Highly oriented single-crystalline gold quantum-dot metamaterials as prospective materials for photonics.

Miniaturization of optical devices is a modern trend essential for optoelectronics, optical sensing, optical computing and other branches of science and technology. To satisfy this trend, optical materials with a small footprint are required. Here we show that extremely thin, flat, nanostructured gold films made of highly oriented single-crystalline gold quantum-dots can provide elements of topological photonics in visible light and be used as high-index dielectric materials in the infrared part of the spectra. We measure and theoretically confirm the presence of topological darkness and associated phase singularities in studied gold films of thickness of below 10 nm placed on MgO substrates in the red part of the spectrum. At telecom wavelengths, the fabricated gold metasurface behaves as a dielectric with the refractive index of n≈2.75 and the absorption coefficient of k≈0.005.

Efficient Ternary Mn-Based Spinel Oxide with Multiple Active Sites for Oxygen Evolution Reaction Discovered via High-Throughput Screening Methods.

The discovery of more efficient and stable catalysts for oxygen evolution reaction (OER) is vital in improving the efficiency of renewable energy generation devices. Given the large numbers of possible binary and ternary metal oxide OER catalysts, high-throughput methods are necessary to accelerate the rate of discovery. Herein, Mn-based spinel oxide, Fe10 Co40 Mn50 O, is identified for the first time using high-throughput methods demonstrating remarkable catalytic activity (overpotential of 310 mV on fluorine-doped tin oxide (FTO) substrate and 237 mV on Ni foam at 10 mA cm-2 ). Using a combination of soft X-ray absorption spectroscopy and electrochemical measurements, the high catalytic activity is attributed to 1) the formation of multiple active sites in different geometric sites, tetrahedral and octahedral sites; and 2) the formation of active oxyhydroxide phase due to the strong interaction of Co2+ and Fe3+ . Structural and surface characterizations after OER show preservation of Fe10 Co40 Mn50 O surface structure highlighting its durability against irreversible redox damage on the catalytic surface. This work demonstrates the use of a high-throughput approach for the rapid identification of a new catalyst, provides a deeper understanding of catalyst design, and addresses the urgent need for a better and stable catalyst to target greener fuel.

A New Spin-Correlated Plasmon in Novel Highly Oriented Single-Crystalline Gold Quantum Dots.

A concept of spin plasmon, a collective mode of spin-density, in strongly correlated electron systems has been proposed since the 1930s. It is expected to bridge between spintronics and plasmonics by strongly confining the photon energy in the subwavelength scale within single magnetic-domain to enable further miniaturizing devices. However, spin plasmon in strongly correlated electron systems is yet to be realized. Herein, we present a new spin correlated-plasmon at room temperature in novel Mott-like insulating highly oriented single-crystalline gold quantum-dots (HOSG-QDs). Interestingly, the spin correlated-plasmon is tunable from the infrared to visible, accompanied by spectral weight transfer yielding a large quantum absorption midgap state, disappearance of low-energy Drude response, and transparency. Supported with theoretical calculations, it occurs due to an interplay of surprisingly strong electron-electron correlations, s-p hybridization and quantum confinement in the s band. The first demonstration of the high sensitivity of spin correlated-plasmon in surface-enhanced Raman spectroscopy is also presented.

Unusual Hole and Electron Midgap States and Orbital Reconstructions Induced Huge Ferroelectric Tunneling Electroresistance in BaTiO3/SrTiO3.

Oxide heterostructures have attracted a lot of interest because of their rich exotic phenomena and potential applications. Recently, a greatly enhanced tunneling electroresistance (TER) of ferroelectric tunnel junctions (FTJs) has been realized in such heterostructures. However, our understanding on the electronic structure of resistance response with polarization reversal and the origin of huge TER is still lacking. Here, we report on electronic structures, particularly at the interface and surface, and the control of the spontaneous polarization of BaTiO3 films by changing the termination of a SrTiO3 substrate. Interestingly, unusual electron and hole midgap states are concurrently formed and accompanied by orbital reconstructions, which determine the ferroelectric polarization orientation in the BaTiO3/SrTiO3. Such unusual midgap states, which yield a strong electronic screening effect, reduce the ferroelectric barrier width and height, and pin the ferroelectric polarization, lead to a dramatic enhancement of the TER effect. The midgap states are also observed in BaTiO3 films on electron-doped Nb/SrTiO3 revealing its universality. Our result provides new insight into the origin of the huge TER effect and opens a new route for designing ferroelectric tunnel junction-based devices with huge TER through interface engineering.

