Noncentrosymmetric Crystals Research Articles

Anomalous interlayer vibrations in strongly coupled layered PdSe2**Notice: This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this

In this work, we show unusual effects of strong interlayer coupling on low-frequency (LF) Raman scattering in exfoliated PdSe2 crystals with different number of layers. Unlike many other layered materials, it is found that the measured frequencies of the breathing modes cannot be simply described by a conventional linear chain model (LCM) that treats each layer as a single rigid object. By using first-principles calculations, we show that strong deviations from layer rigidity can occur for the LF breathing vibrations of PdSe2, which accounts for the observed disagreement with the conventional LCM. The layer non-rigidity and strong interlayer coupling could also explain the unusual strong intensities of the LF breathing modes that are comparable with those of the high-frequency Raman modes. These strong intensities allowed us to use a set of the measured LF Raman lines as unique fingerprints for a precise assignment of the layer numbers. The assignment of the layer numbers was further confirmed using second harmonic generation that appeared only in the noncentrosymmetric even-layer PdSe2 crystals. This work thus demonstrates a simple and fast approach for the determination of the number of layers in 2D materials with strong interlayer coupling and non-rigid interlayer vibrations.

Splitting Fermi Surfaces and Heavy Electronic States in Non-Centrosymmetric U3Ni3Sn4

We report the single-crystal growth of the non-centrosymmetric paramagnet U3Ni3Sn4 by the Bridgman method and the Fermi surface properties detected by de Haas-van Alphen (dHvA) experiments. We have also investigated single-crystal U3Ni3Sn4 by single-crystal X-ray diffraction, magnetization, electrical resistivity, and heat capacity measurements. The angular dependence of the dHvA frequencies reveals many closed Fermi surfaces, which are nearly spherical in topology. The experimental results are in good agreement with local density approximation (LDA) band structure calculations based on the 5f-itinerant model. The band structure calculation predicts many Fermi surfaces, mostly with spherical shape, derived from 12 bands crossing the Fermi energy. To our knowledge, the splitting of Fermi surfaces due to the non-centrosymmetric crystal in 5f-electron systems is experimentally detected for the first time. The temperature dependence of the dHvA amplitude reveals a large cyclotron effective mass of up to 35m0, indicating the heavy electronic state of U3Ni3Sn4 due to the proximity of the quantum critical point. From the field dependence of the dHvA amplitude, a mean free path of conduction electrons of up to 1950A is detected, reflecting the good quality of the grown crystal. The small splitting energy related to the antisymmetric spin-orbit interaction is most likely due to the large cyclotron effective mass.

Room temperature ferroelectricity in donor-acceptor co-doped TiO2 ceramics using doping-engineering

Conventional ferroelectric oxides are of generally non-centrosymmetric crystals resulting from paraelectric-ferroelectric transitions. Here, we present a new donor-acceptor ion co-doping route to room-temperature ferroelectricity in rutile TiO2, where ionic pair of co-doping ions plays very important roles in generating local broken symmetry and polarization. The (Nb + Al) co-doped TiO2 sintered with a two-step method exhibits ferroelectricity and piezoelectric response, and it is believed that Nb5+-Al3+ pairs along TiO2 [001] direction play important role in the ferroelectricity. A large lattice distortion can be induced in the vicinity of the ionic pair, which results in local broken-symmetry. The relative displacements of cations and anions around the ionic pair, induced by the lattice distortion, cause the local polarization. The results and mechanisms presented in this work provide a new approach to the design of new ferroelectrics via doping engineering.

