CN1510724A - 铁电薄膜及其形成方法 - Google Patents

铁电薄膜及其形成方法 Download PDF

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CN1510724A
CN1510724A CNA031278337A CN03127833A CN1510724A CN 1510724 A CN1510724 A CN 1510724A CN A031278337 A CNA031278337 A CN A031278337A CN 03127833 A CN03127833 A CN 03127833A CN 1510724 A CN1510724 A CN 1510724A
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CN1314087C (zh
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李容均
朴永洙
李俊冀
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Samsung Electronics Co Ltd
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Abstract

本发明提供一种形成铁电薄膜的组合物,利用该组合物形成的铁电薄膜,及形成该铁电薄膜的方法。该组合物包含PZT溶胶-凝胶溶液和Bi2SiO5溶胶-凝胶溶液。PZT溶胶-凝胶溶液包括铅(Pb)前体的全部或部分水解产物及Pb前体的全部或部分水解和缩聚的产物中的至少一种;锆(Zr)前体的全部或部分水解产物,Zr前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Zr络合物中的至少一种;以及钛(Ti)前体的全部或部分水解产物,Ti前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Ti络合物中的至少一种。Bi2SiO5溶胶-凝胶溶液包括硅(Si)前体的全部或部分水解产物及Si前体的全部或部分水解和缩聚的产物中的至少一种;及通过回流铋(Bi)前体三苯基铋(Bi(Ph)3)或Bi(tmhd)3与C1-C10烷氧基醇而得到的产物,其中tmhd为2,2,6,6-四甲基庚烷-3,5-二酮化物(dionate)。

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铁电薄膜及其形成方法
                         技术领域
本发明涉及一种铁电薄膜及其形成方法。更具体地,本发明涉及适用于电子装置如集成的非易失性存储器等装置的铁电薄膜,以及利用溶胶-凝胶工艺形成铁电薄膜的方法。
                         背景技术
铁电存储器装置基于铁电薄膜的铁电性质工作,并且具有无需备用电源的非易失性存储器的结构。用于铁电存储器装置的铁电材料需要具有高的剩余极化和低的矫顽磁场。而且,除了低的漏电流之外,为了获得良好的电性能,必须降低因周期性极化转换而导致的极化疲劳。就芯电压的降低和高的集成而言,铁电薄膜需要具有小于数百个nm的厚度。
主要用于铁电存储器装置的铁电材料是锆钛酸铅(PZT),其在块状态(bulk state)具有高的剩余极化。最近,开发了催化剂材料的氧化物材料,该催化剂材料在PZT中包含选自Si,Ge,及Sn中的一种或多种(WO 02/32809A1)。
PZT薄膜可通过图1所示的溶胶-凝胶法形成。然而,组合物,即图1所示的用于形成氧化物薄膜的PZT溶液与Bi2SiO5溶液的混合物,具有非常差的贮存稳定性。另外,通过涂布和热处理该组合物而形成的氧化物薄膜限制了在氧化物薄膜下形成电极的选择。由于这些原因,这种PZT薄膜还没有普遍地使用。
