Interfacial interaction and intense interfacial ultraviolet light emission at an incoherent interface.

Incoherent interfaces with large mismatches usually exhibit very weak interfacial interactions so that they rarely generate intriguing interfacial properties. Here we demonstrate unexpected strong interfacial interactions at the incoherent AlN/Al2O3 (0001) interface with a large mismatch by combining transmission electron microscopy, first-principles calculations, and cathodoluminescence spectroscopy. It is revealed that strong interfacial interactions have significantly tailored the interfacial atomic structure and electronic properties. Misfit dislocation networks and stacking faults are formed at this interface, which is rarely observed at other incoherent interfaces. The band gap of the interface reduces significantly to ~ 3.9 eV due to the competition between the elongated Al-N and Al-O bonds across the interface. Thus this incoherent interface can generate a very strong interfacial ultraviolet light emission. Our findings suggest that incoherent interfaces can exhibit strong interfacial interactions and unique interfacial properties, thereby opening an avenue for the development of related heterojunction materials and devices.

Microstructure and physical properties of ε-Fe2O3 thin films fabricated by pulsed laser deposition.

ε-Fe2O3 has attracted intense interest in the field of magnetoelectric materials due to its promising physical properties. The epitaxial growth of ε-Fe2O3 thin films is challenging since it is a metastable phase of iron oxide. In this study, ε-Fe2O3 (001) thin films are epitaxially grown on SrTiO3 (111) substrates by pulsed laser deposition (PLD). The crystal structure, valence state, and microstructure of the ε-Fe2O3 thin films are investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. It is revealed that the oxygen pressure, deposition and annealing temperatures, and laser beam energy affect significantly the epitaxial growth of ε-Fe2O3 thin films. The orientation relationship between films and substrates is ε-Fe2O3 (001)[010] // SrTiO3 (111)[1¯10]. The magnetic hysteresis loops tested by a superconducting quantum interference device and UV-Vis reflection spectra suggest that the ε-Fe2O3 thin film with thickness of ∼ 20 nm has a strong magnetic anisotropy, a coercivity of 600 Oe, and an indirect band gap of 3.26 eV.

Direct Determination of Band Gap of Defects in a Wide Band Gap Semiconductor.

Crystal defects play an important role in the degradation and failure of semiconductor materials and devices. Direct determination of band gap of defects is a critical step for clarifying how the defects affect the physical properties of semiconductors. Here, high-quality aluminum nitride (AlN) thin films were grown epitaxially on single-crystal Al2O3 substrates via pulsed laser deposition. The atomic structure and band gap of three types of inversion domain boundaries (IDBs) in AlN were determined using aberration-corrected transmission electron microscopy and atomic-resolution valence electron energy-loss spectroscopy. It was found that the band gap of all of the IDBs reduces evidently compared to that of the bulk AlN. The maximum band gap reduction of the IDBs is 1.0 eV. First-principles calculations revealed that the band gap reduction of the IDBs is mainly due to the rise of pz orbital at the valence band maximum, which originates from the elongated Al-N bonds along the [0001] direction at the IDBs. The successful band gap determination of defects paves an avenue for quantitatively evaluating the effect of defects on the performance of semiconductor materials and devices.

Spin Polarization-Assisted Dopant Segregation at a Coherent Phase Boundary.

Coherent phase boundaries are widely expected as segregation-free boundaries due to their low interfacial energies and lack of trapping sites for impurities. Here, we report an equilibrium segregation of W atoms at fully coherent terraces of a Fe3O4 (111)/Fe2O3 (0001) phase boundary that was never expected previously. Through comparison of pristine and W-doped Fe3O4/Fe2O3 phase boundaries, it is revealed that the spin polarization of O atoms at the interface plays an important role in the periodic segregation of W atoms. Unusual spin-polarized O atoms with large magnetic moments are periodically arranged in the interfacial O plane of the pristine phase boundary. After doping of W at this boundary, W atoms will selectively substitute the Fe atoms of Fe2O3 that directly bond with three spin-polarized O atoms, thereby resulting in the complete neutralization of the magnetic moments of the spin-polarized O atoms. These findings reveal that coherent phase boundaries are able to trap impurities and local spin polarization is one of the driving forces for dopant segregation, suggesting that elemental doping is an efficient way for tailoring the physical properties of boundaries in magnetic materials and devices.

High Reversible Strain in Nanotwinned Metals.

