Design and Piezoelectric Energy Harvesting Properties of a Ferroelectric Cyclophosphazene Salt.

Cyclophosphazenes offer a robust and easily modifiable platform for a diverse range of functional systems that have found applications in a wide variety of areas. Herein, for the first time, it reports an organophosphazene-based supramolecular ferroelectric [(PhCH2 NH)6 P3 N3 Me]I, [PMe]I. The compound crystallizes in the polar space group Pc and its thin-film sample exhibits remnant polarization of 5 µC cm-2 . Vector piezoresponse force microscopy (PFM) measurements indicated the presence of multiaxial polarization. Subsequently, flexible composites of [PMe]I are fabricated for piezoelectric energy harvesting applications using thermoplastic polyurethane (TPU) as the matrix. The highest open-circuit voltages of 13.7 V and the maximum power density of 34.60 µW cm-2 are recorded for the poled 20 wt.% [PMe]I/TPU device. To understand the molecular origins of the high performance of [PMe]I-based mechanical energy harvesting devices, piezoelectric charge tensor values are obtained from DFT calculations of the single crystal structure. These indicate that the mechanical stress-induced distortions in the [PMe]I crystals are facilitated by the high flexibility of the layered supramolecular assembly.

Mitigating Dendrite Formation on a Zn Electrode in Aqueous Zinc Chloride by the Competitive Surface Chemistry of an Imidazole Additive.

Electrochemical energy storage systems are critical in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technology, since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a reduction potential of -0.76 V vs SHE) has a significantly higher theoretical volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via experimental (kinetics and imaging) and theoretical density functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concentration of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addition of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-symmetric cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomography reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn symmetric cells. It is observed that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the production of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calculations conform well with the stated experimental observations.

Ultrafine Mix-Phase SnO-SnO2 Nanoparticles Anchored on Reduced Graphene Oxide Boost Reversible Li-Ion Storage Capacity beyond Theoretical Limit.

Tin-based materials with high specific capacity have been studied as high-performance anodes for Li-ion storage devices. Herein, a mix-phase structure of SnO-SnO2@rGO (rGO = reduced graphene oxide) was designed and prepared via a simple chemical method, which leads to the growth of tiny nanoparticles of a mixture of two different tin oxide phases on the crumbled graphene nanosheets. The three-dimensional structure of graphene forms the conductive framework. The as-prepared mix phase SnO-SnO2@rGO exhibits a large Brunauer-Emmett-Teller surface area of 255 m2 g-1 and an excellent ionic diffusion rate. When the resulting mix-phase material was examined for Li-ion battery anode application, the SnO-SnO2@rGO was noted to deliver an ultrahigh reversible capacity of 2604 mA h g-1 at a current density of 0.1 A g-1. It also exhibited superior rate capabilities and more than 82% retention of capacity after 150 charge-discharge cycles at 0.1 A g-1, lasting until 500 cycles at 1 A g-1 with very good retention of the initial capacity. Owing to the uniform defects on the rGO matrix, the formation of LiOH upon lithiation has been suggested to be the primary cause of this very high reversible capacity, which is beyond the theoretical limit. A Li-ion full cell was assembled using LiNi0.5Mn0.3Co0.2O2 (NMC-532) as a high-capacity cathodic counterpart, which showed a very high reversible capacity of 570 mA h g-1 (based on the anode weight) at an applied current density of 0.1 A g-1 with more than 50% retention of capacity after 100 cycles. This work offers a favorable design of electrode material, namely, mix-phase tin oxide-nanocarbon matrix, exhibiting adequate electrochemical performance for Li storage applications.

Fluorescence correlation spectroscopy based insights into diffusion in electrochemical energy systems.

Fluorescence Correlation Spectroscopy, a commonly used technique for measuring diffusion of biomolecules and tracer dyes in different solvents, is employed to characterise the local transport properties in battery electrolytes. Diffusion of ions, a major limiting factor in battery capacity and charging rates, depends on the local interactions and structuredness of the electrolytic species. Structuredness in the electrolyte results from typical solvation behaviour of diffusing ions/molecules leading to long-range interactions. In this work, we have used FCS to measure tracer diffusion of Coumarin 343 in a mixture of Ethylene Carbonate (EC) and Dimethyl Carbonate (DMC), commonly used as electrolyte solvent in Li-ion batteries. The measured diffusion is found to depend on lithium-ion concentrations. It is found that the addition of LiPF6to an EC-DMC equimolar mixture slows down tracer diffusion significantly. Indeed, the bulk viscosity of the electrolyte added with LiPF6salt varies with salt concentration. However, the change in bulk viscosity (global behaviour) at high ion concentrations does not match the one inferred from applying Stoke-Einstein's relation to the diffusion data (local behaviour). This indicates that the homogeneity of the electrolyte does not extend spatially to molecular scales around the diffusing tracer molecule. Measurements made on coin cells prepared with different concentrations of LiPF6show battery performance limited at higher concentrations, characterized by specific capacity loss at faster charging cycles. This limitation is directly related to the local behaviour of the electrolyte as quantified by measurements of tracer diffusion, which slows down, which remarkably outweighs the advantage of high carrier densities.

