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Patent · US9029253B2 · B2 · US

Phase-stabilized thin films, structures and devices including the thin films, and methods of forming same

(11) Publication number
US9029253B2
(21) Application number
13/874,708
(22) Filing date
2013-05-01
(30) Priority date
2012-05-02
(43) Publication date
2015-05-12
(45) Date of grant
2015-05-12
(51) IPC
H01L 29/40; H01L 29/49; H01L 21/20; H01L 21/28
(52) CPC
  • H10D Inorganic electric semiconductor devices: 30/6739, 64/01, 64/01318, 64/667, 64/691
  • H01L Semiconductor devices; electric solid state devices not otherwise provided for: 21/28088, 21/67167, 21/67253, 29/401, 29/4908, 29/4966, 29/517
  • H10P Generic processes or apparatus for the manufacture or treatment of devices covered by class H10: 72/0454, 72/0604
(73) Assignee
ASM IP Holding BV
(72) Inventors
Robert Brennan Milligan; Fred Alokozai
(54) Title
Phase-stabilized thin films, structures and devices including the thin films, and methods of forming same
(57) Abstract

Nitrogen-containing phase-stabilized films, methods of forming phase-stabilized films, and structures and devices including the phase-stabilized films are disclosed. The phase-stabilized films include a matrix material and a phase stabilizer, which provides a morphologically stabilizing effect to a matrix material within the films. The phase-stabilized films may be used as, for example, gate electrodes and similar films in microelectronic devices.

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Claims (11)

  1. A cyclic deposition method of forming a phase-stabilized nitrogen-containing film comprising a solid solution having a stoichiometric ratio of Mm zx Ms (z-x) X, where Mm zx and Ms (z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or to Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, wherein the phase-stabilized nitrogen-containing film comprises a matrix material and a phase stabilizer within the solid solution, wherein the phase-stabilized nitrogen-containing film is formed on a substrate within a reactor by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor, and wherein the phase stabilizer stabilizes the matrix material in a solution phase that is different from a native phase of the matrix material that would be formed under identical film formation conditions.
  2. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride.
  3. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride with Group V transition metal.
  4. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer comprises one or more transition metals selected from the Group IV or from Group VI.
  5. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein Mm zx Ms (z-x) X comprises Ta x Ti (1-x) N.
  6. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines one or more electrical properties of the phase- stabilized nitrogen-containing film.
  7. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines a work function of the phase-stabilized nitrogen-containing film.
  8. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer affects morphological characteristics of the phase-stabilized nitrogen-containing film.
  9. A method of forming a semiconductor structure, comprising a gate dielectric material and a gate electrode overlying the gate dielectric material, wherein the gate electrode comprising a solid solution having a stoichiometric ratio of Mm zx Ms (z-x) X, where Mm zx and Ms (z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, the solid solution comprising a phase stabilizer that stabilizes a metal nitride in a solution phase that is different from a native phase of the metal nitride that would be formed under identical formation conditions, wherein the solid solution is formed on a substrate within a reactor via a cyclic deposition process by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor.
  10. The method of forming the semiconductor structure of claim 9, wherein the metal nitride comprises one or more transition metals selected from Group V of Periodic Table.
  11. The method of forming the semiconductor structure of claim 9, wherein the phase stabilizer comprises one or more transition metals selected from Group IV or from Group VI of Periodic Table.

Description

The present disclosure generally relates to thin-film deposition techniques. More particularly, the disclosure relates to thin films including a phase stabilizer, to structures and devices including the films, and to methods of forming the films, structures, and devices.

Many semiconductor devices include non-silicon work function materials. For example, metal-oxide semiconductor (MOS) devices may include a gate electrode that includes a metal to assist in setting the effective work function for the gate electrode. Use of metal-containing electrodes in such devices has become increasingly important as the feature size of the devices decreases. Although various processes for forming metal gate electrodes have been developed, many of these processes exhibit unacceptable feature-size dependent performance variations. As a result, as the feature sizes of semiconductor devices decrease, these processes become increasingly problematic.

For example, in some devices, the effective work function of a metal-containing gate electrode may be determined by averaging work functions exhibited by domains within the gate electrode film that may have different crystal orientations and/or morphological phases of the metal gate electrode material. In some settings, the size of these domains may vary according to film deposition conditions and/or film thickness. As a gate length becomes smaller in MOS devices, the domain size may occupy a relatively larger portion of gate electrode, potentially leading to domain-specific work function differences that may have a greater effect on the overall work function of the device.

