Crystals — Open Access Journal

Cu ${}_2$ ZnSnS ${}_4$ (CZTS) is a quaternary semiconductor that has emerged as a promising component in solar absorber materials due to its excellent optical properties such as band-gap energy of ca. 1.5 eV and significant absorption coefficient in the order of 10 ${}^4$ cm ${}^{-1}$ . Nevertheless, the energy conversion efficiency of CZTS-based devices has not reached the theoretical limits yet, possibly due to the existence of antisite defects (such as Cu ${}_{\mathrm{Zn}}$ or Zn ${}_{\mathrm{Cu}}$ ) and secondary phases. Based on electronic similarities with Zn, Mg has been proposed for Zn substitution in the CZTS structure in the design of alternative semiconductors for thin-film solar cell applications. This work aims to study the properties of the CZTS having Mg incorporated in the structure replacing Zn, with the following stoichiometry: x = 0, 0.25, 0.5, 0.75, and 1 in the formula Cu ${}_2$ Zn ${}_{1-x}$ Mg ${}_x$ SnS ${}_4$ (CZ-MTS). The semiconductor was prepared by the hot injection method, using oleylamine (OLA) as both surfactant and solvent. The presence and concentration of incorporated Mg allowed the fine-tuning of the CZ-MTS semiconductor’s structural and optical properties. Furthermore, it was observed that the inclusion of Mg in the CZTS structure leads to a better embodiment ratio of the Zn during the synthesis, thus reducing the excess of starting precursors. In summary, CZ-MTS is a promising candidate to fabricate high efficient and cost-effective thin-film solar cells made of earth-abundant elements. Full article

In this paper we investigate transmittance and reflectance spectra of multilayer hyperbolic metamaterials in the presence of strong spatial dispersion. Our analysis revealed a number of intriguing optical phenomena, which cannot be predicted with the local response approximation, such as total reflectance for small angles of incidence or multiple transmittance peaks of resonant character (instead of the respective local counterparts, where almost complete transparency is predicted for small angles of incidence and the broad-angle transparency can be observed within a range of larger angles of incidence). We believe that the observed effects may serve as a working principle in a number of new potential applications, such as spatial filtering, biosensing, or beam steering. Full article

In this article, we theoretically and numerically study the chirality and saddle-splay elastic constant (-enabled stability of multiple twist-like nematic liquid crystal (LC) structures in cylindrical confinement. We focus on the so-called radially z-twisted (RZT) and radially twisted (RT) configurations, which simultaneously exhibit twists in different spatial directions. We express the free energies of the structures in terms of dimensionless wave vectors, which characterise the structures and play the roles of order parameters. The impact of different confinement anchoring conditions is explored. A simple Landau-type analysis provides an insight into how different model parameters influence the stability of structures. We determine conditions for which the structures are stable in chiral and also nonchiral LCs. In particular, we find that the RZT structure could exhibit macroscopic chirality inversion upon varying the relevant parameters. This phenomenon could be exploited for the measurement of. Full article

Two-dimensional (2D) IrTe₂ has a profound charge ordering and superconducting state, which is related to its thickness and doping. Here, we report the chemical vapor deposition (CVD) of IrTe₂ films using different Ir precursors on different substrates. The Ir(acac)₃ precursor and hexagonal boron nitride (h-BN) substrate is found to yield a higher quality of polycrystalline IrTe₂ films. Temperature-dependent Raman spectroscopic characterization has shown the q_1/8 phase to HT phase at ~250 K in the as-grown IrTe₂ films on h-BN. Electrical measurement has shown the HT phase to q_1/5 phase at around 220 K. Full article

Gas-atomized powder of an Mg-4Y-3Nd magnesium alloy was attritor-milled at room temperature in an argon atmosphere for two time periods—1.5 and 5 h. Subsequently, the gas-atomized powder as well as both of the milled powders were spark plasma sintered at four temperatures, 400, 450, 500, and 550 °C, for 3 min. The effect of the milling on the powder particles’ morphology and the microstructure of the consolidated samples were studied by advanced microscopy techniques. The effect of the microstructural changes, resulting from the pre-milling and the sintering temperature, on the mechanical strength was investigated in compression along and perpendicular to the sintering load direction. Both the compression yield strength and ultimate compression strength were significantly affected by the grain size refinement, residual strain, secondary phase particles, and porosity. The results showed that attritor-milling imposed severe deformation to the powder particles, causing a significant grain size refinement in all of the consolidated samples. However, 1.5 h of milling was insufficient to achieve uniform refinement, and these samples also exhibited a distinctive anisotropy in the mechanical properties. Only a negligible anisotropy and superior yield strength were observed in the samples sintered from 5 h milled powder, whereas the ultimate strength was lower than that of the samples sintered from the gas-atomized powder. Full article

