Realizing p-type NbCoSn half-Heusler compounds with enhanced thermoelectric performance via Sc substitution.

N-type half-Heusler NbCoSn is a promising thermoelectric material due to favourable electronic properties. It has attracted much attention for thermoelectric applications while the desired p-type NbCoSn counterpart shows poor thermoelectric performance. In this work, p-type NbCoSn has been obtained using Sc substitution at the Nb site, and their thermoelectric properties were investigated. Of all samples, Nb0.95Sc0.05CoSn compound shows a maximum power factor of 0.54 mW/mK2 which is the highest among the previously reported values of p-type NbCoSn. With the suppression of thermal conductivity, p-type Nb0.95Sc0.05CoSn compound shows the highest measured figure of merit ZT = 0.13 at 879 K.

Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides.

The present work elaborates on the correlation between the amount and ordering of the free carbon phase in silicon oxycarbides and their charge carrier transport behavior. Thus, silicon oxycarbides possessing free carbon contents from 0 to ca. 58 vol.% (SiOC/C) were synthesized and exposed to temperatures from 1100 to 1800 °C. The prepared samples were extensively analyzed concerning the thermal evolution of the sp2 carbon phase by means of Raman spectroscopy. Additionally, electrical conductivity and Hall measurements were performed and correlated with the structural information obtained from the Raman spectroscopic investigation. It is shown that the percolation threshold in SiOC/C samples depends on the temperature of their thermal treatment, varying from ca. 20 vol.% in the samples prepared at 1100 °C to ca. 6 vol.% for the samples annealed at 1600 °C. Moreover, three different conduction regimes are identified in SiOC/C, depending on its sp2 carbon content: (i) at low carbon contents (i.e., <1 vol.%), the silicon oxycarbide glassy matrix dominates the charge carrier transport, which exhibits an activation energy of ca. 1 eV and occurs within localized states, presumably dangling bonds; (ii) near the percolation threshold, tunneling or hopping of charge carriers between spatially separated sp2 carbon precipitates appear to be responsible for the electrical conductivity; (iii) whereas above the percolation threshold, the charge carrier transport is only weakly activated (Ea = 0.03 eV) and is realized through the (continuous) carbon phase. Hall measurements on SiOC/C samples above the percolation threshold indicate p-type carriers mainly contributing to conduction. Their density is shown to vary with the sp2 carbon content in the range from 1014 to 1019 cm-3; whereas their mobility (ca. 3 cm2/V) seems to not depend on the sp2 carbon content.

Pd-M/C (M = Pd, Cu, Pt) Electrocatalysts for Oxygen Reduction Reaction in Alkaline Medium: Correlating the Electronic Structure with Activity.

The increasing global needs for clean and renewable energy have fostered the design of new and highly efficient materials for fuel cells applications. In this work, Pd-M (M = Pd, Cu, Pt) and Pt nanoparticles were prepared by a green synthesis method. The carbon-supported nanoparticles were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium. A comprehensive electronic and structural characterization of these materials was achieved using X-ray diffraction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Their electrochemical properties were investigated by cyclic voltammetry, while their activities for the ORR were characterized using steady-state polarization experiments. The results revealed that the bimetallic nanoparticles consist of highly crystalline nanoalloys with size around 5 nm, in which the charge transfer involving Pd and M atoms affects the activity of the electrocatalysts. Additionally, the samples with higher ORR activity are those whose d-band center is closer to the Fermi level.

Enhanced thermoelectric performance in the p-type half-Heusler (Ti/Zr/Hf)CoSb0.8Sn0.2 system via phase separation.

A novel approach for optimization of the thermoelectric properties of p-type Heusler compounds with a C1b structure was investigated. A successful recipe for achieving intrinsic phase separation in the n-type material based on the TiNiSn system is isoelectronic partial substitution of Ti with its heavier homologues Zr and Hf. We applied this concept to the p-type system MCoSb0.8Sn0.2 by a systematic investigation of samples with different compositions at the Ti position (M = Ti, Zr, Hf, Ti0.5Zr0.5, Zr0.5Hf0.5, and Ti0.5Hf0.5). We thus achieved an approximately 40% reduction of the thermal conductivity and a maximum figure of merit ZT of 0.9 at 700 °C. This is a 80% improvement in peak ZT from 0.5 to 0.9 at 700 °C compared to the best published value of an ingot p-type half-Heusler compound. Thus far, comparable good thermoelectric p-type materials of this structure type have only been realized by a nanostructuring process via ball milling of premelted ingot samples followed by a rapid consolidation method, like hot pressing. The herein-presented simple arc-melting fabrication method reduces the fabrication time as compared to this multi-step nanostructuring process. The high mechanical stability of the Heusler compounds is favorable for the construction of thermoelectric modules. The Vickers hardness values are close to those of the n-type material, leading to good co-processability of both materials.

