TW567508B - Piezoelectric ceramic and piezoelectric ceramic device using the same - Google Patents

Piezoelectric ceramic and piezoelectric ceramic device using the same Download PDF

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TW567508B
TW567508B TW090123350A TW90123350A TW567508B TW 567508 B TW567508 B TW 567508B TW 090123350 A TW090123350 A TW 090123350A TW 90123350 A TW90123350 A TW 90123350A TW 567508 B TW567508 B TW 567508B
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Taiwan
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piezoelectric ceramic
patent application
piezoelectric
piezoelectric ceramics
present
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TW090123350A
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English (en)
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Hirozumi Ogawa
Masahiko Kimura
Akira Ando
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Murata Manufacturing Co
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Description

567508 A7 ___ __B7 五、發明説明0 ") " " 技術領域 本發明係關於壓電陶瓷及使用其之壓電陶瓷元件，尤其 是例如，壓電陶瓷濾波器、壓電陶瓷振盪器、壓電陶瓷振 動器等，作爲壓電陶瓷元件等材料之有用的壓電陶瓷及使 用其之壓電陶瓷元件。 技術背景 先前，壓電陶瓷濾波器、壓電陶瓷振盪器、壓電陶瓷振 動器等之壓電陶瓷元件所廣汎使用之壓電陶瓷，振盪其主 要成分欽酸錯酸錯（ΡΜτίχΖΐΉ)。3)或鈦酸鉛（PbTi03)之壓電 陶资°然而’主要成分爲鈦酸錘酸鉛或鈦酸鉛之壓電陶瓷 ，其組成中包含大量的鉛，於製造過程中因鉛氧化合物之 热發’產生製品均一性低下之問題。爲了防止該問題，使 用壓電陶瓷之組成中完全不含鉛或組成中只含有少量鉛較 好。 從該觀點上，其主要成分爲（：化“744015等鉍層狀化合物 之壓電陶瓷，因其組成中未含有鉛氧化物，作爲解決上述 問題之材料而受到注目。 但是’在將以〇&8丨47^4015等鉍層狀化合物作爲主要成分 之壓電陶瓷使用在壓電陶瓷振盪器時，在頻率範圍内，即 在共振頻率和反共振頻率間之頻數之電器的品質係數 Q (1 / tan d )之最大値Qmax，但有無法得到實用程度之Qmax 的問題。 發明之開示 ， 本發明之主要目的爲提供有用的壓電陶瓷及使用其之壓 本紙張尺度適用中® @家料(CNS) A4規格(21GX 297公《) 567508 A7 B7 五、發明説明（2 ) 電陶瓷元件，其主要成分爲CaBi4Ti4015，完全不包含鉛或 鉛化合物或是只含有少量，作爲顯示能夠實用程度上之 Qmax之壓電陶瓷元件等之材料。 與本發明有關之壓電陶瓷，其主要成分爲鉍層狀化合物 ，其包含Ca、Bi、Ti及氧氣，其特徵在於在設定主要成分 鉍層狀化合物中之Ca、Bi及Ti的莫耳比爲a : b ·· c時，滿 足0.15 S a/c<0.25及3 . 5 S (2a + 3b)/c S 3.88之關係。 與本發明有關之壓電陶瓷，對於主要成分中1 m〇l之Ti含 有C a以外之2價金屬元素或B i以外之3價金屬元素〇 1 m〇1 以下（不包括0)亦可。此情況，主要成分中所含有之Ca以 外之2價金屬元素，係自例如μ g、S r、B a及P b中所選出 之至少一種。又，此情況，主要成分中含有Bi以外之3價 金屬元素，係自例如Sc、Y、La、Ce、pr、Nd、Sm、 Gd、Dy、Er及Yb中所選出之至少一種。 