Temperature-dependent Phase Transition Research Articles

Two-dimensional Fullerene-Based Ferroelectric Materials: Assembly and Effects on Charge Carrier Lifetime.

Manipulating the symmetry of fullerene-based low-dimensional materials is crucial to the development of electronic devices and modern nonvolatile memories. However, there have been few reports on studying the physicochemical properties of fullerene and its derivatives by controlling the symmetries. Herein, we demonstrate ferroelectricity in Sc3N@Ih-C80-Pd/Pt adducts with relatively strong spontaneous polarization. Polarization originates from subtle molecular interactions between Sc3N@Ih-C80 and Pd/Pt atoms, breaking the structural symmetry. Additionally, we investigate how a temperature-dependent polar-nonpolar phase transition affects the corresponding nonadiabatic electron-hole recombination process in the ferroelectric fullerene adduct Sc3N@Ih-C80-Pd. The results indicate that polarization has a greater impact than temperature effects, resulting in an extension of the carrier lifetime in the polar phase by over 3 times compared to that in the nonpolar phase. Our findings unveil new members of the ferroelectric fullerene family and provide guidance for improving the performance of optoelectronic materials.

Prediction of simultaneous enhancement of Goos-Hänchen shift and reflectance in VO2 grating structure

Vanadium dioxide (VO2) material stands out in the family of the phase change materials due to its temperature-dependent phase transition properties, which make it a promising candidate for the temperature-dependent optoelectronic devices. Enhancement of the Goos-Hänchen (GH) shift is essential in VO2-based nanostructures for their applications, but it has been limited to the multilayered structures with VO2 materials so far. Here, we theoretically investigate the GH shift and corresponding reflectance in the VO2-based grating structure. We evidence that this structure has two GH peaks (3107λ and 2266λ) and high reflectance values (both up to 1) when VO2 is in the insulating phase as well as the maximum GH valley (−1061λ) and low reflectance (0.19) when VO2 is in the metallic phase. The electromagnetic field distributions in this hybrid structure suggest that the guided mode resonances (GMRs) can be excited no matter whether VO2 is in its insulating or metallic phases due to the couplings between the incident waves and the adjacent evanescent diffracted order waves, which produces their enhanced GH shifts. Different from the former case with the high reflectances and the large GH shifts, the latter has the low maximum magnetic field intensity due to the lossy property of the metallic VO2, which leads to the low reflectance and small GH valley value. Additionally, we have also found that by the alterations of the temperature-dependent conductivity of VO2 and the geometric parameters of the structure allows for the control the magnitude and position of the GH peak or valley. The simultaneously enhanced GH shifts and reflectances in the VO2-based grating structure, associated with its controllable features, enable it an effective configuration for establishing the temperature sensors and optoelectronic switches.

New Lead-free Hybrid Layered Double Perovskite Halides: Synthesis, Structural Transition and Ultralow Thermal Conductivity.

Hybrid layered double perovskites (HLDPs), representing the two-dimensional manifestation of halide double perovskites, have elicited considerable interest owing to their intricate chemical bonding hierarchy and structural diversity. This intensified interest stems from the diverse options available for selecting alternating octahedral coordinated trivalent [M(III)] and monovalent metal centers [M(I)], along with the distinctive nature of the cationic organic amine located between the layers. Here, we have synthesized three new compounds with general formula (R'/R'')4/2M(III)M(I)Cl8; where R'=C3H7NH3 (i.e. 3N) and R''=NH3C4H8NH3 (i.e. 4N4); M(III)=In3+ or Ru3+; M(I)=Cu+ by simple solution-based acid precipitation method. The structural analysis reveals that (4N4)2CuInCl8 and (4N4)2CuRuCl8 adopt the layered Dion Jacobson (DJ) structure, whereas (3N)4CuInCl8 exhibits layered Ruddlesden Popper (RP) structure. The alternative octahedra within the inorganic layer display distortions and tilting. Three compounds show temperature-dependent structural phase transitions where changes in the staking of inorganic layer, extent of octahedral tilting and reorientation of organic spacers with temperature have been noticed. We have achieved ultralow lattice thermal conductivity (κL) in the HLDPs in the 2 to 300 K range, marking a distinctive feature within the realm of HLDP systems. The RP-HLDP compound, (3N)4CuInCl8, demonstrates anisotropy in κL while measured parallel and perpendicular to layer stacking, showcasing ultralow κL of 0.15 Wm-1K-1 at room temperature, which is one of the lowest values obtained among Pb-free metal halide perovskite. The observed ultralow κL in three new HLDPs is attributed to significant lattice anharmonicity arising from the chemical bonding heterogeneity and soft crystal structure, which resulted in low-energy localized optical phonon modes that suppress heat-carrying acoustic phonons.