Construction of a 2D/2D g-C3N5/NiCr-LDH Heterostructure to Boost the Green Ammonia Production Rate under Visible Light Illumination.

Photocatalytic N2 fixation has emerged as one of the most useful ways to produce NH3, a useful asset for chemical industries and a carbon-free energy source. Recently, significant progress has been made toward designing efficient photocatalysts to achieve this objective. Here, we introduce a highly active type-II heterojunction fabricated via integrating two-dimensional (2D) nanosheets of exfoliated g-C3N5 with nickel-chromium layered double hydroxide (NiCr-LDH). With an optimized loading of NiCr-LDH on exfoliated g-C3N5, excellent performance is realized for green ammonia synthesis under ambient conditions without any noble metal cocatalyst(s). Indeed, the g-C3N5/NiCr-LDH heterostructure with 2 wt % of NiCr-LDH (CN-NCL-2) exhibits an ammonia yield of about 2.523 mmol/g/h, which is about 7.51 and 2.86 times higher than that of solo catalysts, i.e., NiCr-LDH (NC-L) and exfoliated g-C3N5 (CN-5), respectively, where methanol is used as a sacrificial agent. The enhancement of NH3 evolution by the g-C3N5/NiCr-LDH heterostructure can be attributed to the efficient charge transfer, a key factor to the photocatalytic N2 fixation rate enhancement. Additionally, N2 vacancies present in the system help adsorb N2 on the surface, which improves the ammonia production rate further. The best-performing heterostructure also shows long-term stability with the NH3 production rate remaining nearly constant over 20 h, demonstrating the excellent robustness of the photocatalyst.

Designing Nanoengineered Photocatalysts for Hydrogen Generation by Water Splitting and Conversion of Carbon Dioxide to Clean Fuels.

Semiconductor photocatalysis has received tremendous attention in the past decade as it has shown great promise in the context of clean energy harvesting for environmental remediation. Sunlight is an inexhaustible source of energy available to us throughout the year, although it is rather dilutely dispersed. Semiconductor based photocatalysis presents one of the best ways to harness this source of energy to carry out chemical reactions of interest that require external energy input. Photocatalytic hydrogen generation by splitting of water, CO2 mitigation, and CO2 conversion to green fuel have therefore become the highly desirable clean and sustainable processes for a better tomorrow. Although numerous efforts have been made and continue to be expended to search and develop new classes of photocatalyst materials in recent years, several significant challenges still remain to be resolved before photocatalysis can reach its commercial potential. Therefore, major attention is required towards improving the efficiencies of the existing photocatalysts by further manipulating them and parallelly employing newer strategies for novel photocatalyst designs. This personal account aims to provide a broad overview of the field primarily invoking examples of our own research contributions in the field, which include photocatalytic hydrogen generation and CO2 reduction to value added chemicals. This account reviews the state-of-the-art research activities and scientific possibilities which a functional material can offer if its properties are put to best use through goal-oriented design by combining with other compatible materials. We have addressed fundamental principles of photocatalysis, different kind of functional photocatalysts, critical issues associated with them and various strategies to overcome the related hurdles. It is our hope that this current personal account will provide a platform for young researchers to address the bottleneck issues in the field of photocatalysis and photocatalysts with a sense of clarity, and to find innovative solutions to resolve them by a prudent choice of materials, synthesis protocols, and approaches to boost the photocatalysis output. We emphasize that a targeted or goal-directed photocatalyst nanoengineering as perhaps the only way to realize an early success in this multiparametric domain.

Search for New Anode Materials for High Performance Li-Ion Batteries.