The microstructures and mechanical properties of ausrolled nanobainite steel, after being tempered at temperatures in the range of 200−400 °C, were investigated in this study. After being tempered, bainitic ferrite is coarsened and the volume fraction of retained austenite is reduced. The hardness and ultimate tensile strength decrease sharply. The impact energy, yield strength, and elongation increase with elevated tempered temperature at 200–300 °C but decrease with elevated tempered temperature when the samples are tempered at 350 °C and 400 °C. The fracture appearance of all the samples after impact tests is a brittle fracture. The variation of the mechanical properties may be due to partial recovery and recrystallization. Full article

A second-generation Ni-based superalloy has been directionally solidified by using a Bridgman method, and the key processing steps have been investigated with a focus on their effects on microstructure evolution and mechanical properties. The as-grown microstructure is of a typical dendrite structure with microscopic elemental segregation during solidification. Based on the microstructural evidence and the measured phase transformation temperatures, a step-wise solution treatment procedure is designed to effectively eliminate the compositional and microstructural inhomogeneities. Consequently, the homogenized microstructure consisting of γ/γ′ phases (size of γ′ cube is ~400 nm) have been successfully produced after a two-step (solid solution and aging) treatment. The mechanical properties of the resulting alloys with desirable microstructures at room and elevated temperatures are measured by tensile tests. The strength of the alloy is comparable to commercial monocrystalline superalloys, such as DD6 and CMSX-4. The fracture modes of the alloy at various temperatures have also been studied and the corresponding deformation mechanisms are discussed. Full article

A couple of isostructural coordination polymers with the general formula [Ln₄(pymca)₄(AcO)₈]_n have been obtained from reactions between pyrimidine-2-carboxylate (pymca) ligand and rare-earth ions (Ln = Dy (1), Nd (2)). These two-dimensional compounds have been characterized and the crystal structures have been solved by single-crystal X-ray diffraction technique, resulting in layers along the bc plane based on pymca and acetate anions that act as bridging ligands between metal atoms. Given that pymca and acetate anions possess carboxylate and hetero-nitrogen groups, it is possible to build a coordination polymer whose metal centers have a nine coordination. Furthermore, static and dynamic magnetic measurements of compound 1 reveal the lack of single molecule-magnet (SMM) behavior in this system due to the following two effects: (i) the ligand field does not stabilize magnetic ground states well separated from excited states, and (ii) anisotropy axes are not collinear, according to results with Magellan software. On another level, luminescent properties of compounds 1 and 2 are attributed to singlet π-π* transitions centered on pymca ligand as corroborated by time-dependent density functional theory (TD-DFT) calculations. Full article

A brand-new gas sensor nanocomposite, In₂O₃-InN, was synthesized by in-situ partial oxidation of InN and presented fast response–recovery property for NO₂ detecting. The structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray detection (EDX) analysis. The results show that the final In₂O₃-InNcomposites were composed of hexagonal type In₂O₃ and hexagonal type InN, which exhibited bottle nanotube structure on the relative macroscopic level. Microscopically, atthe interface of In₂O₃ and InN, n–n heterojunction formed. Works form gas sensing property found that it is obviously that In₂O₃-InNgot a quite stronger response, 1021, at relatively lower temperature, 100 °С, comparing to pure In₂O₃, 279.1 at 150 °С.After doping, the gas-sensing performance was improved. By analyzing the concentration of oxygen vacation and n–n heterojunctions mechanism, it wasverified that the superiority of gas sensing properties of the In₂O₃-InNcan be attributed to the high concentration of oxygen vacancies and the formation of n–n heterojunctions. Full article

