Br doping-induced evolution of the electronic band structure in dimorphic and hexagonal SnSe2 thermoelectric materials.

SnSe2 with its layered structure is a promising thermoelectric material with intrinsically low lattice thermal conductivity. However, its poor electronic transport properties have motivated extensive doping studies. Br doping effectively improves the power factor and converts the dimorphic SnSe2 to a fully hexagonal structure. To understand the mechanisms underlying the power factor improvement of Br-doped SnSe2, the electronic band parameters of Br-doped dimorphic and hexagonal SnSe2 should be evaluated separately. Using the single parabolic band model, we estimate the intrinsic mobility and effective mass of the Br-doped dimorphic and hexagonal SnSe2. While Br doping significantly improves the mobility of dimorphic SnSe2 (with the dominant hexagonal phase), it results in a combination of band convergence and band flattening in fully hexagonal SnSe2. Br-doped dimorphic SnSe2 is predicted to exhibit higher thermoelectric performance (zT ∼0.23 at 300 K) than Br-doped fully hexagonal SnSe2 (zT ∼0.19 at 300 K). Characterisation of the other, currently unidentified, structural phases of dimorphic SnSe2 will enable us to tailor the thermoelectric properties of Br-doped SnSe2.

Contradicting Influence of Zn Alloying on Electronic and Thermal Properties of a YbCd2 Sb2 -Based Zintl Phase at 700†K.

Zintl compounds are promising thermoelectric materials for power generation as their electronic and thermal transport properties can be simultaneously engineered with anion/cation alloying. Recently, a peak thermoelectric figure-of-merit, zT, of 1.4 was achieved in a (Yb0.9 Mg0.1 )Cd1.2 Mg0.4 Zn0.4 Sb2 Zintl phase at 700 K. Although the effects of alloying Zn in lattice thermal conductivity had been studied thoroughly, how the Zn alloying affects its electronic transport properties has not yet been fully investigated. This study evaluates how the Zn alloying at Cd sites alters the band parameters of (Yb0.9 Mg0.1 )Cd1.6-x Mg0.4 Znx Sb2 (x=0-0.6) using the Single Parabolic Band model at 700 K. The Zn alloying increased the density-of-states effective mass (md * ) from 0.87 to 0.97 m0 . Among Zn-alloyed samples, the md * of the x=0.4 sample was the lowest (0.93 m0 ). The Zn alloying decreased the non-degenerate mobility (µ0 ) from 71 to 57 cm2 s-1 V-1 . Regardless of Zn alloying content, the µ0 of the Zn-alloyed samples were similar (∼57 cm2 s-1 V-1 ). Consequently, the x=0.4 with the highest zT exhibited the lowest weighted mobility (µW ). The lowest µW represents the lowest theoretical electronic transport properties among other x. The highest zT at x=0.4 despite the lowest µW was explained with a significant lattice thermal conductivity reduction achieved with Zn alloying with x=0.4, which outweighed the deteriorated electronic transport properties also due to the alloying.

Ultralow Water Permeation Barrier Films of Triad a-SiNx:H/n-SiOxNy/h-SiOx Structure for Organic Light-Emitting Diodes.

Organic electronic devices such as organic light-emitting diodes (OLEDs), quantum dot LEDs, and organic photovoltaics are promising technologies for future electronics. However, achieving long-term stability of organic-based optoelectronic devices has been regarded as a crucial problem to be solved. In this work, a simple and reproducible fabrication method for ultralow water permeation barrier films having a triple-layered (triad) hydrogenated silicon nitride (a-SiNx:H)/nanosilicon oxynitride (n-SiOxNy)/hybrid silicon oxide (h-SiOx) multistructure is presented. Two triad (a-SiNx:H/n-SiOxNy/h-SiOx)n=2 multistructure barrier films are deposited on both sides of a poly(ethylene terephthalate) substrate using a combination of low-pressure plasma-enhanced chemical vapor deposition and dip coating. The deposited films show a high average transmittance (400-700 nm) of 84% and an ultralow water vapor transmission rate of 2 × 10-6 g/m2/day. In the electroluminescence characteristics of OLEDs encapsulated with two triad barrier films, the operational lifetime (T50) of OLEDs is 1584 h, which is almost similar to that (1416 h) of OLEDs encapsulated with a glass lid.

