Surface pre-treatment for enhancement of nucleation of high dielectric constant materials

Abstract

Embodiments of the present invention relate to a surface preparation treatment for the formation of thin films of high k dielectric materials over substrates. One embodiment of a method of forming a high k dielectric layer over a substrate includes pre-cleaning a surface of a substrate to remove native oxides, pre-treating the surface of the substrate with a hydroxylating agent, and forming a high k dielectric layer over the surface of the substrate. One embodiment of a method of forming a hafnium containing layer over a substrate includes introducing an acid solution to a surface of a substrate, introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate, and forming a hafnium containing layer over the substrate.

1 . A method of forming a high dielectric constant layer over a substrate, comprising: 
 pre-cleaning a surface of a substrate to remove native oxides;    pre-treating the surface of the substrate with an hydroxylating agent; and    forming a high dielectric constant layer over the surface of the substrate.    
     
     
         2 . The method of  claim 1 , wherein pre-cleaning comprises introducing an acid solution to the surface of the substrate.  
     
     
         3 . The method of  claim 2 , wherein the acid solution comprises a hydrofluoric acid solution.  
     
     
         4 . The method of  claim 1 , wherein the hydroxylating agent comprises water vapor.  
     
     
         5 . The method of  claim 4 , wherein a water vapor is generated from a hydrogen containing gas and an oxygen containing gas.  
     
     
         6 . The method of  claim 5 , wherein the hydrogen containing gas is hydrogen (H 2 ) gas and wherein the oxygen containing gas is nitrous oxide (N 2 O) gas.  
     
     
         7 . The method of  claim 1 , wherein the high dielectric constant layer comprises a material selected from the group including hafnium containing materials, aluminum oxides, zirconium oxides, lanthanum oxides, yttrium oxides, tantalum oxides, composites thereof, and combinations thereof.  
     
     
         8 . The method of  claim 1 , wherein the high dielectric constant layer comprises a material selected from the group including hafnium oxides, hafnium silicates, hafnium nitrides, hafnium aluminates, hafnium silicon oxynitrides, composites thereof, and combinations thereof.  
     
     
         9 . The method of  claim 1 , wherein the high dielectric constant layer comprises hafnium oxides, compositions thereof, or combinations thereof.  
     
     
         10 . The method of  claim 1 , wherein the high dielectric constant layer comprises hafnium silicates, composites thereof, or combinations thereof.  
     
     
         11 . The method of  claim 1 , wherein forming the high dielectric constant layer comprises introducing a metal precursor and an oxygen containing compound.  
     
     
         12 . The method of  claim 1 , wherein forming the high dielectric constant layer comprises a deposition technique selected from the group comprising chemical vapor deposition, atomic layer deposition, and physical vapor deposition.  
     
     
         13 . A method of forming a hafnium containing layer over a substrate, comprising: 
 introducing an acid solution to a surface of a substrate;    introducing a hydrogen containing gas and an oxygen containing gas to the surface of the substrate; and    forming a hafnium containing layer over the substrate.    
     
     
         14 . The method of  claim 13 , wherein the hafnium containing layer comprises a material selected from the group including hafnium oxides, hafnium silicates, hafnium nitrides, hafnium aluminates, hafnium silicon oxynitrides, composites thereof, and combinations thereof.  
     
     
         15 . The method of  claim 13 , wherein the hafnium containing layer comprises hafnium oxides, composites thereof, or combinations thereof.  
     
     
         16 . The method of  claim 13 , wherein the hafnium containing layer comprises hafnium silicates, composites thereof, or combinations thereof.  
     
     
         17 . The method of  claim 13 , wherein the acid solution comprises a hydrofluoric acid solution.  
     
     
         18 . The method of  claim 13 , wherein the hydrogen containing gas is hydrogen (H 2 ) gas and wherein the oxygen containing gas is nitrous oxide (N 2 O) gas.  
     