Magnetic Anisotropy of a Quasi Two-Dimensional Canted Antiferromagnet.

We report the control of the interplane magnetic exchange coupling in CaIrO3 perovskite thin films and superlattices with SrTiO3. By analyzing the anisotropic magneto-transport data, we demonstrate that a semimetallic paramagnetic CaIrO3 turns into a canted antiferromagnetic Mott insulator at reduced dimensions. The emergence of a biaxial magneto-crystalline anisotropy indicates the canted moment responding to the cubic symmetry. Extending to superlattices and probing oxygen octahedral rotation by half-integer X-ray Braggs diffraction, a more complete picture about the canted moment evolution with interplane coupling can be understood. Remarkably, a rotation of the canted moments' easy axes by 45° is also observed by a sign reversal of the in-plane strain. These results demonstrate the robustness of anisotropic magnetoresistance in revealing quasi two-dimensional canted antiferromagnets, as well as valuable insights about quadrupolar magnetoelastic coupling, relevant for designing future antiferromagnetic spintronic devices.

Characteristic Lengths of Interlayer Charge Transfer in Correlated Oxide Heterostructures.

Using interlayer interaction to control functional heterostructures with atomic-scale designs has become one of the most effective interface-engineering strategies nowadays. Here, we demonstrate the effect of a crystalline LaFeO3 buffer layer on amorphous and crystalline LaAlO3/SrTiO3 heterostructures. The LaFeO3 buffer layer acts as an energetically favored electron acceptor in both LaAlO3/SrTiO3 systems, resulting in modulation of interfacial carrier density and hence metal-to-insulator transition. For amorphous and crystalline LaAlO3/SrTiO3 heterostructures, the metal-to-insulator transition is found when the LaFeO3 layer thickness crosses 3 and 6 unit cells, respectively. Such different critical LaFeO3 thicknesses are explained in terms of distinct characteristic lengths of the redox-reaction-mediated and polar-catastrophe-dominated charge transfer, controlled by the interfacial atomic contact and Thomas-Fermi screening effect, respectively. Our results not only shed light on the complex interlayer charge transfer across oxide heterostructures but also provide a new route to precisely tailor the charge-transfer process at a functional interface.

Emergent Topological Hall Effect at a Charge-Transfer Interface.

Exploring exotic interface magnetism due to charge transfer and strong spin-orbit coupling has profound application in the future development of spintronic memory. Here, the emergence and tuning of topological Hall effect (THE) from a CaMnO3 /CaIrO3 /CaMnO3 trilayer structure are studied in detail, which suggests the presence of magnetic Skyrmion-like bubbles. First, by tilting the magnetic field direction, the evolution of the Hall signal suggests a transformation of Skyrmions into topologically-trivial stripe domains, consistent with behaviors predicted by micromagnetic simulations. Second, by varying the thickness of CaMnO3 , the optimal thicknesses for the THE signal emergence are found, which allow identification of the source of Dzyaloshinskii-Moriya interaction (DMI) and its competition with antiferromagnetic superexchange. Employing high-resolution transmission electron microscopy, randomly distributed stacking faults are identified only at the bottom interface and may avoid mutual cancellation of DMI. Last, a spin-transfer torque experiment also reveals a low threshold current density of ≈109 A m-2 for initiating the bubbles' motion. This discovery sheds light on a possible strategy for integrating Skyrmions with antiferromagnetic spintronics.

Optical constants and absorption properties of Te and TeO thin films in the 13-14†nm spectral range.

