Ferroelastic Twin Research Articles

Electron Trapping and Detrapping in an Oxide Two-Dimensional Electron Gas: The Role of Ferroelastic Twin Walls

The choice of electrostatic gating over the conventional chemical doping for phase engineering of quantum materials is attributed to the fact that the former can reversibly tune the carrier density without affecting the system's level of disorder. However, this proposition seems to break down in field-effect transistors involving SrTiO$_3$ (STO) based two-dimensional electron gases. Such peculiar behavior is associated with the electron trapping under an external electric field. However, the microscopic nature of trapping centers remains an open question. In this paper, we investigate electric field-induced charge trapping/detrapping phenomena at the conducting interface between band insulators $\gamma$-Al$_2$O$_3$ and STO. Our transport measurements reveal that the charge trapping under +ve back gate voltage ($V_g$) above the tetragonal to cubic structural transition temperature ($T_c$) of STO is contributed by the electric field-assisted thermal escape of electrons from the quantum well, and the clustering of oxygen vacancies (OVs) as well. We observe an additional source of trapping below the $T_c$, which arises from the trapping of free carriers at the ferroelastic twin walls of STO. Application of -ve $V_g$ results in a charge detrapping, which vanishes above $T_c$ also. This feature demonstrates the crucial role of structural domain walls in the electrical transport properties of STO based heterostructures. The number of trapped (detrapped) charges at (from) the twin wall is controlled by the net polarity of the wall and is completely reversible with the sweep of $V_g$.

Ferroelastic Twinning in Minerals: A Source of Trace Elements, Conductivity, and Unexpected Piezoelectricity

Ferroelastic twinning in minerals is a very common phenomenon. The twin laws follow simple symmetry rules and they are observed in minerals, like feldspar, palmierite, leucite, perovskite, and so forth. The major discovery over the last two decades was that the thin areas between the twins yield characteristic physical and chemical properties, but not the twins themselves. Research greatly focusses on these twin walls (or ‘twin boundaries’); therefore, because they possess different crystal structures and generate a large variety of ‘emerging’ properties. Research on wall properties has largely overshadowed research on twin domains. Some wall properties are discussed in this short review, such as their ability for chemical storage, and their structural deformations that generate polarity and piezoelectricity inside the walls, while none of these effects exist in the adjacent domains. Walls contain topological defects, like kinks, and they are strong enough to deform surface regions. These effects have triggered major research initiatives that go well beyond the realm of mineralogy and crystallography. Future work is expected to discover other twin configurations, such as co-elastic twins in quartz and growth twins in other minerals.

Strain relaxation dynamics of multiferroic orthorhombic manganites

Resonant ultrasound spectroscopy has been used to characterise strain coupling and relaxation behavior associated with magnetic/magnetoelectric phase transitions in GdMnO3, TbMnO3 and TbMn0.98Fe0.02O3 through their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic to colinear-sinusoidal incommensurate antiferromagnetic transition at ∼41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ∼150 K is related to a steep increase in electrical conductivity with a polaron mechanism. The activation energy, E a, of ≳0.04 eV from a loss peak at ∼80 K is consistent with the existence of a well-defined temperature interval in which the paramagnetic structure is stabilised by local, dynamic correlations of electric and magnetic polarisation that couple with strain and have relaxation times in the vicinity of ∼10−6 s. Comparison with previously published data for Sm0.6Y0.4MnO3 confirms that this pattern may be typical for multiferroic orthorhombic RMnO3 perovskites (R = Gd, Tb, Dy). A frequency-dependent loss peak near 10 K observed for TbMnO3 and TbMn0.98Fe0.02O3, but not for GdMnO3, yielded E a ⩾ ∼0.002 eV and is interpreted as freezing of some magnetoelastic component of the cycloid structure. Small anomalies in elastic properties associated with the incommensurate and cycloidal magnetic transitions confirm results from thermal expansion data that the magnetic order parameters have weak but significant coupling with strain. Even at strain magnitudes of ∼0.1–1‰, polaron-like strain effects are clearly important in defining the development and evolution of magnetoelectric properties in these materials. Strains associated with the cubic–orthorhombic transition due to the combined Jahn–Teller/octahedral tilting transition in the vicinity of 1500 K are 2–3 orders of magnitude greater. It is inevitable that ferroelastic twin walls due to this transition would have significantly different magnetoelectric properties from homogeneous domains due to magnetoelastic coupling with steep strain gradients.

