Atomic Layer Engineering of Ferroelectricity in Dion-Jacobson Perovskites.

Recent advances in "hybrid-improper" ferroelectricity in Dion-Jacobson (DJ)-type layered perovskites have caused renewed interest in the search for new ferroelectrics. Here, we present an approach for the tailored synthesis of a new homologous series of DJ-type layered perovskites Cs(Bi2Srn-3)(Tin-1Nb)O3n+1. Starting from CsBi2Ti2NbO10 (n = 3), higher-order homologous phases with n = 4 and 5 were successfully synthesized by repeated solid-state calcination with SrTiO3. Characterizations by X-ray diffraction, electron diffraction, transmission electron microscopy, Raman scattering, and second harmonic generation showed the detailed structural features in Cs(Bi2Srn-3)(Tin-1Nb)O3n+1, and the polar structures could be stabilized by proper or hybrid-improper ferroelectricity, depending on the odd or even number of the perovskite layers. Our results provide important insights into the competition between the different mechanisms and the consequences of the ferroelectric properties in homologous layered perovskites.

Observation of Ferrochiral Transition Induced by an Antiferroaxial Ordering of Antipolar Structural Units in Ba(TiO)Cu4(PO4)4.

Ferrochiral transition, i.e., a transition involving an emergence of chirality, provides an unique opportunity to achieve a nonvolatile reversible control of chirality with external fields. However, materials showing pure ferrochiral transitions, which are accompanied by no other types of ferroic transition, are exceedingly rare. In this study, we propose that a pure ferrochiral transition is achieved by a combination of antipolar and antiferroaxial orderings of structural units, and substantiate this proposal through a study of the chiral compound Ba(TiO)Cu4(PO4)4. Single crystal X-ray diffraction measurements have revealed that this material undergoes a second order ferrochiral transition whose order parameter is described by an antiferroaxial (staggered) rotation of antipolar structural units, thus demonstrating our proposal. Furthermore, by measuring spatial distributions of optical rotation, we successfully visualized a temperature evolution of ferrochiral domains across the transition temperature and demonstrated the relationship between chirality and optical rotation. This work provides a guide to find a pure ferrochiral transition, thus providing an opportunity to achieve a ferroic control of chirality.

Structural Transition with a Sharp Change in the Electrical Resistivity and Spin-Orbit Mott Insulating State in a Rhenium Oxide, Sr3Re2O9.

We report the successful synthesis, crystal structure, and electrical properties of Sr3Re2O9, which contains Re6+ with the 5d1 configuration. This compound is isostructural with Ba3Re2O9 and shows a first-order structural phase transition at ∼370 K. The low-temperature (LT) phase crystallizes in a hettotype structure of Ba3Re2O9, which is different from that of the LT phase of Sr3W2O9, suggesting that the electronic state of Re6+ plays an important role in determining the crystal structure of the LT phase. The structural transition is accompanied by a sharp change in the electrical resistivity. This is likely a metal-insulator transition, as suggested by the electronic band calculation and magnetic susceptibility. In the LT phase, the ReO6 octahedra are rotated in a pseudo-a0a0a+ manner in Glazer notation, which corresponds to C-type orbital ordering. Paramagnetic dipole moments were confirmed to exist in the LT phase by muon spin rotation and relaxation measurements. However, the dipole moments shrink greatly because of the strong spin-orbit coupling in the Re ions. Thus, the electronic state of the LT phase corresponds to a Mott insulating state with strong spin-orbit interactions at the Re sites.

Synthesis, Structure, and Anomalous Magnetic Ordering of the Spin-1/2 Coupled Square Tetramer System K(NbO)Cu4(PO4)4.

Quasi-zero-dimensional antiferromagnets with weakly coupled clusters of multiple spins can provide an excellent platform for exploring exotic quantum states of matter. Here, we report the synthesis and the characterization of a copper-based insulating antiferromagnet, K(NbO)Cu4(PO4)4. Single-crystal X-ray diffraction measurements reveal that the crystal structure belongs to the tetragonal space group P4/nmm, in which Cu2+ ions align to form a quasi-two-dimensional layer of spin-1/2 coupled square tetramers. The structure is quasi-isostructural to recently reported magnetoelectric antiferromagnets, A(TiO)Cu4(PO4)4 (A = Ba, Sr, and Pb) with the P4212 space group. Despite their structural similarities, whereas the antiferromagnetic transition in A(TiO)Cu4(PO4)4 produces conventional anomalies in magnetization and heat capacity, that in K(NbO)Cu4(PO4)4 has several unusual features such as an upturn in magnetic susceptibility and a very weak specific heat anomaly that corresponds to a spin entropy release as small as 3%. These results indicate that the magnetism of K(NbO)Cu4(PO4)4 is far different from that of A(TiO)Cu4(PO4)4 and suggest that the ground state is very close to a quantum nonmagnetic singlet state. The origin of the distinct magnetism in K(NbO)Cu4(PO4)4 is discussed in terms of structural modifications of a Cu4O12 unit forming a square tetramer. Our study demonstrates that the present material family, represented by an extended chemical formula A(BO)Cu4(PO4)4 (AB = KNb, BaTi, SrTi, and PbTi), has broad chemical controllability of their magnetism. This makes this system an attractive material platform to study the physics of quantum spin-1/2 coupled square tetramers.

