JP5006481B2 - 不揮発性半導体記憶素子の製造方法 - Google Patents
不揮発性半導体記憶素子の製造方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 62
- 239000004065 semiconductor Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 53
- 238000000059 patterning Methods 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims description 177
- 230000003647 oxidation Effects 0.000 claims description 52
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 175
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000011229 interlayer Substances 0.000 description 17
- 238000000137 annealing Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229910000449 hafnium oxide Inorganic materials 0.000 description 11
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 description 11
- 238000005530 etching Methods 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 238000005546 reactive sputtering Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000003071 parasitic effect Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
- H01L27/10—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration
- H01L27/101—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration including resistors or capacitors only
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- 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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- 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
- H10N70/041—Modification of switching materials after formation, e.g. doping
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- 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
- H10N70/20—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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- 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
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- 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
- H10N70/8833—Binary metal oxides, e.g. TaOx
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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
- G11C13/0007—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
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Description
図1は、本発明の実施の形態1における不揮発性半導体記憶素子の要部の製造方法を示す断面図である。
図5は、本発明の実施の形態2における不揮発性半導体記憶素子の要部の製造方法を示す断面図である。図5において、図1と同じ構成要素については同じ符号を用い、説明を省略する。
上述した、図6で抵抗変化素子の側壁酸化のためのアニールを上部電極107形成の直後に実施すると、実効的な側壁酸化レートが向上することを確認したが、その一方で側壁酸化を過剰にすると、初期抵抗が非常に高抵抗化してブレイクできないメモリセルができることがわかった。これを解析すると、上部電極107が剥離していることが原因であると判明した。これは、抵抗変化層106が全面に残った状態での、酸化処理は、ストレス変動が大きく、その影響を受けて上部電極107が剥離したものによると考えられる。本発明の実施の形態3の製造方法はこれを解決するものである。
101 下層配線
102 層間絶縁層
103 コンタクトホール
104 コンタクトプラグ
105 下部電極
105’ 第1の導電膜
106 抵抗変化層
106a 第1の抵抗変化層
106a’ 第1の抵抗変化膜
106b 第2の抵抗変化層
106b’ 第2の抵抗変化膜
106c、106c’ 絶縁領域
107 上部電極
107’ 第2の導電膜
108 ストレス強化層
108’ ストレス強化膜
Claims (5)
- 基板上にコンタクトプラグを形成する工程と、
前記コンタクトプラグを被覆して第1の導電膜を成膜する工程と、
前記第1の導電膜上に、酸素含有率が異なる複数の遷移金属酸化物層から構成される抵抗変化膜を成膜する工程と、
前記抵抗変化膜上に第2の導電膜を成膜する工程と、
前記第2の導電膜をパターニングして上部電極を形成する工程と、
前記抵抗変化膜をパターニングして抵抗変化層を形成する工程と、
前記第1の導電膜をパターニングして前記コンタクトプラグに接続された下部電極を形成する工程と、を備え、
さらに、少なくとも前記下部電極を形成する工程の前に、前記抵抗変化層の端部又は前記抵抗変化層の端部となる前記抵抗変化膜の一部を絶縁化させるために酸化する工程を有する
不揮発性半導体記憶素子の製造方法。 - 前記抵抗変化層又は前記抵抗変化膜を酸化する工程は、前記抵抗変化層を形成する工程の後に、前記抵抗変化層の端部を絶縁化させるために酸化する工程である
請求項1記載の不揮発性半導体記憶素子の製造方法。 - 前記抵抗変化層又は前記抵抗変化膜を酸化する工程は、前記上部電極を形成する工程と前記抵抗変化層を形成する工程との間に、前記抵抗変化膜の前記一部を絶縁化させるために酸化する工程である
請求項1記載の不揮発性半導体記憶素子の製造方法。 - さらに、前記上部電極の上に前記上部電極よりも高い圧縮応力を有するストレス強化層を形成する工程を有する
請求項1記載の不揮発性半導体記憶素子の製造方法。 - 前記抵抗変化層は、タンタル、ハフニウムまたはジルコニウムの酸化物層から構成される
請求項1乃至4のいずれか1項に記載の不揮発性半導体記憶素子の製造方法。
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PCT/JP2011/006302 WO2012063495A1 (ja) | 2010-11-12 | 2011-11-10 | 不揮発性半導体記憶素子の製造方法 |
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US8808869B2 (en) | 2010-03-26 | 2014-08-19 | Dow Corning Toray Co., Ltd. | Treatment agent for use in lignocellulose material |
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US8889478B2 (en) * | 2010-11-19 | 2014-11-18 | Panasonic Corporation | Method for manufacturing nonvolatile semiconductor memory element, and nonvolatile semiconductor memory element |
JP6410095B2 (ja) | 2013-12-16 | 2018-10-24 | パナソニックIpマネジメント株式会社 | 不揮発性記憶装置およびその製造方法 |
US9385316B2 (en) * | 2014-01-07 | 2016-07-05 | Taiwan Semiconductor Manufacturing Co., Ltd. | RRAM retention by depositing Ti capping layer before HK HfO |
US9505609B2 (en) * | 2015-04-29 | 2016-11-29 | Invensense, Inc. | CMOS-MEMS integrated device with selective bond pad protection |
US10043903B2 (en) | 2015-12-21 | 2018-08-07 | Samsung Electronics Co., Ltd. | Semiconductor devices with source/drain stress liner |
US10355206B2 (en) * | 2017-02-06 | 2019-07-16 | Nantero, Inc. | Sealed resistive change elements |
WO2020154123A1 (en) * | 2019-01-25 | 2020-07-30 | Lam Research Corporation | Resistive random access memory with preformed filaments |
CN112054117A (zh) | 2019-06-05 | 2020-12-08 | 联华电子股份有限公司 | 存储器元件的结构及其制造方法 |
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JP4375561B2 (ja) | 2004-12-28 | 2009-12-02 | セイコーエプソン株式会社 | 半導体記憶装置及びその製造方法 |
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JP2010251352A (ja) * | 2009-04-10 | 2010-11-04 | Panasonic Corp | 不揮発性記憶素子及びその製造方法 |
WO2010125780A1 (ja) * | 2009-04-30 | 2010-11-04 | パナソニック株式会社 | 不揮発性記憶素子及び不揮発性記憶装置 |
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US8808869B2 (en) | 2010-03-26 | 2014-08-19 | Dow Corning Toray Co., Ltd. | Treatment agent for use in lignocellulose material |
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JPWO2012063495A1 (ja) | 2014-05-12 |
US8574957B2 (en) | 2013-11-05 |
WO2012063495A1 (ja) | 2012-05-18 |
US20120238055A1 (en) | 2012-09-20 |
CN102630340B (zh) | 2014-11-12 |
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