Tuning Green to Red Color in Erbium Niobate Micro- and Nanoparticles.

Tetragonal Er0.5Nb0.5O2 and monoclinic ErNbO4 micro- and nanoparticles were prepared by the citrate sol-gel method and heat-treated at temperatures between 700 and 1600 °C. ErNbO4 revealed a spherical-shaped crystallite, whose size increased with heat treatment temperatures. To assess their optical properties at room temperature (RT), a thorough spectroscopic study was conducted. RT photoluminescence (PL) spectroscopy revealed that Er3+ optical activation was achieved in all samples. The photoluminescence spectra show the green/yellow 2H11/2, 4S3/2→4I15/2 and red 4F9/2→4I15/2 intraionic transitions as the main visible recombination, with the number of the crystal field splitting Er3+ multiplets reflecting the ion site symmetry in the crystalline phases. PL excitation allows the identification of Er3+ high-energy excited multiplets as the preferential population paths of the emitting levels. Independently of the crystalline structure, the intensity ratio between the green/yellow and red intraionic transitions was found to be strongly sensitive to the excitation energy. After pumping the samples with a resonant excitation into the 4G11/2 excited multiplet, a green/yellow transition stronger than the red one was observed, whereas the reverse occurred for higher excitation photon energies. Thus, a controllable selective excited tunable green to red color was achieved, which endows new opportunities for photonic and optoelectronic applications.

Formation and Healing of Defects in Atomically Thin GaSe and InSe.

Two dimensional III-VI metal monochalcogenide materials, such as GaSe and InSe, are attracting considerable attention due to their promising electronic and optoelectronic properties. Here, an investigation of point and extended atomic defects formed in mono-, bi-, and few-layer GaSe and InSe crystals is presented. Using state-of-the-art scanning transmission electron microscopy, it is observed that these materials can form both metal and selenium vacancies under the action of the electron beam. Selenium vacancies are observed to be healable: recovering the perfect lattice structure in the presence of selenium or enabling incorporation of dopant atoms in the presence of impurities. Under prolonged imaging, multiple point defects are observed to coalesce to form extended defect structures, with GaSe generally developing trigonal defects and InSe primarily forming line defects. These insights into atomic behavior could be harnessed to synthesize and tune the properties of 2D post-transition-metal monochalcogenide materials for optoelectronic applications.

Indirect to Direct Gap Crossover in Two-Dimensional InSe Revealed by Angle-Resolved Photoemission Spectroscopy.

Atomically thin films of III-VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductors that feature a strong variation of their band gap as a function of the number of layers in the crystal and, specifically for InSe, an expected crossover from a direct gap in the bulk to a weakly indirect band gap in monolayers and bilayers. Here, we apply angle-resolved photoemission spectroscopy with submicrometer spatial resolution (µARPES) to visualize the layer-dependent valence band structure of mechanically exfoliated crystals of InSe. We show that for one-layer and two-layer InSe the valence band maxima are away from the Γ-point, forming an indirect gap, with the conduction band edge known to be at the Γ-point. In contrast, for six or more layers the band gap becomes direct, in good agreement with theoretical predictions. The high-quality monolayer and bilayer samples enable us to resolve, in the photoluminescence spectra, the band-edge exciton (A) from the exciton (B) involving holes in a pair of deeper valence bands, degenerate at Γ, with a splitting that agrees with both µARPES data and the results of DFT modeling. Due to the difference in symmetry between these two valence bands, light emitted by the A-exciton should be predominantly polarized perpendicular to the plane of the two-dimensional crystal, which we have verified for few-layer InSe crystals.

Magnetoresistance in Co-hBN-NiFe Tunnel Junctions Enhanced by Resonant Tunneling through Single Defects in Ultrathin hBN Barriers.

Hexagonal boron nitride (hBN) is a prototypical high-quality two-dimensional insulator and an ideal material to study tunneling phenomena, as it can be easily integrated in vertical van der Waals devices. For spintronic devices, its potential has been demonstrated both for efficient spin injection in lateral spin valves and as a barrier in magnetic tunnel junctions (MTJs). Here we reveal the effect of point defects inevitably present in mechanically exfoliated hBN on the tunnel magnetoresistance of Co-hBN-NiFe MTJs. We observe a clear enhancement of both the conductance and magnetoresistance of the junction at well-defined bias voltages, indicating resonant tunneling through magnetic (spin-polarized) defect states. The spin polarization of the defect states is attributed to exchange coupling of a paramagnetic impurity in the few-atomic-layer thick hBN to the ferromagnetic electrodes. This is confirmed by excellent agreement with theoretical modeling. Our findings should be taken into account in analyzing tunneling processes in hBN-based magnetic devices. More generally, our study shows the potential of using atomically thin hBN barriers with defects to engineer the magnetoresistance of MTJs and to achieve spin filtering, opening the door toward exploiting the spin degree of freedom in current studies of point defects as quantum emitters.

