Epitaxial Co metal thin film grown by pulsed laser deposition using oxide target

We report here the growth of epitaxial Co metal thin film on c-plane sapphire by pulsed laser deposition (RD) using Co:ZnO target utilizing the composition inhomogeneity of the corresponding plasma. Two distinct plasma composition regions have been observed using heavily alloyed Co0.6Zn0.4O target. The central and intense region of the plasma grows Co:ZnO film; the extreme tail grows only Co metal with no trace of either ZnO or Co oxide In between the two extremes, mixed phases (Co +Co-oxides +Co:ZnO) were observed. The Co metal thin film grown in this way shows room temperature ferromagnetism with large in plane magnetization similar to 1288 emu cm(-3) and a coerciviLy of similar to 230 Oe with applied field parallel to the film-substrate interface. Carrier density of the film is similar to 10(22) cm(-3). The film is epiLaxial single phase Co metal which is confirmed by both X-ray diffraction and transmission electron microscopy characierizaLions. Planar Hall Effect (PHE) and Magneto Optic Kerr Effect (MOKE) measurements confirm that the film possesses similar attributes of Co metal. The result shows that the epiLaxial Co metal thin film can be grown from its oxides in the PLD. (C) 2014 Elsevier B.V. All rights reserved.

Effect of Zirconium on the Densification of Reactively Hot-Pressed Zirconium Carbide

Densification mechanisms involved during reactive hot pressing (RHP) of zirconium carbide (ZrC) have been studied. RHP has been carried out using zirconium (Zr) and graphite (C) powders in the molar ratios 1:0.5, 1:0.67, 1:0.8, and 1:1 at 40MPa, 800 degrees C-1200 degrees C for different durations. The volume fractions of phases formed, including porosity, are determined from the measured density and from Rietveld analysis. Increased densification with an increasing nonstoichiometry in carbon has been observed. Microstructural and X-ray diffraction observations coupled with the predictions of a model based on the constitutive laws governing plastic flow of zirconium suggest that the better densification of nonstoichiometric compositions arise from the higher amount of starting Zr and also the longer duration of its availability for plastic flow during RHP. Volume shrinkage due to reaction between Zr and C and the gradual elimination of the soft metal phase limit the final density achievable. Based on these observations, a two-step RHP carried out at 800 degrees C and 1200 degrees C leads to a better densification than a single RHP at 1200 degrees C.

First principles study of metal contacts to monolayer black phosphorous

Atomically thin layered black phosphorous (BP) has recently appeared as an alternative to the transitional metal dichalcogenides for future channel material in a metal-oxide-semiconductor transistor due to its lower carrier effective mass. Investigation of the electronic property of source/drain contact involving metal and two-dimensional material is essential as it impacts the transistor performance. In this paper, we perform a systematic and rigorous study to evaluate the Ohmic nature of the side-contact formed by the monolayer BP (mBP) and metals (gold, titanium, and palladium), which are commonly used in experiments. Employing the Density Functional Theory, we analyse the potential barrier, charge transfer and atomic orbital overlap at the metal-mBP interface in an optimized structure to understand how efficiently carriers could be injected from metal contact to the mBP channel. Our analysis shows that gold forms a Schottky contact with a higher tunnel barrier at the interface in comparison to the titanium and palladium. mBP contact with palladium is found to be purely Ohmic, where as titanium contact demonstrates an intermediate behaviour. (C) 2014 AIP Publishing LLC.

Zinc oxide based photocatalysis: tailoring surface-bulk structure and related interfacial charge carrier dynamics for better environmental applications

As an alternative to the gold standard TiO2 photocatalyst, the use of zinc oxide (ZnO) as a robust candidate for wastewater treatment is widespread due to its similarity in charge carrier dynamics upon bandgap excitation and the generation of reactive oxygen species in aqueous suspensions with TiO2. However, the large bandgap of ZnO, the massive charge carrier recombination, and the photoinduced corrosion-dissolution at extreme pH conditions, together with the formation of inert Zn(OH)(2) during photocatalytic reactions act as barriers for its extensive applicability. To this end, research has been intensified to improve the performance of ZnO by tailoring its surface-bulk structure and by altering its photogenerated charge transfer pathways with an intention to inhibit the surface-bulk charge carrier recombination. For the first time, the several strategies, such as tailoring the intrinsic defects, surface modification with organic compounds, doping with foreign ions, noble metal deposition, heterostructuring with other semiconductors and modification with carbon nanostructures, which have been successfully employed to improve the photoactivity and stability of ZnO are critically reviewed. Such modifications enhance the charge separation and facilitate the generation of reactive oxygenated free radicals, and also the interaction with the pollutant molecules. The synthetic route to obtain hierarchical nanostructured morphologies and study their impact on the photocatalytic performance is explained by considering the morphological influence and the defect-rich chemistry of ZnO. Finally, the crystal facet engineering of polar and non-polar facets and their relevance in photocatalysis is outlined. It is with this intention that the present review directs the further design, tailoring and tuning of the physico-chemical and optoelectronic properties of ZnO for better applications, ranging from photocatalysis to photovoltaics.