Phase separation as a key to a thermoelectric high efficiency.

This work elucidates the possible reasons for the outstanding, but never reproduced thermoelectric properties of the doped Ti(0.5)Zr(0.25)Hf(0.25)NiSn Heusler compounds. The structural investigations done via synchrotron X-ray diffraction measurements and scanning electron microscope measurements, which clearly show that the microstructure consists of three temperature stable C1(b) phases with possible semi-coherent interfaces, are presented. The exceptional thermoelectric properties are due to this intrinsic phase separation. It is possible to reproduce the high Figure of Merit values with ZT = 1.2 at 830 K. Furthermore, the influence of doping different elements on the Sn position in this Heusler material system is investigated.

Symmetry of valence states of Heusler compounds explored by linear dichroism in hard-x-ray photoelectron spectroscopy.

This study reports on the linear dichroism in angular-resolved photoemission from the valence band of the Heusler compounds NiTi0.9Sc0.1Sn and NiMnSb. High-resolution photoelectron spectroscopy was performed with an excitation energy of hν = 7.938 keV. The linear polarization of the photons was changed using an in-vacuum diamond phase retarder. The valence band spectra exhibit the typical structure expected from first-principles calculations of the electronic structure of these compounds. Noticeable linear dichroism is found in the valence band of both materials, and this allows for a symmetry analysis of the contributing states. The differences in the spectra are found to be caused by symmetry-dependent angular asymmetry parameters, and these occur even in polycrystalline samples without preferential crystallographic orientation.

Effects of Doping Ni on the Microstructures and Thermoelectric Properties of Co-Excessive NbCoSn Half-Heusler Compounds.

The half-Heusler (HH) compound NbCoSn with 18 valence electrons is a promising thermoelectric (TE) material due to its appropriate electrical properties as well as its suitable thermal and chemical stability. Nowadays, doping/substitution and tailoring of microstructures are common experimental approaches to enhance the TE performance of HH compounds. However, detailed theoretical insights into the effects of doping on the microstructures and TE properties are still missing. In this work, the microstructure of NbCoSn was tailored through precipitating the full-Heusler phases in the matrix by changing the nominal ratio of Co and Ni on the Co sites, focusing on the resulting TE properties. Further, first-principles calculations were employed to understand the relationship between the microstructure and the TE properties from the thermodynamic point of view. Detailed analysis of the electronic structure reveals that the presence of excess Co/Ni contributes to the increasing carrier concentration. Through an increase in the electrical conductivity and a reduction in the thermal conductivity, the TE performance is improved. Therefore, the present work offers a new pathway and insights to enhance the TE properties by modifying the microstructure of HH compounds via tailoring the chemical compositions.

Rational design of new materials for spintronics: Co2FeZ (Z=Al, Ga, Si, Ge).

Spintronic is a multidisciplinary field and a new research area. New materials must be found for satisfying the different types of demands. The search for stable half-metallic ferromagnets and ferromagnetic semiconductors with Curie temperatures higher than room temperature is still a challenge for solid state scientists. A general understanding of how structures are related to properties is a necessary prerequisite for material design. Computational simulations are an important tool for a rational design of new materials. The new developments in this new field are reported from the point of view of material scientists. The development of magnetic Heusler compounds specifically designed as material for spintronic applications has made tremendous progress in the very recent past. Heusler compounds can be made as half-metals, showing a high spin polarization of the conduction electrons of up to 100% in magnetic tunnel junctions. High Curie temperatures were found in Co2-based Heusler compounds with values up to 1120 K in Co2FeSi. The latest results at the time of writing are a tunnelling magnet resistance (TMR) device made from the Co2FeAl0.5Si0.5 Heusler compound and working at room temperature with a (TMR) effect higher than 200%. Good interfaces and a well-ordered compound are the precondition to realize the predicted half-metallic properties. The series Co2FeAl1- x Si x is found to exhibit half-metallic ferromagnetism over a broad range, and it is shown that electron doping stabilizes the gap in the minority states for x=0.5. This might be a reason for the exceptional temperature behaviour of Co2FeAl0.5Si0.5 TMR devices. Using x-ray diffraction (XRD), it was shown conclusively that Co2FeAl crystallizes in the B2 structure whereas Co2FeSi crystallizes in the L21 structure. For the compounds Co2FeGa or Co2FeGe, with Curie temperatures expected higher than 1000 K, the standard XRD technique using laboratory sources cannot be used to easily distinguish between the two structures. For this reason, the EXAFS technique was used to elucidate the structure of these two compounds. Analysis of the data indicated that both compounds crystallize in the L21 structure which makes these two compounds suitable new candidates as materials in magnetic tunnel junctions.

