Reaction Atmosphere-Controlled Thermal Conversion of Ferrocene to Hematite and Cementite Nanomaterials-Structural and Spectroscopic Investigations.

Recently, we have reported the influence of various reaction atmospheres on the solid-state reaction kinetics of ferrocene, where oxalic acid dihydrate was used as a coprecursor. In this light, present study discusses on the nature of decomposed materials of the solid-state reactions of ferrocene in O2, air, and N2 atmospheres. The ambient and oxidative atmospheres caused the decomposition to yield pure hematite nanomaterials, whereas cementite nanomaterials along with α-Fe were obtained in N2 atmosphere. The obtained materials were mostly agglomerated. Elemental composition of each material was estimated. Using the absorbance data, the energy band gap values were estimated and the related electronic transitions from the observed absorption spectra were explored. Urbach energy was calculated for hematite, which described the role of defects in the decomposed materials. The nanostructures exhibited photoluminescence due to self-trapped states linked to their optical characteristics. Raman spectroscopy of hematite detected seven Raman modes, confirming the rhombohedral structure, whereas the D and G bands were visible in the Raman spectra for cementite. Thus, the reaction atmosphere significantly influenced the thermal decomposition of ferrocene and controls the type of nanomaterials obtained. Plausible reactions of the undergoing solid-state decomposition have been proposed.

Effect of phonon anharmonicity on thermal conductivity of ZnTe Thin films.

The ZnTe thin film is a potential material for optoelectronic devices in extreme temperature and radiation environments. In this report, the thermal conductivity of ZnTe films is measured non-invasively using the micro-Raman method and correlated with the phonon anharmonic effect. The evolution of crystalline ZnTe thin films from Te/ZnO bilayer by thermal annealing at 450 ∘C has been observed above the melting point of Te, which is confirmed from x-ray diffraction and high-resolution transmission electron microscopy. The ZnTe thin films illustrate three longitudinal phonon modes with higher harmonics of nLO (n= 3) at room temperature. Temperature-dependent Raman spectra in the range of 93-303 K are used to analyze the phonon anharmonicity from Raman shift, FWHM, and Phonon lifetime of the thin films. The Balkanski model is used to fit the anharmonicity-induced phonon frequency shift of nLO modes as a function of temperature, taking into account three- and four-phonon interactions. The intensity ratio of the I2LO/I1LOand I3LO/I2LOprovide information about the electron-phonon coupling strength, which is influenced by the anharmonic effect. The laser power-dependent Raman spectra are used to determine the thermal conductivity of the ZnTe films, which is found to be approximately 9.68 Wm-1K-1, remains relatively constant for all nLO modes, indicating that multi-phonon scattering process. The correlation between thermal conductivity and phonon anharmonicity can pave the way for understanding the phonon scattering process in ZnTe thin films for high-performance optoelectronic device applications in harsh conditions.

Influence of defects on the linear and nonlinear optical properties of Cu-doped rutile TiO2 microflowers.

Defects and disorder work as controlling parameters to alter the electronic structure of nanostructures and significantly influence their electronic, magnetic, and nonlinear optical (NLO) properties. In this study, we found that defect engineering is an effective strategy for tailoring the linear and nonlinear optical properties of Cu-doped titanium oxide (TiO2) flower-shaped nanostructures. The concentration of chemical doping of Cu in the TiO2 lattice creates intermediate defect states that impact electronic bandgap reduction and tunable defect luminescence. The estimation of the bandgap from density functional theory calculation follows the same trend of bandgap narrowing with Cu doping. The XPS study reveals that oxygen defects are responsible for bandgap narrowing and quenching of the PL intensity. A single-beam Z-scan technique with open and closed aperture configurations using ultrashort pulses centered at 532 nm excitation wavelength was used to study the NLO measurements. The open aperture reveals saturable absorption, whereas the closed aperture shows self-focusing behavior. The nonlinear absorption coefficient and refractive index extracted from NLO measurements demonstrate the linear dependence on the defect concentration and bandgap. The effects of heterogeneous dopants and lattice disorder on the nonlinear absorption behavior of these nanostructures are discussed in comparison with the figure of merit, non-linear refractive index, and absorption coefficient. The tunable NLO properties achieved by controlling such dopant-induced defects boost the scope of these nanostructures as optical limiting, optical switching, and optical photodiode applications.

Plasmon mediated SERS and photocatalysis enhancement in Au nanoparticle decorated 2D-TiSe2.