Semiconductor to metal transition in bilayer phosphorene under normal compressive strain

Phosphorene, a two-dimensional analog of black phosphorous, has been a subject of immense interest recently, due to its high carrier mobilities and a tunable bandgap. So far, tunability has been predicted to be obtained with very high compressive/tensile in-plane strains, and vertical electric field, which are difficult to achieve experimentally. Here, we show using density functional theory based calculations the possibility of tuning electronic properties by applying normal compressive strain in bilayer phosphorene. A complete and fully reversible semiconductor to metal transition has been observed at similar to 13.35% strain, which can be easily realized experimentally. Furthermore, a direct to indirect bandgap transition has also been observed at similar to 3% strain, which is a signature of unique band-gap modulation pattern in this material. The absence of negative frequencies in phonon spectra as a function of strain demonstrates the structural integrity of the sheets at relatively higher strain range. The carrier mobilities and effective masses also do not change significantly as a function of strain, keeping the transport properties nearly unchanged. This inherent ease of tunability of electronic properties without affecting the excellent transport properties of phosphorene sheets is expected to pave way for further fundamental research leading to phosphorene-based multi-physics devices.

Thermoelectric properties of Co substituted synthetic tetrahedrite

Transition metal atom (Co) substituted synthetic tetrahedrite compounds Cu12-xCoxSb4S13 (x = 0, 0.5, 1.0, 1.5, 2.0) were prepared by solid state synthesis. X-Ray Diffraction (XRD) patterns revealed tetrahedrite as the main phase, whereas for the compounds with x = 0, 0.5 a trace of impurity phase Cu3SbS4 was observed. The surface morphology showed a large grain size with low porosity, which indicated appropriate compaction for the hot pressed samples. The phase purity, as monitored by Electron Probe Micro Analysis (EPMA) is in good agreement with the XRD data. The elemental composition for all the compounds almost matched with the nominal composition. The X-ray Photoelectron Spectroscopy (XPS) data showed that Cu existed in both +1 and +2 states, while Sb exhibited +3 oxidation states. Elastic modulus and hardness showed a systematic variation with increasing Co content. The electrical resistivity and Seebeck coefficient increased with increase in the doping content due to the decrease in the number of carriers caused by the substitution of Co2+ on the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. A combined effect of resistivity and Seebeck coefficient leads to the maximum power factor of 1.76 mW m(-1) K-2 at 673 K for Cu11.5Co0.5Sb4S13. This could be due to the optimization in the carrier concentration by the partial substitution of Co2+ on both the Cu1+ as well as Cu2+ site at the same doping levels, which is also supported by the XPS data. The total thermal conductivity systematically decreased with increase of doping content as it is mainly influenced by the decrease of carrier thermal conductivity. The maximum thermoelectric figure of merit zT = 0.98 was obtained at 673 K for Cu11.5Co0.5Sb4S13. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Prospects of zero Schottky barrier height in a graphene-inserted MoS2-metal interface

A low Schottky barrier height (SBH) at source/drain contact is essential for achieving high drive current in atomic layer MoS(2-)channel-based field effect transistors. Approaches such as choosing metals with appropriate work functions and chemical doping are employed previously to improve the carrier injection from the contact electrodes to the channel and to mitigate the SBH between the MoS2 and metal. Recent experiments demonstrate significant SBH reduction when graphene layer is inserted between metal slab (Ti and Ni) and MoS2. However, the physical or chemical origin of this phenomenon is not yet clearly understood. In this work, density functional theory simulations are performed, employing pseudopotentials with very high basis sets to get insights of the charge transfer between metal and monolayer MoS2 through the inserted graphene layer. Our atomistic simulations on 16 different interfaces involving five different metals (Ti, Ag, Ru, Au, and Pt) reveal that (i) such a decrease in SBH is not consistent among various metals, rather an increase in SBH is observed in case of Au and Pt; (ii) unlike MoS2-metal interface, the projected dispersion of MoS2 remains preserved in any MoS2-graphene- metal system with shift in the bands on the energy axis. (iii) A proper choice of metal (e.g., Ru) may exhibit ohmic nature in a graphene-inserted MoS2-metal contact. These understandings would provide a direction in developing high-performance transistors involving heteroatomic layers as contact electrodes. (c) 2016 AIP Publishing LLC.

