Structural Characterization and Thermoelectric Properties of Br-Doped AgSnm[Sb0.8Bi0.2]Te2+m Systems.

Herein, we report the synthesis, structural and microstructural characterization, and thermoelectric properties of AgSnm[Sb0.8Bi0.2]Te2+m and Br-doped telluride systems. These compounds were prepared by solid-state reaction at high temperature. Powder X-ray diffraction data reveal that these samples exhibit crystal structures related to the NaCl-type lattice. The microstructures and morphologies are investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDS), and high-resolution transmission electron microscopy (HRTEM). Positive values of the Seebeck coefficient (S) indicate that the transport properties are dominated by holes. The S of undoped AgSnm[Sb0.8Bi0.2]Te2+m ranges from +40 to 57 µV·K-1. Br-doped samples with m = 2 show S values of +74 µV·K-1 at RT, and the Seebeck coefficient increases almost linearly with increasing temperature. The total thermal conductivity (κtot) monotonically increases with increasing temperature (10-300 K). The κtot values of undoped AgSnm[Sb0.8Bi0.2]Te2+m are ~1.8 W m-1 K-1 (m = 4) and ~1.0 W m-1 K-1 (m = 2) at 300 K. The electrical conductivity (σ) decreases almost linearly with increasing temperature, indicating metal-like behavior. The ZT value increases as a function of temperature. A maximum ZT value of ~0.07 is achieved at room temperature for the Br-doped phase with m = 4.

Effects of Intermixing in Sb2Te3/Ge1+xTe Multilayers on the Thermoelectric Power Factor.

Over the past few decades, telluride-based chalcogenide multilayers, such as PbSeTe/PbTe, Bi2Te3/Sb2Te3, and Bi2Te3/Bi2Se3, were shown to be promising high-performance thermoelectric films. However, the stability of performance in operating environments, in particular, influenced by intermixing of the sublayers, has been studied rarely. In the present work, the nanostructure, thermal stability, and thermoelectric power factor of Sb2Te3/Ge1+xTe multilayers prepared by pulsed laser deposition are investigated by transmission electron microscopy and Seebeck coefficient/electrical conductivity measurements performed during thermal cycling. Highly textured Sb2Te3 films show p-type semiconducting behavior with superior power factor, while Ge1+xTe films exhibit n-type semiconducting behavior. The elemental mappings indicate that the as-deposited multilayers have well-defined layered structures. Upon heating to 210 °C, these layer structures are unstable against intermixing of sublayers; nanostructural changes occur on initial heating, even though the highest temperature is close to the deposition temperature. Furthermore, the diffusion is more extensive at domain boundaries leading to locally inclined structures there. The Sb2Te3 sublayers gradually dissolve into Ge1+xTe. This dissolution depends markedly on the relative Ge1+xTe film thickness. Rather, full dissolution occurs rapidly at 210 °C when the Ge1+xTe sublayer is substantially thicker than that of Sb2Te3, whereas the dissolution is very limited when the Ge1+xTe sublayer is substantially thinner. The resulting variations of the nanostructure influence the Seebeck coefficient and electrical conductivity and thus the power factor in a systematic manner. Our results shed light on a previously unreported correlation of the power factor with the nanostructural evolution of unstable telluride multilayers.

Compositional Variation in FAPb1-xSnxI3 and Its Impact on the Electronic Structure: A Combined Density Functional Theory and Experimental Study.

Given their comparatively narrow band gap, mixed Pb-Sn iodide perovskites are interesting candidates for bottom cells in all-perovskite tandems or single junction solar cells, and their luminescence around 900 nm offers great potential for near-infrared optoelectronics. Here, we investigate mixed FAPb1-xSnxI3 offering the first accurate determination of the crystal structure over a temperature range from 293 to 100 K. We demonstrate that all compositions exhibit a cubic structure at room temperature and undergo at least two transitions to lower symmetry tetragonal phases upon cooling. Using density functional theory (DFT) calculations based on these structures, we subsequently reveal that the main impact on the band gap bowing is the different energy of the s and p orbital levels derived from Pb and Sn. In addition, this energy mismatch results in strongly composition-dependent luminescence characteristics. Whereas neat and Sn-rich compounds exhibit bright and narrow emission with a clean band gap, Sn-poor compounds intrinsically suffer from increased carrier recombination mediated by in-gap states, as evidenced by the appearance of pronounced low-energy photoluminescence upon cooling. This study is the first to link experimentally determined structures of FAPb1-xSnxI3 with the electronic properties, and we demonstrate that optoelectronic applications based on Pb-Sn iodide compounds should employ Sn-rich compositions.