此外，與本發明有關之壓電陶瓷，對於主要成分中i m〇1 之Ti含有未滿0·25 mol(不包括〇)之Zr亦可。 另外’與本發明有關之壓電陶瓷；，把Μη換算成MnC03， 含有1.5 %以下（不包括〇)之重量亦可。 與本發明有關之壓電陶瓷元件，其爲包含與本發明有關 之壓電陶瓷和形成於壓電陶瓷之電極者。 與本發明有關之壓電陶瓷，其主要成分爲鉍層狀化合物 ，其包含Ca、Bi、Ti及氧氣，’在設定主要成分鉍層狀化合 物中之Ca、Bi及Ti之莫耳比爲: b : c時，爲了滿足〇 15 蠤a/c<0.25及3.5S(2a + 3b)/cS3.88之關係而限定其範圍 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 567508 A7 B7 五、發明説明（3 ) ，此乃係因爲在該範圍外無法得到可供實用程度之Qmax。 再者，與本發明有關之壓電陶瓷，對於主要成分中1 mol 之T i如果含有C a以外之2價金屬元素或B i以外之3價金屬 元素0 · 1 mol以下（不包括0)，該發明之效果將會更爲顯著 。對於主要成分中1 mol之T i，使含有C a以外之2價金屬元 素或Bi以外之3價金屬元素爲0.1 mol以下（不包括〇 )，此乃 係因爲超過此含有量時，Qmax反而比不加該等金屬元素時 低，因而造成無法看出加該等金屬元素之意義。 此外，與本發明有關之壓電陶瓷，若對於主要成分中1 mol之Ti含有未滿0.25 mol(不包括〇)之Zr時，該發明之效 果會更爲顯著。對於主要成分中1 m〇l之Ti，使Zr含有量 爲超過未滿0.25 mol(不包括〇)，此乃係因爲超過此含有量 時，Qmax反而比不加Zr時低，因而無法看出加ζΓ之意義。 再者，與本發明有關之壓電陶瓷，若把Μη換算成MnC03 ’含有1 .5 %以下（不包括〇 )之重量，該發明之效果會更爲 顯著。把Μη換算成MnC03，1 · 5 %以下（不包括〇 )重量， 此乃係因爲超過此含有量時，Qmax反而比不加μ η時低， 因而無法看出加Μη之意義。 圖式之簡要説明 圖1 ’係説明適用於本發明之壓電陶瓷振動器之例子的立 體圖。 圖2，係圖1所示壓電陶瓷振動器之剖面圖。 實施發明之最優良之形態 ， (實施例）
裝 訂
567508 A7 B7 五、發明説明（4 首先，準備開始之原料：SrC03、Bi203、CaC03、BaC03 、Nd203、La203、Ti02、Zr02及MnC03，量取組合該化學式 (CaaBibTic015+xMe+yZr+zMnC〇3(其中，Me 爲 Sr、Ba、Nd 或L a，a、b、c、x、y及z則請參照表1及表2))，利用球 磨機約1 6小時作濕式混合，取得混合物。將取得之混合物 乾燥後，於700〜900。C預燒，獲得預燒物。 該預燒物粗粉碎之後，加入適當之有機粘結劑，使用球 磨機作1 6小時之濕式粉碎，利用亂片法將其做成40 # 111到 80 "m厚度之薄板。關於被形成之薄板，用白金軟膏將電 極印刷於一部分之薄板。將有印刷電極之薄板和未印刷之 薄板壓if*於950 C〜1170。C中燒成，並於1 〇〇。〇〜200。C； 之絕緣油中以8〜10 kV/mm之直流電壓施加1 〇〜3 〇分鐘做分 極之處理，製作成如圖i及圖2所示之能量封閉型之壓電陶 瓷振動器（試樣）。而且，分極之方向爲如圖2箭頭所示，垂 直於電極之方向。 如圖1及圖2所示，壓電陶瓷振動器丨〇包含，例如長方體 狀之壓電陶瓷12。壓電陶瓷12，其包含2張壓電陶瓷層12& 及12b。該等壓電陶瓷層之12a及12b，其包含上述組成式之 壓電陶瓷，經層積且一體成形。又，該等壓電陶瓷層之Ua 及12b ’如圖2箭頭所示，係被依相同厚度分極。 0於I電陶资層12a及12b之間，在其中央部，形成_例如 圓形之振動電極14a,從其振動電極14a至壓電陶瓷U之一 端，形成例如一T字形引出電極16a。又，於壓電陶资層以 之表面，在其中央部，形成一例如圓形之振動電極14b，從 本紙張尺度it財關家標準(CNsilli：格(210 X 297公董)---〇 ___ 567508 A7 B7 五、發明説明（5 ) 其振動電極14b至壓電陶瓷1 2之另一端，形成一例如T字形 引出電極16b。此外，於壓電陶瓷層12b之表面，在其中央 部，形成一例如圓形之振動電極14c，從其振動電極14c至 壓電陶瓷1 2之另一端，形成一例如T字形引出電極16c。即 ，振動電極14a、14b及14c係與從上方之垂直方向所看到之 壓電陶瓷12—致，振動電極14a位於振動電極14b及14c之中 央0 並且，引出電極16a係藉由鉛絲18a與一方外部端子20a連 接，引出電極16b及16c則係藉由別的鉛絲18b與另一方外部 端子20b連接。 