Dimensionality Engineering of Magnetic Anisotropy from the Anomalous Hall Effect in Synthetic SrRuO3 Crystals.

Magnetic anisotropy in atomically thin correlated heterostructures is essential for exploring quantum magnetic phases for next-generation spintronics. Whereas previous studies have mostly focused on van der Waals systems, here we investigate the impact of dimensionality of epitaxially grown correlated oxides down to the monolayer limit on structural, magnetic, and orbital anisotropies. By designing oxide superlattices with a correlated ferromagnetic SrRuO3 and nonmagnetic SrTiO3 layers, we observed modulated ferromagnetic behavior with the change of the SrRuO3 thickness. Especially, for three-unit-cell-thick layers, we observe a significant 1500% improvement of the coercive field in the anomalous Hall effect, which cannot be solely attributed to the dimensional crossover in ferromagnetism. The atomic-scale heterostructures further reveal the systematic modulation of anisotropy for the lattice structure and orbital hybridization, explaining the enhanced magnetic anisotropy. Our findings provide valuable insights into engineering the anisotropic hybridization of synthetic magnetic crystals, offering a tunable spin order for various applications.

In2Ga2ZnO7 oxide semiconductor based charge trap device for NAND flash memory.

The programming characteristics of charge trap flash memory device adopting amorphous In2Ga2ZnO7 (a-IGZO) oxide semiconductors as channel layer were evaluated. Metal-organic chemical vapor deposition (MOCVD) and RF-sputtering processes were used to grow a 45 nm thick a-IGZO layer on a 20 nm thick SiO2 (blocking oxide)/p++-Si (control gate) substrate, where 3 nm thick atomic layer deposited Al2O3 (tunneling oxide) and 5 nm thick low-pressure CVD Si3N4 (charge trap) layers were intervened between the a-IGZO and substrate. Despite the identical stoichiometry and other physicochemical properties of the MOCVD and sputtered a-IGZO, a much faster programming speed of MOCVD a-IGZO was observed. A comparable amount of oxygen vacancies was found in both MOCVD and sputtered a-IGZO, confirmed by x-ray photoelectron spectroscopy and bias-illumination-instability test measurements. Ultraviolet photoelectron spectroscopy analysis revealed a higher Fermi level (E F) of the MOCVD a-IGZO (∼0.3 eV) film than that of the sputtered a-IGZO, which could be ascribed to the higher hydrogen concentration in the MOCVD a-IGZO film. Since the programming in a flash memory device is governed by the tunneling of electrons from the channel to charge trapping layer, the faster programming performance could be the result of a higher E F of MOCVD a-IGZO.

Effect of Zinc Incorporation on the Performance of Red Light Emitting InP Core Nanocrystals.

This report presents a systematic study on the effect of zinc (Zn) carboxylate precursor on the structural and optical properties of red light emitting InP nanocrystals (NCs). NC cores were assessed using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), energy-dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). When moderate Zn:In ratios in the reaction pot were used, the incorporation of Zn in InP was insufficient to change the crystal structure or band gap of the NCs, but photoluminescence quantum yield (PLQY) increased dramatically compared with pure InP NCs. Zn was found to incorporate mostly in the phosphate layer on the NCs. PL, PLQY, and time-resolved PL (TRPL) show that Zn carboxylates added to the precursors during NC cores facilitate the synthesis of high-quality InP NCs by suppressing nonradiative and sub-band-gap recombination, and the effect is visible also after a ZnS shell is grown on the cores.

Optical Spectroscopic Studies of the Metal-Insulator Transition Driven by All-In-All-Out Magnetic Ordering in 5d Pyrochlore Cd(2)Os(2)O(7).

We investigated the metal-insulator transition (MIT) driven by all-in-all-out (AIAO) antiferromagnetic ordering in the 5d pyrochlore Cd(2)Os(2)O(7) using optical spectroscopy and first-principles calculations. We showed that the temperature evolution in the band-gap edge and free carrier density were consistent with rigid upward (downward) shifts of electron (hole) bands, similar to the case of Lifshitz transitions. The delicate relationship between the band gap and free carrier density provides experimental evidence for the presence of an AIAO metallic phase, a natural consequence of such MITs. The associated spectral weight change at high energy and first-principles calculations further support the origin of the MIT from the band shift near the Fermi level. Our data consistently support that the MIT induced by AIAO ordering in Cd(2)Os(2)O(7) is not close to a Slater type but instead to a Lifshitz type.

