TWI692438B - 多結晶介電體薄膜及電容元件 - Google Patents
多結晶介電體薄膜及電容元件 Download PDFInfo
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- TWI692438B TWI692438B TW106103441A TW106103441A TWI692438B TW I692438 B TWI692438 B TW I692438B TW 106103441 A TW106103441 A TW 106103441A TW 106103441 A TW106103441 A TW 106103441A TW I692438 B TWI692438 B TW I692438B
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- polycrystalline dielectric
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- 239000010408 film Substances 0.000 claims abstract description 72
- 239000010409 thin film Substances 0.000 claims abstract description 55
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
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- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 30
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- 238000010586 diagram Methods 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
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- 238000004364 calculation method Methods 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 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
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- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
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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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Abstract
本發明提供介電損失tanδ小的多結晶介電體薄膜及電容元件。係主組成為鈣鈦礦型氮氧化物的多結晶介電體薄膜。鈣鈦礦型氮氧化物以組成式AaBbOoNn(a+b+o+n=5)表示，a/b>1且n≧0.7。
Description
本發明係關於多結晶介電體薄膜及電容元件。
近年來，伴隨數位裝置的小型化、高性能化，需要使用了高性能的介電體薄膜的電容元件。
以往，就介電體薄膜而言，廣泛採用使用了金屬氧化物材料的薄膜。但是金屬氧化物材料製得的介電體薄膜的特性改善已逐漸逼近極限，需要有更高特性的新材料。新材料的候選者之一可列舉鈣鈦礦(perovskite)結晶構造中的氧八面體中的一部分氧原子置換成氮原子而成的金屬氮氧化物材料。但是難以獲得具有金屬氮氧化物材料的介電體薄膜。
例如，專利文獻1及專利文獻2記載了製作鈣鈦礦型氮氧化物ABO2N粉末的方法。但是專利文獻1及專利文獻2針對獲得使用鈣鈦礦型氮氧化物ABO2N之薄膜沒有任何揭示。
又，非專利文獻1及非專利文獻2記載製作由鈣鈦礦型氮氧化物ABO2N構成的薄膜。但非專利文獻1及非專利文獻2獲得的薄膜係磊晶膜(epitaxial film)。
磊晶膜係利用磊晶成長製得的膜。磊晶成長係一種薄膜結晶成長技術，係指在成為基板的結晶上進行結晶成
