Non-centrosymmetric Crystal Structure Research Articles

B20 Weyl Semimetal CoSi Film Fabricated by Flash-Lamp Annealing.

B20-CoSi is a newly discovered Weyl semimetal that crystallizes into a noncentrosymmetric crystal structure. However, the investigation of B20-CoSi has so far been focused on bulk materials, whereas the growth of thin films on technology-relevant substrates is a prerequisite for most practical applications. In this study, we have used millisecond-range flash-lamp annealing, a nonequilibrium solid-state reaction, to grow B20-CoSi thin films. By optimizing the annealing parameters, we were able to obtain thin films with a pure B20-CoSi phase. The magnetic and transport measurements indicate the appearance of the charge density wave and chiral anomaly. Our work presents a promising method for preparing thin films of most binary B20 transition-metal silicides, which are candidates for topological Weyl semimetals.

Kramers nodal lines and Weyl fermions in SmAlSi

Kramers nodal lines (KNLs) have recently been proposed theoretically as a special type of Weyl line degeneracy connecting time-reversal invariant momenta. KNLs are robust to spin orbit coupling and are inherent to all non-centrosymmetric achiral crystal structures, leading to unusual spin, magneto-electric, and optical properties. However, their existence in in real quantum materials has not been experimentally established. Here we gather the experimental evidence pointing at the presence of KNLs in SmAlSi, a non-centrosymmetric metal that develops incommensurate spin density wave order at low temperature. Using angle-resolved photoemission spectroscopy, density functional theory calculations, and magneto-transport methods, we provide evidence suggesting the presence of KNLs, together with observing Weyl fermions under the broken inversion symmetry in the paramagnetic phase of SmAlSi. We discuss the nesting possibilities regarding the emergent magnetic orders in SmAlSi. Our results provide a solid basis of experimental observations for exploring correlated topology in SmAlSi

Large anomalous Hall effect and intrinsic Berry curvature in magnetic Weyl semimetal NdAlGe

Weyl semimetals driven by both time-reversal (TRS) and inversion symmetries (IS) are rare and be a good platform to investigate the relationship between chiral current and magnetic order. NdAlGe compound, grown in a single crystalline form by the flux method, has a noncentrosymmetric I41md crystal structure, which breaks inversion symmetry. The magnetic susceptibility χ(T) shows anisotropic behavior; ferromagnetic with divergence of field cooling (FC) and zero field cooling (ZFC) in H∥c, and antiferromagnetic transition for magnetic field H⊥c. The band structure calculation has revealed that NdAlGe is the type-II Weyl semimetal with four types of Weyl nodes in the ab-plane with a probable Fermi surface nesting vector. The ferromagnetic spin alignment gives a significant anomalous Hall coefficient Rs and large anomalous Hall conductivity σxyA, for H∥c. The giant anomalous Hall conductivity σxyA, constant SH=σxyA/M (H = 50 kOe) value, and their Karplus and Luttinger (KL) analysis support that the giant AHE is associated with the intrinsic Berry curvature in NdAlGe compound. The intrinsic Berry curvature is also confirmed by the planar Hall effect over a wide temperature range, implying that the Weyl semimetallic property is not relevant with the magnetic order.

Superconducting Gap Structure of the Noncentrosymmetric Topological Superconductor Candidate HfRuP

We investigate the gap symmetry of the topological superconductor candidate HfRuP, which crystallizes in a noncentrosymmetric hexagonal crystal structure, using muon spin rotation/relaxation (μSR) measurements in transverse-field (TF) geometry. The temperature and magnetic field dependencies of the superconducting relaxation rate derived from the TF-μSR spectra can be well described by an isotropic s-wave gap. The superconducting carrier density ns = 1.41(1) × 1026 m−3 and the magnetic penetration depth, λ(0) = 603(2) nm, were calculated from the TF-μSR data. Interestingly, the ratio between the superconducting transition temperature and the superfluid density, Tc/λ−2(0) ∼ 3.3, is very close to those of unconventional superconductors. Further, our zero-field (ZF) μSR results do not show any considerable change in the muon spin relaxation above and below the superconducting transition temperature, suggesting that time-reversal symmetry is preserved in the superconducting state of this superconductor.

