Ultrafast Chemical Dynamics in Time Domain Through Fluorescence Spectroscopy

While absorption and emission spectroscopy have always been used to detect and characterize molecules and molecular complexes, the availability of ultrashort laser pulses and associated computer-aided optical detection techniques allowed study of chemical processes directly in the time domain at unprecedented time scales, through appearance and disappearance of fluorescence from participating chemical species. Application of such techniques to chemical dynamics in liquids, where many processes occur with picosecond and femtosecond time scales lead to the discovery of a host of new phenomena that in turn led to the development of many new theories. Experiment and theory together provided new and valuable insight into many fundamental chemical processes, like isomerization dynamics, electron and proton transfer reactions, vibrational energy and phase relaxation, photosynthesis, to name just a few. In this article, we shall review a few of such discoveries in attempt to provide a glimpse of the fascinating research employing fluorescence spectroscopy that changed the field of chemical dynamics forever.

Anodization of Aluminium using a fast two-step process

Ultra-fast two-step anodization method is developed for obtaining ordered nano-pores on aluminium (Al) foil. First anodization was carried out for 10 min, followed by 3 min of second anodization at high voltage (150 V) compared to previous reports of anodization times of 12 h (40-60 V). The pore dimensions on anodized alumina are 180 nm for pore diameter and 130 nm for inter-pore distance. It was evident that by increasing the anodization voltage to 150 V, the diameter of the pores formed was above 150 nm. The electrolyte and its temperature affect the shape and size of the pore formation. At lower anodization temperature, controlled pore formation was observed. The anodized samples were characterized using the field emission scanning electron microscope (FE-SEM) to determine the pore diameter and inter-pore distance. Using UV-Visible spectroscopy, the reflectance spectra of anodized samples were measured. The alumina (Al2O3) peaks were identified by x-ray diffraction (XRD) technique. The x-ray photo electron spectroscopy (XPS) analysis confirmed the Al 2p peak at 73.1 eV along with the oxygen O 1s at 530.9 eV and carbon traces C 1s at 283.6 eV.

Optical-Phonon-Limited High-Field Transport in Layered Materials

An optical-phonon-limited velocity model has been employed to investigate high-field transport in a selection of layered 2-D materials for both, low-power logic switches with scaled supply voltages, and high-power, high-frequency transistors. Drain currents, effective electron velocities, and intrinsic cutoff frequencies as a function of carrier density have been predicted, thus providing a benchmark for the optical-phonon-limited high-field performance limits of these materials. The optical-phonon-limited carrier velocities for a selection of multi-layers of transition metal dichalcogenides and black phosphorus are found to be modest compared to their n-channel silicon counterparts, questioning the utility of biasing these devices in the source-injection dominated regime. h-BN, at the other end of the spectrum, is shown to be a very promising material for high-frequency, high-power devices, subject to the experimental realization of high carrier densities, primarily due to its large optical-phonon energy. Experimentally extracted saturation velocities from few-layer MoS2 devices show reasonable qualitative and quantitative agreement with the predicted values. The temperature dependence of the measured v(sat) is discussed and compared with the theoretically predicted dependence over a range of temperatures.

Detection of quantum well induced single degenerate-transition-dipoles in ZnO nanorods

Quantifying and characterising atomic defects in nanocrystals is difficult and low-throughput using the existing methods such as high resolution transmission electron microscopy (HRTEM). In this article, using a defocused wide-field optical imaging technique, we demonstrate that a single ultrahigh-piezoelectric ZnO nanorod contains a single defect site. We model the observed dipole-emission patterns from optical imaging with a multi-dimensional dipole and find that the experimentally observed dipole pattern and model-calculated patterns are in excellent agreement. This agreement suggests the presence of vertically oriented degenerate-transition-dipoles in vertically aligned ZnO nanorods. The HRTEM of the ZnO nanorod shows the presence of a stacking fault, which generates a localised quantum well induced degenerate-transition-dipole. Finally, we elucidate that defocused wide-field imaging can be widely used to characterise defects in nanomaterials to answer many difficult questions concerning the performance of low-dimensional devices, such as in energy harvesting, advanced metal-oxide-semiconductor storage, and nanoelectromechanical and nanophotonic devices.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

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.

