We present a theoretical study of the structure and functionality of ferroelastic domain walls in tungsten trioxide, WO$_3$. WO$_3$ has a rich structural phase diagram, with the stability and properties of the various structural phases strongly affected both by temperature and by electron doping. The existence of superconductivity is of particular interest, with the underlying mechanism as of now not well understood. In addition, reports of enhanced superconductivity at structural domain walls are particularly intriguing. Focusing specifically on the orthorhombic $β$ phase, we calculate the structure and properties of the domain walls both with and without electron doping. We use two theoretical approaches: Landau-Ginzburg theory, with free energies constructed from symmetry considerations and parameters extracted from our first-principles density functional calculations, and direct calculation using large-scale, GPU-enabled density functional theory. We find that the structure of the $β$-phase domain walls resembles that of the bulk tetragonal $α_1$ phase, and that the electronic charge tends to accumulate at the walls. Motivated by this finding, we perform ab initio computations of electron-phonon coupling in the bulk $α_1$ structure and extract the superconducting critical temperatures , $T_c$, within Bardeen-Cooper-Schrieffer theory. Our results provide insight into the experimentally observed unusual trend of decreasing Tc with increasing electronic charge carrier concentration.
The influence of twin boundaries on the heat capacity and diffuse scattering in a crystal is described within the framework of a macroscopic dynamic theory.
The growth and annealing behavior of strongly twinned homoepitaxial films on Ir(111) has been investigated by scanning tunneling microscopy, low energy electron diffraction and surface X-ray diffraction. In situ surface X-ray diffraction during and after film growth turned out to be an efficient tool for the determination of twin fractions in multilayer films and to uncover the nature of side twin boundaries. The annealing of the twin structures is shown to take place in a two step process, reducing first the length of the boundaries between differently stacked areas and only then the twins th…
Metallic materials, especially steel, underpin transportation technologies. High-manganese twinning induced plasticity (TWIP) austenitic steels exhibit exceptional strength and ductility from twins, low-energy microstructural defects that form during plastic loading. Their high-strength could help light-weighting vehicles, and hence cut carbon emissions. TWIP steels are however very sensitive to hydrogen embrittlement that causes dramatic losses of ductility and toughness leading to catastrophic failure of engineering parts. Here, we examine the atomic-scale chemistry and interaction of hydrog…
The influence of Twin Boundaries (TB) on the Flux Line Lattice(FLL) structure was investigated by Small Angle Neutron Scattering (SANS). YBaCuO single crystals possessing different TB densities were studied. The SANS experiments show that the TB strongly modify the structure of the FLL. The flux lines meander as soon as the magnetic field makes an angle with the TB direction. According to the value of this angle but also to the ratio of the flux lines density over the TB density, one observes that the FLL exhibits two different unit cells in the plane perpendicular to the magnetic field. One i…
Slip transfer at grain boundaries and annealing twin boundaries was studied in polycrystalline Ni by means of slip trace analysis. Slip transfer or blocking was assessed in $>$ 200 boundaries and was related with geometrical criteria that establish the alignment between the active slip systems across the boundaries. It was found that slip transfer mainly occurs at low-angle regular grain boundaries and that a Luster-Morris parameter $>$ 0.8 stands for the best criterion to assess slip transfer. In the case of coherent or incoherent twin boundaries, slip transfer occurs when the residual Burger…
Molecular dynamics simulations were performed to understand the role of twin boundaries on deformation behaviour of body-centred cubic (BCC) iron (Fe) nanopillars. The twin boundaries varying from one to five providing twin boundary spacing in the range 8.5 - 2.8 nm were introduced perpendicular to the loading direction. The simulation results indicated that the twin boundaries in BCC Fe play a contrasting role during deformation under tensile and compressive loadings. During tensile deformation, a large reduction in yield stress was observed in twinned nanopillars compared to perfect nanopill…
In frameworks of the macroscopic dynamic theory of coherent interfaces in crystals the acoustic radiation of coherent boundary at passage along it of localized wave packages is considered. It is shown that the coherent twin boundary of acoustic waves does not radiate.
Twin boundaries play an essential role in the use of magnetic shape memory alloy Ni-Mn-Ga as active material. Only if twin boundaries can be moved by an external magnetic field, high strain values of up to 10 % can be obtained. Therefore, understanding the observed twin microstructure of thin films is crucial for future application. We exemplarily present two different microstructural pattern, type X and type Y microstructure, using the example of two Ni-Mn-Ga films with similar film thickness and composition. The analysis of microstructure and structure of the thin films shows that both, type…
Using a symmetry-based atomic scale theory of lattice distortions, we demonstrate that elastic textures, such as twin and antiphase boundaries, can generate intricate electronic inhomogeneities in materials with strong electron-lattice coupling, as observed in perovskite manganites and other functional materials.