The combination of 2D materials and noble metallic nanostructure is becoming an attractive research domain for label-free, highly sensitive surface-enhanced Raman spectroscopy (SERS) applications. This study demonstrated photocatalysis degradation and SERS enhancements of organic fluorophore (Rhodamine 6G) on two-dimensional (2D) TiSe2using Raman spectroscopy. The Au nanoparticles (NPs) were decorated on TiSe2thin films by thermal annealing at variable temperatures. The selective deposition of Au NPs on the hexagonal TiSe2nanocrystals increases surface roughness, creating a larger surface area for molecule adsorption. It has been observed that the Au decoration at 250 °C on TiSe2exhibits efficient detection capabilities for R6G with the Raman intensity enhancement factors of the order of ≈105along with the significantly improved visible light-induced photodegradation efficiency. The optimized Au NP size creates large electromagnetic hot spots produced by strong plasmon coupling that assists in the charge transfer mechanism among TiSe2, Au NPs, and R6G for enhanced SERS and photocatalysis activities. It has been observed that the intensity of Raman scattering decreases as the Au NP size increases on the TiSe2material. A possible charge transfer mechanism is proposed with an energy band diagram. The simultaneous measurement of SERS and photocatalytic dye degradation in Au decorated TiSe2can be used as a sensitive technique for water pollution treatment and biodegradable organic contaminants for the environmental ecosystem.

Cathodoluminescence and optical absorption spectroscopy of plasmonic modes in chromium micro-rods.

Manipulating light at the sub-wavelength level is a crucial feature of surface plasmon resonance (SPR) properties for a wide range of nanostructures. Noble metals like Au and Ag are most commonly used as SPR materials. Significant attention is being devoted to identify and develop non-noble metal plasmonic materials whose optical properties can be reconfigured for plasmonic response by structural phase changes. Chromium (Cr) which supports plasmon resonance, is a transition metal with shiny finished, highly non-corrosive, and bio-compatible alloys, making it an alternative plasmonic material. We have synthesized Cr micro-rods from a bi-layer of Cr/Au thin films, which evolves from face centered cubic to hexagonal close packed (HCP) phase by thermal activation in a forming gas ambient. We employed optical absorption spectroscopy and cathodoluminescence (CL) imaging spectroscopy to observe the plasmonic modes from the Cr micro-rod. The origin of three emission bands that spread over the UV-Vis-IR energy range is established theoretically by considering the critical points of the second-order derivative of the macroscopic dielectric function obtained from density functional theory (DFT) matches with interband/intraband transition of electrons observed in density of states versus energy graph. The experimentally observed CL emission peaks closely match thes-dandd-dband transition obtained from DFT calculations. Our findings on plasmonic modes in Cr(HCP) phase can expand the range of plasmonic material beyond noble metal with tunable plasmonic emissions for plasmonic-based optical technology.

Modulation of intrinsic defects in vertically grown ZnO nanorods by ion implantation.

Intrinsic defects created by chemically inert gas (Xe) ion implantation in vertically grown ZnO nanorods are studied by optical and X-ray absorption spectroscopy (XAS). The surface defects produced due to dynamic sputtering by ion beams control the fraction of O and Zn with ion fluence, which helps in tuning the optoelectronic properties. The forbidden Raman modes related to Zn interstitials and oxygen vacancies are observed because of the weak Fröhlich interaction, which arises due to disruption of the long-range lattice order. The evolution of the lattice disorder is identified by O K-edge and Zn K-edge scans of XAS. The hybridization strength between the O 2p and Zn 4p states increases with ion fluence and modulates the impact of intrinsic defects. The ion irradiation induced defects also construct intermediate defects bands which reduce the optical bandgap. Density functional theory (DFT) calculations are used to correlate the experimentally observed trend of bandgap narrowing with the origin of electronic states related to Zn interstitial and O vacancy defects within the forbidden energy gap in ZnO. Our finding can be beneficial to achieve enhanced conductivity in ZnO by accurately varying the intrinsic defects through ion irradiation, which may work as a tuning knob to control the optoelectronic properties of the system.

Phase evolution in thermally annealed Ni/Bi multilayers studied by X-ray absorption spectroscopy.