Elastic, magnetic, transport and electronic properties of noncentrosymmetric M2Mo3N (M = Fe, Co, Ni, Rh): A first-principles study

The discovery of magnetic skyrmions has attracted much in the research field due to their potential applications in the storage and logic devices. In this paper, we present a study of elastic, magnetic, transport, and electronic properties of a family of magnetic skyrmions M2Mo3N (M = Fe, Co, Rh) along with their isotypic Ni2Mo3N compound by using density functional theory. The elastic constants and moduli of elasticity are calculated to analyze the stability of M2Mo3N. The noncentrosymmetric M2Mo3N crystals are found to be elastically stable and ductile in nature. The Vickers hardness values indicate that Fe2Mo3N and Ni2Mo3N are relatively hard, Co2Mo3N and Rh2Mo3N are relatively soft materials. The calculated Debye temperature from elastic constants of Rh2Mo3N is reasonably close to the experimental value. The calculated magnetic moment and polarization of M2Mo3N are consistent with the experimental results. The magnetic moment and polarization of Fe2Mo3N are 15.48μB and 62% respectively indicating that it is a potential candidate for applications in the magnetic storage, logic devices, and spintronics. The linear proportionality relation of electronic heat capacity with temperature is only held for Rh2Mo3N indicating its superconducting nature. The density of states at the Fermi energy of M2Mo3N is dominated by M-d and Mo-d orbitals. Rh2Mo3N crystal is found to be a moderately coupled superconductor. The calculated superconducting transition temperature (4.53 K) of Rh2Mo3N is very close to the experimental value (4.3 K).

Nonreciprocal current from electron interactions in noncentrosymmetric crystals: roles of time reversal symmetry and dissipation

In noncentrosymmetric crystals with broken inversion symmetry {boldsymbol{ {mathcal I} }}, the I-V (I: current, V: voltage) characteristic is generally expected to depend on the direction of I, which is known as nonreciprocal response and, for example, found in p-n junction. However, it is a highly nontrivial issue in translationally invariant systems since the time-reversal symmetry T plays an essential role, where the two states at crystal momenta k and −k are connected in the band structure. Therefore, it has been considered that the external magnetic field (B) or the magnetic order which breaks the T-symmetry is necessary to realize the nonreciprocal I-V characteristics, i.e., magnetochiral anisotropy. Here we theoretically show that the electron correlation in T-broken multi-band systems can induce nonreciprocal I-V characteristics without T-breaking. An analog of Onsager’s relation shows that nonreciprocal current response without T -breaking generally requires two effects: dissipation and interactions. By using nonequilibrium Green’s functions, we derive general formula of the nonreciprocal response for two-band systems with onsite interaction. The formula is applied to Rice-Mele model, a representative 1D model with inversion breaking, and some candidate materials are discussed. This finding offers a coherent understanding of the origin of nonreciprocal I-V characteristics, and will pave a way to design it.

Growth and characterization of L-phenylalanine nitric acid (LPN) and tris L-(phenylalanine)-phenylalanininum nitrate (TPLPN) as second and third order nonlinear optical materials

We synthesized noncentrosymmetric single crystals of L-phenylalanine nitrate (LPN) and tris L-(phenylalanine) L-phenylalaninium nitrate (TPLPN) by slow solvent evaporation technique. Both crystallized in monoclinic system with different acentric space groups namely P21 (LPN) and C2 (TPLPN) respectively. The IR and Raman spectral investigation was done for LPN and TPLPN and discussed. The UV-vis-studies accomplished the excitation wavelength of the grown crystals suitable to exhibit second harmonic generation signal. From the absorption data, remarkable optical properties such as direct band gap energy, Urbach energy, extinction coefficient were evaluated. The mechanical strength of the grown crystal was examined by Vickers micro hardness test. The temperature of decomposition was confirmed by TG/DSC analysis. Fluorescence emission spectrum of LPN and TPLPN were recorded and lifetime was also studied. The dielectric constant and dielectric loss of LPN and TPLPN has been determined as a function of frequency and temperature. Also the surface topologies of the crystallized salts were assessed by SEM studies. The third-order nonlinearities of LPN and TPLPN were determined by Z-scan technique with Nd: YAG at 532 nm and thereby from closed and open Z-scan data, third-order susceptibilities were calculated to be χ(3) = 8.826 × 10−6 esu for LPN and χ(3) = 2.552 × 10−7 esu for TPLPN.

