Preparation and properties of semiconductor CuO nanoparticles via a simple precipitation method at different reaction temperatures

Preparation and properties of CuO nanoparticles as an important p-type semiconductor via a simple precipitation method at different reaction temperatures varying from 10 to 115°C using copper acetate as a starting material have been reported. In addition, we investigated the influence of the ultrasonic irradiation through synthesizing the nanosized CuO at 60°C. Samples were characterized by XRD, FT-IR, SEM, TEM and UV-Vis techniques. XRD patterns of samples were identical to the single-phase pure CuO with a monoclinic structure. FT-IR spectra exhibited sharp peaks at around 519 and 598?cm^?1 which can be assigned to vibrations of the Cu-O bond. Results indicated that properties of samples had great dependence on the temperature and ultrasonic irradiation. The crystallite size and crystallization increased with increasing the temperature from 10 to 115°C. The band gap of samples was estimated to be in the range of 1.9–2.9?eV that is larger than the reported value for the bulk CuO (1.85?eV). This study provides a simple method for the preparation of nanosized CuO with a better surface uniformity and a narrow size distribution. Synthesized CuO samples with adjustable and controllable optical properties make the applicability of copper oxide even more versatile.     

Light absorption in Ge nanoclusters embedded in SiO2: comparison between magnetron sputtering and sol–gel synthesis

SiGeO films have been produced by a sol–gel derived approach and by magnetron sputtering deposition. Post-thermal annealing of SiGeO films in forming gas or nitrogen atmosphere between 600 and 900 °C ensured the phase separation of the SiGeO films and synthesis and growth of Ge nanoclusters (NCs) embedded in SiO₂. Rutherford backscattering spectrometry analysis evidenced a similar Ge concentration (~12 %), but a different Ge out-diffusion after annealing between the two types of techniques with the formation of a pure SiO₂ surface layer (~30 nm thick) in sol–gel samples. The thermal evolution of Ge NCs has been followed by transmission electron microscopy and Raman analysis. In both samples, Ge NCs form with similar size increase (from ~3 up to ~7 nm) and with a concomitant amorphous to crystalline transition in the 600–800 °C temperature range. Despite a similar Ge concentration, a significant lower NCs density is observed in sol–gel samples attributed to an incomplete precipitation of Ge, which probably remains still dispersed in the matrix. The optical absorption of Ge NCs has been measured by spectrophotometry analyses. Ge NCs produced by the sol–gel method evidence an optical band gap of around 2 eV, larger than that of NCs produced by sputtering (~1.5 eV). These data are presented and discussed also considering the promising implications of a low-cost sol–gel based technique towards the fabrication of light harvesting devices based on Ge nanostructures.     

Photoluminescence of Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles applied in Bio-LED

In this work, transition elements, including Cu²⁺, Ag⁺, and Au³⁺, were used to dope in zinc sulfide (ZnS) by chemical solution synthesis to prepare Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles, respectively. Transition elements doping ZnS nanoparticles form the electronic energy level between the conduction band and valance band, which will result in the green light emission. There is a zinc sulfide emission shift from blue (~3.01 eV) to green light (~2.15 eV). We also found that Au:ZnS nanoparticles will emit a green light (~2.3 eV) and a blue light (~2.92 eV) at the same time because the mechanism of blue light emission was not broken after Au element had been doped. Furthermore, we used sodium chlorophyllin copper salt to simulate chlorophyll in biological light emission devices (Bio-LED). We combined copper chlorophyll with Cu:ZnS, Ag:ZnS, and Au:ZnS nanoparticles by a self-assembly method. Then, we measured its photoluminescence spectroscopy and X-ray photoelectron spectroscopy to study its emission spectrum and bonding mode. We found that Au:ZnS nanoparticles are able to emit green and blue light to excite the red light emission of copper chlorophyll, which is a potential application of Bio-LED.     

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.     

