Synthesis of CuS nanorods grown at room temperature by electrodeposition method

CuS thin films were deposited on stainless steel substrates from an aqueous solution of CuSO₄, Na₂S₂O₃ and Triethanolamine. Deposited films were characterized by XRD, SEM, EDAX, Raman and Optical measurements. The electrodeposition bath concentration can be used to control the diameter of the electrodeposited nanorods within the range of 35–40 nm. The formation of complexes of copper ions and TEA was found to be a key factor in the nanorods growth process. Films are polycrystalline with hexagonal crystal structure. SEM images indicate that the film surfaces are smooth, homogeneous and well-covered. A new structure of CuS nanorods having length of 5–10 μm and diameter from 35 to 40 nm has been demonstrated. By changing bath concentration and keeping deposition time fixed the agglomeration of rods is enhanced due to the formation of large number of particles during growth process. Raman shifts of samples are detected at wave numbers 473 cm⁻¹. Typical film deposited with optimized bath concentration shows optical band gap of about 2.73 eV.     

Effect of cadmium oxide incorporation on the microstructural and optical properties of pulsed laser deposited nanostructured zinc oxide thin films

CdO doped (doping concentration 0, 1, 3 and 16 wt%) ZnO nanostructured thin films are grown on quartz substrate by pulsed laser deposition and the films are annealed at temperature 500 °C. The structural, morphological and optical properties of the annealed films are systematically studied using grazing incidence X-ray diffraction (GIXRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), atomic force microscopy (AFM), Micro-Raman spectra, UV–vis spectroscopy, photoluminescence spectra and open aperture z-scan. 1 wt% CdO doped ZnO films are annealed at different temperatures viz., 300, 400, 500, 600, 700 and 800 °C and the structural and optical properties of these films are also investigated. The XRD patterns suggest a hexagonal wurtzite structure for the films. The crystallite size, lattice constants, stress and lattice strain in the films are calculated. The presence of high-frequency E₂ mode and the longitudinal optical A₁ (LO) modes in the Raman spectra confirms the hexagonal wurtzite structure for the films. The presence of CdO in the doped films is confirmed from the EDX spectrum. SEM and AFM micrographs show that the films are uniform and the crystallites are in the nano-dimension. AFM picture suggests a porous network structure for 3% CdO doped film. The porosity and refractive indices of the films are calculated from the transmittance and reflectance spectra. Optical band gap energy is found to decrease in the CdO doped films as the CdO doping concentration increases. The PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. The 16CdZnO film shows an intense deep green PL emission. Non-linear optical measurements using the z-scan technique indicate that the saturable absorption (SA) behavior exhibited by undoped ZnO under green light excitation (532 nm) can be changed to reverse saturable absorption (RSA) with CdO doping. From numerical simulations the saturation intensity (I_s) and the effective two-photon absorption coefficient (β) are calculated for the undoped and CdO doped ZnO films.     

Cu2O nanorod thin films prepared by CBD method with CTAB: Substrate effect,deposition mechanism and photoelectrochemical properties

Cuprous oxide (Cu₂O) films with different nanostructures are deposited on different substrates of fluorine-doped SnO₂ (FTO) glass, Cu and Ti foil respectively by using chemical bath deposition (CBD) technique with the presence of cetyltrimethylammonium bromide (CTAB). The samples are characterized by X-ray diffractmeter, scanning electron microscopy and UV–vis diffuse reflectance spectroscopy. The results show that the prepared Cu₂O films are composed of nanorod arrays when there is CTAB in reaction system. Without CTAB, Cu₂O films with nanospheres are formed. The concentration of CTAB is crucial for the controllable synthesis of nanorod structured Cu₂O films with different length to diameter ratio and nanorod array density is dependent on both substrates and CTAB. A possible mechanism for the formation of Cu₂O nanorods is discussed. Additionally, the UV–vis absorption property for Cu₂O nanorods is much better than that for nanospheres. The photovoltage produced under visible light for Cu₂O nanorod films is higher than that for the nanospheres. Although Cu₂O nanorods on Ti foil can absorb the most visible light, those on Cu foil demonstrate better and more stable photoelectrochemical property than those on any other substrates. This study may be extremely useful for Cu₂O based device with nanostructures.     

Preparation and characterization of sol-gel Li and Al codoped ZnO thin films

Li and Al codoped ZnO (LAZO) thin films have been prepared by a sol-gel method and their structural and optical properties have been investigated. The prepared LAZO films had an average transmittance of over 85% in the visible range. The UV absorption edge was red-shifted with Li-doping, whereas it was blue-shifted with Al-doping. A broad yellowish-white emission was observed from the LAZO films annealed above 600 °C. The visible emission was enhanced with increasing annealing temperature and dopant concentration.     

