Mixed metal-silicon-oxide barriers

Abstract

A method of forming a thin barrier film of a mixed metal-silicon-oxide is disclosed. For example, a method of forming an aluminum-silicon-oxide mixture having a refractive index of 1.8 or less comprises exposing a substrate to sequences of a non-hydroxylated silicon-containing precursor, activated oxygen species, and metal-containing precursor until a mixed metal-silicon-oxide film having a thickness of 500 Ångstroms or less is formed on the substrate.

1 . A method of forming a barrier film on a substrate, the method comprising:
 repeating the following sequence of steps until a mixed metal-silicon-oxide film having a thickness of 500 Ångstroms or less is formed on the substrate:   (a) chemisorbing a first precursor on a surface supported by the substrate by exposing the surface to one of a non-hydroxylated silicon-containing precursor or a metalorganic precursor;   (b) after step (a), supplying activated oxygen species to the surface;   (c) chemisorbing a second precursor on the surface by exposing the surface to the other of the non-hydroxylated silicon-containing precursor and the metal-containing precursor; and   (d) after step (c), supplying activated oxygen species to the surface.   
     
     
         2 . The method of  claim 1 , wherein steps (a) and (b) are repeated between two and five times before performing steps (c) and (d). 
     
     
         3 . The method of  claim 1 , wherein supplying activated oxygen species to the surface includes forming activated oxygen species by cracking a dry, oxygen-containing compound. 
     
     
         4 . The method of  claim 3 , wherein the dry, oxygen-containing compound includes one or more of dry air, oxygen (O 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ), nitrogen monoxide (NO), nitrogen dioxide (NO 2 ), or a mixture of N 2  and CO 2 . 
     
     
         5 . The method of  claim 3 , wherein cracking the oxygen-containing compound includes thermal cracking of the dry, gaseous oxygen-containing compound to form activated oxygen species. 
     
     
         6 . The method of  claim 3 , wherein cracking the dry, oxygen-containing compound includes plasma excitation of the dry, gaseous oxygen-containing compound to form oxygen radicals. 
     
     
         7 . The method of  claim 1 , wherein the silicon-containing precursor includes one or more of tris(dimethylamino)silane; tetra(dimethylamino)silane; bis(tertiary-butylamino)silane; trisilylamine; silanediamine, N,N,N′,N′-tetraethyl; or hexakis(ethylamino)disilane. 
     
     
         8 . The method of  claim 1 , wherein the metalorganic precursor includes one or more of trimethylaluminum (TMA), titanium tetrachloride (TiCl 4 ), or diethylzinc (Zn(C 2 H 5 ) 2 ). 
     
     
         9 . The method of  claim 1 , further comprising repeating the sequence at a temperature of 200 degrees Celsius or less. 
     
     
         10 . The method of  claim 1 , wherein the mixed metal-silicon-oxide film consists essentially of a film selected from the group consisting of a Al x Si y O z  film, a Ti x Si y O z  film, and a Zn x Si y O z  film. 
     
     
         11 . The method of  claim 1 , wherein the mixed metal-silicon-oxide film has a refractive index of 1.8 or less. 
     
     
         12 . The method of  claim 11 , wherein the mixed metal-silicon-oxide film has a refractive index of between 1.5 and  1 . 8 . 
     
     
         13 . The method of  claim 1 , wherein the mixed metal-silicon-oxide film has a water vapor transmission rate of 3×10 −1  g/m 2 /day or less. 
     
     
         14 . The method of  claim 1 , further comprising:
 introducing the non-hydroxylated silicon-containing precursor into a first zone;   introducing the metal-containing precursor into a second zone spaced apart from the first zone;   introducing a dry, oxygen-containing compound into an isolation zone positioned between the first and second zones so as to create a positive pressure differential between the isolation zone and the first and second zones;   imparting relative movement between the substrate and the precursor zones; and   cracking the dry, oxygen-containing compound in proximity to the substrate within the isolation zone so as to generate the activated oxygen species.   
     
     
         15 . The method of  claim 1 , further comprising encapsulating the substrate with the barrier film. 
     
     
         16 . The method of  claim 1 , wherein the substrate is rigid. 
     
     
         17 . The method of  claim 1 , wherein the substrate includes an OLED. 
     
     
         18 . The method of  claim 1 , wherein the substrate includes a lighting panel. 
     
     
         19 . A moisture barrier deposited on a substrate, the barrier comprising a thin film of a metal-silicon-oxide mixture less than 500 Angstroms thick and having a refractive index of 1.8 or less. 
     
     
         20 . The moisture barrier of  claim 19 , wherein the moisture barrier has a refractive index of between 1.5 and  1 . 8 . 
     
     
         21 . The moisture barrier of  claim 19 , wherein the moisture barrier has a water vapor transmission rate of 3×10 −1  g/m 2 /day or less. 
     
     
         22 . The moisture barrier of  claim 19 , where the metal-silicon-oxide film consists essentially of a film selected from the group consisting of a Al x Si y O z  film, a Ti x Si y O z  film, and a Zn x Si y O z  film. 
     
     
         23 . The moisture barrier of  claim 19 , wherein the substrate is a flexible polymer film having a glass transition temperature of about 200 degrees Celsius or less. 
     
     
         24 . The moisture barrier of  claim 19 , wherein the substrate is a flexible polymer film having a refractive index of 1.8 or less. 
     
     
         25 . The moisture barrier of  claim 19 , wherein the moisture barrier encapsulates the substrate. 
     
     
         26 . The moisture barrier of  claim 19 , wherein the substrate is rigid. 
     
     
         27 . The moisture barrier of  claim 19 , wherein the substrate includes an OLED display. 
     
     
         28 . The moisture barrier of  claim 19 , wherein the substrate includes a lighting panel.