Isoniazid is used as anti-tuberculosis drug which possesses functional groups capable of forming hydrogen bonds. A series of cocrystals of isoniazid (INH) with polyphenolic coformers such as catechol (CAT), orcinol (ORC), 2-methylresorcinol (MER), pyrogallol (PYR), and phloroglucinol (PLG) were prepared by solvent-assisted grinding. Powder cocrystals were characterized by infrared (IR) spectroscopy and X-ray powder diffraction. The crystal structure of the cocrystals revealed the unexpected hydration of the INH-MER cocrystal and the preference of the (phenol) O–H∙∙∙N (pyridine) and (terminal) N-H∙∙∙O (phenol) heterosynthons in the stabilization of the structures. The supramolecular architecture of the cocrystals is affected by the conformation and the substitution pattern of the hydroxyl groups of the polyphenols. Full article

Herein we report the synthesis and detailed structural characterization of two new centrosymmetric dinuclear coordination compounds of Pb(II) [Pb₂L₂(NCS)₄] (1) and [Pb₂L₂(NO₃)₄]∙2MeOH (2), using the organic ligand 1,2-diphenyl-1,2-bis((methyl(pyridin-2-yl)methylene)hydrazono)ethane (L). In both complexes, each subunit [PbLX₂ (X = NO₃ or NCS)] adopts a quasi-aromatic Möbius metal chelate structure. Each ligand L is coordinated in a tetradentate coordination mode to Pb(II), yielding the 12π electron chelate ring via two pyridyl-imine units. In compound (1), the coordination sphere is completed by one disordered N,S-coordinated thiocyanate anion and two μ_1,1-bridging N-coordinated thiocyanate anions. In compound (2), the coordination sphere of Pb(II) is completed by two monodentate and two bidentate nitrato ligands (two of them acting as bridging ligands). Crystal packing of both compounds is stabilized by intermolecular hydrogen bonds, intra- and intermolecular C–H∙∙∙p interactions. The Hirshfeld molecular surfaces of (1) and (2) demonstrate that their packing is dominated by C–H∙∙∙O/N/S interactions as well as by far less favored H∙∙∙H contacts. Full article

The influence of the anchoring forces on the Freedericksz transition in twisted ferronematics simultaneously subjected to magnetic and laser fields is studied in this work. Using the elastic continuum theory and Gouchen model for molecular anchoring on the cell support plates, the critical field and the saturation field were calculated as a function of the laser intensity and anchoring strength for two types of ferronematics based on 5CB and CCN-37 liquid crystals. Full article

With the rapid improvement of the global economy, the role of energy has become even more vital in the 21st century. In this regard, energy storage/conversion devices have become a major, worldwide research focus. In response to this, we have prepared two-dimensional (2D)-hierarchical sheet-like ZnCo₂O₄ microstructures for supercapacitor applications using a simple hydrothermal method. The 2D-hierarchical sheet-like morphologies with large surface area and smaller thickness enhanced the contact area of active material with the electrolyte, which increased the utilization rate. We investigated the electrochemical performance of sheet-like ZnCo₂O₄ microstructures while using Cyclic voltammetry (CV), Galvanostatic charge-discharge (GCD), and Electrochemical impedance spectroscopy (EIS) analysis. The electrochemical results demonstrated that the ZnCo₂O₄ electrode possesses 16.13 mF cm⁻² of areal capacitance at 10 µA cm⁻² of current density and outstanding cycling performance (170% of capacitance is retained after 1000 cycles at 500 µA cm⁻²). The high areal capacitance and outstanding cycling performance due to the unique sheet-like morphology of the ZnCo₂O₄ electrode makes it an excellent candidate for supercapacitor applications. Full article

Organic pollutants, such as dyes, have a negative effect on the aqueous environment, therefore, their elimination from water bodies is a high priority. In this work, Eichhornia crassipes and Salvinia natans, both model plants with high phytoremediation efficiency, were exposed to various concentrations (C_i = 50–500 mg/L) of Eriochrome Black T (EBT). Their capacity to assimilate EBT was studied for 16 days of exposure, similar to natural conditions and by spectrophotometric monitoring of the dye concentration (E_{E. crassipes; 150 mg/L} = 33%; E_{S. natans; 150 mg/L} = 71.5%). The changes of the experimental parameters (pH—equalised by day 5, temperature, humidity, light intensity) were followed, and plant growth and biochemical responses to toxic stress effects (photosynthetic pigments, Energy-dispersive X-ray spectroscopy (EDX)—decreased effect of P, Mg, Ca, S and K, Scanning electron microscopy (SEM), defense enzyme) were examined. Furthermore, changes in oxidative- and photo-degradation of EBT in time and the solid-state properties (SEM, EDX, Fourier-transform infrared spectroscopy-FTIR) of the dye were investigated. Our results demonstrate that, despite the toxic stress, both species succeeded in reducing the dye-concentration of the water and S. natans proved to be more efficient in binding and removing organic dyes. With our findings, we proved that both plants alleviated the abiotic stress of dye contamination. Full article

