Crystalline Materials Research Articles

General Theory for Longitudinal Nonreciprocal Charge Transport.

The longitudinal nonreciprocal charge transport (NCT) in crystalline materials is a highly nontrivial phenomenon, motivating the design of next generation two-terminal rectification devices (e.g., semiconductor diodes beyond PN junctions). The practical application of such devices is built upon crystalline materials whose longitudinal NCT occurs at room temperature and under low magnetic field. However, materials of this type are rather rare and elusive, and theory guiding the discovery of these materials is lacking. Here, we develop such a theory within the framework of semiclassical Boltzmann transport theory. By symmetry analysis, we classify the complete 122magnetic point groups with respect to the longitudinal NCT phenomenon. The symmetry-adapted Hamiltonian analysis further uncovers a previously overlooked mechanism for this phenomenon. Our theory guides the first-principles prediction of longitudinal NCT in multiferroic ϵ-Fe_{2}O_{3} semiconductor that possibly occurs at room temperature, without the application of external magnetic field. These findings advance our fundamental understandings of longitudinal NCT in crystalline materials, and aid the corresponding materials discoveries.

Ferroelectric nematic fluids as spontaneous polarization field for enhanced orientational-dependent second-harmonic generation

ABSTRACT Second-order nonlinear optical effects have piqued researchers’ interest in fundamental physics and practical perspectives. The ferroelectric nematic liquid crystals (NF LCs) have recently drawn attention to LC nonlinear optical applications due to their relatively high second-harmonic generation output. Further improving the nonlinear optical properties to get closer to the performance of inorganic nonlinear optical materials is challenging. Here, we take a blending strategy to enhance the nonlinear optical response of a prototype NF LC, DIO. We mixed an organic nonlinear optical crystalline material, 3,5,5-trimethyl (cyclohex-2-enylidene) malononitrile (TCM), with DIO and investigated the effects of TCM doping at various concentrations. We quantitatively determined the second-harmonic generation and spontaneous polarization as functions of temperature and concentration. We found that, compared with the pure DIO, the second-harmonic generation performance increased by about 130% at maximum, 93% in maximum for the nonlinear optical coefficient, and 10% in maximum for spontaneous polarization.

High strain-rate strength response of single crystal tantalum through in-situ hole closure imaging experiments

The properties of crystalline materials often depend on directionality and operating conditions. Specifically, the strength of materials can depend anisotropically on crystal direction and the loading condition. To probe these effects, a preliminary series of high strain-rate (>105/s) strength plate-impact hole closure experiments were performed on high purity single crystal tantalum cubes. The orientation of the single crystals with respect to impact/loading were varied to provide data to inform crystal plasticity modeling efforts. The experiments consist of in-situ high-resolution X-ray radiographic imaging of the hole collapse under dynamic compression conditions to infer the material strength via its resistance to closure at increasing levels of plastic strain. The experiments are compared against hydrocode simulation predictions. A comparison with simple elastic perfectly plastic strength model predictions is presented to elucidate the response of the different crystal orientations at high strain-rate and large plastic strains.

Stretched non-negative matrix factorization

A novel algorithm, stretchedNMF, is introduced for non-negative matrix factorization (NMF), accounting for signal stretching along the independent variable’s axis. It addresses signal variability caused by stretching, proving beneficial for analyzing data such as powder diffraction at varying temperatures. This approach provides a more meaningful decomposition, particularly when the component signals resemble those from chemical components in the sample. The stretchedNMF model introduces a stretching factor to accommodate signal expansion, solved using discretization and Block Coordinate Descent algorithms. Initial experimental results indicate that the stretchedNMF model outperforms conventional NMF for datasets exhibiting such expansion. An enhanced version, sparse-stretchedNMF, optimized for powder diffraction data from crystalline materials, leverages signal sparsity for accurate extraction, especially with small stretches. Experimental results showcase its effectiveness in analyzing diffraction data, including success in real-time chemical reaction experiments.

Assembly of Differently Sized Supercharged Protein Nanocages into Superlattices for Construction of Binary Nanoparticle-Protein Materials.

