JP6114525B2 - 酸化ルテニウム膜の成膜方法 - Google Patents
酸化ルテニウム膜の成膜方法 Download PDFInfo
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- JP6114525B2 JP6114525B2 JP2012214090A JP2012214090A JP6114525B2 JP 6114525 B2 JP6114525 B2 JP 6114525B2 JP 2012214090 A JP2012214090 A JP 2012214090A JP 2012214090 A JP2012214090 A JP 2012214090A JP 6114525 B2 JP6114525 B2 JP 6114525B2
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- 238000000034 method Methods 0.000 title claims description 43
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims description 28
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims description 28
- 239000007789 gas Substances 0.000 claims description 163
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 22
- 229910001882 dioxygen Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 60
- 238000002441 X-ray diffraction Methods 0.000 description 28
- 239000012528 membrane Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- 238000001228 spectrum Methods 0.000 description 17
- 230000005587 bubbling Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000000231 atomic layer deposition Methods 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 10
- 238000011534 incubation Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 6
- 229910002367 SrTiO Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 229910019897 RuOx Inorganic materials 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VMPZHUZUESBODJ-UHFFFAOYSA-N 5-methylheptane-2,4-dione Chemical compound CCC(C)C(=O)CC(C)=O VMPZHUZUESBODJ-UHFFFAOYSA-N 0.000 description 1
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001656 lutein Substances 0.000 description 1
- KBPHJBAIARWVSC-RGZFRNHPSA-N lutein Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\[C@H]1C(C)=C[C@H](O)CC1(C)C KBPHJBAIARWVSC-RGZFRNHPSA-N 0.000 description 1
- 229960005375 lutein Drugs 0.000 description 1
- ORAKUVXRZWMARG-WZLJTJAWSA-N lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C ORAKUVXRZWMARG-WZLJTJAWSA-N 0.000 description 1
- 235000012680 lutein Nutrition 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- FJHBOVDFOQMZRV-XQIHNALSSA-N xanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C=C(C)C(O)CC2(C)C FJHBOVDFOQMZRV-XQIHNALSSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/65—Electrodes comprising a noble metal or a noble metal oxide, e.g. platinum (Pt), ruthenium (Ru), ruthenium dioxide (RuO2), iridium (Ir), iridium dioxide (IrO2)
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B12/00—Dynamic random access memory [DRAM] devices
- H10B12/01—Manufacture or treatment
- H10B12/02—Manufacture or treatment for one transistor one-capacitor [1T-1C] memory cells
- H10B12/03—Making the capacitor or connections thereto
- H10B12/033—Making the capacitor or connections thereto the capacitor extending over the transistor
Description
図1は、本発明の一実施形態に係る酸化ルテニウム膜の成膜方法を実施するための成膜装置の一例を示す模式図である。
まず、ゲートバルブ25を開け、搬送装置(図示せず)によりウエハWを、搬入出口24を介してチャンバー1内に搬入し、サセプタ2上に載置する。酸化ルテニウム(RuOx)膜をDRAMキャパシタの下部電極として用いる場合には、図2に示すように、ウエハW(シリコン基板)としてトレンチ101が形成されたものを用い、トレンチ101内に下部電極102としてRuOx膜を形成する。また、DRAMキャパシタの上部電極として用いる場合には、図3に示すように、ウエハWとして、トレンチ101が形成され、トレンチ101内に下部電極102および例えばSrTiOからなる誘電体膜103を形成し、さらにその上に例えばTiN膜からなるバリア膜104を形成したものを用い、バリア膜104の上に上部電極105としてRuOx膜を形成する。
2C16H22O6Ru+39O2→2RuO2+22H2O↑+32CO2↑
ここでは、Ru化合物として上記(3)式の構造のものを用い、Ru化合物バブリングのためのキャリアArガスの流量を400mL/min(sccm)に固定し、O2ガス流量を5、10、20、50、100mL/min(sccm)、チャンバー内の圧力を50Torr(6666.12Pa)、20Torr(2666.45Pa)とし、圧力50Torrでは、いずれのO2ガス流量とも成膜温度を250、270、300、320℃で変化させ、圧力20Torrでは、いずれのO2ガス流量とも成膜温度を270、300、320℃で変化させ、成膜を行った。得られた膜について、結晶構造の同定をX線回折(XRD)により行った。なお、この際のRu化合物流量は、20Torrの場合で5.71mL/min(sccm)、50Torrの場合で2.26mL/min(sccm)である。また、チャンバー内圧力、O2ガス流量、Ru化合物ガス流量からO2ガス分圧、Ru化合物ガス分圧、およびO2ガス分圧/Ru化合物ガス分圧の値(以下O2/Ru化合物分圧比と記す)を計算した。
2;サセプタ
5;ヒーター
10;シャワーヘッド
30;ガス供給機構
31;成膜原料タンク
42;O2ガス供給源
50;制御部
51;プロセスコントローラ
53;記憶部
W;半導体ウエハ
Claims (4)