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{
  "publication_number": "US9029253B2",
  "country": "US",
  "kind": "B2",
  "title": "Phase-stabilized thin films, structures and devices including the thin films, and methods of forming same",
  "abstract": "Nitrogen-containing phase-stabilized films, methods of forming phase-stabilized films, and structures and devices including the phase-stabilized films are disclosed. The phase-stabilized films include a matrix material and a phase stabilizer, which provides a morphologically stabilizing effect to a matrix material within the films. The phase-stabilized films may be used as, for example, gate electrodes and similar films in microelectronic devices.",
  "claims": [
    "1. A cyclic deposition method of forming a phase-stabilized nitrogen-containing film comprising a solid solution having a stoichiometric ratio of Mm zx Ms (z-x) X, where Mm zx and Ms (z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or to Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, wherein the phase-stabilized nitrogen-containing film comprises a matrix material and a phase stabilizer within the solid solution, wherein the phase-stabilized nitrogen-containing film is formed on a substrate within a reactor by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor, and wherein the phase stabilizer stabilizes the matrix material in a solution phase that is different from a native phase of the matrix material that would be formed under identical film formation conditions.",
    "2. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride.",
    "3. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material comprises a metal nitride with Group V transition metal.",
    "4. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer comprises one or more transition metals selected from the Group IV or from Group VI.",
    "5. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein Mm zx Ms (z-x) X comprises Ta x Ti (1-x) N.",
    "6. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines one or more electrical properties of the phase- stabilized nitrogen-containing film.",
    "7. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the matrix material determines a work function of the phase-stabilized nitrogen-containing film.",
    "8. The cyclic deposition method of forming the phase-stabilized nitrogen-containing film of claim 1, wherein the phase stabilizer affects morphological characteristics of the phase-stabilized nitrogen-containing film.",
    "9. A method of forming a semiconductor structure, comprising a gate dielectric material and a gate electrode overlying the gate dielectric material, wherein the gate electrode comprising a solid solution having a stoichiometric ratio of Mm zx Ms (z-x) X, where Mm zx and Ms (z-x) are transition metals, one belonging to Group V, another belonging either to Group IV or Group VI of Periodic Table, x varies in a range from greater than 0 to less than 1 and z varies in a range from greater than x to 1, the solid solution comprising a phase stabilizer that stabilizes a metal nitride in a solution phase that is different from a native phase of the metal nitride that would be formed under identical formation conditions, wherein the solid solution is formed on a substrate within a reactor via a cyclic deposition process by exposing the substrate to a pulse of a matrix material precursor and a phase stabilizer precursor, removing an unreacted matrix material precursor and an unreacted phase stabilizer precursor from the reactor, exposing the substrate to a pulse of a nitrogen-containing reactant, and removing an unreacted nitrogen-containing reactant from the reactor.",
    "10. The method of forming the semiconductor structure of claim 9, wherein the metal nitride comprises one or more transition metals selected from Group V of Periodic Table.",
    "11. The method of forming the semiconductor structure of claim 9, wherein the phase stabilizer comprises one or more transition metals selected from Group IV or from Group VI of Periodic Table."
  ],
  "description_excerpt": "The present disclosure generally relates to thin-film deposition techniques. More particularly, the disclosure relates to thin films including a phase stabilizer, to structures and devices including the films, and to methods of forming the films, structures, and devices.\n\nMany semiconductor devices include non-silicon work function materials. For example, metal-oxide semiconductor (MOS) devices may include a gate electrode that includes a metal to assist in setting the effective work function for the gate electrode. Use of metal-containing electrodes in such devices has become increasingly important as the feature size of the devices decreases. Although various processes for forming metal gate electrodes have been developed, many of these processes exhibit unacceptable feature-size dependent performance variations. As a result, as the feature sizes of semiconductor devices decrease, these processes become increasingly problematic.\n\nFor example, in some devices, the effective work function of a metal-containing gate electrode may be determined by averaging work functions exhibited by domains within the gate electrode film that may have different crystal orientations and/or morphological phases of the metal gate electrode material. In some settings, the size of these domains may vary according to film deposition conditions and/or film thickness. As a gate length becomes smaller in MOS devices, the domain size may occupy a relatively larger portion of gate electrode, potentially leading to domain-specific work function differences that may have a greater effect on the overall work function of the device.",
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  "assignees": [
    "ASM IP Holding BV"
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  "inventors": [
    "Robert Brennan Milligan",
    "Fred Alokozai"
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  "filing_date": "2013-05-01",
  "publication_date": "2015-05-12",
  "grant_date": "2015-05-12",
  "priority_date": "2012-05-02",
  "application_number": "US-201313874708-A",
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