Photoconductivity,photoluminescence and optical Kerr nonlinear effects in zinc oxide films containing chromium nanoclusters

Chromium doped zinc oxide thin solid films were deposited on soda–lime glass substrates. The photoconductivity of the material and its influence on the optical behavior was evaluated. A non-alkoxide sol–gel synthesis approach was used for the preparation of the samples. An enhancement of the photoluminescence response exhibited by the resulting photoconductive films with embedded chromium nanoclusters is presented. The modification in the photoconduction induced by a 445 nm wavelength was measured and then associated with the participation of the optical absorptive response. In order to investigate the third order optical nonlinearities of the samples, a standard time-resolved Optical Kerr Gate configuration with 80 fs pulses at 830 nm was used and a quasi-instantaneous pure electronic nonlinearity without the contribution of nonlinear optical absorption was observed. We estimate that from the inclusion of Cr nanoclusters into the sample results a strong optical Kerr effect originated by quantum confinement. The large photoluminescence response and the important refractive nonlinearity of the photoconductive samples seem to promise potential applications for the development of multifunctional all-optical nanodevices.     

Sonocatalytic epoxidation of alkenes by vanadium-containing polyphosphomolybdate immobilized on multi-wall carbon nanotubes

A Keggin type polyoxometalate (POM) has been immobilized in the unique network structure of multi-wall carbon nanotubes (CNTs). The vanadium-containing polyphosphomolybdate (PVMo) supported on CNTs, which was prepared by a one-step solid-state reaction, was characterized by FT-IR, XRD, SEM and elemental analyses. These uniform nanoparticles have an average size 20–30 nm. Furthermore, due to the chemical interaction between PVMo and carboxylic acid groups, PVMo nanoparticles were successfully immobilized on the CNTs. Moreover, the obtained composite was found as an efficient catalyst for oxidation of hydrocarbons under reflux and ultrasonic irradiation (US) conditions.     

Carbon nanostructures synthesized by arc discharge between carbon and iron electrodes in liquid nitrogen

An idea of using pure iron and graphite electrodes was employed for synthesizing carbon nanoparticles by arc discharge in liquid nitrogen. The synthesized products consist of multiwalled carbon nanotubes (MW–CNT), carbon nanohorns (CNH), and carbon nanocapsules (CNC) with core–shell structure. Effect of metallic cathode and discharge current on product structure and yield had been experimentally investigated. Typical evidence of transmission electron microscopic images revealed that under some certain conditions of discharge in liquid nitrogen the synthesized products mainly consisted of CNCs with mean diameter of 50–400 nm. When conventional graphitic electrodes were employed, CNHs with some MW–CNTs were mainly synthesized. Meanwhile, MW–CNTs with diameter of 8–25 nm and length 150–250 nm became less selectively synthesized as cathode deposit under the condition of discharge in liquid nitrogen with higher arc current. The production yield of carbon nanoparticles synthesized by either carbon–carbon or carbon–iron electrodes became also lower with an increase in the arc current.     

Nonlinear optical study of palladium Schiff base complex using femtosecond differential optical Kerr gate and Z-scan techniques

A femtosecond differential optical Kerr gate (DOKG) and Z-scan techniques, have been applied to investigate the third-order optical nonlinearity of composite film of the coordination complex [PdLPPh₃] (L=N-(2-pyridyl)-N′-(salicylidene)hydrazine, PPh₃=triphenylphosphine). Film exhibits superior nonlinear optical properties in the near-infrared spectral region. The nonlinear response time and third-order nonlinear optical susceptibility of complex were found to be≤90 fs and 3.9×10^?10 esu, respectively. The Z-scan result shows that saturable absorption property of the film and its nonlinear absorption coefficient of the sample was found to be ?23 cm/GW.     

Third order nonlinear optical properties of ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III)

A novel organometallic compound, ethyltriphenylphosphonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate (III), abbreviated as TPEPADT, was synthesized. The TPEPADT doped poly(methyl methacrylate) (PMMA) thin film with a mass fraction of 1% (1 wt.%) was prepared by using a spin-coating method. The third-order nonlinear optical properties of TPEPADT in acetonitrile solution and TPEPADT-doped PMMA thin film were investigated by using the laser Z-scan technique at the wavelength 1064 nm with laser duration of 20 ps. The linear refractive index of the polymer thin film was also studied. The Z-scan curves revealed that both TPEPADT in acetonitrile solution and the polymer thin film possessed negative nonlinear refraction, exhibiting a self-defocusing effect and nonlinear absorption was negligible under the experimental conditions used. The nonlinear refractive index was calculated to be ?1.9 × 10^?18 m²/W for TPEPADT in acetonitrile solution and ?8.9 × 10^?15 m²/W for the polymer thin film. These results suggest that TPEPADT have potential for the application of all-optical switching devices.     

