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Patent · US10734497B2 · B2 · US

Methods for forming a semiconductor device structure and related semiconductor device structures

(11) Publication number
US10734497B2
(21) Application number
16/038,024
(22) Filing date
2018-07-17
(30) Priority date
2017-07-18
(43) Publication date
2020-08-04
(45) Date of grant
2020-08-04
(51) IPC
H01L 21/02; H10D 64/66; H10D 64/68; C23C 16/34; C23C 16/455
(52) CPC
  • H10D Inorganic electric semiconductor devices: 64/01342, 30/027, 64/0134, 64/667, 64/669, 64/691
  • 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: 16/34, 16/45525
  • H01L Semiconductor devices; electric solid state devices not otherwise provided for: 21/02175, 21/02205, 21/0228, 21/28194, 29/4966, 29/517, 29/66568
  • H10P Generic processes or apparatus for the manufacture or treatment of devices covered by class H10: 14/3416, 14/6339, 14/668, 14/6924, 14/6939, 14/69392, 95/90
(73) Assignee
ASM IP Holding BV
(72) Inventors
Chiyu Zhu; Kiran Shrestha; Petri Raisanen; Michael Eugene Givens
(54) Title
Methods for forming a semiconductor device structure and related semiconductor device structures
(57) Abstract

Methods for forming a semiconductor device structure are provided. The methods may include forming a molybdenum nitride film on a substrate by atomic layer deposition by contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor, contacting the substrate with a second vapor phase reactant comprise a nitrogen precursor, and contacting the substrate with a third vapor phase reactant comprising a reducing precursor. The methods provided may also include forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV. Semiconductor device structures including molybdenum nitride films are also provided.

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Claims (20)

  1. A method for forming a semiconductor device structure, the method comprising: forming a molybdenum nitride film on a substrate by atomic layer deposition, wherein forming the molybdenum nitride film comprises: contacting the substrate with a first vapor phase reactant comprising a binary molybdenum halide precursor; after contacting the substrate with the first vapor phase reactant, contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor selected from the group comprising ammonia (NH 3), hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2); and at the same time as or after contacting the substrate with the second vapor phase reactant, contacting the substrate with a third vapor phase reactant comprising a reducing precursor selected from the group comprising hydrogen gas (H 2), silane (SiH 4), disilane (Si 2 H 6), trisilane (Si 3 H 8), tetrasilane (Si 4 H 8), and acetylene (C 2 H 2); and forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV.
  2. The method of claim 1, wherein the binary molybdenum halide precursor is selected from the group comprising molybdenum trichloride (MoCl 3), molybdenum tetrachloride (MoCl 4), molybdenum hexachloride (MoCl 6) and molybdenum hexafluoride (MoF 6).
  3. The method of claim 1, wherein the nitrogen precursor is selected from the group comprising hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2.
  4. The method of claim 1, wherein contacting the substrate with the second vapor phase reactant is performed after contacting the substrate with the first vapor phase reactant.
  5. The method of claim 4, wherein contacting the substrate with the third vapor phase reactant is performed after contacting the substrate with the second vapor phase reactant.
  6. The method of claim 1, wherein the molybdenum nitride film has a thickness of approximately less than 50 Angstroms.
  7. The method of claim 1, wherein the molybdenum nitride film has an electrical resistivity of less than 1200 μΩ-cm.
  8. The method of claim 1, wherein forming the gate electrode structure further comprises forming the gate electrode structure having an effective work function greater than 5.4 eV.
  9. The method of claim 1, wherein forming the molybdenum nitride film further comprises heating the substrate to a temperature greater than approximately 400° C.
  10. The method of claim 1, wherein forming the gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV, further comprises forming the gate electrode structure to have a thickness of less than 30 Angstroms.
  11. The method of claim 1, wherein forming the gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV, further comprises forming the gate electrode structure to have an electrical resistivity of less than 1200 μΩ-cm.
  12. A reaction system configured for forming the molybdenum nitride film of claim 1.
  13. A semiconductor device structure comprising: a PMOS transistor gate structure, comprising: a molybdenum nitride film comprising between 30 atomic % and 60 atomic % molybdenum; a semiconductor body; and a gate dielectric disposed between the molybdenum nitride film and the semiconductor body, wherein the PMOS gate structure has an effective work function greater than 5.0 eV.
  14. The semiconductor device structure of claim 13, wherein the molybdenum nitride film comprises between 40 atomic % and 50 atomic % molybdenum.
  15. The semiconductor device structure of claim 13 wherein the molybdenum nitride film has a thickness of less than 50 Angstroms.
  16. The semiconductor device structure of claim 13, wherein the PMOS gate structure has an effective work function greater than 5.4 eV.
  17. The semiconductor device structure of claim 13, wherein the molybdenum nitride film has an electrical resistivity of less than 1200 μΩ-cm.
  18. The semiconductor device structure of claim 13, wherein the gate dielectric comprises hafnium oxide (HfO 2).
  19. A method for forming a semiconductor device structure, the method comprising: forming a molybdenum nitride film on a substrate by atomic layer deposition, wherein forming the molybdenum nitride film comprises: contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor selected from the group comprising molybdenum trichloride (MoCl 3), molybdenum tetrachloride (MoCl 4), molybdenum hexachloride (MoCl 6), molybdenum hexafluoride (MoF 6), and tetrachloro(cyclopentadienyl)molybdenum, the first vapor phase reactant being free of Nitrogen (N); after contacting the substrate with the first vapor phase reactant, contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor selected from the group comprising hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2); and contacting the substrate with a third vapor phase reactant comprising a reducing precursor selected from the group comprising hydrogen gas (H 2), silane (SiH 4), disilane (Si 2 H 6), trisilane (Si 3 H 8), tetrasilane (Si 4 H 8), and acetylene (C 2 H 2); and forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV.
  20. The method of claim 19, wherein: contacting the substrate with the second vapor phase reactant is performed after contacting the substrate with the first vapor phase reactant; and contacting the substrate with the third vapor phase reactant is performed after contacting the substrate with the second vapor phase reactant.

