Development of liquid-phase fabrication of nanotube array-based multiferroic nanocomposite film
Introduction
Unique mechanical, optical, electric, and magnetic properties can be incorporated into composite materials by forming bottom-up assemblies of nanomaterials [1]. Multiferroicity is one such property, which is strongly dependent on the nanostructure. Considerable number of works investigating nanostructure-related multiferroicity have been reported, including multilayers [2], [3], [4], [5], [6], nanoparticle (NP)-based composite films [7], [8], [9], and nanopillar array-based composite films [10], [11], [12], [13], [14], [15], [16]. Among them, nanopillar array-based composite films have shown interesting features due to the structure-derived strong elastic interaction between magnetic and electric components [30]. Since the multiferroicity can arise from strain transfer at the phase boundaries [17], interface design is important to maximize the strain transfer-driven multiferroicity. Zheng et al. first reported the clear advantages of the vertically aligned ferrimagnetic nanopillars, which were embedded in a ferroelectric matrix [10]. The elastic interaction between the two components increased due to the large interfacial area where the strain was transferred. In addition, the substrate-clamping effect became negligible because the deformation direction of the composite film was perpendicular to the interface between the film and substrate. However, the gas-phase processes caused difficulties in fabricating large-scale composite films and substantially increased manufacturing costs, which are unsuitable for their practical applications [18].
Our group has recently developed affordable liquid-phase processes for the fabrication of nanotube array-based ferroelectric BaTiO3 (BTO)-ferrimagnetic CoFe2O4 (CFO) multiferroic nanocomposite films [19], [20], [21]. The nanostructures resemble the structure of nanopillar array-based composite films, which possess a large interfacial area besides weak clamping effect from the substrate, leading to large multiferroicity. In fact, due to the nanotube array-based structures, an apparent multiferroic magnetoelectric effect was observed in some of the films [21]. A BTO nanotube array film was prepared by the hydrothermal treatment of a TiO2 nanotube array (TNTA) film, which was prepared by the anodization of a Ti foil. Then, the BTO film was spin-coated with the CFO precursor solution. The obtained nanocomposite film possessed random crystal orientations of BTO and CFO, and ca. 5.3% porosity. This porous structure with random crystal orientations leads to weakened elastic interaction between BTO and CFO because pores generally relieve stress, and the stretching directions of BTO and CFO are dependent on their crystal orientations. Therefore, further development was needed to enhance the multiferroicity of the films.
In this work, we developed a liquid-phase fabrication process for a multiferroic nanocomposite film. The process named electric-assisted magnetophoretic deposition (E-MPD) enables the deposition of ferrimagnetic nanoparticles (NPs) on the inner walls of pores in ferroelectric nanotube array film. The obtained multiferroic nanocomposite film possesses a unique nanostructure with a magnetoelectric effect. We believe that the newly developed process, E-MPD, can be one of the promising fabrication processes for not only multiferroic nanocomposite films but also other nanotube array-based nanocomposite films with magnetic NPs.
Section snippets
CFO NPs and their suspension
CFO NPs were synthesized by a coprecipitation method described by Pereira et al. [22]. Briefly, a mixture of 10 mmol CoCl2·6H2O (99% Sigma-Aldrich, Japan) and 60 mmol hydrochloric acid, and another mixture of 0.02 mol FeCl3·6H2O (98%, Sigma-Aldrich, Japan) and 40 ml H2O were separately prepared. After stirring the solutions at 53 °C to completely dissolve the precursors, they were added to 200 ml 3.0 M 1-amino-2-propanol (MIPA) (93%, Sigma-Aldrich, Japan) solution at ~110 °C and stirred for
CFO NPs
Fig. 2 shows the TEM and high-resolution TEM (HRTEM) images of CFO NPs heated at different temperatures. The primary particle size of as-coprecipitated CFO NPs was<5 nm. The fringe spacing observed in the HRTEM image was 0.25 nm, which corresponds to the d-spacing of spinel CFO (3 1 1) planes. The CFO NP size increased to ~30 nm and >50 nm when they were heated at 600 and 1000 °C, respectively. The crystal structure of CFO did not change due to the heat treatment, which was confirmed from the
Discussion
As seen in Fig. 2, Fig. 3, Fig. 4, the sintering of CFO NPs progressed by heat treatment at 600 °C and above, and simultaneously intrinsic ferrimagnetism of CFO appeared. On the other hand, since Ti reacts with O2 and N2 in air at 700 °C and above, the Ti substrate collapses at such a high temperature. Therefore, the heating temperature was fixed at 600 °C because the Ti substrate did not collapse, while the sintering of CFO NPs progressed significantly.
We have fabricated BTO/CFO multiferroic
Conclusions
Anodization process was employed to obtain a TNTA film with a tube length and a caliber size of 3 µm and 80 nm, respectively. We then developed a liquid-phase fabrication process named E-MPD which enabled the deposition of CFO NPs on the inner walls of TNTA. During E-MPD, positively charged CFO NPs were vibrated laterally by the alternating electric field; at the same time, the NPs were attracted to a magnet placed under TNTA, forming a TNTA/CFO nanocomposite film. A hydrothermal treatment in
CRediT authorship contribution statement
Go Kawamura: Conceptualization, Methodology, Validation, Investigation, Writing – original draft, Writing – review & editing, Visualization. Irna Puteri Binti Shahbudin: Conceptualization, Methodology, Validation, Investigation, Resources, Visualization. Wai Kian Tan: Methodology. Taichi Goto: Investigation, Funding acquisition. Yuichi Nakamura: Funding acquisition. Mitsuteru Inoue: Conceptualization, Supervision, Funding acquisition. Hiroyuki Muto: Supervision. Kazuhiro Yamaguchi:
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
This work was financially supported by the Program for Fostering Globally Talented Researchers (R2802), JSPS. TG, YN, and MI acknowledge JSPS KAKENHI [Grant nos. 17K19029, 16H04329, and 26220902]. TG acknowledges JST PRESTO [Grant no. JPMJPR1524], JSPS KAKENHI [Grant nos. 20H02593, and 19H00765], and Research Foundation for the Electrotechnology of Chubu. The authors acknowledge the support of the Cooperative Research Facility Center at Toyohashi University of Technology.
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