長，整齊地排列在基底的基板的結晶面的結晶成長。
磊晶膜有製造非常耗時的缺點。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開昭61-122108號公報
[專利文獻2]日本特開2013-001625號公報
[非專利文獻]
[非專利文獻1]Scientific Reports 4. DOI:10.1038/srep 04987
[非專利文獻2]KAST 平成25年度研究概要 第32-33頁
本發明係有鑑於如此的實情而生，目的在於提供製造效率高、介電損失小的多結晶介電體薄膜及電容元件。
本發明之多結晶介電體薄膜的主組成係鈣鈦礦型氮氧化物，其特徵為：該鈣鈦礦型氮氧化物以組成式AaBbOoNn(a+b+o+n=5)表示，a/b>1
n≧0.7。
本發明之多結晶介電體薄膜藉由具有上述特徵，介電損失可為小。
本發明之多結晶介電體薄膜，前述A係選自Sr、Ba、Ca、La、Ce、Pr、Nd、Na中的1種以上的元素，前述B係選自Ta、Nb、Ti、W中的1種以上的元素為佳。
本發明之多結晶介電體薄膜具有BO4N2之八面體構造且該八面體構造中的N的配置以cis型為主為佳。
本發明之電容元件具有前述多結晶介電體薄膜。
1:薄膜電容器
11:基板
12:下部電極
13:多結晶介電體薄膜
14:上部電極
第1圖顯示本發明之一實施形態之薄膜電容器之概略圖。
第2A圖顯示N之配置為cis型時的示意圖。
第2B圖顯示N之配置為trans型時的示意圖。
第3A圖顯示N之配置為cis型時的示意圖。
第3B圖顯示N之配置為trans型時的示意圖。
第4圖顯示由CaTaO2N構成之磊晶膜的XRD樣式的概略圖。
以下基於實施形態說明本發明。
本實施形態的薄膜電容器的示意圖如第1圖所示。第1圖所示的薄膜電容器1，在基板11上按順序形成下部電極12、多結晶介電體薄膜13，且在多結晶介電體薄膜13的表面具備上部電極14。
基板11之材質無特殊限制，使用單晶矽基板作為基板11的話，取得容易性及成本性優良。當重視撓性時，也可使用鎳箔作為基板。
下部電極12及上部電極14的材質無特殊限制，可作為電極的功用即可。例如可列舉Pt、Ag、Ni等。下部電極12的厚度以0.01~10μm為佳。上部電極14的厚度以0.01~10μm為佳。
多結晶介電體薄膜13係主組成為鈣鈦礦型氮氧化物的多結晶介電體薄膜。
前述鈣鈦礦型氮氧化物能以組成式AaBbOoNn(a+b+o+n=5)表示。A為前述鈣鈦礦型氮氧化物之A位點(A-site)離子即可。B為前述鈣鈦礦型氮氧化物之B位點(B-site)離子即可。
A以選自Sr、Ba、Ca、La、Ce、Pr、Nd、Na中的1種以上的元素為佳。若使用選自Sr、Ba、La、Nd中的1種以上的元素的話，可獲得高電容，故更佳，使用Sr的話最佳。B以選自Ta、Nb、Ti、W中的1種以上的元素為佳。使用Ta、Ti中的1種以上的元素的話，可獲得非均相少的多結晶介電體薄膜13，故更佳，使用Ta最佳。
進一步，a/b>1且n≧0.7為佳。又，a/b為a/b≧1.05更佳。n為n≧0.8更佳。a/b及n藉由為上述範圍內，tanδ可為良好。
又，前述鈣鈦礦型氮氧化物，其A位點離子的平均價數及B位點離子的平均價數的合計為6.7~7.3價。平均價數的合計以7價為佳。
在此，平均價數係將存在於A位點及B位點的離子的價數因應其豐度比(abundance ratio)而平均化得到的值。
例如針對於A位點Sr與La以4：1的比存在，於B位點Ta與Ti以4：1的比存在的情形敘述。Sr離子的價數為2，La離子的價數為3。因此，令其平均價數為α時，α可由下式(1)算出。又，Ta離子的價數為5，Ti離子的價數為4。因此，令其平均價數為β時，β可由下式(2)算出。並且，α=2.2、β=4.8。然後，平均價數的合計(α+β)成為7。
α=(Sr離子的價數)×(Sr離子的豐度比)+(La離子的價數)×(La離子的豐度比)
=2×4/5+3×1/5=2.2‧‧‧式(1)
β=(Ta離子的價數)×(Ta離子的豐度比)+(Ti離子的價數)×(Ti離子的豐度比)
=5×4/5+4×1/5=4.8‧‧‧式(2)
又，本申請案的平均價數的合計的計算中，富含A位點或是富含B位點時，亦即a/b≠1時，亦以a/b=1來處理。例如於上述情形，即使a/b=1.2，平均價數的合計為2.2+4.8=7。
以下，舉鈣鈦礦型氮氧化物為SraTabOoNn的情形為例說明，但A位點元素及/或B位點元素為不同元素的情形亦可套用。
