Influence of Liquid Medium on Optical Characteristics of the Si Nanoparticles Prepared by Submerged Electrical Spark Discharge

We have measured the size, structure, and optical properties for two sets of nanoparticles synthesized via electrical-spark discharge between two plane silicon electrodes immersed in deionized water (DI) and 97 % ethanol. The nanoparticles were characterized by X-ray diffraction (XRD), ultraviolet (UV)-visible absorption spectrometry, Raman spectrometry, transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The size and optical features of the nanoparticles were studied as functions of nature of the liquid. Nearly spherical, single-crystal, and morphologically similar Si nanoparticles with diameters in the 3–8 and 6–13 nm ranges were formed in the colloidal solutions of water and ethanol, with estimated indirect bandgaps of approximately 1.5 and 1.3 eV, respectively. In both cases, the Raman peaks were blue shifted with respect to those of bulk silicon, a result consistent with the small diameters of the particles. The silicon nanoparticles synthesized in water exhibited strong emission in the violet-blue range, with a double peak near 417 and 439 nm. For those synthesized in ethanol, blue-green emission centered at 463 nm was detected.     

Ultrasonic-assisted spark plasma discharge for gold nanoparticles synthesis

We examine the ultrasonic-assisted spark discharge in gold nanoparticles production. A 1 kHz pulsed power supply is used to generate spark discharge plasma. The appropriate range of peak power (pulse peak current) for nanoparticles production was determined by the Dynamic Light Scattering (DLS) method. Colloidal gold nanoparticles were synthesized in 100 mL deionized water and pure ethanol as liquid dielectrics. Scanning Electron Microscopy (SEM) micrographs show that the nanoparticles diameter in the deionized water is larger than in pure ethanol. Transmission Electron Microscopy (TEM) micrographs of the gold nanoparticles also confirm the SEM results with more accuracy. The present study revealed that the ultrasonic wave increases the shape uniformity of the nanoparticles and decreases their size.     

Generation of web-like structures and nanoparticles by femtosecond laser ablation of silicon target in ambient air

Silicon nanoparticles were produced by femtosecond laser ablation in ambient air. Obtained samples were studied using dark-field optical microscopy, scanning electron microscopy and Raman-scattering spectroscopy. Two groups of structures can be found: (1) branched amorphous structures with a minimum element size of about 10 nm and incorporations of nanocrystals (0.6–6.6 nm from Raman scattering analysis); (2) larger crystal particles with smooth surface and a typical size of 50–200 nm that provide directional visible light scattering (at dark-field optical microscopy observations). An influence of environment on resulting phase composition of silicon nanoparticles was investigated by numerical evaluation of nanoparticle’s cooling rate. The calculation shows that cooling in ambient air ensures cooling rate sufficient for crystallization.     

Synthesis and characterization of graphene-based nanocomposites with potential use for biomedical applications

In this paper, GaN nanoparticles were synthesized from the complex Ga(H₂NCONH₂)₆Cl₃ in the flow of NH₃ at a mild temperature (350 °C). Further purification was performed by the ethanol-thermal method. The ethanol-thermal method also prompted the GaN nanoparticles to grow into an anisotropic morphology. XRD patterns reveal that GaN nanoparticles have crystallized in a hexagonal wurtzite structure. TEM observation shows that the average size of the as-prepared nanoparticles is about 5–10 nm. The photoluminescence spectrum exhibits a broad green emission band with a peak at 510 nm. It can be known from the first-principle theoretic simulation by the TDDFT method that this fluorescence emission band is attributed to the hydride defects of V _N-H on the surface of GaN nanoparticles.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Luminescence studies and effect of etching on cerium-doped CaS nanoparticles

