JP6720665B2 - 強誘電体素子及びその製造方法 - Google Patents
強誘電体素子及びその製造方法 Download PDFInfo
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- JP6720665B2 JP6720665B2 JP2016083845A JP2016083845A JP6720665B2 JP 6720665 B2 JP6720665 B2 JP 6720665B2 JP 2016083845 A JP2016083845 A JP 2016083845A JP 2016083845 A JP2016083845 A JP 2016083845A JP 6720665 B2 JP6720665 B2 JP 6720665B2
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- film
- metal
- ferroelectric
- metal substrate
- insulating film
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 163
- 239000002184 metal Substances 0.000 claims description 163
- 239000000758 substrate Substances 0.000 claims description 98
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000005498 polishing Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 230000003746 surface roughness Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910001374 Invar Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004121 SrRuO Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000004151 rapid thermal annealing Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001151 other effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- -1 zirconium alkoxide Chemical class 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005224 laser annealing Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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- 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
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- C23C14/5806—Thermal treatment
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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- C23C18/1254—Sol or sol-gel processing
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- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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Description
図1は、第1の実施の形態に係る強誘電体素子を例示する断面図である。図1を参照するに、第1の実施の形態に係る強誘電体素子1は、金属基板11と、絶縁膜12と、金属膜13と、強誘電体膜14と、上部電極15とを有している。
図3は、第1の実施の形態の変形例1に係る強誘電体素子を例示する断面図である。図3を参照するに、第1の実施の形態の変形例1に係る強誘電体素子2では、絶縁膜12と金属膜13との間に絶縁膜16が追加された点が、強誘電体素子1(図1参照)と相違する。つまり、金属基板11上に形成される絶縁膜が、絶縁膜12と絶縁膜16との積層構造とされている。
図4は、第1の実施の形態の変形例2に係る強誘電体素子を例示する断面図である。図4を参照するに、第1の実施の形態の変形例2に係る強誘電体素子3では、金属膜13と強誘電体膜14との間にシード膜17が追加された点が、強誘電体素子1(図1参照)と相違する。
図5は、第2の実施の形態に係る強誘電体素子を例示する断面図である。図5を参照するに、第2の実施の形態に係る強誘電体素子4では、金属膜13上に部分的に強誘電体膜14が形成され、強誘電体膜14の周囲にPZTアモルファス膜18が形成された点が、強誘電体素子1(図1参照)と相違する。
