Synthesis of BaTiO3 Nanowires via Anodic Aluminum Oxide Template Method Assisted by Vacuum-and-Drop Loading
Synthesis of BaTiO3 Nanowires via Anodic Aluminum Oxide Template Method Assisted by Vacuum-and-Drop Loading
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DOI：
10.15744/2348-9812.1.s101
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发表时间：
2014-04
期刊：
影响因子：
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通讯作者：
K. Aisu;M. Osada;Yoshikazu Suzuki
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文献类型：
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作者：
K. Aisu;M. Osada;Yoshikazu Suzuki
简介 在本文中，我们报道了通过阳极氧化铝模板法合成 BaTiO3 纳米线。为了将 BaTiO3 前驱体填充到阳极氧化铝模板中，使用了我们之前研究中开发的真空和滴落加载方法。 Ba(CH3COO)2（乙酸钡）和C12H28O4Ti（原钛酸四异丙酯）分别用作Ba源和Ti源。使用通孔直径约为 200 nm 的阳极氧化铝膜作为 BaTiO3 纳米线的模板。样品在 700℃下煅烧 2 小时，并用 NaOH 在 40℃ 下处理 72 小时以去除阳极氧化铝，该样品基本上由 BaTiO3 组成。还讨论了介电测量的初步结果。近年来，传感器、执行器、电容器和微机电系统的小型化进展迅速。为了实现进一步的小型化，纳米结构压电陶瓷得到了深入研究。通过控制它们的纳米结构，可以使它们表现出与本体不同的相变行为和介电常数，部分原因是颗粒尺寸效应[1-4]。迄今为止，除了等轴纳米颗粒和纳米陶瓷之外，一维（1-D）铁电和压电纳米材料也受到广泛关注[5-9]。第 1 卷 |问题 1 已经报道了多种合成一维纳米材料的方法。对于氧化物基纳米材料，通常使用三种方法，即（1）水热法（使用各向异性晶体生长）[10,11]，（2）阳极氧化法（来自金属前驱体）[12]和（3）阳极氧化铝（AAO）模板法[13-16]。 AAO模板法是一种利用具有均匀一维孔道的AAO薄膜作为一维纳米结构模板的合成过程[17,18]。由于其广泛的适用性，我们重点关注AAO模板法来制备TiO2纳米棒和纳米线[13]。只需改变 AAO 的孔径和厚度（或 AAO 的渗透深度），就可以轻松控制一维纳米材料的尺寸和纵横比。此外，通过适当去除 AAO 模板，可以合成一维纳米材料的二维阵列。 2003年欧盟颁布有害物质限制指令后，无铅压电材料的开发得到积极开展。尽管居里温度相对较低，BaTiO3 仍是某些特定应用中无铅压电材料的潜在候选材料之一[19,20]。因此，在本文中，我们报道了通过 AAO 模板法合成 BaTiO3 纳米线。为了将 BaTiO3 前驱体填充到 AAO 模板中，使用了我们之前研究中开发的真空滴装法 (VDLM) [13]。实验材料 Ba(CH3COO)2（乙酸钡，99.8%，批号 WEF3058，Wako Pure Chemical Ind. Ltd.，日本大阪）和 C12H28O4Ti（原钛酸四异丙酯，TTIP，批号 T88NH，东京化成工业有限公司，日本东京）分别作为 Ba 源和 Ti 源。 CH3COOH（乙酸，99.9％，批号TLE2561，和光纯药）和C5H8O2（乙酰丙酮，ACA，99.9％，批号TLN0469，和光纯药）分别用作溶剂和螯合剂。添加ACA可有效减缓TTIP的水解反应[6,16]。对于以下样品制备过程，使用摩尔比为 Ba(CH3COO)2: TTIP : ACA = 1:1:1，体积比为 (Ba(CH3COO)2 + TTIP) : (CH3COOH + ACA) = 1:4。
Introduction In this paper, we report on the synthesis of BaTiO3 nanowires via the anodic aluminum oxide template method. To fill in the precursors of BaTiO3 into anodic aluminum oxide templates, the vacuum and drop loading method developed in our previous study was used. Ba(CH3COO)2 (barium acetate) and C12H28O4Ti (tetraisopropyl orthotitanate) were used as Ba and Ti sources, respectively. Anodic aluminum oxide membranes with the through-hole diameter of ~200 nm were used as the template for BaTiO3 nanowires. The sample calcined at 700 ̊C for 2 h with NaOH post treatment at 40 ̊C for 72 h to remove the anodic aluminum oxide was substantially composed of BaTiO3. Preliminary results on dielectric measurements were also discussed. In recent years, miniaturization of sensors, actuators, capacitors and micro-electro-mechanical systems makes rapid progress. In order to realize the further miniaturization, nanostructured piezoelectric ceramics have been intensively studied. By controlling their nanostructures, one can make them to exhibit phase transition behavior and dielectric constants different from those of the bulk, partially due to the particle size effect [1-4]. To date, besides equiaxed nanoparticles and nanoceramics, one-dimensional (1-D) ferroelectric and piezoelectric nanomaterials are of great concern [5-9]. Volume 1 | Issue 1 A variety of methods have been reported to synthesize 1-D nanomaterials. For oxide-based nanomaterials, three methods are typically used, viz., (1) hydrothermal method (using anisotropic crystal growth) [10,11], (2) anodic oxidation method (from metal precursors) [12] and (3) anodic aluminum oxide (AAO) template method [13-16]. The AAO-template method is a synthesis process in which AAO film with uniform 1-D pore channels is used as a template for 1-D nanostructure [17,18]. Due to its versatile applicability, we have focused on the AAO template method to prepare TiO2 nanorods and nanowires [13]. Just by changing the hole diameter and thickness of AAO (or penetration depth into AAO), size and aspect ratio of 1-D nanomaterials can be easily controlled. In addition, 2-D arrays of 1-D nanomaterials can be synthesized through the appropriate removal of the AAO template. After the Restriction of Hazardous Substances Directive by the European Union in 2003, development of lead free piezoelectric materials has been actively conducted. Despite its relatively low Curie temperature, BaTiO3 is one of the potential candidates as lead free piezoelectric materials in some specific applications [19,20]. Hence, in this paper, we report the synthesis of BaTiO3 nanowires via the AAO template method. To fill in the precursors of BaTiO3 into AAO templates, the vacuum-and-drop loading method (VDLM) developed in our previous study was used [13]. Experimental Materials Ba(CH3COO)2 (barium acetate, 99.8%, Lot No. WEF3058, Wako Pure Chemical Ind. Ltd., Osaka Japan) and C12H28O4Ti (tetraisopropyl orthotitanate, TTIP, Lot No. T88NH, Tokyo Chemical Ind. Co. Ltd., Tokyo, Japan) were used as Ba and Ti sources, respectively. CH3COOH (acetic acid, 99.9%, Lot. No. TLE2561, Wako Pure Chemical) and C5H8O2 (acetylacetone, ACA, 99.9%, Lot No. TLN0469, Wako Pure Chemical) were used as solvent and chelating agent, respectively. The addition of ACA is effective to slow down the hydrolysis reaction of TTIP [6,16]. For the following sample preparation procedure, Ba(CH3COO)2: TTIP : ACA = 1:1:1 in molar ratio, and (Ba(CH3COO)2 + TTIP) : (CH3COOH + ACA) = 1:4 in volume ratio were used.