Temperature-dependent optical constants of vanadium dioxide thin films deposited on polar dielectrics

Coating polar dielectrics with thin film vanadium dioxide (VO2) enables one to exploit the temperature-dependent phase transition within VO2 to actively tune and modulate surface phonon polaritons at mid-infrared. However, controlling the behavior of such systems requires intimate knowledge of the temperature-dependent optical constants of VO2, which depend greatly on the growth conditions and substrate material. Here, we accurately determine the complex optical constants of VO2 on polar dielectrics across the insulator-to-metal phase transition (IMT) using only normal incident reflectance spectra by analyzing the reflectance with Kramers–Kronig relations and thin film Fresnel equations. This non-ellipsometry technique offers an advantage in determining the refractive index using a standard infrared spectrometer.

Topological classes of thermodynamics of the static multi-charge AdS black holes in gauged supergravities: novel temperature-dependent thermodynamic topological phase transition

In this paper, we investigate, in the framework of the topological approach to black hole thermodynamics, using the generalized off-shell Helmholtz free energy, the topological numbers of the static multi-charge AdS black holes in four- and five-dimensional gauged supergravities. We find that the topological number of the static-charged AdS black holes in four-dimensional Kaluza-Klein (K-K) gauged supergravity theory is W = 0, while that of the static-charged AdS black holes in four-dimensional gauged –iX0X1-supergravity and STU gauged supergravity theories, and five-dimensional Einstein-Maxwell-dilaton-axion (EMDA) gauged supergravity and STU gauged supergravity, and five-dimensional static-charged AdS Horowitz-Sen black hole are both W = 1. Furthermore, we observe a novel temperature-dependent thermodynamic topological phase transition that can happen in the four-dimensional static-charged AdS black hole in EMDA gauged supergravity theory, the four-dimensional static-charged AdS Horowitz-Sen black hole, and the five-dimensional static-charged AdS black hole in K-K gauged supergravity theory. We believe that the novel temperature-dependent thermodynamic topological phase transition could help us better understand black hole thermodynamics and, further, shed new light on the fundamental nature of gauged supergravity theories.

Phenomenological analysis of positive and negative electrocaloric effects in Rochelle salt

Ferroelectrics exhibiting both positive and negative electrocaloric effects stand out as promising materials for achieving high-efficiency solid-state refrigeration. The phase transition is acknowledged as a crucial factor in designing such materials. This study investigates the electrocaloric behavior and its correlation with phase transitions in Rochelle salt single crystal using Landau thermodynamic theory. Analysis of free energy density, ferroelectric, and dielectric data uncovers a complex temperature-dependent phase transition sequence of paraelectric–ferroelectric–paraelectric. This imparts Rochelle salt single crystal with intriguing field-induced phase transition behaviors and electrocaloric responses. Pronounced positive and negative electrocaloric effects are, respectively, observed near the high-temperature and low-temperature Curie point. The opposite sign of entropy differences between the ferroelectric and the two paraelectric phases is identified as the origin of the difference in electrocaloric response. These findings not only enhance our understanding of the electrocaloric effect but also provide a design solution for materials with the coexistence of positive and negative electrocaloric effects.

Structure and phase transitions in niobium and tantalum derived nanoscale transition metal perovskites, Ba(Ti,MV)O3, M=Nb,Ta.

