Noncentrosymmetric Materials Research Articles

A new non-centrosymmetric material (C5H9N3)[ZnBr4]·H2O : Molecular structure, characterization, optical properties and biological activities

The use of 2,3-diaminopyridine as an aromatic organic molecule in the synthesis of a new hybrid halogenometallate compound by the slow evaporation method afforded an unexpected non-centrosymmetric structure type. The obtained material with the formula (C5H9N3)[ZnBr4]·H2O (1) crystallizes in the triclinic space group P1. The compound was characterized by UV–visible measurements, differential thermal analysis (TG-DTA), single crystal X-ray diffraction and nonlinear optical activity. The structure consists of isolated tetrahedral [ZnBr4]2− anions, 2-amino-3-ammoniopyridinium [C5H9N3]2+ cations and water molecules, which are connected via NH…O/Br and OH…Br hydrogen bonds leading to the formation and strengthening of a three-dimensional supramolecular assembly. The optical band gap and Urbach energy were obtained through Tauc's equation. The direct and indirect band gap values are found to be 3.23 and 3.55 eV, respectively. The bioassay results showed that the compound exhibits modest antibacterial and antifungal activities.

Cs3In(In4Se7)(P2Se6): A Multi-Chromophore Chalcogenide with Excellent Nonlinear Optical Property Designed by Group Grafting.

Non-centrosymmetric (NCS) and polar materials capable of exhibiting many important functional properties are indispensable for electro-optical technologies, yet their rational structural design remains a significant challenge. Here, we report a "group grafting" strategy for designing the first multi-chromophore selenophosphate, Cs3In(In4Se7)(P2Se6), that crystallizes in a NCS and polar space group of Cm. The structure features a unique basic building unit (BBU) [In(In4Se10)(P2Se6)], formed through "grafting [In4Se10] supertetrahedra on the root of [In(P2Se6)2] groups". Theoretical calculations confirm that this [In(In4Se10)(P2Se6)] BBU can achieve a "1+1>2" combination of properties from two chromophores, [In4Se10] supertetrahedron and ethane-like [P2Se6] dimer. That makes Cs3In(In4Se7)(P2Se6) exhibit excellent linear and nonlinear optical (NLO) properties, including a strong second harmonic generation (SHG) response (~6×AgGaS2), a large band gap (2.45 eV), broad infrared (IR) transmission (up to 19.5 μm), a significant birefringence (0.26 @1064 nm) as well as the congruently-melting property at ~700 °C. Therefore, Cs3In(In4Se7)(P2Se6) will be a promising NLO crystal, especially in the IR region, and this research also demonstrates that "group grafting" will be an effective strategy for constructing novel polar BBUs with multi-chromophore to design NCS structures and high-performance IR NLO materials.

Evidence of superconducting Fermi arcs

An essential ingredient for the production of Majorana fermions for use in quantum computing is topological superconductivity1,2. As bulk topological superconductors remain elusive, the most promising approaches exploit proximity-induced superconductivity3, making systems fragile and difficult to realize4–7. Due to their intrinsic topology8, Weyl semimetals are also potential candidates1,2, but have always been connected with bulk superconductivity, leaving the possibility of intrinsic superconductivity of their topological surface states, the Fermi arcs, practically without attention, even from the theory side. Here, by means of angle-resolved photoemission spectroscopy and ab initio calculations, we identify topological Fermi arcs on two opposing surfaces of the non-centrosymmetric Weyl material trigonal PtBi2 (ref. 9). We show these states become superconducting at temperatures around 10 K. Remarkably, the corresponding coherence peaks appear as the strongest and sharpest excitations ever detected by photoemission from solids. Our findings indicate that superconductivity in PtBi2 can occur exclusively at the surface, rendering it a possible platform to host Majorana modes in intrinsically topological superconductor–normal metal–superconductor Josephson junctions.