                         发明内容
本发明提供一种组合物,其借助于溶胶-凝胶法形成贮存稳定性增强的铁电薄膜。
本发明还提供一种形成铁电薄膜的方法,其借助于溶胶-凝胶法并使用所述形成铁电薄膜的组合物。
本发明还提供一种电性能得到改进的铁电薄膜,其采用上述的铁电薄膜。
本发明还提供一种电子装置,其具有增强的集成度。
一方面,本发明提供一种形成铁电薄膜的组合物,其包括PZT溶胶-凝胶溶液和Bi2SiO5溶胶-凝胶溶液。所述PZT溶胶-凝胶溶液包括铅(Pb)前体的全部或部分水解产物和Pb前体的全部或部分水解和缩聚的产物中的至少一种;锆(Zr)前体的全部或部分水解产物,Zr前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Zr络合物中的至少一种;以及钛(Ti)前体的全部或部分水解产物,Ti前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Ti络合物中的至少一种。所述Bi2SiO5溶胶-凝胶溶液包括硅(Si)前体的全部或部分水解产物及Si前体的全部或部分水解和缩聚的产物中的至少一种;以及通过回流铋(Bi)前体三苯基铋(Bi(Ph)3)或Bi(tmhd)3和C1-C10烷氧基醇而得到产物,其中tmhd为2,2,6,6-四甲基庚烷-3,5-二酮化物(dionate)。
另一方面,本发明提供一种通过涂布和加热前述组合物而得到的铁电薄膜。
再一方面,本发明提供一种形成铁电薄膜的方法,包括:(a)将Pb前体溶解于溶剂中以制备Pb前体溶液;(b)稳定化Zr前体和Ti前体以制备Zr前体溶液和Ti前体溶液;(c)将步骤(a)的Pb前体溶液与步骤(b)的Zr前体溶液和Ti前体溶液混合,得到Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物;(d)将(Bi(Ph)3)或Bi(tmhd)3溶解于C1-C10烷氧基醇中并回流所得溶液,以制备Bi前体溶液;(e)将Si前体溶解于溶剂,以制备Si前体溶液,并将该Si前体溶液与步骤(d)的Bi前体溶液混合,得到Bi2SiO5溶胶-凝胶溶液;(f)将步骤(e)的Bi2SiO5溶胶-凝胶溶液与步骤(c)的Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物混合,然后水解所形成的产物,得到形成铁电薄膜的组合物;及(g)将步骤(f)的组合物涂布在基材上并加热所涂布的薄膜。
又一方面,本发明提供一种形成铁电薄膜的方法,包括:(a)溶解Pb前体以制备Pb前体溶液;(b)稳定化Zr前体和Ti前体,以制备Zr前体溶液和Ti前体溶液;(c)将步骤(a)的Pb前体溶液与步骤(b)的Zr前体溶液和Ti前体溶液混合,得到Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物;(d)水解步骤(c)的混合物,以制备PZT溶胶-凝胶溶液;(e)将(Bi(Ph)3)或Bi(tmhd)3溶解于C1-C10烷氧基醇中,并回流所得溶液,以制备Bi前体溶液;(f)将Si前体溶解于醇中,以制备Si前体溶液,并将该Si前体溶液与步骤(e)的Bi前体溶液混合,得到Bi2SiO5溶胶-凝胶溶液;(g)将步骤(f)的Bi2SiO5溶胶-凝胶溶液与步骤(d)的PZT溶胶-凝胶溶液混合,得到形成铁电薄膜的组合物;及(h)涂布步骤(g)的组合物于基材上,并加热所涂布的薄膜。
还有一方面,本发明提供一种采用前述铁电薄膜的电子装置。
                         附图说明
通过参照附图详述其示例性的实施方案,本发明的上述及其它特征和优点将会更加显而易见,在附图中:
图1是形成铁电薄膜的常规方法的流程图;