Indium(III) and Gallium(III) phthalocyanines-based nanohybrid materials for optical limiting

Linear and nonlinear optical properties of a phthalocyanine (Pc)-based nanohybrid material PCIGS [Cu₂(tBu₄PcGa)(tBu₄PcIn)S₂TPP₂] are described. The overall aggregation of phthalocyanines in poly(methylmethacrylate) (PMMA) films was evident, which is indicated by the broadening of linear spectra in the Q-band region and the shift of wavelength. Upon excitation with nanosecond laser pulse at 355 nm, the transient absorption band appeared at about 500 nm is attributed to the triplet–triplet absorption of the Pcs. For PCIGS and its starting materials tBu₄PcGaCl and tBu₄PcInCl, all Z-scans exhibit a decrease in transmittance about the focus typical of an induced positive nonlinear absorption of incident light. The absorption mechanism is due to population of excited states through a multi-step nonlinear absorption. When these Pc compounds were embedded into a commercially available polymer PMMA, all the Pc/PMMA composites display much larger nonlinear absorption coefficient and lower saturable fluence for optical limiting when compared to the same Pc molecules in solution. However, in contrast to tBu₄PcGaCl and tBu₄PcInCl, PCIGS displayed decreased optical limiting response, possibly due to competing electron accepting processes in the In and Ga metals, and the highly ordered structure of the PCIGS complex itself.     

Band gap and dispersive behavior of Ge alloyed a-SbSe thin films using single transmission spectrum

The transparency of SbSeGe glasses in the IR region makes them attractive candidates for low transmission loss applications. The samples of Sb₁₀Se_90−xGe_x (x = 0, 19, 21, 23, 25, 27) glasses have been prepared by melt quench technique. The thin films of these glasses have been deposited by vacuum evaporation technique. The optical study of thin films has been carried out. The refractive index, oscillator parameters, optical band gap and dielectric parameters have been calculated from optical measurements. The optical study reveals that the variation in the density of localized defect states on Ge addition affects the optical parameters of the system. The variation in concentration of localized defect states has been interpreted in terms of the change in structural network of the system.     

Absorption and photoreflectance spectroscopy of zinc phthalocyanine (ZnPc) thin films grown by thermal evaporation

Optical properties of the as-deposited and annealed ZnPc layers have been investigated using absorption, reflectance and modulated photoreflectance methods. The absorption coefficient of ZnPc layers was directly determined from the transmission and reflection spectra. The absorption spectra were analyzed in terms of the mixed Lorentz–Lorenz model. We found that annealing thin layers at 580 K caused a structural transformation, which results in the decrease of the absorption coefficient and the shifting of all peak position to lower energies except for the peak of the N-band. Photoreflectance spectroscopy confirmed that there exist three transitions in the Q-band region of the studied material. Complex refractive index and dielectric constants of the ZnPc layer were directly found from the spectral data.     

Toughness evaluation of hard coatings and thin films

Enormous progress has been achieved over the past decade in evaluating the toughness of hard coatings and thin films. This paper reviews methodologies developed based on indentation, bending, and microtensile testing. In addition, we discuss a recent development in fracture toughness measurement which involves the application of macrotension to a substrate in order to induce microtension in a patterned thin film.     

Optical and other physical characteristics of Ge–Se–Cd thin films

Amorphous Ge₂₀Se_80−xCd_x thin films with different compositions (x = 0, 2.5, 5, 7.5 and 10 at.%) were deposited onto glass substrates by thermal evaporation. The reflection spectra, R(λ), of the films at normal incidence were obtained in the spectral region from 400 to 2500 nm. Based on the use of the maxima and minima of the interference fringes, a straightforward analysis proposed by Minkov has been applied to derive the optical constants and the film thickness for the Ge₂₀Se_80−xCd_x thin films. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple and DiDomenico model. Tauc relation for the allowed non-direct transition describes the optical transition in the studied films. With increasing cadmium content the refractive index increases while the optical band gap decreases. The optical band gap decreases from 2 to 1.5 eV with increasing cadmium content from 0 to 10 at.%. The chemical-bond approach has been applied successfully to obtain the excess of Se–Se homopolar bonds and the cohesive energy of the Ge₂₀Se_80−xCd_x system.     