Isothermal transport properties and majority-type defects of BaCo(0.70)Fe(0.22)Nb(0.08)O(3-δ).

(Ba,Sr)(Co,Fe)O3-δ based mixed conducting oxides, e.g. (Ba0.5Sr0.5)(Co1-xFex)O3-δ and Ba(Co0.7Fe0.3-xNbx)O3-δ, are promising candidates for oxygen permeable membranes and SOFC cathodes due to their excellent ambipolar conductivities. Despite these excellent properties, however, their mass/charge transport properties have not been fully characterized and hence, their defect structure has not been clearly elucidated. Until now, the majority types of ionic and electronic defects have been regarded as oxygen vacancies and localized holes. Holes, whether localized or not, are acceptable as majority electronic carriers on the basis of the as-measured total conductivity, which is essentially electronic, and electronic thermopower. On the other hand, the proposal of oxygen vacancies as majority ionic carriers lacks solid evidence. In this work, we document all the isothermal transport properties of Ba(Co0.70Fe0.22Nb0.08)O3-δ in terms of a 2 × 2 Onsager transport coefficient matrix and its steady-state electronic thermopower against oxygen activity at elevated temperatures, and determine the valences of Co and Fe via soft X-ray absorption spectroscopy. It turns out that the ionic and electronic defects in majority should be oxygen interstitials and at least two kinds of holes, one free and the other trapped. Furthermore, the lattice molecule should be Ba(Co0.7Fe0.3-xNbx)O2+δ, not Ba(Co0.7Fe0.3-xNbx)O3-δ, to be consistent with all the results observed.

Physical origins and suppression of Ag dissolution in GeS(x)-based ECM cells.

Electrochemical metallisation (ECM) memory cells potentially suffer from limited memory retention time, which slows down the future commercialisation of this type of data memory. In this work, we investigate Ag/GeSx/Pt redox-based resistive memory cells (ReRAM) with and without an additional Ta barrier layer by time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray absorption spectroscopy (XAS) and synchrotron high-energy X-ray diffractometry (XRD) to investigate the physical mechanism behind the shift and/or loss of OFF data retention. Electrical measurements demonstrate the effectiveness and high potential of the diffusion barrier layer in practical applications.

Temperature evolution of itinerant ferromagnetism in SrRuO3 probed by optical spectroscopy.

The temperature (T) dependence of the optical conductivity spectra σ(ω) of a single crystal SrRuO(3) thin film is studied over a T range from 5 to 450 K. We observed significant T dependence of the spectral weights of the charge transfer and interband d-d transitions across the ferromagnetic Curie temperature (T(c) ∼ 150 K). Such T dependence was attributed to the increase in the Ru spin moment, which is consistent with the results of density functional theory calculations. T scans of σ(Ω,T) at fixed frequencies Ω reveal a clear T(2) dependence below T(c), demonstrating that the Stoner mechanism is involved in the evolution of the electronic structure. In addition, σ(Ω,T) continues to evolve at temperatures above T(c), indicating that the local spin moment persists in the paramagnetic state. This suggests that SrRuO(3) is an intriguing oxide system with itinerant ferromagnetism.

Chemical Influence of Carbon Interface Layers in Metal/Oxide Resistive Switches.

Thin layers introduced between a metal electrode and a solid electrolyte can significantly alter the transport of mass and charge at the interfaces and influence the rate of electrode reactions. C films embedded in functional materials can change the chemical properties of the host, thereby altering the functionality of the whole device. Using X-ray spectroscopies, here we demonstrate that the chemical and electronic structures in a representative redox-based resistive switching (RS) system, Ta2O5/Ta, can be tuned by inserting a graphene or ultrathin amorphous C layer. The results of the orbitalwise analyses of synchrotron Ta L3-edge, C K-edge, and O K-edge X-ray absorption spectroscopy showed that the C layers between Ta2O5 and Ta are significantly oxidized to form COx and, at the same time, oxidize the Ta layers with different degrees of oxidation depending on the distance: full oxidation at the nearest 5 nm Ta and partial oxidation in the next 15 nm Ta. The depth-resolved information on the electronic structure for each layer further revealed a significant modification of the band alignments due to C insertion. Full oxidation of the Ta metal near the C interlayer suggests that the oxygen-vacancy-related valence change memory mechanism for the RS can be suppressed, thereby changing the RS functionalities fundamentally. The knowledge on the origin of C-enhanced surfaces can be applied to other metal/oxide interfaces and used for the advanced design of memristive devices.