Negative index photonic crystal lenses based on carbon nanotube arrays

We report a novel utilization of periodic arrays of carbon nanotubes in the realization of diffractive photonic crystal lenses. Carbon nanotube arrays with nanoscale dimensions (lattice constant 400 nm and tube radius 50 nm) displayed a negative refractive index in the optical regime where the wavelength is of the order of array spacing. A detailed computational analysis of band gaps and optical transmission through the nanotubes based planar, convex and concave shaped lenses was performed. Due to the negative-index these lenses behaved in an opposite fashion compared to their conventional counter parts. A plano-concave lens was established and numerically tested, displaying ultra-small focal length of 1.5 μm (～2.3 λ) and a near diffraction-limited spot size of 400 nm (～0.61 λ).     

SnO2-decorated multiwalled carbon nanotubes and Vulcan carbon through a sonochemical approach for supercapacitor applications

Multiwalled carbon nanotubes (MWCNTs) and Vulcan carbon (VC) decorated with SnO₂ nanoparticles were synthesized using a facile and versatile sonochemical procedure. The as-prepared nanocomposites were characterized by means of transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infra red spectroscopy. It was evidenced that SnO₂ nanoparticles were uniformly distributed on both carbon surfaces, tightly decorating the MWCNTs and VC. The electrochemical performance of the nanocomposites was evaluated by cyclic voltammetry and galvanostatic charge/discharge cycling. The as-synthesized SnO₂/MWCNTs nanocomposites show a higher capacity than the SnO₂/VC nanocomposites. Concretely, the SnO₂/MWCNTs electrodes exhibit a specific capacitance of 133.33 F g⁻¹, whereas SnO₂/VC electrodes exhibit a specific capacitance of 112.14 F g⁻¹ measured at 0.5 mA cm⁻² in 1 M Na₂SO₄.     

Enhanced nonlinear optical response of linear carbon chain colloid mixed with silver nanoparticles

Nanostructured silver and linear carbon chain (LCC) particle water colloids were prepared by a pulsed laser ablation procedure. Sample's optical transmission response was investigated in the 190–900 nm range, the third-order nonlinear optical properties were studied using the z-scan method and a nanosecond laser. The silver nanoparticles induce a structural change in the LCC colloids: the mixed Ag and LCC optical absorption looses the signature of the short carbon chain maintaining the features attributable to the longer ones. The stability of LCC colloids and their nonlinear response are remarkably improved by the Ag nanoparticles addition to the carbon water colloids. The Ag nanoparticles induce a limiting threshold reduction, an increased nonlinear absorption coefficient β and a marked asymmetrical peak/valley profile of the (Ag:LCC)_mix when compared to the LCC. All these nonlinear contributions determine the increase of the third order susceptibility, while maintaining a significantly high linear transmission value (75%) at 532 nm and high photostability. The magnitude of the nonlinear optical response of these nanohybrids makes them promising candidates for potential optoelectronic applications.     

Comparison of two different carbon nanotube-based surfaces with respect to potassium ferricyanide electrochemistry

This paper describes the electrochemical investigation of two multi-walled carbon nanotube-based electrodes using potassium ferricyanide as a benchmark redox system. Carbon nanotubes were fabricated by chemical vapor deposition on silicon wafer with camphor and ferrocene as precursors. Vertically-aligned as well as islands of horizontally-randomly-oriented carbon nanotubes were obtained by varying the growth parameters. Cyclic voltammetry was the employed method for this electrochemical study. Vertical nanotubes showed a slightly higher kinetic. Regarding the sensing parameters we found a sensitivity for vertical nanotubes almost equal to the sensitivity obtained with horizontally/randomly oriented nanotubes (71.5 ± 0.3 μA/(mM cm²) and 62.8 ± 0.3 μA/(mM cm²), respectively). In addition, values of detection limit are of the same order of magnitude. Although tip contribution to electron emission has been shown to be greatly larger than the lateral contribution on single carbon nanotubes per unit area, the new findings reported in this paper demonstrate that the global effects of nanotube surface on potassium ferricyanide electrochemistry are comparable for these two types of nanostructured surfaces.     