Picometer polar atomic displacements in strontium titanate determined by resonant X-ray diffraction

Physical properties of crystalline materials often manifest themselves as atomic displacements either away from symmetry positions or driven by external fields. Especially the origin of multiferroic or magnetoelectric effects may be hard to ascertain as the related displacements can reach the detection limit. Here we present a resonant X-ray crystal structure analysis technique that shows enhanced sensitivity to minute atomic displacements. It is applied to a recently found crystalline modification of strontium titanate that forms in single crystals under electric field due to oxygen vacancy migration. The phase has demonstrated unexpected properties, including piezoelectricity and pyroelectricity, which can only exist in non-centrosymmetric crystals. Apart from that, the atomic structure has remained elusive and could not be obtained by standard methods. Using resonant X-ray diffraction, we determine atomic displacements with sub-picometer precision and show that the modified structure of strontium titanate corresponds to that of well-known ferroelectrics such as lead titanate.

Supramolecular self-assembly for designing non-centrosymmetric crystals based on Keggin polyoxometallates and crown ether

We report the synthesis of five novel crystals [(4-BrAni+)(DB[18]crown-6)]2[SMo12O402-]·2CH3CN (1), [(4-BrAni+)(B[18]crown-6)]2[SMo12O402-]·CH3CN (2), [(4-BrAni+)(B[18]crown-6)]3[PMo12O402-]·2CH3CN (3), [(3-AP+)3(B[18]crown-6)2][PMo12O403-] (4) and [NBu4+][(3-AP2+)(DB[30]crown-10)][PMo12O403-]·CH3CN (5) (4-BrAni+ = 4-bromoanilinium; B[18]crown-6 = benzo[18]-crown-6; DB[18]crown-6 = dibenzo[18]-crown-6; DB[30]crown-10 = dibenzo[30]-crown-10; 3-AP+ = 3-aminopyridinium; 3-AP2+ = 3-ammoniumpyridinium; NBu4+ = tetrabutylammonium). In order to construct non-centrosymmetric crystals, the five crystals were designed using a method to gradually introduce asymmetry into the building units. Crystal 1 was constructed with a symmetric supramolecular cation (SPC) [(4-BrAni+)(DB[18]crown-6)], resulting in a P21/n space group. The asymmetric SPC [(4-BrAni+)(B[18]crown-6)] was introduced into [SMo12O402-] to obtain crystal 2, which belongs to the symmetric P1[combining macron] space group. Introducing trivalent [PMo12O403-], [(4-BrAni+)(B[18]crown-6)] produced crystal 3 with a non-centrosymmetric Pc space group. The asymmetric sandwich SPC [(3-AP+)3(B[18]crown-6)2] was designed with multiple hydrogen bonding sites on the 3-AP+ cation, and crystal 4 was obtained with trivalent [PMo12O403-]. Crystal 4 has the properties of the chiral P1 space group. The distorted SPC (3-AP2+)(DB[30]crown-10) was constructed using flexible DB[30]crown-10, resulting in crystal 5 which matched the chiral P21 space group with trivalent [PMo12O403-]. This work focuses on strategies for the rational design of novel non-centrosymmetric crystals without a chiral synthon.

Terahertz radiation and second-harmonic generation from a single-component polar organic ferroelectric crystal

A single-component polar organic ferroelectric crystal produces THz and second-harmonic radiation.

Shift current in the ferroelectric semiconductor SbSI

A spontaneous photocurrent, termed a shift current, can flow in noncentrosymmetric bulk crystals due to the topological nature of the constituting electronic bands. A shift current with a less dissipative character may have remarkable advantages over the conventional drift photocurrent driven by a built-in potential or external electric field. We revisit the generation and transport of the shift current in a prototypical ferroelectric semiconductor SbSI near its band-gap energy. It is revealed that a switchable shift current is steadily generated by photoexcitation down to low temperatures, appears over a distance of millimeter range in a highly insulating bulk without noticeable decay, and largely exceeds the polarization charge in the sample, reflecting its Berry phase origin.