Development of bulk metals exhibiting large reversible strain is of great interest, owing to their potential applications in flexible electronic devices. Bulk metals with nanometer-scale twins have demonstrated high strength, good ductility, and promising electrical conductivity. Here, ultrahigh reversible strain as high as ∼7.8% was observed in bent twin lamellae with 1-2 nm thickness in nanotwinned metals, where the maximum reversible strain increases with the reduction in twin lamella thickness. This high reversible strain is attributed to the suppression of dislocation nucleation, including both hard mode dislocations in the bent twin lamellae, while soft mode dislocations along twin boundaries have insignificant contribution. In situ transmission electron microscopy experiments show that higher recoverability was achieved in twinned Au nanorods compared with twin-free ones with similar aspect ratios and diameters during bending deformation, which demonstrates that the introduction of thin twin lamellae also significantly improves the shape recoverability of Au nanorods. This result introduces a novel pathway for developing bulk metals with the capability for large reversible strain.

Single-Dislocation Schottky Diodes.

Dislocations often exhibit unique physical properties distinct from those of the bulk material. However, functional applications of dislocations are challenging due to difficulties in the construction of high-performance devices of dislocations. Here we demonstrate unidirectional single-dislocation Schottky diode arrays in a Fe2O3 thin film on Nb-doped SrTiO3 substrates. Conductivity measurements using conductive atomic force microscopy indicate that a net current will flow through individual dislocation Schottky diodes under forward bias and disappear under reverse bias. Under cyclic bias voltages, the single-dislocation Schottky diodes exhibit a distinct resistive switching behavior containing low-resistance and high-resistance states with a high resistance ratio of ∼103. A combined study of transmission electron microscopy and first-principles calculations reveals that the Fe2O3 dislocations comprise mixed Fe2+ and Fe3+ ions due to O deficiency and exhibit a one-dimensional electrical conductivity. The single-dislocation Schottky diodes may find applications for developing ultrahigh-density electronic and memory devices.

An oxidation-nitridation-denitridation approach to transform metal solids into foams with adjustable pore sizes for energy applications.

Metal foams with hierarchically porous structures are highly desirable in energy applications as active materials or their host substrates. However, conventional preparation methods usually have a quite limited flexibility of adjusting pore size of metal foams. Herein, an alternative new method based on gaseous thermal oxidation-nitridation-denitridation processes was developed to prepare metal (copper and nickel) foams with adjustable pore size by controlling the thermal nitridation temperature. Moreover, this environment-friendly method is independent of the shape of starting pure metal substrates and can be repeatedly applied to the metal substrates to create hierarchical porous structures containing different size pores. As a demonstration of the advantages of the resultant foams with abundant pores by this method, compared with its starting material (commercial Ni foam with the pore size of several millimeters), the resultant hierarchical porous Ni foam gives the remarkably enhanced performance of electrochemical water splitting as HER/OER electrodes and electrochemical energy storage as the host substrate of capacitive material MnO2. The metal foams with adjustable pore size prepared by the developed method will find a wide range of important applications in energy storage and conversion areas.

In situ observation of twin-assisted grain growth in nanometer-scaled metal.

For nanometer-scaled materials, grain boundary behaviors, such as grain coalescence and grain boundary migration, contribute significantly to the plasticity of materials. While mechanically driven grain growth has been observed in nanometer-scaled metals, its underlying mechanisms are still poorly understood especially for those correlated with twins. By using in situ aberration-corrected transmission electron microscopy and precession electron diffraction, we have directly revealed nanotwin assisted grain growth for low angle grain boundaries. The grains with low angle grain boundaries coalesce by firstly forming twin pairs, whose coherent twin boundaries then serve as fast lanes for dislocations, and thus dissolving the low angle grain boundaries. During this process, the constitute dislocations of the low angle grain boundaries decompose into Shockley partial dislocations, which subsequently move along the coherent twin boundaries. After all the constitute dislocations dissociate and move out, two grains will coalesce and twin pairs merge into complete twin lamellae. For high angle grain boundaries, portions of grain boundaries intersected with nanotwins show higher mobility for migration under external stress. This investigation provides insight to twin related grain boundary behaviors in nanometer-scaled metals.

Ferroelectric Oxide Thin Film with an Out-of-Plane Electrical Conductivity.

Ferroelectricity and electrical conductivity are two fundamentally incompatible properties that are difficult to simultaneously achieve in a material. Here, we combine these two contradictory properties by embedding conducting SrNbO3 micro/nanopillars into a ferroelectric SrNbO3.5 (i.e., Sr2Nb2O7) thin film. The high-Tc ferroelectric SrNbO3.5 thin film is epitaxially grown on a LaAlO3 substrate by pulsed laser deposition. The conducting SrNbO3 micro/nanopillars are introduced into the film via an electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation triggered by a focused electron beam. The sizes and distribution of the SrNbO3 micro/nanopillars can be accurately controlled through artificial manipulation of the electron-irradiation-induced SrNbO3.5-to-SrNbO3 phase transformation. The ferroelectric SrNbO3/SrNbO3.5 thin film with an in-plane polarization exhibits an electrical conductivity in the out-of-plane direction. Such conducting ferroelectric thin films may lead to the discovery of plentiful physical phenomena and have great potential for pyroelectric, photoelectric, and multiferroic applications.

