Syed Hamad

Picosecond and femtosecond optical nonlinearities of novel corroles

We present our results from the experimental and modeling studies of picosecond (ps) and femtosecond (fs) nonlinearities of two novel corroles (a) tritolyl corrole (TTC) (b) triphenyl corrole (TPC) using the Z-scan technique. Both open and closed aperture Z-scan curves were recorded with ~2 ps/~40 fs laser pulses at a wavelength of 800 nm and nonlinear optical coefficients were extracted for both studies. Both the molecules possessed negative nonlinear refractive index (n2) as revealed by signature of the closed aperture data in both (ps and fs) time domains. Picosecond nonlinear absorption data of TPC obtained at a concentration of 5 × 10-4 M demonstrated complex behavior with switching from reverse saturable absorption (RSA) within saturable absorption (SA) at lower peak intensities to RSA at higher peak intensities. TTC data recorded at the similar concentration exhibited saturable absorption (SA) type of behavior at lower peak intensities to switching from RSA with in SA at higher peak intensities. At a concentration of 2.5 × 10-4 M, the ps open aperture data at higher peak intensities illustrated effective three-photon absorption (3PA) for both the molecules. We also report the picosecond spectral dependent Z-scan studies performed at 680 nm, 700 nm, and 740 nm. Nonlinear absorption and refraction of both the samples at these three wavelengths were studied in detail. Femtosecond nonlinear absorption data of TPC and TTC demonstrated the behavior of saturable absorption (SA) at a concentration of 1 × 10-3 M. Solvent contribution to the nonlinearity was also identified. We have also evaluated the sign and magnitude of third order nonlinearity. We discuss the nonlinear optical performance of these organic molecules.

Silver nano-entities through ultrafast double ablation in aqueous media for surface enhanced Raman scattering and photonics applications

We have fabricated stable silver nanoparticles (NPs) and nanostructures (NSs) effectively through double ablation of bulk silver substrate immersed in double distilled water using ∼2 ps laser pulses. The effects of multiple/double/single ablation on silver substrates via surface morphology studies along with average size distribution of Ag NPs were investigated. Prepared Ag NPs in solution exhibited yellow color with an absorption peak near 410 nm, assigned to localized surface Plasmon resonance of nano-sized silver. Depending on the ablation parameters average sizes observed were ∼13 nm/∼17 nm in multiple/double ablation case and ∼7 nm in single ablation case. High resolution transmission electron microscope studies highlighted that most of the Ag NPs were spherical and polycrystalline in nature. Surface morphology of the substrates was characterized by field emission scanning electron microscope and atomic force microscope. A different scenario was observed in the double ablation case compared to single...

Influence of picosecond multiple/single line ablation on copper nanoparticles fabricated for surface enhanced Raman spectroscopy and photonics applications

A comprehensive study comprising fabrication of copper nanoparticles (NPs) using picosecond (ps) multiple/single line ablation in various solvents such as acetone, dichloromethane (DCM), acetonitrile (ACN) and chloroform followed by optical, nonlinear optical (NLO), and surface enhanced Raman spectroscopy (SERS) characterization was performed. The influence of surrounding liquid media and the writing conditions resulted in fabrication of Cu NPs in acetone, CuCl NPs in DCM, CuO NPs in ACN and CuCl2 NPs in chloroform. Prepared colloids were characterized through transmission electron microscopy, energy dispersive x-ray spectra, selected area electron diffraction and UV-visible absorption spectra. A detailed investigation of the surface enhanced Raman scattering (SERS) activity and the ps NLO properties of the colloids prepared through multiple/single line ablation techniques revealed that the best performance was achieved by Cu NPs for SERS applications and CuCl2 NPs for NLO applications. (Some figures may appear in colour only in the online journal)

Cost effective nanostructured copper substrates prepared with ultrafast laser pulses for explosives detection using surface enhanced Raman scattering

Ultrafast laser pulses induced surface nanostructures were fabricated on a copper (Cu) target through ablation in acetone, dichloromethane, acetonitrile, and chloroform. Surface morphological information accomplished from the field emission scanning electron microscopic data demonstrated the diversities of ablation mechanism in each case. Fabricated Cu substrates were utilized exultantly to investigate the surface plasmon (localized and propagating) mediated enhancements of different analytes using surface enhance Raman scattering (SERS) studies. Multiple utility of these substrates were efficiently demonstrated by collecting the SERS data of Rhodamine 6G molecule and two different secondary explosive molecules such as 5-amino-3-nitro-l,2,4-triazole and trinitrotoluene on different days which were weeks apart. We achieved significant enhancement factors of >105 through an easily adoptable cleaning procedure.