Shift current photovoltaic effect in a ferroelectric charge-transfer complex

Shift current is a steady-state photocurrent generated in non-centrosymmetric single crystals and has been considered to be one of the major origins of the bulk photovoltaic effect. The mechanism of this effect is the transfer of photogenerated charges by the shift of the wave functions, and its amplitude is closely related to the polarization of the electronic origin. Here, we report the photovoltaic effect in an organic molecular crystal tetrathiafulvalene-p-chloranil with a large ferroelectric polarization mostly induced by the intermolecular charge transfer. We observe a fairly large zero-bias photocurrent with visible-light irradiation and switching of the current direction by the reversal of the polarization. Furthermore, we reveal that the travel distance of photocarriers exceeds 200 μm. These results unveil distinct features of the shift current and the potential application of ferroelectric organic molecular compounds for novel optoelectric devices.

Nonlinear spin current generation in noncentrosymmetric spin-orbit coupled systems

Spin current plays a central role in spintronics. In particular, finding more efficient ways to generate spin current has been an important issue and studied actively. For example, representative methods of spin current generation include spin polarized current injections from ferromagnetic metals, spin Hall effect, and spin battery. Here we theoretically propose a new mechanism of spin current generation based on nonlinear phenomena. By using Boltzmann transport theory, we show that a simple application of the electric field $\bf{E}$ induces spin current proportional to $\bf{E^2}$ in noncentrosymmetric spin-orbit coupled systems. We demonstrate that the nonlinear spin current of the proposed mechanism is supported in the surface state of three-dimensional topological insulators and two-dimensional semiconductors with the Rashba and/or Dresselhaus interaction. In the latter case, the angular dependence of the nonlinear spin current can be manipulated by the direction of the electric field and by the ratio of the Rashba and Dresselhaus interactions. We find that the magnitude of the spin current largely exceeds those in the previous methods for a reasonable magnitude of the electric field. Furthermore, we show that application of AC electric fields (e.g. terahertz light) leads to the rectifying effect of the spin current where DC spin current is generated. These findings will pave a new route to manipulate the spin current in noncentrosymmetric crystals.

Synthesis and optical characterization of In3+-stabilized γ-Bi2O3 sillenite semiconductor with cation deficiency

Bi3+-containing semiconductors usually show rich optical and electronic properties due to the hybridization between 6s and 6p electronic components together with the lone pair in Bi3+ ions. In this work, an In3+-stabilized γ-Bi2O3 sillenite structure, Bi24InO37.5 (Bi12In0.5O18.75), was prepared through the facile sol-gel method. The samples developed into ball-like nanoparticles with size of 200–300nm. The Rietveld structure refinement was performed. Bi24InO37.5 belongs to cubic sillenite-structure of metastable cubic γ-Bi2O3 (space group I23), a well-known group of non-centrosymmetric crystal. The morphological characteristics were tested by SEM, TEM, EDS and Brunauer–Emmett–Teller (BET) measurements. The optical absorption, band gap energy and electronic structures were discussed. In contrast to the reference Bi2O3, Bi24InO37.5 shows a narrower band energy of 2.48eV. Meanwhile, it has a self-activated emission with a low luminescence quenching.

Syntheses, Crystal Structures, and Nonlinear Optical Activity of Cs2Ba[AnO2(C2H5COO)3]4 (An = U, Np, Pu) and Unprecedented Octanuclear Complex Units in KR2(H2O)8[UO2(C2H5COO)3]5 (R = Sr, Ba).