The thin films of Ni and Bi are known to form NiBi3 and NiBi compounds spontaneously at the interface, which become superconducting below 4.2 K and show ferromagnetism either intrinsically or due to Ni impurities. Formation of NiBi3 and NiBi is a slow diffusion reaction, which means the local environment around Ni and Bi atoms may vary with time and temperature. In this report, we assess the feasibility of using X-ray Absorption Spectroscopy (XAS) as a tool to track the changes in local bonding environment in NiBi3 and NiBi. Thermal annealing at temperatures up to 500 °C was used to induce changes in the local environment in NiBi3 system. Consequent decomposition of NiBi3 into NiO and Bi has been tracked through changes in structural and magnetization behavior, which matched well with the findings of XAS. In addition, the magnetic hysteresis measurements indicated that NiO should be the dominant phase when NiBi3 is annealed at 500 °C. This was corroborated from XAS and was found to be >90%. The shift in K-edge of Ni in annealed samples was attributed to increasing charge state on Ni atom, which was ascertained by Bader charge analysis using Density Functional Theory (DFT). This study correlating macroscopic properties of NiBi3 with local bonding environment of the system indicates that XAS can be a very reliable tool for studying dynamics of diffusion in the NiBi3 system.

Temperature-dependent excitonic emission characteristics of lead-free inorganic double perovskites and their third-order optical nonlinearities.

We report temperature-dependent photoluminescence (PL) in the temperature range between 77 K and 300 K, and room temperature nonlinear optical (NLO) properties of solution processed lead-free Cs2NaBiI6 (CNBI) and Cs2KBiI6 (CKBI) perovskite films. The de-convolution analysis of temperature-dependent PL spectra showed thermal quenching behavior of free-exciton (FX) emission, an unusual blue-shift of PL emission, and line broadening with increasing temperature as a consequence of strong exciton-phonon interaction. The nonlinear refractive index (n2) and nonlinear absorption coefficient (ß) of both the CNBI and CKBI films are determined using a closed aperture (CA) and open aperture (OA) Z-scan technique, respectively. Both the CNBI and CKBI perovskites exhibited features of saturable absorption (SA) with ß âˆ¼ -6.23 × 10-12 cm W-1, and -1.14× 10-12 cm W-1, respectively. The CA measurements depicted a self-defocusing effect in both the samples with n2 values ∼-1.06 × 10-14 cm2 W-1 and -1.337× 10-14 cm2 W-1, respectively. With such emission and NLO characteristics, CNBI and CKBI perovskite films can be used for designing eco-friendly optoelectronic and NLO devices.

Excitonic properties of layer-by-layer CVD grown ZnO hexagonal microdisks.

We have investigated the excitonic properties of highly crystalline ZnO hexagonal microdisks grown by the chemical vapour deposition technique. It was observed that a suitable negative catalyst like chlorine suppresses the crystal growth along the (0001) direction. We propose a qualitative model for the experimentally observed layer-by-layer growth mechanism of the microdisks. Room temperature photoluminescence of the microdisks manifests a very high near-band-edge (NBE) emission peak in the UV region and a minor defect peak in the visible region. The excitonic emission of the microdisks was studied using the low-temperature photoluminescence down to 83 K, which reveals a surface exciton peak in the NBE region and well fitted higher-order phonon replicas.

Self-assembled nano-dots structures on Si(111) surfaces by oblique angle sputter-deposition.

Controlled surface modification and nano-dots structures over Si(111) surfaces have been produced by oblique angle sputter deposition of 80 keV Ar+ beam. Temporal parameters such as self-assemble, tunability of size and density of fabricated nano-dots exhibit distinct fluence dependence. Crystalline to amorphous (c/a) phase transition for sputter deposited Si(111) surfaces has been observed. RBS/C reveals the non-linear response of damage distribution with Ar ion fluence. Compositional alterations like degree of amorphization, damage distribution and depth profiling of Ar in these nano-structured surfaces has been correlated with the morphological and structural findings. The underlying self-organization mechanism relies in ion beam sputtering induced erosion and re-deposition of Si atoms thereby leading to mass transport inside the amorphous layers. Such nano-structured Si(111) surfaces could be applied as key engineering substrates for surface reconstruction, optoelectronic devices, data storage devices, recording media and photovoltaic applications.

Carbohydrates and polyphenolics of extracts from genetically altered plant acts as catalysts for in vitro synthesis of silver nanoparticle.

