Low-symmetry Crystal Structures Research Articles

Engineering anisotropy in 2D transition metal dichalcogenides via heterostructures.

Two-dimensional (2D) semiconductors featuring low-symmetry crystal structures hold an immense potential for the design of advanced optoelectronic devices, leveraging their inherent anisotropic attributes. While the synthesis techniques for transition metal dichalcogenides (TMDs) have matured, a promising avenue emerges: the induction of anisotropy within symmetric TMDs through interlayer van der Waals coupling engineering. Here, we unveil the creation of heterostructures (HSs) by stacking highly symmetric MoSe2 with low-symmetry ReS2, introducing artificial anisotropy into monolayer MoSe2. Through a meticulous analysis of angle-dependent photoluminescence (PL) spectra, we discern a remarkable anisotropic intensity ratio of approximately 1.34. Bolstering this observation, the angle-resolved Raman spectra provide unequivocal validation of the anisotropic optical properties inherent to MoSe2. This intriguing behavior can be attributed to the in-plane polarization of MoSe2, incited by the deliberate disruption of lattice symmetry within the monolayer MoSe2 structure. Collectively, our findings furnish a conceptual blueprint for engineering both isotropic and anisotropic HSs, thereby unlocking an expansive spectrum of applications in the realm of high-performance optoelectronic devices.

Enhance cryogenic ductility and strength of body-centered tetragonal Sn by pre-twinning and recrystallization

Previous researches on high-symmetric metallic materials demonstrate that the introduction of twins can overcome the strength-ductility trade-off. However, it is uncertain if such a pathway is valid for metals with a low-symmetry crystal structure. Here, the low-symmetry body-centered tetragonal Sn achieved a simultaneous enhancement in tensile ductility from 6 % to 14 % elongation and strength from 36 MPa to 60 MPa at 77 K through pre-twinning combined with room-temperature self-recrystallization. The in-situ tensile experiments reveal that the pre-existing and new deformation twins, as well as dynamic recrystallization and multiple dislocation planar slip contribute to the enhancement of cryogenic mechanical properties.

Impact of Hydrogen Plasma on Electrical Properties and Deep Trap Spectra in Ga2O3 Polymorphs

In this study, the results of hydrogen plasma treatments of β-Ga2O3, α-Ga2O3, κ-Ga2O3 and γ-Ga2O3 polymorphs are analyzed. For all polymorphs, the results strongly suggest an interplay between donor-like hydrogen configurations and acceptor complexes formed by hydrogen with gallium vacancies. A strong anisotropy of hydrogen plasma effects in the most thermodynamically stable β-Ga2O3 are explained by its low-symmetry monoclinic crystal structure. For the metastable, α-, κ- and γ-polymorphs, it is shown that the net result of hydrogenation is often a strong increase in the density of centers supplying electrons in the near-surface regions. These centers are responsible for prominent, persistent photocapacitance and photocurrent effects.

Enhancement of Out-of-Plane Spin-Orbit Torque by Interfacial Modification.

Spin-orbit torque (SOT)-induced switching of perpendicular magnetization in the absence of magnetic field is crucial for the application of SOT-based spintronic devices. Recent works have demonstrated that the low-symmetry crystal structure in CuPt/CoPt can give rise to an out-of-plane (OOP) spin torque and lead to deterministic magnetization switching without an external field. However, it is essential to improve OOP effective field for the efficient switching. In this work, the impact of interface oxidation on the generation of OOP effective field in a CuPt/ferromagnet heterostructure is systematically studied. By introducing an oxidized CuPt surface, it is found that the field-free switching performance shows remarkable improvement. OOP effective field measurement indicates that the oxidation treatment can enhance the OOP effective field by more than two times. It is also demonstrated that this oxidation-induced OOP SOT efficiency enhancement is independent of the device shapes, magnetic materials, or magnetization easy axis. This work contributes to improve the performance of SOT devices and provides an effective fabrication guidance for future spintronic devices that utilize OOP SOT.