ここで、金属基板11の厚みは100μm以下(例えば、50μm程度)で、絶縁膜12の膜厚は30nm程度しかないので、各層の裏面から表面へ拡散する熱はロスが少ない状態で表面側に到達できる。
実施例1では、図1に示す強誘電体素子1を作製した。具体的には、金属基板11として膜厚50μm程度のNi36%−Feのインバーの金属箔を準備し、金属基板11の一方の面を研磨(鏡面研磨)した。研磨前の金属基板11の表面粗さはRz=0.6μm程度であり、研磨後の表面粗さは例えばRz=0.08μm程度となった。研磨後、アセトンを用いて金属基板11の表面を超音波洗浄した。超音波洗浄後、室温で、EB蒸着法より、金属基板11の一方の面(研磨面)上に、絶縁膜12として、膜厚30nm程度のアルミナ膜(Al2O3膜)を形成した(図2(a)参照)。
比較例1では、実施例1に係る強誘電体素子1において、絶縁膜12として酸化チタン膜(TiOX膜)を用いた。酸化チタン膜は、150℃の温度条件下でスパッタ法で蒸着したチタン膜(Ti膜)を700℃で酸化処理して得た。
比較例2では、実施例1に係る強誘電体素子1において、金属膜13として、膜厚が50nmの白金膜(Pt膜)を用いた。この場合、上下電極間でリーク電流が大きく、P−E曲線の評価をすることができなかった。
比較例3では、実施例1に係る強誘電体素子1において、金属基板11としてPZTの熱膨張率(室温での熱膨張率:9×10−6/K程度)に近いSUS430(室温での熱膨張率:10.5×10−6/K程度)を用いた。
11 金属基板
12、16 絶縁膜
13 金属膜
14、140 強誘電体膜
15 上部電極
17 シード膜
18 PZTアモルファス膜
Claims (15)
- 金属基板の一方の面上にEB蒸着法またはスパッタ法により絶縁膜を形成する絶縁膜形成工程と、
前記絶縁膜上に、スパッタ法により金属膜を形成する金属膜形成工程と、
前記金属基板、前記絶縁膜、及び前記金属膜を含む構造体を300℃よりも高い温度で加熱処理する加熱工程と、
前記加熱工程後に、前記金属膜上にゾルゲル法で強誘電体膜を形成する強誘電体膜形成工程と、を有し、
前記金属基板として、FeとNiを含み、Niの含有量が30%以上40%以下である基板を用いることを特徴とする強誘電体素子の製造方法。 - 前記絶縁膜形成工程よりも前に、前記金属基板の一方の面を研磨する研磨工程を有することを特徴とする請求項1に記載の強誘電体素子の製造方法。
- 前記金属基板の室温での熱膨張率が5×10−6/K以下であることを特徴とする請求項1または2に記載の強誘電体素子の製造方法。
- 前記金属基板はFe、Ni、Co、Pt、Pdの何れか1つ以上の金属を含む基板であることを特徴とする請求項1乃至3の何れか一項に記載の強誘電体素子の製造方法。
- 前記絶縁膜形成工程は、前記金属基板の一方の面上に第1の絶縁膜を形成する工程と、前記第1の絶縁膜上に第2の絶縁膜を形成する工程と、を含むことを特徴とする請求項1乃至4の何れか一項に記載の強誘電体素子の製造方法。
- 前記金属膜形成工程は、前記金属膜を100nm以上500nm以下の膜厚で形成することを特徴とする請求項1乃至5の何れか一項に記載の強誘電体素子の製造方法。
- 前記強誘電体膜形成工程は、前記金属基板をレーザ照射により部分的に加熱して前記強誘電体膜を結晶化する工程を含むことを特徴とする請求項1乃至6の何れか一項に記載の強誘電体素子の製造方法。
- 前記強誘電体膜形成工程では、酸素雰囲気中で前記強誘電体膜を形成することを特徴とする請求項1乃至7の何れか一項に記載の強誘電体素子の製造方法。
- 金属基板と、
前記金属基板上に形成された絶縁膜と、
前記絶縁膜上に形成された金属膜と、
前記金属膜上に形成された強誘電体膜と、を有し、
前記金属基板の強誘電体膜を備える側の表面粗さRzは0.5μm以下であり、
前記金属基板はFeとNiを含み、Niの含有量が30%以上40%以下であることを特徴とする強誘電体素子。 - 前記金属基板の室温での熱膨張率が5×10−6/K以下であることを特徴とする請求項9に記載の強誘電体素子。
- 前記金属基板はFe、Ni、Co、Pt、Pdの何れか1つ以上の金属を含む基板であることを特徴とする請求項9または10に記載の強誘電体素子。
- 前記金属基板の厚さは100μm以下であることを特徴とする請求項9乃至11の何れか一項に記載の強誘電体素子。
- 前記金属膜は、Pt、Pd、Ir、Ti、Rhの何れか1つ以上の金属を含む金属膜、前記何れか1つ以上の金属の合金を含む金属合金膜、または、前記金属膜若しくは前記金属合金膜の中から選択した2以上の膜を積層した積層膜であることを特徴とする請求項9乃至12の何れか一項に記載の強誘電体素子。
- 前記金属膜の膜厚は100nm以上500nm以下であることを特徴とする請求項9乃至13の何れか一項に記載の強誘電体素子。
- 前記絶縁膜形成工程は、前記金属基板の一方の面上に前記EB蒸着法または前記スパッタ法により150℃以下の温度条件下で絶縁膜を形成し、
前記金属膜形成工程は、前記絶縁膜上に、前記スパッタ法により150℃以下の温度条件下で金属膜を形成することを特徴とする請求項1に記載の強誘電体素子の製造方法。
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