One-dimensional (1D) metallic mirror-twin boundaries (MTBs) in monolayer transition metal dichalcogenides (TMDCs) exhibit a periodic charge modulation and provide an ideal platform for exploring collective electron behavior in the confined system. The underlying mechanism of the charge modulation and how the electrons travel in 1D structures remain controversial. Here, for the first time, we observed atomic-scale structures of the charge distribution within one period in MTB of monolayer MoTe2 by using scanning tunneling microscopy/spectroscopy (STM/STS). The coexisting apparent periodic latti…
It is well known that the twinning is an important mode of plastic deformation in nanocrystalline materials. As a result, it is expected that the twin can interact with different grain boundaries (GBs) during the plastic deformation. Understanding these twin-GB interactions is crucial for our understanding of mechanical behavior of materials. In this work, the twin interaction with different $Σ$11 symmetric and asymmetric tilt GBs has been investigated in BCC Fe using molecular dynamics (MD) simulations. The results indicate that twin nucleate from the crack or GB and, its interaction with $Σ$…
In this paper, the effect of twin boundaries on the crack growth behaviour of single crystal BCC Fe has been investigated using molecular dynamics simulations. The growth of an atomically sharp crack with an orientation of (111)$<$110$>$ (crack plane/crack front) has been studied under mode-I loading at constant strain rate. In order to study the influence of twin boundaries on the crack growth behaviour, single and multiple twin boundaries were introduced perpendicular to crack growth direction. The results indicate that the (111)$<$110$>$ crack in single crystal BCC Fe grows in brittle manne…
There have been conflicting reports on the electronic properties of twin domain boundaries (DBs) in MoSe2 monolayer, including the quantum well states, charge density wave, and Tomonaga-Luttinger liquid (TLL). Here we employ low-temperature scanning tunneling spectroscopy to reveal both the quantum confinement effect and signatures of TLL in the one-dimensional DBs. The data do not support the CDW at temperatures down to ~5 K.
We propose a new statistical physics model to study equilibrium solute segregation at grain boundaries and the resulting embrittlement effect. This low-temperature expansion model is general and efficient, and its parameters can be obtained from atomistic calculations. It is possible to take into account multiple species, multiple segregation sites with different segregation free energies, account for configurational entropy, grain radius and site competition between solutes. As an example, the model is then applied to the study of phosphorus and hydrogen co-segregation at $\Sigma3$ $109.5°[0\…
Under high pressures, phase transition, as well as deformation twins, are constantly reported in many BCC metals, whose interactions are of fundamental importance to understand strengthen mechanism of these metals under extreme conditions. However, the interactions between twins and phase transition in BCC metals are remain largely unexplored. In this work, interactions between coherent twin boundaries and $α\to ε$ phase transition of iron are investigated using both non- equilibrium molecular dynamics simulations and nudge elastic band method. Mechanisms of both twin-assisted phase transition…
The search for one-dimensional (1D) topologically-protected electronic states has become an important research goal for condensed matter physics owing to their potential use in spintronic devices or as a building block for topologically non-trivial electronic states. Using low temperature scanning tunneling microscopy, we demonstrate the formation of 1D electronic states at twin boundaries at the surface of the noncentrosymmetric material BiPd. These twin boundaries are topological defects which separate regions with antiparallel orientations of the crystallographic \textit{b} axis. We demonst…
Understanding and engineering the domain boundaries in chemically vapor deposited (CVD) monolayer graphene will be critical for improving its properties. In this study, a combination of transmission electron microscopy (TEM) techniques including selected area electron diffraction (SAED), high resolution transmission electron microscopy (HRTEM), and dark field (DF) TEM was used to study the boundary orientation angle distribution and the nature of the carbon bonds at the domain boundaries. This report provides an important first step towards a fundamental understanding of these domain boundarie…
Twin boundaries (TBs) are assumed to be obstacles to dislocation motion and increase the strength of metals. Here, we report the abnormal phenomenon that TBs reduce the strength of body-centered cubic (BCC) tungsten (W). [1-11]-oriented W nanowires with (121) twin planes and free of dislocations were fabricated by chemical vapor deposition. In situ tensile tests within the transmission electron microscope were performed on single-crystal and twinned W nanowires. The fracture strength of the twinned W nanowire was 13.7 GPa, 16% lower than that of the single-crystal W nanowire (16.3 GPa). The we…