Robust Traffic Light and Arrow Detection Using Digital Map with Spatial Prior Information for Automated Driving.

Traffic light recognition is an indispensable elemental technology for automated driving in urban areas. In this study, we propose an algorithm that recognizes traffic lights and arrow lights by image processing using the digital map and precise vehicle pose which is estimated by a localization module. The use of a digital map allows the determination of a region-of-interest in an image to reduce the computational cost and false detection. In addition, this study develops an algorithm to recognize arrow lights using relative positions of traffic lights, and the arrow light is used as prior spatial information. This allows for the recognition of distant arrow lights that are difficult for humans to see clearly. Experiments were conducted to evaluate the recognition performance of the proposed method and to verify if it matches the performance required for automated driving. Quantitative evaluations indicate that the proposed method achieved 91.8% and 56.7% of the average f-value for traffic lights and arrow lights, respectively. It was confirmed that the arrow-light detection could recognize small arrow objects even if their size was smaller than 10 pixels. The verification experiments indicate that the performance of the proposed method meets the necessary requirements for smooth acceleration or deceleration at intersections in automated driving.

Crystal Structure and Photoluminescence Properties of an Incommensurate Phase in EuO- and P2O5-Doped Ca2SiO4.

We have for the first time clarified the incommensurately modulated crystal structure as well as the photoluminescence properties of Eu2+-activated Ca2SiO4 solid solution, the chemical formula of which is (Ca1.88Eu2+0.01□0.11)(Si0.78P0.22)O4, where □ denotes vacancies in Ca sites with the replacement of Si4+ by P5+. The emission spectrum upon the 335 nm excitation showed a relatively broad band centered at ca. 490 nm and a full width at half-maximum of ca. 80 nm. The crystal structure was made up of the four types of ß-Ca2SiO4-like layers with one type of interlayer. The incommensurate modulation with superspace group Pnma(0 ß 0)00 s was induced by the long-range stacking order of these layers. The modulation wavevector was 0.27404(2) × b*, with the basic unit-cell dimensions being a = 0.68355(2) nm, b = 0.54227(2) nm, and c = 0.93840(3) nm ( Z = 4). The basic structure contained two nonequivalent Ca sites. One site was fully occupied by Ca2+ and free from Eu2+ in the overall incommensurate structure. The occupational modulation at the other site was so significant that the sum of site occupation factors for Ca2+ and Eu2+ as low as 0.5 was seen at the interlayer. This site was too large for accommodation of Ca2+ but was suitable for Eu2+. Thus, the Eu2+ ions would exclusively concentrate at the relevant site, which would cause the emission peak of the incommensurate phase to be shifted to the shorter wavelength ranges as compared with those of the other commensurate phases such as ß and α'L.

Discovery of the High-Pressure Phase of Ba3W2O9 and Determination of Its Crystal Structure.

A new polymorphism of Ba3W2O9 is discovered with the use of a high-pressure synthesis technique and its crystal structure is determined by single-crystal X-ray diffraction and transmission electron microscopy. The crystal structure was isostructural with that of Ba3Re2O9, having a hexagonal unit cell of R3̅m symmetry with a = 0.574060(10) nm and c = 2.08256(4) nm. The high-pressure (HP) phase is obtained from a transformation of an ambient-pressure (AP) phase of the compound, which has the Cs3Tl2Cl9-type structure. The most notable change in the transformation is the connection of WO6 octahedra. The HP phase has corner-sharing octahedra, which form a bilayer structure, while the AP phase has face-sharing octahedra of isolated [W2O9] dimers. This type of the structural phase transition is unreported although it is possibly that a sequence of high-pressure structural transformations occurs for similar chemical compositions. The HP phase has W ions in WO6 octahedra with an unusual off-center displacement; although the displacement is slightly relaxed compared with that of the AP phase. The off-center displacement suggests strong hybridization between the W 5d orbitals and O 2p orbitals.

