TWI648887B - 摻雜Ce之PZT系壓電體膜 - Google Patents
摻雜Ce之PZT系壓電體膜 Download PDFInfo
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- TWI648887B TWI648887B TW104109382A TW104109382A TWI648887B TW I648887 B TWI648887 B TW I648887B TW 104109382 A TW104109382 A TW 104109382A TW 104109382 A TW104109382 A TW 104109382A TW I648887 B TWI648887 B TW I648887B
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- film
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- piezoelectric film
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- 239000000203 mixture Substances 0.000 description 51
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Abstract
此摻雜Ce之PZT系壓電體膜,其係由一般式:PbzCexZryTi1-yO3表示之Ce摻雜之複合金屬氧化物所構成。又,上述一般式中之x、y及z為分別滿足0.005≦x≦0.05、0.40≦y≦0.55、及0.95≦z≦1.15。此外,上述摻雜Ce之PZT系壓電體膜之極化量之磁滯由其中心,往負側位移4kV/cm以上為佳。
Description
本發明係有關形成壓電元件、IPD(Integrated Passive Device)、焦電元件(Pyroelectric Element)、重力感測器(gyrosensor)、振動發電元件、致動器(actuator)等所用的摻雜Ce之PZT系壓電體膜。
本案係依據於2014年3月27日在日本提出申請之特願2014-065632號主張優先權,在此援用其內容。
專利文獻1揭示形成由PLZT、PZT及PT所成群選出之1種強介電體薄膜用之強介電體薄膜形成用組成物為採用在一般式為(PbxLay)(ZrzTi(1-z))O3表示之複合金屬氧化物A中混合有含有Ce之複合金屬氧化物B的混合複合金屬氧化物之形態的薄膜形成用的液狀組成物。前述液狀組成物係由構成複合金屬氧化物A用之原料及構成複合金屬氧化物B用之原料為以提供上述一般式表示之金屬原子比之比例溶解於有機溶劑中之有機金屬化合物溶液所構成的強介電體薄膜形成用組成物。此強介電體
薄膜形成用組成物係上述一般式中的x、y及z分別滿足0.9<x<1.3、0≦y<0.1及0≦z<0.9。
使用如此構成之強介電體薄膜形成用組成物,形成強介電體薄膜時,可以簡便的手法得到具有與一般的強介電體薄膜相同程度之比介電率,且低的漏電流密度之適合高容量密度之薄膜電容器用途的強介電體薄膜。因此,設為與一般的強介電體薄膜相同程度之漏電流密度時,可進一步薄膜化,可得到更高的比介電率。
另外,藉由溶膠凝膠法形成以PbZrxTi1-xO3表示的PZT薄膜中,以添加Nb,提高壓電特性已為人知(例如參照非專利文獻1)。非專利文獻1研究對於在藉由化學溶液沈積(CSD:Chemical Solution Deposition)法所調製之PbTiO3之薄片層上所成長之{100}配向之PZT薄膜中,摻雜Nb時所產生的效果。具體而言,研究配向於{100}之厚度1μm的Pb1.1Zr0.52Ti0.48O3薄膜上,在0~4原子%之範圍內摻雜Nb時的效果。結果起因於厚度數nm之薄的Pb1.05TiO3之薄片層之結合,結果所有的膜可得到97%之高的{100}配向。又,整體上,PZT薄膜之最大極化、殘留極化、直角度及飽和保持力隨著Nb之摻雜等級(level)而減少。又,被摻雜有3%之Nb的PZT薄膜,相較於具有其他摻雜等級之彼等的薄膜,顯示高5~15%、最高12.9C/cm2的壓電常數-e31.f。此外得知介電率對於Nb之摻雜等級,不會受到很大的影響。
〔專利文獻1〕日本特開2010-206151號公報(請求項1、段落[0022])
〔非專利文獻1〕Jian Zhong et al. “Effect of Nb Doping on Highly[100]-Textured PZT Films Grown on CSD-Prepared PbTiO3 Seed Layers”,Integrated Ferroelectrics,130 (2011) 1-11。
但是上述專利文獻1所示之強介電體薄膜形成用組成物,無法提高使用此組成物而形成之強介電體薄膜的壓電常數,有無法降低介電率之不理想的情形。又,上述非專利文獻1所示藉由Nb添加提高PZT薄膜之壓電特性的技術係使用濕式法、亦即將溶膠凝膠液以CSD法形成摻雜有Nb的PZT薄膜(PNbZT薄膜)時,提高壓電常數,但無法降低介電率,不適合感測器或能量攫取器(Energy harvester)之應用。又,上述專利文獻1所示之強介電體薄膜形成用組成物係使用此組成物形成強介電體薄膜隨後,無法作為壓電體使用,為了作為重力感測器等之裝置使用時,外加高的電壓來使用,故必須極化處理。又,即使進行了極化處理,其後之迴焊製程(Reflow
Process)等之熱處理時,有可能脫極化的疑慮,也有極化之安定性低的問題點。
本發明之第1目的係提供藉由摻雜Ce,可提高壓電體膜之壓電常數,可降低介電率之摻雜Ce之PZT系壓電體膜。本發明之第2目的係提供藉由Ce之摻雜及控制膜配向性,在成膜隨後,極化方向一致,藉此可提高裝置化後之極化的安定性,藉由Ce之摻雜及控制膜配向性,在成膜隨後,極化方向更一致,藉此可進一步提高極化的安定性的摻雜Ce之PZT系壓電體膜。