Order–disorder, ferroelasticity and mobility of domain walls in multiferroic Cu–Cl boracite

Domain walls in Cu–Cl boracite develop as a consequence of an improper ferroelastic, improper ferroelectric transition, and have attracted close interest because some are conductive and all can be mechanically written and repositioned by application of an electric field. The phase transition and its associated dynamical properties have been analysed here from the perspective of strain and elasticity. Determination of spontaneous strains from published lattice parameter data has allowed the equilibrium long-range order parameter for F 3c → Pca21 to be modelled simply as being close to the order–disorder limit. High acoustic loss in the cubic phase, revealed by resonant ultrasound spectroscopy, is consistent with the presence of dynamical microdomains of the orthorhombic structure with relaxation times in the vicinity of ∼10−5–10−6 s. Low acoustic loss in the stability field of the orthorhombic structure signifies, on the other hand, that ferroelastic twin walls which develop as a consequence of the order–disorder process are immobile on this time scale. A Debye loss peak accompanied by ∼1% elastic stiffening at ∼40 K is indicative of some freezing of defects which couple with strain or of some more intrinsic freezing process. The activation energy of ⩾∼0.01–0.02 eV implies a mechanism which could involve strain relaxation clouds around local ferroelectric dipoles or freezing of polarons that determine the conductivity of twin walls.

Polarization of domain boundaries in SrTiO3 studied by layer group and order-parameter symmetry

Based on a recently developed combination of layer group analysis with order-parameter symmetry, we study the polarity of antiphase domain boundaries (APBs) and ferroelastic twin boundaries (TBs) in $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$. In addition to the celebrated layer group analysis of domain twins, the present method allows us to investigate tensor properties of domain walls also for the case where order-parameter variables other than the spontaneous ones are active. We find that antiphase boundaries in $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ can carry a polarization if in addition to the spontaneous order parameter $(0,0,{\ensuremath{\phi}}_{s})$ a second component, i.e., $({\ensuremath{\phi}}_{1},0,{\ensuremath{\phi}}_{s})$, develops within the domain wall. This result, which is solely based on symmetry arguments, strongly suggests that polarization in APBs is possible if a phase transition from an Ising-type wall to a N\'eel- or Bloch-like wall occurs. This is in very good agreement with previous calculations based on Landau-Ginzburg free energy expansions including biquadratic ($\ensuremath{\propto}{P}_{i}{P}_{j}{\ensuremath{\phi}}_{k}{\ensuremath{\phi}}_{l}$) [A. K. Tagantsev et al. Phys. Rev. B 64, 224107 (2001)] and flexoelectric ($\ensuremath{\propto}{P}_{k}\frac{\ensuremath{\partial}{u}_{ij}}{\ensuremath{\partial}\ensuremath{\xi}}$) coupling terms [A. N. Morozovska et al. Phys. Rev. B. 85, 094107 (2012)]. The present results also unveil a close connection between the recently discovered macroscopic polarization in antiferrodistortive cycloids of ferroelastic domain walls of $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ and a mechanism for explaining polarization of APBs.