Cerium-doped calcium sulphide nanoparticles were synthesized using the solid state diffusion method. The formed nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible absorption spectroscopy and photoluminescence (PL) spectroscopy. The XRD pattern confirmed a cubic CaS phase with an average grain size of 53 nm of the formed samples. The TEM image showed non-agglomerated particles with an average size of 60 nm, which is in close agreement with the XRD result. The PL-emission spectrum showed peaks at 506 and 565 nm due to the transition from the excited state to the ground state of Ce³⁺. The effect of etching has been studied on the luminescent properties of CaS:Ce phosphors. With an increase in the etching time there is decrease in the size of the particles, as a result of which the PL spectrum showed a slight blue shift. The UV-visible absorption spectrum also showed a blue shift with an increase in etching time, which is in agreement with the nanosize effect.     

Silicon nanoparticles produced by spark discharge

On the example of silicon, the production of nanoparticles using spark discharge is shown to be feasible for semiconductors. The discharge circuit is modelled as a damped oscillator circuit. This analysis reveals that the electrode resistance should be kept low enough to limit energy loss by Joule heating and to enable effective nanoparticle production. The use of doped electrodes results in a thousand-fold increase in the mass production rate as compared to intrinsic silicon. Pure and oxidised uniformly sized silicon nanoparticles with a primary particle diameter of 3–5 nm are produced. It is shown that the colour of the particles can be used as a good indicator of the oxidation state. If oxygen and water are banned from the spark generation system by (a) gas purification, (b) outgassing and (c) by initially using the particles produced as getters, unoxidised Si particles are obtained. They exhibit pyrophoric behaviour. This continuous nanoparticle preparation method can be combined with other processing techniques, including surface functionalization or the immediate impaction of freshly prepared nanoparticles onto a substrate for applications in the field of batteries, hydrogen storage or sensors.     

Synthesis of silicon nanocomposite for printable photovoltaic devices on flexible substrate

Renewed interest has been established in the preparation of silicon nanoparticles for electronic device applications. In this work, we report on the production of silicon powders using a simple ball mill and of silicon nanocomposite ink for screen-printable photovoltaic device on a flexible substrate. Bulk single crystalline silicon was milled for 25 h in the ball mill. The structural properties of the produced silicon nanoparticles were investigated using X-ray diffraction (XRD) and transmission electron microscopy. The results show that the particles remained highly crystalline, though transformed from their original single crystalline state to polycrystalline. The elemental composition using energy dispersive X-ray florescence spectroscopy (EDXRF) revealed that contamination from iron (Fe) and chromium (Cr) of the milling media and oxygen from the atmosphere were insignificant. The size distribution of the nanoparticles follows a lognormal pattern that ranges from 60 nm to about 1.2 μm and a mean particle size of about 103 nm. Electrical characterization of screen-printed PN structures of the nanocomposite formed by embedding the powder into a suitable water-soluble polymer on Kapton sheet reveals an enhanced photocurrent transport resulting from photo-induced carrier generation in the depletion region with energy greater that the Schottky barrier height at the metal-composite interface.     

Surface disorder in c-Si induced by swift heavy ions

The disorders induced in crystalline silicon (c-Si) through the process of electronic energy loss in the swift heavy ion irradiation were investigated. A number of silicon <1 0 0> samples were irradiated with 65 MeV oxygen ions at different fluences, 1×10¹³ to 1.5×10¹⁴ ions/cm², and characterized by the Raman spectroscopy, the optical reflectivity, the X-ray reflectivity, the atomic force microscopy (AFM) and the X-ray diffraction (XRD) techniques. The intensity, redshift, phonon coherence length and asymmetric broadening associated with the Raman peaks reveal that stressed and disordered lattice zones are produced in the surface region of the irradiated silicon. The average crystallite size, obtained by analyzing Raman spectrum with the phonon confinement model, was very large in the virgin silicon but decreased to<100 nm dimension in the ion irradiated silicon. The results of the X-ray reflectivity, AFM and optical reflectivity of 200–700 nm radiation indicate that the roughness of the silicon surface has enhanced substantially after ion irradiation. The diffusion of oxygen in silicon surface during ion irradiation is evident from the oscillation in the X-ray reflectivity spectrum and the sharp decrease in the reflectivity of 200–400 nm radiation. The rise in temperature, estimated from the heat spike model, was high enough to melt the local silicon surface. The results of XRD indicate that lattice defects have been induced and a new plane <2 1 1> has been formed in the silicon <1 0 0>after ion irradiation. The results of the present study show that the energy deposited in crystalline silicon through the process of electronic energy loss ～0.944 keV/nm per ion is sufficient to induce disorders of appreciable magnitude in the silicon surface even at a fluence of ～10¹³ ions/cm².     