Grain Boundary Interfaces Controlled by Reduced Graphene Oxide in Nonstoichiometric SrTiO3-δ Thermoelectrics.

Point defect or doping in Strontium titanium oxide (STO) largely determines the thermoelectric (TE) properties. So far, insufficient knowledge exists on the impact of double Schottky barrier on the TE performance. Herein, we report a drastic effect of double Schottky barrier on the TE performance in undoped STO. It demonstrates that incorporation of Reduced Graphene Oxide (RGO) into undoped STO weakens the double Schottky barrier and thereby results in a simultaneous increase in both carrier concentration and mobility of undoped STO. The enhanced mobility exhibits single crystal-like behavior. This increase in the carrier concentration and mobility boosts the electrical conductivity and power factor of undoped STO, which is attributed to the reduction of the double Schottky barrier height and/or the band alignment of STO and RGO that allow the charge transfer through the interface at grain boundaries. Furthermore, this STO/RGO interface also enhances the phonon scattering, which results in low thermal conductivity. This strategy significantly increases the ratio of σ/κ, resulting in an enhancement in ZT as compared with pure undoped STO. This study opens a new window to optimize the TE properties of many candidate materials.

Enhancing Thermoelectric Performances of Bismuth Antimony Telluride via Synergistic Combination of Multiscale Structuring and Band Alignment by FeTe2 Incorporation.

It has been a difficulty to form well-distributed nano- and mesosized inclusions in a Bi2Te3-based matrix and thereby realizing no degradation of carrier mobility at interfaces between matrix and inclusions for high thermoelectric performances. Herein, we successfully synthesize multistructured thermoelectric Bi0.4Sb1.6Te3 materials with Fe-rich nanoprecipitates and sub-micron FeTe2 inclusions by a conventional solid-state reaction followed by melt-spinning and spark plasma sintering that could be a facile preparation method for scale-up production. This study presents a bismuth antimony telluride based thermoelectric material with a multiscale structure whose lattice thermal conductivity is drastically reduced with minimal degradation on its carrier mobility. This is possible because a carefully chosen FeTe2 incorporated in the matrix allows its interfacial valence band with the matrix to be aligned, leading to a significantly improved p-type thermoelectric power factor. Consequently, an impressively high thermoelectric figure of merit ZT of 1.52 is achieved at 396 K for p-type Bi0.4Sb1.6Te3-8 mol % FeTe2, which is a 43% enhancement in ZT compared to the pristine Bi0.4Sb1.6Te3. This work demonstrates not only the effectiveness of multiscale structuring for lowering lattice thermal conductivities, but also the importance of interfacial band alignment between matrix and inclusions for maintaining high carrier mobilities when designing high-performance thermoelectric materials.

One-step growth of multilayer-graphene hollow nanospheres via the self-elimination of SiC nuclei templates.

We introduce a one-step growth method for producing multilayer-graphene hollow nanospheres via a high-temperature chemical vapor deposition process using tetramethylsilane as an organic precursor. When the SiC nuclei were grown under an excess carbon atmosphere, they were surrounded via desorption of the hydrocarbon gas species, and graphene layers formed on the surface of the SiC nuclei via the rearrangement of solid carbon during the heating and cooling. The core SiC nuclei were spontaneously removed by the subsequent thermal decomposition, which also supplied the carbon for the graphene layers. Hence, multilayer-graphene hollow nanospheres were acquired via a one-step process, which was simply controlled by the growth temperature. In this growth process, the SiC nuclei acted as both the template and carbon source for the formation of multilayer-graphene hollow nanospheres.

Phonon-glass electron-crystals in ZnO-multiwalled carbon nanotube nanocomposites.

