Temperature-driven Transition Research Articles

Revealing the temperature-driven Lifshitz transition in p-type Mg3Sb2-based thermoelectric materials

The manipulation of native atomic defects and their thermal excitations plays vital roles in the thermoelectric performance of Mg3Sb2-based materials. While native defects manipulation has been intensively studied in p-type Mg3Sb2, there exists interesting unsolved issue regarding the abnormal semiconducting electrical behavior in most of samples. In this work, high quality Mg3Sb2 and Mg3Bi2 (00l) films are fabricated by molecular beam epitaxy technique, while variable temperature angle-resolved photoemission spectroscopy and scanning tunneling spectroscopy measurements are utilized for resolving the aforementioned issue. The thermal excitation of Mg interstitials (the electron donor) results in an obvious downshift of valence bands with rising temperature in both the p-type Mg3Sb2 and Mg3Bi2. Meanwhile, the interesting temperature-driven Lifshitz transition is discovered in the p-type Mg3Sb2, as indicated by the change of Fermi surface topology. Above the Lifshitz transition temperature, the Fermi level of p-type Mg3Sb2 will enter the bandgap, which leads to the abnormal semiconducting electrical behavior. This work discloses the excitation of native defects and temperature-driven Lifshitz transition, which are the main causes for the anomalies in electrical transport of p-type Mg3Sb2-based materials, and also provides valuable insights for further improving their thermoelectric performance.

Phonon mode and dielectric function dynamics of Bi0.5Na0.5TiO3-xSm2Ti2O7 ceramics during the phase transitions discovered by Raman scattering and spectroscopic ellipsometry

Recently, Bi0.5Na0.5TiO3-based ceramics have drawn widespread attention due to their excellent energy storage properties. Here, a comprehensive analysis of the composition- and temperature-driven transition processes in (1 − x)Bi0.5Na0.5TiO3-xSm2Ti2O7 (BNST-x) polycrystals have been presented using Raman scattering and spectroscopic ellipsometry. With increasing Sm2Ti2O7 content, BNST-x ceramic gradually becomes disordered and belongs to the superparaelectric state at x = 0.12 near room temperature. Moreover, the thermal evolution of the lattice kinetic behaviors shows two crucial temperatures: the depolarization temperature Td and the temperature at the maximum dielectric permittivity Tm, which suggest the transitions from nonergodic relaxor ferroelectric—ergodic relaxor (ER) ferroelectric and ER ferroelectric—superparaelectric, respectively. It is noteworthy that the series of changes is closely related to the ordering degree of the B-site ion affected by the doping and the temperature. This work gives an insight into the connection among the phonon behavior, electronic transition, and lattice structure of BNST-x ceramics, which can further understand the phase transition mechanisms under the doping and thermal field.

Topological Hall effect and the transition of the anomalous Hall effect mechanism in hexagonal alloys Mn3.1− xFexGe0.9 (x = 1.6, 1.8, 2.0)

Hexagonal Mn3Ge, with both kagome lattice and triangular antiferromagnetism, has gained significant attention due to its large anomalous Hall effect (AHE), resulting from the non-vanishing Berry phase. In this study, we present the magnetic and anomalous transport properties of a series hexagonal D019 type Fe-doped Mn3Ge alloys with the composition of Mn3.1−xFexGe0.9 (x = 1.6, 1.8, 2.0). The ferromagnetic interactions gradually increase with increasing Fe content. The longitudinal resistivity of all alloys exhibits a typical metallic behavior, increasing with temperature from 5 to 390 K. The residual resistivity decreases from 120.4 to 67.8 μΩ·cm as x increases from 1.6 to 2.0. A temperature-driven Lifshitz transition and a spin reorientation have been observed in the x = 1.6 alloy. Topological Hall effect accompanied by the spin reorientation is demonstrated. The maximum value of the topological Hall resistivity ρxyT is approximately 0.16 μΩ·cm. The relationship of ρxyA∝ ρxx in x = 1.6 alloy suggests that the extrinsic skew scattering predominantly contributes to the AHE mechanism. In the case of x = 1.8 and 2.0, both intrinsic and extrinsic factors contribute to the AHE. The anomalous Hall conductivity of our polycrystalline samples at room temperature is comparable to that of single crystal Mn3Ge, which is advantageous for practical applications. This study reveals the effectiveness of chemical engineering in tailoring nontrivial spin textures and the AHE.