A model for two-dimensional electronic, photonic, and mechanical metamaterial systems is presented, which has flat one-dimensional zero-mode energy bands and stable localized states of a topological origin confined within twin boundaries, antiphase boundaries, and at open edges. Topological origins of these flat bands are analyzed for an electronic system as a specific example, using a two-dimensional extension of the Su-Schrieffer-Heeger Hamiltonian with alternating shift of the chains. It is demonstrated that the slow group velocities of the localized flat band states are sensitively control…
One of the most striking signatures of Weyl fermions is their surface Fermi arcs. Less known is that Fermi arcs can also be localized at internal twin boundaries where two Weyl materials of opposite chirality meet. In this work, we derive constraints on the topology and connectivity of these "internal Fermi arcs." We show that internal Fermi arcs can exhibit transport signatures and propose two probes: quantum oscillations and a quantized chiral magnetic current. We propose merohedrally twinned B20 materials as candidates to host internal Fermi arcs, verified through both model and ab initio c…
Careful first-principles density functional calculations reveal the importance of hexagonal versus cubic stacking of closed packed planes of Pd as far as local magnetic properties are concerned. We find that, contrary to the stable face centered cubic phase, which is paramagnetic, the hexagonal close-packed phase of Pd is ferromagnetic with a magnetic moment of 0.35 $μ_{B}$/atom. Our results show that two-dimensional defects with local hcp stacking, like twin boundaries and stacking faults, in the otherwise fcc Pd structure, increase the magnetic susceptibility. The (111) surface also increase…
We present a case study of the complex temperature dependence of grain boundary mobility. The same general incoherent twin boundary in different FCC metals is found to display antithermal, thermal, and mixed mobility during molecular dynamics synthetic driving force simulations. A recently developed energy metric known as the generalized interfacial fault energy (GIFE) surface is used to show that twin boundaries moving in an antithermal manner have a lower energetic barrier to motion than twin boundaries moving in a thermally activated manner. Predicting the temperature dependence of grain bo…
We quantify and explain the effects of both anti-phase boundaries and twin defects in as-transformed $τ$-MnAl by carrying out micromagnetic simulations based closely on the results of microstructural characterization. We demonstrate that magnetic domain walls nucleate readily at anti-phase boundaries and are strongly pinned by them, due to anti-ferromagnetic coupling. Likewise, twin boundaries reduce the external field required to nucleate domain walls and provide strong pinning potentials, with the pinning strength dependent on the twinning angle. The relative strengths of the known twin defe…
Coherent twin boundaries form periodic lamellar twinning in a wide variety of semiconductor nanowires, and are often viewed as near-perfect interfaces with reduced phonon and electron scattering behaviors. Such unique characteristics are of practical interest for high-performance thermoelectrics and optoelectronics; however, insufficient understanding of twin-size effects on thermal boundary resistance poses significant limitations for potential applications. Here, using atomistic simulations and ab-initio calculations, we report direct computational observations showing a crossover from diffu…
Shape memory alloys often show a complex hierarchical morphology in the martensitic state. To understand the formation of this twin-within-twins microstructure, we examine epitaxial Ni-Mn-Ga films as a model system. In-situ scanning electron microscopy experiments show beautiful complex twinning patterns with a number of different mesoscopic twin boundaries and macroscopic twin boundaries between already twinned regions. We explain the appearance and geometry of these patterns by constructing an internally twinned martensitic nucleus, which can take the shape of a diamond or a parallelogram, w…
In recent years, twinned nanopillars have attracted tremendous attention for research due to their superior mechanical properties. However, most of the studies were focused on nanopillars with twin boundaries (TBs) perpendicular to loading direction. Nanopillars with TBs parallel to loading direction have received minimal interest. In this backdrop, the present study is aimed at understanding the role of axial TBs on strength and deformation behaviour of Cu nanopillars using atomistic simulations. Tensile and compression tests have been performed on $<$112$>$ nanopillars with and without TBs. …
Ductility and Brittle Fracture of Tungsten by Disconnection Pile-up on Twin Boundaries
Lawrence Livermore National Laboratory（劳伦斯利弗莫尔国家实验室）；Los Alamos National Laboratory（洛斯阿拉莫斯国家实验室）；University of California Irvine（加州大学尔湾分校）；University of California Los Angeles（加州大学洛杉矶分校）；Lehigh University（理海大学）；Northwestern University（西北大学）
