TW201515028A - 複鐵式奈米尺度薄膜材料，其易合成之方法和在室溫下磁電耦合 - Google Patents

複鐵式奈米尺度薄膜材料，其易合成之方法和在室溫下磁電耦合 Download PDF

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TW201515028A
TW201515028A TW104100535A TW104100535A TW201515028A TW 201515028 A TW201515028 A TW 201515028A TW 104100535 A TW104100535 A TW 104100535A TW 104100535 A TW104100535 A TW 104100535A TW 201515028 A TW201515028 A TW 201515028A
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iron
bifeo
nanocrystal
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Ronald Pirich
Nan-Loh Yang
Kai Su
I-Wei Chu
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Ronald Pirich
Nan-Loh Yang
Kai Su
I-Wei Chu
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Abstract

本發明為製作複鐵式薄膜材料之方法，該方法包含下列步驟：提供複鐵式的前驅物溶劑；提供該前驅物溶劑旋轉拋光製作旋轉拋光薄膜並加熱旋轉拋光薄膜。前驅物溶劑可以包含在乙二醇中之Bi(NO3)3．5H2O和Fe(NO3)3．9H2O，以製作鉍鐵氧磁體薄膜。更進一步，該薄膜可用於各種科技領域，包含用於資訊儲存之記憶體元件。

Description

複鐵式奈米尺度薄膜材料，其易合成之方法和在室溫下磁電耦合
本發明係關於複鐵式薄膜材料及詳細的該材料製作方法。
【相關申請案之交互參照】
本申請案主張於2009年5月18日提申之美國臨時申請案第61/179,214號案之權利，其之教示明確地以參照方式併入。
複鐵式材料的研究於近期出現為材料科學中最令人興奮的新領域之一。複鐵式材料係磁電元件，且由於其共存非平常的電和磁的排序之耦和，在多功能材料的設計及合成上具有潛在的應用。磁性的偏極化能藉由施加一電場而被切換；且鐵電的偏極化在能夠藉由施加一磁場而被切換。因此，複鐵材料在基礎物理研究及新元件的設計概念上皆為重要的材料。該些化合物不只是磁性及鐵電材料當前的機會，也能夠作為可能應用之基礎，包括：調變光學特性、磁電的複鐵共振器、移相器、用於高階的微波和毫米波之延遲線及濾波器、場波動和場監控的偵測器、資訊儲存、自旋電子之出射場以及感測器。
複鐵材料之磁電耦合的行為非常重要。在許多複鐵材料中， 鉍鐵氧體(BiFeO3)是已知唯一的材料在室溫下表現出複鐵特性並且引起相當多的關注。在BiFeO3薄膜中磁電耦合以前還未被完全開發，室溫下在複鐵BiFeO3薄膜中有磁域結構的電控制於2006年首度發現。然而藉由磁場切換鐵電偏極化以前還未被紀錄。
因為有不同方法用於合成複鐵薄膜，例如：脈衝雷射沉積(PLD)、液相磊晶、塗佈方法、以及化學溶劑沉積，所以包括BiFeO3之複鐵化合物的使用在之前已被揭示，然而，用於合成複鐵薄膜之已揭示的全部方法皆需複雜及昂貴的程序。
本發明係關於合成BiFeO3奈米晶體薄膜(約45nm厚)之新穎易做到之程序。由本發明之方法製作該些薄膜不僅維持BiFeO3之鐵電及磁的特性，並且室溫下在同樣的樣本上顯示磁電耦合(即磁性、以及電性的切換)。
本發明提供備製在室溫下能夠磁電耦合之奈米級複鐵薄膜材料，即鐵磁(偏極化)之電場控制以及電場(偏極化)之磁場控制。在一實施例中，該些複鐵薄膜材料為鐵氧磁體且可以為鉍鐵氧磁體。本發明的方法製作該些複鐵薄膜材料可以適用於各種元件之應用，舉例而言但不限於記憶體元件、自旋電子(磁電)、感測器以及其他元件。例如，一記憶體元件能夠利用本發明之複鐵薄膜能，其夠被電寫入以及磁讀取。該鐵電記憶元件之一個實施例可以包括在鈣鈦礦結構中之B位以磁性金屬原子取代Fe原子，該些金屬磁性原子之取代可以選自包括Mn、Ru、Co以及Ni之群組，並可以可選擇的取代位於B位大約1%至10%的Fe原子。此外或是可選擇 地，取代的磁性金屬原子可以比Fe具有更高的價位，並且可能在B位被取代約1%至30%。本發明之複鐵薄膜其它用途之實例包括用於調變光學特性、磁電複鐵共振器、移相器、用於高階的微波和毫米波之延遲線及濾波器以及場波動和場監控的偵測器之應用。
參照詳細說明以及圖式，於本文揭露之不同的實施例之此等以及其他的特色與優點將更容易理解，其中，類似的元件符號指類似的元件，且其中：圖1描述表示本發明的步驟之流程圖。