Domain wall generated polarity in ferroelastics: Results from resonance piezoelectric spectroscopy, piezoelectric force microscopy, and optical second harmonic generation measurements in LaAlO3 with twin and tweed microstructures

Ferroelastic $\mathrm{La}\mathrm{Al}{\mathrm{O}}_{3}$ (space group $R\overline{3}c$) exists with two different microstructures: twins and tweed. Both microstructures contain electrical dipole moments. Polarity inside ferroelastic twin walls has been shown using two complementary experimental techniques and identical samples. PFM reveals a weak piezoelectric effect at the loci of the domain walls. In tweed samples, the PFM signal is finite but variable in the entire sample. PFM shows that same characteristic tweed microstructure as observed optically. The piezoelectric effect is of a similar magnitude inside twin walls and, space averaged, in the tweed microstructure (and approximately one order of magnitude smaller than in $c$-oriented $\mathrm{Pb}\mathrm{Ti}{\mathrm{O}}_{3}$ single crystals). Resonance piezoelectric spectroscopy proves that domain walls vibrate under the application of an external driving electric field. The resonance frequency is very close to stress induced vibrations. This is evidence for weak but finite coupling between the local dipole moments in the domain walls and the external electric field. The same coupling and the piezoelectric response are much stronger in the tweed sample. Symmetry breaking by dipolar vectors in a $\mathrm{La}\mathrm{Al}{\mathrm{O}}_{3}$ sample with tweed has been confirmed by the observation of optical second harmonic signals. The noncentrosymmetric point group is identified as $3m$ in agreement with earlier work on twinned $\mathrm{La}\mathrm{Al}{\mathrm{O}}_{3}$ but in contradiction with predictions of Landau-Ginzburg theory of simple ferroelastic wall structures.

Current vortices and magnetic fields driven by moving polar twin boundaries in ferroelastic materials

Ferroelastic twin boundaries often have properties that do not exist in bulk, such as superconductivity, polarity etc. Designing and optimizing domain walls can hence functionalize ferroelastic materials. Using atomistic simulations, we report that moving domain walls have magnetic properties even when there is no magnetic element in the material. The origin of a robust magnetic signal lies in polar vortex structures induced by moving domain walls, e.g., near the tips of needle domains and near domain wall kinks. These vortices generate displacement currents, which are the origin of magnetic moments perpendicular to the vortex plane. This phenomenon is universal for ionic crystals and holds for all ferroelastic domain boundaries containing dipolar moments. The magnetic moment depends on the speed of the domain boundary, which can reach the speed of sound under strong mechanical forcing. We estimate that the magnetic moment can reach several tens of Bohr magnetons for a collective thin film of 1000 lattice planes and movements of the vortex by the speed of sound. The predicted magnetic fields in thin slabs are much larger than those observed experimentally in SrTiO3/LaAlO3 heterostructures, which may be due to weak (accidental) forcing and slow changes of the domain patterns during their experiments. The dynamical multiferroic properties of ferroelastic domain walls may have the potential to be used to construct localized magnetic memory devices in future.

Glassy Magnetic Transitions and Accurate Estimation of Magnetocaloric Effect in Ni-Mn Heusler Alloys.

In this work, the structural and magnetic transitions of Heusler alloy Ni50Mn34In14Ga2 have been carefully studied through measurements of heat flow and magnetization under DC and AC magnetic fields. This alloy undergoes the transition sequence of spin-glassy martensite (SPM) → ferromagnetic austenite (FA) → paramagnetic austenite at ∼225 and ∼305 K, respectively, during heating. Splitting of zero-field-cooling (ZFC)/field-cooling (FC) curves in martensite is caused by the slowdown dynamics of spin glass as evidenced by frequency dispersion and aging effects. The development of a spin-glass state is believed to be the result of strain relaxation and interaction of ferroelastic twin walls in the martensite. The magnetocaloric effect (MCE) at the SPM-FA transition was then measured using indirect, quasi-direct, and direct methods. The MCE magnitudes are controlled by the entropy changes associated with the first-order martensite transition and magnetic ordering of austenite under the magnetic field. The existence of a spin-glass state in martensite can also improve the reversibility of the magnetostructural transitions, which is beneficial for the improvement of the reversibility of associated MCE. These results provide an in-depth understanding of the transitions and magnetic properties of the Ni-Mn Heusler alloys and suggest that the MCE at the first-order magnetostructural transitions estimated solely using indirect methods may need some revision.

