Cobalt-doped cerium oxide nanoparticles: Enhanced photocatalytic activity under UV and visible light irradiation

CeO₂ nanoparticles (NPs) were synthesized by coprecipitation using cerium(III) nitrate hexahydrate as the precursor and ethanol as the solvent. Different concentration of cobalt-doped cerium oxide NPs (3mol % and 6 mol %) were prepared by adding various concentrations of cobalt chloride to cerium nitrate. The as-synthesized NPs were characterized through X-ray diffraction (XRD) measurements, ultraviolet (UV)–visible spectroscopy, Photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM). XRD results reveal that the as-prepared CeO₂ NPs had a face-centered cubic structure with crystallite size in the range of 5–8 nm. TEM analyses showed that the CeO₂ NPs and Co-doped CeO₂ NPs had a homogenous size distribution (sizes were within 5–12 nm). Band-edge absorption of CeO₂ NPs redshifted upon increasing the Co concentration as compared to undoped CeO₂ NPs. PL spectra reveal a peak shift of CeO₂ emission upon cobalt doping, which were due to an increase in oxygen defects localized between the Ce4f and O2p energy levels (i.e., via formation of Ce³⁺ states). Photocatalytic degradation of methylene blue in aqueous solution under UV and visible (sunlight) irradiation in the presence of pure CeO₂ NPs and of Co-doped CeO₂ NPs was investigated. The efficiency of photocatalytic degradation of CeO₂ NPs increased with the Co concentration both under UV irradiation and under visible light. Co-doped CeO₂ NPs (6 mol%) showed degradation efficiencies of 98% and 89% at 420 min of exposure to UV irradiation and to visible light, respectively.     

Electrochemical investigation of graphene/cerium oxide nanoparticles as an electrode material for supercapacitors

Mechanisms of charge storage, stability, capacitance, morphology and response current of graphene/cerium oxide (CeO₂) nanoparticles as an electrode material for electrochemical capacitors have been investigated. Electrochemical properties of the assembled electrodes were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques in 3 M NaCl, NaOH and KOH electrolytes. Scanning electron microscopy (SEM) is used to characterize the microstructure and the nature of prepared electrodes. SEM images confirm the layered structure (12 nm thickness) of the used graphene. The proposed electrode shows a maximum specific capacitance as high as 11.09 F g⁻¹ in the potential range between −0.55 and 0.3 (V vs. SCE) at scan rate of 5 mV s⁻¹. The charge/discharge cycling test shows a good reversibility and confirms that capacitance will increase after 500 cycles by 37%.     

Defect characterization of Tl4GaIn3Se2S6 layered single crystals by photoluminescence

Photoluminescence (PL) spectra of Tl₄GaIn₃Se₂S₆ layered crystals grown by the Bridgman method have been studied in the energy region of 2.02–2.35 eV and in the temperature range of 16–45 K. A broad PL band centered at 2.20 eV was observed at T=16 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.1 to 149.9 mW cm⁻² range. Radiative transitions from shallow donor level located at 10 meV below the bottom of conduction band to moderately deep acceptor level located at 180 meV above the top of the valence band were suggested to be responsible for the observed PL band. An energy level diagram showing transitions in the band gap of the crystal was plotted taking into account the results of present work and previously reported paper on thermally stimulated current measurements carried out below room temperature. Analysis of the transmission and reflection measurements performed in the wavelength range of 400–1030 nm at room temperature revealed the presence of indirect transitions with 2.22 eV band gap energy.     

Characterization of cadmium sulfide/titania heterostructure films by utilizing microstructure and optical characteristics

Engineering and controlling the bandgap of semiconducting metal oxide (TiO₂) to enhance photoactivity under visible light is challenging. Impact of the changing CdS thickness (50–150 nm) on the structure and optical properties of the CdS/TiO₂ heterostructure films (HSFs) which fabricated by pulsed laser deposition (PLD) was observed. XRD, FE-SEM, AFM, UV–vis and PL spectroscopy measurements were utilized to characterize structural and optical behaviors of the films. XRD measurement shows gradual increments of the lattice constants of the films with the increase of CdS thickness. The mean values of the calculated lattice constants and cell volume (V) were a=b=0.3785 nm, c=0.9475 nm and V=13.58 nm³ respectively. The average of crystallite sizes estimated for TiO₂ and CdS/TiO₂ at various CdS thickness is 12.20, 13.49, 24.24 and 43.10 nm. FESEM images prove the high quality nanocrystalline nature of the films without cracks and dislocation. The root means square roughness of the films was increased with the increase of CdS thickness as showed by AFM images. UV–vis measurement reveals an improvement in the optical absorbance of HSFs in the range of 380–550 nm due to presence of CdS. Interestingly, the PL intensity was enhanced by a factor of nineteen compare to pure TiO₂ attributed to the charge carrier recombination in the band gap. The current results suggest that possibility to improve the optical and structural properties of the TiO₂ films and also it possible to fabricate high quality CdS/TiO₂ HSFs by variation of the CdS thickness.     