Owing to an unmatched combination of power and energy density along with cyclic stability, the Li-ion battery has qualified itself to be the highest performing rechargeable battery. Taking both transportable and stationary energy storage requirements into consideration, Li-ion batteries indeed stand tall in comparison to any other existing rechargeable battery technologies. However, graphite, which is still one of the best performing Li-ion anodes, has specific drawbacks in fulfilling the ever-increasing energy and power density requirements of the modern world. Therefore, further research on alternative anode materials is absolutely essential. Equally important is the search for and enhanced use of right earth abundant materials for battery electrodes so as to bring down the costs of the battery systems. In this spotlight article, we discuss the current research progress in the area of alternative anode materials for Li-ion battery, putting our own research work over the past several years into perspective. Starting from conversion anode systems like oxides and sulfides, to insertion cum alloying systems like transition metal carbides, to molecularly engineered open framework systems like metal organic frameworks (MOFs), covalent organic frameworks (COFs), and organic-inorganic hybrid perovskites (OIHPs), this spotlight provides a complete essence of the recent developments in the area of alternative anodes. The possible and potential impact of these new anode materials is detailed and discussed here.

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation.

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)3 P]3 [Bi2 Br9 ] (MTPBB) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 µC cm-2 . Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d33 ) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 µW cm-2 at an optimal load of 4 MΩ. Moreover, the potential of MTPBB-based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.

Growth of highly conducting MoS2-xNx thin films with enhanced 1T' phase by pulsed laser deposition and exploration of their nanogenerator application.

High-quality growth of MoS2-xNx films is realized on single-crystal c-Al2O3 substrates by the pulsed laser deposition (PLD) in ammonia rendering highly stable and tunable 1T'/2H biphasic constitution. Raman spectroscopy reveals systematic enhancement of 1T' phase component due to the incorporation of covalently bonded N-doping in MoS2 lattice, inducing compressive strain. Interestingly, the film deposited at 300 mTorr NH3 shows ∼80% 1T' phase. The transport measurements performed on MoS2-xNx films deposited at 300 mTorr NH3 display very low room temperature resistivity of 0.03 mΩ-cm which is 100 times enhanced over the undoped MoS2 grown under comparable conditions. A triboelectric nanogenerator (TENG) device containing biphasic MoS2-xNx film as an electron acceptor exhibits a clear enhancement in the output voltage as compared to the pristine MoS2. Device architecture, p-type N doping in MoS2 lattice, favorably increased work-function, multiphasic component of MoS2, and increased surface roughness synergistically contribute to superior TENG performance.

Visible Light-Driven Highly Selective CO2 Reduction to CH4 Using Potassium-Doped g-C3N5.

Establishment of an efficient and robust artificial photocatalytic system to convert solar energy into chemical fuels through CO2 conversion is a cherished goal in the fields of clean energy and environmental protection. In this work, we have explored an emergent low-Z nitrogen-rich carbon nitride material g-C3N5 (analogue of g-C3N4) for CO2 conversion under visible light illumination. A significant enhancement of the CH4 production rate was detected for g-C3N5 in comparison to that of g-C3N4. Notably, g-C3N5 also showed a very impressive selectivity of 100% toward CH4 as compared to 21% for g-C3N4. The photocatalytic CO2 conversion was performed without using sacrificial reagents. We found that 1% K doping in g-C3N5 enhanced its performance even further without compromising the selectivity. Moreover, 1% K-doped g-C3N5 also exhibited better photostability than undoped g-C3N5. We have also employed density functional theory calculation-based analyses to understand and elucidate the possible reasons for the better photocatalytic performance of K-doped g-C3N5.

Process-Structure-Formulation Interactions for Enhanced Sodium Ion Battery Development: A Review.

Before the viability of a cell formulation can be assessed for implementation in commercial sodium ion batteries, processes applied in cell production should be validated and optimized. This review summarizes the steps performed in constructing sodium ion (Na-ion) cells at research scale, highlighting parameters and techniques that are likely to impact measured cycling performance. Consistent process-structure-performance links have been established for typical lithium-ion (Li-ion) cells, which can guide hypotheses to test in Na-ion cells. Liquid electrolyte viscosity, sequence of mixing electrode slurries, rate of drying electrodes and cycling characteristics of formation were found critical to the reported capacity of laboratory cells. Based on the observed importance of processing to battery performance outcomes, the current focus on novel materials in Na-ion research should be balanced with deeper investigation into mechanistic changes of cell components during and after production, to better inform future designs of these promising batteries.

Resistive Switching in HfO2-x/La0.67Sr0.33MnO3 Heterostructures: An Intriguing Case of Low H-Field Susceptibility of an E-Field Controlled Active Interface.