Low-temperature phase transition in polar semimetal Td−MoTe2 probed by nonreciprocal transport

Nonreciprocal transport, which is a rectification effect reflecting noncentrosymmetric crystal structures, is investigated in semimetallic MoTe\penalty1000\-\allowhyphens{}${}_{2}$. It is clarified that nonreciprocal transport is a powerful probe of structural and/or electronic phase transition.

Polarization-Independent Second Harmonic Generation in 2D Van Der Waals Kagome Nb3 SeI7 Crystals.

Second harmonic generation (SHG) of 2D crystals has been of great interest due to its advantages of phase-matching and easy integration into nanophotonic devices. However, the polarization-dependence character of the SHG signal makes it highly troublesome but necessary to match the laser polarization orientation relative to the crystal, thus achieving the maximum polarized SHG intensity. Here, it is demonstrated a polarization-independent SHG, for the first time, in the van der Waals Nb3 SeI7 crystals with a breathing Kagome lattice. The Nb3 triangular clusters and Janus-structure of each Nb3 SeI7 layer are confirmed by the STEM. Nb3 SeI7 flake shows a strong SHG response due to its noncentrosymmetric crystal structure. More interestingly, the SHG signals of Nb3 SeI7 are independent of the polarization of the excitation light owing to the in-plane isotropic arrangement of nonlinear active units. This work provides the first layered nonlinear optical crystal with the polarization-independent SHG effect, providing new possibilities for nonlinear optics.

Rubrene/CuInP2S6 organic/inorganic heterojunctions for ferroelectric organic transistor memory devices

Ferroelectric organic field-effect transistor (Fe-OFET) memory devices exhibit low power consumption, low cost and good flexibility, which are indispensable to next generation flexible and wearable memory devices. However, up until the present, the ferroelectric materials used in Fe-OFETs have been limited to ferroelectric polymers, i.e. poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)], and suffer from large surface roughness and high-risk of depolarization. This work integrates a new two-dimensional CuInP2S6 crystal into Fe-OFET, which can introduce excellent ferroelectric property due to its single crystalline smoothness and noncentrosymmetric crystal structure. Meanwhile, the high-mobility rubrene crystal is selected as the channel material to construct rubrene/CuInP2S6 organic/inorganic van der Waals heterojunctions. Associated with synergetic effect of single-crystalline nature of the heterojunction and atomically flat/defect-free interface, the memory devices possess a high programming speed of 0.5 s and long retention time of 104 s with a current ratio larger than 103. Furthermore, the performance of flexible devices is also demonstrated, including a programming/erase cycle of 1000 with a current on/off ratio approaching 103, data retention time of 104 s with a current on/off ratio of 103 and a current on/off ratio maintained at 102 even after 100 bending cycles under a bending radius of 25 mm, which are qualified for memory buffer usage or short-term data storage especially when they are integrated with other flexible electronics. The proposed configuration of memory transistors using organic/inorganic heterojunctions provides a rational design of device structure toward flexible Fe-OFET non-volatile memory applications.

Electronic structure and physical properties of the candidate topological material GdAgGe

We grew needle-shaped single crystals of GdAgGe, which crystallizes in a noncentrosymmetric hexagonal crystal structure with space group $P\overline{6}$ $2m$ (189). The magnetic susceptibility data for $H \ensuremath{\perp} c$ reveal two pronounced antiferromagnetic transitions at ${T}_{N1}$ = 20 K and ${T}_{N2}$ = 14.5 K. The magnetic susceptibility anomalies are less prominent for $H \ensuremath{\parallel} c$. The transition at ${T}_{N1}$ is accompanied by a pronounced heat capacity anomaly confirming the bulk nature of the magnetic transition. Below ${T}_{N1}$, the electrical resistivity data follows a ${T}^{3/2}$ dependence. In the magnetically ordered state, GdAgGe shows positive transverse magnetoresistance, which increases with decreasing temperature and increasing field, reaching a value of $\ensuremath{\sim}27%$ at 9 T and 10 K. The Hall resistivity data and electronic band structure calculations suggest that both the hole and the electron charge carriers contribute to the transport properties. The electronic band structure displays linear band crossings near the Fermi level. The calculations reveal that GdAgGe has a nodal line with drumhead surface states coupled with a nonzero Berry phase, making it a nontrivial nodal-line semimetal.