With an ongoing discussion on the oxygen diffusion along crystal defects remaining, it is difficult to study this phenomenon in Al containing intermetallic materials due to its rapid and passivating oxide formation. We report here the observation of enhanced oxygen diffusion along crystal defects, i.e. dislocations and twin boundaries, in the C15 Al 2 Ca Laves phase and how the presence of oxygen induces structural changes at these defects. Three main phases were identified and characterized structurally by aberration-corrected, atomic resolution scanning transmission electron microscopy, anal…
Recently, several research groups have reported on the observation of super-large more than 5% magneto-strain effect in some non-stoichiometric Ni-Mn-Ga alloys close to 5.78% value expected from the tetragonality aspect ratio of the martensite crystal lattice. New Ni-Mn-Ga alloys showing giant magneto-strain effect display simultaneously few interesting physical effects and new behavior for some magnetic and mechanical properties which is very different from that earlier observed in Ni-Mn-Ga showing lower magneto-strain effect. This report represents some new experimental results and the quant…
Diffusionless phase transitions are at the core of the multifunctionality of (magnetic) shape memory alloys, ferroelectrics and multiferroics. Giant strain effects under external fields are obtained in low symmetric modulated martensitic phases. We outline the origin of modulated phases, their connection with tetragonal martensite and consequences for their functional properties by analysing the martensitic microstructure of epitaxial Ni-Mn-Ga films from the atomic to macroscale. Geometrical constraints at an austenite-martensite phase boundary act down to the atomic scale. Hence a martensitic…
The excess volume associated with grain boundaries represents a key structural parameter for the characterization of grain boundaries. It plays a critical role in segregation of impurity and alloy elements to grain boundaries, and influences significantly the mechanical and functional properties of materials. We have carried out first-principles density functional calculations on the atomic structure of the (10-12) coherent twin boundary in hexagonal close packed (hcp) Ti and Zr and the basal-prismatic boundary in Zn, Cd, and Zr. We find the calculated excess volume has a vanishing magnitude a…
The Landau spectrum of bismuth is complex and includes many angle-dependent lines in the extreme quantum limit. The adequacy of single-particle theory to describe this spectrum in detail has been an open issue. Here, we present a study of angle-resolved Nernst effect in bismuth, which maps the angle-resolved Landau spectrum for the entire solid angle up to 28 T. The experimental map is in good agreement with the results of a theoretical model with parabolic dispersion for holes and an extended Dirac Hamiltonian for electrons. The angular dependence of additional lines in the Landau spectrum al…
Formation of twin boundaries during the growth of semiconductor nanowires is very common. However, the effects of such planar defects on the electronic and optical properties of nanowires are not very well understood. Here, we use a combination of ab initio simulation and experimental techniques to study these effects. Twin boundaries in GaP are shown to act as an atomically-narrow plane of wurtzite phase with a type-I homostructure band alignment. Twin boundaries and stacking faults (wider regions of the wurtzite phase) lead to the introduction of shallow trap states observed in photoluminesc…
The high mechanical strength and excellent flexibility of 2D materials such as graphene are some of their most important properties [1]. Good flexibility is key for exploiting 2D materials in many emerging technologies, such as wearable electronics, bioelectronics, protective coatings and composites [1] and recently bending has been suggested as a route to tune electronic transport behaviour [2]. For virtually all crystalline materials macroscopic deformation is accommodated by the movement of dislocations and through the formation of twinning defects [3]; it is the geometry of the resulting m…
Mirror twin boundary (MTB) brings unique 1D physics and properties into two-dimensional transition metal dichalcogenides (TMDCs), but they were rarely observed in non-Mo-based TMDCs. Herein, by post-growth Nb doping, high density 4|4E-W and 4|4P-Se MTBs were introduced into molecular beam epitaxy (MBE) grown WSe2 monolayers. Of them, 4|4E-W MTB with a novel structure was discovered experimentally for the first time, while 4|4P-Se MTBs present a random permutations of W and Nb, forming a 1D alloy system. Comparison between the doped and non-doped WSe2 confirmed that Nb dopants are essential for…
Bilinear Flexo-Antiferrodistortive Coupling in Ferroelastics: Polar Twins, Antiphase Boundaries and Fingerprints of Alterelectricity
Frantsevich Institute for Problems in Materials Science, National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰采维奇材料科学问题研究所）；Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Department of Materials Science and Engineering, Pennsylvania State University（宾夕法尼亚州立大学材料科学与工程系）
Twinning in crystalline materials plays an important role in many transformation and deformation processes, where underlying mechanisms can be strongly influenced by the structural, energetic and kinetic properties of associated twin boundaries (TBs). While these properties are well characterized in common cases, the possibility that TBs can display multiple complexions with distinct properties, and phase transitions between them, has not been widely explored, even though such phenomena are established in a few more general grain boundaries. We report experimental findings that {11-24} TBs in …