Organoferroelasticity Mediated by Water of Crystallization

Despite the general conception of brittleness, organic single crystals composed of various kinds of molecules can show ferroelasticity by mechanical twinning. This is attributed to flexibilities in molecular structures, e.g., conformation, and noncovalent bonds, e.g., length and angle. Herein, we find ferroelasticity by mechanical twinning mediated by water of crystallization in a single crystal of a zwitterion: sulfanilic acid monohydrate. Shaping of an organic single crystal is demonstrated ferroelastically from linear to bent shape and from contracted to elongated shape. Rotation of sulfonate anions along with recombination and changes in lengths and angles in flexible hydrogen bonds of small water molecules helps ferroelastic mechanical twinning. Our findings demonstrate designability of mechanically twinnable organic crystals from the viewpoints of organic chemistry and crystal engineering based on hydrogen bonds.

Enhanced piezoelectricity in twinned ferroelastics with nanocavities

Enhancing the electromechanical response by engineering domain boundaries in multiferroics has become a highly active research field in recent years. The starting point is the discovery that ferroelastic twin walls are polar inside a nonpolar matrix. The density of such twin walls is then greatly enhanced by forming complex twin patterns. Our computer simulations show that the interaction of nanocavities with differently charged configurations with twin boundaries generates strong piezoelectricity in ferroelastic (nonferroelectric) crystals. Cavity-induced domain patterns statistically break the inversion symmetry of a sample even when the cavities themselves obey inversion symmetry with relatively weak emerging piezoelectricity $(d\ensuremath{\sim}{10}^{\ensuremath{-}3}\phantom{\rule{0.16em}{0ex}}\mathrm{pm}/\mathrm{V})$ . Stronger piezoelectricity occurs in noncentrosymmetric charged cavity arrangements with a coefficient of $d\ensuremath{\sim}{10}^{\ensuremath{-}1}\mathrm{pm}/\mathrm{V}$. Structurally, the electric field polarizes and shifts the nanocavities by the displacement of trapped surface charges. The related strain fields interact with the ferroelastic domains, which act as soft bridges between the nanocavities. This leads to a significant deformation of the entire sample and hence to enhanced piezoelectricity. Our simulation results point to new directions for designing and enhancing electromechanical nanodevices based on ferroelastic templates even when the bulk material is structurally centrosymmetric.

On the theoretical and phase field modeling of the stress state associated with ferroelastic twin nucleation and propagation near crack tip

Ferroelastic domain switching is considered as that a twin undergoes a lattice orientation described by a deviatoric eigenstrain in this work. A continuum analysis, based on Eshelby equivalent inclusion theory, is derived to study the nucleation and evolution of twin near a pre-existing crack tip (Mode-I) in a mono-phase tetragonal crystal, in an attempt to achieve a better understanding of the contribution that twinning makes to the toughening effect. The analysis develops progressively from the homogenous isotropic, inhomogeneous isotropic to the general anisotropic conditions; and several analytical solutions are evidenced through phase field simulations. Two important critical stresses, defined as the nucleation stress and the fracture-induced twinning (FIT) stress, are found to determine the twin evolution; specifically, the nucleation stress is related to the twinning in a defect-free solid, and the FIT stress is related to the twinning in the vicinity of crack tip. Moreover, considering the inhomogeneity effect, the change of the stress intensity factor (SIF) due to a ferroelastic twin is derived, which provides evidence that the modulus toughening effect originating from the elastic misfit between the parent and twin can be ignored at a relative low applied SIF. Theoretical analysis and phase field simulations both clarify that the shielding/anti-shielding effect to the crack tip is dependent on the nucleation location and the twin size during evolution. The best toughening formula of a ferroelastic ceramic can be obtained by decreasing the FIT stress and increasing the change of SIF simultaneously through adjusting certain material parameters.

