Cation Displacements Research Articles

Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system

Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches, sensors, actuators, etc. However, it remains a challenge to design high-temperature ferroelastic to meet the requirements for the practical applications. Herein, we reported an one-dimensional organic-inorganic hybrid perovskites (OIHP) (3-methylpyrazolium)CdCl3 (3-MBCC), which possesses a mmmF2/m ferroelastic phase transition at 263 K. Moreover, utilizing crystal engineering, we replace ‒CH3 with ‒NH2 and ‒H, which increases the intermolecular force between organic cations and inorganic frameworks. The phase transition temperature of (3-aminopyrazolium)CdCl3 (3-ABCC), and (pyrazolium)CdCl3 (BCC) increased by 73 K and 10 K, respectively. Particularly, BCC undergoes an unconventional inverse temperature symmetry breaking (ISTB) ferroelastic phase transition around 273 K. Differently, it transforms from a high symmetry low-temperature paraelastic phase (point group 2/m) to a low symmetry high-temperature ferroelastic phase (point group 1¯) originating from the rare mechanism of displacement of organic cations phase transition. It means that crystal BCC retains in ferroelastic phase above 273 K until melting point (446 K). Furthermore, characteristic ferroelastic domain patterns on crystal BCC are confirmed with polarized optical microscopy. Our study enriches the molecular mechanism of ferroelastics in the family of organic-inorganic hybrids and opens up a new avenue for exploring high-temperature ferroic materials.

Atomic-scale insight into the epitaxial growth mechanism and interfacial coupling of BNT film prepared by hydrothermal synthesis

Revealing the epitaxial growth mechanism and the interfacial coupling effect between oxide films will help to build a “structure-property” bridge for the design of microelectronic devices. Here, the epitaxial growth mechanism and the interfacial coupling in Bi0.5Na0.5TiO3/SrTiO3 (BNT/STO) heterointerfaces are investigated by the aberration-corrected scanning transmission electron microscopy, which is synthesized by a hydrothermal method. The results illustrate that 4 mol/L NaOH leads to not only the epitaxial growth of the BNT film but also the mutual diffusion of elements. The uneven distribution of local elements in BNT films is observed and confirmed to impact the cation displacements of B-site and lattice distortion. However, the overall trend of B-site cation displacement at the BNT/STO heterointerfaces is dominated by the interfacial strain. Additionally, the oxygen octahedral tilt exhibits continuous tilt patterns of a0a0a0 - a−b0c− - a0a0c− - a0b−c− - a−b−c− from the substrate to BNT film due to the constraint of the substrate and presents a strong correlation with cation displacement. These results are helpful to understand the underlying atomic structures and physical properties of BNT epitaxial thin films.

Surface Defect-Driven Chemical Transformation of MoSe2 Nanosheets

The chemistry of atomically thin two-dimensional layered transition metal dichalcogenides (TMDs) largely depends upon the presence of defect sites in their structures. Here, we demonstrate the role of defects of MoSe2 nanosheets (NSs) in two different transformative reactions for the synthesis of MoSe2–CdS nano-heterostructures (NHSs) and CdSe quantum dots (QDs). MoSe2–CdS NHSs are synthesized via passivating the defects of MoSe2 using thiol moieties, followed by the growth of CdS over the surface of MoSe2 NSs. Furthermore, in the absence of thiols, we observe that defects in MoSe2 NSs significantly accelerate the cation-exchange process upon direct exposure to the cadmium (Cd) precursor, resulting in the formation of CdSe QDs through cation displacement reaction (CDR). We have probed the transformation of MoSe2 NSs into CdSe QDs through Raman and optical spectroscopic measurements. Furthermore, theoretical calculations under the framework of density functional theory (DFT) suggest that CDR is feasible on the surface of defect-rich NSs, which becomes unfavorable in the case of defect-free or thiol-passivated MoSe2 NSs. These results provide new insights into understanding the multifaceted role of defects of TMDs in different transformative reactions.