Structural and optical properties of CdS/PEO nanocomposite solid films

In this paper solution mixing and casting of Cd(NO₃)₂·4H₂O and poly(ethylene oxide) (PEO) at different molar ratios (1:100–1:600) followed by hydrogen sulfide treatment were employed to fabricate solid films of cadmium sulfide (CdS)/polyethylene oxide (PEO) nanocomposites. The nanocomposites were found to exhibit uniform distribution of CdS nanoparticles in the polymer matrix without any additional capping agent. Systematic investigations on the role of PEO on the optical properties of CdS are presented. The optical properties of the composites examined by UV–vis absorption spectroscopy show that the band gap of CdS nanoparticles increases from 2.45 eV to 2.54 eV with decreasing concentration of CdS in PEO films. X-ray diffraction pattern shows the broadening in shape of the PEO peaks which is induced by the CdS particles in PEO matrix. The CdS particle sizes ranging from 10 to 20 nm are clearly seen in a transmission electron microscope (TEM). The X-ray photoelectron spectroscopic studies (XPS) also confirm the presence of CdS in PEO. Fourier transform infrared spectroscopy studies using attenuated total reflectance (FTIR-ATR) indicate the influence of Cd²⁺ ion on C–O–C stretching in PEO and confirm the presence of CdS nanoparticles within PEO. Photoluminescence spectroscopy (PL) shows the broad emission due to the presence of surface trapped carrier states.     

Properties of V–Ce mixed-oxide thin films deposited by RF magnetron sputtering

Thin films of vanadium cerium mixed oxides are good counter-electrodes for electrochromic devices because of their passive optical behavior and very good charge capacity. We deposited thin films of V–Ce mixed oxides on glass substrates by RF magnetron sputtering under argon at room temperature using different power settings. The targets were pressed into pellets of a powder mixture of V₂O₅ and CeO₂ at molar ratios of 2:1, 1:1, and 1:2. For a molar ratio of 2:1, the resulting crystalline film comprised an orthorhombic CeVO₃ phase and the average grain size was 89 nm. For molar ratios of 1:1 and 1:2, the resulting films were completely amorphous in nature. Scanning electron microscopy images and energy-dispersive X-ray spectroscopy data confirmed these results. The optical properties of the films were studied using UV-Vis-NIR spectrophotometry. The transmittance and indirect allowed bandgap for the films increased with the RF power, corresponding to a blue shift of the UV cutoff. The average transmittance increased from 60.9% to 85.3% as the amount of CeO₂ in the target material increased. The optical bandgap also increased from 1.94 to 2.34 eV with increasing CeO₂ content for films prepared at 200 W. Photoacoustic amplitude (PA) spectra were recorded in the range 300–1000 nm. The optical bandgap was calculated from wavelength-dependent normalized PA data and values were in good agreement with those obtained from UV-Vis-NIR data. The thermal diffusivity calculated for the films increased with deposition power. For thin films deposited at 200 W, values of 53.556×10⁻⁸, 1.069×10⁻⁸, and 0.2198×10⁻⁸ m²/s were obtained for 2:1, 1:1, and 1:2 V₂O₅/CeO₂, respectively.     

Effect of europium doping levels on photoluminescence and thermoluminescence of strontium yttrium oxide phosphor