於多結晶介電體薄膜13中，具有BO4N2的八面體構造且前述八面體構造中的N的配置以cis型為主為佳。
在此，氮(N)採順式(cis)配置的構造，係如第2A圖所示的2個N彼此位在相鄰位置的構造。相對於此，N採反式(trans)配置的構造，係如第2B圖所示的2個N彼此位在不相鄰位置的構造。
針對N採cis配置之情形及N採trans配置之情形，分別顯示複數八面體構造相連的情形的圖係第3A圖及第3B圖。由第3A圖可知N採cis配置時，結晶從c軸方向觀察係曲曲折折地延伸。相對於此，由第3B圖可知N採trans配置時，結晶係沿c軸方向一直線地延伸。且，N採trans配置時比起N採cis配置時的c軸較長。
本實施形態之多結晶介電體薄膜中N採cis配置為主的情事可利用中子繞射確認。即使未進行中子繞射，若ABO2N為多結晶體，則可知N採安定的cis配置。另一方面，欲獲得trans配置之ABO2N時，需如非專利文獻1，在基板上使其進行磊晶成長等而對於ABO2N的單晶施加基板應力，trans配置需要準備安定且特殊的狀態。但，cis配置為主的多結晶體中，通常trans配置不會完全成為0。即使cis配置安定，仍有時會因熱運動等造成一部分的N的排列混亂並採trans配置的情形。如此的情形下，就全體數目而言，cis配置為優勢，故在中子繞射中，由位點的存在機率得知為cis配置之結果。
本實施形態之多結晶介電體薄膜係和磊晶膜不同種類的薄膜。在此，以特定基板製作鈣鈦礦型氮氧化物係SraTabOoNn的磊晶膜時，N採trans配置。
為了確認本實施形態之多結晶介電體薄膜不是磊
晶膜，測出鈣鈦礦型氮氧化物係SrTaO2N的磊晶膜的XRD資料，和本實施形態之多結晶介電體薄膜之XRD資料比較，確認並非共通峰部即可。又，第4圖係鈣鈦礦型氮氧化物係CaTaO2N的磊晶膜的XRD資料。和第4圖一樣準備SrTaO2N的磊晶膜的XRD資料即可。又，薄膜為多結晶膜的情事可由XRD數據有峰部，來自其峰部之結晶面並非只是特定的結晶面來確認。
多結晶介電體薄膜13係多結晶膜的一種，也是介電體薄膜的一種。多結晶介電體薄膜13的厚度無特殊限制，以10nm~1μm為佳。
薄膜電容器1之製造方法
其次針對薄膜電容器1之製造方法說明。以下針對A位點原子為Sr、B位點原子為Ta的情形說明，但使用其他種類的原子的情形亦同。
最終成為多結晶介電體薄膜13的薄膜的成膜方法無特殊限制。例如可例示真空蒸鍍法、濺鍍法、PLD法(脈衝雷射蒸鍍法)、MO-CVD(有機金屬化學氣相沉積法)、MOD(有機金屬分解法)、溶膠凝膠法、CSD(化學溶液沉積法)等。又，成膜時使用的原料中有時會含有少量的雜質、副成分，但若是未大幅損及薄膜性能的程度的量則無特別問題。又，本實施形態之多結晶介電體薄膜13，亦為在無大幅損及性能的程度下含有少量雜質、副成分亦無妨。
上述成膜方法之中，若以PLD法、濺鍍法及CSD法等方法成膜，則最終獲得的薄膜容易成為多結晶膜。又，針對本實施形態之多結晶介電體薄膜13，若以PLD法、濺鍍法
及CSD法等方法成膜，容易成為N採cis配置的構造。也可利用CVD法合成，但是因為成分元素數多，PLD法、濺鍍法的組成控制性較高。於本實施形態針對利用PLD法所為的成膜方法說明。
首先，準備單晶矽基板作為基板11。然後，在單晶矽基板按SiO2、TiOx、Pt順序成膜，並形成由Pt構成的下部電極12。形成下部電極12的方法無特殊限制。例如可列舉濺鍍法、CVD等。
然後，在下部電極12上以PLD法形成金屬氧化物薄膜。又，為了使下部電極12的一部分露出，使用金屬遮罩形成有部分未形成薄膜的區域。
PLD法係首先將含有作為目的的多結晶介電體薄膜之構成元素的靶材設置於成膜室內。然後，在靶材的表面上照射脈衝雷射。利用脈衝雷射的強能量，使靶材表面瞬間蒸發。並且，使蒸發物沉積在以面向靶材的方式配置的基板上而成為金屬氧化物薄膜。
靶材的種類無特殊限制，除了含有製作之多結晶介電體薄膜之構成元素之金屬氧化物燒結體以外，可使用合金、氮化物燒結體、金屬氮氧化物燒結體等。又，在靶材中，以各元素平均分布為佳，但是在不影響獲得之多結晶介電體薄膜之品質之範圍內，分布也可以有不均勻。再者，靶材不需要是1個，也可以準備複數個含有多結晶介電體薄膜之構成元素之一部分的靶材用在成膜。靶材形狀亦無限制，製成適合使用之成膜裝置之形狀即可。例如，可藉由調整成膜條件(氧氣壓力、氮
氣壓力、成膜室的大小及氣體導入管的位置等)，以控制最終獲得的多結晶介電體薄膜的a/b。例如靶材的a/b若大，則成膜的膜中的a/b可為大。又，不只是靶材a/b，成膜條件亦為重要。原因在於因為脈衝雷射而從靶材蒸發的金屬元素會受到構成成膜室中的氣體環境的元素的影響，並到達基板的成膜面。
