Bi1.34Fe0.66Nb1.34O6.35 powders were prepared by the sol-gel method, through the citrate route, and heat treated at 500 degrees C. The obtained samples were characterized by X-ray diffraction analysis and by high resolution scanning transmission electron microscopy. An X-ray energy dispersive analysis was also performed. The average crystallite size and lattice strain were studied using the Scherrer's formula and the Williamson Hall (W-H) analysis, assuming Uniform Deformation Model (UDM), Uniform Deformation Stress Model (UDSM) and Uniform Deformation Energy Density Model (UDEDM). The obtained results revealed that the mean crystallite size and lattice strain estimated from the different analysis were highly correlated.

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.

In this work, ErNbO4 samples were prepared using the sol-gel method, through the citrate route, and heat-treated at temperatures between 700 and 1600 degrees C. The structure was studied by X-ray diffraction and Raman spectroscopy. The crystallite size was estimated using the Rietveld refinement and the Sherrer's formula, presenting values from 31.27 to 86.65 nm and from 40.96 to 78.23 nm, respectively. The morphology was studied by scanning electron microscopy. The measurement of the complex permittivity was made using the small perturbation technique, with a cavity operating in TE 105 mode, at resonant frequency of 2.7 GHz. The increase of the treatment temperature promoted the increase of the dielectric constant and the dielectric losses were still maintained with low values, allowing their potential application in electric storage devices. The dielectric constant of ErNbO4 in a zero porosity sample case was estimated and compared with the experimental values.

Vertical stacking of atomically thin layered materials opens new possibilities for the fabrication of heterostructures with favorable optoelectronic properties. The combination of graphene, hexagonal boron nitride and semiconducting transition metal dichalcogenides allows fabrication of electroluminescence (EL) devices, compatible with a wide range of substrates. Here, we demonstrate a full integration of an electroluminescent van der Waals heterostructure in a monolithic optical microcavity made of two high reflectivity dielectric distributed Bragg reflectors (DBRs). Owing to the presence of graphene and hexagonal boron nitride protecting the WSe_2 during the top mirror deposition, we fully preserve the optoelectronic behaviour of the device. Two bright cavity modes appear in the EL spectrum featuring Q-factors of 250 and 580 respectively: the first is attributed directly to the monolayer area, while the second is ascribed to the portion of emission guided outside the WSe_2 island. By embedding the EL device inside the microcavity structure, a significant modification of the directionality of the emitted light is achieved, with the peak intensity increasing by nearly two orders of magnitude at the angle of the maximum emission compared with the same EL device without the top DBR. Furthermore, the coupling of the WSe_2 EL to the cavity mode with a dispersion allows a tuning of the peak emission wavelength exceeding 35 nm (80 meV) by varying the angle at which the EL is observed from the microcavity. This work provides a route for the development of compact vertical-cavity surface-emitting devices based on van der Waals heterostructures.

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Epitaxial films may be released from growth substrates and transferred to structurally and chemically incompatible substrates, but epitaxial films of transition metal perovskite oxides have not been transferred to electroactive substrates for voltage control of their myriad functional properties. Here we demonstrate good strain transmission at the incoherent interface between a strain-released film of epitaxially grown ferromagnetic La 0.7 Sr 0.3 MnO 3 and an electroactive substrate of ferroelectric 0.68Pb(Mg 1/3 Nb 2/3 )O 3 -0.32PbTiO 3 in a different crystallographic orientation. Our strain-mediated magnetoelectric coupling compares well with respect to epitaxial heterostructures, where the epitaxy responsible for strong coupling can degrade film magnetization via strain and dislocations. Moreover, the electrical switching of magnetic anisotropy is repeatable and non-volatile. High-resolution magnetic vector maps reveal that micromagnetic behaviour is governed by electrically controlled strain and cracks in the film. Our demonstration should inspire others to control the physical/chemical properties in strain-released epitaxial oxide films by using electroactive substrates to impart strain via non-epitaxial interfaces.