Synthesis and characterization of graphenated carbon nanotubes on IONPs using acetylene by chemical vapor deposition method

The graphenated carbon nanotubes (G-CNTs) were synthesized on monodisperse spherical iron oxide nanoparticles (IONPs) using acetylene as carbon precursor by simple chemical vapor deposition method. The reaction parameters such as temperature and flow of carbon source were optimized in order to achieve G-CNTs with excellent quality and quantity. Transmission electron microscopy (TEM) clearly illustrated that the graphene flakes are forming along the whole length on CNTs. The degree of graphitization was revealed by X-ray diffraction (XRD) analysis and Raman spectroscopic techniques. The intensity of D to G value was less than one which confirms the obtained G-CNTs have high degree of graphitization. The optimum reaction temperature for the IONPs to form metallic clusters which in turn lead to the formation of G-CNTs with high carbon deposition yield is at 900 °C. The TEM shows the CNTs diameter is 50 nm with foiled graphene flakes of diameter around 70 nm. Our results advocate for IONPs as a promising catalytic template for quantitative and qualitative productivity of nanohybrid G-CNTs. The produced G-CNTs with high degree of graphitization might be an ideal candidate for nanoelectronic application like super capacitors and so on.     

Field electron emission from amorphous carbon thin films grown by RF magnetron sputtering

Using a RF magnetron sputtering, amorphous carbon (a-C) and N-doped a-C (a-C:N) thin films were fabricated as field electron emitter. These thin films were deposited on Si(0 0 1) substrate at several temperatures. The field emission property was improved for a-C thin films grown at higher substrate temperatures. Furthermore, a-C:N film exhibits field emission property better than that of undoped a-C film. These results are explained in terms of the change in surface morphology and structural properties of a-C film.     

Out-of-plane ellipsometry measurements of nanoparticles on surfaces for thin film coated wafer inspection

Measurements of the diameter and size distribution of nanoparticles on wafers are critical parameters in the semiconductor industry, essential to control transistor quality and increase production rate. A goniometric optical scatter instrument (GOSI) has been developed that employs polarized light scattering to make measurements of the diameter and size distribution of nanoparticles on bare and thin film coated wafers. This scatter instrument is capable of distinguishing various types of optical scattering characteristics, which correspond to the diameters of the nanoparticles and thin film thickness, on or near the surfaces using the Mueller matrix calculation in Bobbert and Vlieger (1986) [1]. The experimental results of the GOSI system show good agreement with theoretical predictions for nanoparticles of diameter 100, 200, and 300 nm on wafers coated with thin films of 2, 5, and 10 nm thickness. These results demonstrate that the polarization of light scattered by nanoparticles can be used to determine the size of particulate contaminants on bare and thin film coated silicon wafers.     

Sonochemical modification of carbon nanotubes for enhanced nanocomposite performance

Multi-walled carbon nanotubes (CNTs) have been treated using 20 kHz ultrasound in combination with dilute nitric and sulfuric acids at much lower concentrations than previously reported. The measurements revealed an optimum set of sonication conditions (in this case 30 min at 12 W cm⁻²) exists to overcome aggregation of the nanotubes and to allow efficient dispersion in ethanol or in chitosan. Transmission electron microscopy and Raman spectroscopy suggested the removal of amorphous material and reduction of the CNT diameter as well as modifications to their defect structures. The surface oxidation was determined by FTIR spectroscopy. At longer times or higher ultrasound intensities, degradation such as nanotube shortening and additional defect generation in the graphitic network occurred and the benefits of using ultrasound decreased. The modified CNTs were used as fillers for chitosan films and gave a tenfold increase in tensile strength and integrity of the films. The methodology was combined with sonochemical generation of gold or iron oxide nanoparticles to produce a range of functional membranes for catalytic reductive hydrogenation or dye degradation under conditions that are more environmentally benign than those previously used. Our results further add to the usefulness of sonochemistry as a valuable tool in preparative materials chemistry but also illustrate the crucial importance of careful control over the experimental conditions if optimum results are to be obtained.     

Catalytic oxidation of carbon nanotubes with noble metal nanoparticles

Catalytic oxidation of multi-walled carbon nanotubes (MWNCTs) with some noble metal nanoparticles was observed by environmental transmission electron microscopy (E-TEM). Amoeba-like movement of the nanoparticles was observed even at a temperature of ∼400 °C, which is much lower than the melting points of any of the metals. In particular, rhodium particles reacted intensely with MWCNTs, and assumed a droplet-like shape. On the other hand, gold particles caused very little erosion of the MWCNTs under the conditions of this study.     