Lead-Free Aurivillius Phase Bi2LaNb1.5Mn0.5O9: Structure, Ferroelectric, Magnetic, and Magnetodielectric Effects.

Aurivillius phase Bi2LaNb1.5Mn0.5O9, derived from ferroelectric PbBi2Nb2O9 by simultaneous substitution of the A-site and B-site cations, was synthesized using a molten-salt method. Here, we discuss the structure-property relationships in detail. X-ray and neutron diffraction show that Bi2LaNb1.5Mn0.5O9 adopts an A21am orthorhombic crystal structure. Rietveld refinement analysis, supported by Raman spectroscopy, indicates that the Bi3+ ions occupy the bismuth oxide blocks, La3+ ions occupy the perovskite A-site, and Nb5+/Mn3+ ions occupy the perovskite B-site. Ferroelectric ordering takes place at 535 K, which coexists with local ferromagnetic order below 65 K. The cation disorder on the B-site results in relaxor-ferroelectric behavior, and the short-range ferromagnetic order can be attributed to Mn3+/Mn4+ double-exchange. Magnetodielectric coupling measured at 5 K and 100 kHz in a field of 5 T suggests the existence of intrinsic spin-lattice coupling with a magnetodielectric coefficient of 0.20%. These findings will provide significant impetus for further research into potential devices based on the magnetodielectric effect in Aurivillius materials.

Double Perovskite Single-Crystal Photoluminescence Quenching and Resurge: The Role of Cu Doping on its Photophysics and Crystal Structure.

Cs2AgBiBr6 is a potential lead-free double perovskite candidate for optoelectronic applications; however, its large and indirect band gap imposes limitations. Here, single crystals of Cs2AgBiBr6 are doped with Cu2+ cations to increase the absorption range from the visible region up to 0.5 eV in the near-infrared region. Inductively coupled plasma spectroscopy confirms the presence of 1.9% of copper in the Cs2AgBiBr6 structure. Structural and optical changes caused by Cu doping were studied by Raman spectroscopy combined with X-ray diffraction, heat capacity measurements, and low-temperature photoluminescence spectroscopy. Along with the 1.9 eV emission typical of the pristine Cs2AgBiBr6 single crystals, we report a novel low-energy emission at 0.9 eV related to deep defects. In the doped crystals, these peaks are quenched, and a new emission band at 1.3 eV is visible. This new emission band appears only above 120 K, showing that thermal energy is necessary to trigger the copper-related emission.

Polar Structure and Two-Dimensional Heisenberg Antiferromagnetic Properties of Arylamine-Based Manganese Chloride Layered Organic-Inorganic Perovskites.

The breaking of inversion symmetry can enhance the multifunctional properties of layered hybrid organic-inorganic perovskites. However, the mechanisms by which inversion symmetry can be broken are not well-understood. Here, we study a series of MnCl4-based 2D perovskites with arylamine cations, namely, (C6H5CxH2xNH3)2MnCl4 (x = 0, 1, 2, 3), for which the x = 0, 1, and 3 members are reported for the first time. The compounds with x = 1, 2, and 3 adopt polar crystal structures to well above room temperature. We argue that the inversion symmetry breaking in these compounds is related to the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers. We show that the tilting of MnCl6 octahedra is not the primary mechanism involved in inversion symmetry breaking in these materials. All four compounds show 2D Heisenberg antiferromagnetic behavior. A ferromagnetic component develops in each case below the long-range magnetic ordering temperature of ∼42-46 K due to spin canting.

Morphology of Melt-Quenched Lead Telluride Single Crystals.

Metastable single crystals of nonstoichiometric Pb1-xTe are obtained by rapid cooling from the melt. The composition and crystallographic morphology are studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and electron backscatter diffraction. Most single crystals have cubic, pyramidal, or hemispherical shapes with sizes ranging from 50 to 400 µm. All crystals adopt the same face-centered cubic rock salt structure, and the crystal growth direction is ⟨100⟩. The bulk part of the rapidly cooled material solidifies in the form of a Te-rich polycrystalline material in which grains are separated by the PbTe-Te eutectic phase. The stabilization of nonstoichiometric Pb1-xTe provides further scope for the optimization of lead telluride-based thermoelectric materials.