Visible and infrared photodiode based on γ-InSe/Ge van der Waals heterojunction for polarized detection and imaging.

Broadband photodetectors are a category of optoelectronic devices that have important applications in modern communication information. γ-InSe is a newly developed two-dimensional (2D) layered semiconductor with an air-stable and low-symmetry crystal structure that is suitable for polarization-sensitive photodetection. Herein, we report a P-N photodiode based on 3D Ge/2D γ-InSe van der Waals heterojunction (vdWH). A built-in electric field is introduced at the p-Ge/n-InSe interface to suppress the dark current and accelerate the separation of photogenerated carriers. Moreover, the heterojunction belongs to the accumulation mode with a well-designed type-II band arrangement, which is suitable for the fast separation of photogenerated carriers. Driven by these advantages, the device exhibits excellent photovoltaic performance within the detection range of 400 to 1600 nm and shows a double photocurrent peak at around 405 and 1550 nm. In particular, the responsivity (R) is up to 9.78 A W-1 and the specific detectivity (D*) reaches 5.38 × 1011 Jones with a fast response speed of 46/32 μs under a 1550 nm laser. Under blackbody radiation, the room temperature R and D* in the mid-wavelength infrared region are 0.203 A W-1 and 5.6 × 108 Jones, respectively. Moreover, polarization-sensitive light detection from 405-1550 nm was achieved, with the dichroism ratios of 1.44, 3.01, 1.71, 1.41 and 1.34 at 405, 635, 808, 1310 and 1550 nm, respectively. In addition, high-resolution single-pixel imaging capability is demonstrated at visible and near-infrared wavelengths. This work reveals the great potential of the γ-InSe/Ge photodiode for high-performance, broadband, air-stable and polarization-sensitive photodetection.

Template-confined growth of copper halides micro-wire arrays for highly polarization-sensitive deep-ultraviolet photodetectors with a polarization sensitivity of 4.45

Polarization-sensitive detectors operating in the deep-ultraviolet (DUV) region have been favored for their great meaning in the field of biological tissue morphology, image display systems and sensors. The advantages of intrinsic DUV light absorption, low-symmetry crystal structure and morphology anisotropy make Cs3Cu2I5 micro-wire arrays the perfect choice for polarization-sensitive DUV photodetection. In this work, we demonstrate a polarization-sensitive DUV photodetector developed from the Cs3Cu2I5 micro-wire arrays, which were prepared by a microchannel-confined crystallization strategy, and the optical and optoelectronic anisotropy of Cs3Cu2I5 micro-wire arrays with adjustable sizes were systematically investigated. Owing to the high crystallinity and good carrier transportation ability of the Cs3Cu2I5 micro-wires, the photodetector exhibits a large responsivity of ∼ 23.6 A/W and a fast response speed of 2.9/370.7 μs. Based on the intrinsic anisotropy of the asymmetric structure and external morphology anisotropy of the Cs3Cu2I5 micro-wires, the photodetector exhibits an ultra-high polarization sensitivity of 4.45. Moreover, the photodetector can keep nearly the identical capability even after 40 days exposure in the open air. This work reveals the potential of Cs3Cu2I5 as environmentally-friendly and stable candidates for polarization-sensitive DUV photodetectors, opening up possibilities for developing polarized DUV imaging technology.