Effect of annealing on structural and optical properties of diamond-like nanocomposite thin films

The annealing effect on structural and optical properties of the Diamond-like Nanocomposite (DLN) thin film deposited on glass substrate by Plasma Assisted Chemical Vapor Deposition (PACVD) method has been investigated. The films were annealed at temperature ranging from 300 to 600 °C, with 100 °C interval for 9 minutes by rapid thermal process (RTP) under vacuum. The structural changes of the annealed films have been studied using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Scanning Electron Microscope (SEM), and optical parameters have been determined using transmittance and reflectance spectra in UV-UIS-NIR range. The result shows that the refractive index increases gradually from 1.79 to 2.84 with annealing temperature due to out-diffusion of H by breaking Si–H and C–H bond leads to Si–C bond, i.e. more cross linking structure. In higher temperature range, graphitization also enhanced the refractive index. However, the optical band gap at up to 400 °C initially increases from 3.05 to 3.20 eV and then decreases due to graphitization. The film has a great potential to be used as anti-reflection coating (ARC) on silicon-based solar cell.     

Application of soluble salt-assisted route to synthesis of β-Ga2O3 nanopowders

In the past β-Ga₂O₃ nanopowders were usually prepared from gallium-based compounds via wet chemical processes. However, those wet chemical routes would lead not only to high cost, but also to the inevitable contamination of the targeted products from unexpected doping. In this work, the soluble salt-assisted route has been applied to prepare β-Ga₂O₃ nanopowders with a yield of 96.5 % through the direct oxidation of Ga–Na₂SO₄ mixture at 600 °C followed by water washing. Systematical characterizations including SEM, TEM, XRD, Raman, IR, XPS, BET, UV–Vis diffuse reflectance and PL spectrum were conducted. The as-prepared nanopowders were composed of mesoporous nanoparticles and nanosheets with monoclinic Ga₂O₃, and had a broad UV and blue emissions band from 350  to 550 nm. Furthermore their optical band gap was 4.68 eV, exhibiting a red shift of 0.22 eV in comparison with pure bulk matrix. The interesting results indicated a wide range of soluble salt-assisted route for promising industrial production of β-Ga₂O₃ nanopowders.     

Physical,optical and electrical properties of calcium bismuth borate glasses

The variation in physical, optical and electrical properties has been investigated as a function of Bi₂O₃ content in 20CaO?·?xBi₂O₃?·?(80???x)B₂O₃ (0?≤?x?≤?60, in mol%) glasses. The samples were prepared by normal melt-quenching process, and the optical absorption and reflection spectra were recorded in the wavelength range of 400–950 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The optical band gap, E _g, for indirect allowed and indirect forbidden transitions has been determined from the available theories and its value lies between 1.80–2.37 eV and 1.08–2.19 eV, respectively. The theoretical fitting of the optical absorption indicates that the present glass system behaves as an indirect gap semiconductor. The origin of the Urbach energy, ΔE, has been associated with the phonon-assisted indirect transitions. The refractive index and optical dielectric constant have been evaluated from the reflection spectra. The density and molar volume are found to depend on the molar concentration of Bi₂O₃. The values of DC electrical conductivity have been measured from 373 to 623 K and the activation energy has been calculated. Theoretical optical basicity has been reported as a function of the Bi₂O₃ content. The variations have been discussed in terms of structural changes.     

Thermal conductive performance of deposited amorphous carbon materials by molecular dynamics simulation

A series of diamond-like carbon (DLC) films with different microstructure were prepared by depositing carbon atoms on diamond surface with incident energy ranging from 1 to 100 eV. The thermal conductivity of the deposited films and the Kapitza resistance between the film and the diamond substrate were investigated. Results show that the average density, the average fraction of sp³ bonding and the thermal conductivity of the DLC films increase first, reaching a maximum around 20–40 eV before decreasing, while the Kapitza resistance decreases gradually with increased deposition energy. The analysis suggests that the thermal resistance of the interface layer is in the order of 10^?10 m²K/W, which is not ignorable when measuring the thermal conductivity of the deposited film especially when the thickness of the DLC film is not large enough. The fraction of sp³ bonding in the DLC film decreases gradually normal to the diamond surface. However, the thermal conductivity of the film in normal direction is not affected obviously by this kind of structural variation but depends linearly on the average fraction of sp³ bonding in the entire film. The dependence of the thermal conductivity on the fraction of sp³ bonding was analysed by the phonon theory.     