Study of band offsets at the Cu2SnS3/In2O3: Sn interface using x-ray photoelectron spectroscopy

Cu2SnS3 thins films were deposited onto In2O3: Sn coated soda lime glass substrates by spin coating technique. The films have been structurally characterized using x-ray Diffraction (XRD) and Atomic Force Microscopy (AFM). The morphology of the films was studied using Field Emission Scanning Electron Microscopy (FESEM). The optical properties of the films were determined using UV-vis-NIR spectrophotometer. The electrical properties were measured using Hall effect measurements. The energy band offsets at the Cu2SnS3/In2O3: Sn interface were calculated using x-ray photoelectron spectroscopy (XPS). The valence band offset was found to be -3.4 +/- 0.24 eV. From the valence band offset value, the conduction band offset is calculated to be -1.95 +/- 0.34 eV. The energy band alignment indicates a type-II misaligned heterostructure formation.

Effect of Magnetic Field on Photoresponse of Cobalt Integrated Zinc Oxide Nanorods

Cobalt integrated zinc oxide nanorod (Co-ZnO NR) array is presented as a novel heterostructure for ultraviolet (UV) photodetector (PD). Defect states in Co-ZnO NRs surface induces an enhancement in photocurrent as compared to pristine ZnO NRs PD. Presented Co-ZnO NRs PD is highly sensitive to external magnetic field that demonstrated 185.7% enhancement in response current. It is concluded that the opposite polarizations of electron and holes in the presence of external magnetic field contribute to effective separation of electron hole pairs that have drifted upon UV illumination. Moreover, Co-ZnO NRs PD shows a faster photodetection speed (1.2 s response time and 7.4 s recovery time) as compared to the pristine ZnO NRs where the response and recovery times are observed as 38 and 195 s, respectively.

The influence of current density on the morphology and corrosion properties of MAO coatings on AZ31B magnesium alloy

Micro-arc oxidation (MAO) coatings were prepared on AZ31B magnesium alloy using alkaline silicate electrolyte at different current densities (0.026, 0.046 and 0.067 A/cm(2)). Field Emission Scanning Electron Microscopy (FESEM) analysis of the coating revealed an irregular porous structure with cracked morphology. Compositional analysis carried out for MAO coating showed the presence of almost an equal amount of Mg and 0 (34 wt.%) apart from other elements such as F, Si and AI. The cross-sectional FESEM images clearly portrayed that the MAO coating was dense along with the presence of very few fine pores. The surface roughness (R-a) of the coatings increased with an increase in the current density. Potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies were carried out for both the bare and MAO coated AZ31B Mg alloy in 3.5% NaCl solution. The corrosion potential (E-corr) and corrosion current density (i(corr)) values obtained for the bare substrate were -1.49 V and 46 mu A/cm(2), respectively. The coating prepared at 0.046 A/cm(2) exhibited the lowest i(corr) value of 7.79 x 10(-10) A/cm(2) and highest polarization resistance (41.6 M Omega cm(2)) attesting to the better corrosion resistance of the coating compared to other samples. EIS results also indicated almost similar corrosion behavior for the MAO coatings. Mott-Schottky analysis showed n-type and p-type semiconductor behavior for the oxide layer present on the bare magnesium alloy and MAO coatings respectively. (C) 2016 Published by Elsevier B.V.