We propose a strategy for enhancing thermoelectric performance through the realization of a 'phonon-glass electron-crystal' (PGEC) by interface control using multiwalled carbon nanotubes (MWCNTs). By the consolidation of undoped ZnO nanoparticles with MWCNTs (0.5, 1, and 2 wt%) using spark plasma sintering, we fabricated the interface-controlled ZnO-MWCNT nanocomposites, in which ZnO grains were surrounded with a MWCNT network. Both single crystal-like charge transport (electron-crystal) and considerably reduced thermal conductivity (phonon-glass) were achieved simultaneously thanks to the beneficial effects of the MWCNT network, and this led to the enhancement of the thermoelectric figure of merit. We discussed these findings on PGECs in the ZnO-MWCNT nanocomposites from the viewpoint of interface control in detail, and our strategy may provide a promising way to the realization of PGEC in other hybrid thermoelectric materials.

A gigantically increased ratio of electrical to thermal conductivity and synergistically enhanced thermoelectric properties in interface-controlled TiO2-RGO nanocomposites.

We report synergistically enhanced thermoelectric properties through the independently controlled charge and thermal transport properties in a TiO2-reduced graphene oxide (RGO) nanocomposite. By the consolidation of TiO2-RGO hybrid powder using spark plasma sintering, we prepared an interface-controlled TiO2-RGO nanocomposite where its grain boundaries are covered with the RGO network. Both the enhancement in electrical conductivity and the reduction in thermal conductivity were simultaneously achieved thanks to the beneficial effects of the RGO network, and detailed mechanisms are discussed. This led to the gigantic increase in the ratio of electrical to thermal conductivity by six orders of magnitude and also the synergistic enhancement in the thermoelectric figure of merit by two orders. Our results present a strategy for the realization of 'phonon-glass electron-crystals' through interface control using graphene in graphene hybrid thermoelectric materials.

Effect of topographical control by a micro-molding process on the activity of human Mesenchymal Stem Cells on alumina ceramics.

BACKGROUND: Numerous studies have reported that microgrooves on metal and polymer materials can affect cell adhesion, proliferation, differentiation and guidance. However, our knowledge of the cell activity associated with microgrooves on ceramics, such as alumina, zirconia, hydroxyapatite and etc, is very incomplete, owing to difficulties in the engraving of microgrooves on the hard surface of the base material. In this study, microgrooves on alumina were fabricated by a casting process using a polydimethylsiloxane micro-mold. The cell responses of Human Mesenchymal Stem Cells on the alumina microgrooves were then evaluated. RESULTS: Microgrooves on an alumina surface by micro-mold casting can enhance the adhesion, differentiation of osteoblasts as well as gene expression related to osteoblast differentiation. The ALP activity and calcium concentration of the cells on alumina microgrooves were increased by more than twice compared to a non-microgrooved alumina surface. Moreover, regarding the osteoblast differentiation of hMSCs, the expression of ALP, RUNX2, OSX, OC and OPN on the microgrooved alumina were all significantly increased by 1.5 ~ 2.5 fold compared with the non-microgrooved alumina. CONCLUSION: Altering the topography on alumina by creating microgrooves using a micro-molding process has an important impact on the behavior of hMSCs, including the adhesion, differentiation of osteoblasts and osteoblast-specific gene expression. The significant increase in hMSC activity is explained by the increasing of material transportation in parallel direction and by the extending of spreading distance in perpendicular direction.

Spontaneous Growth of Ultra-Long SiO(x) Nanowires from SiC Thin Films by Thermal Annealing.

The use of a simple thermal treatment for growing ultra-long SiO(x) nanowires on silicon carbide (SiC) thin films is reported for the first time. SiC thin films with a thickness of 100 nm were prepared by sputtering at room temperature followed by annealing in an Ar/H2 gas atmosphere. The growth of SiO(x) nanowires started when the annealing temperature was at 1200 degrees C, and was rapidly and spontaneously grown at temperatures above 1250 degrees C. The diameters of as-grown SiO(x) nanowires with lengths up to several hundred micrometers were determined to be -1 µm.

Structurally nanocrystalline-electrically single crystalline ZnO-reduced graphene oxide composites.