High-performance nonvolatile resistive random access memories (ReRAMs) and their small stimuli control are of immense interest for high-speed computation and big-data processing in the emerging Internet of Things (IoT) arena. Here, we examine the resistive switching (RS) behavior in growth-controlled HfO2/La0.67Sr0.33MnO3 (LSMO) heterostructures and their tunability in a low magnetic field. It is demonstrated that oxygen-deficient HfO2 films show bipolar switching with a high on/off ratio, stable retention, as well as good endurance owing to the orthorhombic-rich phase constitution and charge (de)trapping-enabled Schottky-type conduction. Most importantly, we have demonstrated that RS can be tuned by a very low externally applied magnetic field (∼0-30 mT). Remarkably, application of a magnetic field of 30 mT causes RS to be fully quenched and frozen in the high resistive state (HRS) even after the removal of the magnetic field. However, the quenched state could be resurrected by applying a higher bias voltage than the one for initial switching. This is argued to be a consequence of the electronically and ionically "active" nature of the HfO2-x/LSMO interface on both sides and its susceptibility to the electric and low magnetic field effects. This result could pave the way for new designs of interface-engineered high-performance oxitronic ReRAM devices.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Air exposed 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine: an avant-garde carbonization precursor for multi-functionalized carbon material.

1,4-Bis(trimethysilyl)-1,4-dihydropyrazine 1 has been utilized as a small molecule precursor for carbonization to N,O-containing few-layered carbon sheets 3via the formation of a polymeric material 2 upon simple air exposure at room temperature. Without any further purification, this multi-functionalized carbon material 3 exhibited excellent anode performance in a lithium ion battery.

Tuning the electronic energy level of covalent organic frameworks for crafting high-rate Na-ion battery anode.

Crystalline Covalent Organic Frameworks (COFs) possess ordered accessible nano-channels. When these channels are decorated with redox-active functional groups, they can serve as the anode in metal ion batteries (LIB and SIB). Though sodium's superior relative abundance makes it a better choice over lithium, the energetically unfavourable intercalation of the larger sodium ion makes it incompatible with the commercial graphite anodes used in Li-ion batteries. Also, their sluggish movement inside the electrodes restricts the fast sodiation of SIB. Creating an electronic driving force at the electrodes via chemical manipulation can be a versatile approach to overcome this issue. Herein, we present anodes for SIB drawn on three isostructural COFs with nearly the same Highest Occupied Molecular Orbitals (HOMO) levels but with varying Lowest Unoccupied Molecular Orbitals (LUMO) energy levels. This variation in the LUMO levels has been deliberately obtained by the inclusion of electron-deficient centers (phenyl vs. tetrazine vs. bispyridine-tetrazine) substituents into the modules that make up the COF. With the reduction in the cell-potential, the electrons accumulate in the anti-bonding LUMO. Now, these electron-dosed LUMO levels become efficient anodes for attracting the otherwise sluggish sodium ions from the electrolyte. Also, the intrinsic porosity of the COF favors the lodging and diffusion of the Na+ ions. Cells made with these COFs achieve a high specific capacity (energy density) and rate performance (rapid charging-discharging), something that is not as easy for Na+ compared to the much smaller sized Li+. The bispyridine-tetrazine COF with the lowest LUMO energy shows a specific capacity of 340 mA h g-1 at 1 A g-1 and 128 mA h g-1 at a high current density of 15 A g-1. Only a 24% drop appears on increasing the current density from 0.1 to 1 A g-1, which is the lowest among all the top-performing COF derived Na-ion battery anodes.

Dynamics of Photo-Generated Carriers across the Interface between CsPbBr3 Nanocrystals and Au-Ag Nanostructured Film, and Its Control via Ultrathin MgO Interface Layer.

The dynamics and control of charge transfer between optoelectronically interesting and size-tunable halide perovskite quantum dots and other juxtaposed functional electronic materials are important issues for the emergent device interest involving such a family of materials in heterostructure configurations. Herein, we have grown bimetallic Au-Ag thin films on glass by pulsed laser deposition at room temperature, which bear nanoparticulate character, and the corresponding optical absorption spectra reveal the expected surface plasmon resonance signature(s). Subsequently, spin-coated CsPbBr3 nanoparticle films onto the bimetallic Au-Ag films exhibit surface-enhanced Raman scattering as well as strong photoluminescence quenching, the latter reflecting highly efficient transfer of photo-generated carriers across the CsPbBr3/Au-Ag interface. Surprisingly, when an ultrathin MgO (insulating) layer of optimum thickness is introduced between the CsPbBr3 and Au-Ag films, the charge transfer is further facilitated with the average lifetime of carriers becoming even shorter. By changing the thickness of the thin MgO layer, the carrier lifetime can in fact be tuned; with the charge transfer getting fully blocked for thick enough MgO layers, as expected. Our study thus throws light on the charge-carrier dynamics in halide perovskites, which is of importance to emergent optoelectronic applications.

