Electrochromism in spray deposited iridium oxide thin films

Electrochromic iridium oxide thin films were deposited onto fluorine doped tin oxide coated glass substrates from an aqueous iridium chloride solution by pneumatic spray pyrolysis technique. The as-deposited samples were X-ray amorphous. The electrochromic properties of thin films were studied in an aqueous electrolyte (0.5N H₂SO₄) using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. Iridium oxide films show pronounced anodic electrochromism owing to Ir⁺⁴ ↔ Ir⁺³ intervalency charge transition. The reversibility of cyclic process in Ir oxide films is found to be higher, which increases with increasing number of colour-bleach cycles.     

Photoluminescence and third-order nonlinear optical limiting properties of Sn1-xNdxO2 thin films deposited via spray pyrolysis

In the present work, spray pyrolysis method was adopted to synthesis nano thin films of Sn_1-xNd_xO₂ (x = 0.01 to 0.1) possessing tetragonal structure with (1 1 0) plane orientation. Nd doping reduced the overall crystallinity of the films, however Sn_0.92Nd_0.08O₂ film showed crystallite size of 18.7 nm, similar to that of the pure film. The morphology changed to distinct grains at lower doping concentration, beyond which a fibrous nature evolved but again changed to smaller grains with further increase in the doping. The oxidation states of the constituent elements were confirmed using XPS. The transmittance of the films reduced due to incorporation of Nd ions. A decrease in the energy band gap was also noticed in the films following dopant addition. The PL emissions corresponding to the Nd ion transitions was found in the NIR region resulting from internal 4f-shell transitions of Nd³⁺ ions. Other defect related emissions like the one from oxygen vacancies also showed up in the UV and visible wavelength regions, which were responsible for a near white light emission. The third-order optical nonlinearity of the films was confirmed using the Z-scan technique. All the Sn_1-xNd_xO₂ films till 8 at. % of doping showed reverse saturable absorption. The highest and lowest nonlinear absorption coefficient was exhibited by Sn_0.92Nd_0.08O₂ and Sn_0.98Nd_0.02O₂ films, respectively. Depending on the Nd concentration, the films either showed self-focusing or self-defocusing behavior and influenced the nonlinear refractive indices of the films. The least optical limiting values among the doped films was obtained in the range of 1.73 kJ/cm² for Sn_0.92Nd_0.08O₂ films.     

Effect of structural defects,surface roughness on sensing properties of Al doped ZnO thin films deposited by chemical spray pyrolysis technique

In this article, the gas sensing properties of Al-doped ZnO thin films have been reported where the nanocrystalline ZnO based thin films were well deposited by a simple and inexpensive ‘chemical spray pyrolysis (CSP)’ technique. Films have been found to be uniform, pinhole free and well adherent to the substrate. The morphology, structures, and surface roughness of the deposited Al-doped ZnO thin films were studied by various types of characterization techniques. In addition, the authors have observed that the sensor response and selectivity towards CO gas is improved by the Al doping at a low operating temperature. XRD results showed that the obtained films are nanocrystalline in nature with hexagonal wurtzite phase. Further, the annealed films were used for detection of CO in the air and maximum response was observed at 175 °C. The improvement in sensor response of Al-doped ZnO thin films to CO gas attributed to the defect chemistry, crystallite size and surface roughness.     

Characterization of luminescent SrAl2O4 films doped with terbium and europium ions deposited by ultrasonic spray pyrolysis technique