Atomistic Simulations of the Crystalline-to-Amorphous Transformation of γ-Al2O3 Nanoparticles: Delicate Interplay between Lattice Distortions, Stresses, and Space Charges

The size-dependent phase stability of γ-Al2O3 was studied by large-scale molecular dynamics simulations over a wide temperature range from 300 to 900 K. For the γ-Al2O3 crystal, a bulk transformation to α-Al2O3 by an FCC-to-HCP transition of the O sublattice is still kinetically hindered at 900 K. However, local distortions of the FCC O-sublattice by the formation of quasi-octahedral Al local coordination spheres become thermally activated, as driven by the partial covalency of the Al-O bond. On the contrary, spherical γ-Al2O3 nanoparticles (NPs) (with sizes of 6 and 10 nm) undergo a crystalline-to-amorphous transformation at 900 K, which starts at the reconstructed surface and propagates into the core through collective displacements of anions and cations, resulting in the formation of 7- and 8-fold local coordination spheres of Al. In parallel, the reconstructed Al-enriched surface is separated from the stoichiometric core by a diffuse Al-depleted transition region. This compositional heterogeneity creates an imbalance of charges inside the NP, which induces a net attractive Coulombic force that is strong enough to reverse the initial stress state in the NP core from compressive to tensile. These findings disclose the delicate interplay between lattice distortions, stresses, and space-charge regions in oxide nanosystems. A fundamental explanation for the reported expansion of metal-oxide NPs with decreasing size is provided, which has significant implications for, e.g., heterogeneous catalysis, NP sintering, and additive manufacturing of NP-reinforced metal matrix composites.

Thickness-Dependent Interface Polarity in Infinite-Layer Nickelate Superlattices

The interface polarity plays a vital role in the physical properties of oxide heterointerfaces because it can cause specific modifications of the electronic and atomic structure. Reconstruction due to the strong polarity of the NdNiO2/SrTiO3 interface in recently discovered superconducting nickelate films may play an important role, as no superconductivity has been observed in the bulk. By employing four-dimensional scanning transmission electron microscopy and electron energy-loss spectroscopy, we studied effects of oxygen distribution, polyhedral distortion, elemental intermixing, and dimensionality in NdNiO2/SrTiO3 superlattices grown on SrTiO3 (001) substrates. Oxygen distribution maps show a gradual variation of the oxygen content in the nickelate layer. Remarkably, we demonstrate thickness-dependent interface reconstruction due to a polar discontinuity. An average cation displacement of ∼0.025 nm at interfaces in 8NdNiO2/4SrTiO3 superlattices is twice larger than that in 4NdNiO2/2SrTiO3 superlattices. Our results provide insights into the understanding of reconstructions at NdNiO2/SrTiO3 polar interfaces.

Well-defined double hysteresis loop in NaNbO3 antiferroelectrics

Antiferroelectrics (AFEs) are promising candidates in energy-storage capacitors, electrocaloric solid-cooling, and displacement transducers. As an actively studied lead-free antiferroelectric (AFE) material, NaNbO3 has long suffered from its ferroelectric (FE)-like polarization-electric field (P-E) hysteresis loops with high remnant polarization and large hysteresis. Guided by theoretical calculations, a new strategy of reducing the oxygen octahedral tilting angle is proposed to stabilize the AFE P phase (Space group Pbma) of NaNbO3. To validate this, we judiciously introduced CaHfO3 with a low Goldschmidt tolerance factor and AgNbO3 with a low electronegativity difference into NaNbO3, the decreased cation displacements and [BO6] octahedral tilting angles were confirmed by Synchrotron X-ray powder diffraction and aberration-corrected scanning transmission electron microscopy. Of particular importance is that the 0.75NaNbO3−0.20AgNbO3−0.05CaHfO3 ceramic exhibits highly reversible phase transition between the AFE and FE states, showing well-defined double P-E loops and sprout-shaped strain-electric field curves with reduced hysteresis, low remnant polarization, high AFE-FE phase transition field, and zero negative strain. Our work provides a new strategy for designing NaNbO3-based AFE material with well-defined double P-E loops, which can also be extended to discover a variety of new lead-free AFEs.

Photoinduced control of ferroelectricity in hybrid-improper ferroelectric superlattices

We reveal a photoinduced control of ferroelectricity in hybrid-improper ferroelectric superlattices, using ab initio theory. Along with a notable photostriction effect, thermalized carriers from photoexcitation affect octahedral tiltings along different directions. A trilinear coupling between antipolar and tilting modes drives corresponding cationic displacements, and this results in a decrease in polarization under light. Together with recent experimental evidence, our study therefore demonstrates that light is a viable route to engineer functionalities in materials.