Heat capacity signature of frustrated trimerons in magnetite

Recently it has been proposed that the long-range electronic order formed by trimerons in magnetite should be frustrated due to the great degeneracy of arrangements linking trimerons. This result has important consequences as charge ordering from the condensed minority band electrons leads to a complex 3D antiferro orbital order pattern. Further more, the corner sharing tetrahedra structure of spinel B-sites supports frustration for antiferromagnetic alignments. Therefore frustration due to competing interactions will itself induce disorder and very likely frustration in the spin orientations. Here we present very low temperature specific heat data that show two deviations to the magnons and phonons contributions, that we analyze in terms of Schottky-type anomalies. The first one is associated with the thermal activation across both ferroelastic twin and ferromagnetic anti-phase domains. The second Schottky-type anomaly displays an inverse (1/H) field dependence which is a direct indication of the disordered glassy network with macroscopically degenerated singular ground states.

Magnetoelastic coupling associated with vacancy ordering and ferrimagnetism in natural pyrrhotite, Fe7S8

Magnetoelastic coupling associated with the hexagonal—monoclinic transition in a natural sample of the mineral pyrrhotite, Fe7S8, has been analysed in terms of separate coupling of spontaneous strains with two discrete order parameters, qv for Fe/vacancy ordering and qm for magnetic ordering. Coupling of the two order parameters separately with strain gives rise to two terms for coupling between them, λ and λ, and a pattern of evolution in which qv varies continuously and qm discontinuously through a single transition point. The transition is ferrimagnetic and ferroelastic but the relatively slow relaxation rate for Fe/vacancy ordering, in comparison with magnetic ordering, results in elastic and anelastic properties which are quite different from those observed in other ferroic or multiferroic materials with two instabilities. Instead of classical elastic softening, there is stiffening of the elastic constants which scales with and . Instead of the normal pattern of acoustic loss associated with the mobility and subsequent freezing for ferroelastic twin walls, the loss is consistently low throughout the temperature range 300 K–875 K.

Coupling between phase transitions and glassy magnetic behaviour in Heusler alloy Ni50Mn34In8Ga8

The transition sequence in the Heusler alloy Ni50Mn34In8Ga8 has been determined from measurements of elasticity, heat flow and magnetism to be paramagnetic austenite → paramagnetic martensite → ferromagnetic martensite at ∼335 and ∼260 K, respectively, during cooling. The overall pattern of elastic stiffening/softening and acoustic loss is typical of a system with bilinear coupling between symmetry breaking strain and the driving structural/electronic order parameter, and a temperature interval below the transition point in which ferroelastic twin walls remain mobile under the influence of external stress. Divergence between zero-field-cooling and field-cooling determinations of DC magnetisation below ∼220 K indicates that a frustrated magnetic glass develops in the ferromagnetic martensite. An AC magnetic anomaly which shows Vogel–Fulcher dynamics in the vicinity of ∼160 K is evidence of a further glassy freezing process. This coincides with an acoustic loss peak and slight elastic stiffening that is typical of the outcome of freezing of ferroelastic twin walls. The results suggest that local strain variations associated with the ferroelastic twin walls couple with local moments to induce glassy magnetic behaviour.

Benign ferroelastic twin boundaries in halide perovskites for charge carrier transport and recombination

Grain boundaries have been established to impact charge transport, recombination and thus the power conversion efficiency of metal halide perovskite thin film solar cells. As a special category of grain boundaries, ferroelastic twin boundaries have been recently discovered to exist in both CH3NH3PbI3 thin films and single crystals. However, their impact on the carrier transport and recombination in perovskites remains unexplored. Here, using the scanning photocurrent microscopy, we find that twin boundaries have negligible influence on the carrier transport across them. Photoluminescence (PL) imaging and the spatial-resolved PL intensity and lifetime scanning confirm the electronically benign nature of the twin boundaries, in striking contrast to regular grain boundaries which block the carrier transport and behave as the non-radiative recombination centers. Finally, the twin-boundary areas are found still easier to degrade than grain interior.

