TWI412505B - 微細之以鈦酸鋇為基質之複合氧化物 - Google Patents

微細之以鈦酸鋇為基質之複合氧化物 Download PDF

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Publication number
TWI412505B
TWI412505B TW099107090A TW99107090A TWI412505B TW I412505 B TWI412505 B TW I412505B TW 099107090 A TW099107090 A TW 099107090A TW 99107090 A TW99107090 A TW 99107090A TW I412505 B TWI412505 B TW I412505B
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Taiwan
Prior art keywords
barium titanate
powder
dielectric constant
real number
group
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TW099107090A
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English (en)
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TW201038505A (en
Inventor
Sei Ung Park
Ju Suk Ryu
Seong Jae Lim
In Jae Baek
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Hanwha Chemical Corp
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Priority claimed from KR1020090021198A external-priority patent/KR100921352B1/ko
Priority claimed from KR1020090066243A external-priority patent/KR100955802B1/ko
Application filed by Hanwha Chemical Corp filed Critical Hanwha Chemical Corp
Publication of TW201038505A publication Critical patent/TW201038505A/zh
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    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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Description

微細之以鈦酸鋇為基質之複合氧化物
本發明係關於一種微細之以鈦酸鋇為基質之粉末，其具有高介電常數與低溫電容係數。根據本發明之以鈦酸鋇為基質之粉末具有高燒結密度，低介電損耗與高絕緣電阻。本發明也係關於一種包含該以鈦酸鋇為基質之粉末的介電材料與一種包含該介電材料的陶瓷電子零件。