Stabilizing the metastable superhard material wurtzite boron nitride by three-dimensional networks of planar defects.

Wurtzite boron nitride (w-BN) is a metastable superhard material that is a high-pressure polymorph of BN. Clarifying how the metastable high-pressure material can be stabilized at atmospheric pressure is a challenging issue of fundamental scientific importance and promising technological value. Here, we fabricate millimeter-size w-BN bulk crystals via the hexagonal-to-wurtzite phase transformation at high pressure and high temperature. By combining transmission electron microscopy and ab initio molecular dynamics simulations, we reveal a stabilization mechanism for w-BN, i.e., the metastable high-pressure phase can be stabilized by 3D networks of planar defects which are constructed by a high density of intersecting (0001) stacking faults and {10[Formula: see text]0} inversion domain boundaries. The 3D networks of planar defects segment the w-BN bulk crystal into numerous nanometer-size prismatic domains with the reverse crystallographic polarities. Our findings unambiguously demonstrate the retarding effect of crystal defects on the phase transformations of metastable materials, which is in contrast to the common knowledge that the crystal defects in materials will facilitate the occurrence of phase transformations.

Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals.

Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15°) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.

Precipitation of binary quasicrystals along dislocations.

Dislocations in crystals naturally break the symmetry of the bulk, introducing local atomic configurations with symmetries such as fivefold rings. But dislocations do not usually nucleate aperiodic structure along their length. Here we demonstrate the formation of extended binary quasicrystalline precipitates with Penrose-like random-tiling structures, beginning with chemical ordering within the pentagonal structure at cores of prismatic dislocations in Mg-Zn alloys. Atomic resolution observations indicate that icosahedral chains centered along [0001] pillars of Zn interstitial atoms are formed templated by the fivefold rings at dislocation cores. They subsequently form columns of rhombic and elongated hexagonal tiles parallel to the dislocation lines. Quasicrystalline precipitates are formed by random tiling of these rhombic and hexagonal tiles. Such precipitation may impact dislocation glide and alloy strength.

Atomic structure and chemistry of a[100] dislocation cores in La2/3Sr1/3MnO3 films.

Oxide thin films with perovskite structures possess multifunctional properties, while defects in the films usually have significant influences on their physical properties. Here, the atomic structure and chemistry of a[100] dislocation cores in epitaxial La2/3Sr1/3MnO3 films were investigated by aberration-corrected scanning transmission electron microscopy combining with atomically resolved electron energy-loss spectroscopy imaging. The results demonstrated an edge dislocation terminated with Mn columns and significant nonstoichiometry at the dislocation core region. Quantitative analysis using core-loss spectrum indicates that La/Mn and O/Mn ratios are decreased at the dislocation core. Antisite defects with Mn ions at La-sites were directly determined at the dislocation cores with electron energy-loss spectroscopy. The structure of the dislocation core is discussed on the basis of high-angle annular dark-field imaging and electron energy loss spectroscopy results.

Direct observation of solid-state reversed transformation from crystals to quasicrystals in a Mg alloy.

Phase transformation of quasicrystals is of interest in various fields of science and technology. Interestingly, we directly observed unexpected solid-state epitaxial nucleation and growth of Zn6Mg3Y icosahedral quasicrystals in a Mg alloy at about 573 K which is about 300 K below the melting point of Zn6Mg3Y, in contrast to formation of quasicrystals through solidification that was usually found in many alloys. Maximizing local packing density of atoms associated with segregation of Y and Zn in Mg adjacent to Mg/Zn3MgY interfaces triggered atomic rearrangement in Mg to form icosahedra coupled epitaxially with surface distorted icosahedra of Zn3MgY, which plays a critical role in the nucleation of icosahedral clusters. A local Zn:Mg:Y ratio close to 6:3:1, corresponding to a valence electron concentration of about 2.15, should have been reached to trigger the formation of quasicrystals at Mg/Zn3MgY interfaces. The solid-state icosahedral ordering in crystals opens a new window for growing quasicrystals and understanding their atomic origin mechanisms. Epitaxial growth of quasicrystals onto crystals can modify the surface/interface structures and properties of crystalline materials.

