Swift heavy ion induced modifications in cobalt doped ZnO thin films: Structural and optical studies

Modifications in the structural and optical properties of 100 MeV Ni⁷⁺ ions irradiated cobalt doped ZnO thin films (Zn_1−xCo_xO, x = 0.05) prepared by sol-gel route were studied. The films irradiated with a fluence of 1 × 10¹³ ions/cm² were single phase and show improved crystalline structure with preferred C-axis orientation as revealed from XRD analysis. Effects of irradiation on bond structure of thin films were studied by FTIR spectroscopy. The spectrum shows no change in bonding structure of Zn-O after irradiation. Improved quality of films is further supported by FTIR studies. Optical properties of the pristine and irradiated samples have been determined by using UV-vis spectroscopic technique. Optical absorption spectra show an appreciable red shift in the band gap of irradiated Zn_1−xCo_xO thin film due to sp-d interaction between Co²⁺ ions and ZnO band electrons. Transmission spectra show absorption band edges at 1.8 eV, 2.05 eV and 2.18 eV corresponding to d-d transition of Co²⁺ ions in tetrahedral field of ZnO. The AFM study shows a slight increase in grain size and surface roughness of the thin films after irradiation.     

Synthesis and photoluminescent and nonlinear optical properties of manganese doped ZnS nanoparticles

In this work we synthesized ZnS:Mn²⁺ nanoparticles by chemical method using PVP (polyvinylpyrrolidone) as a capping agent in aqueous solution. The structure and optical properties of the resultant product were characterized using UV-vis optical spectroscopy, X-ray diffraction (XRD), photoluminescence (PL) and z-scan techniques. UV-vis spectra for all samples showed an excitonic peak at around 292 nm, indicating that concentration of Mn²⁺ ions does not alter the band gap of nanoparticles. XRD patterns showed that the ZnS:Mn²⁺ nanoparticles have zinc blende structure with the average crystalline sizes of about 2 nm. The room temperature photoluminescence (PL) spectrum of ZnS:Mn²⁺ exhibited an orange-red emission at 594 nm due to the ⁴T₁-⁶A₁ transition in Mn²⁺. The PL intensity increased with increase in the Mn²⁺ ion concentration. The second-order nonlinear optical properties of nanoparticles were studied using a continuous-wave (CW) He-Ne laser by z-scan technique. The nonlinear refractive indices of nanoparticles were in the order of 10⁻⁸ cm²/W with negative sign and the nonlinear absorption indices of these nanoparticles were obtained to be about 10⁻³ cm/W with positive sign.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.     

Nanocomposite ZnO/Au formation by pulsed laser irradiation

The ZnO/Au nanocomposite formation involves synthesis of Au and ZnO colloidal solutions by 532 nm pulse laser ablation of metal targets in deionized water followed by laser irradiation of the mixed colloidal solution. The transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) images show evolution of spherical particles into ZnO/Au nanonetworks with irradiation time. The formation mechanism of the nanonetwork can be explained on the basis of near resonance absorption of 532 nm irradiation by gold nanoparticles which can cause selective melting and fusion of gold nanoparticles to form network. The ZnO/Au nanocomposites show blue shift in the ZnO exciton absorption and red shift in the Au plasmon resonance absorption due to interfacial charge transfer.     

Preparation and characterization of n-type conductive (Al, Co) co-doped ZnO thin films deposited by sputtering from aerogel nanopowders

Highly transparent, n-type conducting ZnO thin films were obtained by low temperature magnetron sputtering of (Co, Al) co-doped ZnO nanocrystalline aerogels. The nanoparticles of ∼30 nm size were synthesized by a sol-gel method using supercritical drying in ethyl alcohol. The structural, optical and electrical properties of the films were investigated. The ZnO films were polycrystalline textured, preferentially oriented with the (0 0 2) crystallographic direction normal to the film plane. The films show within the visible wavelength region an optical transmittance of more than 90% and a low electrical resistivity of 3.5 × 10⁻⁴ Ω cm at room temperature.     

Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps

Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) complexed with NaF salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Electrical conductivity of the films was measured with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. UV-vis absorption spectra in wavelength region of 200-800 nm were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase in Na⁺ ion concentration. This suggests that NaF, as a dopant, is a good choice to improve the electrical properties of PEO/PVP polymer blend electrolytes.     

Evolution of surface morphology of NiO thin films under swift heavy ion irradiation

NiO nanoparticle thin films grown on Si substrates were irradiated by 107 MeV Ag⁸⁺ ions. The films were characterized by glancing angle X-ray diffraction and atomic force microscopy. Ag ion irradiation was found to influence the shape and size of the nanoparticles. The pristine NiO film consisted of uniform size (∼100 nm along major axis and ∼55 nm along minor axis) elliptical particles, which changed to also of uniform size (∼63 nm) circular shape particles on irradiation at a fluence of 3 × 10¹³ ions cm⁻². Comparison of XRD line width analysis and AFM data revealed that the particles in the pristine films are single crystalline, which turn to polycrystalline on irradiation with 107 MeV Ag ions.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Electrochemical synthesis of Cu/ZnO nanocomposite films and their efficient field emission behaviour

