Patent · US9129897B2 · B2 · US

Metal silicide, metal germanide, methods for making the same

(11) Publication number

US9129897B2

(21) Application number

13/452,402

(22) Filing date

2012-04-20

(30) Priority date

2008-12-19

(43) Publication date

2015-09-08

(45) Date of grant

2015-09-08

(51) IPC

H01L 21/3205; H01L 21/3215; H10W 20/43; C23C 16/06; C23C 16/40; C23C 16/455; H01L 21/285; H01L 29/66; H01L 29/78

(52) CPC

C23C Coating metallic material; coating material with metallic material; surface treatment of metallic material by diffusion into the surface, by chemical conversion or substitution; coating by vacuum evaporation, by sputtering, by ion implantation or by chemical vapour deposition, in general: 16/06, 16/406, 16/45527
H01L Semiconductor devices; electric solid state devices not otherwise provided for: 21/28518, 21/28562, 29/456, 29/4933, 29/665, 29/66666, 29/7827
H10D Inorganic electric semiconductor devices: 30/0212, 30/025, 30/63, 62/83, 64/0112, 64/01125, 64/0131, 64/62, 64/663
H10P Generic processes or apparatus for the manufacture or treatment of devices covered by class H10: 14/43, 14/432, 32/30, 95/90
H10W Generic packages, interconnections, connectors or other constructional details of devices covered by class H10: 20/033, 20/047

(73) Assignee

ASM International NV

(72) Inventors

Viljami J. Pore; Suvi P. Haukka; Tom E. Blomberg; Eva E. Tois

(54) Title

Metal silicide, metal germanide, methods for making the same

(57) Abstract

In one aspect, methods of silicidation and germanidation are provided. In some embodiments, methods for forming metal silicide can include forming a non-oxide interface, such as germanium or solid antimony, over exposed silicon regions of a substrate. Metal oxide is formed over the interface layer. Annealing and reducing causes metal from the metal oxide to react with the underlying silicon and form metal silicide. Additionally, metal germanide can be formed by reduction of metal oxide over germanium, whether or not any underlying silicon is also silicided. In other embodiments, nickel is deposited directly and an interface layer is not used. In another aspect, methods of depositing nickel thin films by vapor phase deposition processes are provided. In some embodiments, nickel thin films are deposited by ALD.

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Claims (29)

A method for silicidation, comprising: providing a substrate having at least one exposed silicon region; depositing an interface layer on the exposed silicon region, wherein the interface layer is a material different from that of the exposed silicon region; depositing by atomic layer deposition (ALD) or CVD a metal oxide film over the interface layer; and heating the substrate to form a metal silicide film over the exposed silicon regions using metal from the metal oxide film and silicon from the exposed silicon region.
The method of claim 1, wherein the interface layer comprises antimony (Sb).
The method of claim 2, wherein the interface layer has a thickness between about 3 nm and 5 nm.
The method of claim 2, wherein the metal oxide film comprises nickel.
The method of claim 2, wherein the metal silicide film is chosen from a group consisting of Ni 2 Si, NiSi, NiSi 2.
The method of claim 2, wherein the substrate comprises a three-dimensional structure.
The method of claim 2, wherein the metal oxide film is reduced to a metal film with a vapor phase reducing agent.
The method of claim 1, wherein the interface layer comprises a semiconductor element.
The method of claim 8, wherein the interface layer comprises a germanium layer.
The method of claim 9, wherein the interface layer comprises an epitaxial germanium layer.
The method of claim 1, wherein the interface layer comprises an elemental film or mixtures of elemental films.
The method of claim 1, further comprising reducing the metal oxide film to a metal.
The method of claim 12, wherein heating the substrate and reducing are performed simultaneously in a reducing environment.
The method of claim 12, wherein heating the substrate comprises providing hydrogen gas in a chamber housing the substrate.
The method of claim 1, wherein depositing by ALD the metal oxide film comprises alternately and sequentially exposing the substrate to a metal source precursor and an oxygen precursor.
The method of claim 15, wherein the metal source precursor comprises at least one of Ni, Co, Cu, Fe, Ru, Rh, Pt and Pd.
The method of claim 16, wherein the metal source precursor comprises nickel.
The method of claim 15, wherein the oxygen source comprises O 3.
The method of claim 1, wherein the metal oxide film comprises two different metals.
The method of claim 1, wherein the interface layer has a thickness of 1 nanometer to 15 nanometers.
The method of claim 20, wherein the interface layer has a thickness of up to 5 nanometers.
A method for selective silicidation, comprising: providing an interface film over an exposed silicon-containing region in a manner that avoids oxidation of the exposed silicon-containing region, wherein the interface film is a material different from that of the exposed silicon-containing region; forming a metal oxide thin film on the interface film by CVD, pulsed CVD or at least one cycle of an atomic layer deposition (ALD) or ALD-type process, wherein one cycle comprises: contacting a substrate with a metal source precursor, and contacting the substrate with an oxygen source precursor; and reacting the metal from the metal oxide film with silicon from the silicon-containing region to form a metal silicide film over remaining portions of the silicon-containing region.
The method of claim 22, wherein the metal source precursor is a nickel source precursor.
The method of claim 22, wherein the oxygen source precursor is chosen from a group consisting of O 2, H 2 O, O 3, oxygen plasma, oxygen radicals or oxygen atoms or a reactive oxygen gas.
A method for forming metal germanide, comprising: providing a substrate having at least one exposed silicon region; depositing a germanium layer on the exposed silicon region; depositing a metal oxide film over germanium layer; and heating the substrate to form a metal germanide film using metal from the metal oxide film and a metal silicide under the metal germanide.
The method of claim 25, wherein the germanium layer is deposited by CVD.
The method of claim 25, wherein the metal oxide is a nickel oxide.
A method for forming a doped metal silicide layer on a substrate, comprising: providing a substrate having at least one exposed silicon region; depositing a metal film comprising a first metal over the silicon region, wherein depositing the metal film comprises multiple cycles of a primary metal atomic layer deposition-type process; depositing a dopant film comprising a second metal over the silicon region, wherein depositing the dopant film comprises one or more cycles of a dopant atomic layer deposition-type process; and annealing the substrate to form a metal silicide of the first metal that is doped with the second metal, wherein the cycles of the primary metal atomic layer deposition-type process and the cycles of the dopant atomic layer deposition-type process are carried out at a specific ratio to achieve a desired dopant concentration in the doped metal silicide layer.
The method of claim 28, wherein the first metal is nickel and the second metal is platinum.