Engineering antiferroelectric nucleation in ferroelectric films with enhanced piezoelectricity

Tailoring ferroelectric-antiferroelectric phase transitions provides strategic advantages for potential applications in digital displacement transducers and ultrathin ferroelectric capacitors. In particular, epitaxy of artificial superlattice has been widely used and proved to be capable of creating antiferroelectric-type characteristics within intrinsic ferroelectrics. Here, we have achieved dedicatedly control of ferroelectric-antiferroelectric phase transition by introducing 2 unit-cells antiferroelectric PbZrO3 layers into the intrinsic ferroelectric BiFeO3 films, with the ultrathin PbZrO3 layers acting as the structural spacer to bridge the robust nucleation of striping phase in BiFeO3 layers. Aberration-corrected scanning transmission electron microscopy characterization revealed that the BiFeO3 layers experienced a transition to the antiferroelectric-like polymorph via interface-transferred lattice distortion of alternate cation displacement, thereby forming the periodic ferroelectric-antiferroelectric nanoscale laminas. Further piezoresponse force measurements gave the direct evidences that the modulated superlattice exhibited improved piezoelectric performance compared with typical rhombohedral BiFeO3 films. This work paves the way for engineering polarity-mismatched superlattices with enhanced piezoelectric response and enriches the fundamental of structure-functionality correlations in oxide heterosystems.

Enhanced Thermoelectric Performance of Nanostructured Cu2SnS3 (CTS) via Ag Doping

The present work aims to investigate the effect of Ag doping on the thermoelectric properties of Cu2SnS3 (CTS). Various Cu2Ag(x)Sn(1–x)S3 (0.05 ≤ x ≤ 0.25) samples were synthesized by mechanical alloying followed by spark plasma sintering, and their structural and transport properties were systematically investigated. The x = 0.15 sample presented a ∼10-fold higher power factor than the undoped CTS. Although, the x = 0.125 sample had a lower power factor than the x = 0.15 sample, owing to its lower thermal conductivity, both the samples showed the highest zT ∼ 0.8 at 723 K. This value is comparable to the best results available in the literature for earth-abundant and eco-friendly thermoelectric materials. Interestingly, the thermal conductivity of Cu2Ag(x)Sn(1–x)S3 samples increased with Ag substitution, which was further investigated using the first-principles and ab initio molecular dynamics calculations. It was observed that the incorporation of Ag into the system decreases the root mean square displacement of the other cations and anions, reducing the scattering of phonons and thereby increasing the lattice thermal conductivity. Moreover, the calculations on the formation energy have revealed the reason for the structural transformation of CTS and similar diamond-like structures toward high symmetry polymorphs by external doping. The increase in zT is directly related to the optimization of the band gap and the weighted mobility, which have been investigated experimentally and using the first principle method.

Defect Passivation Results in the Stability of Cesium Lead Halide Perovskite Nanocrystals

Nanoheterostructures (NHSs) based on lead halide perovskites (LHPs) and chalcogenide quantum dots have proved to be promising candidates for photovoltaic device applications. However, understanding the defect chemistry at the interfaces of LHPs and chalcogenides is essential to stabilize them and further tune their optoelectronic properties. Here, we demonstrate a route for designing CsPbBr3–PbSe NHSs and other derivatives of LHP-based NHSs using defect-rich MoSe2 nanosheets (NSs) and study the effect of the size of PbSe NPs on their optical properties. In this synthesis route, PbSe nanoparticles (NPs) are formed at an early stage of the reaction through a unique cation displacement reaction, over which CsPbBr3 nanocrystals (NCs) are epitaxially grown. Using this methodology, a nearly 3-fold enhancement in photoluminescence (PL) is achieved, whereas other selenium precursors, which form larger PbSe NPs, result in negligible PL enhancement with respect to the pure CsPbBr3 NCs. Detailed density functional theory (DFT) calculations suggest that the PbSe NPs are responsible for passivating the surface defects that consequently enhance the PL intensity. However, in the case of larger PbSe NPs, the associated valence and conduction bands lie within the band-gap region of CsPbBr3, creating a type-I heterostructure between the two materials, thereby affecting the luminescence properties. Strong passivation of surface defects in CsPbBr3–PbSe NHSs is also evidenced from low-temperature PL studies. Furthermore, the resulting CsPbBr3–PbSe NHSs demonstrate enhanced stability in the presence of water and do not degrade under ambient conditions for several months.

