JP4243853B2 - 強誘電体キャパシタの製造方法、および強誘電体メモリの製造方法 - Google Patents
強誘電体キャパシタの製造方法、および強誘電体メモリの製造方法 Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 230000015654 memory Effects 0.000 title claims description 23
- 238000000034 method Methods 0.000 claims description 48
- 238000011084 recovery Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000008199 coating composition Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000001312 dry etching Methods 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- 229910000909 Lead-bismuth eutectic Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000000059 patterning Methods 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 3
- 239000010410 layer Substances 0.000 description 137
- 239000010936 titanium Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- JAPYDHNKRWQEON-UHFFFAOYSA-N lead(2+);propan-1-olate Chemical compound CCCO[Pb]OCCC JAPYDHNKRWQEON-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- 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
- H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
- H01L21/31116—Etching inorganic layers by chemical means by dry-etching
- H01L21/31122—Etching inorganic layers by chemical means by dry-etching of layers not containing Si, e.g. PZT, Al2O3
-
- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
- H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
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Description
(a)基体の上方に下部電極層、強誘電体層、および上部電極層を順次積層することにより強誘電体積層体を形成する工程と、
(b)少なくとも前記上部電極層および前記強誘電体層をドライエッチングすることによりパターニングする工程と、
(c)前記強誘電体層を構成する元素を有する化合物を含む塗布用組成物を、少なくとも前記強誘電体層の側壁に塗布してリカバリー層を形成する工程と、
(d)前記強誘電体層の側壁に塗布した前記塗布用組成物を熱処理する工程と、
を含む。
前記強誘電体層は、下記一般式(1)で表される化合物からなり、
前記塗布用組成物は、少なくともA元素を含む化合物を有する、強誘電体キャパシタの製造方法。
(Aは、Pb、Ca、Sr、およびBaのうち、1または2以上を示す。Bは、Ti、Zr、Sn、およびHfのうち、1または2以上を示す。)
本発明に係る強誘電体キャパシタの製造方法において、
前記強誘電体層は、La、Nb、およびSiのうち少なくとも1つを含むことができる。
前記強誘電体層は、Bi系層状ペロブスカイト構造を有する強誘電体からなり、
前記塗布用組成物は、少なくともBiを含む化合物を有することができる。
前記Bi系層状ペロブスカイト構造を有する強誘電体は、SrBi2Ta2O9、Bi4Ti3O12、(Bi,La)4Ti3O12、SrBi2Nb2O9、CaBi2Ta2O9、CaBi2Nb2O9、PbBi2Ta2O9、PbBi2Nb2O9、Bi3TiTaO9、(Bi,Nd)4Ti3O12、CaBi4Ti4O15、Ca2Bi4Ti5O18、Ca3Bi4Ti6O21、PbBi4Ti4O15、Pb2Bi4Ti5O18、およびPb3Bi4Ti6O21のいずれかを含むことができる。
前記Bi系層状ペロブスカイト構造を有する強誘電体は、Siを含むことができる。
前記工程(b)では、前記上部電極層と前記強誘電体層とを塩素および酸素を含むガスでドライエッチングすることができる。
前記工程(b)の後に、
前記強誘電体積層体を、フッ素を含むプラズマによりドライエッチングする工程と、
酸素プラズマ処理する工程と、
を含むことができる。
基体の上方に形成された下部電極と、
前記下部電極の上方に形成された強誘電体と、
強誘電体の上方に形成された上部電極と、
少なくとも前記強誘電体の側壁に形成されたリカバリー層と、を含み、
前記リカバリー層は、前記強誘電体層を構成する元素を有する化合物を含む。
図1は、本発明の実施形態に係る強誘電体キャパシタ100を模式的に示す断面図である。強誘電体キャパシタ100は、基体10上に形成されている下部電極層20と、下部電極層20上に形成されている強誘電体層30と、強誘電体層30上に形成されている上部電極層40と、上部電極層40上に形成されているハードマスク層50と、リカバリー層60とを含む。基体10は、例えば、シリコン基板とその上に形成された酸化シリコン膜から構成されていてもよい。さらに、基体10には、トランジスタ等の機能デバイスが形成されてもよい。
Aは、Pb、Bi、Ca、Sr、およびBaのいずれかを示す。Bは、Ti、Zr、Sn、およびHfのうち、一または二以上を示す。上記一般式(1)で表される強誘電体の例としては、PZT(Pb(Zr,Ti)O3)などを挙げることができる。また、La、Nb、Siなどを添加しても良い。
mは、1以上の自然数を示す。
本発明に係る強誘電体メモリは、上記強誘電体キャパシタ100を含む。また、かかる強誘電体メモリは、上記強誘電体キャパシタ100の製造方法を用いて製造することができる。
図8は、本実施の形態に係る強誘電体キャパシタのリーク特性を示す。図8に示すグラフの縦軸は、電流の値を示し、横軸は電圧を示す。測定値aは、本実施の形態にかかる強誘電体キャパシタを用いた強誘電体メモリのリーク特性を示し、測定値bは、従来の強誘電体キャパシタを用いた強誘電体メモリのリーク特性を示す。従来の強誘電体キャパシタは、リカバリー層を有さない。
Claims (7)
- (a)基体の上方に下部電極層、強誘電体層、および上部電極層を順次積層することにより強誘電体積層体を形成する工程と、
(b)少なくとも前記上部電極層および前記強誘電体層をドライエッチングすることによりパターニングする工程と、
(c)前記強誘電体層を構成する元素を有する化合物を含む塗布用組成物を、少なくとも前記強誘電体層の側壁に塗布してリカバリー層のための塗膜を形成する工程と、
(d)前記塗膜が前記強誘電体層を覆った状態で熱処理することによりダメージ層および前記塗膜を結晶化する工程と、を含み、
前記工程(b)では、前記ドライエッチングは塩素および酸素を含むガスで行われ、
さらに、前記工程(b)の後であって、前記工程(c)の前に、前記強誘電体積層体を、フッ素を含むプラズマによりドライエッチングした後、酸素プラズマ処理する工程を有する、強誘電体キャパシタの製造方法。 - 請求項1において、