由於鈦酸鋇(BaTiO3)具有高介電常數與優良的極化遲滯與壓電效應，且當添加摻雜劑時即可輕易賦予半導體性質，因此鈦酸鋇廣泛用作陶瓷電子零件的材料，如陶瓷電容器、增幅器、記憶體裝置、調幅器、電聲轉換器、驅動器，其他壓電體、正熱阻器、半導體等。特定言之，正方形鈦酸鋇是一種鐵電體，因而具有相當高的介電常數與極化遲滯，所以正方形鈦酸鋇係廣泛用作多層陶瓷電容器(Multi-layer ceramic capacitors，MLCCs)中之介電材料。
近來，電子儀器迅速地小型化，因此要求陶瓷電子零件需具有小體積與大容量。特定言之，於MLCC的情況，已要求介電層需具有低厚度且叠層數量增高。由於一層介電層中可含有之鈦酸鋇顆粒的數量是有限制的，故當該介電層具有更低厚度時，鈦酸鋇應以更微細之顆粒形式提供。因此，已嘗試過很多，來保持高介電常數(排除提供微細顆粒)，最小化電容的溫度係數，及改善燒結密度、介電耗損與絕緣電阻，使得鈦酸鋇可應用於高容量MLCC。
例如，韓國專利公開案第2002-0048101號揭露一種製造用於X7R MLCCs之鈦酸鋇粉末之方法，其包含：混合與乾燥由碳酸鋇(BaCO3 )與二氧化鈦(TiO2 )所形成的起始原料並且煅燒所得之混合物；粗研磨所得之混合物，添加含有受體、施體、顆粒生長抑制劑與燒結助劑之添加物(以每100公克粉末有1.6至4.0公克之量添加)，及細研磨所得之混合物；乾燥含有該添加物之混合粉末並進一步煅燒該粉末；以及進一步粗研磨所得之粉末，接著再經過一細研磨。然而，該所得之顆粒仍是太粗糙而無法應用於高容量MLCC中且具有大的電容溫度係數。
日本專利公開案第2008-156202揭露一種介電陶瓷，其係包含以鈦酸鋇為基質之粒子與形成於該等粒子間之粒子界(grain boundaries)，該介電陶瓷的特徵在於它包含，以每莫耳形成鈦酸鋇之鋇計，0.01至0.06莫耳之以MgO表示之鎂、0.0015至0.03莫耳之以Y2 O3 表示之釔及0.0002至0.03莫耳之以MnO表示之錳，還包含4.2至33.3重量份之以Nb2 O5 表示之鈮，以每100重量份的鈦酸鋇計，且其粒子的平均粒徑為0.05至0.2微米。然而，該介電陶瓷有非常低的介電常數，所以可能無法應用於高容量MLCC。
一般來說，具較小粒徑的鈦酸鋇具有較低的鐵電正方形相含量與較高的順電立方相含量，使其介電常數下降且電容降低。總之，根據相關技術，是不可能提供呈微細顆粒形式之以鈦酸鋇為基質之粉末，具有高介電常數、低電容溫度係數，並符合一些電性性質，如燒結密度、介電損耗與絕緣電組，而可應用於陶瓷電容器。
本發明之一實施態樣係關於提供一種微細之以鈦酸鋇為基質之粉末，用於以介電材料為基質之陶瓷電子零件，特別是用於高容量MLCC。
為達成本發明之目的，本發明提供一種微細之以鈦酸鋇為基質之粉末，具有高介電常數與低電容溫度係數。該以鈦酸鋇為基質之粉末也具有高燒結密度、低介電損耗與高絕緣電阻。
一方面，提供一種以鈦酸鋇為基質之粉末，其由化學通式1表示：
(Bax R1 r1 R2 r2 )(Tiy R3 r3 R4 r4 )O3 　[化學通式1]
其中R1 係至少一種選自以下群組之元素：釔(Y)與鑭系元素(lanthanoids)；R2 係至少一種選自以下群組之元素：鎂(Mg)、鈣(Ca)與鍶(Sr)；R3 係包含磷(P)與鈮(Nb)；R4 係至少一種選自以下群組之元素：鋁(Al)、釩(V)、鉻(Cr)、錳(Mn)、鈷(Co)、鋯(Zr)與鉭(Ta)；r1 與r3 係各自獨立為一大於0且等於或小於0.05之實數；r2 與r4 係各自獨立為一大於0且等於或小於0.1之實數；以及(x+r1 +r2 )/(y+r3 +r4 )為一0.85至1.15之實數。