Atomic and Electronic Manipulation of Robust Ferroelectric Polymorphs.

Polymorphism allows the symmetry of the lattice and spatial charge distributions of atomically thin materials to be designed. While various polymorphs for superconducting, magnetic, and topological states have been extensively studied, polymorphic control is a challenge for robust ferroelectricity in atomically thin geometries. Here, the atomic and electric manipulation of ferroelectric polymorphs in Mo1- x Wx Te2 is reported. Atomic manipulation for polymorphic control via chemical pressure (substituting tungsten for molybdenum atoms) and charge density modulation can realize tunable polar lattice structures and robust ferroelectricity up to T = 400 K with a constant coercive field in an atomically thin material. Owing to the effective inversion symmetry breaking, the ferroelectric switching withstands a charge carrier density of up to 1.1 × 1013 cm-2 , developing an original diagram for ferroelectric switching in atomically thin materials.

Structural, Optical, and Magnetic Properties of Erbium-Substituted Yttrium Iron Garnets.

We synthesized a series of slightly erbium-substituted yttrium iron garnets (Er:YIG), Y3-x Er x Fe5O12 at different Er concentrations (x = 0, 0.01, 0.05, 0.10, and 0.20) using a solid-state reaction and investigated their structural, magnetic, and optical properties as a function of Er concentration. The volume of the unit cell slightly increased with Er concentration and Er atoms predominately replaced Y atoms in the dodecahedrons of YIG. The optical properties exhibited certain decreases in reflectance in the 1500-1600 nm wavelength range due to the presence of Er3+. Despite the many unpaired 4f electrons in Er3+, the total magnetic moments of Er:YIG showed similar trends with temperatures and magnetic fields above 30 K. An X-ray magnetic circular dichroism study confirmed the robust Fe 3d magnetic moments. However, the magnetic moments suddenly decreased to below 30 K with Er substitution, and the residual magnetism (M R) and coercive field (H C) in the magnetic hysteresis loops decreased to below 30 K with Er substitution. This implies that Er substitution in YIG has a negligible effect on magnetic properties over a wide temperature range except below 30 K where the Er 4f spins are coupled antiparallel to the majority Fe 3d spins. Our studies demonstrated that above 30 K the magnetic properties of YIG are retained even with Er substitution, which is evidence that the Er doping scheme is applicable for YIG-based magneto-optical devices in the mid-infrared regime.

Octahedral Symmetry Modification Induced Orbital Occupancy Variation in VO2.

Octahedral symmetry is one of the parameters to tune the functional properties of complex oxides. VO2, a complex oxide with a 3d1 electronic system, exhibits an insulator-metal transition (IMT) near room temperature (∼68 °C), accompanying a change in the octahedral structure from asymmetrical to symmetrical. However, the role of octahedral symmetry in VO2 on the IMT characteristics is unclear. Crystal and electronic structure analyses combined with density-functional-theory calculations showed the bandwidth-controlled IMT characteristics of monoclinic VO2 with high octahedral symmetry. The expanded apical V-O length for a high octahedral symmetry of a VO2 film increased the bandwidth of the conduction band by depressing V 3d-O 2p hybridization. As a result, the interdimer hopping energy increased and thereby decreased the IMT temperature, although the short V-V chain enhanced electron correlation. These findings suggest that octahedral symmetry can control the IMT characteristics of VO2 by changing the orbital occupancy.

A theoretical model for Schottky diodes for excluding the sneak current in cross bar array resistive memory.

Kirchhoff's law was used to examine the electrical specifications of selection diodes, which are essential for suppressing the read interference problems in nano-scale resistive switching cross bar arrays with a high block density. The diode in the cross bar array with a 100 Mb block density should have a reverse/forward resistance ratio of > 10(8), and a forward current density of > 10(5) A cm(-2) for stable reading and writing operation. Whilst normal circuit simulators are heavily overloaded when the number of cells (m) connected to one bit and word line is larger (m >> 100), which is the desired range for high density cross bar arrays, the present model can provide a simple simulation. The validity of this new method was confirmed by a comparison with the previously reported method based on a voltage estimation.

Phase identification of vanadium oxide thin films prepared by atomic layer deposition using X-ray absorption spectroscopy.