The prospect of creating ferroelectric or high permittivity nanomaterials provides motivation for investigating complex transition metal oxides of the form Ba(Ti, MV)O3, where M = Nb or Ta. Solid state processing typically produces mixtures of crystalline phases, rarely beyond minimally doped Nb/Ta. Using a modified sol-gel method, we prepared single phase nanocrystals of Ba(Ti, M)O3. Compositional and elemental analysis puts the empirical formulas close to BaTi0.5Nb0.5O3-δ and BaTi0.5Ta0.5O3-δ. For both materials, a reversible temperature dependent phase transition (non-centrosymmetric to symmetric) is observed in the Raman spectrum in the region 533-583K (260-310°C); for Ba(Ti, Nb)O3, the onset is at 543K (270°C); and for Ba(Ti, Ta)O3, the onset is at 533K (260°C), which are comparable with 390-393K (117-120°C) for bulk BaTiO3. The crystal structure was resolved by examination of the powder x-ray diffraction and atomic pair distribution function (PDF) analysis of synchrotron total scattering data. It was postulated whether the structure adopted at the nanoscale was single or double perovskite. Double perovskites (A2B'B″O6) are characterized by the type and extent of cation ordering, which gives rise to higher symmetry crystal structures. PDF analysis was used to examine all likely candidate structures and to look for evidence of higher symmetry. The feasible phase space that evolves includes the ordered double perovskite structure Ba2(Ti, MV)O6 (M = Nb, Ta) Fm-3m, a disordered cubic structure, as a suitable high temperature analog, Ba(Ti, MV)O3Pm-3m, and an orthorhombic Ba(Ti, MV)O3Amm2, a room temperature structure that presents an unusually high level of lattice displacement, possibly due to octahedral tilting, and indication of a highly polarized crystal.

Pressure-dependent phase transitions in hybrid improper ferroelectric Ruddlesden-Popper oxides

The temperature-dependent phase transitions in Ruddlesden-Popper oxides with perovskite bilayers have been under increased scrutiny in recent years due to the so-called hybrid improper ferroelectricity that some chemical compositions exhibit. However, little is currently understood about the hydrostatic pressure dependence of these phase transitions. Herein we present the results of a combined high-pressure powder synchrotron x-ray diffraction experiment and abinitio study on the bilayered Ruddlesden-Popper phases Ca3Mn2O7 and Ca3Ti2O7. In both compounds we observe a first-order phase transition, that in combination with our density functional theory calculations, we can confidently assign as being between polar A21am and nonpolar Acaa structures. Interestingly, we show that while the application of pressure ultimately favors a nonpolar phase, as is commonly observed for proper ferroelectrics, regions of response exist where pressure actually acts to increase the polar mode amplitudes. The reason for this can be untangled by considering the varied response of octahedral tilts and rotations to hydrostatic pressure and their trilinear coupling with the polar instability. Published by the American Physical Society 2024

Exploring the temperature-dependent phase transitions of the solid electrolytes copper and silver tetraiodomercurates (Cu2, Ag2) HgI4: a study of thermal and electrical conductivities

Exploring the temperature-dependent phase transitions of the solid electrolytes copper and silver tetraiodomercurates (Cu2, Ag2) HgI4: a study of thermal and electrical conductivities

Dynamical Phase Transition in Kinetically Constrained Models with Energy-Activity Double-Bias Trajectory Ensemble.

We investigate the dynamical phase transitions in two representative kinetically constrained models, the 1D Fredrickson-Andersen and East models, by utilizing a recently developed s,g double-bias ensemble approach. In this ensemble, the fields s and g are applied to bias the dynamical activity and trajectory energy, respectively, in the trajectory ensemble. We first confirm that the dynamical phase transitions are indeed first-order in both the models. The phase diagrams in (s, g, T) space obtained via extensive numerical simulations show good qualitative agreement with the mean-field results. We also demonstrate that the temperature-dependent dynamical phase transition is possible in the systems when both fields are applied simultaneously. The trajectory energy and dynamical activity exhibit strong correlations for both systems. From extensive finite-size scaling analyses using the system size and observation time, we obtain scaling functions for the susceptibility and field and find scaling exponents that are model-dependent.

