K.-T. Ko

Galvanic Replacement Reactions in Metal Oxide Nanocrystals

Hollowing Out Metal Oxide Nanoparticles Corrosion is normally a problem, but it can be useful, for example, when you wish to create hollow metal nanoparticles, whereby the reduction of one metal species in solution drives the dissolution of the core of the particle. Oh et al. (p. 964; see the Perspective by Ibáñez and Cabot) adapted this approach to metal oxide nanoparticles by placing Mn3O4 nanocrystals in solution with Fe2+ ions, which replaces the nanocrystal exterior with γ-Fe2O3. At sufficiently high Fe2+ concentrations, hollow γ-Fe2O3 nanocages formed. These hollow structures could be used as anode materials for lithium ion batteries. Hollow mixed-metal oxide nanoparticles can be made by replacing the metal cations through redox reactions in solution. [Also see Perspective by Ibáñez and Cabot] Galvanic replacement reactions provide a simple and versatile route for producing hollow nanostructures with controllable pore structures and compositions. However, these reactions have previously been limited to the chemical transformation of metallic nanostructures. We demonstrated galvanic replacement reactions in metal oxide nanocrystals as well. When manganese oxide (Mn3O4) nanocrystals were reacted with iron(II) perchlorate, hollow box-shaped nanocrystals of Mn3O4/γ-Fe2O3 (“nanoboxes”) were produced. These nanoboxes ultimately transformed into hollow cagelike nanocrystals of γ-Fe2O3 (“nanocages”). Because of their nonequilibrium compositions and hollow structures, these nanoboxes and nanocages exhibited good performance as anode materials for lithium ion batteries. The generality of this approach was demonstrated with other metal pairs, including Co3O4/SnO2 and Mn3O4/SnO2.

Realization of giant magnetoelectricity in helimagnets.

We show that low field magnetoelectric (ME) properties of helimagnets Ba0.5Sr1.5Zn2(Fe1-xAlx)12O22 can be efficiently tailored by the Al-substitution level. As x increases, the critical magnetic field for switching electric polarization is systematically reduced from approximately 1 T down to approximately 1 mT, and the ME susceptibility is greatly enhanced to reach a giant value of 2.0x10{4} ps/m at an optimum x=0.08. We find that control of the nontrivial orbital moment in the octahedral Fe sites through the Al substitution is crucial for fine-tuning the magnetic anisotropy and obtaining the conspicuously improved ME characteristics.

Concurrent transition of ferroelectric and magnetic ordering near room temperature

Strong spin-lattice coupling in condensed matter gives rise to intriguing physical phenomena such as colossal magnetoresistance and giant magnetoelectric effects. The phenomenological hallmark of such a strong spin-lattice coupling is the manifestation of a large anomaly in the crystal structure at the magnetic transition temperature. Here we report that the magnetic Néel temperature of the multiferroic compound BiFeO(3) is suppressed to around room temperature by heteroepitaxial misfit strain. Remarkably, the ferroelectric state undergoes a first-order transition to another ferroelectric state simultaneously with the magnetic transition temperature. Our findings provide a unique example of a concurrent magnetic and ferroelectric transition at the same temperature among proper ferroelectrics, taking a step toward room temperature magnetoelectric applications.

Electric polarization enhancement in multiferroic CoCr2O4 crystals with Cr-site mixing

Single crystals of multiferroic cobalt chromite Co(Cr2−xCox)O4 have been grown via several methods to have different Co3+ doping levels (x=0.0, 0.14, and 0.18). Under magnetic fields, all the crystals display electric polarization reversal below their spiral spin ordering temperatures. We find that both saturated electric polarization and magnetization under magnetic fields increase significantly with the increase in x. This result can be qualitatively explained by a broken balance between at least two electric polarization contributions existing in CoCr2O4 and is expected to be useful in tailoring electric polarization in similar kinds of multiferroics.