較佳地，r1 、r2 、r3 及r4 係各自獨立為一大於0且等於或小於0.03之實數。
在化學通式1中，R1 是一取代鋇(Ba)元素並與鋇元素之部位合金以產生陽離子空位之元素。所生成之陽離子空缺補償在還原氛圍下燃燒所產生之氧離子空位，因而防止絕緣電阻退化。大部份的稀土元素可包含在內，但是一部份的稀土元素有不同的擴散率，所以可能無法提供前述之效應但會造成異常的顆粒生長。因此，R1 較佳係至少一種選自以下群組之元素：釔與鑭系元素，更佳係釔。
在化學通式1中，R2 是一第二族之元素，其介電常數依溫度而有所變化且提高了其可靠性。此外，R2 取代存在於表面層之Ba元素並與其合金來控制顆粒生長與燒結密度。較佳地，R2 係至少一種選自以下群組之元素：鎂、鈣與鍶，更佳地，R2 係鎂。
R1 與R2 取代Ba元素或以非晶形氧化物存在於表面。當R1 與R2 的存在量太大時，它們可能導致次相(secondary phase)的生成，可能沉澱為結晶氧化物，或是被賦予半導體性質，導致電性性質與可靠性退化。因此，較佳地，r1 係大於0且等於或小於0.05，r2 係大於0且等於或小於0.1；更佳地，r1 與r2 係各自大於0且等於或小於0.03。
在化學通式1中，R3 具有相對小的離子半徑與相對大的擴散係數，因此相較於與表面層合金之元素會更顯著地被合金化，藉此作為一擴散屏障，其作用為防止應出現在表面層之元素擴散至顆粒中。因此，R3 的功用係在於改善介電質之電性性質，增加使用期限與燒結特性，並減少介電常數隨時間的變化。雖然至今鈮已經常用於此目的，但並非較佳的，因為高鈮含量會造成介電常數迅速下降並賦予半導體性質，導致電性性質與可靠性退化。反之，藉由以磷取代一定量的鈮，即使一小量的鈮都可提供所欲的效果。因此，R3 較佳係同時包含鈮與磷。
如上所述，根據本發明之一具體實施態樣之以鈦酸鋇為基質之粉末之特徵係在於同時包含鈮與磷。尤其，該以鈦酸鋇為基質之粉末之特徵係在於鈮對磷之莫耳比率為1：0.1至2.0。當替代鈮之磷的量太低或太高時，該以鈦酸鋇為基質之粉末可能無法提供所欲的效果或可能展現電性性質退化。所以，磷對鈮的莫耳比率較佳為0.1至2.0。
在化學通式1中，R4 是一元素，功能為控制電容溫度係數與改善介電質之電性性質，如介電損耗與絕緣電阻。較佳地，R4 係至少一種選自以下群組之元素：鋁、釩、鉻、錳、鈷、鋯與鉭；更佳地，R4 係包含鋁、釩、鉻與錳。
根據本發明之一較佳具體實施態樣，所提供之以鈦酸鋇為基質之粉末中，R1 係釔(Y)，R2 係鎂(Mg)，R3 係包含磷(P)與鈮(Nb)，並且R4 係包含鋁(Al)、釩(V)、鉻(Cr)與錳(Mn)。
R3 與R4 取代Ti元素，存在於間隙位置或以非晶形氧化物存在於表面層上。當R3 與R4 存在量太大時，它們可能導致次相之生成，可能沉澱為結晶氧化物，或是被賦予半導體性質，導致電性性質與可靠性退化。因此，r3 較佳係大於0且等於或小於0.05；r4 係大於0且等於或小於0.1。更佳地，r3 與r4 係各自大於0且等於或小於0.03。
控制(x+r1 +r2 )/(y+r3 +r4 )值為0.85至1.15也很重要。尤其，鋇、鈦與R1 、R2 、R3 及R4 元素的存在使(x+r1 +r2 )/(y+r3 +r4 )值為0.85至1.15之實數，是在R1 、R2 、R3 及R4 元素完全合金化至鈦酸鋇晶格內或以非晶形氧化物但未形成次相時之形式存在於表面上的範圍內。所以，當該值偏離上述範圍時，介電長數在低溫與高溫下可能發生嚴重的變動，燒結特性可能退化，且可靠性與電性性質如耐電壓可能明顯的降低。更佳地，該上述之值係控制在0.95至1.05。
