Dilip K. Singh

Correlation between microstructure and optical properties of ZnO nanoparticles synthesized by ball milling

Zinc oxide (ZnO) nanoparticles (NPs) in the size range ∼7–35 nm are synthesized by ball-milling technique, and microstructural and optical properties of the NPs are studied using varieties of techniques. Results from ball-milled NPs are compared with those of the commercially available ZnO nanopowder. X-ray diffraction pattern of the milled NPs indicates lattice strain in the NPs. High-resolution transmission electron microscopy analysis reveal severe lattice distortion and reduction in lattice spacing in some of the NPs. Optical absorption spectra of milled NPs show enhanced absorption peaked at 368 nm, which is blueshifted with reference to starting ZnO powder. Room-temperature photoluminescence spectra show five peaks consisting of ultraviolet and visible bands, and relative intensity of these peaks drastically changes with increasing milling time. Raman spectra of milled powders show redshift and broadening of the Raman modes of ZnO, and a new Raman mode evolve in the milled NPs. A correlation between...

Diameter dependence of oxidative stability in multiwalled carbon nanotubes: Role of defects and effect of vacuum annealing

While the oxidative stability of single walled carbon nanotubes has been studied extensively, very little is known about the diameter dependence of oxidative stability in multiwalled carbon nanotubes (MWNTs) and the effect of vacuum annealing on such stability. We have investigated six sets of samples with different diameters in the range of 5–100 nm systematically by thermogravimetric analysis (TGA) before and after vacuum annealing. High resolution transmission electron microscopy studies provide evidence for structural defects in the nanotube walls. Further, it reveals that with increasing diameter, interlayer d-spacing between concentric tubes decreases. Experimental TGA profile is found to constitute multiple components of oxidation as revealed from reverse Sigmoidal fitting. Analysis of the TGA profile shows that the oxidation temperature follows an exponential recovery function with increasing diameter, while width of the differentiated TGA spectra decreases. It is shown that oxidative stability of...

Enhancing the Photostability of Poly(3-hexylthiophene) by Preparing Composites with Multiwalled Carbon Nanotubes

Poly(3-hexylthiophene) (P3HT) degrades in organic solvents containing dissolved molecular oxygen when irradiated with ultraviolet light. Hence, it is important to develop strategies that can enhance the photostability of P3HT and enhance the device performance. In this work, we report that preparing composites of P3HT with appropriate amounts of multiwalled carbon nanotube (MWCNT) results in superior photostability of P3HT. UV-visible and fluorescence spectroscopy have been used as primary tools to study the photostability of P3HT and its composites. Scanning electron microscopy (SEM) images of the composites display dispersed CNTs being well coated by P3HT. Transmission electron microscopy (TEM) micrographs along with SAED patterns reveal that P3HT coats the CNTs, which is the reason for superior dispersion of the composite. ESR spectroscopy was also performed to pursue and follow the degradation of P3HT. Ten weight percent of MWCNTs in P3HT was found to be the optimum loading amount that results in maximum photostability of the P3HT as compared to the other ratios. This enhanced photostability of P3HT on preparing composites with MWCNT in addition to its easy processability directly from solution makes these composites immensely important for optoelectronic applications.

Structural, optical and electronic properties of homoepitaxial GaN nanowalls grown on GaN template by laser molecular beam epitaxy

We have grown homoepitaxial GaN nanowall networks on GaN template using an ultra-high vacuum laser assisted molecular beam epitaxy system by ablating solid GaN target under a constant r.f. nitrogen plasma ambient. The effect of laser repetition rate in the range of 10 to 30 Hz on the structural properties of the GaN nanostructures has been studied using high resolution X-ray diffraction, field emission scanning electron microscopy and Raman spectroscopy. The variation of the laser repetition rate affected the tip width and pore size of the nanowall networks. The z-profile Raman spectroscopy measurements revealed the GaN nanowall network retained the same strain present in the GaN template. The optical properties of these GaN nanowall networks have been studied using photoluminescence and ultrafast spectroscopy and an enhancement of optical band gap has been observed for the nanowalls having a tip width of 10–15 nm due to the quantum carrier confinement effect at the wall edges. The electronic structure of the GaN nanowall networks has been studied using X-ray photoemission spectroscopy and it has been compared to the GaN template. The calculated Ga/N ratio is largest (∼2) for the GaN nanowall network grown at 30 Hz. Surface band bending decreases for the nanowall network with the lowest tip width. The homoepitaxial growth of porous GaN nanowall networks holds promise for the design of nitride based sensor devices.

Optical field enhancement of nanometer-sized gaps at near-infrared frequencies

We report near-field and far-field measurements of transmission through nanometer-sized gaps at near-infrared frequencies with varying the gap size from 1 nm to 10 nm. In the far-field measurements, we excluded direct transmission on the metal film surface via interferometric method. Kirchhoff integral formalism was used to relate the far-field intensity to the electric field at the nanogaps. In near-field measurements, field enhancement factors of the nanogaps were quantified by measuring transmission of the nanogaps using near-field scanning optical microscopy. All the measurements produce similar field enhancements of about ten, which we put in the context of comparing with the giant field enhancements in the terahertz regime.