The present paper deals with the effect of europium (Eu³⁺) doping concentration (0.1–2.5 mol%) on photoluminescence (PL) and thermoluminescence (TL) of strontium yttrium oxide (SrY₂O₄) phosphor. The sample was prepared by the modified solid state reaction method, which is the most suitable method for large-scale production. The prepared phosphor sample was characterized by using X-ray Diffraction (XRD), field emission gun scanning electron microscopy, fourier transform infrared spectroscopy, high resolution transmission electron microscopy, photoluminescence, thermoluminescence and commission internationale de I׳Eclairage techniques. The PL emission was observed in the range of 410–630 nm for the SrY₂O₄ phosphor doped with Eu³⁺. Excitation spectrum was found at 254 and 325 nm, sharp peaks were found around 593, 615 and 625 nm with high intensity. From the XRD data, using Scherrer׳s formula, calculated average crystallite size of Eu³⁺ doped SrY₂O₄ phosphor is around 32 nm. Thermoluminescence study was carried out for the phosphor with UV and gamma irradiation. The TL response of SrY₂O₄:Eu³⁺ phosphor for two different radiations was compared and studied in detail. The present phosphor can act as a single host for white light emission in display devices. The detailed process and possible mechanisms for PL and TL are studied and discussed. For the variable concentration of Eu³⁺ on PL studies the PL intensity increases with increasing the concentration of dopant and the concentration quenching found after 2 mol% of Eu³⁺ the optimized concentration was 2 mol%, which is suitable for the display device application. In TL glow curve the optimized concentration was 1 mol% for the UV irradiated sample and 0.2 mol% of Eu³⁺ for the gamma irradiated sample and beta irradiated sample for 10 Gy dose. The kinetic parameters were calculated by the computerized glow curve deconvolution (CGCD) technique.     

On the current conduction mechanisms of CeO2/La2O3 stacked gate dielectric

It was found that the electrical properties of CeO₂/La₂O₃ stack are much better than a single layer La₂O₃ film. A thin CeO₂ capping layer can effectively suppress the oxygen vacancy formation in the La₂O₃ film. This work further investigates the current conduction mechanisms of the CeO₂ (1 nm thick)/La₂O₃ (4 nm thick) stack. Results show that this thin stacked dielectric film still has a large leakage current density; the typical 1−V leakage can exceed 1 mA/cm² at room temperature. The large leakage current should be due to both the oxide defect centers as well as the film structure. Results show that at low electric field (<0.2 MV/cm), the thermionic emission induced current conduction in this stacked structure is quite pronounced as a result of interface barrier lowering due to the capping CeO₂ film which has a higher k value than that of the La₂O₃ film. At higher electric fields, the current conduction is governed by Poole–Frenkel (PF) emission via defect centers with an effective energy level of 0.119 eV. The temperature dependent current–voltage characteristics further indicate that the dielectric defects may be regenerated as a result of the change of the thermal equilibrium of the redox reaction in CeO₂ film at high temperature and the drift of oxygen under the applied electric field.     

Synthesis and characterization of ZnS/ZnO/CdS nanocomposites

Water-soluble ZnS/ZnO/CdS (0.1–0.5 M) nanocomposites were successfully synthesized by the chemical precipitation method in air. X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible (UV–vis), photoluminescence (PL) and thermo gravimetric-differential thermal analysis (TG-DTA) were used to characterize the synthesized products. It is found that the ZnS/ZnO/CdS (0.1–0.5 M) core–shell nanocomposite is cubic and hexagonal mixed structure. TEM results showed the prepared nanocomposites are monodispersed and uniform in size. It is confined within 4.3–5.6 nm range. UV–vis absorption spectra were confined growth process of multi shells on ZnS. It showed a red shift with respect to the shells thickness. Fluorescence measurement showed the emission band which exists in the visible region. Stability and phase transition were identified by TG-DTA analysis. The results show an improved florescence property, indicating their potential applications in biological labeling.     

Influence of annealing temperature on the structural and optical properties of nanocrystalline zirconium oxide

Nanocrystalline zirconium oxide powder was prepared by sol-gel method using zirconyl chloride octahydrate (ZrOCl₂·8H₂O) and ethylenediaminetetraacitic acid (EDTA) in ammonium hydroxide (NH₄OH) solution. The as-synthesized complex product was annealed at 650 °C, 750 °C and 850 °C for 2 h to get fine ZrO₂ powder. These samples were further analyzed by Scanning electron microscopy (SEM), X- ray diffraction (XRD), Energy-dispersive X- ray spectroscopy (EDX), UV-vis analysis, Fourier transform infrared (FT-IR) spectroscopy, Photoluminescence spectroscopy (PL) and Raman Spectroscopy to study their structural and optical properties. The structural studies revealed that nanocrystalline ZrO₂ powder exhibits monoclinic phase with variation in crystallite size with annealing temperature. The UV–vis absorption band edge of ZrO₂ decreases from 514 nm to 451 nm as annealing temperature rises from 650 °C to 750 °C. It seems that the drastic reduction in band gap energy may be one of the novel unexpected characteristics of ZrO₂. The FTIR analyses further confirmed the formation of nanocrystalline monoclinic ZrO₂. PL analysis revealed the novel emission peaks at 305 and 565 nm. The Raman spectroscopy confirmed the transformation of amorphous zirconium hydroxide to m-ZrO₂ with increase in temperature from 650 °C to 850 °C.     