XRD and Mössbauer studies on Pt–Fe nano-particles synthesized by polyol method for cathode catalyst of PEFCS

Pt₅₀–Fe₅₀ nanoparticles were synthesized by the chemically wet process for developing a new high efficiency cathode catalyst in PEFCs. The particle morphology and crystal structure of as synthesized Pt–Fe particles, and electronic state of Fe atoms in them were evaluated using transmission electron microscopy(TEM), X-ray diffraction(XRD) and transmission Mössbauer spectroscopy (TMS), respectively. They are confirmed to be of chemically disordered fcc structure from XRD pattern and the average diameter of them was estimated to be 3.1 nm from both TEM and the width of (111) peak in XRD pattern. From TMS spectrum, it was concluded to consist of mainly the component of Fe oxides connected with the organic ligands according to XPS results mentioned below. But, probably it contains the component for superparamagnetic Pt–Fe nanoparticles. Also the electrocatalytic activity and a hydrogen adsorption/desorption behavior for as synthesized Pt–Fe nanoparticles was observed by cyclic voltammetry and the oxidation of Fe atoms in as synthesized Pt–Fe nanoparticles, Fe metal and Fe oxides were measured.     

Spectroscopy of Nickel-Doped Zinc Sulfide Nanoparticles

ABSTRACT

In the present study, Zn_1?xNi_xS (x = 0.0–0.8 mol%) nanoparticles were prepared through the chemical route and the synthesis involved the mixing and drying of zinc acetate and sodium sulphide in an appropriate ratio with the addition of Ni²⁺ at a proper concentration. The structural and spectroscopic studies are investigated by X-ray diffraction (XRD), absorption spectra, emission and excitation spectra, and Raman spectra. Compared with that of the pristine materials, the absorption band-edge demonstrates an apparently blue shift, which is attributed to the quantum size effect. The average particle size of ZnS nanoparticles is in the range of 2–4 nm deduced from the XRD line broadening. Excited at about 330 nm, a blue emission band at 425 nm can be observed, which corresponds to Ni²⁺ luminescent center; this result is consistent with the postulation that Ni²⁺ replaced the Zn²⁺ ions in the lattice of ZnS nanocrystals. Excitation spectra also confirm the above postulation. The effect of different concentrations of nickel is also studied by Raman spectra.     

Initial growth region of the glow discharge a-Si: H

The time dependence of the optical emission in SiH 414 nm band and of the temperature of silane gas were measured after the switching on of the r.f. glow discharge. The results emphasize the influence of plasma stabilization on the initial growth region of amorphous silicon. This 60–300 Å thick layer has a higher concentration of gap states.     

Synthesis and characterization of tin oxide (SnO2) nanocrystalline powders by a simple modified sol–gel route

This paper reports the synthesis and characterization of nanocrystalline tin oxide (SnO₂) powders by a simple method using a chitosan–polymer complex solution. To obtain SnO₂ nanocrystalline powders, the precursor was calcined at 500–600 °C in air for 2 h. The phase composition of calcined samples was studied by X-ray diffraction (XRD). The XRD results confirmed the formation of a SnO₂ phase with tetragonal structure. The particle sizes of the powder were found to be 22–23 nm as evaluated by the XRD line broadening method. TEM investigation revealed that the SnO₂ samples consist of crystalline particles of 19–21 nm. The corresponding selected area electron diffraction analysis further confirmed the formation of the tetragonal structure of SnO₂ without any impurity phases. The optical properties of the samples were explored by Fourier transform infrared spectroscopy, optical absorption and Raman studies. The estimated band gaps of the samples were in the range of 3.44–3.73 eV.     