Description

1. Field of the Invention

The invention relates generally to the field of semiconductor device manufacturing and, more particularly, to methods for depositing nickel and forming metal silicide and germanide.

2. Description of the Related Art

In forming advanced semiconductor devices, part of the silicon that is present in gate, source and drain structures can be converted into low-resistivity metal silicides. This is done to realize a conductive path with a low bulk resistivity on the one hand, and to ensure a good contact resistance on the other hand. In the past, TiSi 2 was used for this process; then later CoSi 2 was the silicide of choice for the most advanced devices. As both TiSi 2 and CoSi 2 consume a relatively large amount of silicon, there has been a switch to using NiSi x to form these conductive paths. This silicide combines a low bulk resistivity with a relatively low amount of silicon consumption.

A process of forming NiSi x on a substrate 80 is depicted in FIGS. 1A-1D. First, the basic structure of the transistor is formed, including a gate electrode 10, a gate dielectric 20, a source 30 and a drain 40 (FIG. 1A). On the sides of the polycrystalline silicon (poly-Si) gate, sidewall spacers 50 are deposited to insulate the sidewalls of the poly-Si/gate oxide stack from films that are subsequently formed and facilitate self-aligned doping of the source/ drain regions 30 / 40. A nickel film 60 (Ni) is then deposited, usually through a physical vapor deposition (PVD, e.g., sputtering) process (FIG. 1B).