In Situ Modification of a Delafossite-Type PdCoO2 Bulk Single Crystal for Reversible Hydrogen Sorption and Fast Hydrogen Evolution.

The observation of extraordinarily high conductivity in delafossite-type PdCoO2 is of great current interest, and there is some evidence that electrons behave like a fluid when flowing in bulk crystals of PdCoO2. Thus, this material is an ideal platform for the study of the electron transfer processes in heterogeneous reactions. Here, we report the use of bulk single-crystal PdCoO2 as a promising electrocatalyst for hydrogen evolution reactions (HERs). An overpotential of only 31 mV results in a current density of 10 mA cm-2, accompanied by high long-term stability. We have precisely determined that the crystal surface structure is modified after electrochemical activation with the formation of strained Pd nanoclusters in the surface layer. These nanoclusters exhibit reversible hydrogen sorption and desorption, creating more active sites for hydrogen access. The bulk PdCoO2 single crystal with ultrahigh conductivity, which acts as a natural substrate for the Pd nanoclusters, provides a high-speed channel for electron transfer.

Thermoelectric Performance of Single-Phase Tellurium-Reduced Quaternary (PbTe)0.55(PbS)0.1(PbSe)0.35.

Lead chalcogenide quaternary systems have been shown to provide high thermoelectric (TE) efficiency superior to those of binary and ternary lead chalcogenides, arising from both altered electronic band structures and a reduction in lattice thermal conductivity. Here, we have synthesized single-phase samples of the quaternary compound (PbTe)0.55(PbS)0.1(PbSe)0.35 doped with Na and characterized their TE properties. We show that the dopant solubility is limited to 1 at. %. A very low lattice thermal conductivity of ∼0.6 W m-1 K-1 at 850 K is achieved at all dopant concentrations because of phonon scattering from point defects associated with solute atoms with high contrast atomic mass. As a result, a high TE figure of merit of approximately 1.5 is achieved at 823 K in heavily doped samples. Moreover, the figure of merit is greater than 1 over a wide temperature range above 675 K.

Dirac Nodal Arc Semimetal PtSn4 : An Ideal Platform for Understanding Surface Properties and Catalysis for Hydrogen Evolution.

Conductivity, carrier mobility, and a suitable Gibbs free energy are important criteria that determine the performance of catalysts for a hydrogen evolution reaction (HER). However, it is a challenge to combine these factors into a single compound. Herein, we discover a superior electrocatalyst for a HER in the recently identified Dirac nodal arc semimetal PtSn4 . The determined turnover frequency (TOF) for each active site of PtSn4 is 1.54 H2 s-1 at 100 mV. This sets a benchmark for HER catalysis on Pt-based noble metals and earth-abundant metal catalysts. We make use of the robust surface states of PtSn4 as their electrons can be transferred to the adsorbed hydrogen atoms in the catalytic process more efficiently. In addition, PtSn4 displays excellent chemical and electrochemical stabilities after long-term exposure in air and long-time HER stability tests.

A rhombohedral ferroelectric phase in epitaxially strained Hf0.5Zr0.5O2 thin films.

Hafnia-based thin films are a favoured candidate for the integration of robust ferroelectricity at the nanoscale into next-generation memory and logic devices. This is because their ferroelectric polarization becomes more robust as the size is reduced, exposing a type of ferroelectricity whose mechanism still remains to be understood. Thin films with increased crystal quality are therefore needed. We report the epitaxial growth of Hf0.5Zr0.5O2 thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 substrates. The films, which are under epitaxial compressive strain and predominantly (111)-oriented, display large ferroelectric polarization values up to 34 µC cm-2 and do not need wake-up cycling. Structural characterization reveals a rhombohedral phase, different from the commonly reported polar orthorhombic phase. This finding, in conjunction with density functional theory calculations, allows us to propose a compelling model for the formation of the ferroelectric phase. In addition, these results point towards thin films of simple oxides as a vastly unexplored class of nanoscale ferroelectrics.

Inducing ferromagnetism and Kondo effect in platinum by paramagnetic ionic gating.

Electrically controllable magnetism, which requires the field-effect manipulation of both charge and spin degrees of freedom, has attracted growing interest since the emergence of spintronics. We report the reversible electrical switching of ferromagnetic (FM) states in platinum (Pt) thin films by introducing paramagnetic ionic liquid (PIL) as the gating media. The paramagnetic ionic gating controls the movement of ions with magnetic moments, which induces itinerant ferromagnetism on the surface of Pt films, with large coercivity and perpendicular anisotropy mimicking the ideal two-dimensional Ising-type FM state. The electrical transport of the induced FM state shows Kondo effect at low temperature, suggesting spatially separated coexistence of Kondo scattering beneath the FM interface. The tunable FM state indicates that paramagnetic ionic gating could serve as a versatile method to induce rich transport phenomena combining field effect and magnetism at PIL-gated interfaces.

