Reverse Selective Deposition

Abstract

Methods for selectively depositing on non-metallic surfaces are disclosed. Some embodiments of the disclosure utilize a blocking compound to form a blocking layer on metallic surfaces. Deposition is performed to selectively deposit on the unblocked non-metallic surfaces. Some embodiments of the disclosure relate to methods of forming metallic vias with decreased resistance. Some embodiments utilize an unsaturated hydrocarbon as a blocking compound. Some embodiments utilize a triazole as a blocking compound.

1 . A method of forming a blocking layer, the method comprising exposing a substrate comprising a metallic material having a first surface and a non-metallic material having a second surface to a blocking compound to selectively form a blocking layer on the first surface over the second surface, wherein the blocking compound comprises a triazole. 
     
     
         2 . The method of  claim 1 , wherein the blocking compound further comprises an unsaturated hydrocarbon with a general formula R′≡R″. 
     
     
         3 . The method of  claim 2 , wherein the unsaturated hydrocarbon contains only one triple bond. 
     
     
         4 . The method of  claim 3 , wherein the unsaturated hydrocarbon comprises 3-hexyne. 
     
     
         5 . The method of  claim 2 , wherein R′ is a C1 group. 
     
     
         6 . The method of  claim 5 , wherein R″ is a C3-C18 group. 
     
     
         7 . The method of  claim 1 , wherein the triazole comprises one or more of 1,2,3-triazole, 1,2,4-triazole, benzotriazole, an alkyl substituted 1,2,3-triazole and an alkyl substituted benzotriazole. 
     
     
         8 . The method of  claim 7 , wherein the triazole consists essentially of benzotriazole. 
     
     
         9 . The method of  claim 1 , wherein the metallic material comprises one or more of copper, cobalt, tungsten, molybdenum or ruthenium. 
     
     
         10 . The method of  claim 1 , wherein the non-metallic material comprises silicon oxide. 
     
     
         11 . The method of  claim 1 , further comprising selectively depositing a film on the second surface over the blocked first surface. 
     
     
         12 . The method of  claim 10 , wherein the film is deposited by sequentially exposing the substrate to a metal precursor and a reactant. 
     
     
         13 . The method of  claim 1 , further comprising exposing the substrate to an elevated temperature to remove the blocking layer. 
     
     
         14 . The method of  claim 13 , wherein the elevated temperature is greater than or equal to about 330° C. 
     
     
         15 . A method of selective deposition, the method comprising:
 exposing a substrate comprising a metallic material having a first surface and a non-metallic material having a second surface to a triazole to selectively form a blocking layer on the first surface over the second surface; and   sequentially exposing the substrate to a metal precursor and a reactant to form a film on the second surface over the blocking layer on the first surface; and   removing the blocking layer from the first surface.   
     
     
         16 . The method of  claim 15 , wherein the triazole comprises benzotriazole. 
     
     
         17 . A method of forming low-resistance metal vias, the method comprising:
 providing a substrate having a substrate surface with at least one feature formed therein, the at least one feature having a sidewall and a bottom, the sidewall comprising a non-metallic material surface, the bottom comprising a metallic material surface;   exposing the substrate to a triazole to selectively form a blocking layer on the metallic material surface over the non-metallic material surface;   sequentially exposing the substrate to a metal precursor and a reactant to form a film on the non-metallic material surface over the blocking layer on the metallic material surface;   optionally removing the blocking layer from the metallic material surface; and   depositing a conductive fill material within the at least one feature to form a low-resistance metal via.   
     
     
         18 . The method of  claim 17 , wherein the triazole comprises benzotriazole. 
     
     
         19 . The method of  claim 17 , wherein the film comprises aluminum oxide. 
     
     
         20 . The method of  claim 17 , wherein the low-resistance metal via has a resistance less than or equal to about 80% of a metal via formed without a blocking layer.