Structural and Mössbauer studies of aerosol FeCu nanoparticles in a wide composition range

Structure and magnetic state of aerosol FeCu nanoparticles of 10–30 nm size with Cu content of 0.6–92.1 at.% have been examined by X-ray diffraction and Mössbauer spectroscopy. The FeCu particles have been shown to consist of an iron core surrounded by a copper and Fe oxide shell. With increasing Cu content the iron core having a bcc structure is reduced down to its complete disappearance followed by vanishing ferromagnetism of the particles. Within the copper content from 4.9 to 74.3 at.% the bcc and fcc phases coexist, with the fcc phase having a lattice constant close to that of pure copper and the bcc lattice constant being slightly higher than that for pure Fe due to embedding Cu atoms into the Fe lattice. At Fe-rich FeCu samples a presence of two-spin (ferromagnetic and paramagnetic) components of the fcc Fe is also observed. In the case of a thin copper shell there is only the ferromagnetic fcc Fe, whereas with further thickening of the shell both spin states of the fcc Fe appear existing up to a 20% Cu content. For FeCu samples with a higher Cu content they disappear due to oxidation of the copper grains. The Cu-rich samples with Cu content higher 80 at.% have a fcc structure, with the lattice constant being slightly higher than that of copper and they are paramagnetic. A slight increase of the lattice constant is due to the penetration of small iron aggregations into the Cu grains. In contact with air, the FeCu particles become covered with Fe₃O₄ and Cu₂O. Their long-term exposure to ambient conditions leads to further oxidation process of Cu₂O to CuO.     

Ionic conductivity and dielectric measurements in single crystal βAgI

Ionic conductivity measurements have been made on pure, copper-doped and cadmium-doped single crystals. Dielectric measurements in the frequency range 30Hz–100Hz showed that there was no anomalously to be (0.64 ± 0.02) eV and migration energies for silver ion intersitials and vacancies in the c direction to be (0.41 ± 0.02) eV and (0.50 ± 0.02) eV respectively. ESR measurements have shown that copper exists as Cu⁺ in these crystals. Dielectric measurements in the frequency range (OHz–100KHz showed that there was no anomalously high value for ? as reported earlier.     

Effect of nickel incorporation on the optical properties of diamond-like carbon (DLC) matrix

The present study investigates the optical behavior of composite nanostructured DLC based films and functional coatings. Diamond-like carbon (DLC) thin films were synthesized by electrodeposition method onto SnO₂-coated glass substrates using an electrolyte of a mixture of acetic acid and water. Nanoparticles of nickel were then introduced into the DLC matrix. Morphology of the metal incorporated thin films and distribution of nanoparticles were studied by SEM; continuous homogeneous distribution of the particles was observed. Raman spectroscopy showed additional peaks in addition to the peaks due to DLC matrix. FTIR spectra revealed new peaks in the lower wave number region due to metal inclusion. UV-vis transmittance studies were performed to calculate the band gap of the samples. The estimated band gap from the Tauc relation was found to vary from 2.63 eV for the virgin DLC to 1.48 eV for the metal incorporated DLC.     

Comparative Investigation on the Excitation of Copper Emission Lines Between Argon and Helium Spark Discharge Plasmas

The emission intensities and the signal‐to‐background ratios (SBRs) of copper emission lines in the wavelength range 200–360 nm were observed from a medium‐voltage spark discharge plasma when argon or helium was employed as the surrounding gas. The observed copper spectra comprised Cu(I) lines having excitation energy of 3.8–9.3 eV, and Cu(II) lines assigned to three different transitions: 3d ⁸4p–3d ⁸4s transition (excitation energy of 8.2–9.2 eV), 3d ⁸5s–3d ⁸4p transition (13.4–13.6 eV), and the 3d ⁸4d–3d ⁸4p transition (14.2–14.8 eV). The Cu(I) lines have much smaller intensities in the helium plasma compared with the argon plasma, whereas the Cu(II) lines have similar intensities between both plasmas. The SBRs of some ionic copper lines are larger in the helium plasma compared with the argon plasma. Therefore, when an ionic line has to be measured in the analytical applications, the helium plasma should be recommended.     

Effect of pulse duration on plasmonic enhanced ultrafast laser-induced bubble generation in water

Bubbles generated in water by focusing femtosecond and picosecond laser pulses in the presence of 100 nm gold nanoparticles have been investigated in the fluence range usually used for efficient cell transfection (100–200 mJ/cm²). Since resulting bubbles are at the nanoscale, direct observation using optical microscopy is not possible. An optical in-situ method has been developed to monitor the time-resolved variation in the extinction cross-section of an irradiated nanoparticle solution sample. This method is used to measure the bubbles lifetime and deduce their average diameter. We show that bubbles generated with femtosecond pulses (40–500 fs) last two times longer and are larger in average than those generated with picosecond pulses (0.5–5 ps). Controlling those bubble properties is necessary for optimizing off-resonance plasmonic enhanced ultrafast laser cell transfection.     

