Indium precursors for vapor depositions

Abstract

Disclosed are indium (In)-containing film forming compositions comprising In(III)-containing precursors that contain halogens, methods of synthesizing them and methods of using them to deposit the indium-containing films and/or indium-containing alloy film. The disclosed In(III)-containing precursors contain chlorine with nitrogen based ligands. In particular, the disclosed In(III)-containing precursors contains 1 or 2 amidinate ligands, 1 or 2 iminopyrrolidinate ligands, 1 or 2 amido amino alkane ligands, 1 or 2 μ-diketiminate ligands or a silyl amine ligand. The disclosed In(III)-containing precursors are suitable for vapor phase depositions (e.g., ALD, CVD) of the indium-containing films and/or indium-containing alloy films.

What is claimed is: 
     
         1 . A method for forming an indium(III)-containing film on a substrate, the method comprising the steps of:
 exposing the substrate to a vapor of a film forming composition that contains an indium(III)-containing precursor; and   depositing at least part of the indium(III)-containing precursor onto the substrate to form the indium(III)-containing film on the substrate through a vapor deposition process, wherein the indium(III)-containing precursor has the formula:
   [(R 1 )N C(R 3 ) N(R 2 )]InX 2 , 
   [(R 1 )N C(R 3 ) N(R 2 )] 2 InX 2 , or 
   [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 (μ-X) 2 ,  (a)
 
   
       wherein X is chosen from chlorine, bromine and iodine; R 1  and R 2  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6  wherein R 4 , R 5 , R 6  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 3  is selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or —NR 7 R 8  where R 7  and R 6  are each independently selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups. 
       
         
           
           
               
               
           
         
       
       where X is chosen from chlorine, bromine and iodine, preferably chlorine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group.
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )]InX 2 ,
 
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )] 2 InX, or
 
   [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 (μ-X) 2 ,  (c)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group.
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )]InX 2 , or 
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )] 2 InX,  (d)
 
 
       where X is a halogen, preferably chlorine. R 1 , R 2 , R 3 , R 4  and R 5  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4  and R 5  may also be —SiR 6 R 7 R 8  where R 6 , R 7 , R 8  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group; Groups R 1 , R 2 , R 3  and R 5  may also be selected from fluorinated linear or aromatic groups; and Group R 4  may also be selected from halogens, and
   [N((SiR 1 R 2 R 3 )R 4 )]InX 2   (e)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , and R 3  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups, R 4  is hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7  group wherein R 5 , R 6 , and R 7  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group. 
     
     
         2 . The method of  claim 1 , wherein X is chloride. 
     
     
         3 . The method of  claim 1 , wherein the indium(III)-containing precursor is [(Et)N C(Me) N(tBu)]In(III)Cl 2 . 
     
     
         4 . The method of  claim 1 , wherein the indium(III)-containing precursor is [(iPr)N CH  N(iPr)]In(III)Cl 2  or [((iPr)N C(H) N(iPr))InCl] 2 (μ-Cl) 2 . 
     
     
         5 . The method of  claim 1 , wherein the indium(III)-containing precursor is [(Et)N C(nBu) N(tBu)]In(III)Cl 2 . 
     
     
         6 . The method of  claim 1 , wherein the indium(III)-containing precursor is [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 . 
     
     
         7 . The method of  claim 1 , wherein the indium(III)-containing film is an indium oxide film, or a binary, ternary and quaternary indium alloy film. 
     
     
         8 . The method of  claim 1 , wherein the indium(III)-containing film is InGaAs, In x O y  (x=0.5 to 1.5, y=0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In 2 S 3 , or In(OH) 3 . 
     
     
         9 . The method of  claim 1 , wherein the vapor deposition process is an ALD or a CVD process. 
     
     
         10 . The method of  claim 1 , further comprising the step of exposing the substrate to a co-reactant. 
     
     
         11 . The method of  claim 10 , wherein the co-reactant is selected from O 3 , O 2 , H 2 O, NO, N 2 O, NO 2 , H 2 O 2 , O radicals and combinations thereof. 
     
     
         12 . The method of  claim 10 , wherein the co-reactant is selected from NH 3 , NO, N 2 O, hydrazines, N 2  plasma, N 2 /H 2  plasma, NH 3  plasma, amines and combinations thereof. 
     
