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US6203613B1 Expired / Lapsed US ⏱️ 0.0 years remaining

Atomic layer deposition with nitrate containing precursors

Assignee: International Business Machines Corp
•
Filing: 1999-10-19
•
Granted: 2001-03-20
•
Expires: 2019-10-19
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Abstract

Abstract Metal nitrate-containing precursor compounds are employed in atomic layer deposition processes to form metal-containing films, e.g. metal, metal oxide, and metal nitride, which films exhibit an atomically abrupt interface and an excellent uniformity.

Inventors

  • 👤 Stephen McConnell Gates
  • 👤 Deborah Ann Neumayer

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 04:45
CPC Classifications
C; C30; C30B; C30B25/00; C30B25/02; C30B29/00; C30B29/60; C30B29/68; H; H10; H10P; H10P14/00; H10P14/60; H10P14/63; H10P14/6326; H10P14/6328; H10P14/6334; H10P14/6339; H10P14/66; H10P14/662; H10P14/668; H10P14/69; H10P14/692; H10P14/6921; H10P14/69215; H10P14/6938; H10P14/6939; H10P14/69391; H10P14/69392; H10P14/69395; H10P14/69397; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/033; H10W20/035

Claims Analysis

Total Claims: 61
Claim 1
Independent Claim 29 words
A method of forming a metal-containing film on a substrate comprising an atomic layer deposition process wherein a metal nitrate-containing precursor is introduced into a reactor containing said substrate.
Claim 2
Independent Claim 29 words
A method of forming a metal-containing film on a substrate comprising an atomic layer deposition process wherein a metal nitrate-containing precursor is introduced into a reactor containing said substrate.
Claim 3
Dependent Claim 64 words
The method of claim 1 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 4
Dependent Claim 49 words
The method of claim 2 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and mixtures thereof.
Claim 5
Dependent Claim 27 words
The method of claim 1 wherein a co-reactant gas is employed with said metal nitrate-containing precursor, said co-reactant gas being introduced separately from said metal nitrate-containing precursor.
Claim 6
Dependent Claim 20 words
The method of claim 4 wherein said co-reactant gas is a reducing agent, an oxidizing agent or a nitriding agent.
Claim 7
Dependent Claim 22 words
The method of claim 5 wherein said reducing agent is selected from the group consisting of hydrogen, forming gas and combinations thereof.
Claim 8
Dependent Claim 26 words
The method of claim 5 wherein said oxidizing agent is selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, nitrous oxide and combinations thereof.
Claim 9
Dependent Claim 25 words
The method of claim 5 wherein said nitriding agent is selected from the group consisting of ammonia, hydrazine, hydrogen azide, tertbutylamine, isopropylamine and combinations thereof.
Claim 10
Dependent Claim 31 words
The method of claim 1 wherein an inert gas is employed with said metal nitrate-containing precursor, said inert gas being introduced separately from said metal nitrate-containing precursor as a purge gas.
Claim 11
Dependent Claim 28 words
The method of claim 1 wherein said metal-containing precursor forms a metal nitride film, a metal oxide film, a metal film or any combination, multilayer or multicomponent thereof.
Claim 12
Dependent Claim 35 words
The method of claim 1 wherein one or more metal non-nitrate containing precursors is employed with said metal nitrate-containing precursor, each of said metal non-nitrate containing precursors being introduced separately from said metal nitrate-containing precursors.
Claim 13
Dependent Claim 44 words
The method of claim 11 wherein said metal non-nitrate containing precursor is selected from the group consisting of a metal alkyl, a metal alkoxide, a metal halide, a metal β-diketonate, a metal hydride, a metal silyl, a metal amide and mixtures and combinations thereof.
Claim 14
Independent Claim 61 words
A method for forming a metal oxide film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of three or more different gases to a substrate, wherein one of said gases comprising a metal nitrate-containing precursor, another of said gases is an inert gas and another of said gases is an oxidizing agent.
Claim 15
Independent Claim 61 words
A method for forming a metal oxide film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of three or more different gases to a substrate, wherein one of said gases comprising a metal nitrate-containing precursor, another of said gases is an inert gas and another of said gases is an oxidizing agent.
Claim 16
Dependent Claim 64 words
The method of claim 13 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 17
Dependent Claim 49 words