Simple tuning of carrier type in topological insulator Bi2Se3 by Mn doping

Bi2Te3 is a well-known thermoelectric material for room-temperature operations because it has a high Seebeck coefficient, and the charge carrier type is easily tunable. However, the carrier type of Bi2Se3 is not tunable, which is one of the weaknesses for the thermoelectric applications, in spite of its high Seebeck coefficient. Here, we report the tuning of charge carriers in Bi2Te3 from n type to p type by doping Mn into the Bi sites. The carrier type is n type up to the Mn doping level of 5% and changes to p type above 5% Mn doping. The temperature-dependent resistivity of Bi2−xMnxSe3 shows a metallic behavior for x < 0.05, while for x ≥ 0.05, it shows an upturn at low temperatures. This provides evidence that by Mn doping, the Fermi level is continuously tuned from the bulk conduction band to the bulk valence band. The Seebeck coefficient increases monotonically with increasing temperature, and the absolute values are same for both n- and p-type samples. This implies that Bi2Se3 is another candidate o...

Charge-ordering cascade with spin-orbit Mott dimer states in metallic iridium ditelluride

Spin-orbit coupling results in technologically-crucial phenomena underlying magnetic devices like magnetic memories and energy-efficient motors. In heavy element materials, the strength of spin-orbit coupling becomes large to affect the overall electronic nature and induces novel states such as topological insulators and spin-orbit-integrated Mott states. Here we report an unprecedented charge-ordering cascade in IrTe2 without the loss of metallicity, which involves localized spin-orbit Mott states with diamagnetic Ir(4+)-Ir(4+) dimers. The cascade in cooling, uncompensated in heating, consists of first order-type consecutive transitions from a pure Ir(3+) phase to Ir(3+)-Ir(4+) charge-ordered phases, which originate from Ir 5d to Te 5p charge transfer involving anionic polymeric bond breaking. Considering that the system exhibits superconductivity with suppression of the charge order by doping, analogously to cuprates, these results provide a new electronic paradigm of localized charge-ordered states interacting with itinerant electrons through large spin-orbit coupling.

Electronic and spin states of SrRuO3 thin films: An x-ray magnetic circular dichroism study

We report a study of the local magnetism in thin films of SrRuO3 grown on (111) and (001) oriented SrTiO3 substrates using x-ray magnetic circular dichroism spectroscopy (XMCD) at the Ru-L2,3 edges. The application of the sum rules to the XMCD data gives an almost quenched orbital moment and a spin moment close to the value expected for the low spin state S = 1 . Full-multiplet cluster calculations indicate that the low spin state is quite stable and suggest that the occurrence of a transition to the high spin state S = 2 in strained thin films of SrRuO3 is unlikely as it would be too expensive in energy.

Long-range interactions in the effective low-energy Hamiltonian of Sr2IrO4: A core-to-core resonant inelastic x-ray scattering study

We have investigated the electronic structure of Sr2IrO4 using core level resonant inelastic x-ray scattering. The experimental spectra can be well reproduced using ab initio density functional theory based multiplet ligand field theory calculations, thereby validating these calculations. We found that the low-energy, effective Ir t2g orbitals are practically degenerate in energy. We uncovered that covalency in Sr2IrO4, and generally in iridates, is very large with substantial oxygen ligand hole character in the Ir t2g Wannier orbitals. This has far reaching consequences, as not only the onsite crystal-field energies are determined by the long range crystal-structure, but, more significantly, magnetic exchange interactions will have long range distance dependent anisotropies in the spin direction. These findings set constraints and show pathways for the design of d^5 materials that can host compass-like magnetic interactions.

Bulk and surface electronic properties of SmB6 : A hard x-ray photoelectron spectroscopy study

We have carried out bulk-sensitive hard x-ray photoelectron spectroscopy measurements on in situ cleaved and ex situ polished

Contiguous 3 d and 4 f Magnetism: Strongly Correlated 3 d Electrons in YbFe 2 Al 10

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