Undesired mask-induced effects caused by thick absorber layers in EUV photomasks reduce the quality of the projected patterns at the wafer stage in EUV photolithography scanners. New materials with better absorption properties than the state-of-the-art absorbers, TaN and TaBN, are required to mitigate these effects. In this work, we investigated the optical properties (δ and k) of Te and TeO films in the 13-14 nm range, and the absorption properties of these two materials at 13.5 nm. δ and k are obtained through fitting experimental values of reflectivity versus angle of incidence in the EUV range. We follow a methodology which combines different characterization techniques (X-ray reflectivity, EUV reflectivity, and X-ray photoemission spectroscopy) to reduce the number of free parameters in models and hence, increase the reliability of the optical constants obtained. At 13.5 nm, we obtain δ=0.03120, k = 0.07338 for Te, and δ=0.04099, k = 0.06555 for TeO. To experimentally verify the absorption properties of these materials, different thicknesses of Te and TeO films are cast on top of a state-of-the-art mask-quality EUV multilayer with 66.7% reflectivity at 13.5 nm. We found that a reflectivity of ∼0.7% can be attained with either 32.4 nm of Te, or 34.7 nm of TeO, greatly surpassing the absorption properties of TaN and TaBN. The morphology and surface roughness of the Te and TeO films deposited on the multilayer are also investigated.

Correction: The effect of crystallinity on the surface modification and optical properties of ZnO thin films.

Correction for 'The effect of crystallinity on the surface modification and optical properties of ZnO thin films' by Muhammad Abiyyu Kenichi Purbayanto et al., Phys. Chem. Chem. Phys., 2020, 22, 2010-2018, DOI: 10.1039/C9CP05464B.

The effect of crystallinity on the surface modification and optical properties of ZnO thin films.

We have studied the effects of crystallinity on the emergence of porous morphology and strong green emission in ZnO thin films after H2 annealing treatment. The unique multiple-stacked porous structure is observed after performing H2 annealing treatment on the film with low crystallinity. However, the annealed high-crystallinity film exhibits surface morphology with a shallow porous structure, as revealed by SEM images. To study the effects of these unique porous structures on the optical properties, photoluminescence (PL) spectroscopy, Raman spectroscopy, spectroscopic ellipsometry, and X-ray photoelectron spectroscopy (XPS) are conducted. The multiple-stacked porous structure produces strong green emission as compared to the shallow porous structure centered at 2.5 eV, as detected by PL. Here, the green emission originates from the electronic transition related to the oxygen vacancy (VO). XPS spectra show that the high density of VO located on the multiple-stacked porous surface is much higher as compared to that for the shallow porous structure due to a high surface-to-volume ratio. The results show that the multiple-stacked porous structure has the potential to enhance the functionality of ZnO for applications in light-emitting.

Ultraviolet Interband Plasmonics With Si Nanostructures.

Although Si acts as an electrical semiconductor, it has properties of an optical dielectric. Here, we revisit the behavior of Si as a plasmonic metal. This behavior was previously shown to arise from strong interband transitions that lead to negative permittivity of Si across the ultraviolet spectral range. However, few have studied the plasmonic characteristics of Si, particularly in its nanostructures. In this paper, we report localized plasmon resonances of Si nanostructures and the observation of plasmon hybridization in the UV (∼250 nm wavelength). In addition, simulation results show that Si nanodisk dimers can achieve a local intensity enhancement greater than ∼500-fold in a 1 nm gap. Lastly, we investigate hybrid Si-Al nanostructures to achieve sharp resonances in the UV, due to the coupling between plasmon resonances supported by Si and Al nanostructures. These results will have potential applications in the UV range, such as nanostructured devices for spectral filtering, plasmon-enhanced Si photodetectors, interrogation of molecular chirality, and catalysis. It could have significant impact on UV photolithography on patterned Si structures.

Electronic and Thermoelectric Properties of Layered Oxychalcogenides (BiO)Cu Ch ( Ch = S, Se, Te).

We study the new details of electronic and thermoelectric properties of polycrystalline layered oxychalcogenide systems of (BiO)Cu Ch ( Ch = Se, Te) prepared by using a solid-state reaction. The systems were characterized by using photoemission (PE) spectroscopy and four-probe temperature-dependent electrical resistivity ρ( T). PE spectra are explained by calculating the electronic properties using the generalized-gradient approximation method. PE spectra and ρ( T) show that (BiO)CuSe system is a semiconductor, while (BiO)CuTe system exhibits the metallic behavior that induces the high thermoelectric performance. The calculation of electronic properties of (BiO)Cu Ch ( Ch = S, Se, Te) confirms that the metallic behavior of (BiO)CuTe system is mainly induced by Te 5p states at Fermi energy level, while the indirect bandgaps of 0.68 and 0.40 eV are obtained for (BiO)CuS and (BiO)CuSe systems, respectively. It is also shown that the local symmetry distortion at Cu site strongly stimulates Cu 3d-t2g to be partially hybridized with Ch p orbitals. This study presents the essential properties of the inorganic systems for novel functional device applications.