例如，當最終獲得之多結晶介電體薄膜的組成為SraTabOoNn時，則準備含Sr2Ta2O7之燒結體作為靶材。然後，藉由調整成膜條件(例如氧氣壓力、氮氣壓力、成膜室的大小及氣體導入管的位置等)，可控制最終獲得的多結晶介電體薄膜的a/b。
又，PLD法的情形，為了使成膜的金屬氧化物薄膜結晶化，以於成膜時將基板11以紅外線雷射加熱為佳。基板11之加熱溫度依金屬氧化物薄膜及基板11之構成元素及組成而改變，例如以成為600~800℃的方式加熱並進行成膜。藉由使基板11之溫度為適溫，金屬氮氧化物薄膜容易結晶化的同時，且可防止冷卻時產生裂痕。
於成膜中，藉由導入氮自由基並進行氮化處理，可獲得由鈣鈦礦型氮氧化物構成的多結晶介電體薄膜13。
最後，藉由在多結晶介電體薄膜13上形成上部電極14，可製造薄膜電容器1。又，上部電極14的材質無特殊限制，可使用Ag、Au、Cu等。又，上部電極14之形成方法亦無特殊限制。例如可以利用濺鍍法形成。
以上已針對本發明之實施形態說明，但本發明不受如此的實施形態限定，在不脫離本發明要旨的範圍內當然能
以各種不同的態樣實施。
又，本發明之電容元件係利用介電性的元件，包括電容器(condenser)、熱阻器、濾波器、雙工器、共振器、發信器、天線、壓電元件、電晶體、強介電體記憶體等。本實施形態之多結晶介電體薄膜適合使用在特別要求介電損失小的電容元件。
[實施例]
以下針對本發明進一步依據詳細的實施例說明，但本發明不限於此等實施例。
實驗例1
首先，準備SrCO3粉末及Ta2O5粉末作為當作成膜用靶材使用的Sr2Ta2O7燒結體的原料。稱量SrCO3粉末及Ta2O5粉末，使Sr/Ta的莫耳比成為1。
然後，對於SrCO3粉末及Ta2O5粉末，以使用乙醇溶劑的濕式球磨機混合16小時，獲得混合漿液。
然後，將前述混合漿液以恆溫乾燥機於80℃進行12小時乾燥，獲得混合物。
然後，將前述混合物以乳缽輕輕地解碎，放入陶瓷製的坩堝。然後使用電爐，於大氣環境中於1000℃進行2小時熱處理，獲得假燒物。
然後對於前述假燒物，再次以使用乙醇溶劑的濕式球磨機混合16小時，獲得假燒後漿液。
將獲得的假燒後漿體於恆溫乾燥機於80℃乾燥12小時，獲得假燒後混合物。
對於前述假燒後混合物，添加聚乙烯醇溶液作為黏結劑，混合並獲得造粒物。聚乙烯醇溶液的添加量，相對於粉碎物100重量%為0.6重量%。
將前述造粒物成形為直徑約23mm、高度約9mm的圓柱形狀，獲得成形物。成形方法為CIP成形。
對於前述成形物，使用電爐於大氣環境中於1400℃煅燒2小時，獲得燒結物。進一步，將前述燒結物的頂面及底面進行鏡面研磨，獲得高度5mm的成膜靶材。又，確認獲得之成膜靶材的相對密度為96~98%。
將依上述方式獲得之成膜用靶材設置於成膜裝置，並設置矽基板成為面向成膜用靶材。該矽基板係使用在表面具有Pt膜作為下部電極者。
實驗例1中，以PLD法成膜為厚200nm。藉由調整此時的成膜條件(氧氣壓力、氮氣壓力等)以控制最終獲得之多結晶介電體薄膜之a/b。於成膜中，藉由導入氮自由基並進行氮化處理，以獲得多結晶介電體薄膜。又，成膜時所耗費時間為0.5~2小時。
使用理學公司製全自動水平型多目的X射線繞射裝置SmartLab測定實驗例1獲得的薄膜樣本的XRD樣式。確認實驗例1的實施例皆非磊晶膜。又，使用LECO公司製TC600利用脈衝加熱熔融萃取法(紅外線吸收法)定量獲得的薄膜樣本的o及n。又，由XPS的化學偏移判定Sr離子及Ta離子的價數，並確認價數和原料一樣。具體而言，Sr離子的價數為2，Ta離子的價數為5。又，a/b之值及n之值係利用由脈衝加熱
熔融萃取法定量之值算出。
又，從針對實驗例1獲得之薄膜樣本的XRD樣式，確認實驗例1的實施例皆為多結晶膜。即，確認薄膜結晶化且成為多結晶薄膜。又，確認了獲得的多結晶薄膜並非對特定面配向的配向膜。其成為cis配置係安定的狀態。又，第3A圖未圖示Ta-N鏈，但ABO2N的cis型構造中，Ta-N鏈連成曲曲折折狀。
然後，於實驗例1獲得之薄膜樣本使用蒸鍍形成Ag電極，並測定介電損失(tanδ)
介電損失之測定係利用阻抗分析儀(安捷倫科技公司製)4294A，以測定電壓：100mV、測定頻率：1MHz進行。本實施例中，tanδ為10%以下評為良好。結果示於表1。
依據表1，a/b大於1的實施例1，tanδ為10%以下。相對於此，a/b為1以下的比較例1、2，tanδ超過10%。