This study focuses on the design and characterization of binary nanoparticle superlattices: Two differently sized, supercharged protein nanocages are used to create a matrix for nanoparticle arrangement. We have previously established the assembly of protein nanocages of the same size. Here, we present another approach for multicomponent biohybrid material synthesis by successfully assembling two differently sized supercharged protein nanocages with different symmetries. Typically, the ordered assembly of objects with nonmatching symmetry is challenging, but our electrostatic-based approach overcomes the symmetry mismatch by exploiting electrostatic interactions between oppositely charged cages. Moreover, our study showcases the use of nanoparticles as a contrast enhancer in an elegant way to gain insights into the structural details of crystalline biohybrid materials. The assembled materials were characterized with various methods, including transmission electron microscopy (TEM) and single-crystal small-angle X-ray diffraction (SC-SAXD). We employed cryo-plasma-focused ion beam milling (cryo-PFIB) to prepare lamellae for the investigation of nanoparticle sublattices via electron cryo-tomography. Importantly, we refined superlattice structure data obtained from single-crystal SAXD experiments, providing conclusive evidence of the final assembly type. Our findings highlight the versatility of protein nanocages for creating distinctive types of binary superlattices. Because the nanoparticles do not influence the type of assembly, protein cage matrices can combine various nanoparticles in the solid state. This study not only contributes to the expanding repertoire of nanoparticle assembly methods but also demonstrates the power of advanced characterization techniques in elucidating the structural intricacies of these biohybrid materials.

Identifying the effect of photo-generated carriers on the phonons in rutile TiO2 through Raman spectroscopy

Abstract Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials. Carriers can interact with lattices and influence lattice vibrations; thus, it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors. Rutile is one of the predominant crystalline phases of TiO2, which is a widely utilized metal oxide semiconductor. In this work, rutile TiO2 is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material, thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra. A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO2 during irradiation. Using this setup, the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched. The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons. This work provides a novel approach to researching the effect of carriers on phonons.

Enhanced photocatalytic performance of two-dimensional NixRe1-xSe2 (x = 0 & 0.25) crystalline material: Exploring its potential as a high-efficiency catalyst

Water pollution, stemming primarily from dye effluent discharge in urban and industrial zones, remains a critical environmental issue. Photocatalysis emerges as a promising eco-friendly, cost-effective, solar-dependent, and recyclable solution. This study synthesizes Ni0.25Re0.75Se2 via a simple Direct Vapour Transport (DVT) technique, exploring the impact of doping on ReSe2's structural, optical, and photocatalytic properties. Characterization techniques (PXRD, FESEM, EDAX, Raman spectroscopy, UV–visible absorbance spectroscopy, XPS) were employed for analysis. Photocatalytic experiments with organic dyes like Methylene Blue (MB), Acridine Orange (AO), Crystal Violet (CV) demonstrated efficient AO dye degradation (95.67 %) in 60 min using Ni0.25Re0.75Se2, showcasing effective catalytic properties under 20W LED bulb. Trapping experiments identified hydroxyl radicals and holes as pivotal for AO dye degradation. Ni0.25Re0.75Se2 exhibited stability under varying pH, non-leaching behavior, and retained efficiency over cycles, showcasing potential for sustained use in industrial wastewater treatment. This research advances sustainable solutions to combat water pollution in urban and industrial environments.

Aggregation-Induced Emission Enhancement and Solid-State Photoswitching of Crystalline Carbazole N-Salicylidene Anilines.

The development of fluorescent stimuli-responsive organic materials has attracted substantial interest due to their increasing optoelectronic applications. This study systematically introduces fluorine atoms on one end of carbazole-based N-salicylidene anilines 5a-5f to elucidate the impact in their solution and solid-state photophysics. The addition of fluorine atoms at one end of the molecule induced significant changes, for example, a reduction in the quantum yield (QY) fluorescence emission in solution, going from QY near unity in compound 5a (QY ∼ 100%) to a negligible emission in 5f (QY < 1%). Similarly, compound 5a showed a very strong aggregation-induced enhancement emission behavior, whereas compounds with a higher fluorine content were almost quenched. Furthermore, the crystalline solid-state photoisomerization in N-salicylidene anilines is not trivial, and only compounds with three (5e) and five fluorine atoms (5f) exhibited reversible solid-state photoisomerization under 405 nm light source irradiation. We propose that the presence of the arene-perfluoroarene interaction in the crystalline array facilitates the latter behavior. Our findings present a comprehensive study of crystal engineering for the obtention of photoswitchable crystalline materials and adjustable photophysics response, paving the way for its implementation in other systems.

Melting Curve of Black Phosphorus: Evidence for a Solid-Liquid-Liquid Triple Point.

