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Research into variation of the ferroelectric phase transition of a series of isomorphous donor (D)-acceptor (A) charge-transfer complexes is presented. It was possible to identify the novel electronic state of the DA complex in which the valence state undergoes the quantum fluctuation.

The cooperative charge transfer among constructive molecules in organic crystals of tetrathiafulvalene-chloranil induced by the irradiation of a laser pulse with an 80-fs width are studied. It is shown that the photoinduced neutral-ionic phase transition is bidirectional and that the photoinjected localized excited states grow into the macroscopic metastable phase domain within 1 ns. The photoconverted fraction and the growth dynamics of the localized photoexcited species into the macroscopic domain are also dependent on the excitation intensity.

Skyrmion, a concept originally proposed in particle physics half a century ago, can now find the most fertile field for its applicability, that is, the magnetic skyrmion realized in helimagnetic materials. The spin swirling vortex-like texture of the magnetic skyrmion can define the particle nature by topology; that is, all the constituent spin moments within the two-dimensional sheet wrap the sphere just one time. Such a topological nature of the magnetic skyrmion can lead to extraordinary metastability via topological protection and the driven motion with low electric-current excitation, which may promise future application to spintronics. The skyrmions in the magnetic materials frequently show up as the crystal lattice form, e.g., hexagonal lattice, but sometimes as isolated or independent particles. These skyrmions in magnets were initially found in acentric magnets, such as chiral, polar, and bilayered magnets endowed with antisymmetric spin exchange interaction, while the skyrmion host materials have been explored in a broader family of compounds including centrosymmetric magnets. This review describes the materials science and materials chemistry of magnetic skyrmions using the classification scheme of the skyrmion forming microscopic mechanisms. The emergent phenomena and functions mediated by skyrmions are described, including the generation of emergent magnetic and electric field by statics and dynamics of skrymions and the inherent magnetoelectric effect. The other important magnetic topological defects in two or three dimensions, such as biskyrmions, antiskyrmions, merons, and hedgehogs, are also reviewed in light of their interplay with the skyrmions. [ABSTRACT FROM AUTHOR]

The 2,3,5,6-tetra(2'-pyridyl)pyrazine molecule (TPPZ) as the counterpart of anilic acids was examined to explore the extensive variety of H-bonding modes compatible with ferroelectricity. The observed slow polarization reversal with modest pyroelectricity provide evidence for the room-temperature ferroelectricity of the ([H.sub.2]-TPPZ)[(Hba).sub.2] crystal.

The crystal structures are described for both the paraelectric and ferroelectric phases of the phenazine (Phz) with chloranilic acid ([H.sub.2]ca) and bromanilic acid ([H.sub.2b]a), which is obtained by the neutron diffraction and synchrotron X-ray diffraction. The results show that the H-bond has played a vital role in producing the polarization in this system.

Ferroelectricity and large dielectric susceptibility at room temperature are realized in hydrogen-bonded adducts of phenazine and deuterated chloranilic acids. The effective improvement of Curie temperature (T(sub c)) by deuteration, in analogy with the conventional hydrogen-bonded ferroelectrics, manifests the importance of hydrogen bonds for the ferroelectricity.

A study was conducted to investigate the use of charge-transfer complexes as candidates for molecular ferroelectrics with the use of robust electron-lattice associations. It presents the structural, optical and dielectric attributes of a new complex of 5,10-dihydro-5,10-dimethylphenazine with 2,5-dimethyl-7,7,8,8-tetracyano-p-quinodimethane as an example of dielectric phase transition accompanied by the order-order phenomenon of the deformation of fractionally charged molecules.

A study was conducted to examine band filling control in a conducting system supporting donor pi molecules that is based on bis(ethylenedithio)tetrathiafulvalene cation radical salts. Inductively coupled plasma mass spectrometry was carried out to determine the ratio of M:M in crystal batches. Results indicated that Findings suggested partial electron transfers between donor and anion in doped crystals.

Experiments were conducted to investigate the novel dielectric properties with quantum effect and the phase diagram of an alloy system. The system incorporates the selenium analog of the tetrathiafulvalene and tetraselenafulvalene with larger molecular volume and exhibited modest perturbations in molecular shape, symmetry and ionization energy. The findings provided insights on the chemical control of charge transfer complexes.

