TWI461384B - Barium titanate - based semiconductor ceramics and PTC thermistors using them - Google Patents

Barium titanate - based semiconductor ceramics and PTC thermistors using them Download PDF

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TWI461384B
TWI461384B TW101132066A TW101132066A TWI461384B TW I461384 B TWI461384 B TW I461384B TW 101132066 A TW101132066 A TW 101132066A TW 101132066 A TW101132066 A TW 101132066A TW I461384 B TWI461384 B TW I461384B
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barium titanate
semiconductor ceramic
based semiconductor
sample
ceramic
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TW201323374A (zh
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Wataru Aoto
Hayato Katsu
Yasuhiro Nabika
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Murata Manufacturing Co
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Description

鈦酸鋇系半導體陶瓷及使用其之PTC熱阻器
本發明係關於一種具有正電阻溫度特性之鈦酸鋇系半導體陶瓷及使用該半導體陶瓷之PTC(Positive Temperature Coefficient，正溫度係數)熱阻器。
作為使用有具有正電阻溫度特性之鈦酸鋇系半導體陶瓷之陶瓷元件，例如已知有如專利文獻1所記載之積層型半導體陶瓷元件。
於該專利文獻1之積層型半導體陶瓷元件中，作為構成半導體陶瓷層之陶瓷，使用有如下半導體陶瓷：於鈦酸鋇系之半導體燒結體中，含有硼氧化物及選自鋇、鍶、鈣、鉛、釔、稀土元素中之至少1種之氧化物，且以硼氧化物中之硼(B)以原子比計為0.001≦B/β≦0.50、0.5≦B/(α-β)≦10.0(其中，α：半導體陶瓷中所含之鋇、鍶、鈣、鉛、釔、稀土元素之總量，β：半導體陶瓷中所含之鈦、錫、鋯、鈮、鎢、銻之總量)之方式添加而成(參照專利文獻1)。
一般認為，該專利文獻1所揭示之半導體陶瓷可以1000℃以下之溫度進行煅燒，且可表現優異之PTC特性。
然而，近年來，推進行動電話或PC(Personal Computer，個人電腦)設備等需要具有正電阻溫度特性之半導體陶瓷之過流保護的裝置之高功能化，而要求對應於高電容/大電流驅動之大電流保護。
於是，具有正電阻溫度特性之半導體陶瓷中為了對應大 電流保護，必需為了減少通常時之電力損耗而具有極低之室溫電阻且具備較高之耐電壓。
然而，低室溫電阻與較高之耐電壓性之確保存在折衷之關係而難以實現該等之並存。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2000-256062號公報
本發明係解決上述課題者，其目的在於提供一種室溫比電阻較低而且耐電壓性能較高之具有正電阻溫度特性的鈦酸鋇系半導體陶瓷及使用有該半導體陶瓷之PTC熱阻器。
為了解決上述課題，本發明之鈦酸鋇系半導體陶瓷之特徵在於：其係通式：BaTiO3 所示之具有正電阻溫度特性者，且Ti位之一部分經Zr取代，且Zr之含有比率處於0.14~0.88 mol%之範圍。
本發明之鈦酸鋇系半導體陶瓷較佳為含有選自由Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu所組成之群中之至少一種稀土元素。
藉由含有上述稀土元素，而可切實地獲得PTC特性優異之鈦酸鋇系半導體陶瓷。
然而，藉由以Nb、Sb、W等除稀土元素以外之元素取代 Ti位(B位)之一部分來代替將稀土元素用作施體，亦可使鈦酸鋇系陶瓷半導體化。
又，本發明之PTC熱阻器之特徵在於：其將上述本發明之鈦酸鋇系半導體陶瓷用作具有正電阻溫度特性之熱阻器坯體。