The reaction of (6-Ph₂P-Ace-5-)₂P(O)H with (tht)AuCl₃ proceeds via elimination of tetrahydrothiophene (tht) and HCl, providing the zwitterionic PPP-pincer complex (6-Ph₂P-Ace-5-)₂P(O)AuCl₂ (1) as yellow crystals. The molecular structure of 1 was established and studied by X-ray crystallography. The electronic structure was computationally analyzed using a comprehensive set of real-space bonding indicators derived from electron and electron-pair densities, providing insight into the relative contributions of covalent and non-covalent forces to the polar-covalent Au–Cl, Au–P, and P–O⁻ bonds; the latter being one of the textbook cases for strongly polarized covalent interactions. Partial spatial complementarity between both bonding aspects is suggested by the electronic properties of the distinctively different Au–Cl bonds. Full article

This paper examines different applications of ferroelectric liquid crystal devices based on photo-alignment. Successful application of the photo-alignment technique is considered to be a critical breakthrough. A variety of display and photonic devices with azo dye aligned ferroelectric liquid crystals is presented: smart glasses, liquid crystal Pancharatnam–Berry phase optical elements, 2D/3D switchable lenses, and laser therapy devices. Comparison of electro-optical behavior of ferroelectric liquid crystals is described considering the performance of devices. This paper facilitates the optimization of device design, and broadens the possible applications in the display and photonic area. Full article

The complex and intricate microstructure of B19′ martensite in shape memory nickel titanium alloys is generally explained with the Phenomenological Theory of Martensitic Crystallography (PTMC). Over the last decade, we have developed an alternative approach that supposes the existence of a “natural” parent–daughter orientation relationship (OR). As the previous TEM studies could not capture the global crystallographic characteristics of the B2→B19′ transformation required to discriminate the models, we used Electron BackScatter Diffraction (EBSD) and Transmission Kikuchi Diffraction (TKD) to investigate a polycrystalline NiTi alloy composed of B19′ martensite. The EBSD maps show the large martensite plates and reveal the coexistence of different ORs. The TKD maps permit us to image the “twins” and confirm the continuum of orientations suspected from EBSD. The results are interpreted with the alternative approach. The predominant OR in EBSD is the “natural” OR for which the dense directions and dense planes of B2 and B19′ phases are parallel—i.e., (010)_B19′//(110)_B2 and [101]_B19′//[ $\overline{1}$ 11]_B2. The natural OR was used to automatically reconstruct the prior parent B2 grains in the EBSD and TKD maps. From the distortion matrix associated with this OR, we calculated that the habit plane could be (1 $\overline{1}$ 2)_B2//(10 $\overline{1}$ )_B19′. The traces of these planes are in good agreement with the EBSD maps. We interpret the other ORs as “closing-gap” ORs derived from the natural OR to allow the compatibility between the distortion variants. Each of them restores a parent symmetry element between the variants that was lost by distortion but preserved by correspondence. Full article

Liquid crystal-based reflective polarization volume grating (PVG), also known as a linear Bragg–Berry phase optical element or a member of volume Bragg gratings (VBGs), is a functional planar structure with patterned orientation of optical axis. Due to the strong polarization selectivity, nearly 100% diffraction efficiency, large diffraction angle, and simple fabrication process, PVGs have found potential applications in novel photonic devices and emerging near-eye displays. In this review paper, we describe the operation principles, discuss the optical properties, present the fabrication methods, and provide promising applications of PVGs for near-eye displays and novel photonic devices. Full article

This paper presents the basic elementary tools for describing the global symmetry obtained by overlapping two or more crystal variants of the same structure, differently oriented and displaced one with respect to the other. It gives an explicit simple link between the concepts used in the symmetry studies on grain boundaries on one side and group–subgroup transformations on the other side. These questions are essentially of the same nature and boil down to the resolution of the same problem: identifying the permutation groups that are images of the corresponding applications. Examples are given from both domains, classical grain boundaries with coincidence lattices and group–subgroup phase transformations that illustrate the profound similarities between the two approaches. Full article