Raman spectroscopy in layered hybrid organic-inorganic metal halide perovskites

The continuous progress in the synthesis and characterization of materials in the vast family of hybrid organic-inorganic metal halide perovskites (HOIPs) has been pushed by their exceptional properties mainly in optoelectronic applications. These works highlight the peculiar role of lattice vibrations, which strongly interact with electrons, resulting in coupled states affecting the optical properties. Among these materials, layered (2D) HOIPs have emerged as a promising material platform to address some issues of their three-dimensional counterparts, such as ambient stability and ion migration. Layered HOIPs consist of inorganic layers made of metal halide octahedra separated by layers composed of organic cations. They have attracted much interest not only for applications, but also for their rich phenomenology due to their crystal structure tunability. Here, we give an overview of the main experimental findings achieved via Raman spectroscopy in several configurations and set-ups, and how they contribute to shedding light on the complex structural nature of these fascinating materials. We focus on how the phonon spectrum comes from the interplay of several factors. First, the inorganic and organic parts, whose motions are coupled, contribute with their typical modes which are very different in energy. Nonetheless, the interaction between them is relevant, as it results in low-symmetry crystal structures. Then, the role of external stimuli, such as temperature and pressure, which induce phase transitions affecting the spectrum through change in symmetry of the lattice, octahedral tilting and arrangement of the molecules. Finally, the relevant role of the coupling between the charge carriers and optical phonons is highlighted.

Time-reversal symmetry breaking superconductivity in three-dimensional Dirac semimetallic silicides

Superconductors with broken time-reversal symmetry represent arguably one of the most promising venues for realizing highly sought-after topological superconductivity that is vital to fault-tolerant quantum computation. Here, by using extensive muon-spin relaxation and rotation measurements, we report that the isostructural silicide superconductors (Ta, Nb)OsSi spontaneously break time-reversal symmetry at the superconducting transition while surprisingly showing a fully-gapped superconductivity characteristic of conventional superconductors. The first-principles calculations show that (Ta, Nb)OsSi are three-dimensional Dirac semimetals protected by nonsymmorphic symmetries. Taking advantage of the exceptional low symmetry crystal structure of these materials, we have performed detailed theoretical calculations to establish that the superconducting ground state for both (Ta, Nb)OsSi is most likely a nonunitary triplet state.

Mesoscale Frank–Kasper Crystal Structures from Dendron Assembly by Controlling Core Apex Interactions

Single-component polymeric materials open up a great potential for self-assembly into mesoscale complex crystal structures that are known as Frank-Kasper (FK) phases. Predicting the packing structures of the soft-matter spheres, however, remains a challenge even when the molecular design is precisely known. Here, we investigate the role of the molecules' enthalpic interaction in determining the low-symmetry crystal structures. To this end, we synthesize architecturally asymmetric dendrons by varying their apex functionalities and examine the packing structures of the second-generation (G2) dendritic wedges. Our work shows that weakening the hydrogen bonding of the dendron apex makes the particles softer and smaller, and leads to the formation of various FK structures at lower temperatures, including the new observation of a FK C14 phase in the cone-shaped dendron systems. As a consequence of the free energy balance between the particle's interfacial tension and the chain's stretching, various packing structures are mainly tuned by designing the hydrogen bonding interaction.

Tunable Alloying Improved Wide Spectrum UV-Vis-NIR and Polarization-Sensitive Photodetector Based on Sb–S–Se Nanowires

Polarization-sensitive photodetector based on low-dimensional semiconductor is a kind of special photoelectric device which can take advantage of the semiconductor's anisotropy and convert it into an electrical signal. However, the polarization performance of the photodetector is limited by the challenges of the anisotropy of semiconductors. The design of alloy semiconductors with excellent anisotropy is one of the mainstream methods to improve the dichroic ratio of the polarization-sensitive photodetector. Here, we design the tunable alloying Sb-S-Se nanowires (NWs), which can be used in the research field of polarization-sensitive photodetectors because of their low symmetry crystal structure, suitable bandgap, and high mobility. It is demonstrated that the metal-semiconductor-metal polarization-sensitive photodetector based on Sb-S-Se NWs has great photoelectric properties and polarization performance in UV-Vis-near-infrared response (NIR) spectrum. Under the irradiation laser of the 532-nm, the photoresponsivity ( R) and detectivity ( D*) of the Sb <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (S <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">1/3</sub> Se <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2/3</sub> ) <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> NW-based polarization-sensitive photodetector can reach 6.38 A/W and 1.63 ×10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">9</sup> Jones. By investigating the polarization characteristics of the photodetector, the dichroic ratio of the photodetector can reach 3.8 at 532 nm. By regulating the proportion of each component in the alloy semiconductor, an effective method is provided for adjusting the photoresponse spectrum and optimizing the performance of the polarization-sensitive photodetector, which has a promising research prospect in the future.