本發明之第1鈦酸鋇系半導體陶瓷係通式：BaTiO3 所示之具有正電阻溫度特性者，其中以Zr取代Ti位之一部分且使Zr之含有比率為0.14~0.88 mol%之範圍，因此，可確保較高之耐電壓性能並且可降低室溫比電阻。
再者，一般認為，於本發明之鈦酸鋇系半導體陶瓷中可同時實現低比電阻與高耐電壓性能兩者之原因在於：藉由Zr之添加而提高鈦酸鋇系半導體陶瓷於室溫附近之可極化。
又，本發明之PTC熱阻器係將上述本發明之鈦酸鋇系半導體陶瓷用作具有正電阻溫度特性之熱阻器坯體者，因此可提供消耗電極較少、可靠性較高之PTC熱阻器。
以下，例示本發明之實施形態，進一步詳細說明本發明之特徵部分。
[實施形態1]
圖1係表示使用本發明之鈦酸鋇系半導體陶瓷製作之積層型之PTC熱阻器(正特性熱阻器)的前視剖面圖。
該PTC熱阻器1具有如下構造：隔著包含具有正電阻溫 度特性之半導體陶瓷之半導體陶瓷層2積層複數個內部電極3a、3b，且隔著半導體陶瓷層2互為對向之內部電極3a、3b之一者(內部電極3a)向互為對向之端面4a、4b之一者(端面4a)引出，內部電極3a、3b之另一者(內部電極3b)向互為對向之端面4a、4b之另一者(端面4b)引出；積層半導體陶瓷坯體11之端面4a、4b上配設有與內部電極3a、3b導通之外部電極5a、5b。
繼而，對該PTC熱阻器之製造方法進行說明。
首先，作為具有正電阻溫度特性之半導體陶瓷之起始原料，準備BaCO3 、TiO2 、Sm2 O3 、ZrO2 各粉末。
然後，以成為下述式(1)之比率之方式調配BaCO3 、TiO2 、Sm2 O3 各粉末，並且添加特定量之ZrO2 粉末。
(Ba0.998 Sm0.002 )x TiO3 ………(1)
繼而，對調配有各原料之粉末添加純水並與氧化鋯球一起混合粉碎16小時。其後，藉由進行乾燥並於1100℃下預燒2小時而獲得預燒粉。
然後，對該預燒粉添加有機黏合劑、分散劑及水，與氧化鋯球一起混合數小時，製備陶瓷漿料。
然後，利用刮刀法使該陶瓷漿料成形為片狀並使之乾燥，藉此而製作厚度為30 μm之陶瓷生片。
繼而，使Ni金屬粉末與有機黏合劑分散於有機溶劑中，製作內部電極(Ni內部電極)形成用之導電膏。
然後，藉由絲網印刷法於以上述方式製作之陶瓷生片之主面上印刷該導電膏，而獲得內部電極印刷陶瓷生片。印 刷導電膏時，係以燒結後之內部電極之厚度為0.5~2 μm之方式印刷導電膏。
繼而，以整體計內部電極24片、內部電極間距離(即陶瓷生片之厚度)為30 μm之方式積層內部電極印刷陶瓷生片。進而，藉由將未印刷內部電極之陶瓷生片上下各配置5片並進行壓接，而製作壓接積層體。
然後，以於煅燒後可獲得長度2.0 mm、寬度1.2 mm、厚度1.0 mm之元件之方式切割該壓接積層體，而獲得生晶片。
然後，於將該生晶片於大氣環境中、300℃、12小時之條件下進行熱處理而脫脂後，於N2 /H2 之還原環境下以1180℃~1240℃煅燒2小時，而獲得陶瓷燒結坯體。
繼而，對所獲得之陶瓷燒結坯體施加玻璃塗層並於大氣環境中以700℃進行熱處理，藉此而形成用以提高耐環境性或耐候性之玻璃層，並且進行陶瓷燒結坯體之再氧化。
繼而，進行滾筒研磨而使內部電極於陶瓷燒結坯體之兩端面露出，此後藉由以Cr、NiCu、Ag之順序進行濺鍍而於陶瓷燒結坯體之兩端面形成電極。
然後，利用電解鍍敷於該電極之表面使鍍Sn成膜而形成外部電極，藉此而獲得具備如圖1所示之構成的積層型之PTC熱阻器(試樣)。
於該實施形態中，如上所述，為了混合粉碎原料而使用有氧化鋯球，從而使Zr作為來自該氧化鋯球之污染而混入。
因此，於該實施形態中，係如表1所示般以鈦酸鋇系半導體陶瓷中之Zr之含有比率成為0.00 mol%(試樣編號1)~1.00 mol%(試樣編號7)之範圍而添加ZrO2 粉末，但實際之鈦酸鋇系半導體陶瓷中之Zr之含有比率為包含源自來自氧化鋯球之污染之Zr的值。
表1之試樣編號1之試樣係未添加ZrO2 粉末之試樣，但以0.05 mol%之比率含有源自來自氧化鋯球之污染的Zr。即，表1之試樣編號1之試樣中之Zr 0.05 mol%均係源自氧化鋯球者。
又，於添加有ZrO2 粉末之試樣即試樣編號2~7之試樣中，所獲得之鈦酸鋇系半導體陶瓷中之Zr之含量係如表1所示般，為包含源自添加之ZrO2 粉末之Zr與源自來自氧化鋯球之污染之Zr兩者的值。
即，表1中之Zr含量(mol%)之值與源自添加之ZrO2 粉末之Zr(mol%)之值的差係源自污染之Zr。
再者，於該實施形態中，將Zr定量時，係使用ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrometry，感應耦合電漿原子發射光譜法)進行。