根據本發明之另一較佳具體實施態樣，以鈦酸鋇為基質之粉末中所含的鋇元素係以每莫耳的鈦元素為0.995至1.005莫耳的量存在。當鋇元素的存在量小於0.995莫耳時，一部份的鈦鹽不會轉換成鈦酸鋇但仍以其原本形式存在。此外，如此少量的鋇可能導致異常的顆粒生長並且抑制整體的正方形特點。另一方面，當鋇元素的存在量超過1.005莫耳時，過量的鋇鹽可能存在於以鈦酸鋇為基質之顆粒的表面，導致嚴重的顆粒團聚，並且可能抑制流暢的離子擴散，造成正方形相的含量下降。
根據本發明之一具體實施態樣之由化學通式1表示之以鈦酸鋇為基質之粉末，係藉由所添加的摻雜物之顆粒生長而加以控制，因此易於提供微細之顆粒。特定言之，鈮與磷抑制該刺激立方相之製造的元素合金化至顆粒內。結果，縱使該以鈦酸鋇為基質之粉末係以微細顆粒提供，但其正方形相的含量為60至100重量%並且保持鐵電性，故可具有高的相對介電常數。因此，根據本發明之一具體實施態樣之以鈦酸鋇為基質之粉末的特徵在於，以總重量計，具有60至100重量%之正方形相比例，且較佳具有10至500奈米的顆粒尺寸與2至35平方公尺/克的比表面積。
因為該以鈦酸鋇為基質之粉末具有高正方形相含量與鐵電性，其較佳於25℃具有1500至3000的相對介電常數。此外，該以鈦酸鋇為基質之粉末的相對介電常數，εT ，在-55℃至125℃下符合方程式1。換句話說，該以鈦酸鋇為基質之粉末符合根據EIA定義之陶瓷電容器標準之等級II(高介電常數)X7R標準碼的特性：
其中，ε0 為在25℃下之相對介電常數。
該以鈦酸鋇為基質之粉末可用於所有以鈦酸鋇為基質之陶瓷電子零件，例如，陶瓷電容器、增幅器、記憶體裝置、調幅器、電聲轉換器、驅動器，壓電體、正熱阻器、半導體等。較佳地，該鈦酸鋇為基質之粉末係用作介電材料，更佳係用作陶瓷電容器之材料，且最佳係用作多層陶瓷電容器(MLCCs)之材料。
該以鈦酸鋇為基質之粉末可經由以下方式製備：固相法(包括混合一氧化物或碳酸鹽，接著進行燃燒)、水熱法(包含混合一起始原料之含水溶液與一含水鹼性溶液，接著進行水熱處理與燃燒)、氫氧化物製程或有機酸製程(包含在水沖式系統中合成一氫氧化物鹽或有機酸鹽，接著進行燃燒)、烷氧化物製程(包含水解一烷氧化物混合物，接著進行燃燒)或相似方式。但較佳地，該以鈦酸鋇為基質之粉末可經由以下方式製備。以下將更詳細的說明根據本發明之製備以鈦酸鋇為基質之粉末之方法之一較佳具體實施態樣。
根據本發明之一較佳具體實施態樣，製備由化學通式1表示之以鈦酸鋇為基質之粉末的方法包含：混合碳酸鋇、一鈦鹽與水以提供一懸浮液；使該混合的懸浮液進行濕研磨與乾燥以提供含有碳酸鋇與鈦鹽之混合粉末，且在300℃至900℃下加熱該混合粉末；混合該經熱處理之混合粉末與一氧化物、氯化物、碳酸鹽、磷酸鹽、硝酸鹽、硫酸鹽、醋酸鹽或其混合物(該氧化物、氯化物、碳酸鹽、磷酸鹽、硝酸鹽、硫酸鹽、醋酸鹽或其混合物係含有至少一種選自以下群組之元素：釔(Y)、鑭系元素、鎂(Mg)、鈣(Ca)、鍶(Sr)、磷(P)、鈮(Nb)、鋁(Al)、釩(V)、鉻(Cr)、錳(Mn)、鈷(Co)、鋯(Zr)與鉭(Ta))以及水，以提供一懸浮液；使該混合的懸浮液進行濕研磨與乾燥以提供混合粉末，且更進一步在700℃至1100℃下熱處理該混合粉末，以提供以鈦酸鋇為基質之粉末。
用作起始原料之鈦鹽係由化學通式2表示：
TiO2 ‧n(H2 O)　[化學通式2]
其中，n為一0至2之實數。