Percolative switching in transition metal dichalcogenide field-effect transistors at room temperature

We have addressed the microscopic transport mechanism at the switching or `on-off' transition in transition metal dichalcogenide (TMDC) field-effect transistors (FETs), which has been a controversial topic in TMDC electronics, especially at room temperature. With simultaneous measurement of channel conductivity and its slow time-dependent fluctuation (or noise) in ultrathin WSe2 and MoS2 FETs on insulating SiO2 substrates where noise arises from McWhorter-type carrier number fluctuations, we establish that the switching in conventional backgated TMDC FETs is a classical percolation transition in a medium of inhomogeneous carrier density distribution. From the experimentally observed exponents in the scaling of noise magnitude with conductivity, we observe unambiguous signatures of percolation in a random resistor network, particularly, in WSe2 FETs close to switching, which crosses over to continuum percolation at a higher doping level. We demonstrate a powerful experimental probe to the microscopic nature of near-threshold electrical transport in TMDC FETs, irrespective of the material detail, device geometry, or carrier mobility, which can be extended to other classes of 2D material-based devices as well.

Effect of applied pressure on densification of monolithic ZrCx ceramic by reactive hot pressing

The effect of applied pressure on reactive hot pressing (RHP) of zirconium (Zr):graphite (C) in molar ratios of 1:0.5, 1:0.67, 1:0.8, and 1:1 was studied at 1200 degrees C for 60 min. The relative density achievable increased with increasing pressure and ranged from 99% at 4 MPa for ZrC0.5 to 93% for stoichiometric ZrC at 100 MPa. The diminishing influence of pressure on the final density with increasing stoichiometry is attributed to two causes: the decreasing initial volume fraction of the plastically deforming Zr metal which leads to the earlier formation of a contiguous, stress shielding carbide skeleton and the larger molar volume shrinkage during reaction which leads to pore formation in the final stages. A numerical model of the creep densification of a dynamically evolving microstructure predicts densities that are consistent with observations and confirm that the availability of a soft metal is primarily responsible for the achievement of such elevated densification during RHP. The ability to densify nonstoichiometric compositions like ZrC0.5 at pressures as low as 4 MPa offers an alternate route to fabricating dense nonstoichiometric carbides.

Measurements of thermal radiation in ultralight metal foams with open cells

Highly porous ultralightweight cellular metal foams with open cells have attractive mechanical, thermal, acoustic and other properties and are currently being exploited for high-temperature applications (e.g. acoustic liners for combustion chambers). In such circumstances, thermal radiation in the metal foam becomes a significant mechanism of heat transfer. This paper presents results from experimental measurements on radiative transfer in Fe-Cr-Al-Y (a steel-based high-temperature alloy) foams having high porosity (95 per cent) and different cell sizes, manufactured at low cost from the sintering route. The spectral transmittance and reflectance are measured at different infrared wavelengths ranging from 2.5 to 50 μm, which are subsequently used to determine the extinction coefficient and foam emissivity. The results show that the spectral quantities are strongly dependent on the wavelength, particularly in the short-wavelength regime (less than 25 μm). While the extinction coefficient decreases with increasing cell size, the effect of cell size on foam reflectance is not significant. When the temperature is increased, the total extinction coefficient increases but the total reflectance decreases. The effective radiative conductivity of the metal foam is obtained by using the guarded hot-plate apparatus. With the porosity fixed, the effective radiative conductivity increases with increasing cell size and increasing temperature. © IMechE 2004.

Natural convection in metal foams with open cells

This paper presents a combined experimental and numerical study on natural convection in open-celled metal foams. The effective thermal conductivities of steel alloy (FeCrAlY) samples with different relative densities and cell sizes are measured with the guarded-hot-plate method. To examine the natural convection effect, the measurements are conducted under both vacuum and ambient conditions for a range of temperatures. The experimental results show that natural convection is very significant, accounting for up to 50% of the effective foam conductivity obtained at ambient pressure. This has been attributed to the high porosity (ε > 0.9) and inter-connected open cells of the metal foams studied. Morphological parameters characterizing open-celled FeCrAlY foams are subsequently identified and their cross-relationships are built. The non-equilibrium two-equation energy transfer model is employed, and selected calculations show that the non-equilibrium effect between the solid foam skeleton and air is significant. The study indicates that the combined parameter, i.e., the porous medium Rayleigh number, is no longer appropriate to correlate natural convection by itself when the Darcy number is sufficiently large as in the case of natural convection in open-celled metal foams. Good agreement between model predictions and experimental measurements is obtained. © 2005 Elsevier Ltd. All rights reserved.