前記強誘電体層は、下記一般式(1)で表される化合物からなり、
前記塗布用組成物は、少なくともA元素を含む化合物を有する、強誘電体キャパシタの製造方法。
ABO3 ・・・・(1)
(Aは、Pb、Ca、Sr、およびBaのうち、1または2以上を示す。Bは、Ti、Zr、Sn、およびHfのうち、1または2以上を示す。) - 請求項2において、
前記強誘電体層は、La、Nb、およびSiのうち少なくとも1つを含む、強誘電体キャパシタの製造方法。 - 請求項1において、
前記強誘電体層は、Bi系層状ペロブスカイト構造を有する強誘電体からなり、
前記塗布用組成物は、少なくともBiを含む化合物を有する、強誘電体キャパシタの製造方法。 - 請求項4において、
前記Bi系層状ペロブスカイト構造を有する強誘電体は、SrBi2Ta2O9、Bi4Ti3O12、(Bi,La)4Ti3O12、SrBi2Nb2O9、CaBi2Ta2O9、CaBi2Nb2O9、PbBi2Ta2O9、PbBi2Nb2O9、Bi3TiTaO9、(Bi,Nd)4Ti3O12、CaBi4Ti4O15、Ca2Bi4Ti5O18、Ca3Bi4Ti6O21、PbBi4Ti4O15、Pb2Bi4Ti5O18、およびPb3Bi4Ti6O21のいずれかを含む、強誘電体キャパシタの製造方法。 - 請求項4又は5において、
前記Bi系層状ペロブスカイト構造を有する強誘電体は、Siを含む、強誘電体キャパシタの製造方法。 - 請求項1ないし6のいずれかに記載の強誘電体キャパシタの製造方法を用いた、強誘電体メモリの製造方法。
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EP1675162A3 (en) * | 2004-12-27 | 2007-05-30 | Seiko Epson Corporation | Ferroelectric film, method of manufacturing ferroelectric film, ferroelectric capacitor, and ferroelectric memory |
US7572698B2 (en) * | 2006-05-30 | 2009-08-11 | Texas Instruments Incorporated | Mitigation of edge degradation in ferroelectric memory devices through plasma etch clean |
JP5295740B2 (ja) * | 2008-12-04 | 2013-09-18 | 株式会社東芝 | 不揮発性半導体記憶装置の製造方法 |
CN109796205B (zh) * | 2019-02-20 | 2021-12-28 | 山东大学 | 一种铋层状结构钛钽酸铋高温压电陶瓷材料及其制备方法 |
US11227872B2 (en) | 2019-04-25 | 2022-01-18 | Taiwan Semiconductor Manufacturing Company, Ltd. | FeRAM MFM structure with selective electrode etch |
CN115010493B (zh) * | 2022-05-31 | 2023-01-13 | 清华大学 | 一种高熵焦绿石介电陶瓷材料及其制备方法与应用 |
CN115505880B (zh) * | 2022-09-28 | 2024-03-12 | 中国科学院上海硅酸盐研究所 | 一种具有周期性纳米级微裂纹结构的铌酸铋钙薄膜材料及其制备方法 |
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US6135987A (en) | 1997-12-22 | 2000-10-24 | Kimberly-Clark Worldwide, Inc. | Synthetic fiber |
KR100292819B1 (ko) * | 1998-07-07 | 2001-09-17 | 윤종용 | 커패시터및그의제조방법 |
US6131661A (en) | 1998-08-03 | 2000-10-17 | Tetra Technologies Inc. | Method for removing filtercake |
US6394185B1 (en) | 2000-07-27 | 2002-05-28 | Vernon George Constien | Product and process for coating wellbore screens |
US6494263B2 (en) | 2000-08-01 | 2002-12-17 | Halliburton Energy Services, Inc. | Well drilling and servicing fluids and methods of removing filter cake deposited thereby |
US6793018B2 (en) | 2001-01-09 | 2004-09-21 | Bj Services Company | Fracturing using gel with ester delayed breaking |
US6781184B2 (en) * | 2001-11-29 | 2004-08-24 | Symetrix Corporation | Barrier layers for protecting metal oxides from hydrogen degradation |
JP4314768B2 (ja) | 2002-02-19 | 2009-08-19 | セイコーエプソン株式会社 | 強誘電体メモリ装置の製造方法 |
US20030176073A1 (en) * | 2002-03-12 | 2003-09-18 | Chentsau Ying | Plasma etching of Ir and PZT using a hard mask and C12/N2/O2 and C12/CHF3/O2 chemistry |
US6761218B2 (en) | 2002-04-01 | 2004-07-13 | Halliburton Energy Services, Inc. | Methods and apparatus for improving performance of gravel packing systems |
US7066258B2 (en) | 2003-07-08 | 2006-06-27 | Halliburton Energy Services, Inc. | Reduced-density proppants and methods of using reduced-density proppants to enhance their transport in well bores and fractures |
-
2004
- 2004-06-08 JP JP2004170030A patent/JP4243853B2/ja not_active Expired - Fee Related
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2005
- 2005-06-07 US US11/147,039 patent/US7217576B2/en not_active Expired - Fee Related
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US7217576B2 (en) | 2007-05-15 |
JP2005353673A (ja) | 2005-12-22 |
US20050272171A1 (en) | 2005-12-08 |
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