ZnO, a wide bandgap semiconductor, has attracted much attention due to its multifunctionality, such as transparent conducting oxide, light-emitting diode, photocatalyst, and so on. To improve its performances in the versatile applications, numerous hybrid strategies of ZnO with graphene have been attempted, and various synergistic effects have been achieved in the ZnO-graphene hybrid nanostructures. Here we report extraordinary charge transport behavior in Al-doped ZnO (AZO)-reduced graphene oxide (RGO) nanocomposites. Although the most challenging issue in semiconductor nanocomposites is their low mobilities, the AZO-RGO nanocomposites exhibit single crystal-like Hall mobility despite the large quantity of nanograin boundaries, which hinder the electron transport by the scattering with trapped charges. Because of the significantly weakened grain boundary barrier and the proper band alignment between the AZO and RGO, freely conducting electrons across the nanograin boundaries can be realized in the nanocomposites. This discovery of the structurally nanocrystalline-electrically single crystalline composite demonstrates a new route for enhancing the electrical properties in nanocomposites based on the hybrid strategy.

Thermal stability of gallium-doped zinc oxide thin film on glass substrates by an RF sputtering process.

The effects of a heat treatment on the structural and electrical properties of GZO thin films grown by RF magnetron sputtering were investigated. The heat treatment involved temperatures in the range from 200 degrees C to 500 degrees C under air. As the temperature was increased, the electrical properties of GZO thin films increased exponentially and the surface morphology was drastically altered. The effect of temperature is discussed based on electrical and structural characterization of the materials.

Thermoelectric performance of SrTiO3 enhanced by nanostructuring-self-assembled particulate film of nanocubes.

Self-assembled particulate films with a uniform structure over a large area were prepared from La-SrTiO3 nanocubes for thermoelectric applications. UV irradiation was used to assist the formation of particulate film for decomposition of the organic phase in situ to obtain a mechanically robust structure at high temperature. The thermoelectric properties of the particulate film were measured after calcination at 1000 °C under a reductive atmosphere (Ar/H2 = 60/40). A Seebeck coefficient of S = -239 ± 24 µV/K, electrical conductivity of σ = 160 ± 5 S/cm, and thermal conductivity of κ ≈ 1.5 W/mK were obtained for a self-assembled particulate film (La: 5%) corresponding to a ZT value of 0.2 at room temperature, which exceeded that of a La-SrTiO3 single crystal with similar composition.

Interfacial structure and electrical properties of transparent conducting ZnO thin films on polymer substrates.

The effects of polymer substrates on the interfacial structure and the thermal stability of Ga-doped ZnO (GZO) thin films were investigated. The GZO thin films were deposited on polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) substrates by rf-magnetron sputtering at room temperature, and thermal stability tests of the GZO thin films on the polymer substrates were performed at 150°C up to 8 h in air. Electrical and structural characterizations of the GZO thin films on the PET and the PEN substrates were carried out, and the origins of the stable interfacial structure and the improved thermal stability of the GZO thin film on the PEN substrate were discussed.

Self-assembled-monolayers (SAMs) modified template synthesis and characterization of SrTiO3 nanotube arrays.

A self-assembled-monolayers (SAMs) modified anodic aluminum oxide (AAO) membranes were used to generate crystalline strontium titanate (SrTiO3) nanotube arrays, which have been characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM), coupled with electron diffraction analysis. The possible formation mechanism can be explained by the induced nucleation effect of the functional headgroups in the SAMs.

Hydrothermal synthesis of SrTiO3 nanoplates through epitaxial self-assembly of nanocubes.

SrTiO3 nanoplates are obtained by the precipitation of an aqueous gel suspension. The gel suspension is prepared by hydrolysis of a Titanium isopropoxide [Ti(OCH(CH3)2)4] solution with NaOH and the addition of Sr(NO3)2. The amount of additive oleic acid plays a significant role in the formation of pure SrTiO3 phase with specific morphologies. The results of transmission electron microscopy (TEM) and electron diffraction (ED) investigations provide evidences that the oriented aggregation of small nanocubes is the dominant growth mechanism for the formation of the observed SrTiO3 nanoplates. The primary nanocrystals are self-assembled in a highly oriented fashion, producing defective single-crystal particles. The above results show that the directional aggregation process can be controlled by changing the temperature of the suspension as well as by adding organic molecules, by which the SrTiO3 particles can be obtained with a controlled size and shape.

Emissive ZnO-graphene quantum dots for white-light-emitting diodes.