Fabrication of nanoparticles and nanostructures using ultrafast laser ablation of silver with Bessel beams

Ablation of silver targets immersed in double distilled water (DDW)/acetone was performed with first order, non-diffracting Bessel beams generated by focusing ultrashort Gaussian pulses (~2 and ~40 fs) through an Axicon. The fabricated Ag dispersions were characterized by UV-visible absorption spectroscopy, transmission electron microscopy and the nanostructured Ag targets were characterized by field emission scanning electron microscopy. Ag colloids prepared with ~2 ps laser pulses at various input pulse energies of ~400, ~600, ~800 and ~1000 µJ demonstrated similar localized surface plasmon resonance (LSPR) peaks appearing near 407 nm. Analogous behavior was observed for Ag colloids prepared in acetone and ablated with ~40 fs pulses, wherein the LSPR peak was observed near 412 nm prepared with input energies of ~600, ~800 and ~1000 µJ. Observed parallels in LSPR peaks, average size of NPs, plasmon bandwidths are tentatively explained using cavitation bubble dynamics and simultaneous generation/fragmentation of NPs under the influence of Bessel beam. Fabricated Ag nanostructures in both the cases demonstrated strong enhancement factors (>10 6 ) in surface enhanced Raman scattering studies of the explosive molecule CL-20 (2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) at 5 μM concentration.

Magnetic and nonlinear optical properties of BaTiO3 nanoparticles

In our earlier studies the BaTiO3 samples were processed at higher temperatures like 1000oC and explained the observed magnetism in it. It is found that the charge transfer effects are playing crucial role in explaining the observed ferromagnetism in it. In the present work the samples were processed at lower temperatures like 650oC-800oC. The carrier densities in these particles were estimated to be ∼ 1019-1020/cm3 range. The band gap is in the range of 2.53eV to 3.2eV. It is observed that magnetization increased with band gap narrowing. The higher band gap narrowed particles exhibited increased magnetization with a higher carrier density of 1.23×1020/cm3 near to the Mott critical density. This hint the exchange interactions between the carriers play a dominant role in deciding the magnetic properties of these particles. The increase in charge carrier density in this undoped BaTiO3 is because of oxygen defects only. The oxygen vacancy will introduce electrons in the system and hence more charge carriers ...

Femtosecond and picosecond ablation of aluminum for synthesis of nanoparticles and nanostructures and their optical characterization

In this paper we report the fabrication of nanoparticles and nanostructures through the interaction of ultrashort (~40 fs) and short (~2 ps) laser pulses with bulk Aluminum immersed in various liquid media of different polarity [chloroform which is polar, carbon tetrachloride which is non-polar, water which is polar, dichloromethane (DCM) which is polar, and Cyclohexane which is non-polar] using the laser ablation technique. Except water and Cyclohexane, other media showed yellow coloration after ablation took place indicating formation of nanoparticles in the solution in both fs and ps domains. The coloration of the laser exposed portion in the Al substrate was golden yellow and its closer view depicted micro-grating (~1-2 μm) and nano-ripple (period 330 nm) formation depending on the focal conditions. The investigation of polarization dependence on the ablation was performed for water media. Depending on the ablation threshold, we observed micron sized structures and nano-ripples on the surface. As the rate of ablation depends on the position of the focus on the Al substrate and beam waist parameters, we have studied the liquid level dependence of ablation with different water levels on the Al substrate and we compared these patterns obtained below, near, and above the ablation thresholds of the sample. Field Emission-Scanning Electron Microscope (FE-SEM), UV-Vis absorption spectra, Electron Diffraction Pattern and Transmission Electron Microscope (TEM) were used for the characterization and comparison of products in both domains.