Magnetic shape memory alloys exhibit a hierarchically twinned microstructure, which has been well examined in epitaxial Ni-Mn-Ga films. Here we analyze consequences of this twin within twins microstructure on the magnetic domain pattern. Atomic and magnetic force microscopy are used to probe the correlation between the martensitic microstructure and magnetic domains. We examine consequences of different twin boundary orientations with respect to the substrate normal as well as variant boundaries between differently aligned twinned laminates. A detailed micromagnetic analysis is given which des…
The tensile creep performance of a polycrystalline Co/Ni-base superalloy with a multimodal gamma prime distribution has been examined at 800C and 300MPa. The rupture life of the alloy is comparable to that of RR1000 tested under similar conditions. Microstructural examination of the alloy after testing revealed the presence of continuous gamma prime precipitates and M23C6 carbides along the grain boundaries. Intragranularly, coarsening of the secondary gamma prime precipitates occurred at the expense of the fine tertiary gamma prime. Long planar deformation bands, free of gamma prime, were als…
Probing Topological Surface States and Conduction via Extended Defects in (Bi$_{1-x}$Sb$_x$)$_2$Te$_3$ Films
University of Michigan（密歇根大学）；University of Illinois（伊利诺伊大学）；Kirklareli University（克尔克拉雷利大学）；Penn State University（宾夕法尼亚州立大学）；Istanbul Technical University（伊斯坦布尔理工大学）
Twin boundaries have been exploited to stabilize ultrafine grains and improve the mechanical properties of nanomaterials. The production of twin boundaries and nanotwins is however prohibitively challenging in carbide ceramics. Using scanning transmission electron microscopes as a unique platform for atomic-scale structure engineering, we demonstrate that twin platelets could be produced in carbides by engineering antisite defects. Antisite defects at metal sites in various layered ternary carbides are collectively and controllably generated and the metal elements are homogenized by electron i…
Heat flow control in phononics has received significant attention recently due to its widespread applications in energy transfer, conversion and utilization. Here, we demonstrate that by applying external stress or strain we can effectively tune the thermal conductivity through changing the density of twin boundaries, which in turn offers the intriguing mechanical-controlled thermal switch and hysteresis operations. Twin boundaries perpendicular to the transport direction strongly scatter phonons. As such, the heat flow is in inverse proportional to the density of twin boundaries and hence all…
We present quantum-based simulations of single grain boundary reflectivity of electrons in metals, Cu and Ag. We examine twin and non-twin grain boundaries using non-equilibrium Green's function and first principles methods. We also investigate the mechanism of reflectivity in grain boundaries by modeling atomic vacancies, disorder, and orientation and find that the change in grain orientation and disorder in the boundary itself both contribute significantly to reflectivity. We find that grain boundary reflectivity may vary widely depending on the grain boundary structure consistent with exper…
We have studied the influence of non-magnetic defects throughout the antiferromagnet Co_{1-y}O on the exchange bias (EB) in epitaxially grown Co_{1-y}O/Co bilayers. These defects are either substitutional or structural (twin boundaries and surface morphology) which both lead to an increase of the EB-field. We find a dominance of twin boundaries over surface morphology (roughness) in enhancing EB which is consistent with the domain state model for exchange bias. In contrast, the crystal orientation of the Co_{1-y}O layer does not show a significant effect on the EB in this system.
Synthetic driving force molecular dynamics simulations were utilized to survey grain boundary mobility in three classes of incoherent Σ3 twin boundaries: <112>, <110>, and <111> tilt boundaries. These boundaries are faceted on low energy planes, and step flow boundary motion occurs by glide of the triplets of partial dislocations that comprise the mobile facets. Systematic trends with inclination angle are identified and characterized. Observations of thermally activated, anti-thermal, and athermal motion are explained in terms of the orientation of the Shockley partial dislocations along clos…
High-density and nanosized deformation twins in face-centered cubic (fcc)materials can effectively improve the combination of strength and ductility. However, the microscopic dislocation mechanisms enabling a high twinnability remain elusive. Twinning usually occurs via continuous nucleation and gliding of twinning partial dislocations on consecutive close-packed atomic planes. Here we unveil a completely different twinning mechanism being active in metastable fcc materials. The transformation-mediated twinning (TMT) is featured by a preceding displacive transformation from the fcc phase to th…
