Multiferroics are of interest for memory and logic device applications, as the coupling between ferroelectric and magnetic properties enables the dynamic interaction between these order parameters. Here, we report an approach to control and switch local ferromagnetism with an electric field using multiferroics. We use two types of electromagnetic coupling phenomenon that are manifested in heterostructures consisting of a ferromagnet in intimate contact with the multiferroic BiFeO(3). The first is an internal, magnetoelectric coupling between antiferromagnetism and ferroelectricity in the BiFeO(3) film that leads to electric-field control of the antiferromagnetic order. The second is based on exchange interactions at the interface between a ferromagnet (Co(0.9)Fe(0.1)) and the antiferromagnet. We have discovered a one-to-one mapping of the ferroelectric and ferromagnetic domains, mediated by the colinear coupling between the magnetization in the ferromagnet and the projection of the antiferromagnetic order in the multiferroic. Our preliminary experiments reveal the possibility to locally control ferromagnetism with an electric field.
Multifunctional materials have attracted increasing interest in recent years because of their potential applications in novel technological devices. [1][2][3][4][5][6][7][8][9][10][11] [12] The ferroelectric and magnetic properties as well as the degree of the coupling are critically dependent on the morphology of the nanostructures, including domain patterns and shapes as well as the interfaces. In order to pursue the enhanced multifunctionality, significant effort has been made on understanding the growth mechanism and controlling the morphology of the nanostructures. The morphology adopted by a crystalline material when it nucleates on a substrate surface is one of the fundamental issues of heteroepitaxy. Depending on the surface energy terms, i.e., substrate surface energy c 1 , interface energy c 12 , and surface energy of the crystalline phase c 2 , the equilibrium shape of a crystalline nucleus on a substrate can be determined using the Winterbottom construction.[13] The possible configuration of the crystalline nucleus on the substrate is a Wulff shape that has been cut off by the substrate, translated by the signed distance Dc from the origin. Dc is the wetting strength, which is the energy difference obtained by replacing the substrate surface with an interface, Dc = c 12 -c 1 . In the BiFeO 3 -CoFe 2 O 4 system, BiFeO 3 has a distorted perovskite structure (R3c) [14] and CoFe 2 O 4 has a cubic spinel structure (Fd3m). CoFe 2 O 4 is characterized by the lowest surface energy of {111} surfaces, which is reflected in an equilibrium shape of an octahedron bounded by eight {111} facets. [15,16] In contrast, most perovskite phases have the lowest energy surfaces of {001} surfaces and a corresponding equilibrium shape of a cube dominated by six {100} facets. [17][18][19][20]
We report a discovery that self-assembled perovskite-spinel nanostructures can be controlled simply by selecting single-crystal substrates with different orientations. In a model BiFeO(3)-CoFe(2)O(4) system, a (001) substrate results in rectangular-shaped CoFe(2)O(4) nanopillars in a BiFeO(3) matrix; in contrast, a (111) substrate leads to triangular-shaped BiFeO(3) nanopillars in a CoFe(2)O(4) matrix, irrespective of the volume fraction of the two phases. This dramatic reversal is attributed to the surface energy anisotropy as an intrinsic property of a crystal.
The control of surface properties of all inorganic cesium lead halide perovskite (CsPbX3; X = Cl, Br, or I) quantum dots (QDs) is essential to achieve excellent stability and high photoluminescence quantum yields (PLQYs). Herein, a facile method was performed to simultaneously enhance the stability and PLQYs of CsPbX3 QDs by a ZnX2/hexane solution post-treatment. We show that the halogen defect on the surface of CsPbX3 QDs can be treated in a controlled way, whereby the “black dots” that adhered on the surface as observed by transmission electron microscopy have be completely removed, resulting in enhanced stability and photoluminescence. The PLQYs of CsPbCl3, CsPbBr3, and CsPbI3 increased from 4, 58, and 63% to 86, 93, and 95%, respectively, and the origin of the “black dots” as well as their transformation mechanism has been demonstrated. As a result, the poly(dimethylsiloxane) composite films created by encapsulating stable and nearly defect-free green-emitting CsPbBr3, the red-emitting K2SiF6:Mn4+ phosphor, and a blue emission GaN chip were prepared and used to fabricate a remote-type white light-emitting diode device, which exhibits a high luminescence efficiency (≤98 lm/W) and a wide color gamut (∼130% of the National Television Standard Committee standard), suggesting the potential for liquid crystal display backlight application.