Black phosphorus (bP) is a crystalline material that can be seen as an ordered stacking of two-dimensional layers, which results in outstanding anisotropic physical properties. The knowledge of its pressure (P)-temperature (T) phase diagram, and in particular, of its melting curve is fundamental for a better understanding of the synthesis and stability conditions of this element. Despite the numerous studies devoted to this subject, significant uncertainties remain regarding the determination of the position and slope of its melting curve. Here we measured the melting curve of bP in an extended P, T region from 0.10(3) to 5.05(40) GPa and from 914(25) to 1788(70) K, using in situ high-pressure and high-temperature synchrotron X-ray diffraction. We employed an original metrology based on the anisotropic thermoelastic properties of bP to accurately determine P and T. We observed a monotonic increase of the melting temperature with pressure and the existence of two distinct linear regimes below and above 1.35(15) GPa, with respective slopes of 348 ± 21 and of 105 ± 12 K·GPa-1. These correspond to the melting of bP toward the low-density liquid and the high-density liquid, respectively. The triple point at which solid bP and the two liquids meet is located at 1.35(15) GPa and 1350(25) K. In addition, we have characterized the solid phases after crystallization of the two liquids and found that, while the high-density liquid transforms back to solid bP, the low-density liquid crystallizes into a more complex, partly crystalline and partly amorphous solid. The X-ray diffraction pattern of the crystalline component could be indexed as a mixture of red and violet P.

Critical Model Insight into Broadband Dielectric Properties of Neopentyl Glycol (NPG).

This report presents the low-frequency (LF), static, and dynamic dielectric properties of neopentyl glycol (NPG), an orientationally disordered crystal (ODIC)-forming material important for the barocaloric effect applications. High-resolution tests were carried out for 173K<T<440K, in liquid, ODIC, and solid crystal phases. The support of the innovative distortion-sensitive analysis revealed a set of novel characterizations important for NPG and any ODIC-forming material. First, the dielectric constant in the liquid and ODIC phase follows the Mossotti Catastrophe-like pattern, linked to the Clausius-Mossotti local field. It challenges the heuristic paradigm forbidding such behavior for dipolar liquid dielectrics. For DC electric conductivity, the prevalence of the 'critical and activated' scaling relation is evidenced. It indicates that commonly applied VFT scaling might have only an effective parameterization meaning. The discussion of dielectric behavior in the low-frequency (LF) domain is worth stressing. It is significant for applications but hardly discussed due to the cognitive gap, making an analysis puzzling. For the contribution to the real part of dielectric permittivity in the LF domain, associated with translational processes, exponential changes in the liquid phase and hyperbolic changes in the ODIC phase are evidenced. The novelty also constitutes tgδ temperature dependence, related to energy dissipation. The results presented also reveal the strong postfreezing/pre-melting-type effects on the solid crystal side of the strongly discontinuous ODIC-solid crystal transition. So far, such a phenomenon has been observed only for the liquid-solid crystal melting transition. The discussion of a possible universal picture of the behavior in the liquid phase of liquid crystalline materials and in the liquid and ODIC phases of NPG is particularly worth stressing.

Maneuverability and Processability of Molecular Crystals

AbstractCrystal adaptronics, a burgeoning field at the intersection of materials science and engineering, focuses on harnessing the unique properties of organic molecular crystals to achieve unprecedented levels of maneuverability and processability in various applications. Increasingly, ordered stacks of crystalline materials are being endowed with fascinating mechanical compliance changes in response to external environments. Understanding how these crystals can be manipulated and tailored for specific functions has become paramount in the pursuit of advanced materials with customizable properties. Simultaneously, the processability of organic molecular crystals plays a pivotal role in shaping their utility in real‐world applications. From growth methodologies to fabrication techniques, the ability to precisely machine these crystals opens new avenues for engineering materials with enhanced functionality. These processing methods enhance the versatility of organic crystals, allowing their integration into various devices and technologies, and further expanding the potential applications. This review aims to provide a concise overview of the current landscape in the study of dynamic organic molecular crystals, with an emphasis on the interconnected themes of operability and processability.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic‐Inorganic Hybrid Materials with Controlled Internal Structures