Peculiar band geometry induced giant shift current in ferroelectric SnTe monolayer

The bulk photovoltaic effect (BPVE) occurs when homogeneous noncentrosymmetric materials generate photocurrent or photovoltage under illumination. The intrinsic contribution to this effect is known as the shift current effect. We calculate the shift current conductivities of the ferroelectric SnTe monolayer using first-principles methods. Our results reveal a giant shift-current conductivity near the valley points in the SnTe monolayer. More remarkably, the linear optical absorption coefficient at this energy is very small, resulting in an enormous Glass coefficient that is four orders of magnitude larger than that of BaTiO3. To understand these giant shift-current effects, we employ a three-band model and find that they arise from the nontrivial energy band geometries near the valley points, where the shift-vector diverges. This serves as a prominent example highlighting the crucial role of band geometry in determining the fundamental properties of solids.

Organic Polar Crystals, Second Harmonic Generation, and Piezoelectric Effects from Heteroadamantanes in the Space Group R3m.

Polar crystalline materials, a subset of the non-centrosymmetric materials, are highly sought after. Their symmetry properties make them pyroelectric and also piezoelectric and capable of second-harmonic generation (SHG). For SHG and piezoelectric applications, metal oxides are commonly used. The advantages of oxides are durability and hardness - downsides are the need for high-temperature synthesis/processing and often the need to include toxic metals. Organic polar crystals, on the other hand, can avoid toxic metals and can be amenable to solution-state processing. While the vast majority of polar organic molecules crystallize in non-polar space groups, we found that both 7-chloro-1,3,5-triazaadamantane, for short Cl-TAA, and also the related Br-TAA (but not I-TAA) form polar crystals in the space group R3m, easily obtained from dichloromethane solution. Measurements confirm piezoelectric and SHG properties for Cl-TAA and Br-TAA. When the two species are crystallized together, solid solutions form, suggesting that properties of future materials can be tuned continuously.

Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence

AbstractConsiderable effort has been invested in the development of non‐centrosymmetric (NCS) inorganic solids for ferroelectricity‐, piezoelectricity‐ and, particularly, optical nonlinearity‐related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non‐directionality and unsaturation of the ionic bonds between metal counter‐cations and covalent anionic modules. We report herein a secondary‐bond‐driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second‐harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter‐cation‐free iodate, VO2(H2O)(IO3) (VIO), a new class of iodate, crystallizes in a polar lattice with VO2(H2O)(IO3)] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the VO2(H2O)(IO3)] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high‐performance NLO materials.

Secondary-Bond-Driven Construction of a Polar Material Exhibiting Strong Broad-Spectrum Second-Harmonic Generation and Large Birefringence.

Considerable effort has been invested in the development of non-centrosymmetric (NCS) inorganic solids for ferroelectricity-, piezoelectricity- and, particularly, optical nonlinearity-related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non-directionality and unsaturation of the ionic bonds between metal counter-cations and covalent anionic modules. We report herein a secondary-bond-driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second-harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter-cation-free iodate, VO2 (H2 O)(IO3 ) (VIO), a new class of iodate, crystallizes in a polar lattice with VO2 (H2 O)(IO3 )] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2 PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the VO2 (H2 O)(IO3 )] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high-performance NLO materials.

From NaGa(IO3)3F to NaGa(IO3)2F2 and NaGa(IO3)4: The Effects of Chemical Substitution between F- Anions and IO3- Groups on the Structures and Properties of Gallium Iodates.

Introducing F- anions or substituting F- anions with IO3- groups has been proven to be ideal strategies for designing novel noncentrosymmetric (NCS) and polar materials, yet systematic investigation into the effect of F- anions or the substitution of IO3- for F- anions on structures and properties remains rarely explored. Herein, two new gallium iodates, NaGa(IO3)2F2 (1) and NaGa(IO3)4 (2), were successfully designed and synthesized based on NaGa(IO3)3F by introducing more F- anions and replacing F- anions with IO3 groups, respectively. Structurally, in compound 1, the adjacent [GaF3(IO3)3]3- polyanions are connected in an antiparallel manner, resulting in a complete cancellation of local polarity. While in compound 2, all IO3 groups in 2D [Ga(IO3)4]∞- layers are aligned, leading to large macroscopic polarization. Additionally, chemical substitution also results in a qualitative improvement in the functional properties of compound 2. It possesses strong SHG response (12 × KDP @1064 nm) and broad optical transparency, coupled with large birefringence (0.21 @1064 nm), showcasing its promise as a promising nonlinear optical (NLO) crystal. The effects of chemical substitution between F- anions and IO3- groups on the structures and properties are discussed in detail.