Scanning/transmission electron microscopy (S/TEM) has demonstrated remarkable capabilities in elucidating fundamental understanding in a range of fields.[1,2] Advances in S/TEM instrumentation, have made recording atomic resolution images routine if not trivial.To fully exploit the increased imaging and spectroscopy capabilities of current S/TEM instruments, requires a very thin and clean, undamaged specimen that is representative of the original material.A wide range of techniques are available to prepare S/TEM specimens, with the optimal method determined by the material and desired viewing orientation.The focused ion beam (FIB) is a highly versatile instrument for the preparation of thin S/TEM lamellae with unrivaled site specificity.[3]

Similar to silicon-based semiconductor devices, van der Waals heterostructures require integration with high-k oxides. Here, we demonstrate a method to embed and pattern a multifunctional few-nanometer-thick high-k oxide within various van der Waals devices without degrading the properties of the neighboring two-dimensional materials. This transformation allows for the creation of several fundamental nanoelectronic and optoelectronic devices, including flexible Schottky barrier field-effect transistors, dual-gated graphene transistors, and vertical light-emitting/detecting tunneling transistors. Furthermore, upon dielectric breakdown, electrically conductive filaments are formed. This filamentation process can be used to electrically contact encapsulated conductive materials. Careful control of the filamentation process also allows for reversible switching memories. This nondestructive embedding of a high-k oxide within complex van der Waals heterostructures could play an important role in future flexible multifunctional van der Waals devices.

Atomically thin films of III-VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductor that feature strong variations of their band gap as a function of the number of layers in the crystal [1-4] and, specifically for InSe, an earlier predicted crossover from a direct gap in the bulk [5,6] to a weakly indirect band gap in monolayers and bilayers [7-11]. Here, we apply angle resolved photoemission spectroscopy with submicrometer spatial resolution (μARPES) to visualise the layer-dependent valence band structure of mechanically exfoliated crystals of InSe. We show that for 1 layer and 2 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 bandgap becomes direct, in good agreement with theoretical predictions. The high-quality monolayer and bilayer samples enables 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 the splitting that agrees with both μARPES data and the results of DFT modelling. Due to the difference in symmetry between these two valence bands, light emitted by the A-exciton should be predominantly polarised perpendicular to the plane of the two-dimensional crystal, which we have verified for few-layer InSe crystals.

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.

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.

Scaling improvements in conventional semiconductor devices have been facilitated by incorporating high-k dielectric materials such as HfO 2 [1]. This has led to increased device density and lower drive voltages. Similarly, the rapid technological progress of flexible Van der Waals (VdW) heterostructure devices based on two-dimensional (2D) materials, will also likely require comparable scaling to reduce device drive voltages to a comparable level (~1 V). Typically, flexible VdW heterostructures rely on high purity hexagonal boron nitride dielectrics (hBN) which has a dielectric constant k ~ 4, 4-5 times smaller than HfO 2 [2]. To overcome these limitations, we developed a novel technology to incorporate the high-k dielectric HfO x within VdW heterostructures through photo-oxidation of the 2D semiconductor HfS 2 via laser irradiation. The resultant oxide is found to have a dielectric constant k ~ 15. This oxide can be selectively written even once embedded within complex multi-layer VdW heterostructures, and under metallic contacts. This avoids the need for expensive sputtering and atomic layer deposition techniques, which are known to badly damage 2D materials. We exploit this technology to demonstrate several different VdW devices to suit various functionalities, including: flexible field effect transistors (FETs), resistive switching memory elements (ReRAMs) and light emitting and ultra-fast light detecting quantum well structures. All these devices show performances equal or superior to state-of-the-art VdW devices, with FETs displaying on/off ratios of 10 4 and subthreshold swings of 60 mV/dec.

Gas permeation through nanoscale pores is ubiquitous in nature and has an important role in many technologies1,2. Because the pore size is typically smaller than the mean free path of gas molecules, the flow of the gas molecules is conventionally described by Knudsen theory, which assumes diffuse reflection (random-angle scattering) at confining walls3–7. This assumption holds surprisingly well in experiments, with only a few cases of partially specular (mirror-like) reflection known5,8–11. Here we report gas transport through ångström-scale channels with atomically flat walls12,13 and show that surface scattering can be either diffuse or specular, depending on the fine details of the atomic landscape of the surface, and that quantum effects contribute to the specularity at room temperature. The channels, made from graphene or boron nitride, allow helium gas flow that is orders of magnitude faster than expected from theory. This is explained by specular surface scattering, which leads to ballistic transport and frictionless gas flow. Similar channels, but with molybdenum disulfide walls, exhibit much slower permeation that remains well described by Knudsen diffusion. We attribute the difference to the larger atomic corrugations at molybdenum disulfide surfaces, which are similar in height to the size of the atoms being transported and their de Broglie wavelength. The importance of this matter-wave contribution is corroborated by the observation of a reversed isotope effect, whereby the mass flow of hydrogen is notably higher than that of deuterium, in contrast to the relation expected for classical flows. Our results provide insights into the atomistic details of molecular permeation, which previously could be accessed only in simulations10,14, and demonstrate the possibility of studying gas transport under controlled confinement comparable in size to the quantum-mechanical size of atoms. Specular scattering of atoms of helium gas flowing through atomically flat, two-dimensional channels results in frictionless gas flow, which is much faster than expected assuming purely diffusive scattering.