AbstractEfficient occlusion of particulate additives into a single crystal has garnered an ever‐increasing attention in materials science because it offers a counter‐intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization‐induced self‐assembly is employed to synthesize well‐defined and highly anionic poly(3‐sulfopropyl methacrylate potassium)41‐block‐poly(benzyl methacrylate)500 [PSPMA41‐PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Characterization of ZnWO4, MgWO4, and CaWO4 Ceramics Synthesized in the Field of a Powerful Radiation Flux

This paper presents the results of a study on the morphology, structure, and luminescent properties of ceramics synthesized in the radiation field of MeWO4 compositions (where Me is Mg, Ca, and Zn). The synthesis of ceramics was carried out by the direct action of the electron flux on an initial mixture of powders of the given stoichiometric composition. WO3, ZnO, MgO, and CaO powders with particle sizes in the range of 1–50 microns were used for the synthesis of the samples. It was found that the yield of the radiation synthesis reaction (the ratio of the mass of the sample and the charge used), when treated with an electron flux with an energy of 1.4 MeV and a flux power density of 15–18 kW/cm2, was in the range of 75–99%. The synthesis of all compositions was carried out under the same radiation treatment modes, although the melting temperatures of the starting materials varied significantly and ranged from 1473 °C (WO3) to 2825 °C (MgO). The study of the ceramic structure showed that under the radiation effect of powerful radiation fluxes on the charge, a crystalline phase of the appropriate composition formed, regardless of the synthesis modes. The results of XRD studies show that during the radiation treatment of the charge, ceramics are formed mainly with the crystalline phases ZnWO4, MgWO4, and CaWO4. These resulting MeWO4 ceramics can be used for the same purposes as crystals. Photoluminescence (PL) and cathodoluminescence (CL) were studied under excitation using stationary ultraviolet radiation and nanosecond pulses of electron flux. In general, the PL and CL of synthesized ceramic samples ZnWO4, MgWO4, and CaWO4 showed that their luminescent properties are similar to those of luminescence in corresponding crystalline materials. This indicates the formation of a crystalline phase in synthesized ceramic samples.

Amorphous (lysine)2PbI2 layer enhanced perovskite photovoltaics

Passivation materials play a crucial role in a wide range of high-efficiency, high-stability photovoltaic applications based on crystalline silicon and state-of-the-art perovskite materials. Currently, for perovskite photovoltaic, the mainstream passivation strategies routinely rely on crystalline materials. Herein, we have invented a new amorphous (lysine)2PbI2 layer-enhanced halide perovskite. By utilizing a solid phase reaction between PbI2 and lysine molecule, an amorphous (lysine)2PbI2 layer is formed at surface/grain boundaries in the perovskite films. The amorphous (lysine)2PbI2 with fewer dangling bonds can effectively neutralize surface/interface defects, achieving an impressive efficiency of 26.27% (certified 25.94%). Moreover, this amorphous layer not only reduces crystal lattice stress but also functions as a barrier against the decomposition of organic components, leading to suppressed de-structuring of perovskite and highly stable perovskite solar cells.

Fabrication Methods of Continuous Pure Metal-Organic Framework Membranes and Films: A Review.

Metal-organic frameworks (MOFs) have drawn intensive attention as a class of highly porous, crystalline materials with significant potential in various applications due to their tunable porosity, large internal surface areas, and high crystallinity. This paper comprehensively reviews the fabrication methods of pure MOF membranes and films, including in situ solvothermal synthesis, secondary growth, electrochemical deposition, counter diffusion growth, liquid phase epitaxy and solvent-free synthesis in the category of different MOF families with specific metal species, including Zn-based, Cu-based, Zr-based, Al-based, Ni-based, and Ti-based MOFs.

Uncovering all possible dislocation locks in face-centered cubic materials

Dislocation reactions and locks play an important role in the plastic deformation and mechanical behavior of crystalline materials. Various types of dislocation locks in face-centered cubic (FCC) materials have been reported in the literature pertaining to material-specific molecular-dynamic simulations and high-resolution transmission electron microscopy observations. However, it is unknown how many dislocation locks are possible, and how immobile all the dislocation locks are, with respect to each other. Here we present a discrete mathematics-based approach to reveal all possible dislocation locks in the FCC crystal structure. Totally eight types of dislocation locks are uncovered, resulting from all possible reactions of mobile/glissile (namely, perfect and Shockley partial) dislocations with (a) non-coplanar Burgers vectors which reside on two slip planes intersecting at both obtuse and acute angles and (b) coplanar Burgers vectors. We redefine the degree of dislocation lock immobility based on misorientations between non-close-packed lock planes and close-packed {111} slip planes. The subsequently derived sequences for the dislocation lock immobility and formation tendency are rationalized by the reported experimental and dislocation-dynamics simulation results.