Oxygen Passivation Mediated Tunability of Trion and Excitons in MoS_{2}.

Using wide spectral range in situ spectroscopic ellipsometry with systematic ultrahigh vacuum annealing and in situ exposure to oxygen, we report the complex dielectric function of MoS_{2} isolating the environmental effects and revealing the crucial role of unpassivated and passivated sulphur vacancies. The spectral weights of the A (1.92 eV) and B (2.02 eV) exciton peaks in the dielectric function reduce significantly upon annealing, accompanied by spectral weight transfer in a broad energy range. Interestingly, the original spectral weights are recovered upon controlled oxygen exposure. This tunability of the excitonic effects is likely due to passivation and reemergence of the gap states in the band structure during oxygen adsorption and desorption, respectively, as indicated by ab initio density functional theory calculation results. This Letter unravels and emphasizes the important role of adsorbed oxygen in the optical spectra and many-body interactions of MoS_{2}.

Coexistence of Midgap Antiferromagnetic and Mott States in Undoped, Hole- and Electron-Doped Ambipolar Cuprates.

We report the first observation of the coexistence of a distinct midgap state and a Mott state in undoped and their evolution in electron and hole-doped ambipolar Y_{0.38}La_{0.62}(Ba_{0.82}La_{0.18})_{2}Cu_{3}O_{y} films using spectroscopic ellipsometry and x-ray absorption spectroscopies at the O K and Cu L_{3,2} edges. Supported by theoretical calculations, the midgap state is shown to originate from antiferromagnetic correlation. Surprisingly, while the magnetic state collapses and its correlation strength weakens with dopings, the Mott state in contrast moves toward a higher energy and its correlation strength increases. Our result provides important clues to the mechanism of electronic correlation strengths and superconductivity in cuprates.

Electronic defect states at the LaAlO3/SrTiO3 heterointerface revealed by O K-edge X-ray absorption spectroscopy.

Interfaces of two dissimilar complex oxides exhibit exotic physical properties that are absent in their parent compounds. Of particular interest is insulating LaAlO3 films on an insulating SrTiO3 substrate, where transport measurements have shown a metal-insulator transition as a function of LaAlO3 thickness. Their origin has become the subject of intense research, yet a unifying consensus remains elusive. Here, we report evidence for the electronic reconstruction in both insulating and conducting LaAlO3/SrTiO3 heterointerfaces revealed by O K-edge X-ray absorption spectroscopy. For the insulating samples, the O K-edge XAS spectrum exhibits features characteristic of electronically active point defects identified as noninteger valence states of Ti. For conducting samples, a new shape-resonance at ∼540.5 eV, characteristic of molecular-like oxygen (empty O-2p band), is observed. This implies that the concentration of electronic defects has increased in proportion with LaAlO3 thickness. For larger defect concentrations, the electronic defect states are no longer localized at the Ti orbitals and exhibit pronounced O 2p-O 2p character. Our results demonstrate that, above a critical thickness, the delocalization of O 2p electronic states can be linked to the presence of oxygen vacancies and is responsible for the enhancement of conductivity at the oxide heterointerfaces.

Visible Surface Plasmon Modes in Single Bi2Te3 Nanoplate.

Searching for new plasmonic building blocks which offer tunability and design flexibility beyond noble metals is crucial for advancing the field of plasmonics. Herein, we report that solution-synthesized hexagonal Bi2Te3 nanoplates, in the absence of grating configurations, can exhibit multiple plasmon modes covering the entire visible range, as observed by transmission electron microscopy (TEM)-based electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) spectroscopy. Moreover, different plasmon modes are observed in the center and edge of the single Bi2Te3 nanoplate and a breathing mode is discovered for the first time in a non-noble metal. Theoretical calculations show that the plasmons observed in the visible range are mainly due to strong spin-orbit coupling induced metallic surface states of Bi2Te3. The versatility of shape- and size-engineered Bi2Te3 nanocrystals suggests exciting possibilities in plasmonics-enabled technology.