Orthorhombic perovskites RMnO3 are representative of spin-driven ferroelectrics. When the radius of the rare-earth ion R is smaller than that of Dy, for instance in YMnO3, the orthorhombic phase becomes metastable at ambient pressure, which impedes the crystal growth; thus, the detailed magnetic and multiferroic properties of the metastable phase have not been characterized. In this work, we successfully obtained single crystals of orthorhombic YMnO3 using quasi-hydrothermal conditions under a high pressure of 5.5 GPa. Magnetic and dielectric measurements under magnetic fields revealed that the magnetic ground state is the commensurate E-type antiferromagnetic, while a cycloidal spin phase likely coexists in the intermediate temperature range, which enhances the magnetoelectric response to external fields. [ABSTRACT FROM AUTHOR]

Configurational entropy can impact crystallization processes, tipping the scales between structures of nearly equal internal energy. Using alloyed single crystals of Gd 2 PdSi 3 in the AlB 2 -type structure, we explore the formation of complex layer sequences made from alternating, two-dimensional triangular and honeycomb slabs. A four-period and an eight-period stacking sequence are found to be very close in internal energy, the latter being favored by entropy associated with covering the full configuration space of interlayer bonds. Possible consequences of polytype formation on magnetism in Gd 2 PdSi 3 are discussed.

Topologically nontrivial spin textures, such as skyrmions and dislocations, display emergent electrodynamics and can be moved by spin currents over macroscopic distances. These unique properties and their nanoscale size make them excellent candidates for the development of next-generation race-track memory and unconventional computing. A major challenge for these applications and the investigation of nanoscale magnetic structures in general is the realization of suitable detection schemes. We study magnetic disclinations, dislocations, and domain walls in FeGe and reveal pronounced responses that distinguish them from the helimagnetic background. A combination of magnetic force microscopy (MFM) and micromagnetic simulations links the response to the local magnetic susceptibility, that is, characteristic changes in the spin texture driven by the MFM tip. On the basis of the findings, which we explain using nonlinear response theory, we propose a read-out scheme using superconducting microcoils, presenting an innovative approach for detecting topological spin textures and domain walls in device-relevant geometries.

The formation of topological spin textures at the nanoscale has a significant impact on the long-range order and dynamical response of magnetic materials. We study the relaxation mechanisms at the conical-to-helical phase transition in the chiral magnet FeGe. By combining macroscopic ac susceptibility measurement, surface-sensitive magnetic force microscopy, and micromagnetic simulations, we demonstrate how the motion of magnetic topological defects, here edge dislocations, impacts the local formation of a stable helimagnetic spin structure. Although the simulations show that the edge dislocations can move with a velocity up to 100 m/s through the helimagnetic background, their dynamics are observed to disturb the magnetic order on the time scale of minutes due to randomly distributed pinning sites. The results corroborate the substantial impact of dislocation motions on the nanoscale spin structure in chiral magnets, revealing previously hidden effects on the formation of helimagnetic domains and domain walls.

Magnetic skyrmions are topological spin textures that have shown promise for future nonvolatile memory devices. Herein, we report on the stability of magnetic skyrmions in alloyed cubic B20 Fe 1- x Co x Si nanowires (NWs) determined using off-axis electron holography and magnetotransport measurements. This study presents the real space observation of one-dimensional skyrmion lattice in a NW of Fe 1- x Co x Si which shows that the skyrmion phase in a Fe 0.75 Co 0.25 Si NW exists at lower applied magnetic fields (200 Oe) with a reduced domain size (28 ± 2 nm) in comparison to bulk and thin film samples. Magnetotransport measurements were used to observe the helimagnetic transition temperature dependence on the cobalt concentration in the Fe 1- x Co x Si NWs. Field-dependent magnetoresistance measurements of Fe 1- x Co x Si NWs under applied magnetic field parallel to the NW axis and their second derivative plots reveal the critical fields for the magnetic state transition at different temperatures. A representative magnetic phase diagram constructed with the results from transport measurements of a Fe 0.81 Co 0.19 Si NW clearly shows expanded stability region for magnetic skyrmions in the Fe 1- x Co x Si NWs.