图2是本发明的形成铁电薄膜的方法流程图;
图3A和3B是实施例1和对比例1的铁电薄膜的X-射线衍射(XRD)光谱;
图4A和4B是实施例1和对比例1的铁电薄膜的扫描电子显微镜(SEM)照片;
图5示出了本发明实施例2的铁电薄膜的极化(P)-电场(E)特性;
图6示出了本发明实施例2的铁电薄膜的极化(P)-电压(V)特性;及
图7示出了本发明实施例2的PZT薄膜的疲劳特性。
                      具体实施方式
下面将更详细地说明本发明。
本发明的形成铁电薄膜的组合物包括PZT溶胶-凝胶溶液和Bi2SiO5溶胶-凝胶溶液。优选PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液的摩尔比为1∶0.0001至1∶0.5。如果摩尔比超出该范围,则铁电薄膜的物理性质降低。PZT溶胶-凝胶溶液和Bi2SiO5溶胶-凝胶溶液的示例性溶剂是C1-C10醇,如乙醇,1-丙醇,2-丁醇,及异丁醇以及C1-C10烷氧基醇如2-甲氧基乙醇。
优选形成铁电薄膜的组合物的摩尔浓度为0.001~2M。如果摩尔浓度小于0.001M,则难于形成薄膜。另一方面,如果摩尔浓度超过2M,则不容易获得均匀的组合物。
PZT溶胶-凝胶溶液包括Pb前体的全部或部分水解产物和全部或部分水解和缩聚的产物直到至少一种;Zr前体的全部或部分水解产物,Zr前体的全部或部分水解和缩聚的产物,及具有羟基离子和不可水解配体的Zr络合物中的至少一种;以及Ti前体的全部或部分水解产物,Ti前体的全部或部分水解和缩聚的产物,及具有羟基离子和不可水解配体的Ti络合物中的至少一种。
Pb前体为PbO或Pb(OAc)2·3H2O,Zr前体为Zr(i-OPr)4,Zr(OBu)4,Zr(OEt)2(i-OPr)2,Zr(OEt)2(acac)2,或者Zr(OEt)4,其中OAc为OC(=O)CH3,i-OPr为异丙氧基,OBu为丁氧基,OEt为乙氧基,及acac为乙酰丙酮化物。Ti前体为选自Ti(i-OPr)4,Ti(i-OPr)2(acac)2,Ti(OBu)4,Ti(OEt)2(i-OPr)2,及Ti(OEt)4中的一种或多种。
Ti络合物是与至少一个羟基离子和至少一个不可水解配体络合的钛化合物。不可水解的配体可以是源于醇,羧酸,二酮,β-酮酯,或者β-亚氨基酮的阴离子。不可水解的配体的实例是乙酰丙酮化物(acac)。
Ti络合物的实例包括Ti(OH)2(acac)2,Ti(OH)(acac)3,及Ti(OH)2-a(i-OPr)a(acac)2(其中0<a≤1)。Ti(OH)2(acac)2可以制备如下:将钛四烷氧化物如Ti(i-ORr)4与乙酰丙酮(摩尔比约1∶2)在有机溶剂中彼此进行反应,形成Ti(i-OPr)2(acac)2溶液。然后,向所得溶液中加入水和/或酸性催化剂并加热,直到异丙氧基完全水解得到Ti(OH)2(acac)2为止。如果水解进行得不完全,则生成Ti(OH)2-a(i-OPr)a(acac)2
Zr络合物具有与前述Ti络合物相同的配体。前述Ti络合物的说明性实例和制备方法以相同的方式适用于Zr络合物。
Bi2SiO5溶胶-凝胶溶液包括Si前体的全部或部分水解产物和全部或部分水解和缩聚的产物中的至少一种;及通过回流Bi前体三苯基铋(Bi(Ph)3)或Bi(tmhd)3和C1-C10烷氧基醇而得到的产物。烷氧基醇可以是2-甲氧基甲醇或丙醇。回流过程中,Bi前体的配体全部或部分被烷氧基醇所代替。
Si前体可以是原硅酸四乙酯(TEOS)或四乙基硅烷。
下文中将参照附图详述本发明的形成铁电薄膜的方法。
图2示出了根据本发明的形成铁电薄膜的方法的流程图。
