Manoj K. Jana

The Origin of Ultralow Thermal Conductivity in InTe: Lone-Pair-Induced Anharmonic Rattling.

Understanding the origin of intrinsically low thermal conductivity is fundamentally important to the development of high-performance thermoelectric materials, which can convert waste-heat into electricity. Herein, we report an ultralow lattice thermal conductivity (ca. 0.4 W m(-1)  K(-1) ) in mixed valent InTe (that is, In(+) In(3+) Te2 ), which exhibits an intrinsic bonding asymmetry with coexistent covalent and ionic substructures. The phonon dispersion of InTe exhibits, along with low-energy flat branches, weak instabilities associated with the rattling vibrations of In(+) atoms along the columnar ionic substructure. These weakly unstable phonons originate from the 5s(2) lone pair of the In(+) atom and are strongly anharmonic, which scatter the heat-carrying acoustic phonons through strong anharmonic phonon-phonon interactions, as evident in anomalously high mode Grüneisen parameters. A maximum thermoelectric figure of merit (z T) of about 0.9 is achieved at 600 K for the 0.3 mol % In-deficient sample, making InTe a promising material for mid-temperature thermoelectric applications.

Green ionothermal synthesis of hierarchical nanostructures of SnS2 and their Li-ion storage properties

Flower-like hierarchical architectures of layered SnS2 have been synthesized ionothermally for the first time, using a water soluble EMIM]BF4 ionic liquid (IL) as the solvent medium. At lower reaction temperatures, the hierarchical structures are formed of few-layered polycrystalline 2D nanosheet-petals composed of randomly oriented nanoparticles of SnS2. The supramolecular networks of the IL serve as templates on which the nanoparticles of SnS2 are glued together by combined effects of hydrogen bonding, electrostatic, hydrophobic and imidazolium stacking interactions of the IL, giving rise to polycrystalline 2D nanosheet-petals. At higher reaction temperatures, single crystalline plate-like nanosheets with well-defined crystallographic facets are obtained due to rapid inter-particle diffusion across the IL. Efficient surface charge screening by the IL favors the aggregation of individual nanosheets to form hierarchical flower-like architectures of SnS2. The mechanistic aspects of the ionothermal bottom-up hierarchical assembly of SnS2 nanosheets are discussed in detail. Li-ion storage properties of the pristine SnS2 samples are examined and the electrochemical performance of the sample synthesized at higher temperatures is found to be comparable to that reported for pristine SnS2 samples in the literature.

Intrinsic Rattler-Induced Low Thermal Conductivity in Zintl Type TlInTe2

Understanding the nature of chemical bonding and lattice dynamics together with their influence on phonon-transport is essential to explore and design crystalline solids with ultralow thermal conductivity for various applications including thermoelectrics. TlInTe2, with interlocked rigid and weakly bound substructures, exhibits lattice thermal conductivity as low as ca. 0.5 W/mK near room temperature, owing to rattling dynamics of weakly bound Tl cations. Large displacements of Tl cations along the c-axis, driven by electrostatic repulsion between localized electron clouds on Tl and Te ions, are akin to those of rattling guests in caged-systems. Heat capacity of TlInTe2 exhibits a broad peak at low-temperatures due to contribution from Tl-induced low-frequency Einstein modes as also evidenced from THz time domain spectroscopy. First-principles calculations reveal a strong coupling between large-amplitude coherent optic vibrations of Tl-rattlers along the c-axis, and acoustic phonons that likely causes the low lattice thermal conductivity in TlInTe2.

Near infrared detectors based on HgSe and HgCdSe quantum dots generated at the liquid–liquid interface

HgSe and Hg0.5Cd0.5Se quantum dos (QDs) are synthesized at room temperature by a novel liquid–liquid interface method and their photodetection properties in the near-IR region are investigated. The photodetection properties of our Te-free systems are found to be comparable to those of the previously reported high performance QD vis-IR detectors including HgTe. The present synthesis indicates the cost-effectiveness of selenium based IR detectors owing to the abundance and lower toxicity of selenium compared to tellurium.

Two-dimensional inorganic analogues of graphene: transition metal dichalcogenides.

The discovery of graphene marks a major event in the physics and chemistry of materials. The amazing properties of this two-dimensional (2D) material have prompted research on other 2D layered materials, of which layered transition metal dichalcogenides (TMDCs) are important members. Single-layer and few-layer TMDCs have been synthesized and characterized. They possess a wide range of properties many of which have not been known hitherto. A typical example of such materials is MoS2. In this article, we briefly present various aspects of layered analogues of graphene as exemplified by TMDCs. The discussion includes not only synthesis and characterization, but also various properties and phenomena exhibited by the TMDCs. This article is part of the themed issue ‘Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene’.

Hydrazine as a hydrogen carrier in the photocatalytic generation of H2 using CdS quantum dots

The compelling need for safe storage and transportation of H2 has made liquid-phase materials safer H2-carriers with a high gravimetric and volumetric hydrogen density. Unlike thermal or electrocatalytic decomposition on precious metal catalysts, a photocatalytic route to decomposing these liquid-phase materials can offer triggered onboard production of H2 and help mitigate the safety issues concerned with H2 storage. We have investigated visible-light induced H2 evolution from aqueous hydrazine using CdS quantum dots (QDs) as metal-free photocatalysts. Hydrazine acts as a H2 carrier as well as a donor, giving rise to a visible-light induced H2 evolution activity as high as 33 mmol h-1 g-1 at pH 8. This has been achieved by the use of CdS QDs capped with S2- ligands. The use of larger ligands such as mercaptopropionic acid hinders the adsorption of hydrazine onto CdS QDs and significantly decreases the activity. The effect of pH on the hydrogen yield in aqueous hydrazine has also been examined.

Fabrication of large-area PbSe films at the organic–aqueous interface and their near-infrared photoresponse

An organic–aqueous interfacial reaction at room temperature has been employed to synthesize large-area self-assembled films consisting of PbSe single crystallites. The use of the films for the low-cost fabrication of IR-photodetectors has been explored. (111)-oriented single crystallites of PbSe self-assemble to form robust large-area films. The near-infrared photoresponse of the film measured at room temperature showed large responsivity and gain owing to trap-associated mechanisms. Low-cost, mild reaction conditions and tunability of the nature of deposits make the present strategy useful for synthesizing large-area films of functional materials for possible opto-electronic applications.

Evidence of contact epitaxy in the self-assembly of HgSe nanocrystals formed at a liquid-liquid interface.

The grazing incidence x-ray scattering results presented here show that the self-assembly process of HgSe nanocrystals formed at a liquid-liquid interface is quite different along the in-plane direction and across the interface. In situ x-ray reflectivity and ex situ microscopy measurements suggest quantized out-of-plane growth for HgSe nanoparticles of a size of about [Formula: see text] nm initially. Grazing incidence small-angle x-ray scattering measurements for films transferred from the water-toluene interface at various stages of reaction show that these nanoparticles first form random clusters with an average radius of 2.2 nm, giving rise to equally spaced rings of several orders. Finally, these clusters self-organize into face-centered cubic superstructures, giving sharp x-ray diffraction peaks oriented normal to the liquid-liquid interface with more than 100 nm-coherent domains. We also observed the x-ray diffraction pattern of the HgSe crystalline phase, with the superlattice peaks in these grazing incidence measurements of the transferred films. The electron microscopy and atomic force microscopy results support the x-ray observation of the self-organization of HgSe nanocrystals into close-packed superlattices. These results show that capillary wave fluctuation promotes the oriented attachment of clusters at the liquid-liquid interface, giving direct experimental evidence of contact epitaxy.