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 precursor
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.
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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; anddepositing at least part of the indium(III)-containing precursor onto the s
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; anddepositing 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: [(R1)NC(R3)N(R2)]InX2,[(R1)NC(R3)N(R2)]2InX2, or[((R1)NC(R3)N(R2))InX]2(μ-X)2, (a) wherein X is chosen from chlorine, bromine and iodine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R6 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. where X is chosen from chlorine, bromine and iodine, preferably chlorine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) where X is chosen from chlorine, bromine and iodine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. [(R1)N(R3)C(R4)C(R5)N(R2)]InX2, or[(R1)N(R3)C(R4)C(R5)N(R2)]2InX, (d) where X is a halogen, preferably chlorine. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group; Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups; and Group R4 may also be selected from halogens, and [N((SiR1R2R3)R4)]InX2 (e) where X is chosen from chlorine, bromine and iodine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 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)NC(Me)N(tBu)]In(III)Cl2. 4. The method of claim 1, wherein the indium(III)-containing precursor is [(iPr)NCH N(iPr)]In(III)Cl2 or [((iPr)NC(H)N(iPr))InCl]2(μ-Cl)2. 5. The method of claim 1, wherein the indium(III)-containing precursor is [(Et)NC(nBu)N(tBu)]In(III)Cl2. 6. The method of claim 1, wherein the indium(III)-containing precursor is [(iPr)NC(nBu)N(iPr)]In(III)Cl2. 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, InxOy (x=0.5 to 1.5, y=0.5 to 1.5), InSnO (ITO), InGaZnO (IGZO), InN, InP, InAs, InSb, In2S3, 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 O3, O2, H2O, NO, N2O, NO2, H2O2, O radicals and combinations thereof. 12. The method of claim 10, wherein the co-reactant is selected from NH3, NO, N2O, hydrazines, N2 plasma, N2/H2 plasma, NH3 plasma, amines and combinations thereof. 13. A composition for deposition of a film comprising an indium(III)-containing precursor having the formula: [(R1)NC(R3)N(R2)]InX2,[(R1)NC(R3)N(R2)]2InX2, or[((R1)NC(R3)N(R2))InX]2(μ-X)2, (a) wherein X is chosen from chlorine, bromine and iodine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R8 where R7 and R6 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, where X is chosen from chlorine, bromine and iodine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) where X is chosen from chlorine, bromine and iodine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. [(R1)N(R3)C(R4)C(R5)N(R2)]InX2, or[(R1)N(R3)C(R4)C(R5)N(R2)]2InX, (d) where X is a halogen. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group, and [N((SiR1R2R3)R4)]InX2 (e) where X is chosen from chlorine, bromine and iodine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 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)N132 C(Me)132 N(tBu)]In(III)Cl2, [(iPr)N132 CHN(iPr)]In(III)Cl2, [(Et)NC(Me)N(tBu)]In(III)Cl2 or [(iPr)NC(nBu)N(iPr)]In(III)Cl2. 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: [(R1)NC(R3)N(R2)]InX2,[(R1)NC(R3)N(R2)]2InX2, or[((R1)NC(R3)N(R2))InX]2(μ-X)2, (a) wherein X is chosen from chlorine, bromine and iodine; R1 and R2 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups or —SiR4R5R6 wherein R4, R5, R6 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R3 is selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or —NR7R6 where R7 and R6 are each independently selected from H or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups. where X is chosen from chlorine, bromine and iodine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group, [(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]InX2,[(R2R3)N—(CR6R7)n—C(R4R5)—N(R1)]2InX, or[((R2R3)N—(CR6R7)n—C(R4R5)—N(R1))InX]2(μ-X)2, (c) where X is chosen from chlorine, bromine and iodine; R1, R2, R3, R4, R5, R6 and R7 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4, R5, R6 and R7 may also be —SiR8R9R10 where R8, R9, R10 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group. [(R1)N(R3)C(R4)C(R5)N(R2)]InX2, or[(R1)N(R3)C(R4)C(R5)N(R2)]2InX, (d) where X is a halogen. R1, R2, R3, R4 and R5 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups; R1, R2, R3, R4 and R5 may also be —SiR6R7R8 where R6, R7, R8 are each independently selected from a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group; Groups R1, R2, R3 and R5 may also be selected from fluorinated linear or aromatic groups; and Group R4 may also be selected from halogens, and [N((SiR1R2R3)R4)]InX2 (e) where X is chosen from chlorine, bromine and iodine; R1, R2, and R3 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl groups, R4 is hydrogen or a linear, branched or cyclic C1 to C9 alkyl, vinyl or aryl group or a —SiR5R6R7 group wherein R5, R6, and R7 are each independently selected from hydrogen or a linear, branched or cyclic C1 to C9 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 O3, O2, H2O, NO, N2O, NO2, H2O2, O radicals and combinations thereof. 20. The method of claim 18, wherein the co-reactant is selected from NH3, NO, N2O, hydrazines, N2 plasma, N2/H2 plasma, NH3 plasma, amines and combinations thereof.
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