Needle‐Like Ferroelastic Domains in Individual Ferroelectric Nanoparticles

AbstractSuperior structural, physical, and electronic properties make ferroelectric nanocrystals essential in enabling a range of next‐generation devices. Ferroelectric responses are determined by crystal structure and domain morphology. The ability to reversibly displace, create, and annihilate elastic domains is critical to device applications. Although electric‐field control has been demonstrated for ferroelectric 180° surface domain walls and vortices, similar control of ferroelastic domains and domain boundaries within individual nanocrystals remains challenging. Using controlled external compressive and tensile axial stress, deterministic and reversible control of highly mobile ferroelastic domains and axial polarization in three dimensions is demonstrated. While many studies exist on ferroelastic domains in thin films and bulk, little is known about ferroelastic interactions at the single nanoparticle level, especially involving domain boundaries. Through combining Bragg coherent X‐ray diffractive imaging and Landau theory, strain gradients in individual BaTiO3 nanocrystals are shown to stabilize needle‐like ferroelastic twin domains. These domains are highly labile under applied axial stress, producing a locally enhanced electric polarization mediated by a ferroelectric phase transition. The efficacy of Bragg coherent X‐ray diffractive imaging in studying in operando domains in three dimensions is demonstrated, while synergy with theory provides a paradigm for domain boundary engineering and potential for nanoscale functional devices.

Anisotropic carrier diffusion in single MAPbI3 grains correlates to their twin domains

The anisotropic charge carrier diffusion coupled to ferroelastic twin domains in methylammonium lead iodide opens possibilities for further optimization of perovskite solar cells and optoelectronic devices via strain engineering and heat treatments.

Twin domains modulate light-matter interactions in metal halide perovskites

Despite the extensive insights gained in how the microstructure impacts the device performance of metal halide perovskites (MHPs), little is known about the effect of the ferroelastic twin domains on the optoelectronic properties of MHPs. In this work, the effect of the ferroelastic twin domains on the photoluminescence (PL) behavior of CH3NH3PbI3 is investigated by correlating measurements from multiple microscopies. PL spectra and the confocal PL lifetime maps reveal no difference in wavelength of emitted light and decay dynamics between the neighboring domains, whereas PL intensity is different. We propose that the PL intensity variation is induced by the difference in light-matter interactions between neighboring domains. These results suggest that the effect of ferroelastic twin domains on the intrinsic PL behavior is negligible. We expect that this work will stimulate researchers to further explore the impact of twin domains on the photophysical properties of MHPs.

Electric-field-induced avalanches and glassiness of mobile ferroelastic twin domains in cryogenic SrTiO3

We acknowledge financial support from EPSRC (Grant No. EP/P024904/1) and support from the Spanish Ministerio de Ciencia, Innovacion y Universidades through Grant No. MAT2017-85232-R (AEI/FEDER, EU), Severo Ochoa SEV-2015-0496, the Generalitat de Catalunya through Grant No. 2017 301 SGR1377, and the Academy of Finland (Grant No. 316857).

Light‐Ferroic Interaction in Hybrid Organic–Inorganic Perovskites

AbstractGiven the remarkable performance of hybrid organic–inorganic perovskites (HOIPs) in solar cells, light emitters, and photodetectors, the quest to advance the fundamental understanding of the photophysical properties in this class of materials remains highly relevant. Recently, the discovery of ferroic twin domains in HOIPs has renewed the debate of the ferroic effects on optoelectric processes. This work explores the interaction between light and ferroic twin domains in CH3NH3PbI3. Due to strain and chemical inhomogeneities, photogenerated electrons and holes show a preferential motion in the ferroelastic twin domains. Density functional theory (DFT) shows that electrons and holes result in lattice expansion in CH3NH3PbI3 differently. Hence, light generates strain in the ferroelastic domains due to preferential photocarrier motion, leading to a screening of strain variation. X‐ray diffraction studies verify the DFT simulations and reveal that the photoinduced strain is light intensity dependent, and the photoexcitation is a prerequisite of inducing strain by light. This work extends the fundamental understanding of light‐ferroic interaction and offers guidance for developing functional devices.