Regional consistency between cation displacement and oxygen octahedral tilt in nanodomain of BNKT-SBT relaxor ferroelectrics revealed by atomic-resolution AC-STEM

Since being discovered, relaxor ferroelectrics have attracted continued interest due to their unusual properties. Relaxor behavior is attributed to nanodomains or PNRs. Therefore, nano-scale even atomic-scale structural analysis is crucial to understanding the relaxor properties. However, the atomic-scale nanodomain structure has not been fully understood. For Bi0.5Na0.5TiO3, cation displacement and oxygen octahedral tilt are two common structural distortions. However, the relationship between them has not been proved experimentally. Here, the cation displacement and octahedral tilt were both investigated based on aberration-corrected STEM images. Cation displacement vectors illustrate a vortex structure. Octahedral tilt is regionally consistent with cation displacement that both of them increase gradually from the domain wall to the interior of the nanodomain. The formation of nanodomains may originate from their combined effect, thereby producing relaxor properties. Moreover, oxygen octahedral displacement stemmed from the complex coordinating environments was observed. These findings provide further insights into the nanodomain structure.

Research progress of synthesis of high-performance perovskites and its derivatives based on polyhedral distortion

Corner-shared coordination polyhedral crystals (CSCPCs) represented by perovskites have unique and various properties in optics, electrics, and magnetism, leading to their broad applications such as in serving as ferroelectric material, fast ionic conductors, and electro/photo-catalysts. However, the excellent properties are owned only by a very small fraction of CSCPS phases. How to obtain such phases through structural operation has always been a research hotspot and a bottleneck in related fields. Herein, we review the recent research progress of the synthesis of high-performance CSCPC materials from the perspective of phase structure, in order to clarify the intrinsic rules of phase evolution and reveal the mechanism behind the phase manipulation. We first systematically summarize the types of polyhedra and crystal frameworks in CSCPCs and classify the polyhedral distortions as three main types, i.e. cation displacements, polyhedral rotations, and deformations. Based on that, we further analyze and conclude different material synthesis methods. We find that most traditional synthesis methods rely on the phase transitions induced by the change of external physical conditions at a macroscopic level, such as composition, temperature, and pressure. Recently, there was an emerging synthesis method focusing on the microscopic manipulation of polyhedral geometry and topology, such as phase constructions according to tolerance-factor and substrate-proximity effects. The macroscopic synthesis methods and the microscopic synthesis methods share the same phase manipulation mechanism: making crystals transit into the structure-specified phases by inducing polyhedral distortions. The only difference is that the latter is more target-oriented, but its applications are currently limited to octahedral coordination tilt/rotation systems. Expanding its application scope is still a challenge. In addition, we propose two aspects that may be useful in optimizing the synthesis method: one is to clarify the origin of induced distortions and the interaction between different distortions, and the other is to customize the guidelines based on computer science. We hope that the research progress reviewed in this article can provide some valuable references and inspirations for designing and synthesizing the high-performance CSCPC materials.

Ultrahigh phase-transition electric field and giant energy density in NaNbO3–Bi(Zn0.5Sn0.5)O3 lead-free antiferroelectric ceramics

Synergistic effect of reduced off-centering displacements of B-site cations, enhanced antiferrodistortive and decreased AFE domain size leads to significantly enhanced EAF of ≥45 kV mm−1 and Wrec of ∼5.5 J cm−3 in NaNbO3-based lead-free ceramics.

Tracing the Effect of Replacing [Gly]- with [Ala]- and Hydroxylation of [emim]+ on the Fine-Tuning of the Transport Properties of the Corresponding Amino Acid-Based Ionic Liquids Using MD Simulation.