The method of claim 14 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and combinations thereof.
Claim 18
Dependent Claim 26 words
The method of claim 13 wherein said oxidizing agent is selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, nitrous oxide and combinations thereof.
Claim 19
Dependent Claim 16 words
The method of claim 13 wherein two or more of said metal nitrate-containing precursors are employed.
Claim 20
Independent Claim 33 words
A method of forming a metal film on a substrate by atomic layer deposition comprising subjecting said substrate to alternating pulses of a metal nitrate-containing precursor, a purge gas and a reducing agent.
Claim 21
Independent Claim 33 words
A method of forming a metal film on a substrate by atomic layer deposition comprising subjecting said substrate to alternating pulses of a metal nitrate-containing precursor, a purge gas and a reducing agent.
Claim 22
Dependent Claim 64 words
The method of claim 18 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 23
Dependent Claim 49 words
The method of claim 19 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and mixtures thereof.
Claim 24
Dependent Claim 22 words
The method of claim 18 wherein said reducing agent is selected from the group consisting of hydrogen, forming gas and combinations thereof.
Claim 25
Dependent Claim 14 words
The method of claim 18 wherein two or more metal nitrate-containing precursors are employed.
Claim 26
Independent Claim 36 words
A method of forming a metal nitride film on a substrate by atomic layer deposition said method comprising subjecting said substrate to alternating pulses of a metal nitrate-containing precursor, a purge gas and a nitriding agent.
Claim 27
Independent Claim 36 words
A method of forming a metal nitride film on a substrate by atomic layer deposition said method comprising subjecting said substrate to alternating pulses of a metal nitrate-containing precursor, a purge gas and a nitriding agent.
Claim 28
Dependent Claim 64 words
The method of claim 23 herein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 29
Dependent Claim 49 words
The method of claim 24 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and mixtures thereof.
Claim 30
Dependent Claim 25 words
The method of claim 23 wherein said nitriding agent is selected from the group consisting of ammonia, hydrazine, hydrogen azide, tertbutylamine, isopropylamine and combinations thereof.
Claim 31
Dependent Claim 12 words
The method of claim 23 wherein two or more metal nitrate-containing precursors.
Claim 32
Dependent Claim 87 words
In an atomic layer deposition process for forming a metal-containing film, the improvement comprising at least a step of introducing a metal-containing precursor into a reactor containing a substrate, said metal containing precursor having the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 33
Dependent Claim 87 words
In an atomic layer deposition process for forming a metal-containing film, the improvement comprising at least a step of introducing a metal-containing precursor into a reactor containing a substrate, said metal containing precursor having the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 34
Dependent Claim 49 words
The method of claim 28 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and mixtures thereof.
Claim 35
Dependent Claim 27 words
The method of claim 28 wherein a co-reactant gas is employed with said metal nitrate-containing precursor, said co-reactant gas being introduced separately from said metal nitrate precursor.
Claim 36
Dependent Claim 20 words
The method of claim 30 wherein said co-reactant gas is a reducing agent, an oxidizing agent or a nitriding agent.
Claim 37
Dependent Claim 22 words
The method of claim 31 wherein said reducing agent is selected from the group consisting of hydrogen, forming gas and combinations thereof.
Claim 38
Dependent Claim 26 words
The method of claim 31 wherein said oxidizing agent is selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, nitrous oxide and combinations thereof.
Claim 39
Dependent Claim 25 words
The method of claim 31 wherein said nitriding agent is selected from the group consisting of ammonia, hydrazine, hydrogen azide, tertbutylamine, isopropylamine and combinations thereof.
Claim 40
Dependent Claim 27 words
The method of claim 28 wherein an inert gas is employed with said metal nitrate-containing precursor, said inert gas being introduced separately from said metal nitrate-containing precursor.
Claim 41
Independent Claim 71 words
A method for forming a multicomponent or multilayer metal oxide film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is an oxidizing agent and another of said gases is a metal non-nitrate containing precursor.