Local structure and oxide-ion conduction mechanism in apatite-type lanthanum silicates.

The local structure of apatite-type lanthanum silicates of general formula La9.33+x(SiO4)6O2+3x/2 has been investigated by combining the atomic pair distribution function (PDF) method, conventional X-ray and neutron powder diffraction (NPD) data and density functional theory (DFT) calculations. DFT was used to build structure models with stable positions of excess oxide ions within the conduction channel. Two stable interstitial positions were obtained in accordance with literature, the first one located at the very periphery of the conduction channel, neighbouring the SiO4 tetrahedral units, and the second one closer to the channel axis. The corresponding PDFs and average structures were then calculated and tested against experimental PDFs obtained by X-ray total scattering and NPD Rietveld refinements results gathered from literature. It was shown that of the two stable interstitial positions obtained with DFT only the second one located within the channel is consistent with experimental data. This result consolidates one of the two main conduction mechanisms along the c-axis reported in the literature, namely the one involving cooperative movement of O4 and Oi ions.

Morphological study of efficacy of clarithromycin-loaded nanocarriers for treatment of biofilm infection disease.

In this study, we developed a drug delivery system (DDS) using polymeric nanocarriers for the treatment of biofilm infection disease. Clarithromycin (CAM)-encapsulated and chitosan (CS) modified polymeric nanoparticles (NPs) were prepared using a polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus®) (Sol) and poly-(DL-lactide-co-glycolide), respectively. To understand the availability of the prepared NPs, we made morphological observations of the antibacterial activity derived from the NPs toward the bacterial cells within the biofilm using scanning electron microscopy and transmission electron microscopy measurements. These results revealed different antibacterial activities for the two types of drug carriers. In the case of CAM-encapsulated + CS-modified Sol micelles treatment, NPs can exert their antibacterial activity not only by the surfactant, CAM and CS effects but also by intrusion into the bacterial cells. Thereby, CAM-encapsulated + CS-modified Sol micelles had a higher antibacterial activity. The morphological information is useful to design suitable NPs for the treatment against biofilm infections.

Size control and vacuum-ultraviolet fluorescence of nanosized KMgF3 single crystals prepared using femtosecond laser pulses.

We fabricated nanosized KMgF3 single crystals via a dry pulsed laser ablation process using femtosecond laser pulses. The sizes, shapes, and crystallographic properties of the crystals were evaluated by transmission electron microscopy (TEM). Almost all of the particles were spherical with diameters of less than 100 nm, and they were not highly agglomerated. Selected-area electron diffraction and high-resolution TEM analyses showed that the particles were single crystals. Particle diameter was controlled within a wide range by adjusting the Ar ambient gas pressure. Under low gas pressures (1 and 10 Pa), relatively small particles (primarily 10 nm or less) were observed with a high number density. With increasing pressure, the mean diameter increased and the number density drastically decreased. Vacuum-ultraviolet cathodoluminescence was observed at 140-230 nm with blue shift and broadening of spectrum.

Waning-and-waxing shape changes in ionic nanoplates upon cation exchange.

Flexible control of the composition and morphology of nanocrystals (NCs) over a wide range is an essential technology for the creation of functional nanomaterials. Cation exchange (CE) is a facile method by which to finely tune the compositions of ionic NCs, providing an opportunity to obtain complex nanostructures that are difficult to form using conventional chemical synthesis procedures. However, due to their robust anion frameworks, CE cannot typically be used to modify the original morphology of the host NCs. In this study, we report an anisotropic morphological transformation of Cu1.8S NCs during CE. Upon partial CE of Cu1.8S nanoplates (NPLs) with Mn2+, the hexagonal NPLs are transformed into crescent-shaped Cu1.8S-MnS NPLs. Upon further CE, these crescent-shaped NPLs evolve back into completely hexagonal MnS NPLs. Comprehensive characterization of the intermediates reveals that this waxing-and-waning shape-evolution process is due to dissolution, redeposition, and intraparticle migration of Cu+ and S2-. Furthermore, in addition to Mn2+, this CE-induced transformation process occurs with Zn2+, Cd2+ and Fe3+. This finding presents a strategy by which to create heterostructured NCs with various morphologies and compositions under mild conditions.

Downshift of the Ni d band center over Ni nanoparticles in situ confined within an amorphous silicon nitride matrix.