A giant intrinsic photovoltaic effect in atomically thin ReS2.

The photovoltaic (PV) effect in non-centrosymmetric materials consisting of a single component under homogeneous illumination can exceed the fundamental Shockley-Queisser limit compared to the traditional p-n junctions. Two-dimensional (2D) materials with a reduced dimensionality and smaller bandgap were predicated to be better candidates for the PV effect with high efficiency exceeding that of traditional ferroelectric perovskite oxides. Here, we report the giant intrinsic PV effect in atomically thin rhenium disulfide (ReS2) with centrosymmetry breaking. In graphene/ReS2/graphene sandwich structures, significant short-circuit currents (Isc) were observed with illumination over the visible spectral range, presenting the highest responsivity (110 mA W-1) and external quantum efficiency (25.7%) among those reported PV effects in 2D materials. This giant PV effect could be ascribed to the spontaneous-polarization induced depolarization field in even-number-layered ReS2 flakes benefiting from the distorted 1T lattice structure. Our results provide a new potential candidate material for the development of novel high-efficiency, miniaturized and easily integrated photodetectors and solar cells.

Shift Current with Gaussian Basis Sets and General Prescription for Maximally Symmetric Summations in the Irreducible Brillouin Zone.

The bulk photovoltaic effect is an experimentally verified phenomenon by which a direct charge current is induced within a non-centrosymmetric material by light illumination. Calculations of its intrinsic contribution, the shift current, are nowadays amenable from first-principles employing plane-wave bases. In this work, we present a general method for evaluating the shift conductivity in the framework of localized Gaussian basis sets that can be employed in both the length and velocity gauges, carrying the idiosyncrasies of the quantum-chemistry approach. The (possibly magnetic) symmetry of the system is exploited in order to fold the reciprocal space summations to the representation domain, allowing us to reduce computation time and unveiling the complete symmetry properties of the conductivity tensor under general light polarization.

Helicoidal Structures of Non-Centrosymmetric Magnetic Materials in the Presence of a Biharmonic Light Field

Helicoidal Structures of Non-Centrosymmetric Magnetic Materials in the Presence of a Biharmonic Light Field

Targeting Oxide Concentration in Tantalum Oxide-Fluoride Anions

The design of both molecular and non-molecular solid materials with specific properties fundamentally relies on the controlled synthesis of crystals with desired functional groups, bonding motifs, polarity, chirality, and more. To this end, fluoride and oxide-fluoride anions have been utilized as basic building units (BBUs) in the synthesis of noncentrosymmetric racemic materials for their ability to create polar axes that facilitate the breaking of an inversion center as demonstrated in a series of compounds with [MF6]2- anions (M = Ti, Zr, Hf). Targeting an analog with a [TaOF5]2- anion, the phase space of (CuO, Ta2O5)/bpy/HF(aq)/H2O (bpy = 2,2′-bipyridine) was investigated and three new compounds with Cu-bpy cations and Ta-fluoride or Ta-oxyfluoride anions were synthesized: [Cu(bpy)2][TaF6], [Cu(bpy)2][Ta2OF10], and [Cu(bpy)F(H2O)2]2[TaF7]∙H2O with the anions [TaF6]-, [Ta2OF10]2-, and [TaF7]2-, respectively. The formation of these anions was found to be a product of both the concentration of hydrofluoric acid in solution and the ratio of metal-oxide starting materials to ligand. This work contributes to the understanding of mixed anion formation in the solid state.

Fabrication of Co2RuS6/CdS Z-scheme heterojunction with sulfur vacancy for enhanced piezo-photocatalytic H2 evolution and in-depth analysis of charge-separation mechanism

