Methods Of Selective Atomic Layer Deposition

Abstract

Methods of depositing a film selectively onto a first substrate surface relative to a second substrate surface are described. The methods include exposing the substrate surfaces to a blocking compound to selectively form a blocking layer on at least a portion of the first surface over the second surface. The substrate is sequentially exposed to a metal precursor with a kinetic diameter in excess of 21 angstroms and a reactant to selectively form a metal-containing layer on the second surface over the blocking layer or the first surface. The relatively larger metal precursors of some embodiments allow for the use of blocking layers with gaps or voids without the loss of selectivity.

What is claimed is: 
     
         1 . A selective deposition method comprising:
 providing a substrate with a first surface and a second surface;   exposing the substrate to a blocking compound to selectively form a blocking layer on at least a portion of the first surface over the second surface; and   sequentially exposing the substrate to a metal precursor and a reactant to selectively form a metal-containing layer on the second surface over the blocking layer or the first surface, the metal precursor having a kinetic diameter of greater than or equal to about 21 angstroms.   
     
     
         2 . The method of  claim 1 , wherein the first surface comprises a conductive material and the second surface comprises a dielectric material. 
     
     
         3 . The method of  claim 2 , wherein the blocking compound comprises a blocking molecule with a reactive head group and a carbonaceous tail group, the reactive head group selected from the group consisting of (HO) 2 OP—, HS— and H 3 Si—. 
     
     
         4 . The method of  claim 1 , wherein the first surface comprises a dielectric material and the second surface comprises a conductive material. 
     
     
         5 . The method of  claim 4 , wherein the blocking compound comprises a blocking molecule with a reactive head group and a carbonaceous tail group, the reactive head group is selected from the group consisting of (R 2 N) 3 Si—, X 3 Si— and (RO) 3 Si—, where each R is independently selected from C1-C6 alkyl, C1-C6 cycloakyl and C1-C6 aryl, and each X is independently selected from halogens. 
     
     
         6 . The method of  claim 1 , wherein the metal precursor comprises a period 3 metal and the metal precursor has a kinetic diameter greater than or equal to 22 angstroms. 
     
     
         7 . The method of  claim 1 , wherein the metal precursor comprises a period 4 metal and the metal precursor has a kinetic diameter greater than or equal to 24 angstroms. 
     
     
         8 . The method of  claim 1 , wherein the metal precursor comprises a period 5 metal and the metal precursor has a kinetic diameter greater than or equal to 26 angstroms. 
     
     
         9 . The method of  claim 1 , wherein the metal precursor comprises a period 6 metal and the metal precursor has a kinetic diameter greater than or equal to 28 angstroms. 
     
     
         10 . The method of  claim 1 , wherein the metal precursor comprises one or more of Al, Hf, Zr, Y, Ti, Ta, Si, Cu, Co, W, or Ru. 
     
     
         11 . The method of  claim 1 , wherein the metal precursor comprises one or more of tri-tertbutyl aluminum or tri-neopentyl aluminum. 
     
     
         12 . The method of  claim 1 , wherein the metal precursor comprises one or more of tetrakis(dimethylamido)titanium or tetrakis(diethylamido)titanium. 
     
     
         13 . The method of  claim 1 , wherein the metal-containing layer comprises metal atoms and oxygen atoms, nitrogen atoms, carbon atoms, or combinations thereof. 
     
     
         14 . The method of  claim 13 , wherein the metal-containing layer comprises oxygen atoms and the reactant comprises one or more of water, alcohol, oxygen gas (O 2 ), ozone or peroxide. 
     
     
         15 . The method of  claim 13 , wherein the metal-containing layer comprises nitrogen atoms and the reactant comprises one or more of nitrogen gas (N 2 ), ammonia, hydrazine, hydrazine derivatives, N 2 O or NO 2 . 
     
     
         16 . The method of  claim 1 , wherein the metal-containing layer comprises a pure metal film. 
     
     
         17 . The method of  claim 16 , wherein the reactant comprises one or more of hydrogen gas (H 2 ). 
     
     
         18 . The method of  claim 1 , wherein the portion of the first surface covered by the blocking layer is greater than or equal to about 90% of the first surface. 
     
     
         19 . A selective deposition method comprising:
 providing a substrate with a first material surface and a second material surface, the first material comprising SiO 2 , the second material comprising copper;   exposing the substrate to n-octadecyltris(dimethylamino)silane to selectively form a blocking layer on at least a portion of the first material surface over the second material surface; and   sequentially exposing the substrate to tri-tertbutyl aluminum and water to selectively form an aluminum oxide layer on the second material surface over the blocking layer or the first material surface.   
     
     
         20 . A selective deposition method comprising:
 providing a substrate with a first material surface and a second material surface, the first material comprising SiO 2 , the second material comprising copper;   exposing the substrate to n-octadecyltris(dimethylamino)silane to selectively form a blocking layer on at least a portion of the first material surface over the second material surface; and   sequentially exposing the substrate to tetrakis(dimethylamido)titanium and ammonia to selectively form an titanium nitride layer on the second material surface over the blocking layer or the first material surface.