Creation of surface frustrated Lewis pairs on high-entropy spinel nanocrystals that boosts catalytic transfer hydrogenation reaction

Creating frustrated Lewis pairs (FLPs) on stable high-entropy oxides (HEOs) is a new challenge, and also an uncultivated field in catalysis. Herein, holey layered HEO spinel nanocrystals with rich FLPs were synthesized via a temperature-driven topological transition. The FLPs on the surface of HEO spinel nanocrystals are created by oxygen vacancies (Lewis acid sites) and proximal surface hydroxyls or surface lattice oxygen (Lewis base sites). Rich FLPs furnish HEO nanocrystals a superior activity towards the catalytic transfer hydrogenation reaction of biomass-derived carbonyl compounds at mild conditions. The active regions in between FLPs provide a strong driving force for dissociating alcohols and activating carbonyl groups of substrates, as evidenced by the attenuated total reflectance-infrared spectroscopy (ATR-IR) analysis, which enhances the catalytic activity. This work develops a new kind of hydrogenation catalysts and provides a perspective for creating solid FLPs.

Temperature-driven transition into vortex clusters in low-kappa intertype superconductors

Temperature-driven transition into vortex clusters in low-kappa intertype superconductors

Signatures of Temperature-Driven Lifshitz Transition in Semimetal Hafnium Ditelluride

Temperature-driven change of Fermi surface has been attracting attention recently as it is fundamental and essential to understand a metallic system. We report the magnetotransport anomalies in the semimetal HfTe2 single crystals. The magnetoresistance behavior at high temperatures obeys Kohler’s rule which can lead to the field-induced resistivity upturn behavior as observed. When the temperature is decreased to around 30 K, Kohler’s rule becomes inapplicable, indicating the change of the Fermi surface in HfTe2. The Hall analyses and extended Kohler’s plot reveal abrupt change of carrier densities and mobilities near 30 K. These results suggest that the chemical potential may shift as the temperature increases and the shift causes an electron pocket to vanish. Our work of the temperature-driven Lifshitz transition in HfTe2 is relevant to understanding of the transport anomalies and exotic physical properties in transition-metal dichalcogenides.

Partial Order-Disorder Transition Driving Closure of Band Gap: Example of Thermoelectric Clathrates.

In the quest for efficient thermoelectrics, semiconducting behavior is a targeted property. Yet, this is often difficult to achieve due to the complex interplay between electronic structure, temperature, and disorder. We find this to be the case for the thermoelectric clathrate Ba_{8}Al_{16}Si_{30}: Although this material exhibits a band gap in its ground state, a temperature-driven partial order-disorder transition leads to its effective closing. This finding is enabled by a novel approach to calculate the temperature-dependent effective band structure of alloys. Our method fully accounts for the effects of short-range order and can be applied to complex alloys with many atoms in the primitive cell, without relying on effective medium approximations.

Toward a quasiphase transition in the single-file chain of water molecules: Simple lattice model.

Recently, Ma et al. [Phys. Rev. Lett. 118, 027402 (2017)] have suggested that water molecules encapsulated in (6,5) single-wall carbon nanotube experience a temperature-induced quasiphase transition around 150K interpreted as changes in the water dipoles orientation. We discuss further this temperature-driven quasiphase transition performing quantum chemical calculations and molecular dynamics simulations and, most importantly, suggesting a simple lattice model to reproduce the properties of the one-dimensional confined finite arrays of water molecules. The lattice model takes into account not only the short-range and long-range interactions but also the rotations in a narrow tube, and both ingredients provide an explanation for a temperature-driven orientational ordering of the water molecules, which persists within a relatively wide temperature range.