本發明之第1觀點係一種摻雜Ce之PZT系壓電體膜,其係由一般式:PbzCexZryTi1-yO3表示之Ce摻雜之複合金屬氧化物所構成,前述一般式中之x、y及z為分別滿足0.005≦x≦0.05、0.40≦y≦0.55、及0.95≦z≦1.15。
本發明之第2觀點係依據第1觀點之PZT系壓電體膜的發明,其中進一步極化量之磁滯由其中心,往負側位移4kV/cm以上為佳。
本發明之第3觀點係依據第1或2觀點之PZT系壓電體膜的發明,其中進一步藉由X光繞射之(100)配向度為80%以上為佳。
本發明之第4觀點係依據第1~3觀點中之任一之PZT系壓電體膜的發明,其中進一步膜厚為1000nm
以上且5000nm以下為佳。
本發明之第1觀點的PZT系壓電體膜係藉由Ce之摻雜,可提高壓電常數,故可得到更大的變位,同時可降低介電率,故作為感測器使用時,利益變大。此乃是藉由對於下部電極之法線方向,配向於(100)/(001)之膜摻雜Ce,電域(domain)被釘住(pinning),在成膜隨後,極化方向一致朝下的緣故。此結果,本發明之摻雜Ce之PZT系壓電體膜,藉由在正側外加電壓,在不會極化,而可作為裝置產生作動。又,本發明之摻雜Ce之PZT系壓電體膜作為重力感測器等使用的情形,不需要極化處理,可減低製造步驟。
本發明之第3觀點的PZT系壓電體膜係藉由以X光繞射之(100)配向度設定為80%以上,成膜隨後,可形成極化方向更一致的壓電體膜,可更提高極化之安定性。具體而言,被控制於(100)面優先結晶配向的LNO膜上,藉由以CSD法形成摻雜Ce之PZT系壓電體膜,此壓電體膜之配向被控制於(100)面,成膜隨後,可形成極化方向更一致的壓電體膜,可進一步提高極化之安定性。
11‧‧‧壓電體膜
11a‧‧‧分子
12‧‧‧電極
13‧‧‧電極
14‧‧‧直流電壓
〔圖1〕表示使用本發明實施形態之摻雜Ce之PZT系壓電體膜形成用之組成物的液,成膜時未發生空隙之機構的簡圖。
〔圖2〕表示使用習知例之PZT系壓電體膜形成用之組成物的液,成膜時發生空隙之機構的簡圖。
〔圖3〕表示對本發明實施形態之摻雜Ce之PZT系壓電體膜,外加電壓時之壓電體膜之舉動的簡圖。
〔圖4〕表示實施例15及比較例3之壓電體膜的磁滯曲線的圖。
其次,依據圖面說明實施本發明之形態。本發明之摻雜Ce之PZT系壓電體膜係由一般式:PbzCexZryTi1-yO3表示之Ce摻雜之複合金屬氧化物所構成。上述一般式中之x、y及z為分別滿足0.005≦x≦0.05、0.40≦y≦0.55、及0.95≦z≦1.15。此摻雜Ce之PZT系壓電體膜係在鋯鈦酸鉛(PZT)等之具有含有Pb之鈣鈦礦結構的複合金屬氧化物中,添加有Ce元素的壓電體膜。又,形成上述摻雜Ce之PZT系壓電體膜用之組成物中所含之摻雜Ce之PZT系前驅物係形成後之壓電體膜中,構成上述複合金屬氧化物等用的原料,以提供所望之金屬原子比的比例含有此等原料。具體而言,上述組成物中之金屬原子比(Pb:Ce:Zr:Ti)滿足(1.00~1.20):(
0.005~0.05):(0.40~0.55):(0.60~0.45),且以Zr與Ti之金屬原子比之合計比例成為1的比例,含有PZT系前驅物。在此,將一般式中之x限定為0.005≦x≦0.05之範圍內係因未達0.005時,成膜隨後之壓電體膜之極化方向無法充分一致,超過0.05時,壓電體膜容易產生龜裂的緣故。又,一般式中之y限定為0.40≦y≦0.55之範圍內係因未達0.40時,壓電體之壓電常數未變得充分大,超過0.55時,成膜隨後之壓電體膜之極化方向未一致的緣故。此外,一般式中之z限定為0.95≦z≦1.15之範圍內係因未達0.95時,膜中含有多量焦綠石(pyrochlore)相,壓電特性等之電特性明顯降低,超過1.15時,燒成後之膜中,PbO大量殘留,漏電流增大,膜之電的信賴性降低,亦即,膜中容易殘留過剩的鉛,漏電特性或絕緣特性劣化的緣故。又,一般式中之x、y及z係分別滿足0.01≦x≦0.03、0.50≦y≦0.52及0.99≦z≦1.05為佳。
上述摻雜Ce之PZT系壓電體膜之極化量之磁滯由其中心,往負側位移4kV/cm以上較佳,在9~15V/cm之範圍內位移更佳。
在此,中心係指偏移(bias)0。磁滯之中心係以X軸為電場(kV/cm)、以Y軸為極化量(μC/cm2)之曲線中之正側、負側之矯頑電場的絕對值,作為Ec+、Ec-時,以下述式表示。由以下磁滯中心之偏移(bias)0的偏移作為磁滯的位移。
磁滯之中心=Ec+-{(Ec++Ec-)/2}
又,上述摻雜Ce之PZT系壓電體膜之藉由X光繞射之(100)配向度為80%以上,更佳為95%以上。又,(100)配向度之上限值為100%。
此外,上述摻雜Ce之PZT系壓電體膜之膜厚,較佳為1000nm以上且5000nm以下,更佳為2000nm以上且3000nm以下。
在此,將摻雜Ce之PZT系壓電體膜之極化量之磁滯的位移量限定為由其中心至負側限定為4kV/cm以上係因未達4kV/cm時,極化方向未充分一致的緣故。又,摻雜Ce之PZT系壓電體膜之藉由X光繞射之(100)配向度係定為80%以上係因未達80%時,未見充分之磁滯之位移的緣故。此外,摻雜Ce之PZT系壓電體膜之膜厚限定為1000nm以上且5000nm以下之範圍內係因未達1000nm時,無法得到充分之壓電特性,且超過5000nm時,生產性降低的緣故。
摻雜Ce之PZT系前驅物係有機基經由其氧或氮原子,與Pb、Ce、Zr及Ti之各金屬原子鍵結的化合物,適合作為各金屬源(Pb源、Ce源、Zr源及Ti源)使用。例如,可例示由金屬醇鹽(metal alkoxide)、金屬二醇錯合物、金屬三醇錯合物、金屬羧酸鹽、金屬β-二酮酸鹽錯合物、金屬β-二酮酸酯錯合物、金屬β-亞胺基酮錯合物、及金屬胺基錯合物所成群選出之1種或2種以上。特佳的化合物為金屬醇鹽、其部分水解物、有機酸鹽。