Constituent atoms and electrons determine matter properties together, and they can form long-range ordering respectively. Distinguishing and isolating the electronic ordering out from the lattice crystal is a crucial issue in contemporary materials science. However, the intrinsic structure of a long-range electronic ordering is difficult to observe because it can be easily affected by many external factors. Here, we present the observation of electronic multiple ordering (EMO) and its dynamics at the micrometer scale in a manganite thin film. The strong internal couplings among multiple electronic degrees of freedom in the EMO make its morphology robust against external factors and visible via well-defined boundaries along specific axes and cleavage planes, which behave like a multiple-ordered electronic crystal. A strong magnetic field up to 17.6 T is needed to completely melt such EMO at 7 K, and the corresponding formation, motion, and annihilation dynamics are imaged utilizing a home-built high-field magnetic force microscope. The EMO is parasitic within the lattice crystal house, but its dynamics follows its own rules of electronic correlation, therefore becoming distinguishable and isolatable as the electronic ordering. Our work provides a microscopic foundation for the understanding and control of the electronic ordering and the designs of the corresponding devices.

To utilize magnetic skyrmions, nanoscale vortex-like magnetic structures, experimental elucidation of their dynamics against current application in various circumstances such as in confined structure and mixture of different magnetic phases is indispensable. Here, we investigate the current-induced dynamics of the coexistence state of magnetic skyrmions and helical magnetic structure in a thin plate of B20-type helimagnet FeGe in terms of in situ real-space observation using Lorentz transmission electron microscopy. Current pulses with various heights and widths were applied, and the change of the magnetic domain distribution was analyzed using a machine-learning technique. The observed average driving direction of the two-magnetic-state domain boundary is opposite to the applied electric current, indicating ferromagnetic s-d exchange coupling in the spin-transfer torque mechanism. The evaluated driving distance tends to increase with increasing the pulse duration time, current density (>1 × 10 9 A/m 2 ), and sample temperature, providing valuable information about hitherto unknown current-induced dynamics of the skyrmion-lattice ensemble.

Magnetic skyrmions in Co 8 Zn 8 Mn 4 thin plates are observed to deform in a metastable state prepared in a magnetic-field-cooling process by way of the thermal-equilibrium skyrmion phase. In cooling, the disk-shape skyrmions change to bar- or L-shaped elongated form, whereas the skyrmion density is nearly conserved. The deformation of the skyrmions in the supercooled metastable phase is observed irrespective of the crystallographic orientation of the thin plate, whereas the elongation direction nearly aligns along the magnetic easy axis. It is proposed that the deformation should be induced by a large increase in magnetic modulation wavenumber when decreasing the temperature, whereas the topological protection of the skyrmions keeps the averaged skyrmion density constant.

Three-dimensional forms of skyrmion aggregate, such as a cubic lattice of skyrmions, are anticipated to exist, yet their direct observations remain elusive. Here, we report real-space observations of spin configurations of the skyrmion-antiskyrmion cubic-lattice in MnGe with a very short period (∼3 nm) and hence endowed with the largest skyrmion number density. The skyrmion lattices parallel to the {100} atomic lattices are directly observed using high-resolution Lorentz transmission electron microscopes, simultaneously with underlying atomic-lattice fringes.

A single crystal of bismuth diselenide, BiSe2, containing both monochalcogen (Se(2-)) and dichalcogen (Se2(2-)) ions, was prepared at a high pressure of 5.5 GPa. Its crystal structure, substitution chemistry, and physical properties were investigated. X-ray analysis showed that BiSe2 is in a monoclinic system (space group C2/m) with the following lattice parameters: a = 16.740(3) Å, b = 4.1410(11) Å, c = 12.027(3) Å, and β = 127.658(13)°. A crystal structure of BiSe2 can be viewed as a layered structure with stacks of neutral BiSe2 blocks along the c-axis, or alternatively as a quasi-one-dimensional structure with double chains of BiSe5 pyramids along the b-axis. Each Bi is coordinated with three Se(2-) ions and two Se2(2-) ions, and the bond valence analysis indicated that Bi was trivalent. BiSe2 and BiS2 form a solid solution in the whole range while retaining the same structure, and the partial substitution of Sb for Bi is also achieved at 10%. All the compounds show a semiconducting property and diamagnetism that can be attributed to the closed-shell ion core. In spite of the compositional analogy with Bi2Se3, BiSe2 is proven by the first-principles calculations not to be a topological insulator.