SrAl₂O₄, SrAl₂O₄:Tb³⁺ and SrAl₂O₄:Eu³⁺:Eu²⁺ films were synthesized by means of the ultrasonic spray pyrolysis technique. These samples, characterized by X-Ray Diffraction, showed the monoclinic phase of the strontium aluminate. Images of the surface morphology of these films were obtained by SEM and the chemical composition was measured by EDS and XPS. The photoluminescence and cathodoluminescence characteristics of the films were studied as a function of the terbium and europium concentrations. The optimal PL emission intensities were reached at 8?at% for terbium doped films and 6?at% for europium doped samples. The CL emission spectra for europium doped films showed the typical bands of Eu³⁺ ions and also a broadband centered at 525?nm which is attributed to Eu²⁺ ions. XPS measurements confirm the presence of Eu³⁺ and Eu²⁺ in europium doped SrAl₂O₄ films, without having been subjected to a reducing atmosphere. Chromatic diagrams exhibited green color for SrAl₂O₄:Tb³⁺ films, red and yellow colors for SrAl₂O₄:Eu³⁺:Eu²⁺ films. The PL decay curves were also obtained: the averaged decay time was 2.7?ms for SrAl₂O₄:Tb³⁺ films and 1.9?ms for SrAl₂O₄:Eu³⁺ films. Similar results were obtained by the stretched exponential model.     

Structural, optical, electrical and photovoltaic electrochemical characterization of spray deposited NiWO4 thin films

The preparation of nickel tungstate (NiWO₄) thin film by spray pyrolysis (SP) with ammonical solution is presented. The phase and surface morphology characterizations have been carried out by X-ray diffraction (XRD) and scanning electron microscope (SEM) analysis, respectively. The study of optical absorption spectrum in the wavelength range 350-850 nm shows the presence of direct as well as indirect band gaps in the material, respectively found to be 2.28 and 2.00 eV. The thin film material shows semiconducting behaviour and highly resistive at room temperature as evident from its dc electrical conductivity measurements obtained by the Two Point Probe method in the temperature range 310-500 K. The thin films deposited on fluorine doped tin oxide (FTO) coated conducting glass substrates are used as photoanode in photovoltaic electrochemical (PVEC) cell. The PVEC cell configuration is: NiWO₄|Ce⁴⁺, Ce³⁺|Pt; 0.1 M in 0.1N H₂SO₄. The PVEC characterization reveals the fill factor and power conversion efficiency to be 0.47 and 0.78%, respectively. The flat band potential is found to be −0.32 V (SCE).     

p-type conductive NiOx: Cu thin films with high carrier mobility deposited by ion beam assisted deposition

Transparent conductive NiO thin films with 18 at% Cu dopant were fabricated by ion beam assisted deposition (IBAD). Their structural and optoelectronic properties were compared with undoped NiO films and NiO films doped with 12 at% Cu, and also compared with NiO:Cu (18 at%) films deposited by RF sputtering as reported in our previous work. The results show that the crystallinity of NiO thin films deposited through IBAD technology is much better than that of the films deposited by RF sputtering. Thanks to this reason, the highest carrier mobility above 45 cm²V^?1s^?1 for NiO:Cu (18 at%) film can be realized here. Meanwhile, the films’ resistivity remains an acceptable value, varying from 2.05 to 0.064 Ω cm with oxygen ion beam current changing from 0.2 to 0.8 A. This feature is imperative for p-type transparent conductive oxides (TCOs) applied in various domains. In addition, with oxygen ion beam current increase, the increase of the Ni³⁺/Ni²⁺ ratio leads to more Ni²⁺ vacancies be introduced into NiO films, which is beneficial to generate holes and improve carrier concentration. In this work, the optimal carrier mobility of NiO film doped with 18 at% Cu is obtained when the oxygen ion beam current is 0.2 A. Its carrier concentration and electrical resistivity are 7.26 $\times$10¹⁶ cm^?3 and 2.05 Ω cm, respectively.     

Spray deposited titanium oxide thin films as passive counter electrodes

Titanium dioxide (TiO₂) thin films were deposited from methanolic solution onto fluorine doped tin oxide coated conducting glass substrates by spray pyrolysis technique. The electrochemical properties of TiO₂ thin films were investigated using cyclic voltammetry, chronoamperometry, chronocoulometry and iono-optical studies, in 0.1N H₂SO₄ electrolyte. Performance of the films deposited at three different substrate temperatures, viz. 350, 400 and 450 °C is discussed in view of their utilization in electrochromic devices, as counter electrode. The magnitude of charge storage capacity, Q/t (4.75-6.13 × 10⁻³ mC/(cm² nm)) and colouration efficiency (3.2-4.3 cm²/mC) of TiO₂ rank these films among the promising counter electrodes in electrochromic devices.     