Bulk photovoltaic effect in ferroelectric nematic liquid crystals.

The bulk photovoltaic (BPV) effect in ferroelectric liquid crystals is of increasing scientific interest owing to its great potential for light-energy conversion. The ferroelectric nematic phase exhibits a huge spontaneous polarization that can be aligned to a preferred direction. In this Letter, we investigate the tensorial properties of the BPV effect in the planarly aligned ferroelectric nematic phase of the liquid crystalline material RM734. A steady-state short-circuit photocurrent of ~160 pA and an open-circuit photovoltage of ~50 mV were observed in a cell with a thickness of 5.5 µm under the illumination of ultraviolet light without any bias voltage. Based on the photocurrent measurements in different electrode configurations, the non-zero elements of the BPV tensor were obtained. The BPV effect is attributed to the combination of the spontaneous polarization and the asymmetric distribution of photoinduced charge carriers. This study not only provides an understanding of the bulk PV mechanism in soft ferroelectrics but also promises a wide range of unprecedented, to the best of our knowledge, benefits for light harvesting to engineer marketable photovoltaic devices.

Enhanced Electrochemical Performance and Cycling Stability of the (NH4)8[VIV12VV7O41(OH)9]·11H2O Cathode in Aqueous Zinc Ion Batteries.

Although vanadium-based compounds possess several advantageous characteristics, such as multivalency, open structure, and high theoretical specific capacity, which render them highly promising candidates for cathode materials in aqueous zinc ion batteries (AZIBs), their large-scale application still necessitates addressing the challenges posed by slow kinetics resulting from low conductivity and capacity degradation caused by material dissolution. Therefore, we have successfully synthesized high-purity mixed multivalent (NH4)8[VIV12VV7O41(OH)9]·11H2O (NVO) crystalline materials via a liquid-phase precipitation modulation method and employed it as an innovative AZIB cathode material for the first time. It exhibits a remarkable reversible specific capacity of 240 and 102.2 mAh g-1 after undergoing 1000 cycles at current densities of 1 and 5 A g-1, respectively, highlighting its exceptional cycling stability and electrochemical performance. The results from cyclic voltammetry (CV) and GITT tests demonstrate that the dominant factor influencing the charge storage is the pseudocapacitive behavior, which is accompanied by an exceptionally high diffusion coefficient of Zn2+ at a rate of 10-10 cm2 s-1. The highly reversible intercalation-deintercalation of Zn2+ in NVO/Zn cells is demonstrated through ex-situ TEM, XRD, and XPS analyses. This work provides a benchmark for the development of high-performance POV electrode materials.

Characterization of extended defects in 2D materials using aperture-based dark-field STEM in SEM

Quantitative diffraction contrast analysis with defined diffraction vectors is a well-established method in TEM for studying defects in crystalline materials. A comparable transmission technique is however not available in the more widely used SEM platforms. In this work, we transfer the aperture-based dark-field imaging method from the TEM to the SEM, thus enabling quantitative diffraction contrast studies at lower voltages in SEM. This is achieved in STEM mode by inserting a custom-made aperture between the sample and the STEM detector and centering the hole on a desired reflection. To select individual reflections for dark-field imaging, we use our Low Energy Nanodiffraction (LEND) setup [Schweizer et al., Ultramicroscopy 213, 112956 (2020)], which captures transmission diffraction patterns from a fluorescent screen positioned below the sample. The aperture-based dark-field STEM method is particularly useful for studying extended defects in 2D materials, where (i) stronger diffraction at the lower voltages used in SEM is advantageous, but (ii) two-beam conditions cannot be established, making quantitative diffraction contrast analysis with standard bright-field and annular dark-field detectors impossible. We demonstrate the method by studying basal plane dislocations in bilayer graphene, which have attracted considerable research interest due to their exceptional structural and electronic properties. Direct comparison of results obtained on identical dislocations by the established TEM method and by the new aperture-based dark-field STEM method in SEM shows that a reliable Burgers vector analysis is possible by applying the well-known g·b=0 invisibility criterion. We further use the LEND setup to acquire 4D-STEM data and show that the virtual dark-field images match well with those in aperture-based dark-field STEM images for reliable Burgers vector analysis.