Barrier characteristics of biopolymer-based organic/inorganic Au/CTS/n-InP hybrid junctions

Thin film of biopolymeric compound chitosan (CTS) has been surfaced on moderately doped n-InP substrate as an interfacial layer by means of spin coating for the electronic modification of Au/n-InP structure. Electrical characterization of Au/CTS/n-InP hybrid junction has been performed by I–V and C–V measurements at room temperature. An effective barrier height (BH) value of 0.678 eV and an ideality factor of n = 1.665 have been obtained for the hybrid junction. The CTS interfacial layer has been found to reduce the reverse bias leakage current of the junction by about three orders of magnitude and enhance the BH by about 0.213 eV. Furthermore, the BH value of the hybrid junction has been obtained as 0.693 eV by C–V measurement. Good performance of the device could be ascribed to the passivation effect of the CTS interfacial layer between Au and n-InP. The BH values of 0.678 and 0.693 eV for the hybrid junction have been significantly higher than that of the conventional Au/n-InP junction (~0.465 eV). The results indicated that biopolymeric thin interfacial CTS layer might lead to the modification of the potential barrier for metal/n-InP junctions. Moreover, band gap of the CTS layer has been determined as 4.60 eV via UV–vis spectroscopy.     

Tuning of optical properties of CdS nanoparticles synthesized in a glass matrix

Attempts were made to provide the data concerning directed synthesis of semiconductor nanoparticles in a dielectric silica-based glass matrix. These attempts involve finding out the connections between the structure, size of CdS nanoparticles, and optical properties of the nanocomposites produced. High-resolution focused ion beam scanning electron microscopy images of CdS nanoparticles incorporated in glass and SAXS results confirm the formation of uniformly distributed spherical CdS nanoparticles with an average diameter of about 6.2 nm. UV–Vis measurements show that CdS composites possess a direct bandgap wider than 2.45 eV depending on the heat treatment conditions; thus, heat treatment can be used to control nanoparticle size in each selected composite. The emission spectra showed a maximum at about 603 nm and a red shift of about 100 nm with increasing annealing temperature that is associated with the presence of defect states in the nanoparticles. In addition, semiconductor phase concentration in the glass matrix was found by using optical absorption data for the first time, which allows understanding the effect of nanocomposite structure on luminescence properties.     

Electronic excitations and optical response of metal nanocomposites under heavy ion implantation

The optical transmission and ion-induced luminescence under implantation of copper ions into quartz glass (a-SiO₂) have been measured to study the processes of formation of copper nanoparticles. It is shown that in situ measurements are more informative in comparison with the ordinary approach—investigation of the properties of ion-implanted nanocomposites only after implantation. A series of experiments was performed to prove that the ion-induced luminescence band at 545–550 nm is due to Cu⁺ ions dissolved in a-SiO₂. The combined use of in situ optical techniques makes it possible to monitor the states of implanted copper (metal nanoparticles and dissolved atoms) by the change in the optical absorption near the surface plasmon resonance of nanoparticles and by the intensity of ion-induced luminescence of Cu⁺ states in solid solution. It is shown that the optical bands of defects, dissolved copper, and nanoparticles can be separated within a simple linear approximation. Near the surface plasmon resonance and defect bands, ion-induced transient optical absorption has been revealed. The transient optical absorption near the surface plasmon resonance is explained by the temperature effect. The relationship between the electronic excitation, radiation-induced optical response, and the kinetics of nanoparticle formation is analyzed. Several stages of nanoparticle formation have been established: accumulation of implanted copper in solid solution, nucleation of nanoparticles, coalescence, growth of nanoparticles, and saturation of nanocomposites.     

