Selective deposition using hydrolysis

Abstract

Methods and apparatuses for selective deposition of metal oxides on metal surfaces relative to dielectric surfaces are provided. Selective deposition is achieved by exposing metal and dielectric surfaces to a blocking reagent capable of forming a hydrolyzable bond with metal while forming a non-hydrolyzable bond with the dielectric, and dipping the surfaces in water to cleave the hydrolyzable bond and leave a blocked surface on the dielectric surface, followed by depositing metal oxide selectively on the metal surface relative to the dielectric surface. Blocking reagents are deposited by wet or dry techniques and may include an alkylaminosilane or alkylchlorosilane as examples.

What is claimed is: 
     
         1 . A method of selectively depositing metal oxide on an exposed metal surface relative to a dielectric material on a substrate, the method comprising:
 (a) providing the substrate comprising the dielectric material and the exposed metal surface;   (b) prior to depositing the metal oxide, exposing the substrate to a blocking reagent to non-selectively adsorb the blocking reagent onto both the dielectric material and the exposed metal surface;   (c) after exposing the substrate to the blocking reagent and prior to depositing the metal oxide, selectively removing the blocking reagent from the exposed metal surface; and   (d) selectively depositing the metal oxide on the exposed metal surface relative to the dielectric material on the substrate;   
       wherein the exposed metal surface comprises a metal selected from the group consisting of tungsten, titanium, and aluminum. 
     
     
         2 . The method of  claim 1 , wherein selectively removing the blocking reagent is performed by contacting the substrate with water. 
     
     
         3 . The method of  claim 1 , wherein selectively removing the blocking reagent is performed by dipping the substrate in water. 
     
     
         4 . The method of  claim 1 , wherein the blocking reagent is a silicon amide, alkylchlorosilane or alkylaminosilane. 
     
     
         5 . The method of  claim 4 , wherein the alkylchlorosilane has a chemical structure of Cl x Si([CH 3 (CH 2 ) y ]) (4-x) , where x is an integer between and including 1 and 3, and y is an integer greater than or equal to 1. 
     
     
         6 . The method of  claim 4 , wherein the alkylaminosilane has a chemical structure of [(CH 3 ) 2 N] x Si([CH 3 (CH 2 ) y ]) (4-x) , where x is an integer between and including 1 and 3, and y is an integer greater than or equal to 1. 
     
     
         7 . The method of  claim 1 , wherein the blocking reagent forms a hydrolyzable bond with the exposed metal surface but does not form a hydrolyzable bond with the dielectric material. 
     
     
         8 . The method of  claim 1 , wherein the substrate is exposed to the blocking reagent by dipping the substrate in a wet solution of the blocking reagent. 
     
     
         9 . The method of  claim 8 , wherein the substrate is exposed to the blocking reagent at a temperature between about 25° C. and about 100° C. or between about 60° C. and about 100° C. 
     
     
         10 . The method of  claim 1 , wherein the substrate is exposed to the blocking reagent by introducing the blocking reagent in vapor phase. 
     
     
         11 . The method of  claim 10 , wherein the substrate is exposed to the blocking reagent at a temperature between about 100° C. and about 300° C. or between about 200° C. and about 250° C. 
     
     
         12 . The method of  claim 1 , wherein the substrate is exposed to the blocking reagent for a duration between about 10 seconds and about 60 seconds. 
     
     
         13 . The method of  claim 1 , wherein selectively removing the blocking reagent is performed at room temperature. 
     
     
         14 . The method of  claim 1 , wherein selectively removing the blocking reagent selectively hydrolyzes bonds between the blocking reagent and the exposed metal surface. 
     
     
         15 . The method of  claim 1 , wherein the metal oxide is alumina. 
     
     
         16 . The method of  claim 1 , wherein the metal oxide is selectively deposited on the exposed metal surface relative to the dielectric material using atomic layer deposition. 
     
     
         17 . The method of  claim 1 , wherein the dielectric material comprises silicon. 
     
     
         18 . The method of  claim 17 , wherein the dielectric material is selected from the group consisting of silicon oxide, silicon nitride, carbon-doped silicon oxide. 
     
     
         19 . The method of  claim 1 , wherein the substrate is patterned. 
     
     
         20 . The method of  claim 1 , wherein the hydrolyzing results in the exposed metal surface having a hydrogen-terminated and/or hydroxyl-terminated surface.