壓電陶瓷振動器1 0係因電壓印加在外部端子20a及20b之 間，振動電極14a和振動電極14b及14c間產生電位差，能以 厚度垂直振動2次高頻方式激勵。 關於所測得到之試樣，以厚度垂直振動2次高頻模式進行 測定，測得Qmax。其結果示於表1及表2。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 567508 A7 B7 五、發明説明（6 ) 表 1 試樣 號碼 a b c Me X y z 燒成温度 (°C) 〇max r 1.0 4.0 4.0 - 0 0 0 1,170 10.1 2* 1.0 4.2 4.0 - 0 0 0 1,100 14.4 3* 0.9 4.0 4.0 - 0 0 0 1,170 9.8 4 0.9 4.1 4.0 - 0 0 0 1,120 23.9 5 0.9 4.4 4.0 - 0 0 0 1,100 21.8 6* 0.9 4.6 4.0 - 0 0 0 950 7.8 7* 0.8 4.0 4.0 - 0 0 0 1,170 9.5 8 0.8 4.2 4.0 - 0 0 0 1,120 22.1 9 0.8 4.5 4.0 - 0 0 0 1,100 21.6 10* 0.8 4.7 4.0 - 0 0 0 950 5.3 ir 0.7 4.1 4.0 - 0 0 0 1,150 8.4 12 0.7 4.2 4.0 - 0 0 0 ,)1,120 21.6 13 0.7 4.7 4.0 - 0， 0 0 1,100 20.5 14" 0.7 4.8 4.0 - 0 0 0 950 3.2 15* 0.6 4.2 4.0 - 0 0 0 1,150 9.3 16 0.6 4.3 4.0 - 0 0 0 1,120 18.8 17 0.6 4.7 4.0 - 0 0 0 1,100 16.3 18* 0.6 ] 4.8 4.0 - • 0 0 0 950 3.5 19* 0.5 4.4 4.0 - 0 0 0 1,150 11.1 20* 0.5 4.6 4.0 - 0 0 0 1,100 8.5 21 0.9 4.1 4.0 - 0 0 0.5 1,120 30.1 22 0.9 4.4 4.0 - 0 0 0.5 1,100 23.4 23 0.9 4.1 4.0 - 0 0 1.5 1,120 26.3 24 0.9 4.4 4.0 - 0 0 1.5 1,100 22.5 25 0.9 4.1 4.0 - 0 0 1.6 1,120 17.4 26 0.9 4.4 4.0 - 0 0 1.6 1,100 16.2 27 0.9 4.1 4.0 Nd 0.1 0 0 1,120 27.3 28 0.9 4.1 4.0 Nd 0.4 0 0 1,120 25.7 29 0.9 4.1 4:0 Nd 0.5 0 0 1,120 16.1 30 0.9 4.1 4.0 Ba 0.1 0 〇 1,120 25.2 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 567508 A7 B7 表2 試樣 號碼 a b c Me X y 2 --- 燒成溫度 Qmax 31 0.9 4.1 4.0 Ba 0.4 1 120 24 6 32 0.9 4.1 4.0 Ba 0.5 0 0 1 1 9Π i C Q 33 0.9 4.1 4.0 Sr 0.1 0 0 1 1 ?0 10.0 26 1 34 0.9 4.1 4.0 Sr 0.4 0 0 lion OA Q 35 0.9 4.1 4.0 Sr 0.5 6~ 1 i?n 15 3 36 0.9 4.1 4.0 La 0.1 0 1 1 on 7 37 0.9 4.1 4.0 La 0.4 0 J 0 l ·丨 ‘u lion ilO· f 〇A R 38 0.9 4.1 4.0 La 0.5 0 0 lion /LH.O i c 〇 39 0.9 4.1 4.0 - 0 10.1 ^ 0 1.12D I 0.0 27 q 40 0.9 4.1 4.0 - 0 0.2 0 1 i 9Π 〇 41 0.9 4.1. 4.0 - 0 0.9 0 1 1 on 〇C A 42 0.9 4.1 4.0 - 0 1 0 1,120 ^ 0 · u 15.2 五、發明説明（7 ) 試樣號碼欄之*印，表示該試樣爲本發明範圍之外。 於表1及表2，Qmax係於相同組成之試樣中，所得到最大 Qmax之條件（預燒溫度，燒成溫度，分極時之絕緣油溫度 及直流電壓）時之値。又，雖Qmax之値係依試樣之形狀、 振動模式或電極之種類而不同，但在此所使用之條件中， Qmax之値若爲1 5以上，遂可以視其爲實用之程度。 