The switching of electric polarization induced by electric fields, a fundamental functionality of ferroelectrics, is closely associated with the motions of the domain walls that separate regions with distinct polarization directions. Therefore, understanding domain-walls dynamics is of essential importance for advancing ferroelectric applications. In this Letter, we show that the topology of the multidomain structure can have an intrinsic impact on the degree of switchable polarization. Using a combination of polarization hysteresis measurements and piezoresponse force microscopy on a uniaxial organic ferroelectric, α-6,6'-dimethyl-2,2'-bipyridinium chloranilate, we found that the head-to-head (or tail-to-tail) charged domain walls are strongly pinned and thus impede the switching process; in contrast, if the charged domain walls are replaced with electrically neutral antiparallel domain walls, bulk polarization switching is achieved. Our findings suggest that manipulation of the multidomain topology can potentially control the switchable polarization.

We report here the real-space observation of skyrmions and helical magnetic domains in a MnSi nanowire (NW) using Lorentz transmission electron microscopy (LTEM). The MnSi NW was thinned to a rectangular cross-section by focused-ion beam milling to reduce obstructive Fresnel fringes. Helimagnetic domains, imaged as alternating bright and dark contrast stripes with an 18 nm period, were observed to be the spontaneous magnetic ground state at 6 K, while the hexagonal skyrmion lattice (SkX) with a domain diameter of 18 nm was observed under a normal magnetic field of 210 mT. Temperature-dependent measurements reveal that the SkX is stable over a larger range in this NW system (6-35 K) compared to the narrow temperature regime of skyrmion phase in bulk MnSi (26-30 K) and thin films of MnSi (5-23 K).

Observing and characterizing the spin distributions on a nanometer scale are of vital importance for understanding nanomagnetism and its application to spintronics. The magnetic structure in MnSi thin samples prepared from a bulk, which undergoes a transition from a helix to a skyrmion lattice, was investigated by in situ observation using Lorentz microscopy. Stripe domains were observed at zero applied field below 22.5 K. A skyrmion lattice with 6-fold symmetry in real space appeared when a field of 0.18 T was applied normal to the film plane. The lattice constant was estimated to be 18 nm, almost identical to the helical period. In comparison with the marginally stable skyrmion phase in a bulk sample, the skyrmion phase was stable over a wide range of temperatures and magnetic fields in the thin samples., (© 2012 American Chemical Society)

Supramolecular ferroelectric cocrystals of phenazine (Phz) with chloranilic acid (H(2)ca), bromanilic acid (H(2)ba), and fluoranilic acid (H(2)fa) have been characterized by the interplay between their structural transformations and solid-state acid-base (proton transfer) reactions. At ambient pressure, the Phz-H(2)ca, Phz-H(2)ba, and their deuterated crystals exhibit incomplete proton displacement, which transforms the neutral molecules into semi-ionic at low temperatures below the Curie point (T(c)(IC) < T < T(c)(I)). For the cocrystal of the less acidic H(2)fa, the ferroelectric phase is induced only by applying hydrostatic pressure above ~0.6 GPa. According to the combined studies of temperature-dependent dielectric permittivity and synchrotron X-ray diffraction, it was proved that the ferroelectric (FE-I) phase is always accompanied at lower temperatures by successive phase transitions to the lattice modulated phases with incommensurate periodicities (IC phase, T(c)(II) < T < T(c)(IC)) and with commensurate (2- or 3-fold) periodicities (FE-II or FE-III phase, T < T(c)(II)). Whereas the ground-state structures at ambient pressure are different from one another among the Phz-H(2)ca (FE-II form), Phz-H(2)ba (FE-III form), and Phz-H(2)fa (paraelectric form), their systematic changes under pressure depict a universal pressure-temperature phase diagram. The possible origins of structural changes are assigned to the valence instability and the frustrated Coulomb interactions that induce the charge disproportionation (coexisting neutral ionic) states with the staging spatial orders., (© 2011 American Chemical Society)

Orthorhombic perovskites RMnO(3) are representative of spin-driven ferroelectrics. When the radius of the rare-earth ion R is smaller than that of Dy, for instance in YMnO(3), the orthorhombic phase becomes metastable at ambient pressure, which impedes the crystal growth; thus, the detailed magnetic and multiferroic properties of the metastable phase have not been characterized. In this work, we successfully obtained single crystals of orthorhombic YMnO(3) using quasi-hydrothermal conditions under a high pressure of 5.5 GPa. Magnetic and dielectric measurements under magnetic fields revealed that the magnetic ground state is the commensurate E-type antiferromagnetic, while a cycloidal spin phase likely coexists in the intermediate temperature range, which enhances the magnetoelectric response to external fields.