Lanthanide precursors and deposition of lanthanide-containing films using the same

Abstract

Lanthanide-containing film forming compositions comprising Lanthanide precursors having the general formulae: wherein Ln is a Lanthanide; A is independently N, Si, B, P or O; each E is independently C, Si, B or P; m and n are independently 0, 1 or 2; m+n>1; each R is independently an H or a C 1 -C 4 hydrocarbyl group; L is a −1 anionic ligand selected from the group consisting of NR′ 2 , OR′, Cp, amidinate, β-diketonate, or keto-iminate, wherein R′ is an H or a C 1 -C 4 hydrocarbon group; and L′ is NR″ or O, wherein R″ is an H or a C 1 -C 4 hydrocarbon group. Also disclosed are methods of synthesizing and using the disclosed precursors to deposit Lanthanide-containing films on one or more substrates via vapor deposition processes.

What is claimed is: 
     
         1 . A composition comprising a Lanthanide precursor of the general formulae:
   L-Ln-C 5 R 4 -[(ER 2 ) m -(ER 2 ) n -L′]-,
     L-Ln-C 4 AR 3 -3-[(ER 2 ) m -(ER 2 ) n -L′]-,
     L-Ln-C 3 (m-A 2 )R 2 -4-[(ER 2 ) m -(ER 2 ) n -L′]-,
   referring to the following structure formula, respectively:   
       
         
           
           
               
               
           
         
         wherein Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an η 5  bonding mode to the aromatic group; A is independently N, Si, B, P or O; each E is independently C, Si, B or P; m and n are independently 0, 1 or 2; m+n>1; each R is independently an H or a C 1 -C 4  hydrocarbyl group; each L is independently a −1 anionic ligand; 
         and each L′ is independently NR″ or O, wherein R″ is an H or a C1-C 4  hydrocarbon group. 
       
     
     
         2 . The 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 an H or a C 1 -C 4  hydrocarbon group. 
     
     
         3 . The composition of  claim 1 , wherein the Lanthanide precursor is selected from the group consisting of (Me 2 N)-La-C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Y—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sc—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ce—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Pr—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Nd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Eu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Gd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Dy—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ho—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Er—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Yb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Lu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—La—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Y—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Sc—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Ce—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Pr—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Nd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Sm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Eu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Gd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Tb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Dy—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Ho—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Yb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, and (Me 2 N)—Lu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—. 
     
     
         4 . A method of forming a Lanthanide-containing film on a substrate, the method comprising the steps of:
 introducing the Lanthanide precursor of  claim 1  into a reactor having a substrate disposed therein; and   depositing at least part of the Lanthanide precursor onto the substrate to form the Lanthanide-containing film on the substrate using a vapor deposition process.   
     
     
         5 . The method of  claim 4 , further comprising introducing a reactant species into the reactor. 
     
     
         6 . The method of  claim 5 , wherein the reactant species is selected from the group consisting of O 2 , O 3 , H 2 O, H 2 O 2 , acetic acid, formalin, para-formaldehyde, and combinations thereof. 
     
     
         7 . The method of  claim 6 , wherein the reactant species is ozone. 
     
     
         8 . The method of  claim 4 , wherein the Lanthanide precursor is selected from the group consisting of (Me 2 N)-La-C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Y—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sc—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ce—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Pr—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Nd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Eu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Gd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Dy—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ho—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Er—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Yb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Lu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—La—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Y—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Sc—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Ce—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Pr—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Nd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Sm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Eu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Gd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Tb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Dy—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Ho—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, (Me 2 N)—Yb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—, and (Me 2 N)—Lu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —O)—. 
     
     
         9 . The method of  claim 6 , wherein the Lanthanide-containing film is selected from the group consisting of La 2 O 3 , (LaLn)O 3 , La 2 O 3 —Ln 2 O 3 , LaSi x O y , LaGe x O y , (Al, Ga, Mn)LnO 3 , HfLaO x , ZrLaO x , LaSrCoO 4 , and LaSrMnO 4 , where Ln is a different Lanthanide and x and y are each independently selected from a number ranging from 1 to 5 inclusive. 
     
     
         10 . The method of  claim 4 , further comprising introducing a precursor into the reactor, wherein the precursor is different from the Lanthanide precursor, and depositing at least part of the precursor to form the Lanthanide-containing film on the substrate. 
     
     
         11 . The method of  claim 10 , wherein the precursor contains an element selected from the group consisting of Hf, Si, Al, Ga, Mn, Ti, Ta, Bi, Zr, Pb, Nb, Mg, Sr, Ba, Ca, and combinations thereof. 
     
     
         12 . The method of  claim 4 , wherein the deposition process is a chemical vapor deposition process. 
     
     
         13 . The method of  claim 4 , wherein the deposition process is an atomic layer deposition process. 
     
     
         14 . The method of  claim 8 , wherein the deposition process is an atomic layer deposition process.