Wavelength dependent nonlinear optical switching in electron beam irradiated CuTTBPc thin film

The main aim of the present work is to investigate the role of 8 MeV electron beam interaction in modifying the linear and nonlinear optical (NLO) properties of thermally evaporated copper tetra tert-butyl phthalocyanine (CuTTBPc) thin films. The irradiation dose dependent change in linear optical band gap and roughness changes after electron irradiation have been explored. Third order NLO investigations were performed for unirradiated and 10 kGy irradiated CuTTBPc films with the femtosecond (fs) Z-scan technique at wavelengths of 800 nm and 900 nm. The unirradiated film depicted both reverse saturable and saturable kinds of nonlinear absorption behaviour as expected from the band gap restrictions on two photon absorption. A switch over to reverse saturable absorption within saturable absorption of the irradiated film at 900 nm laser excitation is explained using the irradiation induced band gap shifts of the material due to localized defects formation within the band gap region.

Morphologically manipulated Ag/ZnO nanostructures as surface enhanced Raman scattering probes for explosives detection

The detection of secondary explosive molecules (e.g., ANTA, FOX-7, and CL-20) using Ag decorated ZnO nanostructures as surface enhanced Raman scattering (SERS) probes is demonstrated. ZnO nanostructures were grown on borosilicate glass substrates by rapid thermal oxidation of metallic Zn films at 500 °C. The oxide nanostructures, including nanosheets and nanowires, emerged over the surface of the Zn film leaving behind the metal residue. We demonstrate that SERS measurements with concentrations as low as 10 μM, of the three explosive molecules ANTA, FOX-7, and CL-20 over ZnO/Ag nanostructures, resulted in enhancement factors of ∼107, ∼107, and ∼104, respectively. These measurements validate the high sensitivity of detection of explosive molecules using Ag decorated ZnO nanostructures as SERS substrates. The Zn metal residue and conditions of annealing play an important role in determining the detection sensitivity.

Studies on linear, nonlinear optical and excited state dynamics of silicon nanoparticles prepared by picosecond laser ablation

We report results from our studies on the fabrication and characterization of silicon (Si) nanoparticles (NPs) and nanostructures (NSs) achieved through the ablation of Si target in four different liquids using ∼2 picosecond (ps) pulses. The consequence of using different liquid media on the ablation of Si target was investigated by studying the surface morphology along with material composition of Si based NPs. The recorded mean sizes of these NPs were ∼9.5 nm, ∼37 nm, ∼45 nm and ∼42 nm obtained in acetone, water, dichloromethane (DCM) and chloroform, respectively. The generated NPs were characterized by selected area electron diffraction(SAED), high resolution transmission microscopy(HRTEM), Raman spectroscopic techniques and Photoluminescence(PL) studies. SAED,HRTEM and Raman spectroscopy data confirmed that the material composition was Si NPs in acetone, Si/SiO2 NPs in water, Si-C NPs in DCM and Si-C NPs in chloroform and all of them were confirmed to be polycrystalline in nature. Surface morphological information of the fabricated Si substrates was obtained using the field emission scanning electron microscopic (FESEM) technique. FESEM data revealed the formation of laser induced periodic surface structures (LIPSS) for the case of ablation in acetone and water while random NSs were observed for the case of ablation in DCM and chloroform. Femtosecond (fs) nonlinear optical properties and excited state dynamics of these colloidal Si NPs were investigated using the Z-scan and pump-probe techniques with ∼150 fs (100 MHz) and ∼70 fs (1 kHz) laser pulses, respectively. The fs pump-probe data obtained at 600 nm consisted of single and double exponential decays which were tentatively assigned to electron-electron collisional relaxation ( 1 ps). Large third order optical nonlinearities (∼10−14 e.s.u.) for these colloids have been estimated from Z-scan data at an excitation wavelength of 680 nm suggesting that the colloidal Si NPs find potential applications in photonic devices.