参照图2,首先,将Pb前体溶解于一种或多种选自酸和醇的溶剂并搅拌,制得Pb前体溶液。搅拌温度为50~80℃,优选约70℃。用于Pb前体溶液的酸是pH为4或更大的弱酸如乙酸。醇的实例包括2-甲氧基乙醇,正丙醇,1,3-丙二醇,1,4-丁二醇,1,2-丙二醇,及乙二醇。调节溶剂的含量,使Pb前体溶液的浓度为0.001~2M。
然后,将Zr前体和Ti前体中的每一种与有机化合物如乙酰丙酮,2-甲氧基乙醇,及丙醇混合,并且进行搅拌以使前体稳定。对于Zr前体,上述有机化合物于醇溶剂如正丙醇和异丙醇中的溶液可以加到Zr前体中,以调节Zr前体的配体取代反应的反应活性。调节与基化合物的含量,使Zr前体溶液和Ti前体溶液的浓度均为0.0001~2M。
当使用乙酰丙酮作为有机化合物时,乙酰丙酮取代Zr前体和Ti前体的全部或部分配体。另一方面,当使用醇如2-甲氧基乙醇作为有机化合物时,则不发生配体取代反应。
对搅拌温度没有特殊的限制。然而,优选在室温下进行搅拌过程。
将稳定化的Zr前体溶液和Ti前体溶液与Pb前体溶液混合并搅拌,制得混合物。
另一方面,将Bi前体如(Bi(Ph)3)和Bi(tmhd)3溶解于C1-C10烷氧基醇并回流,制得Bi前体溶液。回流期间,Bi前体全部或部分地进行配体取代反应。调节烷氧基醇的含量,使Bi前体溶液的浓度为0.0001~2M。如果烷氧基醇的含量超出该范围,则Bi前体的配体取代反应的反应活性差。
将Si前体溶解于醇并于室温下搅拌,制得Si前体溶液。将Si前体溶液与Bi前体溶液混合,得到Bi2SiO5溶胶-凝胶溶液。
用于Si前体溶液的醇的实例包括2-甲氧基乙醇,2-甲氧基甲醇,及丙醇。调节醇的含量,使Si前体溶液的浓度为0.0001~6M,优选1~6M。
根据图2所示的(a),将Bi2SiO5溶胶-凝胶溶液与包含Zr前体溶液和Ti前体溶液的混合物混合并水解,制得形成铁电薄膜的组合物。
作为选择,根据图2所示的(b),首先,将包含Zr前体溶液和Ti前体溶液的混合物水解,制得PZT溶胶-凝胶溶液的水解溶液。然后将Bi2SiO5溶胶-凝胶溶液加到PZT溶胶-凝胶溶液中,制得形成铁电薄膜的组合物。
将形成铁电薄膜的组合物涂布在基材上并加热。对涂布方法没有特殊的限制,可以使用旋涂法。
加热过程包括在100~450℃烘焙所涂布的薄膜,并在450~700℃的氧气氛下煅烧所烘焙的薄膜。需要时,烘焙和煅烧过程可重复若干次。煅烧可以在炉中进行,或者通过迅速的热处理(RTP)来进行。
如果烘焙温度小于100℃,则不发生醇分解,如果其超过450℃,则形成不合乎需要的次生相。另一方面,如果煅烧温度小于450℃,则形成不合乎需要的相,如果煅烧温度超过700℃,则增加生产成本。
在涂布过程之前,可将PTO(PbTiO3)晶种层涂布在基材上。晶种层提供优选的铁电薄膜取向。
图2示出了将Zr前体溶液和Ti前体溶液依次加到事先制备的Pb前体溶液中。对该过程的顺序没有限制,在Zr前体和Ti前体稳定化并得到各自的前体溶液之后,可以将Pb前体溶液加到Zr与Ti前体溶液的混合物中。同样,图2示出了将Si前体溶液加到事先制备的Bi前体溶液中。然而,还可以将Bi前体溶液加到事先制备的Si前体中。如上所述,在本发明的形成铁电薄膜的方法中,工艺顺序是可以改变的,只要能够实现本发明的目的。
Bi2SiO5充当加热以进行PZT或PLZT结晶期间促进钙钛矿或层状钙钛矿相形成,晶核形成,及结晶能降低的催化剂。一旦Bi2SiO5的表面上形成晶核,Bi2SiO5就不再充当晶核形成的催化剂了。随后,当温度降低时,Bi2SiO5与下面式1的钙钛矿PZT或者式2的钙钛矿PLZT一起形成固溶体。
             式1:    Pb(ZrxTi1-x)O3
             式2:Pb1-yLay(ZrxTi1-x)1-y/4O3
式中,x为0.001~1,特别是0.01~1,且y为0.0001~1。
本发明的铁电薄膜具有1~1000nm的厚度。因此,它适合用作半导体电容器的介电层及晶体管的门介电薄膜。另外,它可以应用于各种高度集成的电子装置中。可应用的代表性的电子装置是非易失性存储器装置,如铁电随机存储器(FRAM)装置。