On the Phase Separation in n-Type Thermoelectric Half-Heusler Materials.

Half-Heusler compounds have been in focus as potential materials for thermoelectric energy conversion in the mid-temperature range, e.g., as in automotive or industrial waste heat recovery, for more than ten years now. Because of their mechanical and thermal stability, these compounds are advantageous for common thermoelectric materials such as Bi 2 Te 3 , SiGe, clathrates or filled skutterudites. A further advantage lies in the tunability of Heusler compounds, allowing one to avoid expensive and toxic elements. Half-Heusler compounds usually exhibit a high electrical conductivity σ , resulting in high power factors. The main drawback of half-Heusler compounds is their high lattice thermal conductivity. Here, we present a detailed study of the phase separation in an n-type Heusler materials system, showing that the Ti x Zr y Hf z NiSn system is not a solid solution. We also show that this phase separation is key to the thermoelectric high efficiency of n-type Heusler materials. These results strongly underline the importance of phase separation as a powerful tool for designing highly efficient materials for thermoelectric applications that fulfill the industrial demands of a thermoelectric converter.

Spintronics: a challenge for materials science and solid-state chemistry.

Spintronics is a multidisciplinary field involving physics, chemistry, and engineering, and is a new research area for solid-state scientists. A variety of new materials must be found to satisfy different demands. The search for ferromagnetic semiconductors and stable half-metallic ferromagnets with Curie temperatures higher than room temperature remains a priority for solid-state chemistry. A general understanding of structure-property relationships is a necessary prerequisite for the design of new materials. In this Review, the most important developments in the field of spintronics are described from the point of view of materials science.

Facile hybridization of Ni@Fe2O3 superparticles with functionalized reduced graphene oxide and its application as anode material in lithium-ion batteries.

In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly improved performance as anode material in lithium-ion batteries (compared to unwrapped Ni@Fe2O3) as it offers a reversible capacity of 1051mAhg(-1) after 40 cycles at C/20, compared with 460mAhg(-1) for unwrapped Ni@Fe2O3. The C rate capability is also improved by the wrapping approach, as specific capacities for wrapped particles are about twice of those offered by unwrapped particles. Additionally, the benefit for the use of the advanced superparticle morphology is demonstrated by comparing wrapped Ni@Fe2O3 particles with wrapped Fe2O3 nanorice.

Design scheme of new tetragonal Heusler compounds for spin-transfer torque applications and its experimental realization.

Band Jahn-Teller type structural instabilities of cubic Mn(2)YZ Heusler compounds causing tetragonal distortions can be predicted by ab initio band-structure calculations. This allows for identification of new Heusler materials with tunable magnetic and structural properties that can satisfy the demands for spintronic applications, such as in spin-transfer torque-based devices.

Anomalous transport properties of the half-metallic ferromagnets Co2TiSi, Co2TiGe and Co2TiSn.

In this work, the theoretical and experimental investigations of Co2TiZ (Z=Si, Ge or Sn) compounds are reported. Half-metallic ferromagnetism is predicted for all three compounds with only two bands crossing the Fermi energy in the majority channel. The magnetic moments fulfil the Slater-Pauling rule and the Curie temperatures are well above room temperature. All compounds show a metallic-like resistivity for low temperatures up to their Curie temperature, above the resistivity changes to semiconducting-like behaviour. A large negative magnetoresistance (MR) of 55 per cent is observed for Co2TiSn at room temperature in an applied magnetic field of µ(0)H=4T, which is comparable to the large negative MRs of the manganites. The Seebeck coefficients are negative for all three compounds and reach their maximum values at their respective Curie temperatures and stay almost constant up to 950 K. The highest value achieved is -52 µVK(-1) for Co2TiSn, which is large for a metal. The combination of half-metallicity and the constant large Seebeck coefficient over a wide temperature range makes these compounds interesting materials for thermoelectric applications and further spincaloric investigations.