Modeling ferroelectric phase transitions with graph convolutional neural networks

Ferroelectric materials are widely used in functional devices, however, it has been a long-standing issue to achieve convenient and accurate theoretical modeling of them. Herein, a noval approach to modeling ferroelectric materials is proposed by using graph convolutional neural networks (GCNs). In this approach, the potential energy surface of ferroelectric materials is described by GCNs, which then serves as a calculator to conduct large-scale molecular dynamics simulations. Given atomic positions, the well-trained GCN model can provide accurate predictions of the potential energy and atomic forces, with an accuracy reaching up to 1 meV per atom. The accuracy of GCNs is comparable to that of <i>ab inito</i> calculations, while the computing speed is faster than that of <i>ab inito</i> calculations by a few orders. Benefiting from the high accuracy and fast prediction of the GCN model, we further combine it with molecular dynamics simulations to investigate two representative ferroelectric materials—bulk GeTe and CsSnI<sub>3</sub>, and successfully produce their temperature-dependent structural phase transitions, which are in good agreement with the experimental observations. For GeTe, we observe an unusual negative thermal expansion around the region of its ferroelectric phase transition, which has been reported in previous experiments. For CsSnI<sub>3</sub>, we correctly obtain the octahedron tilting patterns associated with its phase transition sequence. These results demonstrate the accuracy and reliability of GCNs in the modeling of potential energy surfaces for ferroelectric materials, thus providing a universal approach for investigating them theoretically.

An adhesion-switchable hydrogel dressing for painless dressing removal without secondary damage.

Hydrogels with strong adhesion to wet tissues are considered promising for wound dressings. However, the clinical application of adhesive hydrogel dressing remains a challenge due to the issues of secondary damage during dressing changes. Herein, we fabricated an adhesion-switchable hydrogel formed with poly(acrylamide)-co-poly(N-isopropyl acrylamide), quaternary ammonium chitosan and tannic acid. This hydrogel forms instant and robust adhesion to the skin at body temperature. However, as the temperature rises above the lower critical solution temperature (LCST), the hydrogel loses its adhesion towards the wound area due to the temperature-dependent volume phase transition of the copolymer, occurring around 45 °C. Consequently, the designed hydrogel can be easily detached from adhered tissues upon demand, providing a facile and effective method for painless dressing changes without secondary damage. This hydrogel holds great promise for long-term application in wound dressings.

Temperature-dependent solid-state phase transition with twinning in the crystal structure of 4-meth-oxy-anilinium chloride.

At room temperature, the title salt, C7H10NO+·Cl-, is ortho-rhom-bic, space group Pbca with Z' = 1, as previously reported [Zhao (2009 ▸). Acta Cryst. E65, o2378]. Between 250 and 200 K, there is a solid-state phase transition to a twinned monoclinic P21/c structure with Z' = 2. We report the high temperature structure at 250 K and the low-temperature structure at 100 K. In the low-temperature structure, the -NH3 hydrogen atoms are ordered and this group has a different orientation in each independent mol-ecule, in keeping with optimizing N-H⋯Cl hydrogen bonding, some of which are bifurcated: these hydrogen bonds have N⋯Cl distances in the range 3.1201 (8)-3.4047 (8) Å. In the single cation of the high-temperature structure, the NH hydrogen atoms are disordered into the average of the two low-temperature positions and the N⋯Cl hydrogen bond distances are in the range 3.1570 (15)-3.3323 (18) Å. At both temperatures, the meth-oxy group is nearly coplanar with the rest of the mol-ecule, with the C-C-O-C torsion angles being -7.0 (2)° at 250 K and -6.94 (12) and -9.35 (12)° at 100 K. In the extended ortho-rhom-bic structure, (001) hydrogen-bonded sheets occur; in the monoclinic structure, the sheets propagate in the (010) plane.