X-ray diffraction was applied to the elucidation of crystal structures of single crystals of Cs2Ba[AnO2(C2H5COO)3]4, where An = U(I), Np(II), Pu(III), and KR2(H2O)8[UO2(C2H5COO)3]5, where R = Sr(IV), Ba (polymorphs V-a and V-b). FTIR spectra were analyzed for the uranium-containing crystals I, IV, and V-b. Isostructural cubic crystals I-III are constructed of typical mononuclear anionic complex units [AnO2(C2H5COO)3]- and charge-balancing Cs and Ba cations. Features of actinide contraction in the six U-Np-Pu isostructural series known to date are analyzed. In crystal structures of IV and V two typical complexes [UO2(C2H5COO)3]- bind with a hydrated Sr or Ba cation to form the rare trinuclear neutral complex unit {R(H2O)4[UO2(C2H5COO)3]2}, where R = Sr, Ba. Two such trinuclear units and one typical mononuclear unit further bind with a K cation to form the unprecedented octanuclear neutral complex unit K[UO2(C2H5COO)3]{R(H2O)4[UO2(C2H5COO)3]2}2. As the derived polynuclear complexes of uranyl ion with carboxylate ligands in the crystal structures of IV and V are not the first but are rare examples, the equilibrium between mono and polynuclear complex units in aqueous solutions is discussed. The two polymorphic modifications V-a and V-b were studied at 100 K and at room temperature, respectively. Peculiarities of noncovalent interactions in crystal structures of the two polymorphs are revealed using Voronoi-Dirichlet tessellation. The nonlinear optical activity of noncentrosymmetric crystals I was estimated by its ability for second harmonic generation.

Surface sum frequency generation spectroscopy on non-centrosymmetric crystal GaAs (001)

Femtosecond broadband sum frequency generation (SFG) spectroscopy is applied to surface studies of the archetypical non-centrosymmetric semiconductor GaAs (001). Azimuthal angular dependence studies in reflection geometry under eight possible polarization configurations reveal strong surface-bulk interference owing to heterodyne amplification. The crystal symmetry and the surface quadrupole contributions need to be considered to properly interpret the resulting nonlinear spectroscopic signals. In addition, over bandgap excitation by one of the incident beams brings the semiconductor surface to a transient excited state, enabling enhanced sensitivity of broadband SFG to probe the surface electronic properties of non-centrosymmetric semiconductors. These findings suggest that this technique can be generally applied to surface studies of other non-centrosymmetric crystals.

Synthesis, Crystal Structure and Nonlinear Optical Property of RbHgI3

Searching for new nonlinear optical (NLO) crystals to be used in the infrared (IR) region is still a challenge. This paper presents the synthesis, crystal structure and properties of a new halide, RbHgI3. Its non-centrosymmetric single crystal can be grown in solution. In its crystal structure, all the polar [HgI4]2− groups align in such a way that brings a favorable net polarization. The measurement by Kurtz–Perry powder technique indicates that RbHgI3 shows a phase-matchable second harmonic generation (SHG) property seven times stronger than that of KH2PO4 (KDP). RbHgI3 displays excellent transparency in the range of 0.48–25 μm with relatively good thermal stability. The UV absorption implies that this yellow compound’s band gap is about 2.56 eV, close to that of AgGaS2. A preliminary measurement indicates that the laser-induced damage threshold of the crystal is about 28.3 MW/cm2. These preliminary experimental data reveal that RbHgI3 is a new candidate as nonlinear optical material in the infrared region.

Crystal growth, crystal structure, vibrational spectroscopy, linear and nonlinear optical properties of guanidinium phosphates

Of the three guanidinium phosphates GuH2PO4 (space group P21/c), Gu2HPO4·H2O (space group P4¯21c) and Gu3PO4· 32 H2O (space group Cc) crystal structures and a vibrational spectroscopy study are presented. Large single crystals of GuH2PO4 and Gu2HPO4·H2O are grown. Refractive indices and their dispersion in the wavelength range 365 nm – 1083 nm are determined and used for the analysis of phase matching conditions for collinear SHG in the case of the non-centrosymmetric crystals of Gu2HPO4·H2O. The crystals are not phase-matchable within their transmission range. Both independent components of the SHG tensor of Gu2HPO4·H2O, determined by the Maker fringe method, are given, with d14 = 0.23 pm/V and d36 = 0.22 pm/V. In addition, the thermal stability and the anisotropy of thermal expansion of GuH2PO4 and Gu2HPO4·H2O is reported.