在下文中,将参照下面的制备例和实施例描述本发明,但本发明并不受其限制。
制备例1
将Pb(OAc)2·3H2O与乙酸混合并于70℃下搅拌,制得Pb前体的约0.15M溶液。
将通过溶解乙酰丙酮于1,3-丙二醇中而得到的乙酰丙酮溶液缓慢地滴加到Zr(n-BuO)4中并于室温下搅拌,制得Zr前体的0.3~0.4M溶液。
将乙酰丙酮滴加到Ti(i-OPr)4中并于室温下搅拌,制得Ti前体的0.6~0.8M溶液。
另一方面,将Bi(Ph)3和2-甲氧基乙醇混合并回流,制得Bi前体的约0.00045M溶液。
将原硅酸四乙酯(TEOS)和2-甲氧基乙醇在室温下搅拌。然后,将所得混合物与Bi前体溶液混合,制得Bi2SiO5溶胶-凝胶溶液。
将Pb前体溶液,Zr前体溶液,及Ti前体溶液混合,制得PZT溶胶-凝胶溶液。将PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液混合。然后,将所得混合物水解,制得约0.015M的形成铁电薄膜的组合物。
制备例2
将Pb(OAc)2·3H2O与乙酸混合并于70℃下搅拌,制得Pb前体的约0.15M溶液。
将2-甲氧基乙醇加到Zr(n-BuO)4中并于室温下搅拌,制得Zr前体的0.3~.4M溶液。
将2-甲氧基乙醇滴加到Ti(i-OPr)4中并于室温下搅拌,制得Ti前体的0.6~0.8M溶液。
另一方面,将Bi(tmhd)3与2-甲氧基乙醇混合并回流制得Bi前体的约0.00045M溶液。
将TEOS和2-甲氧基乙醇在室温下搅拌,制得Si前体溶液,然后将Si前体溶液与Bi前体溶液混合,制得Bi2SiO5溶胶-凝胶溶液。
将Pb前体溶液,Zr前体溶液,及Ti前体溶液混合,制得PZT溶胶-凝胶溶液。将PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液混合。然后,将所得的混合物水解,制得约0.015M的形成铁电薄膜的组合物。
制备对比例1
将Pb(OAc)2·3H2OA与2-甲氧基乙醇混合并脱水,制得Pb前体溶液。
将2-甲氧基乙醇加到Zr(n-BuO)4中并搅拌,制得Zr前体溶液。将2-甲氧基乙醇加到Ti(i-OPr)4中并搅拌,制得Ti前体溶液。
将Pb前体溶液,Zr前体溶液,及Ti前体溶液混合,并通过加水和2-甲氧基乙醇进行水解,从而制得PZT溶胶-凝胶溶液。
另一方面,将TEOS,水,及2-甲氧基乙醇混合并脱水。然后,将Bi(OC2H5)3与2-甲氧基乙醇的混合物加到脱水的混合物中。接着将水和2-甲氧基乙醇加到所得的混合物中,制得Bi2SiO5溶胶-凝胶溶液。
将PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液混合,制得约0.015M的形成铁电薄膜的组合物。
实施例1
将制备例1的组合物旋涂在由Pt(100nm)/Ti(30nm)/SiO2(200nm)/Si制成的基材上。将所涂布的薄膜在约300~400℃的空气中烘焙10分钟,并通过RTP于500℃的氧气氛中煅烧10分钟。将烘焙和煅烧重复数次,得到铁电薄膜。
实施例2
将PTO(PbTiO3)晶种层旋涂在Pt电极的上表面,并于300~450℃下煅烧,形成厚度约30 nm的PTO晶种层。然后,将制备例2的组合物旋涂在晶种层上。将所涂布的薄膜在约300~400℃的空气中烘焙10分钟,然后通过RTP在550~650℃的氧气氛中煅烧10分钟。将烘焙和煅烧充分若干次,得到铁电薄膜。
对比例1
按与实施例1相同的方式制备铁电薄膜,只是使用制备对比例1的组合物。
评价制备例1~2及制备对比例1的组合物的贮存稳定性。为此,将组合物在25℃下静置2400小时至3个月,然后评价各组合物的状态。
