INDIUM PRECURSORS FOR VAPOR DEPOSITIONS
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.
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.