The current photocatalytic hydrogen production performance is still limited by severe electron hole recombination. Notably, non-centrosymmetric piezoelectric materials could generate piezoelectric fields by mechanical forces to that promote the separation of photogenerated charges. Therefore, the combination of piezocatalysis and photocatalysis is expected to greatly promote the hydrogen production performance. In this work, a novel Z-type heterojunction Co2RuS6/CdS with sulfur vacancies (CRS/CdS-30) piezo-photocatalytic material was firstly primaried to boost H2 production activity. 10 % CRS/CdS-30 composite catalyst reached an impressive hydrogen production rate as 110.66 mmol·g−1·h−1 into combined effect of light and ultrasound, which was higher than the sum of pure photocatalytic (72.97 mmol·g−1·h−1) and pure piezoelectric performance (0.86 mmol·g−1·h−1). Moreover, H2 production rate for CRS/CdS-30 is 24, 14 and 15 times that of pure CdS, 10 % Co9S8/CdS-30 and 10 % RuS2/CdS-30, respectively. It has been confirmed through various characterization methods that: (1) The presence of sulfur vacancies greatly increases the catalytic active sites; (2) The transfer of photogenerated charges in the CRS/CdS-30 heterojunction follows the Z-scheme; (3) The piezoelectric field in CdS eliminates electrostatic shielding and tremendously enhances the separation efficiency of electron-hole pairs. This study supplies a new approach for constructing efficient piezo-photocatalytic materials.

Computationally-driven discovery of second harmonic generation in EuBa3(B3O6)3 through inversion symmetry breaking

Nonlinear optical (NLO) crystals with superior properties are significant for advancing laser technologies and applications. Introducing rare earth metals to borates is a promising and effective way to modify the electronic structure of a crystal to improve its optical properties in the visible and ultraviolet range. In this work, we computationally discover inversion symmetry breaking in EuBa3(B3O6)3, which was previously identified as centric, and demonstrate noncentrosymmetry via synthesizing single crystals for the first time by the floating zone method. We determine the correct space group to be P6¯. The material has a large direct bandgap of 5.56 eV and is transparent down to 250 nm. The complete anisotropic linear and nonlinear optical properties were also investigated with a d11 of ∼0.52 pm/V for optical second harmonic generation. Further, it is Type I and Type II phase matchable. This work suggests that rare earth metal borates are an excellent crystal family for exploring future deep ultraviolet (DUV) NLO crystals. It also highlights how first principles computations combined with experiments can be used to identify noncentrosymmetric materials that have been wrongly assigned to be centrosymmetric.

Unconventional Nonreciprocal Voltage Transition in Ag2Te Nanobelts

Nonreciprocal effects are consistently observed in noncentrosymmetric materials due to the intrinsic symmetry breaking and in high-conductivity systems due to the extrinsic thermoelectric effect. Meanwhile, nonreciprocal charge transport is widely utilized as an effective experimental technique for detecting intrinsic unidirectional electrical contributions. Here, we show an unconventional nonreciprocal voltage transition in topological insulator Ag2Te nanobelts. The nonreciprocal voltage develops from nearly zero to giant values under the applied current I ac and external magnetic fields, while remaining unchanged under various current I dc. This unidirectional electrical contribution is further evidenced by the differential resistance (dV/dI) measurements. Furthermore, the transition possesses two-dimensional properties under a tilted magnetic field and occurs when the voltage between two electrodes exceeds a certain value. We propose a possible mechanism based on the development of edge channels in Ag2Te nanobelts to interpret the phenomenon. Our results not only introduce a peculiar nonreciprocal voltage transition in topological materials but also enrich the understanding of the intrinsic mechanism that strongly affects nonreciprocal charge transport.

Nonreciprocal Transport and Optical Phenomena in Quantum Materials

In noncentrosymmetric materials, the responses (for example, electrical and optical) generally depend on the direction of the external stimuli, called nonreciprocal phenomena. In quantum materials, these nonreciprocal responses are governed by the quantum geometric properties and symmetries of the electronic states. In particular, spatial inversion ([Formula: see text]) and time-reversal ([Formula: see text]) symmetries play crucial roles, which are also relevant to the geometric Berry phase. Here, we give a comprehensive review of the nonreciprocal transport and optical responses including ( a) the magnetochiral anisotropy, i.e., the nonlinear resistivity with respect to the electric field, in semiconductors and metals, ( b) the nonreciprocal transport in superconductors such as the nonreciprocal paraconductivity and the superconducting diode effect in bulk and Josephson junctions, and ( c) the second-order nonlinear optical effects in the electric field of light, including the geometric shift current in nonmagnetic systems, magnetic systems, and superconductors.