Chiral-fluctuations mediated helical to paramagnetic phase transition and scaling study in β-Mn type Co8Zn8Mn4 chiral magnet

We report detailed magnetization and ac susceptibility studies on a chiral cubic β-Mn type Co8Zn8Mn4 alloy near the onset of magnetic ordering temperature. The Co8Zn8Mn4 alloy undergoes a complex series of temperature-driven transition from paramagnetic (PM) to helimagnetic phase through an intermediate inhomogeneous chiral fluctuations phase. The Gaussian shaped peak in ( = 0 Oe) at 343.19 K is analogous to that of the zero-field transition to long-period modulated helical state. Moreover, a pronounced field-induced anomaly in (T, 500 Oe) rises quickly with field above like a fingerprint, evident of a field-induced crossover into a precursor region. The in-field critical behavior characterizing a ferromagnetic-PM phase transition in the vicinity of ordering temperature confirms that Co8Zn8Mn4 chiral magnet belongs to the 3D-Heisenberg universality class. The existence of precursor region and the sizable expansion in the transition temperature, can be explained by the Landau equation.

Unreliability of two-band model analysis of magnetoresistivities in unveiling temperature-driven Lifshitz transition

Recently, anomalies in the temperature dependences of the carrier density and/or mobility derived from analysis of the magnetoresistivities using the conventional two-band model have been used to unveil intriguing temperature-induced Lifshitz transitions in various materials. For instance, two temperature-driven Lifshitz transitions were inferred to exist in the Dirac nodal-line semimetal ZrSiSe, based on two-band model analysis of the Hall magnetoconductivities where the second band exhibits a change in the carrier type from holes to electrons when the temperature decreases below $T=106\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and a dip is observed in the mobility vs temperature curve at $T=80\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. Here, we revisit the experiments and two-band model analysis on ZrSiSe. We show that the anomalies in the second band may be spurious because the first band dominates the Hall magnetoconductivities at $T>80\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, making the carrier type and mobility obtained for the second band from the two-band model analysis unreliable. That is, care must be taken in interpreting these anomalies as evidence for temperature-driven Lifshitz transitions. Our skepticism on the existence of such phase transitions in ZrSiSe is further supported by the validation of Kohler's rule for magnetoresistances for $T\ensuremath{\le}180\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. In this paper, we showcase potential issues in interpreting anomalies in the temperature dependence of the carrier density and mobility derived from the analysis of magnetoconductivities or magnetoresistivities using the conventional two-band model.

Control of structural and magnetic transition in GeNCr3 by doping manganese ions

As an archetypal antiperovskite nitride compound, GeNCr3 undergoes a temperature-driven first-order antiferromagnetic-paramagnetic transition at approximately 418 K, accompanied with a structural phase transition from space group P-421m to I4/mcm. In this paper, we show that the critical temperature of GeNCr3 can be tuned from 418 to 240 K by doping manganese ions. Simultaneously, the evolution of the magnetic transition is consistent with the structural transition. Using temperature-dependent X-ray diffraction and X-ray photoelectron spectroscopy, in combination with first-principles calculations, we demonstrate that doping manganese ions tend to occupy the equatorial plane of the nitrogen octahedron.

Clamping effect on temperature-induced valence transition in epitaxial EuPd2Si2 thin films grown on MgO(001)

Bulk ${\mathrm{EuPd}}_{2}{\mathrm{Si}}_{2}$ show a temperature-driven valence transition of europium from $\ensuremath{\sim}+2$ above 200 K to $\ensuremath{\sim}+3$ below 100 K, which is correlated with a shrinking by approximately 2% of the tetragonal crystal lattice along the two $a$-axes. Due to this interconnection between lattice and electronic degrees of freedom the influence of strain in epitaxial thin films is particularly interesting. Ambient x-ray diffraction (XRD) confirms an epitaxial relationship of tetragonal ${\mathrm{EuPd}}_{2}{\mathrm{Si}}_{2}$ on MgO(001) with an out-of plane $c$-axis orientation for the thin film, whereby the $a$-axes of both lattices align. XRD at low temperatures reveals a strong coupling of the thin film lattice to the substrate, showing no abrupt compression over the temperature range from 300 to 10 K. Hard x-ray photoelectron spectroscopy at 300 and 20 K reveals a temperature-independent valence of $+2.0$ for Eu. The evolving biaxial tensile strain upon cooling is suggested to suppress the valence transition. Instead temperature-dependent transport measurements of the resistivity and the Hall effect in a magnetic field up to 5 T point to a film thickness independent phase transition at 16 to 20 K, indicating magnetic ordering.