Twin boundary defects form in virtually all crystalline materials as part of their response to applied deformation or thermal stress. For nearly six decades, graphite has been used as a textbook example of twinning with illustrations showing atomically sharp interfaces between parent and twin. Using state-of-the-art high-resolution annular dark-field scanning transmission electron microscopy, we have captured atomic resolution images of graphitic twin boundaries and find that these interfaces are far more complex than previously supposed. Density functional theory calculations confirm that the presence of van der Waals bonding eliminates the requirement for an atomically sharp interface, resulting in long-range bending across multiple unit cells. We show these remarkable structures are common to other van der Waals materials, leading to extraordinary microstructures, Raman-active stacking faults, and sub-surface exfoliation within bulk crystals.

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 modelling. 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 towards exploiting the spin degree of freedom in current studies of point defects as quantum emitters.

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.

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.

Graphene is hailed as an ideal material for spintronics due to weak intrinsic spin-orbit interaction that facilitates lateral spin transport and tunability of its electronic properties, including a possibility to induce magnetism in graphene. Another promising application of graphene is related to its use as a spacer separating ferromagnetic metals (FMs) in vertical magnetoresistive devices, the most prominent class of spintronic devices widely used as magnetic sensors. In particular, few-layer graphene was predicted to act as a perfect spin filter. Here we show that the role of graphene in such devices (at least in the absence of epitaxial alignment between graphene and the FMs) is different and determined by proximity-induced spin splitting and charge transfer with adjacent ferromagnetic metals, making graphene a weak FM electrode rather than a spin filter. To this end, we report observations of magnetoresistance (MR) in vertical Co-graphene-NiFe junctions with 1 to 4 graphene layers separating the ferromagnets, and demonstrate that the dependence of the MR sign on the number of layers and its inversion at relatively small bias voltages is consistent with spin transport between weakly doped and differently spin-polarized layers of graphene. The proposed interpretation is supported by the observation of an MR sign reversal in biased Co-graphene-hBN-NiFe devices and by comprehensive structural characterization. Our results suggest a new architecture for vertical devices with electrically controlled MR.

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.

Journal Article Understanding 2D Crystal Vertical Heterostructures at the Atomic Scale Using Advanced Scanning Transmission Electron Microscopy Get access Sarah J Haigh, Sarah J Haigh School of Materials, University of Manchester, Manchester, M13 9PL, UKNational Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Aidan P Rooney, Aidan P Rooney School of Materials, University of Manchester, Manchester, M13 9PL, UKNational Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Tom JA Slater, Tom JA Slater School of Materials, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Eric Prestat, Eric Prestat School of Materials, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Ekaterina Khestanova, Ekaterina Khestanova National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Rob Dryfe, Rob Dryfe School of Chemistry, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Matej Velický, Matej Velický School of Chemistry, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Roman V Gorbachev, Roman V Gorbachev National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Rada Boya, Rada Boya National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Yang Cao, Yang Cao National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar ... Show more Irina Grigorieva, Irina Grigorieva National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Kostya Novoselov, Kostya Novoselov National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Fred Withers, Fred Withers National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Andre K Geim Andre K Geim National Graphene Institute, University of Manchester, Manchester, M13 9PL, UK Search for other works by this author on: Oxford Academic Google Scholar Microscopy and Microanalysis, Volume 23, Issue S1, 1 July 2017, Pages 1714–1715, https://doi.org/10.1017/S1431927617009230 Published: 04 August 2017