Direct observation of atomic dynamics and silicon doping at a topological defect in graphene.

Chemical decoration of defects is an effective way to functionalize graphene and to study mechanisms of their interaction with environment. We monitored dynamic atomic processes during the formation of a rotary Si trimer in monolayer graphene using an aberration-corrected scanning-transmission electron microscope. An incoming Si atom competed with and replaced a metastable C dimer next to a pair of Si substitutional atoms at a topological defect in graphene, producing a Si trimer. Other atomic events including removal of single C atoms, incorporation and relocation of a C dimer, reversible C-C bond rotation, and vibration of Si atoms occurred before the final formation of the Si trimer. Theoretical calculations indicate that it requires 2.0 eV to rotate the Si trimer. Our real-time results provide insight with atomic precision for reaction dynamics during chemical doping at defects in graphene, which have implications for defect nanoengineering of graphene.

Undulating slip in Laves phase and implications for deformation in brittle materials.

By combining density-functional theory calculations and aberration-corrected transmission electron microscopy, dislocations in Laves phase (a typical complex intermetallic compound) are shown to slip in an undulating path. During the slip, the dislocation cores jump up and down between a weakly bound plane and an adjacent strongly bound plane for gliding and atomic shuffling, respectively. This is different from the conventional slip process in simple metals, which is continuous within a single plane, as described in the paradigm of the generalized stacking fault energy.

Icosahedral face-centered cubic Fe nanoparticles: facile synthesis and characterization with aberration-corrected TEM.

Iron nanoparticles are highly desirable for their potential applications in magnetic and catalytic industry. However, their shape-controlled fabrication is still an important challenge. Here we successfully synthesized icosahedral face-centered cubic (fcc) Fe nanoparticles with size of 5-13 nm by a specifically designed thermodynamic governed synthetic route, which is facile but highly efficient and reproducible. With the aberration-corrected transmission electron microscopy (TEM), the unique icosahedral structure's pseudo-2-fold, 3-fold, and pseudo-5-fold axes were directly observed for the first time and verified by computer simulation, which reveals that nanoparticles' orientations have a large impact on HRTEM images at ultrahigh resolution. It is expected that as-synthesized Fe nanoparticles with sharp corners and edges would be beneficial for tailoring chemical and physical properties at the nanoscale.

On the accuracy of maximum entropy reconstruction of high-resolution Z-contrast STEM images.

The accuracy of maximum entropy reconstruction of Z-contrast STEM images has been evaluated with the effects of experimental variables and noise taken into account by the means of image simulation. As the specimen contains atom species of greatly different atomic numbers, special attention is given to the reliability of the position and composition of lighter atoms that are determined from Z-contrast images in the presence of heavier atoms. When the noise is moderate (SNR >2.5), the position of atom columns can be measured within an accuracy of 0.03 nm. With a higher signal-to-noise ratio (SNR >5) the composition of lighter atoms can be resolved reliably from the Z-contrast images. However, when image noise increases, the relative intensity of lighter atoms may deviate from the actual value in the specimen object function.

Anisotropic and passivation-dependent quantum confinement effects in germanium nanowires: a comparison with silicon nanowires.

Electronic structures of hydrogen-passivated germanium nanowires (GeNWs) along the [100], [110], [111], and [112] directions are studied by using the density functional theory within the generalized gradient approximation. The band gaps of the fully relaxed GeNWs along the [100], [110], and [111] directions are all direct at the smaller sizes, while those of the wires along the [112] direction remain indirect. The magnitude of the band gaps of the GeNWs for a given size approximately follows the order of E(g)[100] > E(g)[111] > E(g)[112] > E(g)[110]. Compared with silicon nanowires, GeNWs exhibit stronger quantum confinement effects. Replacement of H by the more stable ethine group is found to lead to a weakening of the quantum confinement effects of GeNWs.

Structural and electronic properties of fluorinated boron nitride nanotubes.

The effects of F doping on the structural and electronic properties of the (5, 5) single-walled boron nitride nanotube (BNNT) are investigated by using the density functional theory method. The chemiadsorption of F maintains the hexagonal BN network, increases the lattice constant, and introduces acceptor impurity states. On the other hand, substitutional doping of F destroys the hexagonal BN network, decreases the lattice constant, but does not alter the insulating feature of the BNNT. The observed insulator-to-semiconducting transition, a lattice contraction, and a highly disordered atom arrangement in the sidewall of BNNTs upon F doping appear to be most reasonably attributed to a codoping of dominating substitutional F over chemiabsorbed F, which can induce deep donor impurity states, a lattice contraction, and a destruction of the hexagonal BN network simultaneously.