WO2010024936A1 - Phase change memory materials - Google Patents

Phase change memory materials Download PDF

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Publication number
WO2010024936A1
WO2010024936A1 PCT/US2009/004922 US2009004922W WO2010024936A1 WO 2010024936 A1 WO2010024936 A1 WO 2010024936A1 US 2009004922 W US2009004922 W US 2009004922W WO 2010024936 A1 WO2010024936 A1 WO 2010024936A1
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WO
WIPO (PCT)
Prior art keywords
atomic percent
phase change
change memory
phase
combination
Prior art date
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Ceased
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PCT/US2009/004922
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English (en)
French (fr)
Inventor
Bruce G. Aitken
Charlene M. Smith
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Corning Inc
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Corning Inc
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Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Priority to JP2011525009A priority Critical patent/JP2012501511A/ja
Priority to KR1020117007093A priority patent/KR101715956B1/ko
Priority to EP09789238A priority patent/EP2335297A1/en
Priority to CN200980134692.6A priority patent/CN102138233B/zh
Publication of WO2010024936A1 publication Critical patent/WO2010024936A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B7/2433—Metals or elements of Groups 13, 14, 15 or 16 of the Periodic Table, e.g. B, Si, Ge, As, Sb, Bi, Se or Te
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
    • H10N70/8828—Tellurides, e.g. GeSbTe
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24312—Metals or metalloids group 14 elements (e.g. Si, Ge, Sn)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24314—Metals or metalloids group 15 elements (e.g. Sb, Bi)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
    • G11B2007/24302—Metals or metalloids
    • G11B2007/24316—Metals or metalloids group 16 elements (i.e. chalcogenides, Se, Te)
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12674—Ge- or Si-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12681—Ga-, In-, Tl- or Group VA metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/21—Circular sheet or circular blank
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • Embodiments of the invention relate to phase change memory materials and more particularly to GeAs telluride materials useful for phase change memory applications, for example, optical and electronic data storage.
  • phase change memory devices utilize materials which can change between two phases having distinct properties.
  • the materials typically, can change from an amorphous phase to a crystalline phase, and the phases can have considerably different properties, for example, different resistivities, conductivities, and/or reflectivities.
  • Phase change from an amorphous phase to a crystalline phase can be achieved through heating the amorphous material to a temperature which promotes nucleation, crystal formation, and then crystallization. The phase change back to amorphous can be achieved by heating the crystalline phase above the melting temperature.
  • Chalcogenide materials for example, Ge, Sb, and Te alloys are currently used in phase change memory applications such as for storing information in over writable disks.
  • phase change memory materials identified to date have been developed by workers at Matsushita/Panasonic and IBM. Representative materials include compositions on the GeTe-Sb 2 Te 3 join, particularly Ge 2 Sb 2 Te 5 (GST), and Au, In-doped Sb telluride (AIST) . These materials can be cycled on a -10ns time scale between a high conductivity, high reflectivity- crystalline phase and a low conductivity, low reflectivity amorphous phase under laser heating or current pulses .
  • GST and AIST have good properties for non-volatile memory applications, it would be advantageous to have phase change memory materials that have faster phase transitions and/or longer write/rewrite potential.
  • Embodiments of the invention are GeAsTe-based compositions for phase change memory applications that lie outside of the canonical GeSbTe system. Moreover, as certain GeAsTe compositions can be made into bulk glasses, the stability of the GeAsTe amorphous phase is likely to be greater than that of the GeSbTe analogues where bulk glass formation is not possible. This feature may result in an increased number of write/rewrite cycles without degradation of conductivity/reflectivity contrast as well as longer data retention.
  • One embodiment of the invention is an article comprising a crystallized thin film comprising a composition having at least one hexagonal phase, or a crystallizable composition capable of having at least one hexagonal phase in a crystallized form.
  • Another embodiment of the invention is a method comprising providing a thin film comprising a phase change memory amorphous material, and converting the phase change memory amorphous material to a hexagonal crystalline phase.
  • Yet another embodiment of the invention is a method comprising providing a thin film comprising a phase change memory material having a hexagonal crystalline phase, and converting the hexagonal crystalline phase to an amorphous phase .
  • Figure 1 is a composition diagram for GeAsTe materials.
  • Figure 2 is a graph of reflectivity data for a material according to one embodiment.
  • Figure 3 is a graph of reflectivity data for a material according to one embodiment.
  • Figure 4 and Figure 5 are graphs of X-ray diffraction data for conventional phase change memory materials.
  • Figure 6 and Figure 7 are graphs of X-ray diffraction data for phase change memory materials according to the present invention..
  • One embodiment of the invention is an article comprising a crystallized thin film comprising a composition having at least one hexagonal phase, or a crystallizable composition capable of having at least one hexagonal phase in a crystallized form.
  • composition comprises in atomic percent:
  • composition comprises in atomic percent:
  • the composition can further comprise Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof is 20 percent or less, in some embodiments.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof is 15 percent or less, in some embodiments.
  • the thin film is disposed on a substrate.
  • the thin film can be deposited on a substrate, according to one embodiment.
  • the substrate comprises a glass, a glass ceramic, a ceramic, a polymer, a metal, or combinations thereof, in some embodiments.
  • GeAsTe glasses and their crystalline analogues have the potential of being phase change materials characterized by a glassy state that can be more stable than that of conventional phase change materials such as GST and AIST.