Preparation and characterization of CuO nanostructures on copper substrate as selective solar absorbers

Selective solar absorber coatings of copper oxide (CuO) on copper substrates are prepared by room temperature oxidation of copper at different alkaline conditions. The surface morphology and structural analyses of the CuO coatings are carried out by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and Raman spectroscopy techniques. XRD and Raman studies indicated the single phase nature and high crystallinity of the prepared CuO nanostructures. Different CuO nanostructures, viz., nanoneedles, nanofibers and nanoparticles are formed at different alkaline conditions. The influence of reaction time on morphology of the CuO nanostructures is also studied. The thermal emittance values of these nanostructured CuO samples are found to be in the range of 6–7% and their solar absorptances are ranged between 84 and 90%. The observed high solar selectivity values (>12.7) suggest that these coatings can be used as selective absorbers in solar thermal gadgets.     

Preparation and characterization of chemically deposited PbSnS3 thin films

High-quality and well-reproducible PbSnS₃ thin films have been prepared by a simple and inexpensive chemical-bath deposition method from an aqueous medium, using thioacetamide as a sulphide ion source. X-ray diffraction analysis of the deposited films revealed that the as-deposited films were amorphous, however, an amorphous-to-crystalline phase transition was observed as the result of thermal annealing at 425 K for 1 h. The X-ray structure analysis of the collected powder from the bath annealed at 425 K for 1.5 h revealed an orthorhombic phase.

Analysis of the optical absorption data of crystalline PbSnS₃ films revealed that both direct and indirect optical transitions exist in the photon energy range 1.24–2.48 eV with optical band gaps of 1.68 and 1.42 eV, respectively. However, a forbidden direct optical transition with a band gap value of 1.038 eV dominates at low energy (<1.24 eV). The refractive index changes from 3.38 to 2.16 in the range 500–1300 nm. The high frequency dielectric constant and the carrier concentration to the effective mass ratio calculated from the refractive index analysis were found to be 4.79 and 2.3×10²⁰ cm⁻³, respectively. The temperature dependence of the electrical resistivity of the deposited films follows the semiconductor behaviour with extrinsic and intrinsic conduction. The determined activation energies range are 0.35–0.42 and 0.76–85 eV, respectively.     

Compositional dependence optical properties study of As40Se60 − xSbx thin films

Thin films were thermally evaporated from the bulk glasses of As₄₀Se_60 − xSb_x (with x = 0, 5, 10, 15 at.%) under high vacuum. We have characterized the deposited films by Fourier Transform Infrared spectroscopy. The relationship between the structural and optical properties and the compositional variation has been investigated. Increasing Sb content was found to affect the thermal and optical properties of these films. Non-direct electronic transition was found to be responsible for the photon absorption inside the investigated films. It was found that, the optical band gap E_o decreases while the width of localized states (Urbach energy) E_e increases.     

Preparation and characterization of amorphous manganese sulfide thin films by SILAR method

Manganese sulfide thin films were deposited by a simple and inexpensive successive ionic layer adsorption and reaction (SILAR) method using manganese acetate as a manganese and sodium sulfide as sulfide ion sources, respectively. Manganese sulfide films were characterized for their structural, surface morphological and optical properties by means of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques. The as-deposited film on glass substrate was amorphous. The optical band gap of the film was found to be thickness dependent. As thickness increases optical band gap was found to be increase. The water angle contact was found to be 34°, suggesting hydrophilic nature of manganese sulfide thin films. The presence of Mn and S in thin film was confirmed by energy dispersive X-ray analysis.     

Some studies on successive ionic layer adsorption and reaction (SILAR) grown indium sulphide thin films

Indium sulphide (In₂S₃) thin films were grown on amorphous glass substrate by the successive ionic layer adsorption and reaction (SILAR) method. X-ray diffraction, optical absorption, scanning electron microscopy (SEM) and Rutherford back scattering (RBS) were applied to study the structural, optical, surface morphological and compositional properties of the indium sulphide thin films. Utilization of triethanolamine and hydrazine hydrate complexed indium sulphate and sodium sulphide as precursors resulted in nanocrystalline In₂S₃ thin film. The optical band gap was found to be 2.7 eV. The film appeared to be smooth and homogeneous from SEM study.     

Optical properties change in amorphous (As2S3)0.87Sb0.13 thin films by photo and thermal induced process

Exposure with above band gap light and thermal annealing at a temperature near to glass transition temperature, of thermally evaporated amorphous (As₂S₃)_0.87Sb_0.13 thin films of 1 μm thickness, were found to be accompanied by structural effects, which in turn, lead to changes in the optical properties. The optical properties of thin films induced by illumination and annealing were studied by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photo darkening or photo bleaching was observed in the film depending upon the conditions of the light exposure or annealing. These changes of the optical properties are assigned to the change of homopolar bond densities.     