如表1及表2所示，與本發明有關之各項試樣，任一項之 Qmax均爲1 5以上，顯然爲作爲壓電陶瓷元件，特別是，唇 電陶瓷振盪器等材料之有用的壓電陶瓷。所以，根據本發 明，可以獲得有用的壓電陶瓷，其完全不包含鉛或鉛化合 物，或是只含有少量，作爲顯示能夠得到實用程度之卩㈤⑽ 之壓電陶瓷元件等材料。 此外，與本發明之實施例有關，之各項試樣，任—項均即 使在CaBuTUO"燒成條件以下之燒成溫度下形成亦具有較 -10· 本紙張尺度如T㈣轉準(CNS) A4規格(⑽χ 297公爱) 567508 A7 B7 五、發明説明（8 ) 大的Qmax。所以，由此可知本發明之次要效果細微能夠降 低燒成之溫度。藉由降低燒成溫度，可減低燒成時所須之 電力等能量.，又，藉由燒成時延長收納壓電陶瓷容器之壽 命，能降低製造成本。 另外，本發明有關之壓電陶瓷，其並不只限於上述實施 例之組成，只要滿足0.15蠤a/c<0.25及3.5S(2a + 3b)/cS 3.88之關係，遂可確定Qmax爲15以上。 又，於上述之實施例，已説明關於Qmax爲厚度垂直振動 2次高頻模式之例子，但本發明之效果並未受厚度垂直振動 2次高頻模式之限定，厚度滑行振動和厚度垂直振動之基本 波等，壓電陶瓷元件，特別是在利用壓電陶瓷振盪器之其 它振動方式上，厚度垂直振動2次高頻之情形也同樣有效。 再者，例如於Jpn. J. Appl. Pys·，Vol. 34，Part 1，9B， 卩卩5096-5099上，1\八151!1<丨等之報告中指出將作爲鐵電記憶 體用之薄膜材料之鉍層狀化合物SrBi2Ta209改換成 Sr0.7B2.4Ta2O9之情況下殘留分極値上昇。但，該發明之對象 爲與此研究相異之組成系。又，本發明目的爲獲得有用的 壓電陶瓷以作爲壓電陶瓷元件之材料，本發明與T . Atsuki 等之研究係在不同之使用領域中，此外因鐵電記憶用之材 料和壓電陶瓷元件用之材料所要求之性能也不同，所以並 無法輕易從T. Atsuki等之研究中想出本發明。 產業上利用之可能性 本發明之壓電陶瓷係能使用於各種壓電陶瓷元件，特別 是適宜使用於壓電陶瓷振盪器。 -11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 裝 訂

Claims (1)

  1. 567508 第090123350號專利申請案 中文申凊專利範圍替換本(92年9月） A8 B8 C8
    々、申請專利範圍
    &化<0.25及3.5^(2& + 31))/(^3.88之關係。 如1中睛專利範圍第1項之壓雷输遂，甘a ^ 4、，
    金屬元素或Bi以外之3價金屬元素。 要成分中1 3 ·如申請專利範圍第2項之壓電陶瓷，其中前述主要成分 中所含有之Ca以外之2價金屬元素係從Mg、Sr、Ba& P b中所選出之至少一種。 4·如申請專利範圍第2項之壓電陶瓷，其中前述主要成分 中所含有之Bi以外之3價金屬元素係從Sc、Y、La、Ce 、Pr、Nd、Sm、Gd、Dy、Ει·及Yb中所選出至少一種。 5 ·如申請專利範圍第1項至第4項中任一項之壓電陶究，其 中相對於前述主要成分中1 mol之Ti含有不到〇25m〇1 之Zr 〇 6 ·如申請專利範圍第1項至第4項中任一項之壓電陶究，其 中把Μη換算成MnC03，含有1 .5重量％以下。 7_ —種壓電陶瓷元件，其特徵在於包含： 如申請專利範圍第1項至第6項中任一項之壓電陶瓷所成 之壓電陶瓷，及 印刷導電軟膏之後燒成之而形成於前述壓電陶瓷之電極 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
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JP2002097073A (ja) 2002-04-02
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JP3815197B2 (ja) 2006-08-30
US6753642B2 (en) 2004-06-22
KR20020063574A (ko) 2002-08-03
CN1145594C (zh) 2004-04-14
EP1327615A4 (en) 2006-05-24
EP1327615A1 (en) 2003-07-16
US20030001460A1 (en) 2003-01-02
WO2002024602A1 (fr) 2002-03-28
CN1392871A (zh) 2003-01-22
DE60139492D1 (de) 2009-09-17

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