- 処理容器内にアスペクト比が50以上の凹部が形成された基板を収容し、Ruに2個のβ−ジケトン、および、2個のカルボニルが配位した以下の(3)式の構造を有し、組成式がC16H22O6Ruであるルテニウム化合物を気相状態で基板上に供給し、かつ酸素ガスを基板上に供給して、前記ルテニウム化合物ガスと酸素ガスとの反応により前記基板上の前記凹部内に酸化ルテニウム膜を成膜し、
前記酸素ガスは、前記ルテニウム化合物を金属ルテニウムに還元するとともに、還元された金属ルテニウムを酸化させるに十分な量に調整され、
前記処理容器内の酸素ガス分圧が16.6Torr以上、かつ、酸素ガス/ルテニウム化合物の分圧比が88.5以上となるように酸素ガスおよびルテニウム化合物を供給することを特徴とする酸化ルテニウム膜の成膜方法。
- 前記処理容器内に前記ルテニウム化合物ガスと酸素ガスとを同時に供給することを特徴とする請求項1に記載の酸化ルテニウム膜の成膜方法。
- 前記処理容器内に前記ルテニウム化合物ガスと酸素ガスとを前記処理容器内のパージを挟んで交互的に供給することを特徴とする請求項1に記載の酸化ルテニウム膜の成膜方法。
- コンピュータ上で動作し、成膜装置を制御するためのプログラムが記憶された記憶媒体であって、前記プログラムは、実行時に、請求項1から請求項3のいずれかの酸化ルテニウム膜の成膜方法が行われるように、コンピュータに前記成膜装置を制御させることを特徴とする記憶媒体。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012214090A JP6114525B2 (ja) | 2011-11-04 | 2012-09-27 | 酸化ルテニウム膜の成膜方法 |
US13/661,514 US20130115367A1 (en) | 2011-11-04 | 2012-10-26 | Method for forming ruthenium oxide film |
KR20120123505A KR101493130B1 (ko) | 2011-11-04 | 2012-11-02 | 산화루테늄막의 성막 방법 및 기억 매체 |
TW101140783A TWI555871B (zh) | 2011-11-04 | 2012-11-02 | Method for film formation of ruthenium oxide film |
Applications Claiming Priority (3)
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JP2011242630 | 2011-11-04 | ||
JP2011242630 | 2011-11-04 | ||
JP2012214090A JP6114525B2 (ja) | 2011-11-04 | 2012-09-27 | 酸化ルテニウム膜の成膜方法 |
Publications (3)
Publication Number | Publication Date |
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JP2013117067A JP2013117067A (ja) | 2013-06-13 |
JP2013117067A5 JP2013117067A5 (ja) | 2015-10-15 |
JP6114525B2 true JP6114525B2 (ja) | 2017-04-12 |
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JP2012214090A Active JP6114525B2 (ja) | 2011-11-04 | 2012-09-27 | 酸化ルテニウム膜の成膜方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20130115367A1 (ja) |
JP (1) | JP6114525B2 (ja) |
KR (1) | KR101493130B1 (ja) |
TW (1) | TWI555871B (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6118149B2 (ja) * | 2013-03-21 | 2017-04-19 | 東京エレクトロン株式会社 | ルテニウム膜の形成方法および記憶媒体 |
KR101628843B1 (ko) * | 2014-02-24 | 2016-06-10 | 영남대학교 산학협력단 | 원자층 증착법에 의한 루테늄 박막 형성 방법 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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JP3224450B2 (ja) * | 1993-03-26 | 2001-10-29 | 日本酸素株式会社 | 酸化ルテニウムの成膜方法 |
JP3676004B2 (ja) * | 1996-11-28 | 2005-07-27 | 富士通株式会社 | 酸化ルテニウム膜の形成方法および半導体装置の製造方法 |
JP4152028B2 (ja) * | 1999-01-25 | 2008-09-17 | 株式会社Adeka | ルテニウム系薄膜の製造方法 |
US6303809B1 (en) * | 1999-12-10 | 2001-10-16 | Yun Chi | Organometallic ruthenium and osmium source reagents for chemical vapor deposition |
KR100727372B1 (ko) * | 2001-09-12 | 2007-06-12 | 토소가부시키가이샤 | 루테늄착체, 그 제조방법 및 박막의 제조방법 |
JP4097979B2 (ja) * | 2002-04-18 | 2008-06-11 | 田中貴金属工業株式会社 | Cvd用原料化合物及びルテニウム又はルテニウム化合物薄膜の化学気相蒸着方法 |
US6784096B2 (en) * | 2002-09-11 | 2004-08-31 | Applied Materials, Inc. | Methods and apparatus for forming barrier layers in high aspect ratio vias |
KR100505674B1 (ko) * | 2003-02-26 | 2005-08-03 | 삼성전자주식회사 | 루테늄 박막을 제조하는 방법 및 이를 이용한 mim캐패시터의 제조방법 |
US20070014919A1 (en) * | 2005-07-15 | 2007-01-18 | Jani Hamalainen | Atomic layer deposition of noble metal oxides |
KR101576033B1 (ko) * | 2008-08-19 | 2015-12-11 | 삼성전자주식회사 | 전구체 조성물, 박막 형성 방법, 이를 이용한 게이트 구조물의 제조 방법 및 커패시터의 제조 방법 |
JP4746141B1 (ja) * | 2010-06-24 | 2011-08-10 | 田中貴金属工業株式会社 | 化学蒸着用の有機ルテニウム化合物及び該有機ルテニウム化合物を用いた化学蒸着方法 |
-
2012
- 2012-09-27 JP JP2012214090A patent/JP6114525B2/ja active Active
- 2012-10-26 US US13/661,514 patent/US20130115367A1/en not_active Abandoned
- 2012-11-02 KR KR20120123505A patent/KR101493130B1/ko active IP Right Grant
- 2012-11-02 TW TW101140783A patent/TWI555871B/zh active
Also Published As
Publication number | Publication date |
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US20130115367A1 (en) | 2013-05-09 |
JP2013117067A (ja) | 2013-06-13 |
TWI555871B (zh) | 2016-11-01 |
TW201333249A (zh) | 2013-08-16 |
KR101493130B1 (ko) | 2015-02-12 |
KR20130049743A (ko) | 2013-05-14 |
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