Electroactive properties and piezo-tribo hybrid energy harvesting performances of PVDF-AlFeO3 composites: role of crystal symmetry and agglomeration of fillers.

Inorganic filler-loaded PVDF-based composites have been very widely used for electrical and energy harvesting applications in recent times. In this regard, the effects of different parameters of fillers like size, shape, chemical states, distribution, functional properties, and many others on the output performance of PVDF have been widely studied. However, the effect of another important parameter, namely the crystal symmetry of the filler, in tuning the energy harvesting performance of PVDF has been rarely explored. Therefore, to explore this fact, here we develop PVDF-based composite films by using two types of AlFeO3 fillers, one with rhombohedral R3̄c symmetry (AFRH) and another with an orthorhombic Pc21n structure. Ferrite-based oxides have been chosen here as fillers due to their good dielectric compatibility with PVDF. On the other hand, AlFeO3 has been chosen due to the simplicity of synthesizing it with both centrosymmetric and non-centrosymmetric crystal structures and the scarcity of reports exploring the energy-harvesting performance of AlFeO3-based polymer composites. A significant difference in particle agglomeration has also been observed here between the mentioned two types of AlFeO3 fillers which was mainly due to their specific synthesis conditions. The electroactive properties of PVDF have been observed to be mostly dependent on filler agglomeration. However, the crystal symmetry has shown a strong effect on the piezoelectric energy harvesting performances. As a result of these facts, the piezo-tribo hybrid energy harvesting performance, which depends on both the dielectric permittivity and piezoelectric activity, has been observed to be better for the AFRH5-based hybrid device (AFRH5H) (with ∼72 V open circuit voltage and ∼45 μW cm-2 power density) compared to that of the AFOR5-based hybrid device (AFOR5H). The real-life applications of all the energy harvesting devices have also been demonstrated here.

Time reversal invariant single-gap superconductivity with upper critical field larger than the Pauli limit in NbIr2B2

Recently, compounds with noncentrosymmetric crystal structure have attracted much attention for providing a rich playground in search for unconventional superconductivity. NbIr$_2$B$_2$ is a new member to this class of materials harboring superconductivity below $T_{\rm c} = 7.3(2)$~K and very high upper critical field that exceeds Pauli limit. Here we report on muon spin rotation ($\mu$SR) experiments probing the temperature and field dependence of effective magnetic penetration depth in this compound. Our transverse-field -$\mu$SR results suggest a fully gaped $s$-wave superconductvity. Further, the estimated high value of upper critical field is also supplemented by high field transport measurements. Remarkably, the ratio $T_{\rm c}$/$\lambda^{-2}(0)$ obtained for NbIr$_2$B$_2$ ($\sim$2) is comparable to those of unconventional superconductors. Zero-field $\mu$SR data reveals no significant change in the muon spin relaxation rate above and below $T_{\rm c}$, evincing that time-reversal symmetry is preserved in the superconducting state. The presented results will stimulate theoretical investigations to obtain a microscopic understanding of the origin of superconductivity with preserved time reversal symmetry in this unique noncentrosymmetric system.