Naturally occurring layered mineral franckeite with anisotropic Raman scattering and third-harmonic generation responses

Vertically stacked van der Waals (vdW) heterostructures have introduced a unique way to engineer optical and electronic responses in multifunctional photonic and quantum devices. However, the technical challenges associated with the artificially fabricated vertical heterostructures have emerged as a bottleneck to restrict their proficient utilization, which emphasizes the necessity of exploring naturally occurring vdW heterostructures. As one type of naturally occurring vdW heterostructures, franckeite has recently attracted significant interest in optoelectronic applications, but the understanding of light–matter interactions in such layered mineral is still very limited especially in the nonlinear optical regime. Herein, the anisotropic Raman scattering and third-harmonic generation (THG) from mechanically exfoliated franckeite thin flakes are investigated. The observed highly anisotropic Raman modes and THG emission patterns originate from the low-symmetry crystal structure of franckeite induced by the lattice incommensurability between two constituent stacked layers. The thickness-dependent anisotropic THG response is further analyzed to retrieve the third-order nonlinear susceptibility for franckeite crystal. The results discussed herein not only provide new insights in engineering the nonlinear light–matter interactions in natural vdW heterostructures, but also develop a testbed for designing future miniaturized quantum photonics devices and circuits based on such heterostructures.

Evolution of Texture and Deformation Mechanisms During Repeated Deformation and Heat Treating Cycles of U-6Nb

The evolution of the crystallographic texture and lattice strain of uranium 6-weight percent niobium alloy samples are tracked during multiple deformation and heat treating cycles in an effort to understand and control the mechanical properties of the material following thermo-mechanical processing. The heavily twinned microstructure and low-symmetry crystal structure of U-6Nb result in multiple sequential active deformation mechanisms associated with distinctive deformation textures in strain ranges from 0-0.15 true strain. It is found that heating into the high-temperature γ-phase erases much of the texture formed during deformation at room temperature in the α′′-phase and resets the active deformation mechanisms. Through a small number of deformation/heat treat cycles to moderate strains, i.e., ~ 0.13 per cycle, the flow strength of the material is recovered to its original value. However, on the fourth such cycle, a reduction of strength is observed and the sample failed.

Room Temperature Synthesis of Ordered Intermetallic Electrocatalysts

The conversion of O2 to H2O is an important fuel cell reaction for the recovery of renewable electricity from chemical fuels. Alloys of Pt-group metals (PGMs) with transition metals have emerged as catalysts with enhanced activity and durability for the oxygen reduction reaction (ORR). To date, most studies focus exclusively on alloys that adopt a Face-centered cubic (FCC) or Face-centered tetragonal (FCT) crystal lattice. Under ORR operating conditions, these materials evolve from alloys to Pt core-alloy shell materials, in this case both the alloy core and Pt shell retains the FCC or FCT type crystal structure; indicating that materials can dynamically change during catalysis.Here we present the synthesis of Pd-Bi based ordered intermetallics by partial dealloying of a Bi rich alloy. We found that under ORR operation conditions, β-PdBi2 (I4/mmm space group) which adopts a tetragonal lattice, transforms to α-Pd3Bi (Pmma space group) which adopts an orthorhombic crystal structure; this transformation is mediated by oxidative Bi corrosion under potential cycling, and reconstruction of the atoms in the bulk. To the best of our knowledge, this is the first report of a material that exhibits an electrochemically driven, non-congruent phase transition among materials with different crystal structures. The resulting phase-converted Pd3Bi is stable and exhibits high performance for ORR. Phase-converted Pd3Bi outperform Pt and Pd metal, reaching mass activities of 2.6 A/mgPd, which is nearly 10X higher than Pt/C (~0.3 A/mgPt) and Pd/C (~0.2 A/mg) at 0.9 V vs the Real Hydrogen Electrode (RHE). The mass activity of Pd3Bi decreases by ~38% after 10,000 cycles, indicating that it is stable. Activation energy (Ea) determined by temperature dependent electro-kinetic measurements indicates that the activity enhancement on phase-converted Pd3Bi originates from anion-poisoning resistant behavior. These results establish that PGMs-based ordered intermetallics with low-symmetry crystal structures can be highly active and durable electrocatalysts.