  • a wide range of GeAsTe glasses, according to the invention can transform to a more reflective crystalline phase upon heating than the above described conventional materials. For glasses on the Te-GeAs 2 join, this phenomenon has been demonstrated for compositions containing from 45 to 65 atomic percent Te. Many of these materials, when crystallized, consist of at least two phases: either two crystalline phases or one crystalline phase plus a residual glass phase.
  • Glasses with compositions on the As 2 Te 3 -GeTe join can be crystallized to a single phase and, as such, can exhibit maximum conductivity/reflectivity contrast between the glassy and crystalline state.
  • Such glasses can be doped with constituents compatible with the crystalline phase, such as Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof without forming a second phase in the heated state.
  • compositions according to the invention, are shown in Table 1 and Table 2.
  • Another embodiment of the invention is a method comprising providing a thin film comprising a phase change memory amorphous material, and converting the phase change memory amorphous material to a hexagonal crystalline phase.
  • Phase change from an amorphous phase to a hexagonal crystalline phase can be achieved through heating the amorphous material to a temperature which promotes nucleation, crystal formation, and then crystallization.
  • Converting the phase change memory amorphous material to a hexagonal crystalline phase can comprise heating. Isothermal heating, for example, electrical heating using resistive and/or inductive heating; laser heating; or the like can be used to heat the thin film to induce phase change.
  • the phase change memory amorphous material comprises in atomic percent: 5 to 45 Ge; 5 to 40 As, or a combination of As and Sb, wherein the atomic percent of As is greater than the atomic percent of Sb; and
  • the phase change memory amorphous material comprises in atomic percent: 10 to 30 Ge; 15 to 30 As, or a combination of As and Sb, wherein the atomic percent of As is greater than the atomic percent of Sb; and
  • the phase change memory amorphous material can further comprise Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof is 20 percent or less, in some embodiments.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof can be 15 percent or less.
  • Yet another embodiment of the invention is a method comprising providing a thin film comprising a phase change memory material having a hexagonal crystalline phase, and converting the hexagonal crystalline phase to an amorphous phase.
  • This phase change to the amorphous phase can be achieved by heating the crystalline phase above the melting temperature of the phase change memory material.
  • converting the phase change memory material having the hexagonal crystalline phase to the amorphous phase comprises heating.
  • Isothermal heating for example, electrical heating using resistive and/or inductive heating; laser heating; or the like can be used to heat the thin film to induce phase change.
  • the phase change memory material comprises in atomic percent:
  • phase change memory material comprises in atomic percent:
  • the phase change memory material can further comprise Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof is 20 percent or less, in some embodiments.
  • the atomic percent of the Al, Si, Ga, Se, In, Sn, Tl, Pb, Bi, P, S, or a combination thereof can be 15 percent or less.
  • Bulk GeAsTe glasses such as those indicated by the solid circles 10 in Figure 1, can be thermally crystallized to yield a highly reflective phase or phase assemblage.
  • this phase is one of the homologous series of mixed layer compounds that can be represented by the formula: A ⁇ 2 Te 3 (GeTe) n , where n is an integer.
  • These bulk glasses can be prepared using the chalcogenide glass processing technique of ampoule melting.
  • Thin films can be fabricated by a variety of techniques, for example, magnetron sputtering, thermal evaporation and pulsed laser deposition. These thin films can be deposited onto a substrate and can be utilized in phase change memory devices.
  • the thin films are 2 microns or less in thickness, for example, 1 micron or less, for example, .5 microns or less.
  • the thickness of the thin film ranges from 20 nanometers to 1 micron, for example, 40 nanometers to 1 micron, for example, 50 nanometers to 1 micron. Although specific ranges are indicated, in other embodiments, the thickness may be any numerical value within the ranges including decimals.
  • X-ray diffraction data for materials according to the present invention is shown in Figure 6 and Figure 7, respectively.
  • the increased number of peaks as compared to the cubic materials demonstrates that the materials according to the present invention comprise a hexagonal crystalline phase.
  • X-ray diffraction data of the additional compositions shown in Table 1 were found to have peaks consistent with a hexagonal crystalline phase.
  • Additional Ge I4-3 As 2S ⁇ Te 57 . ! thin film articles were heated at 350 0 C in air for times ranging from 1 to 10 mins. Reflectivity data for these articles is shown in Figure 3. Increased reflectivity was evident from the as deposited articles shown by line 26 to those articles heated for 1 min, 5 mins, and 10 mins, shown by lines 28, 30, and 32, respectively.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Semiconductor Memories (AREA)
  • Physical Vapour Deposition (AREA)
  • Manufacturing Optical Record Carriers (AREA)
  • Glass Compositions (AREA)
PCT/US2009/004922 2008-08-29 2009-08-28 Phase change memory materials Ceased WO2010024936A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2011525009A JP2012501511A (ja) 2008-08-29 2009-08-28 相変化記憶材料
KR1020117007093A KR101715956B1 (ko) 2008-08-29 2009-08-28 상 변화 메모리 물질
EP09789238A EP2335297A1 (en) 2008-08-29 2009-08-28 Phase change memory materials
CN200980134692.6A CN102138233B (zh) 2008-08-29 2009-08-28 相变记忆材料

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9286808P 2008-08-29 2008-08-29
US61/092,868 2008-08-29
US12/503,156 US8206804B2 (en) 2008-08-29 2009-07-15 Phase change memory materials
US12/503,156 2009-07-15

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WO2010024936A1 true WO2010024936A1 (en) 2010-03-04

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US (1) US8206804B2 (enExample)
EP (1) EP2335297A1 (enExample)
JP (2) JP2012501511A (enExample)
KR (1) KR101715956B1 (enExample)
CN (1) CN102138233B (enExample)
TW (1) TWI404633B (enExample)
WO (1) WO2010024936A1 (enExample)

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* Cited by examiner, † Cited by third party
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CN109880451A (zh) * 2019-01-18 2019-06-14 申再军 基于相变的陶瓷包覆材料、墙体保温材料及其制备方法

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