然後，對以上述方式製作之試樣編號1~7之試樣研究室溫比電阻(Ω．cm)與耐電壓(V/mm)。將其結果示於表1。
再者，於表1中，試樣編號標註有＊ 之試樣係作為Zr之含有比率脫離本發明之範圍之比較例的試樣。
如表1所示般確認，於Zr之含量為0.14 mol%以下之試樣編號1之試樣的情形時，室溫比電阻較高為21.5 Ω．cm，又，於Zr之含量為0.88 mol%以上且較高為1.07 mol%之試樣編號7之試樣的情形時，室溫比電阻亦較高為25.8 Ω．cm。
相對於上述情況，於在0.14~0.88 mol%之範圍內含有Zr之試樣編號2、3、4、5、6之滿足本發明之要件之試樣的情形時，可一面維持與先前同等之耐電壓一面使室溫比電阻與先前相比降低約40%。
又，關於耐電壓，確認於試樣編號1~7之任一試樣之情形時，均可實現550 V/mm。
根據該結果可知，藉由於0.14~0.88 mol%之範圍內含有Zr並以Zr取代Ti位之一部分，而可同時實現低比電阻、高耐電壓。
再者，於上述實施形態中製作之各試樣中，源自氧化鋯球之Zr之量處於0.04~0.08 mol%之範圍。因此，雖亦取決於製造步驟中之混合粉碎之條件，但可藉由添加自目標之Zr含量中減去源自氧化鋯球之Zr之量而得之量的Zr原料，而製造含有意圖之量之Zr之半導體陶瓷。
於本發明中，可藉由於鈦酸鋇系半導體陶瓷中以特定比率含有Zr而降低室溫比電阻的機制雖未必明確，但推測：藉由使鈦酸鋇系半導體陶瓷中含有Zr，而室溫下之鈦酸鋇系半導體陶瓷之可極化提高，藉此補償晶界所捕獲之界面電荷(降低晶界能量障壁)之效果提高，因此室溫比電阻降低。
此處，將表1之試樣編號1之試樣(Zr：0.05 mol%)與試樣編號6之試樣(Zr：0.88 mol%)的極化值-電場之磁滯曲線示於圖2。
如圖2所示可知，於Zr：0.88 mol%之試樣編號6之試樣之情形時，與Zr：0.05 mol%之試樣編號1之試樣相比殘留極化值上升，可極化提高。此種情況符合如下想法：藉由於特定範圍內含有Zr，而室溫下之可極化提高，藉由降低晶界能量障壁而降低電阻。
再者，於上述實施形態中，作為施體即稀土元素，使用Sm(作為原料之形態為Sm2 O3 粉末)，但亦可使用Y、La、Ce、Pr、Nd、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等其他稀土元素。
又，亦可於通常之範圍內變更施體之種類及量，於此種 情形時亦可獲得相同之效果。
又，即便藉由以Nb、Sb、W等除稀土元素以外之元素取代Ti位(B位)來代替將稀土元素用作施體，亦可實現鈦酸鋇系陶瓷之半導體化，於使用此種鈦酸鋇系陶瓷之情形時，亦可使用本發明而實現低電阻化。
再者，上述實施形態中使用ZrO2 粉末作為Zr原料，但ZrO2 亦可不以粉末之形態而例如以分散於水溶液中之溶膠之形態進行添加，且亦可使用其他形態者。
又，上述實施形態中，以積層型之PTC熱阻器為例進行了說明，但本發明之半導體陶瓷亦可應用於例如具有於板狀之半導體陶瓷坯體之兩主面形成有電極之構造的單板型之PTC熱阻器中。
又，上述實施形態中，藉由以Cr、NiCu、Ag之順序進行濺鍍而形成外部電極，並進而於外部電極之表面藉由電解鍍敷而使鍍Sn成膜，但外部電極之構成並無特別制約，可設為各種構成。
又，本發明之鈦酸鋇系半導體陶瓷及PTC熱阻器於其他方面亦不限定於上述實施形態，可於本發明之範圍內施加各種應用、變形。
1‧‧‧PTC熱阻器
2‧‧‧半導體陶瓷層
3a、3b‧‧‧內部電極
4a、4b‧‧‧積層半導體陶瓷坯體之互為對向之端面
5a、5b‧‧‧外部電極
11‧‧‧積層半導體陶瓷坯體
圖1係表示本發明之一實施形態(實施形態1)之PTC熱阻器之構成的前視剖面圖。
圖2係表示表1之試樣編號1之試樣與試樣編號6之試樣之極化值-電場之磁滯曲線的圖。
1‧‧‧PTC熱阻器
2‧‧‧半導體陶瓷層
3a、3b‧‧‧內部電極
4a、4b‧‧‧積層半導體陶瓷坯體之互為對向之端面
5a、5b‧‧‧外部電極
11‧‧‧積層半導體陶瓷坯體

Claims (3)

  1. 一種鈦酸鋇系半導體陶瓷，其特徵在於：其係通式：BaTiO3 所示之具有正電阻溫度特性者，並且Ti位之一部分經Zr取代，且Zr之含有比率處於0.14~0.88mol%之範圍、惟不包含0.2~0.88mol%之範圍。
  2. 如請求項1之鈦酸鋇系半導體陶瓷，其含有選自由Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu所組成之群中之至少一種稀土元素。
  3. 一種PTC熱阻器，其特徵在於：其將如請求項1或2之鈦酸鋇系半導體陶瓷用作具有正電阻溫度特性之熱阻器坯體。
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