JP2012199336A - 記憶素子および記憶装置 - Google Patents
記憶素子および記憶装置 Download PDFInfo
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- 230000015654 memory Effects 0.000 title claims abstract description 152
- 150000002500 ions Chemical class 0.000 claims abstract description 134
- 230000004888 barrier function Effects 0.000 claims abstract description 56
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 150000004767 nitrides Chemical class 0.000 claims abstract description 13
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 230000008859 change Effects 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 48
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 229910003087 TiOx Inorganic materials 0.000 description 13
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 13
- 229910052798 chalcogen Inorganic materials 0.000 description 12
- 150000001787 chalcogens Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
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- 239000004065 semiconductor Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910017139 AlTe Inorganic materials 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910017107 AlOx Inorganic materials 0.000 description 4
- 229910017680 MgTe Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229910002531 CuTe Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910007709 ZnTe Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 description 1
- 229910001408 cation oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 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
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 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
- H10N70/24—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies
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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
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- G11C13/0069—Writing or programming circuits or methods
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- G11C16/00—Erasable programmable read-only memories
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- G11C16/04—Erasable programmable read-only memories electrically programmable using variable threshold transistors, e.g. FAMOS
- G11C16/0466—Erasable programmable read-only memories electrically programmable using variable threshold transistors, e.g. FAMOS comprising cells with charge storage in an insulating layer, e.g. metal-nitride-oxide-silicon [MNOS], silicon-oxide-nitride-oxide-silicon [SONOS]
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- G11C16/00—Erasable programmable read-only memories
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- G11C16/06—Auxiliary circuits, e.g. for writing into memory