With an ever-expanding demand for data storage, transducers, and microelectromechanical (MEMS) systems applications, materials with superior ferroelectric and piezoelectric responses are of great interest. The lead zirconate titanate (PZT) family of materials has served as the cornerstone for such applications up until now. A critical drawback of this material, however, is the presence of lead and the recent concerns about the toxicity of lead-containing devices. Recently, the lead-free ferroelectric BiFeO 3 (BFO) has attracted a great deal of attention because of its superior thin-film ferroelectric properties, [1,2] which are comparable to those of the tetragonal, Ti-rich PZT system; therefore, BFO provides an alternate choice as a "green" ferro/piezoelectric material. Another advantage of BFO is its high ferroelectric Curie temperature (T c = 850°C in single crystals), [3,4] which enables it to be used reliably at high temperatures. The ferroelectric domain structure of epitaxial BFO films are typically discussed in the context of the crystallographic model of Kubel and Schmid; [5] however, by suppressing other structural variants in BFO, we can obtain periodic domain structures that may open additional application opportunities for this material. Ferroelectrics with periodic domain structures are of great interest for applications in photonic devices [6] and nanolithography.[7] Such a periodic polarization could be obtained by applying an external electric field while utilizing lithographically defined electrodes or by a direct writing process. [8,9] To obtain sub-micrometer feature sizes, however, domain engineering using a scanning force microscope with an appropriate bias voltage must be used to fabricate the patterned domain structures.[10] Unfortunately, this method works only on small areas and is limited by its slow scanning rate. Theoretical models predict the feasibility of controlling the domain architecture in thin films through suitable control over the heteroepitaxial constraints. [11] In the case of BFO thin films, we have found that such a control is indeed possible, mainly through control over the growth of the underlying SrRuO 3 electrode. Using this approach, we demonstrate the growth of highly ordered 1D ferroelectric domains in 120 nm thick BFO films. On the (001) C perovskite surface there are eight possible ferroelectric polarization directions corresponding to four structural variants of the rhombohedral ferroelectric thin film. (For simplicity, the c and o subscripts refer to the pseudocubic structures for BFO and orthorhombic structures of SrRuO 3 (SRO) and DyScO 3 (110) O (DSO), respectively.) Domain patterns can develop with either {100} C or {101} C boundaries for (001) C -oriented rhombohedral films. [12] In both cases, the individual domains in the patterns are energetically degenerate and thus equal-width stripe patterns are theoretically predicted. When the spontaneous polarization is included in the analysis, the {100} C boundary patterns have no normal component of the net po...
We have grown BiFeO3 thin films on SrRuO3∕SrTiO3 and SrRuO3∕SrTiO3∕Si using liquid delivery metalorganic chemical vapor deposition. Epitaxial BiFeO3 films were successfully prepared through the systematic control of the chemical reaction and deposition process. We found that the film composition and phase equilibrium are sensitive to the Bi:Fe ratio in the precursor. Fe-rich mixtures show the existence of α-Fe2O3, while Bi-rich mixtures show the presence of β-Bi2O3 as a second phase at the surface. In the optimized films, we were able to obtain an epitaxial single perovskite phase thin film. Electrical measurements using both quasistatic hysteresis and pulsed polarization measurements confirm the existence of ferroelectricity with a switched polarization of 110–120μC∕cm2, ΔP(=P*−P̂). Out-of plane piezoelectric (d33) measurements using an atomic force microscope yield a value of 50–60pm∕V.
Ferroelectric size effects in multiferroic BiFeO 3 have been studied using a host of complementary measurements. The structure of such epitaxial films has been investigated using atomic force microscopy, transmission electron microscopy, and x-ray diffraction. The crystal structure of the films has been identified as a monoclinic phase, which suggests that the polarization direction is close to ͗111͘. Such behavior has also been confirmed by piezoforce microscopy measurements. That also reveals that the ferroelectricity is down to at least 2 nm.
Predicting and understanding the cation distribution in spinels has been one of the most interesting problems in materials science. The present work investigates the effect of cation redistribution on the structural, electrical, optical and magnetic properties of mixed-valent inverse spinel NiCo2O4(NCO) thin films. It is observed that the films grown at low temperatures (T < 400 °C) exhibit metallic behavior while that grown at higher temperatures (T > 400 °C) are insulators with lower ferrimagnetic-paramagnetic phase transition temperature. So far, n-type Fe3O4 has been used as a conducting layer for the spinel thin films based devices and the search for a p-type counterpart still remains elusive. The inherent coexistence and coupling of ferrimagnetic order and the metallic nature in p-type NCO makes it a promising candidate for spintronic devices. Detailed X-ray Absorption and X–ray Magnetic Circular Dichroism studies revealed a strong correlation between the mixed-valent cation distribution and the resulting ferrimagnetic-metallic/insulating behavior. Our study clearly demonstrates that it is the concentration of Ni3+ions and the Ni3+–O2−Ni2+ double exchange interaction that is crucial in dictating the metallic behavior in NCO ferrimagnet. The metal-insulator and the associated magnetic order-disorder transitions can be tuned by the degree of cation site disorder via growth conditions.
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