Hybrid nanostructures combining inorganic materials and graphene are being developed for applications such as fuel cells, batteries, photovoltaics and sensors. However, the absence of a bandgap in graphene has restricted the electrical and optical characteristics of these hybrids, particularly their emissive properties. Here, we use a simple solution method to prepare emissive hybrid quantum dots consisting of a ZnO core wrapped in a shell of single-layer graphene. We then use these quantum dots to make a white-light-emitting diode with a brightness of 798 cd m(-2). The strain introduced by curvature opens an electronic bandgap of 250 meV in the graphene, and two additional blue emission peaks are observed in the luminescent spectrum of the quantum dot. Density functional theory calculations reveal that these additional peaks result from a splitting of the lowest unoccupied orbitals of the graphene into three orbitals with distinct energy levels. White emission is achieved by combining the quantum dots with other emissive materials in a multilayer light-emitting diode.

Thermoelectric properties of Cu-dispersed bi0.5sb1.5te3.

A novel and simple approach was used to disperse Cu nanoparticles uniformly in the Bi0.5Sb1.5Te3 matrix, and the thermoelectric properties were evaluated for the Cu-dispersed Bi0.5Sb1.5Te3. Polycrystalline Bi0.5Sb1.5Te3 powder prepared by encapsulated melting and grinding was dry-mixed with Cu(OAc)2 powder. After Cu(OAc)2 decomposition, the Cu-dispersed Bi0.5Sb1.5Te3 was hot-pressed. Cu nanoparticles were well-dispersed in the Bi0.5Sb1.5Te3 matrix and acted as effective phonon scattering centers. The electrical conductivity increased systematically with increasing level of Cu nanoparticle dispersion. All specimens had a positive Seebeck coefficient, which confirmed that the electrical charge was transported mainly by holes. The thermoelectric figure of merit was enhanced remarkably over a wide temperature range of 323-523 K.PACS: 72.15.Jf: 72.20.Pa.

Exfoliation of layers in NaxCoO2.

We proposed and developed an exfoliation process for layer-structured NaxCoO2 to prepare CoO nanosheets. Na+ ion exchange by acid treatment was utilized to expand the spacing between the two CoO2 layers in NaxCoO2. Ethylamine was then effectively utilized for the exfoliation of cobalt oxide sheets having nanometer-order thickness and high aspect ratio. CoO nanosheets were observed by TEM micrographs and electron diffraction patterns after drying. Further efforts are needed for the application of exfoliated sheets to an integration process to fabricate self-assembled nanomaterials such as desired layer structures composed of two (or more) kinds of nanosheets.

The formation mechanism of a textured ceramic of thermoelectric [Ca2CoO3](0.62)[CoO2] on beta-Co(OH)2 templates through in situ topotactic conversion.

We investigated the formation mechanism of thermoelectric [Ca(2)CoO(3)](0.62)[CoO(2)] (CCO) on beta-Co(OH)(2) templates with maintained orientations by identifying the intermediate phases and specifying the relationship between their crystallographic orientations. We mixed beta-Co(OH)(2) templates with the complementary reactant CaCO(3) and prepared a compact by tape casting, with the developed (001) plane of the templates aligned along the casting plane. High-temperature XRD of the compact revealed that beta-Co(OH)(2) decomposed into Co(3)O(4) by 873 K, and Co(3)O(4) reacted with CaO to form CCO by 1193 K via the formation of the newly detected intermediate phase beta-Na(x)()CoO(2)-type Ca(x)()CoO(2) at 913-973 K. Pole figure measurements and SEM and TEM observations revealed that the relationship between the crystallographic planes was (001) beta-Co(OH)(2)//{111} Co(3)O(4)//(001) Ca(x)()CoO(2)//(001) CCO. The crystal structures of the four materials possess the common CoO(2) layer (or similar), which is composed of edge-sharing CoO(6) octahedra, parallel to the planes. The cross-sectional HRTEM analysis of an incompletely reacted specimen showed transient lattice images from Ca(x)()CoO(2) into CCO, in which every other CoO(2) layer of Ca(x)()CoO(2) was preserved. Thus, it was demonstrated that a textured CCO ceramic is produced through a series of in situ topotactic conversion reactions with a preserved CoO(2) layer of its template.