Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same

Abstract

Group 4 transition metal-containing film forming compositions comprising Group 4 transition metal precursors having the formula: wherein M is Ti, Zr, or Hf; each E is independently C, Si, B or P; m and n is independently 0, 1 or 2; m+n>1; o and p is independently 0, 1 or 2; p>1; each R is independently hydrogen or a C 1 -C 4 hydrocarbon group; each L is independently a −1 anionic ligand selected from the group consisting of NR′ 2 , OR′, Cp, amidinate, β-diketonate or keto-iminate, wherein R′ is a H or a C 1 -C 4 hydrocarbon group; and each L′ is independently NR″ or O, wherein R″ is a H or a C 1 -C 4 hydrocarbon group. Also disclosed are methods of synthesizing and using the disclosed precursors to deposit Group 4 transition metal-containing films on one or more substrates via vapor deposition processes.

We claim: 
     
         1 . A Group 4 transition metal-containing film forming composition comprising a Group 4 transition metal precursor having the following formula:
   L-M-C 5 R 3 -1-[(ER 2 ) m -(ER 2 ) n -L′]-2-[(ER 2 ) o -(ER 2 ) p -L′]- and
     L-M-C 5 R 3 -1-[(ER 2 ) n -(ER 2 ) m )-L′]-3-[(ER 2 ) o -(ER 2 ) p -L′],
   referring to the following structure formula, respectively:   
       
         
           
           
               
               
           
         
         wherein M is Ti, Zr, or Hf bonded in an η 5  bonding mode to the Cp group; each E is independently C, Si, B or P; m and n is independently 0, 1 or 2; m+n>1; o and p is independently 0, 1 or 2; o+p>1; each R is independently hydrogen or a C 1 -C 4  hydrocarbon group; each L is independently a −1 anionic ligand; and each L′ is independently NR″ or O, wherein R″ is a H or a C 1 -C 4  hydrocarbon group. 
       
     
     
         2 . The Group 4 transition metal-containing film forming composition of  claim 1 , wherein the −1 anionic ligand is selected from the group consisting of NR′ 2 , OR′, Cp, Amidinate, β-diketonate, and keto-iminate, wherein R′ is a H or a C 1 -C 4  hydrocarbon group. 
     
     
         3 . The Group 4 transition metal-containing film forming composition of  claim 2 , wherein the Group 4 transitional metal-containing precursor is selected from E is C. 
     
     
         4 . The Group 4 transition metal-containing film forming composition of  claim 3 , wherein M is Zr. 
     
     
         5 . The Group 4 transition metal-containing film forming composition of  claim 4 , wherein the Group 4 transitional metal precursor is selected from the group consisting of (Me 2 N)—Zr—C 5 H 3 -1-(CH 2 —CH 2 —NMe)-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)-Zr—C 5 H 2 -1-Me-2-(CH 2 —CH 2 —NMe)-4-(CH 2 —CH 2 —NMe)-, (Cp)-Zr-C 5 H 3 -1-(CH 2 —CH 2 -NMe)-3-(CH 2 —CH 2 —NMe)-, and (Cp)-Zr—C 5 H 2 -1-Me-2-(CH 2 —CH 2 —NMe)-4-(CH 2 —CH 2 -NMe)-. 
     
     
         6 . The Group 4 transition metal-containing film forming composition of  claim 3 , wherein M is Hf. 
     
     
         7 . The Group 4 transition metal-containing film forming composition of  claim 6 , wherein the Group 4 transitional metal precursor is selected from the group consisting of (Me 2 N)—Hf—C 5 H 3 -1-(CH 2 —CH 2 —NMe)-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Hf—C 5 H 2 -1-Me-2-(CH 2 —CH 2 —NMe)-4-(CH 2 —CH 2 —NMe)-, (Cp)-Hf—C 5 H 3 -1-(CH 2 —CH 2 —NMe)-3-(CH 2 —CH 2 —NMe)- and (Cp)-Hf—C 5 H 2 -1-Me-2-(CH 2 —CH 2 —NMe)-4-(CH 2 —CH 2 —NMe)-. 
     
     
         8 . The Group 4 transition metal-containing film forming composition of  claim 3 , wherein M is Ti.