Strain study of gold nanomaterials as HR-TEM calibration standard

This work presents the use of high resolution electron microscopy (HREM) and geometric phase analysis (GPA) to measure the interplanar spacing and strain distribution of three gold nanomaterials, respectively. The results showed that the {1 1 1} strain was smaller than the {0 0 2} strain for any kind of gold materials at the condition of same measuring method. The 0.65% of {1 1 1} strain in gold film measured by HREM (0.26% measured by GPA) was smaller than the {1 1 1} strains in two gold particles. The presence of lattice strain was interpreted according to the growth mechanism of metallic thin film. It is deduced that the {1 1 1} interplanar spacing of the gold thin film is suitable for high magnification calibration of transmission electron microscopy (TEM) and the gold film is potential to be a new calibration standard of TEM.     

Nonlinear properties of polyurethane-urea/multi-wall carbon nanotube composite films

The third-order nonlinear optical properties of polyurethane-urea/multiwalled carbon nanotube composites (PU/MWNT) films with different MWNT concentrations are investigated by the use of the Z-scan technique at a wavelength of 532 nm with a pulse duration of 8 ns. The results reveal that the nonlinear refraction and absorption coefficients are linearly dependent on the MWNT concentration. The negative nonlinear refraction effect is validated from the closed-aperture Z-scan measurements. We find that PU/MWNT films are promising nonlinear optical materials, and the nonlinear coefficients can be controlled.     

Phonon dispersion of carbon nanotubes

We present the phonon dispersion relations of single-wall carbon nanotubes calculated within a force-constants approach. By using the full symmetry group of the tubes, we are able to calculate the dispersion relations for any chirality starting from one single carbon atom. We find an overbending in the highest optical branch between 6 and 12 cm⁻¹ independent of the tube diameter. The order of the high-energy modes at the Γ-point differs from the results derived from simple zone folding. The splitting between the two Raman active optical modes with A₁ symmetry at the Γ-point of chiral tubes is ≈4 cm⁻¹ for typical diameters; it increases with decreasing tube diameter.     

Comparative study on structural and optical properties of ZnO thin films prepared by PLD using ZnO powder target and ceramic target

Zinc oxide thin films have been obtained in O₂ ambient at a pressure of 1.3 Pa by pulsed laser deposition (PLD) using ZnO powder target and ceramic target. The effect of temperature on structural and optical properties of ZnO thin films was investigated systematically by XRD, SEM, FTIR and PL spectra. The results show that the best structural and optical properties can be achieved for ZnO thin film fabricated at 700 °C using powder target and at 400 °C using ceramic target, respectively. The PL spectrum reveals that the efficiency of UV emission of ZnO thin film fabricated by using powder target is low, and the defect emission of ZnO thin film derived from Zn_i and O_i is high.     

Diffraction patterns and nonlinear optical properties of gold nanoparticles

Stable gold nanoparticles have been prepared by using soluble starch as both the reducing and stabilizing agents; this reaction was carried out at 40 °C for 5 h. The obtained gold nanoparticles were characterized by UV–Vis absorption spectroscopy, transmission electron microscopy (TEM) and z-scan technique. The size of these nanoparticles was found to be in the range of 12–22 nm as analyzed using transmission electron micrographs. The optical properties of gold nanoparticles have been measured showing the surface plasmon resonance. The second-order nonlinear optical (NLO) properties were investigated by using a continuous-wave (CW) He–Ne laser beam with a wavelength of 632.8 nm at three different incident intensities by means of single beam techniques. The nonlinear refractive indices of gold nanoparticles were obtained from close aperture z-scan in order of 10^?7 cm²/W. Then, they were compared with diffraction patterns observed in far-field. The nonlinear absorption of these nanoparticles was obtained from open aperture z-scan technique. The values of nonlinear absorption coefficient are obtained in order of 10^?1 cm/W.     

CVD synthesis and radial deformations of large diameter single-walled CNTs

Single-walled carbon nanotubes (CNTs) were synthesized by a chemical vapor deposition (CVD) method on transmission electron microscopy (TEM) silica coated nickel grids using carbon monoxide as carbon source and iron nanoparticles as catalyst. The produced CNTs were as large as 11 nm in diameter. Investigations on the CNT deformations based on high-resolution TEM images showed that the deformation of CNTs due to their interaction with the substrate occurs at diameters larger than 2.7 nm. Small deformation of free standing tubes was found to occur at diameters above approximately 4.5 nm.