The chemical and local structures of vanadium oxide (VO x ) thin films prepared by atomic layer deposition (ALD) were investigated by soft X-ray absorption spectroscopy. It is shown that the as-deposited film was a mixture of VO2 and V2O5 in disordered form, while the chemistry changed significantly after heat treatment, subject to the different gas environment. Forming gas (95% N2 + 5% H2) annealing resulted in a VO2 composition, consisting mostly of the VO2 (B) phase with small amount of the VO2 (M) phase, whereas O2 annealing resulted in the V2O5 phase. An X-ray circular magnetic dichroism study further revealed the absence of ferromagnetic ordering, confirming the absence of oxygen vacancies despite the reduction of V ions in VO2 (V4+) with respect to the precursor used in the ALD (V5+). This implies that the prevalence of VO2 in the ALD films cannot be attributed to a simple oxygen-deficiency-related reduction scheme but should be explained by the metastability of the local VO2 structures.

Direct Evidence of Electronic Interaction at the Atomic-Layer-Deposited MoS2 Monolayer/SiO2 Interface.

The electronic structure of an atomic-layer-deposited MoS2 monolayer on SiO2 was investigated using X-ray absorption spectroscopy (XAS) and synchrotron X-ray photoelectron spectroscopy (XPS). The angle-dependent evolution of the XAS spectra and the photon-energy-dependent evolution of the XPS spectra were analyzed in detail using an ab initio electronic structure simulation. Although similar to the theoretical spectra of an ideal free-standing MoS2 ML, the experimental spectra exhibit features that are distinct from those of an ideal ML, which can be interpreted as a consequence of S-O van der Waals (vdW) interactions. The strong consensus among the experimental and theoretical spectra suggests that the vdW interactions between MoS2 and adjacent SiO2 layers can influence the electronic structure of the system, manifesting a substantial electronic interaction at the MoS2-SiO2 interface.

X-ray spectroscopy study on the electronic structure of Sn-added p-type SnO films.

The electronic structure of the Sn-added p-type SnO thin film was examined using x-ray absorption spectroscopy (XAS). Sn was intentionally added to a pristine SnO film, and the film was annealed to form p-type SnO. Sn L1- and L3-edge XAS was used to examine the oxidation states of the Sn-added p-type SnO. Compared to the case of the reference SnO, the spectrum of the Sn-added SnO (after annealing) partly contained the lineshape for SnO2, suggesting that the oxidation of Sn + SnO was progressed such that the film became preferably SnO2 + SnO rather than Sn + SnO2. O K-edge XAS, x-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE) were also used to scrutinize the electronic structure. The direct bandgap of the annealed film was estimated to be ~3.6 eV, consistent with the reported SnO2 bandgap, while that of the as-deposited Sn-added SnO was <2.5 eV. The large bandgap after annealing suggests that the metallic Sn was no longer in existence and manifested the functionality of the annealed Sn + SnO as a p-type semiconductor.

Propagation Control of Octahedral Tilt in SrRuO3 via Artificial Heterostructuring.

Bonding geometry engineering of metal-oxygen octahedra is a facile way of tailoring various functional properties of transition metal oxides. Several approaches, including epitaxial strain, thickness, and stoichiometry control, have been proposed to efficiently tune the rotation and tilt of the octahedra, but these approaches are inevitably accompanied by unnecessary structural modifications such as changes in thin-film lattice parameters. In this study, a method to selectively engineer the octahedral bonding geometries is proposed, while maintaining other parameters that might implicitly influence the functional properties. A concept of octahedral tilt propagation engineering is developed using atomically designed SrRuO3/SrTiO3 (SRO/STO) superlattices. In particular, the propagation of RuO6 octahedral tilt within the SRO layers having identical thicknesses is systematically controlled by varying the thickness of adjacent STO layers. This leads to a substantial modification in the electromagnetic properties of the SRO layer, significantly enhancing the magnetic moment of Ru. This approach provides a method to selectively manipulate the bonding geometry of strongly correlated oxides, thereby enabling a better understanding and greater controllability of their functional properties.

Precision Interface Engineering of an Atomic Layer in Bulk Bi2Te3 Alloys for High Thermoelectric Performance.