原則上，當n為0時，該鈦鹽為二氧化鈦；當n為1時，其係偏鈦酸；當n為2時，其係正鈦酸。但是，實際應用上，如此的定義並不能很清楚地相互區分，因為近來用作鋇酸鈦之起始原料之鈦化合物係以微細顆粒的形式提供。特定言之，由四氯化鈦、二氯化鈦與硫酸氧鈦製備之鈦鹽是從非常微細且無初始之類顆粒形狀之非晶相開始，且當結晶作用開始進行，其n值逐漸減少。
在本方法中，碳酸鋇與鈦鹽較佳以微細之顆粒提供。例如，於鈦鹽之情況下，當n接近0時會發生強烈的結晶作用，而且當晶體生長時會得到粗顆粒。因此，n較佳為等於或大於0.5且其比表面積較佳為100平方公尺/公克或更高。
該微細之以鈦酸鋇為基質之粉末滿足高容量MLCCs需求之高介電常數與低電容溫度係數。更特定言之，該以鈦酸鋇為基質之粉末符合根據EIA定義之陶瓷電容器標準之等級II(高介電常數)X7R標準碼之特性。該以鈦酸鋇為基質之粉末也具有優良的燒結密度、介電損耗與絕緣電阻。
本發明之優點、特徵及各方面係以下參考所附圖式之實施態樣的敘述而更為清楚。
[實施例1]
a)製備含有碳酸鋇與鈦鹽之懸浮液
首先，將422公升純水倒入反應槽內，然後加入104.0公斤之鈦鹽(由Millennium Inorganic Chemicals取得之TiO2 ‧0.84(H2 O))與216.3公斤之碳酸鋇(BaCO3 )並攪動以提供懸浮液。
b)製備並熱處理含有碳酸鋇與鈦鹽之混合粉末
使用併含直徑0.3毫米之以二氧化鋯為基質之球珠的珠粒磨機研磨並充分混合由a)獲得之懸浮液。接著，取出一小部份的懸浮液並予以乾燥。根據X射線螢光光譜法(XRF)，Ba/Ti的莫耳比率係1.001。完成研磨與混合後，噴霧乾燥該懸浮液以獲得含有碳酸鋇與鈦鹽之混合粉末。之後，在500℃的環境壓力下熱處理該混合粉末歷時4小時。
c)製備含有摻雜劑之懸浮液
根據表1所列組成秤重三氧化二釔(Y2 O3 )、碳酸鎂(MgCO3 )、五氧化二鈮(Nb2 O5 )、五氧化二磷(P2 O5 )、三氧化二鋁(Al2 O3 )、五氧化二釩(V2 O5 )、三氧化二鉻(Cr2 O3 )與二氧化錳(MnO2 )並加入至經b)熱處理之粉末中。然後加入純水以提供一懸浮液。
d)製備含有摻雜劑之混合粉末與最終熱處理
以與b)相同方式使用濕式珠粒磨機研磨並混合由c)獲得之懸浮液並予以充分地噴霧乾燥，然後注入950℃的電爐中於環境壓力下進行以煅燒2小時，藉此提供以鈦酸鋇為基質之粉末。進行XRF測定莫耳比率，顯示該所得粉末具有如表1所列之相同組成。分析所得以鈦酸鋇為基質之粉末的物理性質並結果列於表2中。藉由布厄特法(Brunauer,Emmett and Teller(BET) method)測定比表面積；使用50,000X放大率的掃描式電子顯微鏡(SEM)圖像測定平均顆粒尺寸，於此，以具有相同面積之圓的直徑計算顆粒尺寸。另外，以使用里特伯爾德(Rietveld)法之多相分析法分析正方形相的比例。
[實施例2至9]
重複實施例1，惟c)之摻雜物改為如表1所述的量添加。其他操作以與實施例1敘述之相同方式進行。分析每個具有不同含量摻雜物之以鈦酸鋇為基質之粉末的物理性質，結果顯示在表2中。
[測試實施例1]