Synthesis, structural, optical and electrical properties of metal nanoparticle–rare earth ion dispersed in polymer film

Cu-nanoparticles have been prepared by ablating a copper target submerged in benzene with laser pulses of Nd:YAG (wavelength: 355, 532 nm and 1,064 nm). Colloidal nanoparticles have been characterized by UV–Vis spectroscopy and transmission electron microscopy. The obtained radius for the nanoparticles prepared using 1,064 nm irradiation lies in the range 15–30 nm, with absorption peak at 572 nm. Luminescence properties of Tb³⁺ ions in the presence and absence of Cu-nanoparticles have been investigated using 355 nm excitation. An enhancement in luminescence of Tb³⁺ by local field effect causing increase in lifetime of ⁵D₄ level of Tb³⁺ ion has been observed. Frequency and temperature-dependent conductivity of Tb³⁺ doped PVA thin films with and without Cu-nanoparticles have been measured in the frequency range 20 Hz–1 MHz and in the temperature range 318–338 K (well below its melting temperature). Real part of the conductivity spectra has been explained in terms of power law. The electrical properties of the thin films show a decrease in dc conductivity on incorporation of the Cu-nanoparticles.     

RF-plasma assisted pulsed laser deposition of nitrogen-doped SrTiO3 thin films

Perovskite-type nitrogen substituted SrTiO₃ thin films were deposited with a one-step process by RF-plasma assisted pulsed laser deposition from a SrTiO₃ target using a N₂ plasma, while deposition with a NH₃ plasma yields films with almost no incorporated nitrogen. The deposited films exhibit a cubic perovskite-type crystal structure and reveal oriented growth on MgO(100) substrates. The unit cell parameters of the studied N-doped SrTiO₃ films range within 3.905<a<3.918 Å, which is slightly larger than for SrTiO₃ (a=3.905 Å). The nitrogen content in the deposited films varies from 0.2 to 0.7 atom%. The amount of incorporated nitrogen in the films decreases with increasing RF-power, while the N₂ flow rate does not have any pronounced influence on the N content. Nitrogen incorporation results in an increased optical absorption at 400–600 nm, which is associated with N(2p) energy states that have a higher energy level than the valence band in strontium titanate. The optical band gap energies in the studied N-doped SrTiO₃ films are at 3.2–3.3 eV, which is very similar to that of pure strontium titanate (～3.2 eV). Films deposited with NH₃ for the RF-plasma exhibit a lower degree of crystallinity and reveal almost no nitrogen incorporation into the crystal lattice.     

Athermal migration of vacancies in iron and copper induced by electron irradiation

Abstract

Irradiation with high-energy particles induces athermal migration of point defects, which affects defect reactions at low temperatures where thermal migration is negligible. We conducted molecular dynamics simulations of vacancy migration in iron and copper driven by recoil energies under electron irradiation in a high-voltage electron microscope. Minimum kinetic energy required for migration was about 0.8 and 1.0 eV in iron and copper at 20 K, which was slightly higher than the activation energy for vacancy migration. Around the minimum energy, the migration succeeded only when a first nearest neighbour (1NN) atom received the kinetic energy towards the vacancy. The migration was induced by higher kinetic energies even with larger deflection angles. Above several electron-volts and a few 10s of electron-volts, vacancies migrated directly to 2NN and 3NN sites, respectively. Vacancy migration had complicated directional dependence at higher kinetic energies through multiple collisions and replacement of atoms. The probability of vacancy migration increased with the kinetic energy and remained around 0.3–0.5 jumps per recoil event for 20–100 eV. At higher temperatures, thermal energies slightly increased the probability for kinetic energies less than 1.5 eV. The cross section of vacancy migration was 3040 and 2940 barns for 1NN atoms in iron and copper under irradiation with 1.25 MV electrons at 20 K: the previous result was overestimated by about five times.     

Hydrothermal synthesis of MnO2 nanowires: structural characterizations,optical and magnetic properties

In this paper, 1D single-crystalline MnO₂ nanowires have been successfully synthesized by hydrothermal method using KMnO₄ and (NH₄)₂S₂O₈ as raw materials. X-ray diffraction patterns and high-resolution TEM images reveal pure tetragonal MnO₂ phase with diameters of 15–20 nm. Photoluminescence studies exhibited a strong ultraviolet (UV) emission band at 380 nm, blue emission at 452 nm and an extra weak defect-related green emission at 542 nm. UV–visible spectrophotometery was used to determine the absorption behavior of nanostructured MnO₂ and a direct optical band gap of 2.5 eV was acquired by Davis–Mott model. The magnetic properties of the products have been evaluated using vibrating sample magnetometer, which showed that MnO₂ nanowires exhibited a superparamagnetic behavior at room temperature. The magnetization versus temperature curve of the as-obtained MnO₂ nanowires shows that antiferromagnetic transition temperature is 99 K.