Eco-friendly biosynthetic approach for silver nanoparticles production using plant extracts is an exciting advancement in bio-nanotechnology and has been successfully attempted in nearly 41 plant species. However, an established model plant system for systematically unraveling the biochemical components required for silver nanoparticles production is lacking. Here we used Arabidopsis thaliana as the model plant for silver nanoparticles biosynthesis in vitro. Employing biochemical, spectroscopic methods, selected mutants and over-expressor plants of Arabidopsis involved in pleotropic functions and sugar homeostasis, we show that carbohydrates, polyphenolics and glyco-proteins are essential components which stimulated silver nanoparticles synthesis. Using molecular genetics as a tool, our data enforces the requirement of sugar conjugated proteins as essentials for AgNPs synthesis over protein alone. Additionally, a comparative analysis of AgNPs synthesis using the aqueous extracts of some of the plant species found in a brackish water ecosystem (Gracilaria, Potamogeton, Enteromorpha and Scendesmus) were explored. Plant extract of Potamogeton showed the highest potential of nanoparticles production comparable to that of Arabidopsis among the species tested. Silver nanoparticles production in the model plant Arabidopsis not only opens up a possibility of using molecular genetics tool to understand the biochemical pathways and components in detail for its synthesis.

Suppression of near band edge emission in specially engineered ZnO twin nanorods.

We report the synthesis of a unique zinc oxide nanorod structure in which an amorphous ZnO layer is sandwiched between two identical crystalline segments of ZnO. A simple hydrothermal reaction method was used for this purpose, which allowed us to tune the amorphous and crystalline sections of the nanorods via reaction temperature. A systematic study of the morphology and dimensions of the nanorods grown under various conditions was performed using a combination of scanning and transmission electron microscopy. Transmission electron microscopy (TEM) clearly showed an amorphous separation between the two crystalline segments. UV-vis absorption spectroscopy of the twin nanorods (TNRs) showed a redshift in the optical band gap as a function of the growth duration, indicating slightly stressed growth of the crystalline segments. For a longer growth duration, as the amorphous gap starts to get bridged by crystalline growth, redshift in optical band gap becomes constant. This confirms a true mechanical gap between the two crystalline segments of the nanorods. Temperature dependent photoluminescence (PL) spectra of the TNRs showed a variation in free exciton (FX) emission energy, which fitted very well to a model incorporating lattice dilation in addition to the standard electron-phonon interactions. At low temperatures (below ∼180 K) we observed the appearance of visible emission peaks due to localization of defect levels. A loss in the near band edge emission intensity was observed at low temperatures, commensurate with the appearance of defect emission in the visible range.

Nanoscale interface engineering in ZnO twin nanorods for proposed phonon tunnel devices.

Zinc oxide twin nanorods, with two identical crystalline sections connected by an amorphous layer, were reproducibly grown using a simple one-step hydrothermal technique. The thickness of the amorphous layer between the crystalline segments was tunable with growth parameters, as confirmed by high resolution transmission electron microscopy. The photoluminescence spectra of these twin nanorods exhibit strong near band edge emission in the UV range, with convoluted phonon sidebands. De-convolution analyses of these spectra showed that the amorphous interlayers act as effective phonon barriers beyond a certain thickness. Such oriented grown individual crystalline-amorphous-crystalline structures may be a suitable test system for fundamental studies of phonon tunneling in the nanostructure. While physical vapor deposition techniques are seriously constrained in realizing crystalline-amorphous-crystalline structures, our results show the viability of engineering embedded interfaces via chemical routes.

Nanofabrication of broad-band antireflective surfaces using self-assembly of block copolymers.

We present a simple and cost-effective method for the fabrication of antireflective surfaces by self-assembly of block copolymers and subsequent plasma etching. The block copolymers create randomly oriented periodic patterns, which are further transferred into fused silica substrates. The reflection on the patterned fused silica surface is reduced to well below 1% in the ultraviolet, visible, and near-infrared ranges by exploiting subwavelength nanostructures with periodicities down to 48 nm. We show that by choosing the appropriate block copolymers and pattern transfer parameters the optical properties of the antireflective surface can be easily tuned, and the spectral measurements verify a significant reduction of the reflectivity by a factor of 10. The experiments, confirmed with simulations based on rigorous diffraction theory, also show that the tapered shape of the nanostructures gives rise to a graded index surface, resulting in a broad-band antireflective behavior.

Biosensing by densely packed and optically coupled plasmonic particle arrays.

Densely packed plasmonic particle arrays are investigated for biosensing applications. Such particle arrays exhibit interparticle optical coupling creating a strong field between the particles, which is useful for sensing purposes. The sensor properties, such as bulk sensitivity, layer sensitivity, and the depth of sensitivity are investigated with the aid of a multiple multipole program. Sensitivity to the analyte with low concentration is also examined by a dynamic adsorption processes. The detectable concentration limit of streptavidin within 3000 s in the detection system is expected from the signal-to-noise to be less than 150 pM.