Description

The present disclosure relates generally to methods for forming a semiconductor device structure including a molybdenum nitride film and related semiconductor device structures.

Metal-oxide-semiconductor (MOS) technology has conventionally utilized n-type doped polysilicon as the gate electrode material. However, doped polysilicon may not be an ideal gate electrode material for advanced node applications. For example, although doped polysilicon is conductive, there may still be a surface region which can be depleted of carriers under bias conditions. This region may appear as an extra gate insulator thickness, commonly referred to as gate depletion, and may contribute to the equivalent oxide thickness. While the gate depletion region may be thin, on the order of a few angstroms (Å), it may become significant as the gate oxide thicknesses are reduced in advance node applications. As a further example, polysilicon does not exhibit an ideal effective work function (eWF) for both NMOS and PMOS devices. To overcome the non-ideal effective work function of doped polysilicon, a threshold voltage adjustment implantation may be utilized. However, as device geometries reduce in advanced node applications, the threshold voltage adjustment implantation processes may become increasingly complex and impractical.

To overcome the problems associated with doped polysilicon gate electrodes, the non-ideal doped polysilicon gate material may be replaced with an alternative material, such as, for example, a transition metal nitride.

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{
  "publication_number": "US10734497B2",
  "country": "US",
  "kind": "B2",
  "title": "Methods for forming a semiconductor device structure and related semiconductor device structures",
  "abstract": "Methods for forming a semiconductor device structure are provided. The methods may include forming a molybdenum nitride film on a substrate by atomic layer deposition by contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor, contacting the substrate with a second vapor phase reactant comprise a nitrogen precursor, and contacting the substrate with a third vapor phase reactant comprising a reducing precursor. The methods provided may also include forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV. Semiconductor device structures including molybdenum nitride films are also provided.",
  "claims": [
    "1. A method for forming a semiconductor device structure, the method comprising: forming a molybdenum nitride film on a substrate by atomic layer deposition, wherein forming the molybdenum nitride film comprises: contacting the substrate with a first vapor phase reactant comprising a binary molybdenum halide precursor; after contacting the substrate with the first vapor phase reactant, contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor selected from the group comprising ammonia (NH 3), hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2); and at the same time as or after contacting the substrate with the second vapor phase reactant, contacting the substrate with a third vapor phase reactant comprising a reducing precursor selected from the group comprising hydrogen gas (H 2), silane (SiH 4), disilane (Si 2 H 6), trisilane (Si 3 H 8), tetrasilane (Si 4 H 8), and acetylene (C 2 H 2); and forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV.",
    "2. The method of claim 1, wherein the binary molybdenum halide precursor is selected from the group comprising molybdenum trichloride (MoCl 3), molybdenum tetrachloride (MoCl 4), molybdenum hexachloride (MoCl 6) and molybdenum hexafluoride (MoF 6).",
    "3. The method of claim 1, wherein the nitrogen precursor is selected from the group comprising hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2.",
    "4. The method of claim 1, wherein contacting the substrate with the second vapor phase reactant is performed after contacting the substrate with the first vapor phase reactant.",
    "5. The method of claim 4, wherein contacting the substrate with the third vapor phase reactant is performed after contacting the substrate with the second vapor phase reactant.",
    "6. The method of claim 1, wherein the molybdenum nitride film has a thickness of approximately less than 50 Angstroms.",
    "7. The method of claim 1, wherein the molybdenum nitride film has an electrical resistivity of less than 1200 μΩ-cm.",
    "8. The method of claim 1, wherein forming the gate electrode structure further comprises forming the gate electrode structure having an effective work function greater than 5.4 eV.",
    "9. The method of claim 1, wherein forming the molybdenum nitride film further comprises heating the substrate to a temperature greater than approximately 400° C.",
    "10. The method of claim 1, wherein forming the gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV, further comprises forming the gate electrode structure to have a thickness of less than 30 Angstroms.",
    "11. The method of claim 1, wherein forming the gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV, further comprises forming the gate electrode structure to have an electrical resistivity of less than 1200 μΩ-cm.",
    "12. A reaction system configured for forming the molybdenum nitride film of claim 1.",