於下文提出之詳細說明其意欲做為本發明之目前較佳實施例之描述，不意欲表示本發明可以被製造或使用之唯一型式。該說明闡述用於製造以及操作本發明之功能及步驟程序。然而要暸解的是，由不同實施例可以完成相同或是等效功能及程序，而其也意指為包含於本發明之範疇之內。
本發明提供一用於製造一定義明確的BiFeO3(BFO)奈米結晶薄膜之簡單以及低成本程序。
本發明之一實施例包含下列步驟：提供一複鐵前驅物溶劑10；提供該前驅物溶劑於旋轉拋光以製造一旋轉拋光膜20；及加熱該旋轉拋光膜30。在實施例中，該複鐵薄膜材料為鐵氧體且可以明確地為鉍鐵氧體。
該複鐵前驅物溶劑可以包括：鉍、鐵以及氧。特別是該複鐵 前驅物溶劑可以包括：Bi(NO3)3．5H2O和Fe(NO3)3．9H2O。當複鐵前驅物溶劑由Bi(NO3)3．5H2O和Fe(NO3)3．9H2O組成時，其可以在溶劑中出現之莫耳比例為1：1。該前驅物溶劑可以溶解於任何適當的稀釋液中。適當稀釋液之一實例為乙二醇。
旋轉拋光之後，該膜被加熱高於室溫。特別地，該膜可以被加熱到溫度接近600℃。
本發明之方法能夠在最終的膜上製作一均勻排列之奈米結晶。例如：由本發明之方法製作之奈米結晶可以為直徑約200奈米以及高度約45奈米。
本發明更進一步想到由本文揭露之該方法製作之一複鐵薄膜材料。由本發明製作之該複鐵薄膜材料在大約室溫下可以能夠磁電耦合，其與複鐵材料在目前技術中須低溫才能磁電耦合形成鮮明對比。該產生之薄膜材料可以適合於許多應用，包括但不限於使用於資訊儲存之記憶體元件。
當組成這樣一鐵電記憶體元件時，在鈣鈦礦結構中形成BFO鐵電層係較佳的，其中由磁性金屬原子取代某些位於B位之Fe原子。例如：該些磁性金屬原子可以至少為Mn、Ru、Co以及Ni其中之一。當該些原子取代於B位時，BFO鐵電層之磁性被增強且其介電特徵改善，導致改善性能。該些磁性金屬原子可以取代在BFO中，位於B位大約1%至10%的Fe原子，此外或是可選擇地，該些磁性原子可以為具有高於Fe的價位之原子，例如：V、Nb、Ta、W、Ti、Zr以及Hf。藉由取代於B位之原子具有高於Fe之價位，假如位於A位之Bi消失，則位於B位具有較高價位之原子幫助 維持整體晶體之中性及絕緣。藉此預防可能的漏電流。於一實施例中，該些較高價位磁性金屬原子取代在BFO層中位於B位大約1%至30%之Fe原子。
執行於本文揭露之步驟得到大約45奈米厚之定義明確的BFO奈米結晶薄膜。亦即Bi(NO3)3．5H2O和Fe(NO3)3．9H2O以1：1莫耳比溶於乙二醇中以製作前驅物溶劑。該前驅物溶劑接著提供旋轉拋光接著以600℃加熱。在室溫下使用磁力顯微鏡(Magnetic Force Microscopy,MFM)以及表面電位顯微鏡(Kelvin Probe Force Microscopy,KPFM)觀察在該合成的複鐵BFO薄膜中之磁性及電性之排序以及其耦合。在相同的複鐵樣本中發現磁性與鐵電性排序之室溫耦合。
該BFO薄膜之X射線繞射(X-Ray Diffraction,XRD)圖清楚地顯示菱形晶系的變形鈣鈦礦之結晶結構。更進一步地，使用X射線能量散射光譜儀(X-Ray Energy Dispersive Spectroscopy,XEDS)之元素分析顯示鉍對鐵之1對1元素比。
本發明之鐵薄膜之型態使用掃描式電子顯微鏡(Scanning Electron Microscopy,SEM)以及原子力顯微鏡(Atomic Force Microscopy,AFM)而被建立。SEM與AFM結果皆顯示擁有均勻且密集排列之奈米結晶的膜，奈米結晶具有平均直徑為200奈米以及平均高度為45奈米。為了該BFO薄膜之奈米級磁特性之觀察，使用一具有相偵測之動態模型執行MFM量測(△Z=82奈米，尖端到表面)。造成之相影像清楚指出磁性的排列垂於直樣本的表面(z方向)
KPFM用來量測BFO膜(△Z=50奈米)之鐵電特性。施以不 同直流偏壓(-1、+1以及+2伏特)於具有平均高度為45奈米BFO膜之地形表面以寫入電偏極化，且顯示符合具有感應的偶極之粒子之電位的特徵。為了移除已存在之表面電荷且觀測鐵電偏極化，使用零偏壓AFM掃描，以具有接地端之接觸模式執行於相同區域。接著，自基板以不同程度及方向施加一直流偏壓以產生電偏極化。於-1伏特直流偏壓下之表面電位在BFO奈米結晶之上表面清楚地顯示一負的(大約-10毫伏)偏極化。在改變該直流偏壓從-1伏特至+1伏特之後，BFO上之偏極化顯示一方向的翻轉。當施以更高之+2伏特直流偏壓時，觀測到一幾乎顛倒之影像，明顯的表示鐵電域之偏極化方向藉由外加的電場而被切換。也注意到的事，鐵電偏極化維持至少18.5小時，而僅在電場移開後有適度的減少。
為了證明電場導致BFO膜之磁性排序，當MFM實驗被執行成像以及操縱由於該施加電場的BFO膜之磁性時，施一外加電場於樣本。該磁尖被抬起至100奈米，以減少來自以前存在的樣品磁場之影響至可忽略的程度。在△Z=100奈米下，MFM相影像沒有顯示在尖端與表面有重大的磁交互作用，只是於磁尖上之影響被排除。在第一痕跡中，施以不同程度之直流偏壓以感應BFO膜表面之磁性。在施以一電場之後，由該電場感應之BFO膜之磁性影像排序被紀錄。為了監控在BFO膜的磁性上正電場的影響程度，+2伏特及+4伏特直流偏壓被施加於個別組的連續掃描之第一痕跡。其建立較高之偏壓場導致更強的磁性排序。藉由單一10分鐘之掃描以偏壓步階從零至+2伏特以及+2伏特至+4伏特顯示反應時間之時域。