Ultrathin hexagonal hybrid nanosheets synthesized by graphene oxide-assisted exfoliation of ß-Co(OH)2 mesocrystals.

In the present study, we report the synthesis of a high-quality, single-crystal hexagonal ß-Co(OH)2 nanosheet, exhibiting a thickness down to ten atomic layers and an aspect ratio exceeding 900, by using graphene oxide (GO) as an exfoliant of ß-Co(OH)2 nanoflowers. Unlike conventional approaches using ionic precursors in which morphological control is realized by structure-directing molecules, the ß-Co(OH)2 flower-like superstructures were first grown by a nanoparticle-mediated crystallization process, which results in large 3D superstructure consisting of ultrathin nanosheets interspaced by polydimethoxyaniline (PDMA). Thereafter, ß-Co(OH)2 nanoflowers were chemically exfoliated by surface-active GO under hydrothermal conditions into unilamellar single-crystal nanosheets. In this reaction, GO acts as a two-dimensional (2D) amphiphile to facilitate the exfoliation process through tailored interactions between organic and inorganic molecules. Meanwhile, the on-site conjugation of GO and Co(OH)2 promotes the thermodynamic stability of freestanding ultrathin nanosheets and restrains further growth through Oswald ripening. The unique 2D structure combined with functionalities of the hybrid ultrathin Co(OH)2 nanosheets on rGO resulted in a remarkably enhanced lithium-ion storage performance as anode materials, maintaining a reversible capacity of 860 mA h g(-1) for as many as 30 cycles. Since mesocrystals are ubiquitous and rich in morphological diversity, the strategy of the GO-assisted exfoliation of mesocrystals developed here provides an opportunity for the synthesis of new functional nanostructures that could bear importance in clean renewable energy, catalysis, photoelectronics, and photonics.

A Facile Two-Step Hydrothermal Synthesis of Co(OH)2@NiCo2O4 Nanosheet Nanocomposites for Supercapacitor Electrodes.

The composites of NiCo2O4 with unique structures were substantially investigated as promising electrodes. In this study, the unique structured nanosheets anchored on nickel foam (Ni foam) were prepared under the hydrothermal technique of NiCo2O4 and subsequent preparation of Co(OH)2. The Co(OH)2@NiCo2O4 nanosheet composite has demonstrated higher specific capacitances owing to its excellent specific surface region, enhanced rate properties, and outstanding electrical conductivities. Moreover, the electrochemical properties were analyzed in a three-electrode configuration to study the sample material. The as-designed Co(OH)2@NiCo2O4 nanosheet achieves higher specific capacitances of 1308 F·g-1 at 0.5 A·g-1 and notable long cycles with 92.83% capacity retention over 6000 cycles. The Co(OH)2@NiCo2O4 nanosheet electrode exhibits a long life span and high capacitances compared with the NiCo2O4 and Co(OH)2 electrodes, respectively. These outstanding electrochemical properties are mainly because of their porous construction and the synergistic effects between NiCo2O4 and Co(OH)2. Such unique Co(OH)2@NiCo2O4 nanosheets not only display promising applications in renewable storage but also reiterate to scientists of the unlimited potential of high-performance materials.

Unrevealing tunable resonant excitons and correlated plasmons and their coupling in new amorphous carbon-like for highly efficient photovoltaic devices.

An understanding on roles of excitons and plasmons is important in excitonic solar cells and photovoltaic (PV) technologies. Here, we produce new amorphous carbon (a-C) like films on Indium Tin Oxide (ITO) generating PV cells with efficiency three order of magnitude higher than the existing biomass-derived a-C. The amorphous carbon films are prepared from the bioproduct of palmyra sap with a simple, environmentally friendly, and highly reproducible method. Using spectroscopic ellipsometry, we measure simultaneously complex dielectric function, loss function as well as reflectivity and reveal coexistence of many-body resonant excitons and correlated-plasmons occurring due to strong electronic correlations. X-ray absorption and photoemission spectroscopies show the nature of electron and hole in defining the energy of the excitons and plasmons as a function of N or B doping. Our result shows new a-C like films and the importance of the coupling of resonant excitons and correlated plasmons in determining efficiency of photovoltaic devices.