Understanding the thermal degradation mechanism of perovskite solar cells via dielectric and noise measurements.

Long term stability is a major obstacle to the success of perovskite solar cell (PSC) photovoltaic technology. PSC performance deteriorates significantly in the presence of humidity, oxygen and exposure to UV light and heat. Here the change in charge transport properties of PSC with temperature and the associated significant drop in device performance at high temperature have been investigated. The latter is shown to be primarily due to an increase in charge carrier recombination, which impacts the open-circuit voltage. To understand the pathway of temperature-induced degradation, low-frequency 1/f noise characteristics, and the capacitance-frequency, as well as capacitance-voltage characteristics have been investigated under various conditions. The results show that at high operating temperature accumulation of ions and charge carriers at the interface increase the surface recombination. Aging experiments at different temperatures show high stability of PSCs up to temperature <70 °C, but a drastic, irreversible degradation occurs at higher temperature (≥80 °C). Low-frequency 1/f noise study revealed that the magnitude of normalized noise in degraded perovskite solar cells is four orders of magnitude higher than the pristine device. This study shows the power of low-frequency noise measurement technique as a highly sensitive non-invasive tool to study the degradation mechanism of PSCs.

Comparative evaluation of MAX, MXene, NanoMAX, and NanoMAX-derived-MXene for microwave absorption and Li ion battery anode applications.

MAX and MXene phases possess unique physical properties, encompassing the realms of both ceramics and metals. Their nanolaminated layered configuration, high anisotropic electrical conductivity, and ability to scatter electromagnetic radiation are beneficial in multiple applications. Herein, detailed applications of MAX and MXene are studied in the fields of microwave absorption and Li ion batteries (LIB). In particular, coatings based on MAX, MXene, ball-milled NanoMAX, and NanoMAX-derived-MXene (MXene-N) and their composites are examined in terms of their comparative efficacy for the aforesaid applications. NanoMAX and MXene-N based composites with graphite exhibit superior performance with specific reflection loss values (representing absorbance when measured with metal-backing) of -21.4 and -19 dB cm3 g-1, respectively, as compared to their bulk counterparts, that too with a low density (0.63 g cm-3) and very small thickness (0.03 mm). These performance improvements in absorbance in only 30 µm coatings can be attributed to reflective losses compounded with multiple internal reflections within the nanocomposite intensified by dielectric losses, arising from high interface density. The pristine samples were also studied for their performance as Li ion battery anodes. Herein, MXene-N exhibits the best performance with a specific capacity of 330 mA h g-1 at 100 mA g-1 and excellent cycling stability tested up to 1000 cycles.

Coherent Solution-phase Synthesis of a Germanium-Graphitic Nanocomposite and Its Evaluation for Lithium-Ion Battery Anodes: Non-innocent Role of the Mashima Reagent.

The organosilicon reagent 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene 2 plays the binary role of the simultaneous reduction of GeCl2 .dioxane 1 dissolved in oleylamine to Ge nanocrystals and the formation of graphitic sheets under hot-injection conditions. This colloidal synthetic route to germanium nanocrystals embedded on N-doped graphitic nanosheets Ge/NG is free of any template or catalyst and involves easy purification techniques. The Ge/NG/C obtained after carbonization has been explored for anode performance in lithium-ion batteries. Both Ge/NG and Ge/NG/C can be obtained on a gram scale and are bottleable under argon for months.

Temperature Dependence of the Spin Seebeck Effect in a Mixed Valent Manganite.

We report on temperature dependent measurements of the longitudinal spin Seebeck effect (LSSE) in the mixed valent manganite La_{0.7}Ca_{0.3}MnO_{3}. By disentangling the contribution arising due to the anisotropic Nernst effect, we observe that in the low temperature regime, the LSSE exhibits a T^{0.5} dependence, which matches well with that predicted by the magnon-driven spin current model. Across the double exchange driven paramagnetic-ferromagnetic transition, the LSSE exponent is significantly higher than the magnetization one, and also depends on the thickness of the spin-to-charge conversion layer. These observations highlight the importance of individually ascertaining the temperature evolution of different mechanisms-especially the spin mixing conductance-which contribute to the measured spin Seebeck signal.