為了研究以磁場產生之鐵電排序，該樣品在KPFM量測前被置於一外加磁場中。除了沒有直流偏壓施於表面之外，該些成像實驗相 似於一般之KPFM。首先先實施AFM地形圖，接著做KPFM研究。表面電位影像被記錄在具有△Z=50奈米之第二痕跡。實驗在相同的樣本區域上有以及沒有外加磁場之結果與磁電耦合比較。在第一實驗中，繪製出沒有電場或是磁場之BFO膜之表面電位影像，且顯示出在BFO膜表面沒有顯著之表面電位。在第一掃描之後，該BFO膜被置於一極間隙為0.5英吋以及磁場強度為10,500厄斯特之兩磁極間，30分鐘以及15小時。在30分鐘以及15小時的磁化之後，該表面電位影響被記錄。如被發現的，經過30分鐘的磁化後，影像開始顯示出該BFO表面上有表面電位。經過15小時的磁化後，表面電位影像顯示強大的鐵電排序。這是第一次發現室溫磁場感應電偏極化。然而，由磁場感應的鐵電排序不如電場感應之排序來的有效率。
上述說明係藉由實例而提出，但不限於此。鑑於上述揭露內容，熟習本項技術者能夠想出揭露於此之本發明的範疇及精神之內之變化，包括前驅物稀釋、旋轉拋光程序以及加熱長度之各種優化。更進一步地，揭露於此之實施例的各種特點能夠被單獨使用或是互相以各種方式組合，但非意指侷限於描述於此之特殊的組合。所以申請專利範圍之範疇不受限於所說明之實施例。

Claims (16)

  1. 一種製作複鐵薄膜材料之方法，該方法包含下列步驟：a)提供一複鐵前驅物溶劑，其包含鉍、鐵以及氧；b)旋轉拋光該前驅物溶劑，以製造一旋轉拋光膜；及c)加熱該旋轉拋光膜以形成複鐵鉍鐵氧磁體(BiFeO3)薄膜，其中該BiFeO3薄膜在一鈣鈦礦結構中具有BiFeO3奈米結晶，該鈣鈦礦結構具有於該鈣鈦礦結構中位於B位之鐵原子，鐵原子被具有高於鐵原子之價位之磁性金屬原子取代，以維持電中性以及該BiFeO3薄膜的絕緣，且其中該BiFeO3薄膜陳列均勻排列之BiFeO3奈米結晶，其在室溫下能夠磁電耦合。
  2. 如申請專利範圍第1項之方法，其中，該複鐵前驅物溶劑包含Bi(NO3)3．5H2O和Fe(NO3)3．9H2O。
  3. 如申請專利範圍第2項之方法，其中，Bi(NO3)3．5H2O和Fe(NO3)3．9H2O以1：1莫耳比出現。
  4. 如申請專利範圍第2項之方法，其中，Bi(NO3)3．5H2O和Fe(NO3)3．9H2O溶於乙二醇。
  5. 如申請專利範圍第1項之方法，其中，於步驟(c)該旋轉拋光膜被加熱至600℃。
  6. 如申請專利範圍第5項之方法，其中，該奈米結晶直徑是200奈米以及高度是45奈米。
  7. 如申請專利範圍第1項之方法，進一步包括回應於一施加磁場以調節BiFeO3奈米結晶的電偏極化的步驟。
  8. 如申請專利範圍第1項之方法，其中該BiFeO3奈米結 晶在室溫下受到磁場感應電偏極化影響。
  9. 如申請專利範圍第1項之方法，進一步包括回應於一施加電場以調節BiFeO3奈米結晶的鐵磁偏極化的步驟。
  10. 如申請專利範圍第1項之方法，其中該BiFeO3奈米結晶受到該奈米結晶的該鐵磁偏極化的電場控制影響。
  11. 如申請專利範圍第1項之方法，其中該奈米結晶的該鐵磁特性受到電場控制影響，並且該奈米結晶的該鐵電特性受到磁場控制影響。
  12. 如申請專利範圍第1項之方法，其中該奈米結晶的該鐵電特性受到磁場控制影響。
  13. 如申請專利範圍第1項之方法，其中該奈米結晶的該鐵磁特性受到電場控制影響。
  14. 如申請專利範圍第1項之方法，進一步包括具有比鐵更高價位的磁性金屬原子取代位於該鈣鈦礦結構中B位之鐵原子，以維持該BiFeO3薄膜的中性和絕緣。
  15. 如申請專利範圍第14項之方法，其中該些較高價位磁性金屬原子取代位於B位大約1%至30%之鐵原子。
  16. 如申請專利範圍第15項之方法，其中該些較高價位磁性金屬原子係為選自由V、Nb、Ta、W、Ti、Zr以及Hf組成之群組。
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Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5885931B2 (ja) * 2010-03-15 2016-03-16 キヤノン株式会社 ビスマス鉄酸化物粉体、その製造方法、誘電体セラミックス、圧電素子、液体吐出ヘッドおよび超音波モータ
CN102320666B (zh) * 2011-06-21 2013-04-03 南京大学 氟替代铁酸铋晶格中氧的制备方法
KR20140072047A (ko) 2011-08-17 2014-06-12 리전츠 오브 더 유니버시티 오브 미네소타 질화철 영구 자석 및 질화철 영구 자석을 형성하기 위한 기술