Hole doping in a negative charge transfer insulator

RENiO3 is a negative charge transfer energy system and exhibits a temperature-driven metal-insulator transition (MIT), which is also accompanied by a bond disproportionation (BD) transition. In order to explore how hole doping affects the BD transition, we have investigated the electronic structure of single-crystalline thin films of Nd1−xCaxNiO3 by synchrotron based experiments and ab-initio calculations. Here we show that for a small value of x, the doped holes are localized on one or more Ni sites around the dopant Ca2+ ions, while the BD state for the rest of the lattice remains intact. The effective charge transfer energy (Δ) increases with Ca concentration and the formation of BD phase is not favored above a critical x, suppressing the insulating phase. Our present study firmly demonstrates that the appearance of BD mode is essential for the MIT of the RENiO3 series.

Nanoscale Femtosecond Dynamics of Mott Insulator (Ca0.99Sr0.01)2RuO4

Ca2RuO4 is a transition-metal oxide that exhibits a Mott insulator-metal transition (IMT) concurrent with a symmetry-preserving Jahn-Teller distortion (JT) at 350 K. The coincidence of these two transitions demonstrates a high level of coupling between the electronic and structural degrees of freedom in Ca2RuO4. Using spectroscopic measurements with nanoscale spatial resolution, we interrogate the interplay of the JT and IMT through the temperature-driven transition. Then, we introduce photoexcitation with subpicosecond temporal resolution to explore the coupling of the JT and IMT via electron-hole injection under ambient conditions. Through the temperature-driven IMT, we observe phase coexistence in the form of a stripe phase existing at the domain wall between macroscopic insulating and metallic domains. Through ultrafast carrier injection, we observe the formation of midgap states via enhanced optical absorption. We propose that these midgap states become trapped by lattice polarons originating from the local perturbation of the JT.

Temperature-driven order-disorder structural transition in the oxygen sub-lattice and the complex superstructure of the high-temperature polymorph of CaSrZn2Ga2O7.

Structural order-disorder plays a decisive role in the physical properties of materials, such as magnetism, second-order harmonic generation, and ionic conductivity, and it is thus widely utilized to manipulate the crystal structure and understand structure-property correlations. Herein, we report the structural polymorphism, complex crystal structure and temperature-driven irreversible order-disorder phase transition of the polar oxides (Sr1-xCax)SrZn2Ga2O7. The low-temperature (LT) structure crystallizes in Pna21 with partial Zn/Ga ordering. Upon heating, (Sr1-xCax)SrZn2Ga2O7 undergoes an irreversible phase transition from orthorhombic Pna21 to hexagonal P63. Interestingly, the high-temperature (HT) P63 structure possesses an unexpected 3/2-fold superstructure rather than a substructure of the low-temperature (LT) Pna21 structure, which is a rare structural phenomenon in solid-state chemistry. This new HT superstructure is the most complex one in this series of oxides with 21 crystallographically independent sites determined accurately by a combination of the maximum entropy method and Rietveld refinement against high-resolution neutron powder diffraction data. In terms of the mechanism, this is a temperature-driven order-to-disorder transition in the oxygen sublattice. A careful structural analysis revealed that the oxygen disordering mainly occurs in the [SrO3] layers of the HT structure and it can be understood as respective clockwise and anticlockwise rotations of distinct GaO4-tetrahedra along the c-axis. Alternating current electrochemical impedance spectroscopic analysis revealed that the oxygen disordering in the HT structure is incapable of giving rise to oxide ionic conductivity but does lead to increased electronic conduction compared to the LT structure. The optical properties of the CaSrZn2Ga2O7 and Sr2Zn2Ga2O7 representatives are also investigated in-depth via diffuse reflectance spectroscopy and theoretic calculations.