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Record as JSON

{
  "publication_number": "US9129897B2",
  "country": "US",
  "kind": "B2",
  "title": "Metal silicide, metal germanide, methods for making the same",
  "abstract": "In one aspect, methods of silicidation and germanidation are provided. In some embodiments, methods for forming metal silicide can include forming a non-oxide interface, such as germanium or solid antimony, over exposed silicon regions of a substrate. Metal oxide is formed over the interface layer. Annealing and reducing causes metal from the metal oxide to react with the underlying silicon and form metal silicide. Additionally, metal germanide can be formed by reduction of metal oxide over germanium, whether or not any underlying silicon is also silicided. In other embodiments, nickel is deposited directly and an interface layer is not used. In another aspect, methods of depositing nickel thin films by vapor phase deposition processes are provided. In some embodiments, nickel thin films are deposited by ALD.",
  "claims": [
    "1. A method for silicidation, comprising: providing a substrate having at least one exposed silicon region; depositing an interface layer on the exposed silicon region, wherein the interface layer is a material different from that of the exposed silicon region; depositing by atomic layer deposition (ALD) or CVD a metal oxide film over the interface layer; and heating the substrate to form a metal silicide film over the exposed silicon regions using metal from the metal oxide film and silicon from the exposed silicon region.",
    "2. The method of claim 1, wherein the interface layer comprises antimony (Sb).",
    "3. The method of claim 2, wherein the interface layer has a thickness between about 3 nm and 5 nm.",
    "4. The method of claim 2, wherein the metal oxide film comprises nickel.",
    "5. The method of claim 2, wherein the metal silicide film is chosen from a group consisting of Ni 2 Si, NiSi, NiSi 2.",
    "6. The method of claim 2, wherein the substrate comprises a three-dimensional structure.",
    "7. The method of claim 2, wherein the metal oxide film is reduced to a metal film with a vapor phase reducing agent.",
    "8. The method of claim 1, wherein the interface layer comprises a semiconductor element.",
    "9. The method of claim 8, wherein the interface layer comprises a germanium layer.",
    "10. The method of claim 9, wherein the interface layer comprises an epitaxial germanium layer.",
    "11. The method of claim 1, wherein the interface layer comprises an elemental film or mixtures of elemental films.",
    "12. The method of claim 1, further comprising reducing the metal oxide film to a metal.",
    "13. The method of claim 12, wherein heating the substrate and reducing are performed simultaneously in a reducing environment.",
    "14. The method of claim 12, wherein heating the substrate comprises providing hydrogen gas in a chamber housing the substrate.",
    "15. The method of claim 1, wherein depositing by ALD the metal oxide film comprises alternately and sequentially exposing the substrate to a metal source precursor and an oxygen precursor.",
    "16. The method of claim 15, wherein the metal source precursor comprises at least one of Ni, Co, Cu, Fe, Ru, Rh, Pt and Pd.",
    "17. The method of claim 16, wherein the metal source precursor comprises nickel.",
    "18. The method of claim 15, wherein the oxygen source comprises O 3.",
    "19. The method of claim 1, wherein the metal oxide film comprises two different metals.",
    "20. The method of claim 1, wherein the interface layer has a thickness of 1 nanometer to 15 nanometers.",
    "21. The method of claim 20, wherein the interface layer has a thickness of up to 5 nanometers.",
    "22. A method for selective silicidation, comprising: providing an interface film over an exposed silicon-containing region in a manner that avoids oxidation of the exposed silicon-containing region, wherein the interface film is a material different from that of the exposed silicon-containing region; forming a metal oxide thin film on the interface film by CVD, pulsed CVD or at least one cycle of an atomic layer deposition (ALD) or ALD-type process, wherein one cycle comprises: contacting a substrate with a metal source precursor, and contacting the substrate with an oxygen source precursor; and reacting the metal from the metal oxide film with silicon from the silicon-containing region to form a metal silicide film over remaining portions of the silicon-containing region.",
    "23. The method of claim 22, wherein the metal source precursor is a nickel source precursor.",
    "24. The method of claim 22, wherein the oxygen source precursor is chosen from a group consisting of O 2, H 2 O, O 3, oxygen plasma, oxygen radicals or oxygen atoms or a reactive oxygen gas.",
    "25. A method for forming metal germanide, comprising: providing a substrate having at least one exposed silicon region; depositing a germanium layer on the exposed silicon region; depositing a metal oxide film over germanium layer; and heating the substrate to form a metal germanide film using metal from the metal oxide film and a metal silicide under the metal germanide.",
    "26. The method of claim 25, wherein the germanium layer is deposited by CVD.",
    "27. The method of claim 25, wherein the metal oxide is a nickel oxide.",
    "28. A method for forming a doped metal silicide layer on a substrate, comprising: providing a substrate having at least one exposed silicon region; depositing a metal film comprising a first metal over the silicon region, wherein depositing the metal film comprises multiple cycles of a primary metal atomic layer deposition-type process; depositing a dopant film comprising a second metal over the silicon region, wherein depositing the dopant film comprises one or more cycles of a dopant atomic layer deposition-type process; and annealing the substrate to form a metal silicide of the first metal that is doped with the second metal, wherein the cycles of the primary metal atomic layer deposition-type process and the cycles of the dopant atomic layer deposition-type process are carried out at a specific ratio to achieve a desired dopant concentration in the doped metal silicide layer.",
    "29. The method of claim 28, wherein the first metal is nickel and the second metal is platinum."
  ],
  "description_excerpt": "1. Field of the Invention\n\nThe invention relates generally to the field of semiconductor device manufacturing and, more particularly, to methods for depositing nickel and forming metal silicide and germanide.\n\n2. Description of the Related Art\n\nIn forming advanced semiconductor devices, part of the silicon that is present in gate, source and drain structures can be converted into low-resistivity metal silicides. This is done to realize a conductive path with a low bulk resistivity on the one hand, and to ensure a good contact resistance on the other hand. In the past, TiSi 2 was used for this process; then later CoSi 2 was the silicide of choice for the most advanced devices. As both TiSi 2 and CoSi 2 consume a relatively large amount of silicon, there has been a switch to using NiSi x to form these conductive paths. This silicide combines a low bulk resistivity with a relatively low amount of silicon consumption.\n\nA process of forming NiSi x on a substrate 80 is depicted in FIGS. 1A-1D. First, the basic structure of the transistor is formed, including a gate electrode 10, a gate dielectric 20, a source 30 and a drain 40 (FIG. 1A). On the sides of the polycrystalline silicon (poly-Si) gate, sidewall spacers 50 are deposited to insulate the sidewalls of the poly-Si/gate oxide stack from films that are subsequently formed and facilitate self-aligned doping of the source/ drain regions 30 / 40. A nickel film 60 (Ni) is then deposited, usually through a physical vapor deposition (PVD, e.g., sputtering) process (FIG. 1B).",
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  "ipc": [
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  "assignees": [
    "ASM International NV"
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  "inventors": [
    "Viljami J. Pore",
    "Suvi P. Haukka",
    "Tom E. Blomberg",
    "Eva E. Tois"
  ],
  "filing_date": "2012-04-20",
  "publication_date": "2015-09-08",
  "grant_date": "2015-09-08",
  "priority_date": "2008-12-19",
  "application_number": "US-201213452402-A",
  "family_id": "47021657",
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