US9130144B2 (en) * 2012-05-31 2015-09-08 Rhode Island Board Of Education, State Of Rhode Island And Providence Plantations Multiferro-heterostructure composition having tunable magnetic coupling at room temperature
EP2954540A4 (en) 2013-02-07 2017-06-28 Regents of the University of Minnesota Iron nitride permanent magnet and technique for forming iron nitride permanent magnet
WO2014210027A1 (en) 2013-06-27 2014-12-31 Regents Of The University Of Minnesota Iron nitride materials and magnets including iron nitride materials
AU2015235987B2 (en) 2014-03-28 2017-03-16 Regents Of The University Of Minnesota Iron nitride magnetic material including coated nanoparticles
US9994949B2 (en) 2014-06-30 2018-06-12 Regents Of The University Of Minnesota Applied magnetic field synthesis and processing of iron nitride magnetic materials
AU2015301062A1 (en) 2014-08-08 2017-03-02 Regents Of The University Of Minnesota Multilayer iron nitride hard magnetic materials
US10002694B2 (en) 2014-08-08 2018-06-19 Regents Of The University Of Minnesota Inductor including alpha″-Fe16Z2 or alpha″-Fe16(NxZ1-x)2, where Z includes at least one of C, B, or O
US10358716B2 (en) * 2014-08-08 2019-07-23 Regents Of The University Of Minnesota Forming iron nitride hard magnetic materials using chemical vapor deposition or liquid phase epitaxy
US10072356B2 (en) 2014-08-08 2018-09-11 Regents Of The University Of Minnesota Magnetic material including α″-Fe16(NxZ1-x)2 or a mixture of α″-Fe16Z2 and α″-Fe16N2, where Z includes at least one of C, B, or O
JP2016111102A (ja) * 2014-12-03 2016-06-20 国立大学法人東北大学 マルチフェロイック素子
GB201504418D0 (en) * 2015-03-16 2015-04-29 Univ Liverpool Multiferroic materials
CN105006329B (zh) * 2015-07-20 2018-02-02 重庆科技学院 一种多铁性液体及其制备方法
CN106066925A (zh) * 2016-07-05 2016-11-02 南昌航空大学 磁电耦合超材料本构矩阵获取法
CN106111482B (zh) * 2016-08-09 2020-02-14 南京邮电大学 一种刮涂制备铁酸铋薄膜的方法
KR102100436B1 (ko) 2018-10-30 2020-04-13 울산과학기술원 강자성 원소 치환형 상온 다강성 물질 및 그 제조 방법
CN109516796B (zh) * 2018-11-30 2021-07-09 江西科技学院 一种多铁性固溶体陶瓷及其制备方法
CN109627043B (zh) * 2019-01-24 2021-06-25 南京邮电大学 具有高度择优取向的纯相铁酸铋薄膜的制备方法
CN112537952B (zh) * 2020-12-04 2023-05-09 安徽工业大学 一种具有优异磁电性能的铁酸铋基陶瓷及其制备方法
CN113149080A (zh) * 2021-06-11 2021-07-23 中国科学技术大学 一种多铁性铁酸铋纳米粒子及其制备方法