Solution-Grown Ternary Semiconductors: Nanostructuring and Stereoelectronic Lone Pair Distortions in I–V–VI2 Materials

Alkali pnictogen dichalcogenides─I–V–VI2 or APnCh2─have been identified as promising semiconducting materials for energy conversion devices. However, the controlled nanoscale synthesis and our understanding of the effects of cation ordering and stereochemically active lone pairs on the structures of these ternary compounds remain underdeveloped. Here, we use solution-phase chemistry to synthesize a family of APnCh2 materials, including LiSbSe2, NaSbS2, NaSbSe2, NaBiS2, and NaBiSe2. Our approach utilizes alkali metal hydrides (AH) or carboxylates, A(O2CR), PnPh3, and elemental chalcogens as synthetic precursors and oleylamine or 1-octadecene as solvents. Synthetic manipulation via fine-tuning of reaction temperature enables control over the degree of ordering caused by the Sb 5s2 lone pair-induced distortions in NaSbS2. Pair distribution function analysis demonstrates that the structure of the Sb-containing phases deviates much more from a disordered rock salt structure than that of the Bi-containing phases. This local distortion, induced by the Sb lone pair, leads to a previously unreported noncentrosymmetric NaSbS2 crystal structure, which is additionally supported by second-harmonic generation measurements. Infrared and multinuclear solid-state NMR spectroscopies show that oleylamine or chelating carboxylates and, in some cases, unreacted precursors (LiH and PnPh3) remain bound to the nanocrystalline surfaces. A deeper understanding of the local atomic environment, long-range ordering, surface chemistry, and optoelectronic properties of these materials may speed up their fundamental study and application.

Self-frequency-conversion nanowire lasers

Semiconductor nanowires (NWs) could simultaneously provide gain medium and optical cavity for performing nanoscale lasers with easy integration, ultracompact footprint, and low energy consumption. Here, we report III–V semiconductor NW lasers can also be used for self-frequency conversion to extend their output wavelengths, as a result of their non-centrosymmetric crystal structure and strongly localized optical field in the NWs. From a GaAs/In0.16Ga0.84As core/shell NW lasing at 1016 nm, an extra visible laser output at 508 nm is obtained via the process of second-harmonic generation, as confirmed by the far-field polarization dependence measurements and numerical modeling. From another NW laser with a larger diameter which supports multiple fundamental lasing wavelengths, multiple self-frequency-conversion lasing modes are observed due to second-harmonic generation and sum-frequency generation. The demonstrated self-frequency conversion of NW lasers opens an avenue for extending the working wavelengths of nanoscale lasers, even to the deep ultraviolet and THz range.

Dynamically tunable second-harmonic generation using hybrid nanostructures incorporating phase-change chalcogenides

Abstract Nonlinear metasurfaces with high conversion efficiencies have been vastly investigated. However, strong dynamic tunability of such devices is limited in conventional passive plasmonic and dielectric material platforms. Germanium antimony telluride (GST) is a promising phase-change chalcogenide for the reconfiguration of metamaterials due to strong nonvolatile changes of the real and imaginary parts of the refraction index through amorphous-crystalline phase change. The orderly structured GST has an even higher potential in tunable second-harmonic generation (SHG) with a non-centrosymmetric crystal structure at the crystalline phase, while the amorphous phase of GST does not exhibit bulk second-order nonlinearity. Here, we experimentally demonstrate SHG switches by actively controlling the crystalline phase of GST for a GST-based hybrid metasurface featuring a gap-surface plasmon resonance, and a quarter-wave asymmetric Fabry–Perot (F–P) cavity incorporating GST. We obtain SHG switches with modulation depths as high as ∼ 20 dB for the wavelengths at the on-state resonance. We also demonstrate the feasibility of multi-level SHG modulation by leveraging three controlled GST phases, i.e., amorphous, semi-crystalline, and crystalline, for the gap-surface plasmon hybrid device, which features stronger light–matter interaction and has higher resonant SHG efficiencies than the asymmetric F–P cavity device at respective GST phases. This research reveals that GST-based dynamic SHG switches can be potentially employed in practical applications, such as microscopy, optical communication, and photonic computing in the nonlinear regime.