Herein, nanocomposites made of Ni nanoparticles in situ distributed in an amorphous silicon nitride (Ni/a-Si3N4) matrix, on the one hand, and within an amorphous silicon dioxide (Ni/a-SiO2) matrix, on the other hand, were synthesized from the same Ni-modified polysilazane precursor. In both compounds, the Ni/Si atomic ratio (0.06-0.07), average Ni nanocrystallite size (7.0-7.6 nm) and micro/mesoporosity of the matrix were rigorously fixed. Hydrogen (H2)-temperature-programmed desorption (TPD) profile analysis revealed that the activation energy for H2 desorption at about 100-130 °C evaluated for the Ni/a-Si3N4 sample (47.4 kJ mol-1) was lower than that for the Ni/a-SiO2 sample (68.0 kJ mol-1). Mechanistic study with X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations revealed that, at Ni nanoparticle/matrix heterointerfaces, Ni becomes more covalently bonded to N atoms in the a-Si3N4 matrix compared to O atoms in the a-SiO2 matrix. Therefore, based on experimental and theoretical studies, we elucidated that nickel-nitrogen (Ni-N) interactions at the heterointerface lead to remarkable Ni d band broadening and downshifting of the d band center relative to those generated by Ni-oxygen (Ni-O) interactions at the heterointerface. This facilitates H2 desorption, as experimentally observed in the Ni/a-Si3N4 sample.

Synthesis and disordered crystal structure of Al3O3.5C0.5.

The crystal structure of Al3O3.5C0.5 (Z = 3) has been characterized by X-ray powder diffraction (XRPD), transmission electron microscopy, and electron probe microanalysis. The title compound is trigonal with space group R3̅m (centrosymmetric) and hexagonal unit-cell dimensions a = 0.29588(1) nm, c = 2.84080(7) nm, and V = 0.21538(1) nm(3). The initial structural model was determined by the charge-flipping method and subsequently refined by the Rietveld method. The final structural model showed the positional disordering of one of the two types of Al sites. The maximum-entropy method-based pattern fitting (MPF) method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were Rwp = 4.03%, S (= Rwp/Re) = 1.17, Rp = 3.08%, RB = 0.82%, and RF = 0.72%. The crystal was composed of antiphase domains, suggesting the occurrence of the high-low phase transition during the cooling process. The transition would be accompanied by the loss of unit-lattice translation, and hence the disordered structural model determined by XRPD might be of the average structure of the low-temperature phase.

Element-selective imaging of atomic columns in a crystal using STEM and EELS.

Microstructure characterization has become indispensable to the study of complex materials, such as strongly correlated oxides, and can obtain useful information about the origin of their physical properties. Although atomically resolved measurements have long been possible, an important goal in microstructure characterization is to achieve element-selective imaging at atomic resolution. A combination of scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) is a promising technique for atomic-column analysis. However, two-dimensional analysis has not yet been performed owing to several difficulties, such as delocalization in inelastic scattering or instrumentation instabilities. Here we demonstrate atomic-column imaging of a crystal specimen using localized inelastic scattering and a stabilized scanning transmission electron microscope. The atomic columns of La, Mn and O in the layered manganite La1.2Sr1.8Mn2O7 are visualized as two-dimensional images.

Carbonization of a Molybdenum Substrate Surface and Nanoparticles by a One-Step Method of Femtosecond Laser Ablation in a Hexane Solution.

Molybdenum carbides (MoC and Mo2C) are being reported for various applications, for example, catalysts for sustainable energies, nonlinear materials for laser applications, protective coatings for improving tribological performance, and so on. A one-step method for simultaneously fabricating molybdenum monocarbide (MoC) nanoparticles (NPs) and MoC surfaces with a laser-induced periodic surface structure (LIPSS) was developed by using pulsed laser ablation of a molybdenum (Mo) substrate in hexane. Spherical NPs with an average diameter of 61 nm were observed by scanning electron microscopy. The X-ray diffraction pattern and electron diffraction (ED) pattern results indicate that a face-centered cubic MoC was successfully synthesized for the NPs and on the laser-irradiated area. Notably, the ED pattern suggests that the observed NPs are nanosized single crystals, and a carbon shell was observed on the surface of MoC NPs. The X-ray diffraction pattern of both MoC NPs and LIPSS surface indicates the formation of FCC MoC, agreeing with the results of ED. The results of X-ray photoelectron spectroscopy also showed the bonding energy attributed to Mo-C, and the sp2-sp3 transition was confirmed on the LIPSS surface. The results of Raman spectroscopy have also supported the formation of MoC and amorphous carbon structures. This simple synthesis method for MoC may provide new possibilities for preparing Mo x C-based devices and nanomaterials, which may contribute to the development of catalytic, photonic, and tribological fields.

One-step and room-temperature fabrication of carbon nanocomposites including Ni nanoparticles for supercapacitor electrodes.