     
         19 . The method of  claim 13 , wherein the ratio of oxygen containing gas to hydrogen containing gas is between about 65:35 and about 99.9:0.1.  
     
     
         20 . The method of  claim 13 , further comprising introducing a non-reactive gas during the step of introducing a hydrogen containing gas and an oxygen containing gas.  
     
     
         21 . The method of  claim 20 , wherein the non-reactive gas comprises helium gas.  
     
     
         22 . The method of  claim 13 , wherein the substrate is at a temperature between about 400° C. and about 1,250° C. during the step of introducing a hydrogen containing gas and an oxygen containing gas.  
     
     
         23 . The method of  claim 13 , wherein the substrate is at a temperature between about 700° C. and about 900° C. during the step of introducing a hydrogen containing gas and an oxygen containing gas.  
     
     
         24 . The method of  claim 13 , wherein the hydrogen containing gas and the oxygen containing gas are introduced to the surface of the substrate for a time period of about 1 minute or less.  
     
     
         25 . The method of  claim 13 , wherein the hydrogen containing gas and the oxygen containing gas are introduced to the surface of the substrate for a time period of about 10 seconds or less.  
     
     
         26 . The method of  claim 13 , wherein forming a hafnium containing layer comprises introducing a hafnium precursor and an oxygen containing compound.  
     
     
         27 . A structure, comprising: 
 a substrate;    an interfacial layer formed over the substrate, the interfacial layer having a thickness of about 13 Å or less; and    one or more hafnium containing layers formed over the interfacial layer.    
     
     
         28 . The structure of  claim 27 , wherein the interfacial layer has a thickness of about 6 Å or less.  
     
     
         29 . The structure of  claim 27 , wherein the hafnium containing layer is amorphous.  
     
     
         30 . The structure of  claim 27 , wherein the hafnium containing layer has a surface roughness (Rms) of about 0.4 nm or less.  
     
     
         31 . The structure of  claim 27 , wherein the hafnium containing layer has a surface roughness (Rms) of about 0.3 nm or less.  
     
     
         32 . The structure of  claim 27 , wherein the one or more hafnium containing layers are formed to a combined thickness of about 50 Å or less.  
     
     
         33 . The structure of  claim 27 , wherein the hafnium containing layer is formed to a thickness of about 40 Å or less.  
     
     
         34 . An integrated system for forming a hafnium containing high dielectric constant layer over a substrate, comprising: 
 one or more rapid thermal processing chambers adapted to generate steam by introducing a hydrogen containing gas and an oxygen containing gas;    one or more deposition chambers adapted to deposit a hafnium containing layer;    a transfer chamber in communication with the rapid thermal processing chambers and the deposition chambers; and    one or more load lock chambers.    
     
     
         35 . The system of  claim 34 , wherein the rapid thermal processing chambers are adapted to introducing hydrogen (H 2 ) gas and nitrous oxide (N 2 O) gas to generate steam.  
     
     
         36 . The system of  claim 34 , wherein the deposition chambers are adapted to form a hafnium containing layer by introducing a hafnium precursor and an oxygen containing gas.  
     
     
         37 . The system of  claim 34 , further comprising a cleaning module in communication with the load lock chambers.  
     
     
         38 . The system of  claim 37 , wherein the cleaning module comprises one or more single-substrate clean chambers.  
     
     
         39 . A method of forming a hafnium containing layer on a substrate, comprising: 
 remove native oxides from a surface of the substrate;    hydroxylating the surface of the substrate to form a hydroxylated surface; and    forming a hafnium containing layer over the hydroxylated surface.    
     
     
         40 . The method of  claim 39 , wherein forming a hafnium containing layer comprises forming an interfacial layer to a thickness of about 13 Å or less.  
     
     
         41 . The method of  claim 39 , wherein forming a hafnium containing layer comprises forming an interfacial layer to a thickness of about 6 Å or less.