具體而言,Pb化合物可列舉乙酸鉛:Pb(OAc)2等之乙酸鹽或、二異丙醇鉛:Pb(OiPr)2等之醇鹽。又,Ce化合物可列舉2-乙基己酸鈰、2-乙基丁酸鈰等之有機酸鹽或三n-丁醇鈰、三乙醇鈰等之醇鹽或三(三乙醯丙酮)鈰等之金屬β-二酮酸鹽(diketonate)錯合物。又,Ti化合物可列舉四乙醇鈦:Ti(OEt)4、四異丙醇鈦:Ti(OiPr)4、四n-丁醇鈦:Ti(OnBu)4、四異丁醇鈦:Ti(OiBu)4、四t-丁醇鈦:Ti(OtBu)4、二甲氧基二異丙醇鈦:Ti(OMe)2(OiPr)2等之醇鹽。此外,Zr化合物較佳為與上述Ti化合物同樣的醇鹽類,亦即,四乙醇鋯:Zr(OEt)4、四異丙醇鋯:Zr(OiPr)4、四n-丁醇鋯:Zr(OnBu)4、四異丁醇鋯:Zr(OiBu)4、四t-丁醇鋯:Zr(OtBu)4、二甲氧基二異丙醇鋯:Zr(OMe)2(OiPr)2等。金屬醇鹽可直接使用,但是為了促進分解,也可使用其部分水解物。
形成上述摻雜Ce之PZT系壓電體膜用之組成物,除上述摻雜Ce之PZT系前驅物外,含有二醇與聚乙烯基吡咯烷酮或聚乙二醇為佳。
組成物中所含之二醇係成為組成物之溶劑的成分。具體而言,可列舉丙二醇、乙二醇或1,3-丙二醇等。其中,較佳為丙二醇或乙二醇。藉由以二醇作為必須的溶劑成分,可提高組成物之保存安定性。又,聚乙烯基吡咯烷酮(PVP)或聚乙二醇可作為龜裂抑制材來添加。
又,形成上述摻雜Ce之PZT系壓電體膜用之組成物
可含有直鏈狀單醇。直鏈狀單醇特別是碳數為6以上12以下之直鏈狀單醇,因與PZT前驅物質之親和性低,且蒸汽壓低,故較佳。
又,其他的溶劑,可列舉羧酸、醇(例如乙醇或1-丁醇、二醇以外的多元醇)、酯、酮類(例如丙酮、甲基乙基酮)、醚類(例如二甲基醚、二乙基醚)、環烷類(例如環己烷、環己醇)、芳香族系(例如苯、甲苯、二甲苯)、其他四氫呋喃等,也可為在二醇中再添加有此等之1種或2種以上的混合溶劑。
羧酸具體而言,使用n-丁酸、α-甲基丁酸、i-戊酸、2-乙基丁酸、2,2-二甲基丁酸、3,3-二甲基丁酸、2,3-二甲基丁酸、3-甲基戊酸(pentanoic acid)、4-甲基戊酸、2-乙基戊酸、3-乙基戊酸、2,2-二甲基戊酸、3,3-二甲基戊酸、2,3-二甲基戊酸、2-乙基己酸、3-乙基己酸為佳。
又,酯使用乙酸乙酯、乙酸丙酯、乙酸n-丁酯、乙酸sec-丁酯、乙酸tert-丁酯、乙酸異丁酯、乙酸n-戊酯、乙酸sec-戊酯、乙酸tert-戊酯、乙酸異戊酯為佳,醇使用1-丙醇、2-丙醇、1-丁醇、2-丁醇、異-丁基醇、1-戊醇、2-戊醇、2-甲基-2-戊醇、2-甲氧基乙醇為佳。
又,上述成分以外,必要時,也可以(安定化劑分子數)/(金屬原子數)為0.2~3左右添加下述安定化劑,例如有β-二酮類(例如,乙醯基丙酮、七氟丁醯基三甲基乙醯基甲烷、二(三甲基乙醯基)甲烷、三氟乙醯
基丙酮、苯甲醯基丙酮等)、β-酮酸類(例如,乙醯乙酸、丙醯基乙酸、苯甲醯基乙酸等)、β-酮酸酯類(例如,上述酮酸之甲酯、丙酯、丁酯等之低級烷基酯類)、含氧酸類(例如,乳酸、乙二醇酸、α-羥基丁酸、水楊酸等)、上述含氧酸之低級烷基酯類、羥基酮類(例如,二丙酮醇、3-羥基丁酮等)、二醇、三醇、高級羧酸、烷醇胺類(例如,二乙醇胺、三乙醇胺、單乙醇胺)、多價胺等。其中,安定化劑較佳為β-二酮類之乙醯基丙酮。
接著說明本發明之摻雜Ce之PZT系壓電體膜形成用組成物之製造方法。首先,分別準備上述Pb化合物等之PZT系前驅物,使成為提供上述所望之金屬原子比的比例量秤此等前驅物。將量秤之上述PZT系前驅物與二醇投入反應容器內,進行混合,較佳為於氮環境中,於130~175℃之溫度下,迴流0.5~3小時使反應調製合成液。迴流後,藉由常壓蒸餾或減壓蒸餾的方法,進行脫溶劑為佳。又,添加乙醯基丙酮等之安定化劑的情形,將此等安定化劑添加於脫溶劑後之合成液中,在氮環境中,於130~175℃之溫度下,進行迴流0.5~5小時為佳。然後,藉由在室溫下,放置冷卻,將合成液冷卻至室溫(25℃左右)。
冷卻後之合成液中,添加直鏈狀單醇,調製溶膠凝膠液。此時組成物100質量%中所佔之PZT系前驅物的濃度,以氧化物濃度表示,調整為17~35質量%,二醇之濃度調整為16~56質量%。又,上述溶膠凝膠液中,
添加二醇以外之溶劑為佳。其次,將上述溶膠凝膠液於特定之環境中,例如氮環境中,於100~175℃之溫度下再迴流0.5~10小時。
而且,添加相對於PZT系前驅物1莫耳之比例,以單體換算成為0.01~0.25莫耳之量的聚乙烯基吡咯烷酮或聚乙二醇,藉由攪拌使均勻分散。藉此,可得到本發明之摻雜Ce之PZT系壓電體膜形成用組成物。
在此,摻雜Ce之PZT系前驅物1莫耳係表示前驅物質所含之PbzCexZryTi1-yO3為1莫耳。
又,單體換算係指以構成聚合物之單體之分子量為基準(1莫耳),換算聚合物之分子量所得的值。
又,組成物之調製後,藉由過濾處理等除去顆粒,粒徑0.5μm以上(特別是0.3μm以上,尤其是0.2μm以上)之顆粒的個數,在組成物1ml中,為50個以下者為佳。組成物中之粒徑0.5μm以上之顆粒的個數,在組成物1ml中超過50個時,成為長期保存安定性差者。此組成物中之粒徑0.5μm以上之顆粒之個數,越少越佳,特別是組成物1ml中,30個以下為佳。
又,藉由以過濾處理等除去顆粒,組成物內之0.2μm以上之顆粒被除去的狀態為佳。此外,組成物中之顆粒之個數之測量係使用光散射式顆粒計數器。
為了將顆粒之個數調整成為上述範圍內後的組成物進行處理的方法無特別限定,例如可列舉以下的方法。第1方法係使用市售之0.2μm孔徑之薄膜過濾器,以
注射筒壓送的過濾法。第2方法為組合有市售之0.05μm孔徑之薄膜過濾器與加壓槽的加壓過濾法。第3方法為組合有上述第2方法使用的過濾器與溶液循環槽的循環過濾法。
不論何種方法,也因組成物之壓送壓力,藉由過濾器之顆粒捕捉率而不同。壓力越低,捕捉率變得越高乃是一般為人所知,特別是為了以第1方法或第2方法,實現粒徑0.5μm以上之顆粒之個數在組成物1ml中為50個以下的條件時,使組成物以低壓且非常緩慢通過過濾器為佳。
