Strain-induced electronic phase transition and strong enhancement of thermopower of TiS2

Using first principles density functional theory calculations, we show a semimetal to semiconducting electronic phase transition for bulk TiS 2 by applying uniform biaxial tensile strain. This electronic phase transition is triggered by charge transfer from Ti to S, which eventually reduces the overlap between Ti-(d) and S-(p) orbitals. The electronic transport calculations show a large anisotropy in electrical conductivity and thermopower, which is due to the difference in the effective masses along the in-plane and out of plane directions. Strain induced opening of band gap together with changes in dispersion of bands lead to three-fold enhancement in thermopower for both p- and n-type TiS2 . We further demonstrate that the uniform tensile strain, which enhances the thermoelectric performance, can be achieved by doping TiS2 with larger iso-electronic elements such as Zr or Hf at Ti sites.Comment: 8 pages, 6 figure

Large Thermoelectric Power Factor in TiS2 Crystal with Nearly Stoichiometric Composition

A TiS$_{2}$ crystal with a layered structure was found to have a large thermoelectric power factor.The in-plane power factor $S^{2}/ \rho$ at 300 K is 37.1~$\mu$W/K$^{2}$cm with resistivity ($\rho$) of 1.7 m$\Omega$cm and thermopower ($S$) of -251~$\mu$V/K, and this value is comparable to that of the best thermoelectric material, Bi$_{2}$Te$_{3}$ alloy. The electrical resistivity shows both metallic and highly anisotropic behaviors, suggesting that the electronic structure of this TiS$_{2}$ crystal has a quasi-two-dimensional nature. The large thermoelectric response can be ascribed to the large density of state just above the Fermi energy and inter-valley scattering. In spite of the large power factor, the figure of merit, $ZT$ of TiS$_{2}$ is 0.16 at 300 K, because of relatively large thermal conductivity, 68~mW/Kcm. However, most of this value comes from reducible lattice contribution. Thus, $ZT$ can be improved by reducing lattice thermal conductivity, e.g., by introducing a rattling unit into the inter-layer sites.Comment: 11 pages, 4 figures, to be published in Physical Review

Charge Control Investigation of Rechargeable Lithium Cells

An ambient temperature rechargeable Li-TiS2 cell was cycled under conditions which simulate aerospace applications. A novel charge/discharge state-of-charge control scheme was used, together with tapered current charging, to overcome deleterious effects associated with end-of-charge and end-of-discharge voltages. The study indicates that Li-TiS2 cells hold promise for eventual synchronous satellite-type applications. Problem areas associated with performance degradation and reconditioning effects are identified

Growth and characterisation of titanium sulphide nanostructures by surface-assisted vapour transport methods; from trisulphide ribbons to disulphide nanosheets

Surface Assisted Chemical Vapour Transport (SACVT) methods have been employed to grow nanostructures of titanium disulphide (TiS2) and titanium trisulphide (TiS3). SACVT reactions occur between titanium and sulphur powders to form TiSx species transported in the vapour phase to grow nanometric flower-like structures on titanium-coated silica substrates. The evolution of structure and composition has been followed by powder X-ray diffraction, electron microscopy and Raman spectroscopy. At 1 : 2 Ti : S ratios, the size and shape of the hexagonal 1T-TiS2 titanium disulphide structures formed can be varied from flower-like growths with 'petals' formed from nanosheets 10 nm thick to platelets microns across. Increasing the proportion of sulphur (Ti : S 1 : 4) enables TiS3 flower-like structures composed of radiating nanoribbons to grow at elevated temperatures without decomposition to TiS2. TEM/SAED suggests that individual trisulphide ribbons grow along the [010] direction. Magnetic properties of the disulphide nanomaterials have been determined using SQUID magnetometry and Raman spectra for disulphides suggest that their crystal and electronic structures may be more complex than expected for bulk, stoichiometric, CdI2-structured TiS2

Software-Based Self-Test of Set-Associative Cache Memories

Embedded microprocessor cache memories suffer from limited observability and controllability creating problems during in-system tests. This paper presents a procedure to transform traditional march tests into software-based self-test programs for set-associative cache memories with LRU replacement. Among all the different cache blocks in a microprocessor, testing instruction caches represents a major challenge due to limitations in two areas: 1) test patterns which must be composed of valid instruction opcodes and 2) test result observability: the results can only be observed through the results of executed instructions. For these reasons, the proposed methodology will concentrate on the implementation of test programs for instruction caches. The main contribution of this work lies in the possibility of applying state-of-the-art memory test algorithms to embedded cache memories without introducing any hardware or performance overheads and guaranteeing the detection of typical faults arising in nanometer CMOS technologie

Thermally stable electrolytes for rechargeable lithium batteries, phase 2

During the second year of research under NASA SBIR Contract NAS7-967, Covalent Associates and NASA contract monitors at the Jet Propulsion Laboratory agreed to perform an evaluation of the three best electrolytes developed during Phase 2. Due to the extensive period of time required to collect meaningful cycling data, we realized the study would extend well beyond the original formal end of the Phase 2 program (August 31, 1988). The substitution of this effort in lieu of an earlier proposed 20-cell final deliverable is formally documented in Modification No. 1 of Contract NAS7-967 as task 7. This Addendum contains the results of the cycling studies performed at Covalent Associates. In addition, sealed ampoules of each of these three electrolytes were delivered to the Jet Propulsion Laboratory Electrochemical Power Group. Their concurrent evaluation in a different test vehicle has also been recently concluded and their results are also summarized herein

Intrinsic effects of substitution and intercalation on thermal transport in two-dimensional TiS2_2 single crystals

The promising thermoelectric material TiS$_2$ can be easily chemically doped and intercalated. We present here studies of single crystals that are intercalated with excess Ti or Co, or substituted with Ta. We demonstrate the intrinsic impact of these dopants on the thermal transport in the absence of grain boundary scattering. We show that Ta doping has the greatest impact on the thermal scattering rate per ion added, leading to a five-fold reduction in the lattice thermal conductivity as compared to stoichiometric single crystals.Comment: 5 pages, 2 figure

Two dimensional crystals in three dimensions: electronic decoupling of single-layered platelets in colloidal nanoparticles

Two-dimensional crystals, single sheets of layered materials, often show distinct properties desired for optoelectronic applications, such as larger and direct band gaps, valley- and spinorbit effects. Being atomically thin, the low amount of material is a bottleneck in photophysical and photochemical applications. Here, we propose the formation of stacks of two-dimensional crystals intercalated with small surfactant molecules. We show, using first principles calculations, that already the very short surfactant methyl amine electronically decouples the layers. We demonstrate the indirect-direct band gap transition characteristic for Group 6 transition metal dichalcogenides experimentally by observing the emergence of a strong photoluminescence signal for ethoxide-intercalated WSe2 and MoSe2 multilayered nanoparticles with lateral size of about 10 nm and beyond. The proposed hybrid materials offer the highest possible density of the two-dimensional crystals with electronic properties typical for monolayers. Variation of the surfactant's chemical potential allows fine-tuning of electronic properties and potentially elimination of trap states caused by defects