With the increasing importance of power storage devices, demand for the development of supercapacitors possessing both rapid reversible chargeability and high energy density is accelerating. Here we propose a simple process for the room temperature fabrication of pseudocapacitor electrodes consisting of a faradaic redox reaction layer on a metallic electrode with an enhanced surface area. As a model metallic electrode, an Au foil was irradiated with Ar+ ions with a simultaneous supply of C and Ni at room temperature, resulting in fine metallic Ni nanoparticles dispersed in the carbon matrix with local graphitization on the ion-induced roughened Au surface. A carbon layer including fine Ni nanoparticles acted as an excellent faradaic redox reaction layer and the roughened surface contributed to an increase in surface area. The fabricated electrode, which included only 14 µg cm-2 of Ni, showed a stored charge ability three times as large as that of the bulky Ni foil. Thus, it is believed that a carbon layer including Ni nanoparticles fabricated on the charge collective electrode with an ion-irradiation method is promising for the development of supercapacitors from the viewpoints of the reduced use of rare metal and excellent supercapacitor performance.

Determinants of crystal structure transformation of ionic nanocrystals in cation exchange reactions.

Changes in the crystal system of an ionic nanocrystal during a cation exchange reaction are unusual yet remain to be systematically investigated. In this study, chemical synthesis and computational modeling demonstrated that the height of hexagonal-prism roxbyite (Cu1.8S) nanocrystals with a distorted hexagonal close-packed sulfide anion (S2-) sublattice determines the final crystal phase of the cation-exchanged products with Co2+ [wurtzite cobalt sulfide (CoS) with hexagonal close-packed S2- and/or cobalt pentlandite (Co9S8) with cubic close-packed S2-]. Thermodynamic instability of exposed planes drives reconstruction of anion frameworks under mild reaction conditions. Other incoming cations (Mn2+, Zn2+, and Ni2+) modulate crystal structure transformation during cation exchange reactions by various means, such as volume, thermodynamic stability, and coordination environment.

Unique octahedral rotation pattern in the oxygen-deficient Ruddlesden-Popper compound Gd3Ba2Fe4O12.

A novel Ruddlesden-Popper-related compound, Gd3Ba2Fe4O12, was discovered and its crystal structure was determined via single-crystal X-ray diffraction. The structure has an ordered structure of octahedra and pyramids along the c axis. Gd3Ba2Fe4O12 belongs to the tetragonal system P42/ncm, with a = 5.59040 (10) Šand c = 35.1899 (10) Å. The A-site ions in the Ruddlesden-Popper structure, i.e. Gd3+ and Ba2+, exhibit an ordering along the c axis. The perfect oxygen deficiency is accommodated at the GdO layers in the proper Ruddlesden-Popper structure. Using the bond-valence-sum method, the Fe ions in the FeO6 octahedra and FeO5 pyramids represent valence states of +3 and +2.5, respectively, demonstrating a two-dimensional charge disproportionation. The corner-sharing FeO6 octahedra and FeO5 pyramids are tilted in opposite directions, with the neighbours around one axis of the simple perovskite configuration, which, using Glazer's notation, can be represented as a-b0c0/b0a-c0. In the perovskite blocks, the facing FeO5 pyramids across the Gd layer rotate in the same sense, which is a unique rotation feature related to oxygen deficiency.

Low temperature in situ formation of cobalt in silicon nitride toward functional nitride nanocomposites.

This work highlights the first demonstration of a low-temperature in situ formation of Co nanocrystallites embedded within an amorphous silicon nitride matrix through careful control of the chemistry behind material design using perhydropolysilazane (PHPS) as a Si3N4 precursor further coordinated with CoCl2 and ammonia as a pyrolysis atmosphere. The Co nucleation was allowed to proceed at temperatures as low as 400 °C via thermal decomposition of Co2N pre-formed in situ by the reaction of CoCl2 with the Si centers of PHPS at the early stage of pyrolysis (220-350 °C).

Relationship between magnetic domain configuration and crystallographic orientation in a colossal magnetoresistive material.

We investigated the relationship between the magnetic domain (MD) configuration and crystallographic orientation in a colossal magnetoresistive (CMR) material La(0.69)Ca(0.31)MnO(3) in which anisotropic magnetoresistance (AMR) was observed as well. It was observed that the MD structure with a micrometre scale in the (001) plane collapses when a modulated structure with a nanometre scale emerges near the Curie temperature (T(c)). On the other hand, twin boundaries were observed to develop in the (110) plate, and they pin the MD walls. Like the pinning effect on MD walls, the emergence of vortex-like tadpole closure MDs upon the application of external magnetic field may be an origin of the AMR in La(0.69)Ca(0.31)MnO(3).