其次,說明本發明之摻雜Ce之PZT系壓電體膜之形成方法。此形成方法係藉由溶膠凝膠法之壓電體膜的形成方法,原料溶液使用上述本發明之摻雜Ce之PZT系壓電體膜形成用組成物。
首先,在基板上塗佈上述摻雜Ce之PZT系壓電體膜形成用組成物,形成具有所望之厚度的塗膜(凝膠膜)。塗佈法無特別限定,可列舉旋轉塗佈法、浸漬塗佈、LSMCD(Liquid Source Misted Chemical Deposition)法或靜電噴霧法等。形成壓電體膜的基板,可使用形成有配向控制膜或下部電極的矽基板或藍寶石基板等之耐熱性基板。形成於基板上的配向控制膜係藉由被控制於(100)面優先結晶配向的LNO膜(LaNiO3膜)等而形成。又,形成於基板上的下部電極係藉由Pt、TiOX、Ir、Ru等之具有導電性,且不會與壓電體膜反應的材料而形成。例
如,可使下部電極由基板側依序形成TiOX膜及Pt膜之2層構造。上述TiOX膜之具體例,可列舉TiO2膜。此外,基板使用矽基板的情形,可在此基板表面形成SiO2膜。
於基板上形成塗膜後,將此塗膜進行煅燒,再進行燒成使結晶化。煅燒係使用加熱板或急速加熱處理(RTA)等,以特定之條件進行。煅燒係除去溶劑,同時為了將金屬化合物進行熱分解或水解,轉化成複合氧化物而進行煅燒,因此,在空氣中,氧化環境中,或含水蒸氣環境中進行為佳。即使空氣中之加熱,藉由空氣中的濕氣,可充分地確保水解所需的水分。又,煅燒前,特別是為了除去低沸點溶劑或經吸附的水分子,因此,可使用加熱板等,於70~90℃之溫度下,進行0.5~5分鐘低溫加熱。
燒成係將煅燒後之塗膜以結晶化溫度以上的溫度進行燒成,為了使結晶化的步驟,藉此,可得到壓電體膜。此結晶化步驟之燒成環境,較佳為O2、N2、Ar、N2O或H2等或此等之混合氣體等。燒成係在600~700℃下進行1~5分鐘左右。燒成也可以急速加熱處理(RTA)來進行。以急速加熱處理(RTA)燒成的情形,其昇溫速度設定為2.5~100℃/秒較佳。
又,形成上述摻雜Ce之PZT系壓電體膜的步驟係在PZT系壓電體膜形成用組成物中含有1-辛醇等之直鏈狀單醇時,如圖1(a)~(e)所示,使凝膠膜內部之液體以毛細管力上升至表面附近,藉由將凝膠進行乾燥.
燒成,可形成內部無空隙之緻密的結晶膜。具體而言,如圖1(a)~(b)所示,藉由毛細管力使1-辛醇等之直鏈狀單醇蒸發,如圖1(c)所示,形成適合第1煅燒膜的間隙。再將第1煅燒膜進行加熱時,如圖1(d)所示,可得到其他的溶劑成分(丙二醇或聚乙烯基吡咯烷酮)進行氣體化,通過上述間隙快速蒸發的膜。因此,如圖1(e)所示,可得到緻密的結晶膜。
另外,如圖2(a)~(d)所示,不存在著如1-辛醇,藉由毛細管力上升至凝膠膜表面,進行蒸發的溶劑的情形,如圖2(a)~(c)所示,在煅燒膜之內部未形成間隙,煅燒膜內生成類鑽碳(diamond-like carbon)(圖2(d))。此類鑽碳成為在燒成後,結晶膜內發生空隙(圖2(e))的原因。
藉由以上的步驟可得到摻雜Ce之PZT系壓電體膜。此壓電體膜係藉由摻雜Ce,可提高壓電常數,故可得到更大的變位,同時可降低介電率,故作為感測器使用的情形,利益變大。因此,本發明之摻雜Ce之PZT系壓電體膜,可適合作為壓電元件、IPD、焦電元件、重力感測器、振動發電元件、致動器(actuator)等之複合電子零件中之構成材料(電極)使用。
此外,藉由在PZT附近添加Ce,電域(domain)被釘住(pinninig),磁滯由其中心位移至負側,可得到壓電體膜全體為成膜隨後,極化一致朝下的膜。此結果,本發明之摻雜Ce之PZT系壓電體膜,藉由
在正側外加電壓,可未極化,作為裝置作動。又,本發明之摻雜Ce之PZT系壓電體膜作為重力感測器等使用的情形,不需要極化處理,故可減低製造步驟。此外,本發明之摻雜Ce之PZT系壓電體膜係因經過600~700℃之高溫燒成來製作,故使用壓電體膜之裝置即使因回焊方式之硬焊而暴露於高溫,也不會失去壓電特性。
具體而言,如圖3所示,在分別配置於壓電體膜11之兩面的電極12,13間,外加直流電壓14之前,保持壓電體膜11中之各分子11a進行極化後的狀態(圖3(a))。又,被控制於(100)面優先結晶配向的LNO膜上,以CSD法形成摻雜Ce之PZT系壓電體膜,此壓電體膜之配向被控制於(100)面,成膜隨後可形成極化方向一致的壓電體膜。此結果,可更提高極化之安定性,故形成於上述LNO膜上之上述壓電體膜可適用於重力感測器等。此外,如圖3(b)所示,在分別配置於壓電體膜11之兩面的電極12,13間,外加電壓時,壓電體膜11在外加電壓之方向延伸,此電壓設定為零時,在外加電壓之方向延伸的壓電體膜11,產生收縮回復原狀(圖3(a)),因此可適用於壓電元件等。而此實施形態,可列舉具有在外加電壓之方向延伸之特性的壓電體膜,但是也可為具有與外加電壓之方向正交之方向延伸之特性的壓電體膜。
其次,詳細說明本發明之實施例及比較例。
首先,在反應容器中置入乙酸鉛三水合物(Pb源)與丙二醇(二醇),在氮環境中,於150℃之溫度下迴流1小時後,再於此反應容器中添加2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)、四異丙醇鈦(Ti源)及乙醯基丙酮(安定化劑),藉由氮環境中,於150℃之溫度下迴流1小時使反應,調製合成液。在此,使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.005:0.40:0.60,來量秤上述乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)。又,相對於摻雜Ce之PZT系前驅物100質量%,添加30質量%之丙二醇(二醇),相對於摻雜Ce之PZT系前驅物1莫耳,添加2莫耳之乙醯基丙酮(安定化劑)。接著,進行減壓蒸餾除去不要的溶劑,使上述合成液100質量%中所佔之摻雜Ce之PZT系前驅物之濃度,以氧化物濃度表示成為35%。在此,合成液中所佔之摻雜Ce之PZT系前驅物之濃度中的氧化物濃度係假設合成液所含之所有金屬原子成為目的之氧化物而算出之合成液100質量%中所佔之金屬氧化物的濃度。