Emergence of large thermal noise close to a temperature-driven metal-insulator transition

We report that close to a Mott transition there is an emergence of large thermal noise (${S}_{\mathrm{th}}$) which occurs concomitantly with large correlated flicker noise ($\frac{1}{f}$ noise) with significant non-Gaussian content. This was observed in films of ${\text{NdNiO}}_{3}$ (thickness 15 nm) grown on crystalline ${\text{SrTiO}}_{3}$ substrates with different crystallographic orientations that show a hysteretic transition from a high temperature metallic phase to a low temperature insulating phase in the temperature range 160 to 211 K depending on the substrate orientation and the heating and cooling cycle. The thermal noise, which is distinct from the flicker noise, deviates from the canonical Johnson-Nyquist value of $4{k}_{B}TR$ as measured through the ratio $\ensuremath{\zeta}(T)(\ensuremath{\equiv}\frac{{S}_{\mathrm{th}}(T)}{4{k}_{B}TR})$. The ratio $\ensuremath{\zeta}$ reaches a maximum value of ${\ensuremath{\zeta}}_{M}$ at a temperature ${T}^{*}$ that is close to but distinct from the metal-insulator transition (MIT) temperature ${T}_{\mathrm{MI}}$. In all the films near ${T}^{*}$, the scaled thermal noise maxima ${\ensuremath{\zeta}}_{M}\ensuremath{\gg}1$. The films were found to be largely strain relaxed with residual in-plane and out-of-plane strain as measured by x-ray reciprocal space mapping. It has been observed that the ratio $\frac{{T}^{*}}{{T}_{\mathrm{MI}}}$ as well as ${\ensuremath{\zeta}}_{M}$ have a close dependence on the in-plane-strain in the film. The enhanced thermal noise that occurs along with large correlated flicker noise both arise from slow kinetics of relaxation as established from temperature dependence of the correlation time ($\ensuremath{\tau}$) that gets significantly larger in the temperature range around ${T}^{*}$, reaching a maxima at $T={T}^{*}$. It has been proposed that the existence of large noise (both thermal and flicker noise) owes its origin to electronic phase separation (EPS) that exists near the MIT. A physical model has been suggested that EPS near MIT temperature can give rise to a sparse phase of nanometric small pockets of metallic phases (nanopuddles) that are surrounded by and embedded within the minority insulating phase. The nanopuddles act as a source of charge fluctuations and are coupled weakly to the majority metallic phase by tunneling through the layer of the minority insulating phase. Such isolated metallic nanopuddles can be Coulomb charged if the charging energy ${E}_{C}\ensuremath{\ge}{k}_{B}T$ and can have slow relaxation of fluctuations acting as a source of large noise. It has been argued that the size distribution of the nanopuddles, their average size $\ensuremath{\langle}d\ensuremath{\rangle}$, as well as the temperature dependence of their number density ${N}_{d}$ can determine the temperature ${T}^{*}$.

Stimuli‐Driven Insulator–Conductor Transition in a Flexible Polymer Composite Enabled by Biphasic Liquid Metal

Metal-polymer composites (MPCs) with combined properties of metals and polymers have achieved much industrial success. However, metals in MPCs are thought to be ordinary and invariable electrically conductive fillers in supportive polymers to show limited use in modern technologies. This work that is disclosed here, for the first time, introduces stimuli-driven transition from biphasic to monophasic state of liquid metal into polymer science to form dynamic soft conductors from the binary metal-polymer composites. The binary metal that exhibits temperature-driven reversible transition between solid and liquid states via a biphasic state is fabricated. A conducting stretchable polymer composite is developed using the judiciously chosen biphasic binary metal that undergoes conductor to insulator transition upon stretching. Insulating stretched films become conducting upon heating. A "tube" model elegantly describes such distinctive deformation/temperature-dependent behaviors. Moreover, the conducting polymer composite shows decrease in its resistance upon increasing the sample temperature. The resistance can be tuned from 1 to 108 Ω depending on the state of binary metal in the phase diagram. This work would build the intimate and interesting connection between metal phases and polymer science toward next-generation soft conductors and beyond.