CN114229911B (zh) * 2021-12-31 2022-08-12 湖南大学 一种铁酸铋薄膜的制备方法

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4129525A (en) 1977-12-02 1978-12-12 Exxon Research & Engineering Co. Method of making lead-rich and bismuth-rich pyrochlore compounds using an alkaline medium
EP0331360B1 (en) 1988-02-26 1994-02-02 Hitachi, Ltd. Method of preparing an oxide high-temperature superconducting material
JPH085749B2 (ja) 1989-03-30 1996-01-24 日本碍子株式会社 旋光性単結晶およびその製造方法
US5015461A (en) 1989-06-26 1991-05-14 Exxon Research & Engineering Company Novel high surface area oxide compositions with a pyrochlore structure, methods for their preparation, and conversion processes utilizing same
US5073537A (en) 1990-02-06 1991-12-17 Eastman Kodak Company Electrically conductive article
US5516363A (en) 1991-12-13 1996-05-14 Symetrix Corporation Specially doped precursor solutions for use in methods of producing doped ABO3 -type average perovskite thin-film capacitors
JPH08204132A (ja) * 1995-01-25 1996-08-09 Murata Mfg Co Ltd 半導体集積回路装置
US6344271B1 (en) 1998-11-06 2002-02-05 Nanoenergy Corporation Materials and products using nanostructured non-stoichiometric substances
US6017504A (en) 1998-07-16 2000-01-25 Universite Laval Process for synthesizing perovskites using high energy milling
US6576291B2 (en) 2000-12-08 2003-06-10 Massachusetts Institute Of Technology Preparation of nanocrystallites
DE60224748T2 (de) 2001-04-23 2009-02-05 Kabushiki Kaisha Toyota Chuo Kenkyusho Kornorientierte Keramik und Verfahren zu ihrer Herstellung, sowie anisotrop geformtes Pulver und Verfahren zu seiner Herstellung
JP3735686B2 (ja) 2001-10-30 2006-01-18 独立行政法人理化学研究所 金属酸化物強誘電体粒子結晶の製造方法
WO2003074427A1 (fr) 2002-03-07 2003-09-12 Japan Science And Technology Agency Oxyde mésoporeux non siliceux présentant un périodisme amélioré de structure de pores, procédé de production de l'oxyde mésoporeux et procédé de cristallisation de paroi de pore d'oxyde mésoporeux non siliceux à l'aide d'un composé structurant destiné à remplir les pores
US7056471B1 (en) 2002-12-16 2006-06-06 Agency For Science Technology & Research Ternary and quarternary nanocrystals, processes for their production and uses thereof