Grafting nanotechnology on thermoelectric materials leads to significant advances in their performance. Creation of structural defects including nano-inclusion and interfaces via nanostructuring achieves higher thermoelectric efficiencies. However, it is still challenging to optimize the nanostructure via conventional fabrication techniques. The thermal instability of nanostructures remains an issue in the reproducibility of fabrication processes and long-term stability during operation. This work presents a versatile strategy to create numerous interfaces in a thermoelectric material via an atomic-layer deposition (ALD) technique. An extremely thin ZnO layer was conformally formed via ALD over the Bi0.4Sb1.6Te3 powders, and numerous heterogeneous interfaces were generated from the formation of Bi0.4Sb1.6Te3-ZnO core-shell structures even after high-temperature sintering. The incorporation of ALD-grown ZnO into the Bi0.4Sb1.6Te3 matrix blocks phonon propagation and also provides tunability in electronic carrier density via impurity doping at the heterogeneous grain boundaries. The exquisite control in the ALD cycles provides a high thermoelectric performance of zT = 1.50 ± 0.15 (at 329-360 K). Specifically, ALD is an industry compatible technique that allows uniform and conformal coating over large quantities of powders. The study is promising in terms of the mass production of nanostructured thermoelectric materials with considerable improvements in performance via an industry compatible and reproducible route.

Crystal and Magnetic Structures of La2CoPtO6 Double Perovskite.

We investigated the crystal structure and magnetic structure in cobaltite-platinate double perovskite of La2CoPtO6, employing various techniques of X-ray diffraction, neutron diffraction, and the extended X-ray absorption fine structure analysis. It is shown that the crystal symmetry is maintained as P21/n in the temperature range of <500 °C, whereas the lattice constants and the Co-Co distances undergo a continuous structural evolution toward the high-symmetry phases with increasing temperature. The Co-O bonds were overall longer and had a larger degree of structural and thermal disorders than the Pt-O bonds. As for the magnetism, an antiferromagnetic order is stabilized in the Co2+ sublattice at temperatures below 28 K. It is demonstrated that owing to the substantial distortions (quantified by a distortion parameter Σ > 0.03 Å) of the Co-Co networks, the system is not subject to spin frustration effect. Details in the magnetic structure are determined; at 12 K, the Co magnetic moment was (0.8, 0, 2.7) Bohr magneton, the magnetic propagation vector was (-0.5, 0, 0.5), and the magnetic symmetry was preferably Γ1(Ag).

Field-Effect Device Using Quasi-Two-Dimensional Electron Gas in Mass-Producible Atomic-Layer-Deposited Al2O3/TiO2 Ultrathin (<10 nm) Film Heterostructures.

We report the field-effect transistors using quasi-two-dimensional electron gas generated at an ultrathin (∼10 nm) Al2O3/TiO2 heterostructure interface grown via atomic layer deposition (ALD) on a SiO2/Si substrate without using a single crystal substrate. The 2DEG at the Al2O3/TiO2 interface originates from oxygen vacancies generated at the surface of the TiO2 bottom layer during ALD of the Al2O3 overlayer. High-density electrons (∼1014 cm-2) are confined within a ∼2.2 nm distance from the Al2O3/TiO2 interface, resulting in a high on-current of ∼12 µA/µm. The ultrathin TiO2 bottom layer is easy to fully deplete, allowing an extremely low off-current, a high on/off current ratio over 108, and a low subthreshold swing of ∼100 mV/decade. Via the implementation of ALD, a mature thin-film process can facilitate mass production as well as three-dimensional integration of the devices.

Composition, Microstructure, and Electrical Performance of Sputtered SnO Thin Films for p-Type Oxide Semiconductor.

p-Type SnO thin films were deposited on a Si substrate by a cosputtering process using ceramic SnO and metal Sn targets at room temperature without adding oxygen. By varying the dc sputtering power applied to the Sn target while maintaining a constant radio frequency power to the SnO target, the Sn/O ratio varied from 56:44 to 74:26 at the as-deposited state. After thermal annealing at 180 °C for 25 min under air atmosphere using a microwave annealing system, the films were crystallized into tetragonal SnO when the Sn/O ratio increased from 44:56 to 57:43. Notably, the metallic Sn remained when the Sn/O ratio was higher than 55:45 at an annealed state. When the ratio was lower than 55:45 at the annealed state, the incorporated Sn fully oxidized to SnO, making the films useful p-type semiconductors, whereas the films became metallic conductors at higher Sn/O ratios. At the Sn/O ratio of 55:45 at the annealed state, the film showed the highest Hall mobility of 8.8 cm2 V-1 s-1 and a hole concentration of 5.4 × 1018 cm-3. Interestingly, the electrical conduction behavior showed trap-mediated hopping when the Sn metal was cosputtered, whereas the single SnO film showed regular band conduction behavior. The residual stress effect could interpret such property variation originated from the sputtering power and postoxidation-induced volumetric effects. This report makes a critical contribution to the in-depth understanding of the composition-structure-property relationship of this technically important thin film material.