Unusual superconductivity in the topological nodal-line semimetal candidate Sn x NbSe2-δ

We report the superconductivity of the topological nodal-line semimetal candidate Sn x NbSe2-δ with a noncentrosymmetric crystal structure. The superconducting transition temperature T c of Sn x NbSe2-δ drastically varies with the Sn concentration x and the Se deficiency δ, and reaches 12 K, relatively higher than those of known topological superconductors. The upper critical field of this compound shows unusual temperature dependence, inconsistent with the WHH theory for conventional type-II superconductors. In a low-Tc sample, the zero-temperature limit of the upper critical field parallel to the ab plane exceeds the Pauli paramagnetic limit estimated from the simple BCS weak coupling model by a factor of ∼ 2, suggestive of unusual superconductivity stabilized in Sn x NbSe2-δ . Together with the robust superconductivity against disorder, these observations indicate that Sn x NbSe2-δ is a promising candidate to explore topological superconductivity.

Induced giant piezoelectricity in centrosymmetric oxides.

Piezoelectrics are materials that linearly deform in response to an applied electric field. As a fundamental prerequisite, piezoelectric materials must have a noncentrosymmetric crystal structure. For more than a century, this has remained a major obstacle for finding piezoelectric materials. We circumvented this limitation by breaking the crystallographic symmetry and inducing large and sustainable piezoelectric effects in centrosymmetric materials by the electric field-induced rearrangement of oxygen vacancies. Our results show the generation of extraordinarily large piezoelectric responses [with piezoelectric strain coefficients (d33) of ~200,000 picometers per volt at millihertz frequencies] in cubic fluorite gadolinium-doped CeO2-x films, which are two orders of magnitude larger than the responses observed in the presently best-known lead-based piezoelectric relaxor-ferroelectric oxide at kilohertz frequencies. These findings provide opportunities to design piezoelectric materials from environmentally friendly centrosymmetric ones.

Nanoscale-Thick Ni-Based Half-Heusler Alloys with Structural Ordering-Dependent Ultralow Magnetic Damping: Implications for Spintronic Applications

Atomic ordering and its consequence on the crystal structure are fundamental issues in the application of half-metallic Heusler alloys considered as a high spin-polarized electron source. NiMnSb is a promising half-metallic half-Heusler alloy for spintronic devices due to its low magnetic damping, non-centrosymmetric crystal structure, and rich anisotropies. Here, we report a high-quality half-metallic epitaxial nano-scale thick NiMnSb alloy film grown on a Cr/Ag-buffered MgO (001) single crystalline substrate. High temperature deposition is a crucial parameter for crystal growth and magneto-dynamic properties such as damping, anisotropy, magnetization, etc. After investigating the ferromagnetic resonance (FMR) spectroscopy using a time-resolved magneto-optical Kerr (TRMOKE) microscope and calculating the crystal structure using VESTA and the density of states from first-principles calculations, we discuss how the deposition temperature influences the crystal ordering, damping, and magnetization. Ultralow Gilbert damping with high anisotropic field and saturation magnetization were found for the highly ordered C1b structured nano-scale thick NiMnSb film deposited at 573 K. We also found quite nice agreement between theoretical and experimental data of crystal ordering and damping that explains how the ordering affects the magnetic parameter as well as sample quality. Furthermore, the negative anisotropic magnetoresistance ratio implies the robust bulk half-metallicity. Such unique combination of highly ordered half-metallic NiMnSb alloy in the nano-scale regime with ultralow damping can be regarded as an advantage for applications in spintronic devices.

Piezo-phototronics in quantum well structures

Quantum well (QW) structures are formed in nanometer-thickness-scale semiconductors with different bandgaps in sandwiched configurations and can offer a wide variety of advantages as active layers for optoelectronic devices, e.g., laser diodes, light emit diodes, photodetectors, and solar cells. Due to the non-centrosymmetric crystal structure, the third-generation semiconductor, such as ZnO, AlN, GaN, and InN, can generate a piezopotential within the crystal by applying an external or internal strain and lead to an effective modulation of the optoelectronic device performance, which is also called piezo-phototronics. With reducing the feature size of materials into several tens of nanometers (e.g., forming QW structures), the multiway coupling effects of quantum physics and piezo-phototronics (coupling with piezoelectricity, photoexcitation, and semiconductor properties) make this research topic more attractive and open a new window for fabricating advanced intelligent optoelectronic devices. This Perspective reviews the recent advances of piezo-phototronics in QW structures, including the fundamental theories and device performance enhancements, and aims to offer a summary and outlook for future research directions and practical applications of piezo-phototronic QW devices.