Claim 42
Independent Claim 71 words
A method for forming a multicomponent or multilayer metal oxide film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is an oxidizing agent and another of said gases is a metal non-nitrate containing precursor.
Claim 43
Dependent Claim 64 words
The method of claim 36 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 44
Dependent Claim 49 words
The method of claim 37 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and combinations thereof.
Claim 45
Dependent Claim 26 words
The method of claim 36 wherein said oxidizing agent is selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, nitrous oxide and combinations thereof.
Claim 46
Dependent Claim 16 words
The method of claim 36 wherein two or more of said metal nitrate-containing precursors are employed.
Claim 47
Dependent Claim 44 words
The method of claim 36 wherein said metal non-nitrate containing precursor is selected from the group consisting of a metal alkyl, a metal alkoxide, a metal halide, a metal β-diketonate, a metal hydride, a metal silyl, a metal amide and mixtures and combinations thereof.
Claim 48
Independent Claim 70 words
A method for forming a multicomponent or multilayer metal film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is a reducing agent and another of said gases is a metal non-nitrate containing precursor.
Claim 49
Independent Claim 70 words
A method for forming a multicomponent or multilayer metal film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is a reducing agent and another of said gases is a metal non-nitrate containing precursor.
Claim 50
Dependent Claim 64 words
The method of claim 42 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 51
Dependent Claim 49 words
The method of claim 43 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and combinations thereof.
Claim 52
Dependent Claim 22 words
The method of claim 42 wherein said reducing agent is selected from the group consisting of hydrogen, forming gas and combinations thereof.
Claim 53
Dependent Claim 16 words
The method of claim 42 wherein two or more of said metal nitrate-containing precursors are employed.
Claim 54
Dependent Claim 44 words
The method of claim 42 wherein said metal non-nitrate containing precursor is selected from the group consisting of a metal alkyl, a metal alkoxide, a metal halide, a metal β-diketonate, a metal hydride, a metal silyl, a metal amide and mixtures and combinations thereof.
Claim 55
Independent Claim 71 words
A method for forming a multicomponent or multilayer metal nitride film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is a nitriding agent and another of said gases is a metal non-nitrate containing precursor.
Claim 56
Independent Claim 71 words
A method for forming a multicomponent or multilayer metal nitride film on a substrate by atomic layer deposition comprising subjecting said substrate to a sequence of alternating pulses of four or more different gases, wherein one of said gases comprises a metal nitrate-containing precursor, another of said gases is an inert gas, another of said gases is a nitriding agent and another of said gases is a metal non-nitrate containing precursor.
Claim 57
Dependent Claim 64 words
The method of claim 48 wherein said metal nitrate-containing precursor has the formula M(NO 3 ) x wherein M is a metal selected from the group consisting of Ti, Ga, Zr, Sn, Co, V, Pt, Pd, Fe, Ni, Mo, W, Ag, Au, Hf, Cr, Cu, Mn, La, Y, Al, Gd, Nd, Sm, Si, Nb, Ta, and In; and x is the valence of M.
Claim 58
Dependent Claim 49 words
The method of claim 49 wherein some, but not all, of said NO 3 ligands of said metal nitrate-containing precursor are replaced with a substituent R, said substituent R being selected from the group consisting of hydrogen, oxygen, oxo-nitrate, hydroxyl, aromatic, alkyl, amine, silyl, alkoxide, β-diketone and combinations thereof.
Claim 59
Dependent Claim 25 words
The method of claim 48 wherein said nitriding agent is selected from the group consisting of ammonia, hydrazine, hydrogen azide, tertbutylamine, isopropylamine and combinations thereof.
Claim 60
Dependent Claim 16 words
The method of claim 48 wherein two or more of said metal nitrate-containing precursors are employed.
Claim 61
Dependent Claim 44 words
The method of claim 48 wherein said metal non-nitrate containing precursor is selected from the group consisting of a metal alkyl, a metal alkoxide, a metal halide, a metal β-diketonate, a metal hydride, a metal silyl, a metal amide and mixtures and combinations thereof.

References Cited (Backward Citations)

US4058430A Cited
US4861417A Cited
US5166092A Cited
US5256244A Cited

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