Effect of Eu,Mn co-doping on structural,optical and magnetic properties of BiFeO3 nanoparticles

Multiferroic Bi_1−xEu_xFe_0.975Mn_0.025O₃ (x=0.025, 0.05, 0.075, 0.1) nanoparticles were prepared by sol-gel route. The impacts of Eu, Mn co-doping samples on the properties of structural, morphology, optical band gap, ferroelectric and ferromagnetic have been systematic investigated. X-ray diffraction and rietveld refinement data reveal that Eu, Mn co-substitution could trigger cubic phase transformation. From the SEM images, the grains of all the samples are asymmetrical and anomalous in shape and interestingly, the particle size of the samples decrease from 200 to 500 nm to ~100 nm after doping. And we can obtain the content of dopants in the samples by energy-dispersive X-ray spectroscopy (EDS) analysis. UV–vis absorption spectra demonstrate a gradually decreasing of the direct optical band gap from 2.40 eV to ~1.49 eV with doping Eu and Mn in BFO. X-ray photoelectron spectroscopy (XPS) analyses illuminate that Eu, Mn-doping results in the increase of Fe³⁺ ions content in the samples. The significantly increased the remanent magnetization (M_r) and coercive field (E_c) were caused by Eu and Mn co-doping.     

Photophysical properties of nano Si/SiOx composites in Al/composite/mono Si structures for green light emitting and photodetector-Schottky diodes

The concept of the self-formation of a nanocrystallite (nc-) Si/SiO_x : Si_zO_yAl nanocomposite at the Al/oxidized porous silicon interface in the result of solid-phase processes between Al and oxidized porous Si (PS) and the influence of its composition on photophysical properties were developed and experimentally confirmed for the Si chip with optical intra-chip interconnect consisting of light emitting and photodetector diodes and alumina waveguide on oxidized PS surface with aluminum electrodes. The peculiarities of nanocomposite photophysical properties (the refractive index, photoluminiscence (PL) peak situation, PL spectrum shape in the green range) have been shown to be due to the quantum confinement effects (revealed by XPS, Raman spectroscopy) and depend on the Al presence in the nanocomposite (obtained by XPS, IR spectroscopy). The experimental confirmation of this concept is (i) the shift of the nc-Si valence band relatively to that of monocrystalline Si (c-Si) on 0.2–0.7 eV for nc-Si size in 2.5–6.5 nm range; (ii) the decrease of Si nanocrystallite size in the Al presence; (iii) the approach of the value of the refractive index of nc-Si : SiO : Si₂O₃ : Si_zO_yAl nanocomposite at λ=236 nm to that of porous Si with 45% porosity and (iv) the stable green PL spectra in the Si_zO_yAl presence in the nanocomposite.     

Local electronic structure,optical bandgap and photoluminescence (PL) properties of Ba(Zr0.75Ti0.25)O3 powders

Ba(Zr_0.75Ti_0.25)O₃ (BZT-75/25) powders were synthesized by the polymeric precursor method. Samples were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques. Their electronic structures were evaluated by first-principle quantum mechanical calculations based on density functional theory at the B3LYP level. Their optical properties were investigated by ultraviolet-visible (UV-Vis) spectroscopy and photoluminescence (PL) measurements at room temperature. XRD patterns and Rietveld refinement data indicate that the samples have a cubic structure. XANES spectra confirm the presence of pyramidal [TiO₅] clusters and octahedral [TiO₆] clusters in the disordered BZT-75/25 powders. EXAFS spectra indicate distortion of Ti–O and Ti–O–Ti bonds the first and second coordination shells, respectively. UV-Vis absorption spectra confirm the presence of different optical bandgap values and the band structure indicates an indirect bandgap for this material. The density of states demonstrates that intermediate energy levels occur between the valence band (VB) and the conduction band (CB). These electronic levels are due to the predominance of 4d orbitals of Zr atoms in relation to 3d orbitals of Ti atoms in the CB, while the VB is dominated by 2p orbitals related to O atoms. There was good correlation between the experimental and theoretical optical bandgap values. When excited at 482 nm at room temperature, BZT-75/25 powder treated at 500 °C for 2 h exhibited broad and intense PL emission with a maximum at 578 nm in the yellow region.     