其次,藉由將合成液在室溫放置冷卻,冷卻至25℃。藉由在此合成液中添加1-辛醇(碳數8之直鏈狀單醇)與乙醇(溶劑),得到溶膠凝膠液100質量%中
所佔之摻雜Ce之PZT系前驅物之濃度,以氧化物濃度表示為25質量%的溶膠凝膠液。換言之,在合成液中添加1-辛醇(碳數8之直鏈狀單醇)與乙醇(溶劑),直到成為上述目的濃度為止。在此,溶膠凝膠液中所佔之摻雜Ce之PZT系前驅物之濃度中之氧化物濃度係假設溶膠凝膠液中所含之所有金屬原子成為目的之氧化物而算出之溶膠凝膠液100質量%中所佔之金屬氧化物的濃度。
其次,在上述溶膠凝膠液中,相對於上述摻雜Ce之PZT系前驅物1莫耳,添加0.02莫耳的聚乙烯基吡咯烷酮(PVP:k值=30),藉由於室溫(25℃)下攪拌24小時,得到摻雜Ce之PZT系壓電體膜形成用的組成物。此組成物係使用市售之0.05μm孔徑之薄膜過濾器,藉由以注射筒壓送過濾,粒徑0.5μm以上之顆粒個數係各自在溶液1ml中為1個。又,上述組成物100質量%中所佔之摻雜Ce之PZT系前驅物的濃度,以氧化物濃度表示為25質量%。又,1-辛醇(碳數8之直鏈狀單醇)係相對於上述組成物100質量%,含有4質量%。此外,丙二醇(二醇)係相對於上述組成物100質量%,含有30質量%。
上述k值係指與分子量相關的黏性特性值,藉由毛細管黏度計所測量的相對黏度值(25℃),使用下述Fikentscher之式子算出的值。
k值=(1.5 logηrel-1)/(0.15+0.003c)+(300clogηrel+(c+1.5clogηrel)2)1/2/(0.15c+0.003c2)
上述式中,「ηrel」表示聚乙烯基吡咯烷酮水溶液相對於水的相對黏度,「c」表示聚乙烯基吡咯烷酮水溶液中之聚乙烯基吡咯烷酮濃度(質量%)。
使所得之組成物滴下至SiO2膜、TiO2膜、Pt膜及LNO膜(配向控制膜:被控制於(100)面優先結晶配向的LaNiO3)由下朝上,依序被層合,且裝設於旋轉塗佈器上之矽基板之最上層的LNO膜上,藉由以2100rpm之旋轉速度,進行60秒鐘旋轉塗佈,在上述LNO膜上形成塗膜(凝膠膜)。將形成有此塗膜(凝膠膜)之矽基板,使用加熱板在65℃加熱保持(乾燥)2分鐘,除去低沸點溶劑或水後,藉由以300℃之加熱板加熱保持(第一段煅燒)5分鐘,加熱分解凝膠膜,再以450℃之加熱板,加熱保持(第二段煅燒)5分鐘,除去殘存於凝膠膜中之有機物或吸附水。如此,得到厚度200nm之煅燒膜(摻雜Ce之PZT非晶質膜)。與上述同樣的操作重複2次,得到厚度400nm之煅燒膜。此外,將形成有上述厚度400nm之煅燒膜的矽基板,藉由急速加熱處理(RTA),在氧環境中,於700℃保持1分鐘,進行燒成。此時之昇溫速度為10℃/秒。如此在LNO膜(配向控制膜)上形成厚度400nm之摻雜Ce之PZT膜。藉由上述操作重複5次,製作最終膜厚為2000nm的摻雜Ce之PZT系壓電體膜。又,壓電體膜之膜厚係藉由SEM(日立公司製:S4300)測量壓電體膜之剖面的厚度(總厚)。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為
1.15:0.005:0.40:0.60,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.40:0.60,以一般式:Pb1.01Ce0.005Zr0.40Ti0.60O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.005:0.50:0.50,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.50:0.50,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.50:0.50,以一般式:Pb1.01Ce0.005Zr0.50Ti0.50O3表示。
除了摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.005:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.52:
0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.52:0.48,以一般式:Pb1.01Ce0.005Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.005:0.55:0.45,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.55:0.45,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.55:0.45,以一般式:Pb1.01Ce0.005Zr0.55Ti0.45O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.01:0.40:0.60,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.40:
0.60,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.40:0.60,以一般式:Pb1.01Ce0.005Zr0.40Ti0.60O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.01:0.50:0.50,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.50:0.50,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.50:0.50,以一般式:Pb1.01Ce0.005Zr0.50Ti0.50O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.52:
0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.52:0.48,以一般式:Pb1.01Ce0.005Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.05:0.55:0.45,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.55:0.45,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.01:0.005:0.55:0.45,以一般式:Pb1.01Ce0.005Zr0.55Ti0.45O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.40:0.60,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.40:
0.60,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.03:0.005:0.40:0.60,以一般式:Pb1.03Ce0.005Zr0.40Ti0.60O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.50:0.50,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.50:0.50,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.03:0.005:0.50:0.50,以一般式:Pb1.03Ce0.005Zr0.50Ti0.50O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.52:
0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.03:0.005:0.52:0.48,以一般式:Pb1.03Ce0.005Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.55:0.45,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.55:0.45,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.03:0.005:0.55:0.45,以一般式:Pb1.03Ce0.005Zr0.55Ti0.45O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.05:0.40:0.60,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.40:
0.60,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.04:0.005:0.40:0.60,以一般式:Pb1.04Ce0.005Zr0.40Ti0.60O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.05:0.50:0.50,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.50:0.50,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.04:0.005:0.50:0.50,以一般式:Pb1.04Ce0.005Zr0.50Ti0.50O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.05:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.52:
0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.04:0.005:0.52:0.48,以一般式:Pb1.04Ce0.005Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.05:0.55:0.45,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.005:0.55:0.45,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.04:0.005:0.55:0.45,以一般式:Pb1.04Ce0.005Zr0.55Ti0.45O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.08:0.03:0.52:0.48,來量秤量乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源),相對於摻雜Ce之PZT系前驅物1莫耳而言,聚乙烯基吡咯烷酮(PVP)之混合比例為0.05莫耳,此外,相對於組成物100質量%而
言,丙二醇(二醇)之混合比例設為30質量%外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.08:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為0.95:0.03:0.52:0.48,以一般式:Pb0.95Ce0.03Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.12:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例17同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.12:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為0.99:0.03:0.52:0.48,以一般式:Pb0.99Ce0.03Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.18:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇
鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例17同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.18:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.05:0.03:0.52:0.48,以一般式:Pb1.05Ce0.03Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.18:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例17同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.18:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.52:0.48,以一般式:Pb1.15Ce0.03Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.004:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇
鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.004:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.00:0.004:0.52:0.48,以一般式:PbCe0.004Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.06:0.40:0.60,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.06:0.40:0.60,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.00:0.06:0.40:0.60,以一般式:PbCe0.06Zr0.40Ti0.60O3表示。
除了未添加2-乙基己酸鈰(Ce源),亦即,使PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙
基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.02:0:0.52:0.48,以一般式:Pb1.02Zr0.52Ti0.48O3表示。
除了使PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.38:0.62,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.03:0.38:0.62,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.02:0.03:0.38:0.62,以一般式:Pb1.02Ce0.03Zr0.38Ti0.62O3表示。
除了使PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.15:0.03:0.57:0.43,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例1同樣形成PZT
系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.15:0.03:0.57:0.43,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.02:0.03:0.57:0.43,以一般式:Pb1.02Ce0.03Zr0.57Ti0.43O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.07:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例17同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)為1.07:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為0.94:0.03:0.52:0.48,以一般式:Pb0.94Ce0.03Zr0.52Ti0.48O3表示。
除了使摻雜Ce之PZT系前驅物之金屬原子比(Pb:Ce:Zr:Ti)成為1.29:0.03:0.52:0.48,來量秤乙酸鉛三水合物(Pb源)、2-乙基己酸鈰(Ce源)、四丁醇鋯(Zr源)及四異丙醇鈦(Ti源)外,與實施例17同樣形成摻雜Ce之PZT系壓電體膜。又,PZT系前驅物之金
屬原子比(Pb:Ce:Zr:Ti)為1.29:0.03:0.52:0.48,但是Pb之一部份因燒成而蒸發飛散,燒成後之摻雜Ce之PZT系壓電體膜係金屬原子比(Pb:Ce:Zr:Ti)成為1.16:0.03:0.52:0.48,以一般式:Pb1.16Ce0.03Zr0.52Ti0.48O3表示。
對於以實施例1~20及比較例1~7形成的摻雜Ce之PZT系壓電體膜,分別測定膜組成、極化量之磁滯之偏移、配向度、壓電常數e31.f、及龜裂之有無。