依據表1，a/b越高，則tanδ越接近0%。此係ABO2N特有的現象。依理論計算，推測當出現陰離子缺陷時，容易藉由A位點成為缺陷而補償。但A位點若成為缺陷，據認為介電性降低，tanδ上升。而據認為藉由a/b為高，含有比起化學計量(a/b=1)更多的A位點元素，則不易發生A位點缺陷，tanδ可為小。
實驗例2
將SrCO3粉末及Ta2O5粉末替換為使用La2O3粉末及TiO2粉末，除此以外和實驗例1同樣進行，製作實施例11及比較例11的薄膜樣本，並進行各種測定。進一步，使用BaO粉末及Ta2O5粉末，除此以外，和實驗例1同樣進行，製作實施例12及比較例12之薄膜樣本，並進行各種測定。進一步，使用Nd2O3粉末及TiO2粉末，除此以外，和實驗例1同樣進行，製作實施例13及比較例13之薄膜樣本，並進行各種測定。結果示於表2。又，針對實驗例2獲得之實施例之薄膜樣本進行XRD測定。依照XRD測定，確認了實施例2的實施例及比較例也皆非磊晶膜而是多結晶薄膜。進而，確認了N之配置為cis型。又，關於實施例11及比較例11，從XPS的化學偏移判定La離子及Ti離子的價數，並確認了價數和原料一樣。具體而言，La離子的價數為3，Ti離子的價數為4。關於實施例12及比較例12，從XPS的化學偏移判定Ba離子及Ta離子的價數，並確認了價數和原料一樣。具體而言，Ba離子的價數為2，Ta離子的價數為5。進而關於實施例13及比較例13，從XPS的化學偏移判定Nd離子及Ti離子的價數，並確認了價數和原料一樣。具體而言，Nd離子的價數為3，Ti離子的價數為4。
依表2，a/b比起1大的實施例11，tanδ為10%以下。反觀a/b為1以下的比較例11，tanδ超過10%。
實驗例3
針對實施例1(n=0.8)，使n值變化，獲得實施例21及比較例21、22。結果示於表3。
依表3，n≧0.7的實施例，tanδ為10%以下，成為介電損失優良的多結晶介電體薄膜。反觀n<0.7的比較例21、22，tanδ超過10%，係惡化。
推測n<0.7時，不會充分地構成Ta-N鏈相連成曲曲折折狀的構造，故tanδ惡化。
Claims (3)
- 一種多結晶介電體薄膜，其為主組成係鈣鈦礦型氮氧化物之多結晶介電體薄膜，其特徵為：該鈣鈦礦型氮氧化物以組成式AaBbOoNn(a+b+o+n=5)表示，其中該A係選自Sr、Ba、La、Nd中的1種以上的元素；該B係選自Ta、Ti中的1種以上的元素；a/b>1；以及0.7≦n≦1.0，將存在於A位點的離子的平均價數設為α，存在於B位點的離子的平均價數設為β，6.7≦α+β≦7.3，且tanδ為10%以下。
- 如申請專利範圍第1項所述之多結晶介電體薄膜，具有BO4N2之八面體構造且該八面體構造中的N的配置為cis型。
- 一種電容元件，具有如申請專利範圍第1或2項所述之多結晶介電體薄膜。
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| FR2573060B1 (fr) | 1984-11-13 | 1987-02-20 | Centre Nat Rech Scient | Composes azotes ou oxyazotes a structure perovskite, leur preparation et leur application a la fabrication de composants dielectriques |
| JP3730840B2 (ja) * | 1999-08-20 | 2006-01-05 | 松下電器産業株式会社 | 誘電体膜及びその製造方法 |
| JP5807861B2 (ja) | 2011-06-21 | 2015-11-10 | 昭和電工株式会社 | 誘電体組成物及びその製造方法 |
| WO2015025753A1 (ja) * | 2013-08-19 | 2015-02-26 | 株式会社村田製作所 | Ｅｓｄ保護機能付薄膜キャパシタ装置およびその製造方法 |
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2017
- 2017-02-01 JP JP2017565580A patent/JP6866852B2/ja active Active
- 2017-02-01 US US16/068,762 patent/US10611693B2/en active Active
- 2017-02-01 EP EP17747450.9A patent/EP3392889A4/en not_active Withdrawn