Electronic structure of highly crystalline polyaniline by study of tunneling conduction in n+-Si/self-assembled monolayer/polyaniline heterostructures

Highly crystalline polyaniline (PANI) films were deposited on degenerated silicon (n⁺-Si) substrates covered with its native oxide (SiO₂), surface modified with amino-silane self-assembled monolayers (SAM). Scanning electron microscopy studies reveal formation of single crystal domains scattered all over the surface of film. Height and current images obtained using current-sensing AFM (C-AFM) exhibit pyramidal topography of crystallites, and inhomogeneous conductivity. As the native oxide and SAM acts as a very thin insulating layer (<2 nm) between the metal-like substrate (degenerated Si) and the PANI film, it forms n⁺-Si/SiO₂/SAM/PANI metal-insulator-semiconductor (MIS) heterostructure. C-AFM probe was used for I–V measurements on the MIS structures and study the tunneling conduction across it. The conductance spectra derived from I–V characteristics corroborates well with the polaron-lattice band structure of doped PANI with presence of polaron bands between the HOMO-LUMO energy gap. These polaron bands are well-resolved from our C-AFM measurements and they are located about 0.25 eV below the LUMO and above the HOMO.     

Green and blue–green light-emitting electrochemical cells based on cationic iridium complexes with 2-(4-ethyl-2-pyridyl)-1H-imidazole ancillary ligand

The ionic iridium complexes, [Ir(ppy)₂(EP-Imid)]PF₆ (Complex 1) and [Ir(dfppy)₂(EP-Imid)]PF₆ (Complex 2) are used as the light-emitting material for the fabrication of light-emitting electrochemical cells (LECs). These complexes have been synthesized, employing 2-(4-ethyl-2-pyridyl)-1H-imidazole (EP-Imid) as the ancillary ligand, 2-phenylpyridine (ppy) and 2-(2,4-difluorophenyl)pyridine (dfppy) as the cyclometalated ligands, which were characterized by various spectroscopic, photophysical and electrochemical methods. The photoluminescence (PL) emission spectra in acetonitrile solution show blue–green and blue light emission for Complexes 1 and 2 respectively. However, LECs incorporating these complexes resulted in green (522 nm) light emission for Complex 1 with the Commission Internationale de L’Eclairage (CIE) coordinates of (0.33, 0.56) and blue–green (500 nm) light emission for Complex 2 with the CIE coordinates of (0.24, 0.44). Using Complex 1, a maximum luminance of 1191 cd m⁻² and current efficiency of 1.0 cd A⁻¹ are obtained while that of Complex 2 are 741 cd m⁻² and 0.88 cd A⁻¹ respectively.     

Red luminescence of spherical CuxZn1−xS semiconductor nanoparticles using 2-mercaptoethanol as capping agent

Cu²⁺-doped (0–2 at%) ZnS nanoparticles stabilized by 2-mercaptoethanol (2-ME) were successfully prepared using wet precipitation route in aqueous solution. The structural and optical characteristics were studied by various techniques. XRD pattern showed zinc blende cubic structure of Cu²⁺-doped ZnS with grain size of 4±0.5 nm. Spherical shape and well distribution of particles is confirmed by TEM, SEM and STM microscopy. Copper doping were identified by elemental dispersive (EDS) spectrometry. UV–vis spectroscopy revealed strong confinement effect due to blue shift in absorption shoulder peak as compared to bulk ZnS. Red luminescence band at～657 nm on Cu²⁺ doping may be arising from recombination of electrons at sulfur vacancies (V_s) and Cu(t₂) states formed at ZnS band gap. Optimum concentration of 0.25 at% (red band) of Cu²⁺ doping was selected by the observed enhanced PL emission.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

The effect of oxide layer thickness on the quantification of 1.5 MeV γ–radiation induced interface traps in the Ag/SiO2/Si MOS devices