Chiral 2D organic-inorganic hybrid perovskites based on L-histidine.

Novel chiral hybrid perovskites are highly demanded for various advanced applications such as spintronics, optoelectronics, photovoltaics etc. However, the scope of these new materials is still limited. Herein, we present new 2D hybrid perovskites based upon chiral α-amino acid L-histidine. The generalized formula of these new compounds can be denoted as (L-HisH)2PbBrxI4-x (where L-His = L-histidine; x = 4, 3, 2, 1, 0.4 and 0). All perovskites are characterized by a very similar structural motif that consists of corner-sharing lead halide octahedra arranged in one-layer thin inorganic slabs interleaved by organic layers established by L-histidinium(1+) cations. L-Histidine provides a breaking of spatial parity of these perovskites that results in their non-centrosymmetric crystal structures. These compounds show a multiband absorption up to 590 nm for iodide perovskite. In addition, new compounds display pronounced single-peak photoluminescence, which finely blue shifts upon the gradual substitution of iodine by bromine. New perovskites exhibit excellent thermal stability up to 490 K and 445 K for bromide and iodide compounds, respectively. These results show the ability of L-histidine to produce novel and highly demanded chiral hybrid perovskites.

First-principles study of structure prediction and electronic properties of two-dimensional SiP<sub>2</sub> allotropes

Since the successful preparation of single-layer graphene in 2004, the two-dimensional (2D) materials have received widespread attention. Driven by this research upsurge, many kinds of 2D compound materials with different properties have been discovered one after another, and some of these 2D materials have a variety of allotropes, showing more abundant properties. Our computational studies focus on searching for new stable 2D SiP<sub>2</sub> allotropes, and studying their binding energy, phonon dispersions, electronic band structures, strain-dependent bandgap modulation behaviors, piezoelectric properties, etc. In this paper, three novel 2D SiP<sub>2</sub> allotrope structures, i.e. α-SiP<sub>2</sub>, β-SiP<sub>2</sub>, and γ-SiP<sub>2</sub>, are found by the random prediction method of crystal structure based on group theory and graph theory (RG<sup>2</sup>). Their stabilities and electronic properties are investigated by using the first-principles method based on the density functional theory. The results show that the three novel SiP<sub>2</sub> structures are stable thermodynamically, dynamically and mechanically. Using the GW calculations, three novel SiP<sub>2</sub> structures possess indirect band gaps of 2.62, 2.99 and 3.00 eV, respectively. Their band gaps are feasible to modulate effectively by applying strain. The band gaps of the three novel SiP<sub>2</sub> isomers are reduced significantly when subjected to a large strainused, and the three novel SiP<sub>2</sub> isomers exhibit indirect-to-direct bandgap transitions when experienced by a certain strain along the x-axis direction. These properties make them potential materials that are suitable for serving as nanoscale photocatalysts. Moreover, three SiP<sub>2</sub> isomers have non-centrosymmetric crystal structures, which enable them to exhibit their piezoelectricities. Therefore, we study their piezoelectric properties by combining the Berry phase theory. Our studies show that three novel 2D SiP<sub>2</sub> allotropes have good piezoelectric properties. The piezoelectric coefficient of the α-SiP<sub>2</sub> isomer and the β-SiP<sub>2</sub> isomer are both larger than that of h-BN, and they are comparable to the counterpart of MoS<sub>2</sub>. These novel structures promise to be used to fabricate nano-electromechanical devices for micro- and nano-scaled electromechanical conversion and electromechanical sensing and controlling.

Control of supramolecular chirality in co-crystals of achiral moleculesviastacking interactions and hydrogen bonding

An approach is proposed to obtain non-centrosymmetric multicomponent crystal structures by co-crystallization of achiral molecules that can form both H-bonded chains along a 2-fold screw axis and infinite π-stacks propagating by translation.