Ultrasensitive and fast detection of denaturation of milk by coherent backscattering of light.

In this work, Coherence backscattering (CBS) of light has been used to detect the onset of denaturation of milk. The CBS cone shape and its enhancement factor are found to be highly sensitive to the physical state of the milk particles. The onset of denaturing of milk not visible to the naked eye, can be easily detected from changes in the CBS cone shape. The onset of denaturation is confirmed by spectral changes in Raman spectra from these milk samples. Further, the possibility to estimate the dilution of milk by water as an adulterant is demonstrated. The method reported has a broad scope in industry for making an inline ultrafast cost effective sensor for milk quality monitoring during production and before consumption.

IMPROVED CHEMICAL SYNTHESIS OF GRAPHENE USING A SAFER SOLVOTHERMAL ROUTE

Graphene has been synthesized using thermal decomposition of ethyl alcohol in a medium pressure autoclave. The synthesis was carried out in the presence of strong alkaline solution at a temperature of ~230°C and pressure of 60 bar. The as-synthesized graphene has been characterized using atomic force microscopy (AFM) and high-resolution transmission electron microscopy (HRTEM). AFM analysis on various graphene sheets shows the presence of monolayer (n = 1) to trilayer (n = 3) graphene sheets with thickness of ~1.168 nm. HRTEM studies confirm the high quality of graphene obtained after purification of as-synthesized product. Use of chemically nonexplosive material for synthesis and reduced reaction time along with the absence of post-pyrolysis process make it a commercially viable process for bulk production of graphene.

Distinguishing defect induced intermediate frequency modes from combination modes in the Raman spectrum of single walled carbon nanotubes

Understanding of the origin of some of the intermediate frequency modes (IFMs) in the Raman spectrum of carbon nanotubes has remained controversial in the literature. In this work, through controlled introduction and elimination of defects in carbon nanotubes, we attempt to isolate the IFMs due to structural defects from that of the combination modes in single walled carbon nanotubes (SWCNTs). Our investigations on pristine and defect engineered SWCNTs using ion-irradiation, thermal annealing, and laser processing show systematic changes in the IFMs in the range 400–1200 cm−1 and its manipulation with the processing parameters. In particular, we found that the intensity of IFM at 929 cm−1 scale up with the increasing defect concentration, while that at 668 cm−1 follows opposite behavior. New IFM peaks were observed upon the creation of a controlled amount of structural defects through 30 keV N+ ion irradiation. Elimination of defects through vacuum annealing results into reduction of intensity of some IFM...

Studies on Zinc Oxide Nanorods Grown by Electron Beam Evaporation Technique

Nanocrystalline zinc oxide-thin films have drawn the attention of researchers due to its attractive properties like transparency in visible region, abundance in nature and gas sensitivity. Nanostructured Zinc oxide (ZnO) thin films were grown on silicon, alumina and glass substrates at various substrate temperatures using a 6 kW electron beam evaporation technique. The effects of film thickness, growth temperature and substrate on the crystallinity of deposited ZnO films were investigated using X‐ray diffraction, scanning electron microscopy, optical absorption and photoluminescence studies. Our studies show that good quality films are obtained for silicon substrate for a growth temperature of 250°C. Film thickness plays an important role on the evolution of the nanostructures. SEM studies combined with XRD analysis reveal that ultrathin nanorods are grown with (002), (101) and (102) orientations. All the ZnO films show room temperature photoluminescence emission bands at 394 nm and 468 nm. Optical absorption studies show strong absorption at 377 nm. Details of the structure and optical properties correlation will be presented and potential of a simple technique such as e‐beam deposition to grown ZnO nanostructures suitable for optoelectronic application will be assessed.

Emerging photoluminescence from bilayer large-area 2D MoS2 films grown by pulsed laser deposition on different substrates

We report the growth of continuous large area bilayer films of MoS2 on different substrates by pulsed laser deposition (PLD). The growth parameters for PLD were modified in such a way that results in bilayer 2D-MoS2 films on both c-Al2O3 (0001) (sapphire) and SiO2/Si (SO) substrates. The bilayer large area crystalline nature of growth in the 2 H-phase is determined by Raman spectroscopy. Cross-sectional transmission electron microscopy confirms the distinct thinnest ordered layered structure of MoS2. Chemical analysis reveals an almost stoichiometric 2 H-phase on both the substrates. The photoluminescence intensities of both the films match very well with those of the corresponding exfoliated flakes, as well as chemical vapor deposited (CVD) films as reported in the literature. The in-situ post growth annealing with optimal film thickness acts as a solid phase epitaxy process which provides continuous crystalline layers with a smooth interface and regulates the photoluminescence properties. In contrast, t...