Natural amino acid-based ionic liquids (AAILs) composed of deprotonated amino acids, [AA]-, as anions and hydroxylated imidazolium cations provide an eco-friendly nontoxic IL family with the growing number of chemical and biochemical revolutionary applications. In this paper, the transport properties of four AAILs composed of 1-(2-hydroxyethyl)-3-methylimidazolium ([HOemim]+) and 1-ethyl-3-methylimidazolium ([emim]+) cations with alaninate and glycinate anions were studied by molecular dynamics (MD) simulations. A nonpolarizable all-atom force field with the scaled charge (±0.8e) on each of the ions was applied and compared with the unit charge model in some cases. The tunable effects of the presence of the hydroxyl group in the side chain of the imidazolium cation, the type of amino acid anion, and the varied temperature on the dynamical behavior of AAILs were investigated in detail. The experimentally compatible trends of the simulated ionic self-diffusion coefficients, ionic conductivity, and ionicity were found to be inverse to the viscosity and ionic association of these ILs as [emim][Gly] > [emim][Ala] > [HOemim][Gly] > [HOemim][Ala]. The main reason behind these trends is the higher ability of the hydroxylated cation for the hydrogen-bond formation with [AA]-. The mean square displacement (MSD), self-diffusion, and transference number of imidazolium cations are larger than those of [AA]- anions, except in the case of [HOemim][Gly]. It was found that the activation energy for diffusion of [AA]- is lower than that of [HOemim]+ but higher than that of [emim]+ in [HOemim][AA] and [emim][AA] ILs, respectively. The computed velocity autocorrelation function (VACF) showed that [Gly]-, as the lightest ion, has the shortest mean collision time and velocity randomization time among the ions, especially in the [HOemim][Gly] IL. Replacing [emim]+ with [HOemim]+, similar to the effect of decreasing temperature, causes significant decreasing of the ionic self-diffusion and increasing of the well depth of the first minimum of the ionic VACFs. Current findings show that introducing suitable functional groups in the side chain of imidazolium cations can be a viable approach for efficient engineering design and fine-tuning of the transport properties of these AAILs.

Cation ordering induced two-dimensional vertical ferroelectricity in tungsten and molybdenum trioxides

Two-dimensional (2D) materials that exhibit vertical polarization might provide ground-breaking device applications, compatible with electric-field switching even in the presence of a surface-depolarizing field. Here, using first-principles calculations, we focus on vertical cationic off-plane displacements in transition metal trioxides ${M\mathrm{O}}_{3}$ $(M=\mathrm{W}, \mathrm{Mo})$, with a configuration similar to ${\mathrm{CrI}}_{3}$-like hexagonal trihalides. We further design a ${\mathrm{WMoO}}_{6}$ monolayer, with W and Mo arranged in an energetically stable honeycomb-checkerboard pattern, showing a net vertical ferroelectric polarization and a wide band gap. Moreover, the structural, electronic, and ferroelectric properties of ${\mathrm{WMoO}}_{6}$ monolayers are found to be significantly strain tunable. Our results put forward a transition metal trioxide monolayer with switchable vertical ferroelectricity, thus broadening the range of 2D functional ferroelectrics.

Enhanced Second-Harmonic Generation of van der Waals CuInP2S6 via Pressure-Regulated Cationic Displacement

Design and exploration of high-performance nonlinear optical (NLO) materials have long been sought with the goal of tunable local structures and NLO properties for advanced laser technology. Thus far, the design strategies for second-order NLO materials have been mainly focused on anionic groups that have made great progress in the development of new NLO compounds. However, few studies have focused on the effects of cationic components and their contributions to NLO properties have long been underappreciated and remain unclear. Here, by introducing pressure to continuously tune the Cu displacement, we demonstrate the significant role of the cationic configuration in NLO properties, and a remarkable enhancement by one order of magnitude in second-harmonic generation (SHG) has been achieved at 3.4 GPa in thiophosphate CuInP2S6 (CIPS). In situ high-pressure structural characterization indicates that Cu cations move from the van der Waals edge to the cages of S6 octahedra during compression and subsequently form highly distorted [CuS6] octahedra at 3.2 GPa. We quantitively demonstrate the contributions of cationic displacement on the octahedral distortion and interband dipole moments, which dominate optical nonlinearity and determine the enhanced SHG. This work deepens the fundamental understanding of the relationship between cationic displacement and SHG properties, thus providing new paths to NLO material design by optimizing the cationic configurations.