根据评价结果,制备对比例1的组合物在1~5小时后分解。另一方面,制备例1和2的组合物保持稳定的结构约3个月。
将实施例1和对比例1的铁电薄膜进行X-射线衍射(XRD)分析和扫描电子显微镜(SEM)分析。XRD光谱和SEM照片分别示于图3A-3B和4A-4B中。
参照示出对比例1的铁电薄膜的XRD光谱和SEM照片的图3B和4B,主要存在Bi-基的烧绿石相。另一方面,参照示出实施例1的铁电薄膜的XRD光谱和SEM照片的图3A和4A,Bi-基的烧绿石相不存在。而是,主要观察到PZT钙钛矿相。这些结果证实,实施例1的铁电薄膜具有非常可取的极化取向。
图5示出了实施例2的铁电薄膜的极化(P)-电场(E)特性。如图5所示,实施例2的铁电薄膜具有良好的极化。
图6示出了实施例2的铁电薄膜的极化(P)-电压(V)特性。如图6所示,实施例2的铁电薄膜具有良好的适于实用的电压(Vc)范围。
另外,评价实施例2的PZT薄膜的疲劳特性。疲劳特性的研究借助于RT66A,以1μHz进行10000秒。
实施例2的PZT薄膜的疲劳特性见图7。如图7所示,实施例2的PZT薄膜很少遭受疲劳。
从上述说明可以看出,本发明提供具有优异贮存特性的形成铁电薄膜的组合物和具有优异电性能的铁电薄膜。另外,本发明提供一种电子装置,特别是集成度增强的非易失性存储器装置。
尽管已经参照其示例性实施方案具体地展示和说明了本发明,但是本领域的技术人员应当理解,其中可以作出各种形式和内容上的改变而不脱离权利要求书中所定义的本发明的构思和范围。

Claims (40)

1.一种形成铁电薄膜的组合物,包括PZT溶胶-凝胶溶液和Bi2SiO5溶胶-凝胶溶液,
所述PZT溶胶-凝胶溶液包括:
铅(Pb)前体的全部或部分水解产物及Pb前体的全部或部分水解和缩聚的产物中的至少一种;
锆(Zr)前体的全部或部分水解产物,Zr前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Zr络合物中的至少一种;及
钛(Ti)前体的全部或部分水解产物,Ti前体的全部或部分水解和缩聚的产物,及具有至少一个羟基离子和至少一个不可水解配体的Ti络合物中的至少一种,以及
所述Bi2SiO5溶胶-凝胶溶液包括:
硅(Si)前体的全部或部分水解产物及Si前体的全部或部分水解和缩聚的产物中的至少一种;及
通过回流铋(Bi)前体三苯基铋(Bi(Ph)3)或Bi(tmhd)3与C1-C10烷氧基醇而得到的产物,其中tmhd为2,2,6,6-四甲基庚烷-3,5-二酮化物。
2.根据权利要求1的组合物,其中所述PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液的摩尔比为1∶0.0001至1∶0.5。
3.根据权利要求1的组合物,其中所述C1-C10烷氧基醇为选自2-甲氧基乙醇,丙醇,及乙酰丙酮中的至少一种。
4.根据权利要求1的组合物,其中PZT溶胶-凝胶溶液还包括选自镧(La)前体的全部或部分水解产物及La前体的全部或部分水解和缩聚的产物中的至少一种。
5.根据权利要求4的组合物,其中该镧前体为乙酸镧。
6.根据权利要求1的组合物,其中该Pb前体为PbO或Pb(OAc)2·3H2O,式中OAc为-OC(=O)CH3
7.根据权利要求1的组合物,其中该Ti前体为选自Ti(i-OPr)4,Ti(i-OPr)2(acac)2,Ti(i-OBu)4,Ti(OEt)2(i-OPr)2,及Ti(OEt)4中的一种或多种,式中i-OPr为异丙氧基,acac为乙酰丙酮化物,OBu丁氧基,及OEt为乙氧基。
8.根据权利要求1的组合物,其中该Zr前体为选自Zr(i-OPr)4,Zr(OBu)4,Zr(OEt)2(i-OPr)2,Zr(OEt)2(acac)2,及Zr(OEt)4中的一种或多种。
9.根据权利要求1的组合物,其中该Si前体为选自原硅酸四乙酯(TEOS)和四乙基硅烷中的一种或多种。