Observation of Size-Dependent Electron-Phonon Scattering and Temperature-Dependent Photoluminescence Quenching in Triangular-Shaped Silver Nanoparticles

Research studies on plasmonic properties of triangular-shaped silver nanoparticles might lead to several interesting applications. However, in this work, triangular-shaped silver nanoparticles have been synthesized by simple solvothermal technique and reported the effect of size on the electron-phonon scattering in the synthesized materials by analyzing their temperature-dependent photoluminescence (PL) emission characteristics. It has been observed that total integrated PL emission intensity is quenched by 33 % with the increase in temperature from 278 to 323 K. The observed decrease in PL emission intensity has been ascribed to the increase of electron-phonon scattering rate with the increase in temperature. The values of electron-phonon coupling strength (S) for synthesized samples have been evaluated by theoretical fitting of the experimentally obtained PL emission data. Smaller sized triangular nanoparticle has been found to exhibit stronger temperature dependence in PL emission, which strongly suggests that smaller sized triangular silver nanostructures have better electron-phonon coupling.

Tetraphenylethene-Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star-shaped, novel, fluoranthene-tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation-induced blue-shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature-dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6-trinitrophenol (PA) with high sensitivity and a high Stern-Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70% water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70% exhibit high Stern-Volmer constants (K-sv=79998 and 51120m(-1), respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra-low-level detection of PA for real-time field analysis.

Low Threshold Quantum Dot Lasers

Semiconductor quantum dots have replaced conventional inorganic phosphors in numerous applications. Despite their overall successes as emitters, their impact as laser materials has been severely limited. Eliciting stimulated emission from quantum dots requires excitation by intense short pulses of light typically generated using other lasers. In this Letter, we develop a new class of quantum dots that exhibit gain under conditions of extremely low levels of continuous wave illumination. We observe thresholds as low as 74 mW/cm(2) in lasers made from these materials. Due to their strong optical absorption as well as low lasing threshold, these materials could possibly convert light from diffuse, polychromatic sources into a laser beam.

Electron-hole asymmetry in the electron-phonon coupling in top-gated phosphorene transistor

Using in situ Raman scattering from phosphorene channel in an electrochemically top-gated field effect transistor, we show that phonons with A(g) symmetry depend much more strongly on concentration of electrons than that of holes, wheras phonons with B-g symmetry are insensitive to doping. With first-principles theoretical analysis, we show that the observed electon-hole asymmetry arises from the radically different constitution of its conduction and valence bands involving pi and sigma bonding states respectively, whose symmetry permits coupling with only the phonons that preserve the lattice symmetry. Thus, Raman spectroscopy is a non-invasive tool for measuring electron concentration in phosphorene-based nanoelectronic devices.

High Frequency Acousto-electric Single Photon Source

We propose a single optical photon source for quantum cryptography based on the acousto-electric effect. Surface acoustic waves (SAWs) propagating through a quasi-one-dimensional channel have been shown to produce packets of electrons which reside in the SAW minima and travel at the velocity of sound. In our scheme these electron packets are injected into a p-type region, resulting in photon emission. Since the number of electrons in each packet can be controlled down to a single electron, a stream of single (or N) photon states, with a creation time strongly correlated with the driving acoustic field, should be generated.

Zinc oxide nanostructures and high electron mobility nanocomposite thin film transistors

This paper reports on the synthesis of zinc oxide (ZnO) nanostructures and examines the performance of nanocomposite thin-film transistors (TFTs) fabricated using ZnO dispersed in both n- and p-type polymer host matrices. The ZnO nanostructures considered here comprise nanowires and tetrapods and were synthesized using vapor phase deposition techniques involving the carbothermal reduction of solid-phase zinc-containing compounds. Measurement results of nanocomposite TFTs based on dispersion of ZnO nanorods in an n-type organic semiconductor ([6, 6]-phenyl-C61-butyric acid methyl ester) show electron field-effect mobilities in the range 0.3-0.6 cm2V-1 s-1. representing an approximate enhancement by as much as a factor of 40 from the pristine state. The on/off current ratio of the nanocomposite TFTs approach 106 at saturation with off-currents on the order of 10 pA. The results presented here, although preliminary, show a highly promising enhancement for realization of high-performance solution-processable n-type organic TFTs. © 2008 IEEE.