The effect of aggregation on the nonlinear optical absorption performance of indium and gallium phthalocyanines in a solution and co-polymer host

The nonlinear optical properties (NLO) of Pcs can be modified by substituting different metal atoms into the ring or altering peripheral and axial functionalities. In this study, nonlinear optical absorption properties of tetra-substituted gallium and indium phthalocyanine complexes both in solution and polymeric film have been investigated by open aperture Z-scan measurements with nanosecond pulses at 532 nm. All investigated compounds exhibited reverse saturable absorption for both solution and film experiments. The investigated compounds in the solution showed better nonlinear optical absorption properties than polymeric films. The observed nonlinear optical absorption differences depending on the aggregation are discussed using the ultrafast dynamics and decay processes of excited states found from femtosecond pump-probe spectroscopy with white light continuum experiments.     

Preparation and characterization of flash-evaporated CuInSe2 thin films

Thin films of CuInSe₂ have been evaporated onto glass substrates by flash evaporation. The as-deposited films are amorphous and annealing in selenium atmosphere produces polycrystalline films. The films were characterized bytem and x-ray diffraction techniques. The optical absorption of the films shows three energy gaps of 1·03, 1·07 and 1·22 eV. The crystal field and spin-orbit splitting are thus found to be 0·04 eV and 0·16 eV respectively. The percentaged-character of the valence band states is ∼35%. The Arrhenius plot of electrical conductivity of films showed impurity ionization ofE _A = 75 meV.     

Effect of Zr (IV) doping on the optical properties of sol–gel based nanostructured indium oxide films on glass

Zr (IV) doped indium oxide thin films (55 nm) were deposited onto pure silica glass by the sol–gel dip coating technique utilizing the precursors of 6 wt% equivalent oxide content. Three different Zr (IV) oxide (ZrO₂) dopant concentrations (5.0, 10.0 and 15.0 wt% w.r.t. total oxides) were chosen. XRD patterns suggested the films were of distinct cubic symmetry of In₂O₃. Nanostructured surface feature was revealed by FESEM images. Average cluster size decreased with increasing dopant concentration as evidenced from TEM study. Blue shift of band gap and UV cut off wavelength (lambda-50) occurred with increase in dopant concentration. The refractive index gradually increased with doping. Baking atmosphere plays an important role in tailoring the refractive index (RI) of the films and relatively high RI was obtained in the case of baking in pure oxygen. Presence of both free and bound excitons was detected by the photoluminescence (PL) study. The 5 wt% doped film exhibited relatively high PL intensity at 380 nm responsible for free exciton. The PL emissions gradually quenched with increase in dopant concentration. Similar behaviour was also observed when the film was baked in pure oxygen atmosphere.     

Novel transparent ternary nanocomposite films of trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania with incorporating networks

Novel ternary nanocomposite trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania optical films were successfully prepared through a nonaqueous in situ sol–gel method. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). PMMA/ZrO₂–TiO₂ incorporating networks formed from alcoholysis of poly(MMA-co-MSMA), zirconium n-butoxide and titanium isoproproxide. The structure, morphology and property of the obtained nanocomposite films were investigated by X-ray photoelectron spectra, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, scanning probe microscopy, thermogravimetric analyses, UV–vis spectrum and spectro-ellipsometer. The nanoparticle size, roughness, thermal stability, UV-shielding property, and refractive index of nanocomposite films increase with the increasing of inorganic contents. The formation mechanism and reason of such improvements were examined and interpreted in a theoretical model. The nanocomposite films possess interesting properties in thermal stability and optical response due to the uniform incorporating networks between organic polymer chains and inorganic clusters.     

Growth and characterization of electrosynthesised zinc oxide thin films

Zinc oxide (ZnO) films have been electrodeposited from an aqueous solution containing 0.1 M zinc nitrate as the electrolyte with pH around 5±0.1. The deposition was carried out by galvanostatic reduction with an applied cathodic current density in the range between 5 and 20 mA cm⁻². The influence of bath composition on the preparation of ZnO films is studied. The effects of zinc nitrate concentration and cathodic current density on the deposition rate of ZnO films were also studied. An optimum current density of 10 mA cm⁻² is identified for the growth of ZnO film with improved crystallinity and optical transmittance. The crystalline structure of the deposits studied by X-ray diffraction reveals the possibility of growing hexagonal ZnO films under suitable electrochemical conditions. The surface morphological studies by scanning electron micrographs revealed the presence of nodular appearance for films deposited at 800 °C bath temperatures.