Crystal growth, structural, spectral, thermal, linear and nonlinear optical characterization of a new organic nonlinear chiral compound: l-tryptophan-fumaric acid-water (1/1/1) suitable for laser frequency conversion

A new organic active nonlinear optical crystal l-tryptophan fumaric acid water (1/1/1), (C15H17N2 O7. H2O)(LTFAW), consisting of zwitterion tryptophan molecule in conjunction with a fumaric acid molecule and a water molecule was grown by slow solvent evaporation technique from aqueous solution. The organic chromophore crystallizes from water in its zwitterions exhibiting tabular habit in monoclinic system with acentric space group C2 (Z = 4). The sharp peaks observed in Powder X-ray diffractogram depicts the crystalline nature. The presence of functional groups in the grown crystal was analyzed using FT-IR spectrum. The carbon and hydrogen environment in molecular structure was investigated using FT-NMR technique using deuterated DMSO solution. Ultraviolet–visible spectral analysis reveal that the crystal possess lower cut-off wavelength down to 275 nm, is a key factor to exhibit Second Harmonic Generation (SHG) signal. The direct optical band gap is evaluated to be 5.28 eV from the UV absorption profile. The evaluation of optical constants by employing UV–visible absorbance data such as, extinction coefficient, reflectance, refractive index, optical conductivity are supportive towards good performance as NLO devices. Temperature of decomposition was investigated using thermogravimetric analysis/differential thermal analysis techniques (TG/DTA). The luminescence profile exhibited two peaks (362 nm, 683 nm) due to the donation of protons from carboxylic group to amino group. The nonlinear optical behavior from the noncentrosymmetric crystal was observed by the generation of frequency doubled (2ω) optical radiation when subjected to pulsed Nd:YAG laser (1064 nm, 10 ns, 10 Hz) using Kurtz-Perry method. The variation of dielectric constant (εʹ) and dielectric loss (εʹʹ) vs. Log f for the title compound was analysed at a few selected temperatures and frequencies.

Structural, electronic and magnetic properties of metal thiophosphate InPS4

The non-centrosymmetric crystal, InPS4, has been investigated by means of density functional theory (DFT). In this paper we have calculated the structural parameters, electronic band structures, density of states plot and magnetic properties using full potential linearized augmented plane wave (FP-LAPW) method. The exchange correlation has been solved employing the generalised gradient approximation due to Perdew-Burke-Ernzerhof. The calculations are performed both without spin as well as spin polarized. The results show that InPS4 is an indirect band gap semiconductor with (N-Г) energy gap of 2.32eV (without spin) and 1.86eV in spin up and down channels.The obtained lattice parameters and energy gap agree well with the experimental results. Our reported magnetic moment results show that the property of InPS4is nonmagnetic.

Modeling Step Velocities and Edge Surface Structures during Growth of Non-Centrosymmetric Crystals

Almost all molecules are non-centrosymmetric, which produces interaction anisotropy within a crystal lattice. This anisotropy generates multiple types of kink sites on each crystal step and repeating patterns of rows with different growth units from the perspective of the lattice interaction environment, even for pure molecular crystals. As a result, unstable edge rows may be generated that dissolve under conditions of crystal growth. A method to account for edge surface structures, considering such effects, is required to accurately model the step velocity, which is vital for a mechanistic description of crystal growth. We classify both thermodynamic and kinetic contributions to step row instability and develop expressions for kink densities and step velocities that capture these important non-centrosymmetric phenomena. To demonstrate the utility of our framework, we consider in depth the case of an alternating-row A–B step. Our mechanistic predictions compare favorably to kinetic Monte Carlo simulations...