reacted film.    
     
     
         36 . The article according to  claim 35 , wherein the predetermined property value of the amorphous metal film is different than the predetermined property value of the crystalline metal film and of the amorphous reacted metal film and within the predetermined value range.  
     
     
         37 . The article according to  claim 35 , wherein the predetermined property is hardness and the amorphous metal film is harder than crystalline metal film and softer than the amorphous reacted metal films.  
     
     
         38 . The article according to  claim 35 , wherein the predetermined property is visible light transmittance and the crystalline metal film has a percent transmission lower than the percent transmission of the amorphous reacted metal film and the amorphous metal film has a percent transmission greater than the percent transmission of the crystalline metal film and less than the percent transmission of the amorphous reacted metal film wherein the thickness of the crystalline metal film, amorphous reacted metal film and amorphous metal film being substantially equal.  
     
     
         39 . The article according to  claim 38 , wherein the difference between the percent transmission of the crystalline metal film and the amorphous metal film is less than the difference between the percent transmission of the amorphous metal film and the amorphous reacted metal film.  
     
     
         40 . The article according to  claim 35 , wherein the predetermined property is selected from the group consisting of electrical conductivity, percent reflectance, and density.