Phase Transition Engineering of Vanadium Dioxide Induced by Oxygen Vacancies

A reconfigurable optical functional system is a pioneering and comprehensive approach for portable future flexible electronics, irrespective of traditional silicon-based technology. VO2 shows tremendous temperature-dependent structural and electrical phase transitions as a complex correlated metal oxide, presenting it as a potential candidate for bolometers, thermal camouflage, and optoelectronics applications. However, the structural stability and high transition temperature restrict room-temperature applications. The present study reports the oxygen vacancies-assisted phase transition engineering in the VO2/muscovite heterostructure. The ion bombardment alters the oxygen stoichiometry of VO2/muscovite thin film at room temperature. A significant decrease in lattice constant has been observed during the transition of the insulating M1 (monoclinic) phase into the metallic R (tetragonal) phase, which was confirmed through high-resolution XRD. The change in oxygen vacancy concentration determined using X-ray photoelectron spectroscopy (XPS) actively suppressed and stabilized the epitaxial thin film of VO2 near room temperature. We investigated whether applying increasing power-mediated ion bombardment for a few minutes affects the oxygen vacancy formation on the VO2/muscovite film’s surface. Consequently, a change in KPFM and 4 orders of magnitude change in resistance of VO2 thin film have been observed. This report reveals the fundamental understanding of controlling the MIT in epitaxial VO2 thin film via facile and clean phase transition engineering techniques for advanced flexible electronic devices.

Thermally processed phase change behavior on the stoichiometric efficacy of quaternary Se77.5-X Te20 Sn2.5 AgX (X = 2.5, 5, 7.5) thin films

Thin films of the quaternary metal chalcogenide have recently gained attention due to their improved electrical, optical, thermal, and structural properties. The structural, thermal, morphological, optical, and electrical properties of Ag-modified novel quaternary Se–Te–Sn–Ag thin film systems are investigated in this paper. Temperature-dependent structural, electrical, and thermoelectric properties are given special attention. From Differential Thermal Analysis/Thermogravimetric Analysis (DTA/TGA), the Ag content in this composition induces thermal stability and crystalline phase as well as glass phase transitions. High-temperature X-ray diffraction (HTXRD) patterns were used to investigate the temperature-dependent structural phase transition, grain size, lattice strain, and dislocation density. The morphological observations show that Ag concentration promotes the nucleation and growth processes of nanorod structures in as-deposited thin films. Optical characteristics reveal higher IR transparency in thin films and high refractive indexes in the range of 3.22–3.29. The as-deposited thin films resistivity decreases with increasing temperature and silver content. The Hall measurement corroborates the results obtained from the Seebeck measurements, indicating that the samples are n-type. The phase change switching mechanism of phase change devices is still unclear; there are two possible mechanisms: thermal and electronic models. This work proposes thermally processed phase transition behaviors in structural and electrical studies. The result of the above analyses shows that the quaternary Se–Te–Sn–Ag thin film will be a potential candidate for phase change device applications.

Wideband multimode smart modulator based on phase change materials

Optical components with switchable optical properties have garnered significant attention due to their wide range of potential applications in the fields of optical detection, radiative cooling, and energy conservation, etc. Most modulators focus on modulating a single parameter within a narrow spectral range, which often falls short of meeting the increasing demands of advanced photonic systems. In this study, we introduce a smart modulator capable of wideband modulation across three modes: transmission, absorption, and reflection. This modulation is triggered by the temperature-dependent phase transition of Vanadium dioxide (VO2) and In3SbTe2 (IST). We optimized the optical properties of the smart modulator using a combination of the Rigorous Coupled Wave Analysis method and Genetic Algorithm. As a result, we achieved average transmissivity, absorptivity, and reflectivity values of 0.785, 0.812, and 0.798, respectively, across the spectral range of 2.5 to 15 µm for each corresponding mode. Importantly, the multimode modulation performance remains excellent even at large incident angles. Furthermore, we demonstrate the exceptional performance of the smart modulator in practical applications, taking thermal fuses as an example. This showcases its effectiveness in thermal protection and modulation. The development of such wideband multimode smart modulators holds the potential to expedite the creation of compact, efficient, and multifunctional optical systems.

Phase Transitions in Boron Carbide.