Super-assembled mesoporous thin films with asymmetric nanofluidic channels for sensitive and reversible electrical sensing

Bioinspired artificial nanochannels have emerged as promising candidates for developing smart nanofluidic sensors due to their highly controllable size and surface functionality. However, little attention has been paid to the role of the outer surface of the nanochannels in enhancing the detection sensitivity. Herein, an asymmetric nanochannel-based responsive detection platform with ultrathin tannic acid modified mesoporous silica (TA-MS) layer and alumina oxide (AAO) thin film is prepared through super-assembly strategy. The functional TA-MS outer surface layer provides abundant phenolic groups on the nanochannels for ions and molecules transport, which paves the way for the development of heterochannels for label-free, reversible and highly sensitive dopamine (DA) detection based off of cation displacement effect. Notably, by engineering optimal thickness of the TA-MS, the sensing performance can be further improved. After optimization, the linear response ranges for DA detection are 0.001–1 μM, 1–10 μM and 10–200 μM with the detection limit of 0.1 nM. The prepared sensor exhibits stable reversibility after several detection cycles. In addition, this method was successfully applied for DA detection in fetal bovine serum sample. Theoretical calculations further prove the detection mechanism. This work opens a new horizon of using mesoporous materials to construct nanofluidic sensors for ultrasensitive small molecule detection and recognition.

THz-induced activation of hidden states in rare-earth-doped BiFeO3 solid solutions

An atomistic effective Hamiltonian is used to study the response of a $(\mathrm{Bi},\mathrm{Nd}){\mathrm{FeO}}_{3}$ (BNFO) solid solution to a train of THz electric field pulses. Several hidden states (i.e., states that are usually not thermodynamically accessible) with various magnitudes of the electric polarization as well as different oxygen octahedral tilting patterns and antipolar arrangements are found, which is promising for designing ultrafast neuromorprhic architectures. The occurrence of these hidden states, along with the accompanying polarization pumping, originates from the specific trilinear and biquadratic couplings between oxygen octahedral tiltings and cation displacements. Consequently, the THz-activated transformation between these different states can be thought to be a ratchet mechanism both in real and reciprocal spaces.

Protonation-Induced Colossal Chemical Expansion and Property Tuning in NdNiO3 Revealed by Proton Concentration Gradient Thin Films.

Protonation can be used to tune diverse physical and chemical properties of functional oxides. Although protonation of nickelate perovskites has been reported, details on the crystal structure of the protonated phase and a quantitative understanding of the effect of protons on physical properties are still lacking. Therefore, in this work, we select NdNiO3 (NNO) as a model system to understand the protonation process from pristine NNO to protonated HxNdNiO3 (H-NNO). We used a reliable electrochemical method with well-defined reference electrode to trigger the protonation-induced phase transition. We found that the protonated H-NNO phase showed a colossal ∼13% lattice expansion caused by a large tilt of NiO6 octahedra and displacement of Nd cations. Importantly, we further designed a novel device configuration to induce a gradient of proton concentration into a single NNO thin film to establish a quantitative correlation between the proton concentration and the lattice constant and transport property of H-NNO.

Octahedral Tilting in Homologous Perovskite Series CaMoO3-SrMoO3-BaMoO3 Probed by Temperature-Dependent EXAFS Spectroscopy

Local distortions in perovskites can be induced by cation displacements and/or by the tilting and rotating of cation-anion octahedra. Both phenomena have been subject to intense investigations over many years. However, there are still controversies in the results obtained from experimental techniques that are sensitive to long-range order (X-ray, neutron, or electron diffraction) and those sensitive to short-range order (X-ray absorption spectroscopy). In this study, we probed the details of the local environment in AMoO3 perovskites (A = Ca, Sr, Ba) using extended X-ray absorption fine structure (EXAFS) in a wide temperature range (10-300 K). An advanced analysis of the EXAFS spectra within the multiple-scattering formalism using the reverse Monte Carlo method enhanced by an evolutionary algorithm allowed us (i) to extract detailed information on metal-oxygen and metal-metal radial distribution functions, and metal-oxygen-metal and oxygen-metal-oxygen bond angle distribution functions, and (ii) to perform polyhedral analysis. The obtained results demonstrate the strong sensitivity of the EXAFS spectra to the tilting of [MoO6] octahedra induced by the differences in the sizes of alkaline earth metal cations (Ca2+, Sr2+, and Ba2+).