Thickness dependence of electronic structures in VO2 ultrathin films: Suppression of the cooperative Mott-Peierls transition

Through ${in~situ}$ photoemission spectroscopy, we investigated the change in the electronic and crystal structures of dimensionality-controlled VO$_2$ films coherently grown on TiO$_2$(001) substrates. In the nanostructured films, the balance between the instabilities of a bandlike Peierls transition and a Mott transition is controlled as a function of thickness. The characteristic spectral change associated with temperature-driven metal-insulator transition in VO$_2$ thick films holds down to 1.5 nm (roughly corresponding to five V atoms along the [001] direction), whereas VO$_2$ films of less than 1.0 nm exhibit insulating nature without V-V dimerization. These results suggest that the delicate balance between a Mott instability and a bandlike Peierls instability is modulated at a scale of a few nanometers by the dimensional crossover effects and confinement effects, which consequently induce the complicated electronic phase diagram of ultrathin VO$_2$ films.

Extracellular ionic fluxes suggest the basis for cellular life at the 1/f ridge of extended criticality

The criticality hypothesis states that a system may be poised in a critical state at the boundary between different types of dynamics. Previous studies have suggested that criticality has been evolutionarily selected, and examples have been found in cortical cell cultures and in the human nervous system. However, no one has yet reported a single- or multi-cell ensemble that was investigated ex vivo and found to be in the critical state. Here, the precise 1/f noise was found for pollen tube cells of optimum growth and for the physiological (“healthy”) state of blood cells. We show that the multi-scale processes that arise from the so-called critical phenomena can be a fundamental property of a living cell. Our results reveal that cell life is conducted at the border between order and disorder, and that the dynamics themselves drive a system towards a critical state. Moreover, a temperature-driven re-entrant state transition, manifest in the form of a Lorentz resonance, was found in the fluctuation amplitude of the extracellular ionic fluxes for the ensemble of elongating pollen tubes of Nicotiana tabacum L. or Hyacintus orientalis L. Since this system is fine-tuned for rapid expansion to reach the ovule at a critical temperature which results in fertilisation, the core nature of criticality (long-range coherence) offers an explanation for its potential in cell growth. We suggest that the autonomous organisation of expansive growth is accomplished by self-organised criticality, which is an orchestrated instability that occurs in an evolving cell.Graphic abstract

Temperature-Induced Lifshitz Transition and Charge Density Wave in InTe1−δ Thermoelectric Materials

We investigated the thermoelectric transport properties of InTe1−δ (δ = 0.0, 0.1, and 0.2) compounds and interpreted their unusual behavior in terms of electronic and phonon band dispersions. The temperature-dependent electrical resistivity ρ(T) and Seebeck coefficient S(T) exhibit the charge density wave (CDW) transition near 87 K for InTe1−δ (δ = 0.1 and 0.2) compounds. The CDW transitions on the Te-deficient compounds can be supported by the Fermi surface nesting along the M–X line in InTe1−δ (δ = 0.25). The temperature-dependent Hall carrier density nH shows unusual behavior in that the nH(T) is increased by the Fermi surface reconstruction. From the temperature-dependent X-ray diffraction measurements, we found the superstructural lattice distortion at low temperatures (T ≤ 175 K), implying the intrinsic lattice instability. During the structural phase transition from tetragonal (I4/mcm) or orthorhombic (Ibam) to superstructural orthorhombic (Pbca) in InTe and Te-deficient InTe0.8, we observed a negative thermal expansion coefficient, giving rise to the large variation of negative Grüneisen parameters. Owing to the significant change in thermal expansion coefficients and Grüneisen parameters with respect to temperature, the energy band structure, in other words, Fermi surface, depends on the temperature, indicating a temperature-driven Lifshitz transition in InTe1−δ compounds. The Te-deficiency induces significant anharmonicity of phonons from the numerous flat bands and negative phonon branches. The coexistences of temperature-driven Lifshitz transition, CDW formation, and lattice anharmonicity with high negative Grüneisen parameter in InTe1−δ are very exceptional cases and suggest the profound physical properties in the compounds.