The Cu/ZnO nanocomposite films have been synthesized by cathodic electrodeposition and characterized using X-ray diffractometer (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), photoluminescence (PL) and field emission microscope (FEM). The XRD pattern shows a set of well defined diffraction peaks, which could be indexed to the wurtzite hexagonal phase of ZnO. In addition, characteristic diffraction peaks corresponding to Cu and Zn are also observed. The SEM image shows formation of two-dimensional (2D) hexagonal sheets randomly distributed and aligned almost normal to the substrate. Uniformly distributed small clusters of Cu nanoparticles possessing average diameter of ∼25 nm, as revealed from the TEM image, are seen to be present on these 2D ZnO sheets. The selected area electron diffraction (SAED) image confirms the nanocrystalline nature of the Cu particles. From the field emission studies, carried out at the base pressure of ∼1 × 10⁻⁸ mbar, the turn-on field required for an emission current density of 0.1 μA/cm² is found to be 1.56 V/μm and emission current density of ∼100 μA/cm² has been drawn at an applied field of 3.12 V/μm. The Cu/ZnO nanocomposite film exhibits good emission current stability at the pre-set value of ∼10 μA over a duration of 5 h. The simplicity of the synthesis route coupled with the better emission properties propose the electrochemically synthesized Cu/ZnO nanocomposite film emitter as a promising electron source for high current density applications.     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

Effect of implantation regimes of silver ions on the structure and optical properties of zinc-oxide nanocrystalline films

Thin (about 270 nm) nanocrystalline films of zinc oxide (ZnO) are obtained on quartz substrates using ion sputtering and irradiated with Ag⁺ ions at an energy of 30 keV and relatively high fluences at ion current densities of 4, 8, and 12 µA/cm². The X-ray analysis, scanning electron microscopy, and optical spectroscopy are used to study the effect of irradiation dose and ion current density on the structural modification and optical properties of the ZnO films. Nontrivial dependences of the structural and optical parameters of the films on the ion irradiation regimes are due to radiation heating and film sputtering under the action of the ion beam, diffusion of impurity, formation of silver nanoparticles in the irradiated layer at high implantation fluences, and the diffusion of implanted impurity at relatively high ion current densities.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.     

Preparation and the optical nonlinearity of surface chemistry improved titania nanoparticles in poly(methyl methacrylate)-titania hybrid thin films

With 800-nm, 120-fs laser pulses, optical nonlinearity has been studied in a series of thin films containing poly(methyl methacrylate) (PMMA), filled with surfactant acetylacetone (Acac) capped TiO₂ nanoparticles, which were synthesized by a simple in situ sol-gel/polymerization process, assisted by spin coating and multi-step baking. The resulting nanohybrid thin films have highly optical transparency and demonstrate a unique nonlinear optical (NLO) response. The highest nonlinear refractive index (n₂) is observed up to 6.55 × 10⁻² cm² GW⁻¹ in the nanohybrid thin film of 60 wt% Ti(OBu)₄ in PMMA, with a negligible two-photon absorption (TPA), as confirmed by the Z-scan technique. The titanium precursor loading combined with the nature of the capping molecules are used to influence the ability of nanoparticles to nonlinear optical response. Indeed, the ligands at the nanoparticles’ surface can not only control the extent of the interaction between the organic molecules and the embedded nanoparticles but also influence the optical nonlinearities of nanoparticles.     

Effects of the oxygen partial pressure and annealing atmospheres on the microstructures and optical properties of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (1 0 0) substrates at 200 °C under various oxygen partial pressures by using radio frequency reactive magnetron sputtering. The properties of the films were characterized by the X-ray diffraction spectroscopy (XRD), energy dispersive spectrometer, X-ray photoelectron spectroscopy (XPS) and fluorescence spectrophotometer with the emphasis on the evolution of microstructures, element composition, valence state of Cu, optical properties. The results indicated that the properties of ZnO:Cu films were significantly affected by oxygen partial pressures. XRD measurements revealed that the sample prepared at the ratio of O₂:Ar of 15:10 sccm had the best crystal quality among all ZnO:Cu films. XPS analysis results suggested that the valence of Cu in the ZnO films was a mixed state of +1 and +2, and the integrated intensity ratio of Cu²⁺ to Cu⁺ increased with the increment of oxygen partial pressure. The photoluminescence measurements at room temperature revealed a violet, two blue and a green emission. We considered that the origin of green emission came from various oxygen defects when the ZnO:Cu films grew in oxygen poor and enriched environment. Furthermore, the influence of annealing atmosphere on the microstructures and optical properties of ZnO:Cu films were discussed.     

Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films

Undoped and lithium (Li)-doped ZnO films were prepared by sol-gel method using spin coating technique. The effects of Li content on the crystallinity and morphological properties of ZnO films were assessed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD patterns of the films showed the hexagonal wurtzite type polycrystalline structure and that the incorporation of lithium leads to substantial changes in the structural characteristics of ZnO films. The SEM and AFM measurements showed that the surface morphology of the films was affected from the lithium incorporation. The wrinkle network was observed on the surface from both SEM and AFM results for undoped ZnO. The wrinkle structure disappeared with increasing Li content. The absorption spectra of the ZnO and 5% Li-doped ZnO (LZO5) films were carried out between 140 and 400 K temperatures. The optical band gap of ZnO and LZO5 films (calculated at various temperatures) showed a linear dependence on the temperature. The absolute zero value optical band gap and the rate of change of the band gap with temperature of the ZnO and LZO5 films were found to be 3.339 and 3.322 eV, and 2.95 × 10⁻⁴ and 1.60 × 10⁻⁴ eV/K, respectively. The transport mechanisms in the ZnO and LZO5 films have been investigated by analyzing of the temperature (80-300 K) dependence of the conductivity. The activation energies of the ZnO film increased with Li content.     

Effect of complexing agent on the photoelectrochemical properties of bath deposited CdS thin films

In the present paper photoelectrochemical (PEC) performance of bath deposited CdS thin films based on complexing agents i.e. ammonia and triethanolamine (TEA) has been discussed. Effect of annealing has also been analyzed. The as-deposited and annealed (at 523 K for 1 h in air) films were characterized by X-ray diffraction (XRD), ultraviolet-visible (UV-vis) absorption spectroscopy, SEM, electrochemical impedance spectroscopy (EIS), and PEC properties. XRD studies revealed that the films were nanocrystalline in nature with mixed hexagonal and cubic phases. TEA complex resulted in better crystallinity. Further improvement in the crystallinity of the films was observed after air annealing. The marigold flower-like structure, in addition to flakes morphology, was observed with TEA complex, whereas for ammonia complex only flakes morphology was observed. The UV-vis absorption studies revealed that the optical absorption edge for the films with ammonia and TEA complex was around 475 nm and 500 nm, respectively. Annealing of the films resulted in red shift in the UV-vis absorption. The PEC cell performance of CdS films was found to be strongly affected by crystallinity and morphology of the films resulted due to complexing agent and annealing. The air annealed film deposited using TEA complex showed maximum short circuit current density (J_sc) and open circuit voltage (V_oc) i.e. 99 μA/cm² and 376 mV respectively, under 10 mW/cm² of illumination. The films deposited using TEA complex showed good stability under PEC cell conditions.     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

Formation of gold nanoparticles in heat-treated reactive co-sputtered Au-SiO2 thin films

In this work, formation of gold nanoparticles in radio frequency (RF) reactive magnetron co-sputtered Au-SiO₂ thin films post annealed at different temperatures in Ar + H₂ atmosphere has been investigated. Optical, surface topography, chemical state and crystalline properties of the prepared films were analyzed by using UV-visible spectrophotometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD) techniques, respectively. Optical absorption spectrum of the Au-SiO₂ thin films annealed at 800 °C showed one surface plasmon resonance (SPR) absorption peak located at 520 nm relating to gold nanoparticles. According to XPS analysis, it was found that the gold nanoparticles had a tendency to accumulate on surface of the heat-treated films in the metallic state. AFM images showed that the nanoparticles were uniformly distributed on the film surface with grain size of about 30 nm. Using XRD analysis average crystalline size of the Au particles was estimated to about 20 nm.     

Influence of X-ray irradiation on the optical properties of CoMTPP thin films

Thin films of 5,10,15,20-Tetrakis (4-methoxyphenyl)-21H,23H-porphine cobalt (II), CoMTPP were prepared at room temperature (300K) by the thermal evaporation technique under vacuum pressure about 2 × 10^− 4Pa. The X-ray diffraction patterns showed the amorphous nature for the as-deposited and the irradiated films, whereas the powder has shown a polycrystalline with triclinic structure. Miller's indices, hkl, values for each diffraction peak in the XRD spectrum were calculated. Optical properties of CoMTPP thin films were characterized by using spectrophotometric measurements of transmittance and reflectance in the spectral range from 200 to 2500 nm. The refractive index, n, and the absorption index, k, were calculated. The obtained data were used to estimate the type of transitions and the optical and fundamental gaps before and after X-ray irradiation. In addition, the normal dispersion of the refractive index is discussed in terms of lorentz-lorentz free single oscillator model and modified lorentz Drude model of free carrier contribution.     

Mn doped ZnO nanostructured thin films prepared by ultrasonic spray pyrolysis method

Mn-doped ZnO thin films with different percentage of Mn content (0, 1, 3 and 5 at.%) and substrate temperature of 350 °C, were deposited by a simple ultrasonic spray pyrolysis method under atmospheric pressure. We have studied the structural and optical properties by using X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and ultra-violet visible near infrared (UV–Vis-NIR) spectroscopy. The lattice parameters calculated for the Mn-doped ZnO from XRD pattern were found to be slightly larger than those of the undoped ZnO, which indicate substitution of Mn in ZnO lattice. Compared with the Raman spectra for ZnO pure films, the Mn-doping effect on the spectra is revealed by the presence of additional peak around 524 cm⁻¹ due to Mn incorporation. With increasing Mn doping the optical band gap increases indicating the Burstein–Moss effect.