Thermal conductivity of rutile germanium dioxide

Power electronics seek to improve power conversion of devices by utilizing materials with a wide bandgap, high carrier mobility, and high thermal conductivity. Due to its wide bandgap of 4.5 eV, β-Ga2O3 has received much attention for high-voltage electronic device research. However, it suffers from inefficient thermal conduction that originates from its low-symmetry crystal structure. Rutile germanium oxide (r-GeO2) has been identified as an alternative ultra-wide-bandgap (4.68 eV) semiconductor with a predicted high electron mobility and ambipolar dopability; however, its thermal conductivity is unknown. Here, we characterize the thermal conductivity of r-GeO2 as a function of temperature by first-principles calculations, experimental synthesis, and thermal characterization. The calculations predict an anisotropic phonon-limited thermal conductivity for r-GeO2 of 37 W m−1 K−1 along the a direction and 58 W m−1 K−1 along the c direction at 300 K where the phonon-limited thermal conductivity predominantly occurs via the acoustic modes. Experimentally, we measured a value of 51 W m−1 K−1 at 300 K for hot-pressed, polycrystalline r-GeO2 pellets. The measured value is close to our directionally averaged theoretical value, and the temperature dependence of ∼1/T is also consistent with our theory prediction, indicating that thermal transport in our r-GeO2 samples at room temperature and above is governed by phonon scattering. Our results reveal that high-symmetry UWBG materials, such as r-GeO2, may be the key to efficient power electronics.

Adaptive dipolar correlation in ferroelectric x(Ba0.7Ca0.3)TiO3−(1−x)Ba(Zr0.2Ti0.8)O3

Deriving structure-property relationships for multicomponent ferroelectric materials has always been a challenging problem because the properties are mostly driven by subtle nanoscale correlations which are hard to detect. Here we have studied the famous Pb-free material $x({\mathrm{Ba}}_{0.7}{\mathrm{Ca}}_{0.3}){\mathrm{TiO}}_{3}\text{\ensuremath{-}}(1\ensuremath{-}x)\mathrm{Ba}({\mathrm{Zr}}_{0.2}{\mathrm{Ti}}_{0.8}){\mathrm{O}}_{3}$ $(x\mathrm{BCT}\text{\ensuremath{-}}\mathrm{BZT})$ which has been at the center of attention for approximately the last 10 years because of its unprecedented piezoelectric properties. However, the structure-property relationship for $x\mathrm{BCT}$-BZT remains elusive as neither the common concepts nor the experimental results lead to satisfactory models which can fully explain its unusual piezoelectric properties as a function of composition as well as recognize its uniqueness compared to other similar systems. Hence we have applied total neutron-scattering and Raman-scattering methods to examine the local structural correlations of $x\mathrm{BCT}$-BZT in the range $0.40\ensuremath{\le}x\ensuremath{\le}0.60$ at ambient conditions. By refining large-box atomistic models against the neutron pair distribution functions, we have observed an emerging coherence in the polar displacements of the cations at $x=0.50$, leading to an increased structural ergodicity at the key orthorhombic-tetragonal phase boundary. Given the very similar level of local structural disorder and spontaneous polarization found in the system with $x$, we propose that the abrupt amplification of piezoelectric properties in this material at a region of phase instability is a consequence of enhanced collaboration amongst the all cations in a strain-reduced local environment. It also indicates that the popular structure-property concept entailing a low-symmetry crystal structure cannot be a generic concept or a precondition.