    "13. A semiconductor device structure comprising: a PMOS transistor gate structure, comprising: a molybdenum nitride film comprising between 30 atomic % and 60 atomic % molybdenum; a semiconductor body; and a gate dielectric disposed between the molybdenum nitride film and the semiconductor body, wherein the PMOS gate structure has an effective work function greater than 5.0 eV.",
    "14. The semiconductor device structure of claim 13, wherein the molybdenum nitride film comprises between 40 atomic % and 50 atomic % molybdenum.",
    "15. The semiconductor device structure of claim 13 wherein the molybdenum nitride film has a thickness of less than 50 Angstroms.",
    "16. The semiconductor device structure of claim 13, wherein the PMOS gate structure has an effective work function greater than 5.4 eV.",
    "17. The semiconductor device structure of claim 13, wherein the molybdenum nitride film has an electrical resistivity of less than 1200 μΩ-cm.",
    "18. The semiconductor device structure of claim 13, wherein the gate dielectric comprises hafnium oxide (HfO 2).",
    "19. A method for forming a semiconductor device structure, the method comprising: forming a molybdenum nitride film on a substrate by atomic layer deposition, wherein forming the molybdenum nitride film comprises: contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor selected from the group comprising molybdenum trichloride (MoCl 3), molybdenum tetrachloride (MoCl 4), molybdenum hexachloride (MoCl 6), molybdenum hexafluoride (MoF 6), and tetrachloro(cyclopentadienyl)molybdenum, the first vapor phase reactant being free of Nitrogen (N); after contacting the substrate with the first vapor phase reactant, contacting the substrate with a second vapor phase reactant comprising a nitrogen precursor selected from the group comprising hydrazine (N 2 H 4), triazane (N 3 H 5), tertbutylhydrazine (C 4 H 9 N 2 H 3), methylhydrazine (CH 3 NHNH 2), and dimethylhydrazine ((CH 3) 2 N 2 H 2); and contacting the substrate with a third vapor phase reactant comprising a reducing precursor selected from the group comprising hydrogen gas (H 2), silane (SiH 4), disilane (Si 2 H 6), trisilane (Si 3 H 8), tetrasilane (Si 4 H 8), and acetylene (C 2 H 2); and forming a gate electrode structure comprising the molybdenum nitride film, the gate electrode structure having an effective work function greater than approximately 5.0 eV.",
    "20. The method of claim 19, wherein: contacting the substrate with the second vapor phase reactant is performed after contacting the substrate with the first vapor phase reactant; and contacting the substrate with the third vapor phase reactant is performed after contacting the substrate with the second vapor phase reactant."
  ],
  "description_excerpt": "The present disclosure relates generally to methods for forming a semiconductor device structure including a molybdenum nitride film and related semiconductor device structures.\n\nMetal-oxide-semiconductor (MOS) technology has conventionally utilized n-type doped polysilicon as the gate electrode material. However, doped polysilicon may not be an ideal gate electrode material for advanced node applications. For example, although doped polysilicon is conductive, there may still be a surface region which can be depleted of carriers under bias conditions. This region may appear as an extra gate insulator thickness, commonly referred to as gate depletion, and may contribute to the equivalent oxide thickness. While the gate depletion region may be thin, on the order of a few angstroms (Å), it may become significant as the gate oxide thicknesses are reduced in advance node applications. As a further example, polysilicon does not exhibit an ideal effective work function (eWF) for both NMOS and PMOS devices. To overcome the non-ideal effective work function of doped polysilicon, a threshold voltage adjustment implantation may be utilized. However, as device geometries reduce in advanced node applications, the threshold voltage adjustment implantation processes may become increasingly complex and impractical.\n\nTo overcome the problems associated with doped polysilicon gate electrodes, the non-ideal doped polysilicon gate material may be replaced with an alternative material, such as, for example, a transition metal nitride.",
  "cpc": [
    "H10D 64/01342",
    "C23C 16/34",
    "C23C 16/45525",
    "H01L 21/02175",
    "H01L 21/02205",
    "H01L 21/0228",
    "H01L 21/28194",
    "H01L 29/4966",
    "H01L 29/517",
    "H01L 29/66568",
    "H10D 30/027",
    "H10D 64/0134",
    "H10D 64/667",
    "H10D 64/669",
    "H10D 64/691",
    "H10P 14/3416",
    "H10P 14/6339",
    "H10P 14/668",
    "H10P 14/6924",
    "H10P 14/6939",
    "H10P 14/69392",
    "H10P 95/90"
  ],
  "ipc": [
    "H01L 21/02",
    "H10D 64/66",
    "H10D 64/68",
    "C23C 16/34",
    "C23C 16/455"
  ],
  "assignees": [
    "ASM IP Holding BV"
  ],
  "inventors": [
    "Chiyu Zhu",
    "Kiran Shrestha",
    "Petri Raisanen",
    "Michael Eugene Givens"
  ],
  "filing_date": "2018-07-17",
  "publication_date": "2020-08-04",
  "grant_date": "2020-08-04",
  "priority_date": "2017-07-18",
  "application_number": "US-201816038024-A",
  "family_id": "65023256",
  "cited_by_count": 282,
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}

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