10.一种铁电薄膜,其是通过涂布并加热根据权利要求1的组合物而得到的。
11.根据权利要求10的铁电薄膜,其中所述加热包括在100~450℃的空气中烘焙所涂布的薄膜,及在450~700℃的氧气氛下煅烧所烘焙的薄膜。
12.根据权利要求10的铁电薄膜,其中所述薄膜包含Bi2SiO5与下面式1所示的锆钛酸铅(PZT)的固溶体:
                  Pb(ZrxTi1-x)O3              (1)式中x为0.001~1。
13.根据权利要求10的铁电薄膜,其中所述薄膜包含Bi2SiO5与下面式2所示的含镧的锆钛酸铅(PLZT)的固溶体:
                  Pb1-yLay(ZrxTi1-x)1-y/4O3  (2)式中x为0.001~1且y为0.0001~1。
14.一种形成铁电薄膜的方法,包括:
(a)将Pb前体溶解于溶剂中以制备Pb前体溶液;
(b)将Zr前体和Ti前体稳定化,以制备Zr前体溶液和Ti前体溶液;
(c)将步骤(a)的Pb前体溶液与步骤(b)的Zr前体溶液和Ti前体溶液混合,得到Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物;
(d)将(Bi(Ph)3)或Bi(tmhd)3溶解于C1-C10烷氧基醇中并回流所得的溶液,以制备Bi前体溶液;
(e)将Si前体溶解于溶剂中,以制备Si前体溶液,并将该Si前体溶液与步骤(d)的Bi前体溶液混合,得到Bi2SiO5溶胶-凝胶溶液;
(f)将步骤(e)的Bi2SiO5溶胶-凝胶溶液与步骤(c)的Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物混合,然后将所得产物水解,得到形成铁电薄膜的组合物;及
(g)将步骤(f)的组合物涂布在基材上并加热所涂布的薄膜。
15.根据权利要求14的方法,其中在步骤(d)中,所述C1-C10烷氧基醇为2-甲氧基乙醇。
16.根据权利要求14的方法,其中在步骤(a)中,将所述Pb前体溶解于一种或多种选自乙酸,正丙醇,2-甲氧基乙醇,及乙酰丙酮的溶剂中。
17.根据权利要求14的方法,其中在步骤(a)中,所述Pb前体为PbO或Pb(OAc)2·3H2O。
18.根据权利要求14的方法,其中在步骤(b)中,所述Ti前体为选自Ti(i-OPr)4,Ti(i-OPr)2(acac)2,Ti(i-OBu)4,Ti(i-OEt)2(i-OPr)2,及Ti(i-OEt)4中的一种或多种。
19.根据权利要求14的方法,其中在步骤(b)中,所述Zr前体为选自Zr(i-OPr)4,Zr(OBu)4,Zr(OEt)2(i-OPr)2,Zr(OEt)2(acac)2或Zr(OEt)4中的至少一种。
20.根据权利要求14的方法,其中在步骤(b)中,将所述Zr前体和Ti前体稳定于选自乙酰丙酮,2-甲氧基乙醇,正丙醇,及异丙醇中的一种或多种中。
21.根据权利要求14的方法,其中在步骤(f)中,所述PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液的摩尔比为1∶0.0001至1∶0.5。
22.根据权利要求14的方法,其中在步骤(e)中,所述Si前体为选自TEOS或四乙基硅烷中的一种或多种。
23.根据权利要求14的方法,其中所述形成铁电薄膜的组合物的摩尔浓度为0.001~2M。
24.根据权利要求14的方法,还包括将镧前体溶液加到步骤(c)的混合物中。
25.根据权利要求24的方法,其中所述镧前体为乙酸镧。
26.根据权利要求14的方法,其中步骤(g)的加热包括:
在100~450℃的空气中烘焙所涂布的薄膜;及
在450~700℃的氧气氛下煅烧所烘焙的薄膜。
27.一种形成铁电薄膜的方法,包括:
(a)溶解Pb前体以制备Pb前体溶液;