This work presents the effect of varied thickness of oxide layer and radiation dose on electrical characteristics of Ag/SiO₂/Si MOS devices irradiated by 1.5 MeV γ–radiations of varied doses. SiO₂ layers of 50, 100, 150 and 200 nm thickness were grown on Si substrates using dry oxidation and exposed to radiation doses of 1, 10 and 100 kGy. The exposure to radiation resulted in generation of fixed charge centers and interface traps in the SiO₂ and at the Si/SiO₂ interface. Capacitance-conductance-voltage (C-G-V) and capacitance-conductance-frequency (C-G-f) measurements were performed at room temperature for all MOS devices to quantify the active traps and their lifetimes. It is shown that accumulation and minimum capacitances decreased as the thickness of SiO₂ layer increased. For the unexposed MOS devices, the flat band voltage V_FB decreased at a rate of −0.12 V/nm, density of active traps increased by 4.5 times and depletion capacitance C_DP, increased by 2.5 times with the increase of oxide layer thickness from 50 to 200 nm. The density of active traps showed strong dependence on the frequency of the applied signal and the thickness of the oxide layer. The MOS device with 200 nm thick oxide layer irradiated with 100 kGy showed density of active interface traps was high at 50 kHz and was 3.6×10¹⁰ eV⁻¹ cm⁻². The relaxation time of the interface traps also increased with the exposure of γ–radiation and reached to 9.8 µs at 32 kHz in 200 nm thick oxide MOS device exposed with a dose of 100 kGy. It was inferred that this was due to formation of continuum energy states within the band gap and activation of these defects depended on the thickness of oxide layer, applied reverse bias and the working frequency. The present study highlighted the role of thickness of oxide layer in radiation hard environments and that only at high frequency, radiation induced traps remain passivated due to long relaxation times.     

Electrochemical growth of tin(II) oxide films: Application in photocatalytic degradation of methylene blue

We have investigated the semiconducting and photoelectrochemical properties of SnO films grown potentiostatically on tin substrate. The oxide is characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The anodic process corresponds to the formation of SnO·nH₂O pre-passive layer that is removed upon increasing potential due to surface etching at the metal/oxide interface. SnO films deposited for long durations (>50 mn) are uniform and well adhered; they thicken up to ~50 nm by diffusion-controlled process and the growth follows a direct logarithmic law. The thickness is determined by coulometry and the X-ray diffraction indicates the tetragonal SnO phase (SG: P4/mmm) with a crystallite size of 32 nm. The Mott–Schottky plot is characteristic of n type conductivity with an electrons density of 5.72×10¹⁸ cm⁻³, a flat band potential of −0.09 V_SCE and a depletion width of ~10 nm. The valence band, located at 5.91 eV below, vacuum is made up of hybridized O²⁻:2p Sn²⁺:5s while the conduction band (4.45 eV) derives from Sn²⁺:5p orbital. The electrochemical impedance spectroscopy (EIS) measured in the range (10⁻²–10⁵ Hz) shows the contribution of the bulk and grain boundaries. The energy band diagram predicts the photodegradation of methylene blue on SnO films. 67% of the initial concentration (10 mg L⁻¹) disappears after 3 h of exposure to visible light (9 mW cm⁻²) with a quantum yield of 0.072.     

Effect of substrate temperature on structural,morphological, optical and electrical properties of MnIn2S4 thin films prepared by nebulizer spray pyrolysis technique

Manganese indium sulphide (MnIn₂S₄) thin films were deposited using an aqueous solution of MnCl₂, InCl₃ and (NH₂)₂CS in the molar ratio 1:2:4 by simple chemical spray pyrolysis technique. The thin film substrates were annealed in the temperature range between 250 and 350 °C to study their various physical properties. The structural properties as studied by X-ray diffraction showed that MnIn₂S₄ thin films have cubic spinel structure. The formation of cube and needle shaped grains was clearly observed from FE-SEM analysis. The energy dispersive spectrum (EDS) predicts the presence of Mn, In and S in the synthesized thin film. From the optical studies, it is analyzed that the maximum absorption co-efficient is in the order between 10⁴ and 10⁵ cm⁻¹ and the maximum transmittance (75%) was noted in the visible and infrared regions. It is noted that, the band gap energy decreases (from 3.20 to 2.77 eV) with an increase of substrate temperature (from 250 to 350 °C). The observations from photoluminescence studies confirm the emission of blue, green, yellow and red bands which corresponds to the wavelength range 370–680 nm. Moreover, from the electrical studies, it is observed that, as the substrate temperature increases the conductivity also increases in the range 0.29–0.41×10⁻⁴ Ω⁻¹ m⁻¹. This confirms the highly semiconducting nature of the film. The thickness of the films was also measured and the values ranged between 537 nm (250 °C) to 483 nm (350 °C). This indicates that, as the substrate temperature increases, the thickness of the film decreases. From the present study, it is reported that the MnIn₂S₄ thin films are polycrystalline in nature and can be used as a suitable ternary semiconductor material for photovoltaic applications.