- 2017-02-01 WO PCT/JP2017/003577 patent/WO2017135294A1/ja active Application Filing
- 2017-02-01 CN CN201780006873.5A patent/CN108475580B/zh active Active
- 2017-02-01 KR KR1020187019705A patent/KR20180094020A/ko not_active IP Right Cessation
- 2017-02-02 TW TW108115017A patent/TWI692439B/zh active
- 2017-02-02 TW TW106103441A patent/TWI692438B/zh active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102858691A (zh) * | 2010-04-28 | 2013-01-02 | 株式会社村田制作所 | 具有阴离子控制的介电性质的钙钛矿材料、薄膜电容器器件及其制造方法 |
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| C. Le Paven等撰寫，「Growth of (Sr,La)-(Ta,Ti)-O-N perovskite oxide and oxynitride films by radio frequency magnetron sputtering: Influence of the reactive atmosphere on the film structure」，Journal of Crystal Growth，Vol. 413，2015年3月出版，pp. 5~11 |
| C. Le Paven等撰寫，「Growth of (Sr,La)-(Ta,Ti)-O-N perovskite oxide and oxynitride films by radio frequency magnetron sputtering: Influence of the reactive atmosphere on the film structure」，Journal of Crystal Growth，Vol. 413，2015年3月出版，pp. 5~11 Ya-Ru Zhang等撰寫，「Sintering and dielectric properties of perovskite SrTaO2N ceramics」，Journal of the European Ceramic Society，Vol. 32，2012年出版，pp. 1269~1274 * |
| Ya-Ru Zhang等撰寫，「Sintering and dielectric properties of perovskite SrTaO2N ceramics」，Journal of the European Ceramic Society，Vol. 32，2012年出版，pp. 1269~1274 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3392889A4 (en) | 2019-08-14 |
| TWI692439B (zh) | 2020-05-01 |
| JP6866852B2 (ja) | 2021-04-28 |
| TW201728528A (zh) | 2017-08-16 |
| WO2017135294A1 (ja) | 2017-08-10 |
| CN108475580B (zh) | 2020-06-02 |
| US20190023616A1 (en) | 2019-01-24 |
| JPWO2017135294A1 (ja) | 2018-11-29 |
| US10611693B2 (en) | 2020-04-07 |
| TW201930182A (zh) | 2019-08-01 |
| KR20180094020A (ko) | 2018-08-22 |
| EP3392889A1 (en) | 2018-10-24 |
| CN108475580A (zh) | 2018-08-31 |
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