The idealized rhombohedral unit cell of boron carbide is formed by a 12-atom icosahedron and a 3-atom linear chain. Phase transitions are second order and caused by the exchange of B and C sites or by vacancies in the structure. Nevertheless, the impact of such minimal structural changes on the properties can be significant. As the X-ray scattering cross sections of B and C isotopes are very similar, the capability of X-ray fine structure investigation is substantially restricted. Phonon spectroscopy helps close this gap as the frequency and strength of phonons sensitively depend on the bonding force and mass of the vibrating atoms concerned. Phase transitions known to date have been identified due to significant changes of properties: (1) The phase transition near the chemical composition B8C by clear change of the electronic structure; (2) the endothermic temperature-dependent phase transition at 712 K according to the change of specific heat; (3) the high-pressure phase transition at 33.2 GPa by the drastic change of optical appearance from opacity to transparency. These phase transitions affect IR- and Raman-active phonons and other solid-state properties. The phase transitions at B~8C and 712 K mean that a well-defined distorted structure is converted into another one. In the high-pressure phase transition, an apparently well-defined distorted structure changes into a highly ordered one. In all these cases, the distribution of polar C atoms in the icosahedra plays a crucial role.

Intrinsic Atomic-Scale Antiferroelectric VOF3 Nanowire with Ultrahigh-Energy Storage Properties.

Antiferroelectrics with antiparallel dipoles are receiving tremendous attention for their technological importance and fundamental interest. However, intrinsic one-dimensional (1D) materials harboring antiferroelectric ordering have rarely been reported despite the promise of novel paradigms for miniaturized and high-density electronics. Herein, based on first- and second-principles calculations, we demonstrate the VOF3 atomic wire, exfoliated from an experimentally synthesized yet underexplored 1D van der Waals (vdW) bulk, as a new 1D antiferroelectric material. The energetic, thermal, and dynamic stabilities of the nanowire are confirmed theoretically. Moreover, the temperature-dependent phase transitions and double-hysteresis polarization-field loops are computed for the VOF3 nanowire by constructing the second-principles model. According to the hysteresis loops, high energy densities and efficiencies can be obtained simultaneously at room temperature in the VOF3 nanowire under moderate applied fields. Our identified 1D atomic wire not only expands the family of antiferroelectricity but also holds potential for novel high-power energy storage nanodevices.

Printed and Room Temperature Processed Nanoparticulate VO2 Thin Films Toward Memristive Device Applications

Vanadium dioxide (VO2) has received tremendous research interest in recent years for its versatile electronic application possibilities based on its reversible metal-insulator transition (MIT) behavior, which can be triggered by a large set of stimuli, such as current, electric field, or light. VO2 undergoes a phase transition from a semi-insulating monoclinic to metallic rutile phase at a low critical temperature of 68 °C, which is very close to room temperature, and compatible with any inexpensive flexible substrate. However, owing to the existence of various vanadium oxide polymorphs, the synthesis of the pure monoclinic VO2 (M) phase is a challenge. In fact, the difficulty level increases further when it is to be solution-processed. However, synthesis protocol for phase-pure VO2 (M) following wet chemical routes is essential to obtain high throughput, cost-efficient, and substrate-independent fabrication routine for the large volume of devices. In this regard, in the present study, we report a solution-based synthesis of ultra-small VO2 (M) nanoparticles that are phase-pure and the small nanoparticles may easily be used to formulate inkjet printable VO2 nanoparticulate. The printed VO2 (M) films have been found to be homogeneous, crack-free and the memristor device thus fabricated has demonstrated temperature-dependent phase transition and a resistance change of more than three orders of magnitude around 68 °C; on the other hand, retention of the metallic and insulating state has also been demonstrated for 180 minutes.

Re-Annealing-Induced Recovery in 7nm Hf0.5Zr0.5O2 Ferroelectric Film: Phase Transition and Non-Switchable Region Repair

To achieve HfO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> -based ferroelectric (FE) devices with robust reliabilities, the impacts of re-annealing on 7nm FE-Hf <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">0.5</sub> Zr <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">0.5</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (HZO) capacitors are comprehensively studied in this work. Impressively, the re-initialization phenomenon can be clearly observed by re-annealing cycled HZO capacitors. It is found that FE properties (remanent polarization (Pr), coercive electric field (E <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">C</sub> ), polarization switching speed, wakeup/fatigue effect, and symmetry) can be obviously improved after re-annealing. With in-depth discussions, it is considered that temperature-dependent phase transition and non-switchable region repairing could be the dominant mechanisms. Our results indicate that re-annealing could effectively improve FE-HZO performance and shed light on reliability optimizations.