Micropatterned 2D Hybrid Perovskite Thin Films with Enhanced Photoluminescence Lifetimes.

The application of luminescent materials in display screens and devices requires micropatterned structures. In this work, we have successfully printed microstructures of a two-dimensional (2D), orange-colored organic/inorganic hybrid perovskite ((C6H5CH2NH3)2PbI4) using two different soft lithography techniques. Notably, both techniques yield microstructures with very high aspect ratios in the range of 1.5-1.8. X-ray diffraction reveals a strong preferential orientation of the crystallites along the c-axis in both patterned structures, when compared to nonpatterned, drop-casted thin films. Furthermore, (time-resolved) photoluminescence (PL) measurements reveal that the optical properties of (C6H5CH2NH3)2PbI4 are conserved upon patterning. We find that the larger grain sizes of the patterned films with respect to the nonpatterned film give rise to an enhanced PL lifetime. Thus, our results demonstrate easy and cost-effective ways to manufacture patterns of 2D organic/inorganic hybrid perovskites, while even improving their optical properties. This demonstrates the potential use of color-tunable 2D hybrids in optoelectronic devices.

A cubic room temperature polymorph of thermoelectric TAGS-85.

The alloy (GeTe)85(AgSbTe2)15, commonly known as TAGS-85, is one of the best performing p-type thermoelectric materials in the temperature range 200-500 °C. In all reports thus far, TAGS-85 adopts a rhombohedral crystal structure at room temperature and undergoes a reversible transition to a cubic phase in the middle of the operating temperature range. Here, we report on a novel, metrically cubic polymorph of TAGS-85 that can be obtained at room temperature using a particular cooling protocol during initial synthesis. This polymorph transforms irreversibly on initial heating to a 21-layer trigonal structure containing ordered cation vacancy layers, driven by the spontaneous precipitation of argyrodite-type Ag8GeTe6. We show that the precipitation of Ag8GeTe6 is detrimental to the thermoelectric performance of TAGS-85 due to an increase in the vacancy concentration, which makes the samples more metallic in character and significantly reduces the Seebeck coefficient. The precipitation of Ag8GeTe6 can be suppressed by careful control of the synthesis conditions.

Phase Transitions of Thermoelectric TAGS-85.

The alloys (GeTe)x(AgSbTe2)100-x, commonly known as TAGS-x, are among the best performing p-type thermoelectric materials for the composition range 80 ≤ x ≤ 90 and in the temperature range 200-500 °C. They adopt a rhombohedrally distorted rocksalt structure at room temperature and are reported to undergo a reversible phase transition to a cubic structure at ∼250 °C. However, we show that, for the optimal x = 85 composition (TAGS-85), both the structural and thermoelectric properties are highly sensitive to the initial synthesis method employed. Single-phase rhombohedral samples exhibit the best thermoelectric properties but can only be obtained after an annealing step at 600 °C during initial cooling from the melt. Under faster cooling conditions, the samples obtained are inhomogeneous, containing multiple rhombohedral phases with a range of lattice parameters and exhibiting inferior thermoelectric properties. We also find that when the room-temperature rhombohedral phase is heated, an intermediate trigonal structure containing ordered cation vacancy layers is formed at ∼200 °C, driven by the spontaneous precipitation of argyrodite-type Ag8GeTe6 which alters the stoichiometry of the TAGS-85 matrix. The rhombohedral and trigonal phases of TAGS-85 coexist up to 380 °C, above which a single cubic phase is obtained and the Ag8GeTe6 precipitates redissolve into the matrix. On subsequent cooling a mixture of rhombohedral, trigonal, and Ag8GeTe6 phases is again obtained. Initially single-phase samples exhibit thermoelectric power factors of up to 0.0035 W m-1 K-2 at 500 °C, a value that is maintained on subsequent thermal cycling and which represents the highest power factor yet reported for undoped TAGS-85. Therefore, control over the structural homogeneity of TAGS-85 as demonstrated here is essential in order to optimize the thermoelectric performance.

