Method for hafnium nitride deposition

Abstract

The present invention generally is a method for forming a high-k dielectric layer, comprising depositing a hafnium compound by atomic layer deposition to a substrate, comprising, delivering a hafnium precursor to a surface of the substrate, reacting the hafnium precursor and forming a hafnium containing layer to the surface, delivering a nitrogen precursor to the hafnium containing layer, forming at least one hafnium nitrogen bond and depositing the hafnium compound to the surface.

1 . A method for forming a layer comprising hafnium on a substrate surface, sequentially comprising: 
 a) exposing the substrate surface to a hafnium precursor to form a hafnium containing layer on the substrate surface;    b) purging the chamber with a purge gas;    c) reacting a second precursor with the hafnium containing layer;    d) purging the chamber with the purge gas;    e) reacting a third precursor with the hafnium containing layer;    f) purging the chamber with the purge gas;    g) reacting a fourth precursor with the hafnium containing layer; and    h) purging the chamber with the purge gas.    
     
     
         2 . The method of  claim 1 , wherein the layer comprising hafnium is hafnium silicon oxynitride.  
     
     
         3 . The method of  claim 1 , further comprising repeating steps a-h to deposit the layer comprising hafnium at a thickness from about 2 Å to about 1,000 Å.  
     
     
         4 . The method of  claim 3 , wherein the thickness is from about 10 Å to about 50 Å.  
     
     
         5 . The method of  claim 1 , wherein the hafnium precursor is selected from the group consisting of (Et 2 N) 4 Hf, (Me 2 N) 4 Hf, (EtMeN) 4 Hf and Cl 4 Hf.  
     
     
         6 . The method of  claim 5 , wherein the second precursor is selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.  
     
     
         7 . The method of  claim 6 , wherein the third precursor is selected from the group consisting of SiH 4 , Si 2 H 6 , Si 3 H 8 , Si 2 Cl 6 , (Et 2 N) 4 Si, (Me 2 N) 4 Si, (Et 2 N) 3 SiH and (Me 2 N) 3 SiH.  
     
     
         8 . The method of  claim 7 , wherein the fourth precursor is selected from the group consisting of H 2 O, H 2 O 2 , organic peroxides, O, O 2 , O 3  and radical oxygen compounds.  
     
     
         9 . The method of  claim 1 , further comprising: 
 i) reacting a fifth precursor with the hafnium containing layer; and    j) purging the chamber with the purge gas.    
     
     
         10 . The method of  claim 9 , wherein the fifth precursor is selected from the group consisting of Me 3 Al, Me 2 AlH, AlCl 3 , Me 2 AlCl and (PrO) 3 Al.  
     
     
         11 . A method for growing a layer comprising hafnium, comprising: 
 exposing a substrate sequentially to at least four precursors during an ALD cycle to deposit a compound film comprising hafnium and at least three elements selected from the group consisting of silicon, aluminum, oxygen and nitrogen.    
     
     
         12 . The method of  claim 11 , wherein the at least four precursors include a hafnium precursor selected from the group consisting of (Et 2 N) 4 Hf, (Me 2 N) 4 Hf, (EtMeN) 4 Hf and Cl 4 Hf.  
     
     
         13 . The method of  claim 11 , wherein the at least four precursors include a silicon precursor selected from the group consisting of SiH 4 , Si 2 H 6 , Si 3 H 8 , Si 2 Cl 6 , (Et 2 N) 4 Si, (Me 2 N) 4 Si, (Et 2 N) 3 SiH and (Me 2 N) 3 SiH.  
     
     
         14 . The method of  claim 11 , wherein the at least four precursors include a nitrogen precursor selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.  
     
     
         15 . The method of  claim 11 , wherein the at least four precursors include an oxygen precursor selected from the group consisting of H 2 O, H 2 O 2 , organic peroxides, O, O 2 , O 3  and radical oxygen compounds.  
     
     
         16 . The method of  claim 11 , wherein the at least four precursors include an aluminum precursor selected from the group consisting of Me 3 Al, Me 2 AlH, AlCl 3 , Me 2 AlCl and (PrO) 3 Al.  
     
     
         17 . The method of  claim 11 , wherein the layer comprising hafnium is deposited to a thickness from about 2 Å to about 1,000 Å.  
     
     
         18 . The method of  claim 17 , wherein the thickness is from about 10 Å to about 50 Å.  
     
     
         19 . A method for depositing a hafnium compound on a substrate in a chamber during an atomic layer deposition process, comprising: 
 conducting a first half reaction comprising a hafnium precursor;    conducting a second half reaction comprising an oxygen precursor;    conducting a third half reaction comprising a nitrogen precursor; and    conducting a fourth half reaction comprising a silicon precursor.    
     
     
         20 . The method of  claim 19 , wherein the hafnium precursor is selected from the group consisting of (Et 2 N) 4 Hf, (Me 2 N) 4 Hf, (EtMeN) 4 Hf and Cl 4 Hf.  
     
     
         21 . The method of  claim 20 , wherein the silicon precursor is selected from the group consisting of SiH 4 , Si 2 H 6 , Si 3 H 8 , Si 2 Cl 6 , (Et 2 N) 4 Si, (Me 2 N) 4 Si, (Et 2 N) 3 SiH and (Me 2 N) 3 SiH.  
     
     
         22 . The method of  claim 21 , wherein the nitrogen precursor is selected from the group consisting of ammonia, hydrazines, azides and radical nitrogen compounds.  
     
     
         23 . The method of  claim 22 , wherein the oxygen precursor is selected from the group consisting of H 2 O, H 2 O 2 , organic peroxides, O, O 2 , O 3  and radical oxygen compounds.  
     
     
         24 . The method of  claim 19 , further comprising conducting a fifth half reaction comprising an aluminum precursor selected from the group consisting of Me 3 Al, Me 2 AlH, AlCl 3 , Me 2 AlCl and (PrO) 3 Al.  
     
     
         25 . A composition of a semiconductor material, comprising HfSi x O y N z , 
 wherein x is at least about 0.2 and less than about 4;    y is at least about 0.5 and less than about 4; and    z is at least about 0.05 and less than about 2.