Skyrmions in van der Waals centrosymmetric materials with Dzyaloshinskii–Moriya interactions

Skyrmions can appear in non-centrosymmetric materials because of non-vanishing Dzyaloshinskii–Moriya interactions (DMIs). We investigate the magnetic properties of rhombohedral MX3 (M: V, Cr, Mn, Fe; X: Cl, Br, I) van der Waals materials with centrosymmetric lattices by combining first-principle calculations and Monte Carlo simulations. We determine that the Dzyaloshinskii–Moriya vector acting between the second nearest neighbor sites of the intralayer is non-zero and large in MX3, owing to the breaking of the local inversion symmetry. Large DMIs cause nanoscale magnetic vortices, i.e. that is, skyrmions. We observe both conventional skyrmions in CrCl3 and VCl3 and antiferromagnetic skyrmions in FeCl3 and merons in MnCl3. Furthermore, the skyrmions in CrCl3 and VCl3 have different helicities, indicating the possibility of controlling the helicity by electron/hole doping in MX3 materials. Van der Waals materials have high degrees of freedom in heterostructures and twisted structures, demonstrating promising potential as skyrmion materials.

Pyro-phototronic effect coupled in self-powered, fast and broadband photodetector based on CIS/CTS heterojunction

The pyro-phototronic effect has been demonstrated as a successful approach to optimize the performance of heterojunction-based photodetector (PD) devices. Beyond the conventional restriction imposed by materials with intrinsic symmetry, pyroelectricity can be induced from the symmetry modulated at the interface of centrosymmetric components. Here, a self-powered PD based on cost-effective and eco-friendly p-type CuInS2 (CIS)/p-type Cu2SnS3 (CTS) nanocrystals (NCs) layers heterostructure is fabricated. By introducing the pyro-phototronic effect derived from the built-in electric field at the CIS/CTS interface, the PD realizes broadband detection in the ultraviolent (UV) (390 nm) to near infrared (NIR) (950 nm) range. The maximum responsivity and detectivity reach 9.053 mA/W and 5.05 × 1010 Jones for 390 nm illumination, 18.8 mA/W and 1.49 × 1011 Jones for 750 nm illumination and 42.5 mA/W and 6.507 × 1011 Jones for 950 nm illumination, at zero bias. These results show a ∼ 6-fold improvement, compared with those only based on the photovoltaic effect-induced photo-response (for 950 nm illumination). Upon 950 nm illumination, PD exhibits a fast photo-response component with rise time and fall time of 49.6 ms and 34.7 ms, respectively. This work offers a simple and promising approach to develop high-performance self-powered and broad-spectrum isotype heterojunction-based PDs (UV–vis-NIR) using the photovoltaic–pyroelectric coupled effect, while are no restricted to non-centrosymmetric materials.

Giant room-temperature nonlinearities in a monolayer Janus topological semiconductor

Nonlinear optical materials possess wide applications, ranging from terahertz and mid-infrared detection to energy harvesting. Recently, the correlations between nonlinear optical responses and certain topological properties, such as the Berry curvature and the quantum metric tensor, have attracted considerable interest. Here, we report giant room-temperature nonlinearities in non-centrosymmetric two-dimensional topological materials—the Janus transition metal dichalcogenides in the 1 T’ phase, synthesized by an advanced atomic-layer substitution method. High harmonic generation, terahertz emission spectroscopy, and second harmonic generation measurements consistently show orders-of-the-magnitude enhancement in terahertz-frequency nonlinearities in 1 T’ MoSSe (e.g., > 50 times higher than 2H MoS2 for 18th order harmonic generation; > 20 times higher than 2H MoS2 for terahertz emission). We link this giant nonlinear optical response to topological band mixing and strong inversion symmetry breaking due to the Janus structure. Our work defines general protocols for designing materials with large nonlinearities and heralds the applications of topological materials in optoelectronics down to the monolayer limit.

Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates.

The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H2O)(bpy)2]2[MF6]2·2H2O (bpy = 2,2'=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna21, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H2O)(dmbpy)2]2[MF6]2·xH2O (dmbpy = 4,4'/5,5'-dimethyl-2,2'-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)2(H2O)2+ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.