A novel approach towards the production of luminescent silicon nanoparticles: sputtering, gas aggregation and co-deposition with H2O

Silicon clusters were produced by sputtering of a p-doped Si target and aggregation of the Si atoms in an argon gas atmosphere. The clusters were deposited in ultra high vacuum onto either (i) carbon transmission electron microscope (TEM) grids or (ii) a liquid nitrogen cooled finger on which a thick layer of ice was co-deposited during the exposure to the cluster beam. The ice layer containing the clusters was melted to form a liquid sample which showed luminescence peaking at 421 nm when excited at 307.5 nm. The luminescence is attributed to electron-hole recombination in oxygen deficient defects in the Si–SiO₂ interface region. TEM images of the nanoparticles deposited on the carbon grids show spherical particles with diameters ranging from 4 to 50 nm, flake-like structures or nanotube-like shapes. Grids with higher deposited densities reveal clusters that are agglomerated into chains, TEM images of the dried liquid sample show a network of fibres indicating that growth into fibres is further promoted when the clusters gain mobility in the melted ice.     

pH-Dependent shape changes of water-soluble CdS nanoparticles

Annealing of silicon-carbon nanoparticles was performed in argon at atmospheric pressure to enable formation of silicon carbide nanomaterials and/or carbon structures. Three precursor powders with increasing crystallinity and annealing temperatures from 1,900 to 2,600 °C were used to gain information about the effect of precursor properties (e.g. amorphous vs. nanocrystalline, carbon content) and annealing temperature on the produced materials. Three structures were found after annealing, i.e. silicon carbide crystals, carbon sheets and spherical carbon particles. The produced SiC crystals consisted of several polytypes. Low annealing temperature and increasing crystallinity of the precursor promoted the formation of the 3C-SiC polytype. Raman analysis indicated the presence of single-layer, undoped graphene in the sheets. The spherical carbon particles consisted of curved carbon layers growing from the amorphous Si–C core and forming a ‘nanoflower’ with a diameter below 60 nm. To our knowledge, the formation of this kind of structures has not been reported previously. The core was visible in transmission electron microscopy analysis at the annealing temperature of 1,900 °C, decreased in size with increasing temperature and disappeared above an annealing temperature of 2,200 °C. With increasing crystallinity of the precursor material, fewer layers (~5 with the most crystalline precursor) were detected in the carbon nanoflowers. The method presented opens up the possibility to produce new carbon nanostructures whose properties can be controlled by changing the properties of the precursor material or by adjusting an annealing temperature.     

A study of oleic acid-based hydrothermal preparation of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles

Nearly monodisperse, well crystalline, superparamagnetic CoFe₂O₄ nanoparticles with diameter of 6 nm were synthesized in oleic acid–water–pentanol system at 180 °C. Hydrothermal procedure, as an efficient and environment friendly alternative to organic decomposition methods, was investigated by variation of reaction conditions, and the particle formation mechanism was finally proposed (i.e., hydrolysis of metal oleates in organic phase, with size of the particles (5–8 nm) controlled by polarity-driven precipitation into water phase). As-prepared particles were hydrophobic due to coating by oleic acid. Further modification with dimercaptosuccinic acid led to water-dispersible particles with hydrodynamic diameter of 20 nm. Prepared particles were investigated by TEM, XRD, ICP-AES, light scattering, SQUID magnetometry, and Mössbauer spectroscopy.     