JP3873935B2 (ja) 2003-06-18 2007-01-31 セイコーエプソン株式会社 強誘電体メモリ素子
JP2005191437A (ja) * 2003-12-26 2005-07-14 Ricoh Co Ltd 半導体装置、その製造方法、および表示装置
US20050145908A1 (en) 2003-12-30 2005-07-07 Moise Theodore S.Iv High polarization ferroelectric capacitors for integrated circuits
WO2005110916A2 (en) 2004-05-10 2005-11-24 Evident Technologies Iii-v semiconductor nanocrystal complexes and methods of making same
JP2006004995A (ja) * 2004-06-15 2006-01-05 Mitsubishi Chemicals Corp 電界効果トランジスタ
US20060025301A1 (en) 2004-07-30 2006-02-02 Reddy Benjaram M Process for preparing nanosized, thermally stable, and high surface area multi-component metal oxides
JP2006176366A (ja) 2004-12-22 2006-07-06 Fujitsu Ltd 強誘電体材料、その製造方法及び強誘電体メモリ
US7585474B2 (en) 2005-10-13 2009-09-08 The Research Foundation Of State University Of New York Ternary oxide nanostructures and methods of making same
JP4693634B2 (ja) 2006-01-17 2011-06-01 株式会社東芝 スピンｆｅｔ
JP5012795B2 (ja) 2006-03-29 2012-08-29 富士通株式会社 半導体記憶装置及びその製造方法
US7706103B2 (en) 2006-07-25 2010-04-27 Seagate Technology Llc Electric field assisted writing using a multiferroic recording media
US8124254B2 (en) 2006-12-19 2012-02-28 Boston Applied Technologies, Inc Heterostructure of ferromagnetic and ferroelectric materials with magneto-optic and electro-optic effects
US7573734B2 (en) 2007-07-13 2009-08-11 Consejo Superior De Investigaciones Cientificas Magnetoelectric device and method for writing non-volatile information into said magnetoelectric device
KR20090022188A (ko) 2007-08-29 2009-03-04 삼성전자주식회사 자기헤드, 자기기록매체 및 이를 채용한 자기기록장치
US8123973B2 (en) * 2008-12-10 2012-02-28 Cheng Uei Precision Industry Co. Method of manufacturing magnetic material
US8216858B2 (en) * 2009-02-18 2012-07-10 Canon Kabushiki Kaisha Ferroelectric material, method of producing ferroelectric material, and ferroelectric device
US8400047B2 (en) * 2009-03-12 2013-03-19 Canon Kabushiki Kaisha Piezoelectric material, piezoelectric device, and method of producing the piezoelectric device

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US20100288964A1 (en) 2010-11-18
DE112010002019T5 (de) 2012-08-02
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