Performance of spray deposited Gd-doped barium cerate thin films for proton conducting SOFCs

Doped barium cerate is a promising solid electrolyte for intermediate temperature fuel cells as a protonic conductor. In the present paper, the nanocrystalline Gd-doped barium cerate (BaCe_0.7Gd_0.1Y_0.2O_2.9) thin films have been successfully deposited on alumina substrate by spray pyrolysis technique. The films deposited from 0.1 M concentration and annealed at five different temperatures were characterized with different physio-chemical techniques. The BCGY is crystallized in orthorhombic perovskite structure with slight shift to the lower 2θ value compared with barium cerate (BC) and yttrium doped barium cerate (BCY). The grain growth and hence densification is also investigated by using SEM and AFM. The grain growth is almost complete at 1000 °C and the surface of the film appears to be smooth with typical roughness of 152 nm. Raman spectrum of BCGY film shows intense band at 463.8 cm⁻¹ compared to pure BC and BCY indicating the presence of more oxygen vacancies due to Gd doping. The proton conductivity of BCGY thin film in moist atmosphere is 1×10⁻³ Scm⁻¹.     

Effect of post annealing treatment on electrochromic properties of spray deposited niobium oxide thin films

Niobium oxide thin films were deposited on the glass and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive spray pyrolysis technique. During deposition of the films various process parameters like nozzle to substrate distance, spray rate, concentration of sprayed solution were optimized to obtain well adherent and transparent films. The films prepared were further annealed and effect of post annealing on the structural, morphological, optical and electrochromic properties was studied. Structural and morphological characterizations of the films were carried out using scanning electron microscopy, atomic force microscopy and X-ray diffraction techniques. Electrochemical properties of the niobium oxide thin films were studied by using cyclic-voltammetry, chronoamperometry and chronocoulometry.     

Dispersive optical constants and electrical properties of nanocrystalline CuInS2 thin films prepared by chemical spray pyrolysis

Nanocrystalline CuInS₂ thin films were deposited on borosilicate glass substrates via chemical spray pyrolysis method. The structural, morphological, optical, and electrical properties were studied as a function of increasing annealing temperature from 250 to 350 ̊C. XRD analysis showed mixed phases at lower temperatures with the preferred orientation shifting towards the (112) chalcopyrite CuInS₂ plane at higher substrate temperature. The crystallite size increased slightly between 13 and 18 nm with increase in annealing temperature. The optical band gap was determined on basis of Tauc extrapolation method and the Wemple–Di-Domenico single oscillator model. Possible structural and quantum confinement effect may have resulted in relatively larger band gaps of 1.67–2.04 eV, relative to the bulk value of 1.5 eV. The presence of Cu_xS in the as-deposited and wurtzite peaks after annealing at 350 ^̊C play a role in influencing the optical and electrical properties of CuInS₂ thin films.     

Highly conducting and transparent antimony doped tin oxide thin films: the role of sputtering power density

Sb doped SnO₂ thin films were deposited on quartz substrates by magnetron sputtering at 600 °C and the effects of sputtering power density on the preferential orientation, structural, surface morphological, optical and electrical properties had been studied. The XRD analyses confirm the formation of cassiterite tetragonal structure and the presence of preferential orientation in (2 1 1) direction for tin oxygen thin films. The dislocation density analyses reveal that the generated defects can be suppressed by the appropriate sputtering power density in the SnO₂ lattice. The studies of surface morphologies show that grain sizes and surface roughness are remarkably affected by the sputtering power density. The resistivity of Sb doped SnO₂ thin films gradually decreases as increasing the sputtering power density, reaches a minimum value of 8.23×10⁻⁴ Ω cm at 7.65/cm² and starts increasing thereafter. The possible mechanisms for the change in resistivity are proposed. The average transmittances are more than 83% in the visible region (380–780 nm) for all the thin films, the optical band gaps are above 4.1 eV. And the mechanisms of the variation of optical properties at different sputtering power densities are addressed.     