Accessing Catalytically Active Ordered Intermetallics Compounds Via Electrochemically Driven Phase Transformations

The conversion of O2 to H2O is an important fuel cell reaction for the recovery of renewable electricity from chemical fuels. Alloys of Pt-group metals (PGMs) with transition metals have emerged as catalysts with enhanced activity and durability for the oxygen reduction reaction (ORR). To date, most studies focus exclusively on alloys that adopt a Face-centered cubic (FCC) or Face-centered tetragonal (FCT) crystal lattice. Under ORR operating conditions, these materials evolve from alloys to Pt core-alloy shell materials, in this case both the alloy core and Pt shell retains the CCP type crystal structure; indicating that materials can dynamically change during catalysis.Here we present the synthesis of Pd-Bi based ordered intermetallics by partial dealloying of a Bi rich alloy. We found that under ORR operation conditions, ß-PdBi2 which adopts a tetragonal lattice, transforms to Pd3B orthorhombic crystal structure; this transformation is mediated by oxidative Bi corrosion under potential cycling, and reconstruction of the atoms in the bulk. To the best of our knowledge, this is the first report of a material that exhibits an electrochemically driven, non-congruent phase transition among materials with different crystal structures. The resulting phase-converted Pd3Bi is stable and exhibits high performance for ORR. Phase-converted Pd3Bi outperform Pt and Pd metal, reaching mass activities of 2.6 A/mgPd, which is nearly 10X higher than Pt/C (~0.3 A/mgPt) and Pd/C (~0.2 A/mg) at 0.9 V vs the Real Hydrogen Electrode (RHE). The mass activity of Pd3Bi decreases by ~38% after 10,000 cycles, indicating that it is stable. Activation energy (Ea) determined by temperature dependent electro-kinetic measurements indicates that the activity enhancement on phase-converted Pd3Bi originates from anion-poisoning resistant behavior. These results establish that PGMs-based ordered intermetallics with low-symmetry crystal structures can be highly active and durable electrocatalysts.

Defect-induced Dzyaloshinskii–Moriya interaction in a nanocrystalline two-phase alloy

The Dzyaloshinskii–Moriya interaction (DMI) is believed to be operative in low-symmetry crystal structures lacking space-inversion symmetry. However, already in 1963, Arrott pointed out that even in a high-symmetry lattice, where the DMI would normally vanish, this interaction is present in the vicinity of any lattice defect. Based on these considerations and recent theoretical work, first experimental studies of the impact of the DMI on the spin-polarized magnetic small-angle neutron scattering (SANS) of polycrystalline magnets exhibiting a large density of microstructural defects have been performed. They demonstrated that an asymmetry in the difference between the two polarized SANS cross sections is induced by the DMI in nanocrystalline terbium and holmium as well as in mechanically-deformed microcrystalline cobalt. Here, we present a more complicated case, the nanocrystalline magnetically-textured soft magnet Vitroperm (Fe73Si16B7Nb3Cu1), where the interface between the FeSi nanoparticles and the amorphous magnetic matrix serves as the defect. The SANS cross section exhibits the polarization-dependent asymmetric term originating from the DMI. The effect has a magnetic field dependence and is less pronounced at higher fields until it eventually vanishes at full saturation. The result supports the generic relevance of the DMI for the magnetic structure of defect-rich ferromagnets. Furthermore, it shows that polarized SANS is a particularly powerful tool for investigating defect-induced DMI, which is a consequence of the unique dependence of the SANS cross section on the chiral interactions.