Rashba spin–orbit effect on dwell time in graphene asymmetrical barrier

Monodisperse and spherical α-alumina nanoparticles with a narrow size distribution in range of 11–18 nm have been prepared via the simple chemical precipitation and a new heat-treatment method, namely isolation-medium-assisted calcination. As-prepared α-alumina nanoparticles were characterized by means of X-ray diffraction analyses (XRD), thermogravimetry and differential thermal analyzer (TG–DTA), Fourier transform infrared spectroscopy, and field emission transmission electron microscope (TEM). XRD results confirm that the α-alumina in corundum structure is obtained by heating at 1,000 °C for 3 h. And TEM observations reveal the additional isolation medium surrounded α-alumina precursor forms the lamella, which effectively reduces direct contacts between precursor particles and prevents the agglomerating of the aluminum hydroxides during drying process and then the sintering and growth of the alumina nanoparticles are avoided during calcination. The highly uniform and monodisperse α-alumina nanoparticles are obtained.     

Semi-quantitative Surface Enhanced Raman Scattering Spectroscopic Creatinine Measurement in Human Urine Samples

This paper presents the development of a semi-quantitative method of measuring the creatinine biomolecule in human urine by the surface enhanced Raman scattering (SERS) technique. Creatinine is one of the major components of urine and can be used to represent the metabolic and renal function of the human body. The Raman signal of creatinine is enhanced by 50 nm Au nanoparticles. Raman spectra between 1400 and 1500 cm^?1 were analyzed to obtain the relationship between the SERS band area and creatinine concentration. The square of the correlation coefficient is 0.99 in artificial urine over the creatinine range 38.4–153.6 mg/dl. In a human urine experiment, a good linear correlation is observed over the creatinine concentration range 2.56–6.4 mg/dl. The square of correlation coefficient is 0.96.     

Microstructural properties and local atomic structures of cobalt oxide nanoparticles synthesised by mechanical ball-milling process

In this study, facile preparation of pure and nano-sized cobalt oxides particles was achieved using low-cost mechanical ball-milling synthesis route. Microstructural and morphological properties of synthesised products were characterised by X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques. XRD results indicated that the fabricated samples composed of cubic pure phase CoO and Co₃O₄ nanocrystalline particles with an average crystallite size of 37.2 and 31.8 nm, respectively. TEM images showed that the resulting samples consisted of agglomerates of particles with average diameter of about 37.6 nm for CoO and 31.9 nm for Co₃O₄. Phase purity of the prepared samples was further investigated due to their promising technological applications. Local atomic structure properties of the prepared nanoparticles were probed using synchrotron radiation-based X-ray absorption spectroscopy (XAS) including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). EXAFS data analysis further confirmed the formation of single-phase CoO and Co₃O₄ nanoparticles. In addition, structural properties of cobalt oxide nanoparticles were investigated by performing density functional theory calculations at B3LYP/TZVP level and Born–Oppenheimer molecular dynamics. Theoretical calculations for both prepared samples were found to be consistent with the experimental results derived from EXAFS analysis. Obtained results herein reveals that highly crystalline and pure phase CoO and Co₃O₄ nanoparticles can be synthesised using simple, inexpensive and eco-friendly ball-milling method for renewable energy applications involving fuel cells and water splitting devices.     

Gold nanoparticle-coated silicon cone array for surface-enhanced Raman spectroscopy

ABSTRACT

We demonstrate a silicon cone array substrate coated with gold nanoparticles and which was highly sensitive, homogeneous, and provided a large area for surface-enhanced Raman spectroscopy (SERS). A deep reactive ion-etching process was used to fabricate the high-density silicon cone array, and gold nanoparticles were formed on the silicon cone surface by magnetron sputtering. The substrate was tested with 10^?6 M rhodamine 6 G solution. Enhancement of the substrate was about 60-fold greater than that of flat substrate. Moreover, SERS signals obtained from 24 random areas on the substrate showed good homogeneity with an average standard deviation of 3.9%.