Effect of doping concentration on the properties of aluminium doped zinc oxide thin films prepared by spray pyrolysis for transparent electrode applications

Zinc oxide possesses many interesting properties, such as modifiable conductivity, wide band gap, high excitonic binding energy, piezo-electric polarisation and cathodoluminiscence. In this study transparent conducting aluminium doped zinc oxide (ZnO:Al) thin films were deposited on float glass substrates by tailor made spray pyrolysis with adaptation for measuring the actual temperature of the substrate surface during deposition. The films were characterised and the effect of aluminium doping concentration [Al/Zn] on their optical, electrical and structural properties was investigated as a function of aluminium doping between 0 and 10 at.%. There was widening of optical band gap with increasing doping concentration. ZnO:Al films with low resistivity of 2.8 × 10⁻² Ω cm and high transmittance of over 85% at 550 nm which are crucial for opto-electrical applications were obtained at a doping ratio of 2 at.%.     

Effect of Ar:N2 flow rate on morphology,optical and electrical properties of CCTO thin films deposited by RF magnetron sputtering

Calcium copper titanate (CCTO) thin films were deposited on indium tin oxide (ITO) substrates using radio frequency (RF) magnetron sputtering, at selected Ar:N₂ flow rates (1:1, 1:2, 1:4, and 1:6 sccm) at ambient temperature. The effect of Ar:N₂ flow rate on the morphology, optical and electrical properties of the CCTO thin films were investigated using FESEM, XRD, AFM, Hall effect measurement, and UV–Vis spectroscopy. It was confirmed by XRD analysis that the thin films were produced is CCTO with cubic crystal structure. As the flow rate of Ar:N₂ increased up to 1:6 sccm, the thin film thickness reduced from 87 nm to 35 nm while the crystallite size of CCTO thin film decreased from 27 nm to 20 nm. Consequently, the surface roughness of thin film was halved from 8.74 nm to 4.02 nm. In addition, the CCTO thin films deposited at the highest Ar:N₂ flow rate studied, at 1:6 sccm; are having the highest sheet resistivity (13.27 Ω/sq) and the largest optical energy bandgap (3.68 eV). The results articulate that Ar:N₂ flow rate was one of the important process parameters in RF magnetron sputtering that could affect the morphology, electrical properties and optical properties of CCTO thin films.     

Optimized weighted mobility induced high thermoelectric performance of ZnO-based multilayered thin films

As a transparent thermoelectric oxide, gallium-doped zinc oxide (GZO) has the potential to power wearable or portable electronics and may be used in the integrated circuits industry for chip cooling. Constructing ZnO–GZO interfaces has been proposed as an effective strategy for improving thermoelectric performance of GZO thin films. However, without the aid of band structure calculation for multilayered films, it is hard to directly elucidate the underlying mechanisms of carrier transport. Weighted mobility is an indicator that reveals the inherent electronic transport properties like carrier scattering, electronic band structure, and so on. Thus, to further investigate the effects of ZnO–GZO interfaces on electrical properties of GZO thin films, the structures containing different numbers of ZnO–GZO interfaces were designed and the correlations among numbers of ZnO–GZO interfaces, weighted mobility, and electrical properties were explored. It was found that with more ZnO–GZO interfaces, the weighted mobility increased, and the power factor values also improved as well. Consequently, an enhanced power factor value reached 439 μW m⁻¹ K⁻² at 623 K. This work demonstrated the beneficial effects of multiple interfaces on the improvements of electrical transport performance through analyzing weighted mobility, which laid a foundation for further optimization of thermoelectric performance.     