Quantitative theory of triplet pairing in the unconventional superconductor LaNiGa2

The exceptionally low-symmetry crystal structures of the time-reversal symmetry breaking superconductors LaNiC$_2$ and LaNiGa$_2$ lead to an internally-antisymmetric non-unitary triplet (INT) state as the only possibility compatible with experiments. We argue that this state has a distinct signature: a double-peak structure in the Density of States (DOS) which resolves in the spin channel in a particular way. We construct a detailed model of LaNiGa$_2$ capturing its electronic band structure and magnetic properties ab initio. The pairing mechanism is described via a single adjustable parameter. The latter is fixed by the critical temperature $T_c$ allowing parameter-free predictions. We compute the electronic specific heat and find excellent agreement with experiment. The size of the ordered moment in the superconducting state is compatible with zero-field muon spin relaxation experiments and the predicted spin-resolved DOS suggests the spin-splitting is within the reach of present experimental technology.

Infrared active phonons in monoclinic lutetium oxyorthosilicate

A combined generalized spectroscopic ellipsometry measurement and density functional theory calculation analysis is performed to obtain the complete set of infrared active phonon modes in Lu2SiO5 with a monoclinic crystal structure. Two different crystals, each cut perpendicular to a different crystal axis, are investigated. Ellipsometry measurements from 40to1200cm−1 are used to determine the frequency dependent dielectric function tensor elements. The eigendielectric displacement vector summation approach and the eigendielectric displacement loss vector summation approach, both augmented with anharmonic lattice broadening parameters proposed recently for low-symmetry crystal structures [Mock et al., Phys. Rev. B 95, 165202 (2017)], are applied for our ellipsometry data analysis. All measured and model calculated dielectric function tensor and inverse dielectric function tensor elements match excellently. 23 Au symmetry and 22 Bu symmetry infrared active transverse and longitudinal optical modes are found. We also determine the directional limiting modes and the order of the phonon modes within the monoclinic plane. Results from density functional theory and ellipsometry measurements are compared and nearly perfect agreement is observed. We further compare our results to those obtained recently for the monoclinic crystal Y2SiO5, which is isostructural to Lu2SiO5 [Mock et al., Phys. Rev. B 97, 165203 (2018)]. We find that the lattice mode behavior of monoclinic Lu2SiO5 is qualitatively identical with Y2SiO5 and differs only quantitatively. We anticipate that members of the isostructural group of monoclinic symmetry oxyorthosilicates such as Dy2SiO5 or Yb2SiO5 will likely behave very similar in their phonon mode properties as reported here for Lu2SiO5.

Predicting deformation behavior of α-uranium during tension, compression, load reversal, rolling, and sheet forming using elasto-plastic, multi-level crystal plasticity coupled with finite elements

An elasto-plastic self-consistent (EPSC) polycrystal plasticity formulation is adapted to model deformation of wrought α-uranium (α-U) accommodated by a combination of elasticity, dislocation glide, and deformation twinning. The EPSC model incorporates a strain-path, strain rate, and temperature sensitive dislocation density-based hardening law for the evolution of resistance to slip, twinning, and de-twinning and a slip system-level kinematic back-stress law to influence the driving force for activation. The model is used to interpret the complex deformation behavior of α-U as a function of strain-path and temperature. Samples of α-U with different initial orientation distributions are experimentally evaluated in simple compression, tension, and load reversal at room temperature and in compression and rolling at 573 K under a quasi-static deformation rate. Evolution of texture and twinning is characterized using electron backscattered diffraction and in-situ and ex-situ neutron diffraction during deformation. It is observed that the behavior of the material is highly anisotropic owing to its low-symmetry orthorhombic crystal structure and different activation stresses for crystallographic deformation modes. The model is calibrated and validated under these deformation conditions and predicts the stress-strain responses, amount of twinning, texture evolution, and lattice strains with one set of parameters for the hardening and back-stress evolution laws. Subsequently, the developed model is used as a constitutive law in the implicit finite element (FE) framework to simulate drawing of a hemispherical part from a rolled sheet of α-U. Here, the FE-EPSC model is a two-level homogenization scheme with EPSC relating the grain-level to the polycrystalline aggregate-level response, while the FE framework scales the polycrystalline to the part-level response. The simulation results and insights from the calculations, such as location dependent texture evolution is in good agreement with experiments.