各實施例所示之燒成後之摻雜Ce之PZT系壓電體膜之膜組成(原子金屬比)係藉由使用螢光X光分析裝置(Rigaku公司製型式名:Primus III+)之螢光X光分析來測定。
壓電體膜之極化之磁滯之偏移係使用TF-analyzer 2000(aix ACCT公司製)測量。具體而言,首先,藉由濺鍍法分別於摻雜Ce之PZT系壓電體膜之兩面,形成直徑200μm之一對電極後,進行急速加熱處理(RTA),氧環境中,於700℃保持1分鐘,進行損傷恢復用的退火,分別製作MIM(Metal-Insulator-Metal)電容器(capacitor)構造。其次,此等作為試驗用樣品,於1kHz的頻率下,外加25V的電壓,測量壓電體膜之極化量的磁滯,求所得之極化量之磁滯的偏移。
摻雜Ce之PZT系壓電體膜之結晶之(100)
面之配向度係由藉由使用X光繞射(XRD)裝置(PANalytical公司製、型式名:Empyrean)之集中法所得之繞射結果,藉由計算(100)面之強度/{(100)面之強度+(110)面之強度+(111)面之強度}來算出。
壓電常數e31.f之測量係使用壓電評價裝置(aix ACCT公司製:4-Point Bending System)測量。又,上述測量係在1kHz之頻率下進行。
龜裂之有無係藉由上述膜厚測量所使用的掃描型電子顯微鏡,觀察藉由掃描型電子顯微鏡(SEM)對於膜表面及膜剖面之組織進行攝影的圖像,由SEM圖像觀察龜裂之有無。在此,龜裂係指26μm×19μm(倍率:×5000)之SEM圖像中之短徑30nm以上、長徑200nm以上的龜裂。對於各實施例及比較例所得之壓電體膜,在不規則選擇3處的區域進行測量。未觀察到龜裂的狀態時,以『無龜裂』表示,觀察到龜裂時,以『有龜裂』表示。此等結果如表1及表2所示。
由表1得知,Ce之摻雜量為0.004之較少的比較例1及完全未摻雜Ce的比較例3,其壓電體膜雖未發生龜裂,但是P-V磁滯之偏移小為1kV/cm及0kV/cm,壓電常數e31.f之絕對值小為4.3C/m2及0.3C/m2。又,Ce之摻雜量為0.06之較多的比較例2,其P-V磁滯之偏移大為15kV/cm,但是壓電體膜發生龜裂,壓電常數e31.f之絕對值小為6.2C/m2。然而,Ce之摻雜量在0.005~0.05之適當範圍內的實施例1~16,其壓電體膜未發生龜裂,P-V磁滯之偏移大為4~16kV/cm,壓電常數e31.f之絕對值變大為8.2~16.1C/m2。
又,Zr/Ti之原子比為0.38/0.62之較小的比較例4及Zr/Ti之原子比為0.57/0.43之較大的比較例5係P-V磁滯之偏移變大成為8C/m2及6C/m2,壓電體膜未發生龜裂,但是壓電常數e31.f之絕對值小為3.8C/m2及5.2C/m2。相對於此等,Zr/Ti之原子比為0.40/0.60~0.55/0.45,在適當範圍內的實施例1~16係壓電體膜未發生龜裂,且P-V磁滯之偏移變大為4~16kV/cm,壓電常數
e31.f之絕對值變大成為8.2~16.1C/m2。
此外,由表2得知,PZT系壓電體膜中之Pb的含有比例為0.94之較少的比較例6係壓電常數e31.f之絕對值小為7.2C/m2,PZT系壓電體膜中之Pb的含有比例為1.16之較多的比較例7係壓電常數e31.f之絕對值小為8.0C/m2,然而,PZT系壓電體膜中之Pb的含有比例為0.95~1.15之適當的範圍內之實施例17~20係壓電常數e31.f之絕對值變大成為11.8~14.2C/m2。由此可知,控制組成物中之Pb濃度,使PZT系壓電體膜中之Pb的含有比例z成為0.95≦z≦1.15是很重要的。
另外,對於以實施例15及比較例3形成的摻雜Ce之PZT系壓電體膜,將以上述比較試驗1測量磁滯之偏移時的磁滯曲線描繪於圖4。由被描繪於此圖4之磁滯曲線可知,相較於比較例3之壓電體膜時,實施例15之壓電體膜更位移至的負側。
又,未在表1及2揭示,但是對於以各實施例及比較例形成的摻雜Ce之PZT系壓電體膜,使用aix ACCT公司製TF-Analyzer 2000測量介電率。結果如下述。實施例1:850、實施例2:1280、實施例3:1300、實施例4:1280、實施例5:800、實施例6:1190、實施例7:1210、實施例8:1190、實施例9:720、實施例10:1090、實施例11:1120、實施例12:1100、實施例13:670、實施例14:1010、實施例15:1030、實施例16:1020、實施例17:1010、實施例18:1100、實施例
19:1130、實施例20:1140、比較例1:1390、比較例2:620、比較例3:1420、比較例4:680、比較例5:1320、比較例6:1050、比較例7:1140。如上述,藉由摻雜Ce,可得到母材的PZT之介電率減少,作為感測器用途之利益較大的膜。
以上,說明本發明之較佳的實施例,但是本發明不限於此等實施例。在不脫離本發明之技術特徵的範圍內,可進行構成之附加、省略、取代及其他的變更。本發明不為前述說明所限定,僅受附加之申請專利範圍的範圍所限定。
本發明之摻雜Ce之PZT系壓電體膜,可利用於壓電元件、IPD、焦電元件、重力感測器、振動發電元件、致動器等之複合電子零件中之構成材料(電極)之製造。
Claims (3)
- 一種摻雜Ce之PZT系壓電體膜,其係由一般式:PbzCexZryTi1-yO3表示之Ce摻雜之複合金屬氧化物所構成,前述一般式中之x、y及z為分別滿足0.005≦x≦0.05、0.40≦y≦0.55、及0.95≦z≦1.15,其中極化量之磁滯由其中心,往負側位移4kV/cm以上。
- 如申請專利範圍第1項之摻雜Ce之PZT系壓電體膜,其中藉由X光繞射之(100)配向度為80%以上。
- 如申請專利範圍第1或2項之摻雜Ce之PZT系壓電體膜,其中膜厚為1000nm以上且5000nm以下。
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