The Role of Connectivity on Electronic Properties of Lead Iodide Perovskite-Derived Compounds.

We use a layered solution crystal growth method to synthesize high-quality single crystals of two different benzylammonium lead iodide perovskite-like organic/inorganic hybrids. The well-known (C6H5CH2NH3)2PbI4 phase is obtained in the form of bright orange platelets, with a structure comprised of single ⟨100⟩-terminated sheets of corner-sharing PbI6 octahedra separated by bilayers of the organic cations. The presence of water during synthesis leads to formation of a novel minority phase that crystallizes in the form of nearly transparent, light yellow bar-shaped crystals. This phase adopts the monoclinic space group P21/n and incorporates water molecules, with structural formula (C6H5CH2NH3)4Pb5I14·2H2O. The crystal structure consists of ribbons of edge-sharing PbI6 octahedra separated by the organic cations. Density functional theory calculations including spin-orbit coupling show that these edge-sharing PbI6 octahedra cause the band gap to increase with respect to corner-sharing PbI6 octahedra in (C6H5CH2NH3)2PbI4. To gain systematic insight, we model the effect of the connectivity of PbI6 octahedra on the band gap in idealized lead iodide perovskite-derived compounds. We find that increasing the connectivity from corner-, via edge-, to face-sharing causes a significant increase in the band gap. This provides a new mechanism to tailor the optical properties in organic/inorganic hybrid compounds.

Vacancies in functional materials for clean energy storage and harvesting: the perfect imperfection.

Vacancies exist throughout nature and determine the physical properties of materials. By manipulating the density and distribution of vacancies, it is possible to influence their physical properties such as band-gap, conductivity, magnetism, etc. This can generate exciting applications in the fields of water treatment, energy storage, and physical devices such as resistance-change memories. In this review, we focus on recent progress in vacancy engineering for the design of materials for energy harvesting applications. A brief discription of the concept of vacancies, the way to create and control them, as well as their fundamental properties, is first provided. Then, emphasis is placed on the strategies used to tailor vacancies for metal-insulator transitions, electronic structures, and introducing magnetism in non-magnetic materials. Finally, we present representative applications of different structures with vacancies as active electrode materials of lithium or sodium ion batteries, catalysts for water splitting, and hydrogen evolution.

Thermoelectric Performance of Na-Doped GeSe.

Recently, hole-doped GeSe materials have been predicted to exhibit extraordinary thermoelectric performance owing largely to extremely low thermal conductivity. However, experimental research on the thermoelectric properties of GeSe has received less attention. Here, we have synthesized polycrystalline Na-doped GeSe compounds, characterized their crystal structure, and measured their thermoelectric properties. The Seebeck coefficient decreases with increasing Na content up to x = 0.01 due to an increase in the hole carrier concentration and remains roughly constant at higher concentrations of Na, consistent with the electrical resistivity variation. However, the electrical resistivity is large for all samples, leading to low power factors. Powder X-ray diffraction and scanning electron microscopy/energy-dispersive spectrometry results show the presence of a ternary impurity phase within the GeSe matrix for all doped samples, which suggests that the optimal carrier concentration cannot be reached by doping with Na. Nevertheless, the lattice thermal conductivity and carrier mobility of GeSe is similar to those of polycrystalline samples of the leading thermoelectric material SnSe, leading to quality factors of comparable magnitude. This implies that GeSe shows promise as a thermoelectric material if a more suitable dopant can be found.

Polar Nature of (CH3NH3)3Bi2I9 Perovskite-Like Hybrids.

High-quality single crystals of perovskite-like (CH3NH3)3Bi2I9 hybrids have been synthesized, using a layered-solution crystal-growth technique. The large dielectric constant is strongly affected by the polar ordering of its constituents. Progressive dipolar ordering of the methylammonium cation upon cooling below 300 K gradually converts the hexagonal structure (space group P63/mmc) into a monoclinic phase (C2/c) at 160 K. A well-pronounced, ferrielectric phase transition at 143 K is governed by in-plane ordering of the bismuth lone pair that breaks inversion symmetry and results in a polar phase (space group P21). The dielectric constant is markedly higher in the C2/c phase above this transition. Here, the bismuth lone pair is disordered in-plane, allowing the polarizability to be substantially enhanced. Density functional theory calculations estimate a large ferroelectric polarization of 7.94 µC/cm2 along the polar axis in the P21 phase. The calculated polarization has almost equal contributions of the methylammonium and Bi3+ lone pair, which are fairly decoupled.