添加碳酸鋇與二氧化矽粉末至由實施例1至9獲得之以鈦酸鋇為基質之粉末中，皆以每100莫耳的以鈦酸鋇為基質之粉末為1莫耳與1.5莫耳的量存在。於作為溶劑之含有體積比率為1：1之乙醇與甲苯的混合溶液存在下，在使用直徑3毫米的二氧化鋯球珠之球磨機中對所得混合粉末進行溼式混合歷時15小時，藉此提供一懸浮液，其固體內含物係充分地分散於其中。接著，添加10重量%之作為以聚乙烯為基質之黏合劑的聚乙烯丁醛至該懸浮液中，基於以鈦酸鋇為基質之粉末的重量。然後，於球磨機中進一步對所得混合物進行濕式混合歷時10小時，並且經由薄帶成形法(tape casting process)形成20微米厚之薄片。所得薄係經層壓與壓縮以提供10毫米寬、10毫米長與1毫米高之模製體。該模製體係在450℃氮氣氛圍下進行脫脂(debining)歷時12小時，並保持在1200℃之具有10-11 部份壓力之氫氣氛圍下歷時2小時，然後在1000℃的50 ppm氧氣氛圍下進行再氧化歷時3小時，藉此提供燒製樣本。施用一鎵銦固溶液糊劑(由Sigma-Aldrich公司取得之99.9+% Gallium-Indium EUTECTUC)至燒製樣本的頂部表面與底部表面，並接著乾燥。之後，測量25℃下的相對介電常數、介電耗損與絕緣電阻。此外，改變溫度之同時測量電容溫度係數。該等電性性質之測試條件與儀器係如表3中所列，測試結果則顯示於表4中。可發現，該以鈦酸鋇為基質之粉末符合根據由EIA定義之陶瓷電容器標準之等級II(高介電常數)X7R標準碼之特性。
雖然已描述本發明某些特定實施態樣，然本技術領域中具有通常知識者可清楚瞭解，在不違背本發明之精神及範疇的情況下，可進行各種變化及修飾，如後附申請專利範圍中所述。
第1圖係本案實施例1獲得之以鈦酸鋇為基質之粉末之SEM照片。

Claims (9)

  1. 一種以鈦酸鋇為基質之粉末，其由化學通式1表示：(Bax R1 r1 R2 r2 )(Tiy R3 r3 R4 r4 )O3 [化學通式1]其中R1 係至少一種選自以下群組之元素：釔(Y)與鑭系元素(lanthanoids)；R2 係至少一種選自以下群組之元素：鎂(Mg)、鈣(Ca)與鍶(Sr)；R3 係包含磷(P)與鈮(Nb)；R4 係至少一種選自以下群組之元素：鋁(Al)、釩(V)、鉻(Cr)、錳(Mn)、鈷(Co)、鋯(Zr)與鉭(Ta)；r1 與r3 係各自獨立為一大於0且等於或小於0.05之實數；r2 與r4 係各自獨立為一大於0且等於或小於0.1之實數；鈮(Nb)與磷(P)之莫耳比率為1：0.1至2.0；以及(x+r1 +r2 )/(y+r3 +r4 )為一0.85至1.15之實數。
  2. 如請求項1之以鈦酸鋇為基質之粉末，其中r1 、r2 、r3 與r4 係各自獨立為一大於0且等於或小於0.03之數值。
  3. 如請求項1之以鈦酸鋇為基質之粉末，其中R1 為釔(Y)，R2 為鎂(Mg)，R3 包含磷(P)與鈮(Nb)，且R4 包含鋁(Al)、釩(V)、鉻(Cr)及錳(Mn)。
  4. 如請求項1之以鈦酸鋇為基質之粉末，其中該以鈦酸鋇為基質之粉末中所含的鋇元素係以每莫耳的鈦元素為0.995至1.005莫耳的量存在。
  5. 如請求項1之以鈦酸鋇為基質之粉末，其包含比例為60至100重量%之正方形相(tetragonal phase)，基於以鈦酸鋇為基質之粉末的總重量。
  6. 如請求項1之以鈦酸鋇為基質之粉末，其具有10至500奈米的顆粒尺寸與2至35平方公尺/克的比表面積。
  7. 如請求項1之以鈦酸鋇為基質之粉末，其於25℃具有1500至3000的相對介電常數。
  8. 如請求項1之以鈦酸鋇為基質之粉末，其於-55℃至125C具有符合方程式1之相對介電常數，εT ：0.85×ε0 εT 1.15×ε0 [方程式1]其中，ε0 為在25℃下之相對介電常數。
  9. 如請求項1至8中任一項之以鈦酸鋇為基質之粉末，其係用於介電材料與陶瓷電子零件中。
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