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- H10N70/245—Multistable switching devices, e.g. memristors based on migration or redistribution of ionic species, e.g. anions, vacancies the species being metal cations, e.g. programmable metallization cells
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Abstract
【解決手段】下部電極10、記憶層20および上部電極30をこの順に積層した記憶素子1において、記憶層20は、イオン源層21,中間層23および抵抗変化層24が積層されると共に、イオン源層21と中間層23との間または中間層と抵抗変化層との間に、遷移金属あるいはその窒化物を含むバリア層21が設けられている。これにより、イオン源層21からの金属イオンの拡散による酸化膜の生成が抑制され、抵抗値の上昇が抑えられる。
【選択図】図1
Description
[一実施の形態]
(1)記憶素子(イオン源層と中間層との間にバリア層を有する記憶素子)
(2)記憶装置
[変形例]
(中間層と抵抗変化層との間にバリア層を有する記憶素子)
[実施例]
(記憶素子)
図1は、本発明の一実施の形態に係る記憶素子1の断面構成図である。この記憶素子1は、下部電極10(第1電極)、記憶層20および上部電極30(第2電極)をこの順に有するものである。
上記記憶素子1を多数、例えば列状やマトリクス状に配列することにより、記憶装置(メモリ)を構成することができる。このとき、各記憶素子1に、必要に応じて、素子選択用のMOSトランジスタ、或いはダイオードを接続してメモリセルを構成し、更に、配線を介して、センスアンプ、アドレスデコーダ、書き込み・消去・読み出し回路等に接続すればよい。
図4は本発明の変形例に係る記憶素子2の断面構成を表したものである。上記実施の形態と同一構成部分については同一符号を付してその説明は省略する。記憶素子2は、下部電極10(第1電極)、記憶層60および上部電極30(第2電極)をこの順に有し、記憶層60が上部電極30側からイオン源層61,中間層63,バリア層64および抵抗変化層62の順に積層された点が上記実施の形態と異なる。
以下、本発明の具体的な実施例について説明する。
(実験例1)TiN/TiOx/Te/Zr/CuZrTeAlGe/W
(実験例2)TiN/TiOx/Te/CuZrTeAlGe/W
(実験例3)TiN/TiOx/Te/CuZrTeAlGe/W
(実験例4)TiN/TiOx/Te/Zr/CuZrTeAlGe/W
(実験例5)TiN/TiOx/Te/Zr/CuZrTeAlGe/W
(実験例6)TiN/TiOx/Te/Zr/CuZrTeAlGe/W
(実験例7)TiN/TiOx/Te/Zr/CuZrTeAlGe/W
(実験例8)TiN/TiOx/CuZr/Te/CuZrTeAlGe/W
(実験例9)TiN/TiOx/CuZr/Te/CuZrTeAlGe/W
(実験例10)TiN/TiOx/CuZr/Te/CuZrTeAlGe/W
(実験例11)TiN/TiOx/CuZr/Te/CuZrTeAlGe/W
(実験例12)TiN/TiOx/CuZr/Te/CuZrTeAlGe/W
Claims (11)
- 第1電極、記憶層および第2電極をこの順に有し、
前記記憶層は、
前記第1電極側に設けられた抵抗変化層と、
前記第2電極側に設けられたイオン源層と、
前記抵抗変化層と前記イオン源層との間に設けられた中間層と、
前記イオン源層と前記中間層との間および前記中間層と前記抵抗変化層との間の少なくとも一方に設けられると共に、遷移金属あるいはその窒化物を含むバリア層と
を備えた記憶素子。 - 前記バリア層は、銅(Cu),チタン(Ti),ジルコニウム(Zr),ハフニウム(Hf),バナジウム(V),ニオブ(Nb),タンタル(Ta),クロム(Cr),モリブデン(Mo),およびタングステン(W)のうちの少なくとも1種類の遷移金属元素を含む、請求項1に記載の記憶素子。
- 前記バリア層の膜厚は0.1nmよりも厚く1nmよりも薄い、請求項1に記載の記憶素子。
- 前記イオン源層は、アルミニウム(Al),銅(Cu),銀(Ag)および亜鉛(Zn)のうち少なくとも1種のイオン化可能な金属元素を含むと共に、酸素(O),テルル(Te),硫黄(S)およびセレン(Se)のうちの少なくとも1種類を含む、請求項1に記載の記憶素子。
- 前記バリア層は、前記イオン源層に含まれる前記金属元素の前記第1電極側への移動を抑制する、請求項4に記載の記憶素子。
- 前記中間層は前記イオン源層よりも抵抗が高く、前記金属元素の移動が可能な電解質層である、請求項1に記載の記憶素子。
- 前記中間層はTeおよびAlを含む、請求項1に記載の記憶素子。
- 前記抵抗変化層は、前記イオン源層および前記中間層の少なくとも一方に含まれる金属元素の酸化物と、前記バリア層に含まれる遷移金属元素の酸化物とを含む、請求項1に記載の記憶素子。
- 前記抵抗変化層は、前記イオン源層および中間層の少なくとも一方に含まれるAlの拡散により形成されたアルミニウム酸化物を含む層と、前記遷移金属の酸化物を含む層との積層構造、または、前記アルミニウム酸化物と前記遷移金属の酸化物とが混在した構造を有する、請求項1に記載の記憶素子。
- 前記第1電極および前記第2電極への電圧印加によって前記抵抗変化層内に前記金属元素を含む低抵抗部が形成されることにより抵抗値が変化する、請求項1に記載の記憶素子。
- 第1電極、記憶層および第2電極をこの順に有する複数の記憶素子と、前記複数の記憶素子に対して選択的に電圧または電流のパルスを印加するパルス印加手段とを備え、
前記記憶層は、
前記第1電極側に設けられた抵抗変化層と、
前記第2電極側に設けられたイオン源層と、
前記抵抗変化層と前記イオン源層との間に設けられた中間層と、
前記イオン源層と前記中間層との間または前記中間層と前記抵抗変化層との間の少なくとも一方に設けられると共に、遷移金属あるいはその窒化物を含むバリア層と
を有する記憶装置。
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