Realization of Eu-doped p-SnO2 thin film by spray pyrolysis deposition

We report the fabrication of p-SnO₂ thin films by spray pyrolysis deposition using europium (Eu) as an acceptor. Structural and chemical investigations verified that Eu³⁺ ions were successfully incorporated into the SnO₂ crystal by substituting the Sn⁴⁺ sites in the lattice. Even though the undoped SnO₂ thin film showed n-type properties with a charge carrier concentration of −2.343 × 10¹⁸ cm⁻³, SnO₂ showed p-type properties as the Eu was incorporated. In addition, the charge carrier concentration of the Eu-doped SnO₂ increased to 9.121 × 10¹⁹ cm⁻³ as the molar content of the Eu source was increased to 0.2 mM. The optical transmittance was not degraded by the Eu doping and was maintained between 70 and 80% in the visible wavelength spectral range, while the optical band gap of the Eu-doped SnO₂ increased due to the Burstein-Moss effect. The thin film field-effect transistor fabricated by using the Eu-doped SnO₂ showed the typical gate-modulated drain current characteristic of a p-channel transistor with depletion mode. These results demonstrated the effectiveness of Eu as a dopant for p-SnO₂.     

Synthesis and characterization of Cu1-xZnxO composite thin films for sensor application

Cu_1-xZn_xO composite thin films were prepared using industrially applicable spray pyrolysis technique for volatile organic compound (VOCs) sensor application. Sensing properties for different concentration of VOCs such as acetone, ethanol and methanol were studied at different sensor operating temperature. XRD studies on prepared thin films confirmed formation of CuOZnO composite thin films with presence of different peaks for monoclinic structured CuO and hexagonal structure ZnO, it was also observed that formation of composite material improves sensing property towards VOCs. Granular morphology observed from SEM images were also contributed to enhance sensitivity of Cu_1-xZn_xO thin films. Hot probe experiment reveals that all the thin films were p-type in conductivity nature. Maximum electrical conductivity was achieved for Cu_0.75Zn_0.25O composite thin films, which also showed highest sensing property for VOCs. Cu_0.75Zn_0.25O thin films were selective towards ethanol and were capable of detecting 1 ppm of ethanol at operating temperature of 290 °C.     

Change of the properties of nanostructured MoO3 thin films using gamma-ray irradiation

Thin films of Molybdenum trioxide (MoO₃) were deposited on glass substrates by the spray pyrolysis at 500?°C and the samples were then exposed to gamma γ radiation doses by ⁶⁰Co radioisotope at different doses (0.1, 10 and 50 kGy). The effects of gamma irradiation on the properties of MoO3 thin films were investigated. The XRD pattern and Raman spectroscopy of as-deposited MoO₃ samples show an orthorhombic structure related to α-MoO₃ with (0k0) preferred orientations. Uv‐vis spectra were studied to investigate the transmission measurements of MoO₃ films. The optical energy band gap and Urbach energy were found to be gamma-dose dependent. Photoluminescence measurements at room temperature using 300?nm wavelength excitation were investigated. SEM images indicate the formation of α-MoO₃ nanorods.     

Influence of yttrium doping on the structural,morphological and optical properties of nanostructured ZnO thin films grown by spray pyrolysis

This study reports on the deposition of highly transparent, n-type ZnO thin films on glass substrate at 450?°C using spray pyrolysis processing, with the simultaneous insertion of yttrium (Y) at different percentages (0, 2, 5, 7?at%) as a dopant. The effect of Y doping on the structure, morphology and optical properties of Y doped ZnO (ZnO:Y) was investigated for optoelectronic applications. The obtained thin films were characterized by means of X-ray diffraction, field-emission scanning electron microscopy (FESEM), UV–visible absorbance measurements, photoluminescence (PL) and cathodoluminescence (CL) spectroscopy. The as-prepared films exhibit well-defined hexagonal wurtzite structure grown along [002]. Field emission scanning electron microscope micrographs of the pure ZnO and ZnO:Y showed that the films acquired a dominance of hexagonal-like grains, the morphology was influenced by Y incorporation. All the films showed high transparency in the visible domain with an average transmittance of 83%. The band gap energy, E_g, increased from 3.12?eV to 3.18?eV by increasing the Y doping concentration up to 5?at% and then decreased to 3.15?eV for 7?at% Y content. The PL and CL measurements reveal a strong ultraviolet (UV) emission, suggesting that the as-prepared ZnO:Y thin films can potentially be used in optoelectronic devices.