The energy spectra of uranium atoms sputtered from uranium metal and uranium dioxide targets

The energy spectra of ²³⁵U atoms sputtered from a 93% enriched ²³⁵U metal foil and a hot pressed ²³⁵U0₂ pellet by an 80 keV ⁴⁰Ar⁺ beam have been measured in the range 1 eV to 1 keV. The measurements were made using a mechanical time-of-flight spectrometer in conjunction with the fission track technique for detecting ²³⁵U. The design and construction of this spectrometer are discussed in detail, and its operation is mathematically analyzed.

The results of the experiment are discussed in the context of the random collision cascade model of sputtering. The spectrum obtained by the sputtering of the ²³⁵U metal target was found to be well described by the functional form E(E+E_b)^-2.77, where E_b = 5.4 eV. The ²³⁵U0₂ target produced a spectrum that peaked at a lower energy (~ 2 eV) and decreased somewhat more rapidly for E ≳ 100 eV.

Superionic Noble Metal Chalcogenide Thermoelectrics

Measurements and modeling of Cu₂Se, Ag₂Se, and Cu₂S show that superionic conductors have great potential as thermoelectric materials. Cu₂Se and Ag₂Se are predicted to reach a zT of 1.2 at room temperature if their carrier concentrations can be reduced, and Cu-vacancy doped Cu₂S reaches a maximum zT of 1.7 at 1000 K. Te-doped Ag₂Se achieves a zT of 1.2 at 520 K, and could reach a zT of 1.7 if its carrier concentration could be reduced. However, superionic conductors tend to have high carrier concentrations due to the presence of metal defects. The carrier concentration has been found to be difficult to reduce by altering the defect concentration, therefore materials that are underdoped relative to the optimum carrier concentration are easier to optimize. The results of Te-doping of Ag₂Se show that reducing the carrier concentration is possible by reducing the maximum Fermi level in the material.

Two new methods for analyzing thermoelectric transport data were developed. The first involves scaling the temperature-dependent transport data according to the temperature dependences expected of a single parabolic band model and using all of the scaled data to perform a single parabolic band analysis, instead of being restricted to using one data point per sample at a fixed temperature. This allows for a more efficient use of the transport data. The second involves scaling only the Seebeck coefficient and electrical conductivity. This allows for an estimate of the quality factor (and therefore the maximum zT in the material) without using Hall effect data, which are not always available due to time and budget constraints and are difficult to obtain in high-resistivity materials. Methods for solving the coherent potential approximation effective medium equations were developed in conjunction with measurements of the resistivity tensor elements of composite materials. This allows the electrical conductivity and mobility of each phase in the composite to be determined from measurements of the bulk. This points out a new method for measuring the pure-phase electrical properties in impure materials, for measuring the electrical properties of unknown phases in composites, and for quantifying the effects of quantum interactions in composites.

Classical and Quantum Effects in Plasmonic Metals

The field of plasmonics exploits the unique optical properties of metallic nanostructures to concentrate and manipulate light at subwavelength length scales. Metallic nanostructures get their unique properties from their ability to support surface plasmons– coherent wave-like oscillations of the free electrons at the interface between a conductive and dielectric medium. Recent advancements in the ability to fabricate metallic nanostructures with subwavelength length scales have created new possibilities in technology and research in a broad range of applications.

In the first part of this thesis, we present two investigations of the relationship between the charge state and optical state of plasmonic metal nanoparticles. Using experimental bias-dependent extinction measurements, we derive a potential- dependent dielectric function for Au nanoparticles that accounts for changes in the physical properties due to an applied bias that contribute to the optical extinction. We also present theory and experiment for the reverse effect– the manipulation of the carrier density of Au nanoparticles via controlled optical excitation. This plasmoelectric effect takes advantage of the strong resonant properties of plasmonic materials and the relationship between charge state and optical properties to eluci- date a new avenue for conversion of optical power to electrical potential.

The second topic of this thesis is the non-radiative decay of plasmons to a hot-carrier distribution, and the distribution’s subsequent relaxation. We present first-principles calculations that capture all of the significant microscopic mechanisms underlying surface plasmon decay and predict the initial excited carrier distributions so generated. We also preform ab initio calculations of the electron-temperature dependent heat capacities and electron-phonon coupling coefficients of plasmonic metals. We extend these first-principle methods to calculate the electron-temperature dependent dielectric response of hot electrons in plasmonic metals, including direct interband and phonon-assisted intraband transitions. Finally, we combine these first-principles calculations of carrier dynamics and optical response to produce a complete theoretical description of ultrafast pump-probe measurements, free of any fitting parameters that are typical in previous analyses.