     
         13 . A composition for deposition of a film comprising an indium(III)-containing precursor having the formula:
   [(R 1 )N C(R 3 ) N(R 2 )]InX 2 ,     [(R 1 )N C(R 3 ) N(R 2 )] 2 InX 2 , or     [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 (μ-X) 2 ,  (a)
   
       wherein X is chosen from chlorine, bromine and iodine; R 1  and R 2  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6  wherein R 4 , R 5 , R 6  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 3  is selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or —NR 7 R 8  where R 7  and R 6  are each independently selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups, 
       
         
           
           
               
               
           
         
       
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group.
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )]InX 2 ,
 
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )] 2 InX, or
 
   [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 (μ-X) 2 ,  (c)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group.
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )]InX 2 , or 
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )] 2 InX,  (d)
 
 
       where X is a halogen. R 1 , R 2 , R 3 , R 4  and R 5  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4  and R 5  may also be —SiR 6 R 7 R 8  where R 6 , R 7 , R 8  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group, and
   [N((SiR 1 R 2 R 3 )R 4 )]InX 2   (e)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , and R 3  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups, R 4  is hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7  group wherein R 5 , R 6 , and R 7  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group. 
     
     
         14 . The composition of  claim 13 , wherein X is chloride. 
     
     
         15 . The composition of  claim 13 , wherein the indium(III)-containing precursor is selected from [(Et)N   132  C(Me)   132  N(tBu)]In(III)Cl 2 , [(iPr)N   132  CH N(iPr)]In(III)Cl 2 , [(Et)N C(Me) N(tBu)]In(III)Cl 2  or [(iPr)N C(nBu) N(iPr)]In(III)Cl 2 . 
     
     
         16 . A method for forming an indium(III)-containing film on a substrate, the method comprising the steps of:
 forming a chemisorbed and/or physisorbed film, on the surface of the substrate, of an indium(III)-containing precursor having the formula:
   [(R 1 )N C(R 3 ) N(R 2 )]InX 2 , 
   [(R 1 )N C(R 3 ) N(R 2 )] 2 InX 2 , or 
   [((R 1 )N C(R 3 ) N(R 2 ))InX] 2 (μ-X) 2 ,  (a)
 
   
       wherein X is chosen from chlorine, bromine and iodine; R 1  and R 2  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups or —SiR 4 R 5 R 6  wherein R 4 , R 5 , R 6  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 3  is selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or —NR 7 R 6  where R 7  and R 6  are each independently selected from H or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups. 
       
         
           
           
               
               
           
         
       
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group,
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )]InX 2 ,
 
   [(R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 )] 2 InX, or
 
   [((R 2 R 3 )N—(CR 6 R 7 ) n —C(R 4 R 5 )—N(R 1 ))InX] 2 (μ-X) 2 ,  (c)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  may also be —SiR 8 R 9 R 10  where R 8 , R 9 , R 10  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group.
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )]InX 2 , or 
   [(R 1 )N (R 3 ) C(R 4 ) C(R 5 ) N(R 2 )] 2 InX,  (d)
 
 
       where X is a halogen. R 1 , R 2 , R 3 , R 4  and R 5  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups; R 1 , R 2 , R 3 , R 4  and R 5  may also be —SiR 6 R 7 R 8  where R 6 , R 7 , R 8  are each independently selected from a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group; Groups R 1 , R 2 , R 3  and R 5  may also be selected from fluorinated linear or aromatic groups; and Group R 4  may also be selected from halogens, and
   [N((SiR 1 R 2 R 3 )R 4 )]InX 2   (e)
 
 
       where X is chosen from chlorine, bromine and iodine; R 1 , R 2 , and R 3  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl groups, R 4  is hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group or a —SiR 5 R 6 R 7  group wherein R 5 , R 6 , and R 7  are each independently selected from hydrogen or a linear, branched or cyclic C 1  to C 9  alkyl, vinyl or aryl group. 
     
     
         17 . The method of  claim 16 , further comprising the step of chemically reacting the chemisorbed and/or physisorbed film comprising the indium(III)-containing precursor with a co-reactant. 
     
     
         18 . The method of  claim 17 , wherein the co-reactant reacting with the indium(III)-containing precursor in the chemisorbed and/or physisorbed film produces a reaction product that forms the indium(III)-containing film on the surface of the substrate. 
     
     
         19 . The method of  claim 18 , wherein the co-reactant is selected from O 3 , O 2 , H 2 O, NO, N 2 O, NO 2 , H 2 O 2 , O radicals and combinations thereof. 
     
     
         20 . The method of  claim 18 , wherein the co-reactant is selected from NH 3 , NO, N 2 O, hydrazines, N 2  plasma, N 2 /H 2  plasma, NH 3  plasma, amines and combinations thereof.