JP3919205B2 - 抵抗変化素子とその製造方法 - Google Patents
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- 230000008859 change Effects 0.000 title claims abstract description 199
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 22
- 239000011029 spinel Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 187
- 238000000034 method Methods 0.000 description 62
- 239000000523 sample Substances 0.000 description 52
- 239000010408 film Substances 0.000 description 32
- 230000008569 process Effects 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910004121 SrRuO Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000007737 ion beam deposition Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 plasma Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
- G11C11/56—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using storage elements with more than two stable states represented by steps, e.g. of voltage, current, phase, frequency
- G11C11/5685—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using storage elements with more than two stable states represented by steps, e.g. of voltage, current, phase, frequency using storage elements comprising metal oxide memory material, e.g. perovskites
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0007—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements comprising metal oxide memory material, e.g. perovskites
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0021—Auxiliary circuits
- G11C13/004—Reading or sensing circuits or methods
-
- 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
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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
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/061—Shaping switching materials
- H10N70/063—Shaping switching materials by etching of pre-deposited switching material layers, e.g. lithography
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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
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/061—Shaping switching materials
- H10N70/066—Shaping switching materials by filling of openings, e.g. damascene method
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- H—ELECTRICITY
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- 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
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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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/821—Device geometry
- H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
-
- 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
- H10N70/841—Electrodes
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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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8836—Complex metal oxides, e.g. perovskites, spinels
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C13/00—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00
- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0021—Auxiliary circuits
- G11C13/004—Reading or sensing circuits or methods
- G11C2013/0054—Read is performed on a reference element, e.g. cell, and the reference sensed value is used to compare the sensed value of the selected cell
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
- G11C2213/30—Resistive cell, memory material aspects
- G11C2213/31—Material having complex metal oxide, e.g. perovskite structure
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- G11—INFORMATION STORAGE
- G11C—STATIC STORES
- G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
- G11C2213/70—Resistive array aspects
- G11C2213/71—Three dimensional array
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- G11C2213/00—Indexing scheme relating to G11C13/00 for features not covered by this group
- G11C2213/70—Resistive array aspects
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
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Description
実施例1では、スピネル構造を有する抵抗変化層3として、MFe2O4(M=Fe:以下、FFO)層を用いた。
最初に、基板12として、表面に熱酸化膜(SiO2膜)が形成されたSi基板を用い、当該Si基板上に、サンプル1−1と同様に、Al層(厚さ400nm)を積層し、かつ、そのSi基板側とは反対側の表面を酸化処理した。
最初に、基板12として、表面に熱酸化膜(SiO2膜)が形成されたSi基板を用い、当該Si基板上に、サンプル1−1と同様にTi層(厚さ400nm)を積層し、かつ、そのSi基板側とは反対側の表面を酸化処理した。
最初に、基板12として、表面に熱酸化膜(SiO2膜)が形成されたSi基板を用い、当該Si基板上に、サンプル1−1と同様に、Al層(厚さ400nm)を積層した。
Claims (10)
- 電気抵抗値が異なる2以上の状態が存在し、
所定の電圧または電流の印加により、前記2以上の状態から選ばれる1つの状態から他の状態へと変化する抵抗変化素子であって、
上部電極および下部電極と、双方の前記電極により狭持された抵抗変化層とを含む多層構造体が基板上に配置され、
前記抵抗変化層は、スピネル構造を有し、
前記下部電極における前記抵抗変化層側の表面が、酸化されている抵抗変化素子。 - 前記下部電極における前記表面に、前記下部電極を構成する元素の酸化膜が形成されている請求項1に記載の抵抗変化素子。
- 前記下部電極が、Ru、Ti、Al、Ta、Cu、WおよびNiから選ばれる少なくとも1種の元素を含む請求項1に記載の抵抗変化素子。
- 前記抵抗変化層が、式MM’ 2O4により示される組成を有する酸化物を含む請求項1に記載の抵抗変化素子。
ただし、前記MおよびM’は、Mn、Fe、Co、Ni、CuおよびZnから選ばれる少なくとも1種の元素であり、互いに異なっていても、同一であってもよい。 - 前記M’が、Feである請求項4に記載の抵抗変化素子。
- 抵抗変化率が、400%以上である請求項1に記載の抵抗変化素子。
- 抵抗変化率が、850%以上である請求項1に記載の抵抗変化素子。
- 前記所定の電圧または電流が、パルス状である請求項1に記載の抵抗変化素子。
- 請求項1に記載の抵抗変化素子の製造方法であって、
基板上に下部電極を形成し、
前記形成した下部電極の表面を酸化処理し、
前記処理した下部電極上に、スピネル構造を有する抵抗変化層、および、上部電極を順に形成する抵抗変化素子の製造方法。 - 前記下部電極、前記抵抗変化層および前記上部電極の形成を、前記基板の温度を400℃以下として行う請求項9に記載の抵抗変化素子の製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004261920 | 2004-09-09 | ||
JP2004261920 | 2004-09-09 | ||
PCT/JP2005/016396 WO2006028117A1 (ja) | 2004-09-09 | 2005-09-07 | 抵抗変化素子とその製造方法 |
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JP3919205B2 true JP3919205B2 (ja) | 2007-05-23 |
JPWO2006028117A1 JPWO2006028117A1 (ja) | 2008-05-08 |
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US (1) | US7446391B2 (ja) |
JP (1) | JP3919205B2 (ja) |
CN (1) | CN100477225C (ja) |
WO (1) | WO2006028117A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8324608B2 (en) | 2009-10-27 | 2012-12-04 | Canon Anelva Corporation | Nonvolatile storage element and manufacturing method thereof |
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EP1153434A1 (en) * | 1999-02-17 | 2001-11-14 | International Business Machines Corporation | Microelectronic device for storing information and method thereof |
JP4854233B2 (ja) * | 2005-08-15 | 2012-01-18 | 独立行政法人産業技術総合研究所 | スイッチング素子 |
US7733684B2 (en) * | 2005-12-13 | 2010-06-08 | Kabushiki Kaisha Toshiba | Data read/write device |
JP5049491B2 (ja) * | 2005-12-22 | 2012-10-17 | パナソニック株式会社 | 電気素子,メモリ装置,および半導体集積回路 |
JP2007258533A (ja) * | 2006-03-24 | 2007-10-04 | Fujitsu Ltd | 半導体記憶装置及びその駆動方法 |
JP4699932B2 (ja) * | 2006-04-13 | 2011-06-15 | パナソニック株式会社 | 抵抗変化素子とそれを用いた抵抗変化型メモリならびにその製造方法 |
KR101239962B1 (ko) * | 2006-05-04 | 2013-03-06 | 삼성전자주식회사 | 하부 전극 상에 형성된 버퍼층을 포함하는 가변 저항메모리 소자 |
JP2008021750A (ja) * | 2006-07-11 | 2008-01-31 | Matsushita Electric Ind Co Ltd | 抵抗変化素子およびその製造方法、ならびにそれを用いた抵抗変化型メモリ |
WO2008038365A1 (en) * | 2006-09-28 | 2008-04-03 | Fujitsu Limited | Variable-resistance element |
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US8324608B2 (en) | 2009-10-27 | 2012-12-04 | Canon Anelva Corporation | Nonvolatile storage element and manufacturing method thereof |
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