(b)稳定化Zr前体和Ti前体,以制备Zr前体溶液和Ti前体溶液;
(c)将步骤(a)的Pb前体溶液与步骤(b)的Zr前体溶液和Ti前体溶液混合,得到Pb前体溶液,Zr前体溶液,及Ti前体溶液的混合物;
(d)水解步骤(c)的混合物,以制备PZT溶胶-凝胶溶液;
(e)将(Bi(Ph)3)或Bi(tmhd)3溶解于C1-C10烷氧基醇中,并回流所得溶液,以制备Bi前体溶液;
(f)将Si前体溶解于醇中,以制备Si前体溶液,并将该Si前体溶液与步骤(e)的Bi前体溶液混合,得到Bi2SiO5溶胶-凝胶溶液;
(g)将步骤(f)的Bi2SiO5溶胶-凝胶溶液与步骤(d)的PZT溶胶-凝胶溶液混合,得到形成铁电薄膜的组合物;及
(h)涂布步骤(g)的组合物于基材上,并加热所涂布的薄膜。
28.根据权利要求27的方法,其中在步骤(e)中,所述C1-C10烷氧基醇为2-甲氧基乙醇。
29.根据权利要求27的方法,其中在步骤(a)中,将所述Pb前体溶解于一种或多种选自乙酸,正丙醇,2-甲氧基乙醇,及乙酰丙酮的溶剂中。
30.根据权利要求27的方法,其中在步骤(a)中,所述Pb前体为PbO或Pb(OAc)2·3H2O。
31.根据权利要求27的方法,其中在步骤(b)中,所述Ti前体为选自Ti(i-OPr)4,Ti(i-OPr)2(acac)2,Ti(OBu)4,Ti(OEt)2(i-OPr)2,及Ti(OEt)4中的一种或多种。
32.根据权利要求27的方法,其中在步骤(b)中,所述Zr前体为选自Zr(i-OPr)4,Zr(OBu)4,Zr(OEt)2(i-OPr)2,Zr(OEt)2(acac)2,及Zr(OEt)4中的一种或多种。
33.根据权利要求27的方法,其中在步骤(b)中,将所述Zr前体和Ti前体稳定于选自乙酰丙酮,2-甲氧基乙醇,正丙醇,及异丙醇中的一种或多种中。
34.根据权利要求27的方法,其中在步骤(g)中,所述PZT溶胶-凝胶溶液与Bi2SiO5溶胶-凝胶溶液的摩尔比为1∶0.0001至1∶0.5。
35.根据权利要求27的方法,其中在步骤(f)中,所述Si前体为选自TEOS和四乙基硅烷中的一种或多种。
36.根据权利要求27的方法,其中所述形成铁电薄膜的组合物的摩尔浓度为0.001~2M。
37.根据权利要求27的方法,还包括向其中步骤(c)的混合物中加入镧前体溶液。
38.根据权利要求37的方法,其中所述镧前体为乙酸镧。
39.根据权利要求27的方法,其中步骤(h)的加热包括:
在100~450℃的空气中烘焙所涂布的薄膜;及
在450~700℃的氧气氛下煅烧所烘焙的薄膜。
40.一种采用权利要求10的铁电薄膜的电子装置。
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CN103360064B (zh) * 2012-03-29 2016-03-16 三菱综合材料株式会社 铁电薄膜的制造方法和静电喷涂用液
CN103456723A (zh) * 2012-06-04 2013-12-18 友技科株式会社 铁电晶体膜、电子元件、铁电晶体膜的制造方法和铁电晶体膜的制造装置
CN114262882A (zh) * 2016-12-22 2022-04-01 法国电力公司 在金属基底上生成防腐蚀涂层的溶胶-凝胶方法

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CN1314087C (zh) 2007-05-02
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US20080237551A1 (en) 2008-10-02
US7560042B2 (en) 2009-07-14
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