Atomic-Scale Insights into the Oxidation of Aluminum.

The surface oxidation of aluminum is still poorly understood despite its vital role as an insulator in electronics, in aluminum-air batteries, and in protecting the metal against corrosion. Here we use atomic resolution imaging in an environmental transmission electron microscope (TEM) to investigate the mechanism of aluminum oxide formation. Harnessing electron beam sputtering we prepare a pristine, oxide-free metal surface in the TEM. This allows us to study, as a function of crystallographic orientation and oxygen gas pressure, the full oxide growth regime from the first oxide nucleation to a complete saturated, few-nanometers-thick surface film.

Observing Imperfection in Atomic Interfaces for van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures are a lucrative platform for exploring the rich electronic and optoelectronic phenomena in two-dimensional materials. Their performance will be strongly affected by impurities and defects at the interfaces. Here we present the first systematic study of interfaces in van der Waals heterostructure using cross-sectional scanning transmission electron microscope (STEM) imaging. By measuring interlayer separations and comparing these to density functional theory (DFT) calculations we find that pristine interfaces exist between hBN and MoS2 or WS2 for stacks prepared by mechanical exfoliation in air. However, for two technologically important transition metal dichalcogenide (TMDC) systems, MoSe2 and WSe2, our measurement of interlayer separations provide the first evidence for impurity species being trapped at buried interfaces with hBN interfaces that are flat at the nanometer length scale. While decreasing the thickness of encapsulated WSe2 from bulk to monolayer we see a systematic increase in the interlayer separation. We attribute these differences to the thinnest TMDC flakes being flexible and hence able to deform mechanically around a sparse population of protruding interfacial impurities. We show that the air sensitive two-dimensional (2D) crystal NbSe2 can be fabricated into heterostructures with pristine interfaces by processing in an inert-gas environment. Finally we find that adopting glovebox transfer significantly improves the quality of interfaces for WSe2 compared to processing in air.

Exfoliation of natural van der Waals heterostructures to a single unit cell thickness.

Weak interlayer interactions in van der Waals crystals facilitate their mechanical exfoliation to monolayer and few-layer two-dimensional materials, which often exhibit striking physical phenomena absent in their bulk form. Here we utilize mechanical exfoliation to produce a two-dimensional form of a mineral franckeite and show that the phase segregation of chemical species into discrete layers at the sub-nanometre scale facilitates franckeite's layered structure and basal cleavage down to a single unit cell thickness. This behaviour is likely to be common in a wider family of complex minerals and could be exploited for a single-step synthesis of van der Waals heterostructures, as an alternative to artificial stacking of individual two-dimensional crystals. We demonstrate p-type electrical conductivity and remarkable electrochemical properties of the exfoliated crystals, showing promise for a range of applications, and use the density functional theory calculations of franckeite's electronic band structure to rationalize the experimental results.

Nanostructured Aptamer-Functionalized Black Phosphorus Sensing Platform for Label-Free Detection of Myoglobin, a Cardiovascular Disease Biomarker.

We report the electrochemical detection of the redox active cardiac biomarker myoglobin (Mb) using aptamer-functionalized black phosphorus nanostructured electrodes by measuring direct electron transfer. The as-synthesized few-layer black phosphorus nanosheets have been functionalized with poly-l-lysine (PLL) to facilitate binding with generated anti-Mb DNA aptamers on nanostructured electrodes. This aptasensor platform has a record-low detection limit (∼0.524 pg mL(-1)) and sensitivity (36 µA pg(-1) mL cm(-2)) toward Mb with a dynamic response range from 1 pg mL(-1) to 16 µg mL(-1) for Mb in serum samples. This strategy opens up avenues to bedside technologies for multiplexed diagnosis of cardiovascular diseases in complex human samples.

Controlled folding of graphene: GraFold printing.

We have used elastomeric stamps with periodically varying adhesive properties to introduce structure and print folded graphene films. The structure of the induced folds is investigated with scanning probe techniques, high-resolution electron-microscopy, and tip-enhanced Raman spectroscopy. Furthermore, a finite element model is developed to show the fold formation process. Terahertz spectroscopy reveals induced anisotropy of carrier mobility along, and perpendicular to, the graphene folds. Graphene fold printing is a new technique which allows for significant modification of the properties of 2D materials without damaging or chemically modifying them.