Effect of precursor solutions on the structural and optical properties of sprayed NiO thin films

Nickel oxide thin films were deposited by a simple and low-cost spray pyrolysis technique using three different precursors: nickel nitrate, nickel chloride, and nickel acetate on corning glass substrates. X-ray diffraction show that the NiO films are polycrystalline and have a cubic crystal structure, although predominantly with a preferred 111-orientation in the growth direction and a random in-plane orientation. The deconvolution of the Ni 2p and O 1s core level X-ray photoelectron-spectra of nickel oxides produced by using different precursors indicates a shift of the binding energies. The sprayed NiO deposited from nickel nitrate has an optical transmittance in the range of 60–65% in the visible region. The optical band gap energies of the sprayed NiO films deposited from nickel nitrate, nickel chloride and nickel acetate are 3.5, 3.2 and 3.43 eV respectively. Also, the extinction coefficient and refractive index of NiO films have been calculated from transmittance and reflectance measurements. The average value of refractive index for sprayed films by nickel nitrate, nickel chloride and nickel acetate are 2.1, 1.6 and 1.85 respectively. It is revealed that the band gap and refractive index of NiO films by using nickel nitrate corresponds to the commonly reported values. We attribute the observed behavior in the optical band gap and optical constants as due to the change of the Ni/O ratio.     

Effect of doping concentration on the properties of bismuth doped tin sulfide thin films prepared by spray pyrolysis

Bismuth doped tin sulfide (SnS:Bi) thin films were deposited onto glass substrates by the spray pyrolysis technique at the substrate temperature of 350 °C. The effect of doping concentration [Bi/Sn] on their structural, optical and electrical properties was investigated as a function of bismuth doping between 0 and 8 at%. The XRD results showed that the films were polycrystalline SnS with orthorhombic structure and the crystallites in the films were oriented along (111) direction. Atomic force microscopy revealed that the particle size and surface roughness of the films increased due to Bi-doping. Optical analysis exhibited the band gap value of 1.40 eV for SnS:Bi (6 at%) which was lower than the band gap value for 0 at% of Bi (1.60 eV). The film has low resistivity of 4.788×10⁻¹ Ω-cm and higher carrier concentration of 3.625×10¹⁸ cm⁻³ was obtained at a doping ratio of 6 at%.     

Effect of fluorine doping on the structural,optical and electrical properties of spray deposited cadmium stannate thin films

Cadmium stannate (Cd₂SnO₄) thin films were coated on Corning 1737 glass substrates at 540 °C by spray pyrolysis technique, from the aqueous solution of cadmium acetate and tin (II) chloride precursors. Fluorine doped Cd₂SnO₄ (F: Cd₂SnO₄) thin films were prepared by adding ammonium fluoride in the range of 0–5 wt% of the total weight of cadmium acetate and tin (II) chloride in the spray solution. Thickness of the prepared films is about 300 nm. X-ray diffraction analysis of the Cd₂SnO₄ and 3 wt% F: Cd₂SnO₄ films shows the signature for the growth along (222) direction. Scanning electron micrographs showed that fluorine doping effectively modifies the surface morphology of Cd₂SnO₄ films. Average optical transmittance in the visible region (500–850 nm) for Cd₂SnO₄ is ~79% and it is increased to ~83% for 1 wt% doping concentration of the NH₄F in the solution. Fluorescence spectra of F: Cd₂SnO₄ (1 wt% and 3 wt%) exhibit peak at 601 nm. F: Cd₂SnO₄ film (1 wt%) shows mobility of ~42 cm²/V s, carrier concentration of ~9.5×10¹⁹ cm^?3 and resistivity of ~1.5×10^?3 Ω cm.     

Physical investigations on Sb2S3 sprayed thin film for optoelectronic applications

Sb₂S₃ thin films have been obtained at 250 °C on glass substrates using the spray pyrolysis techniques. The structural study by means of XRD analysis shows that Sb₂S₃ thin film crystallized in the orthorhombic phase. The discussion of some structural constants has been made by means of both XRD and AFM investigations. Moreover, the optical analysis via the transmittance and the reflectance measurements reveals that Sb₂S₃ sprayed thin film has a direct transition with the band gap energy E_g equal to 1.72 eV. The analysis in 300–2500 nm domain of the refractive index data through Wemple–DiDomenico model leads to the single oscillator energy (E₀=2.32 eV), and the dispersion energy (E_d=10.03 eV). The electrical study leads to the dc activation energy is of the order of 0.72 eV and the maximum barrier high is W_M=0.87 eV. From the power exponent variation in terms of the heated temperature, it is found that the mechanism of conduction matches well the correlated barrier hopping CBH model.     

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.     

Effect of annealing temperature on optical and electrical properties of lead sulfide thin films

Lead sulfide (PbS) thin films with 150 nm thickness were prepared onto ultra-clean quartz substrate by the RF-sputtering deposition method. Deposited thin films of PbS were annealed at different temperatures 100 °C, 150 °C, 200 °C, 250 °C and 300 °C. X-ray diffraction pattern of thin films revealed that thin films crystallized at 150 °C. Crystalline thin films had cubic phase and rock salt structure. The average crystallite size of crystalline thin films was 22 nm, 28 nm and 29 nm for 150 °C, 200 °C and 250 °C respectively. From 150 °C to 250 °C increase in annealing temperature leads to increase in crystallite arrangement. FESEM images of thin films revealed that crystallite arrangement improved by increasing annealing temperature up to 250 °C. Increase in DC electrical conductivity by increasing temperature confirmed the semiconductor nature of crystalline thin films. Increase in dark current by increasing annealing temperature showed the effect of crystallite arrangement on carrier transport. Photosensitivity decreased by increasing annealing temperature for crystalline thin films that it was explained at the base of thermal quenching of photoconductivity and adsorption of oxygen at the surface of thin films that leads to the formation of PbO at higher temperatures.     

Influence of Mn doping on structural,optical and electrical properties of CdO thin films prepared by cost effective spray pyrolysis method

Transparent and conducting cadmium oxide (CdO) and manganese doped CdO (Mn: CdO) thin films were deposited using a low cost spray pyrolysis method on the glass substrate at 300 °C. For Mn doping, various concentrations of manganese acetate (1–3 wt%) was used in the spraying precursor solution. The structural, electrical and optical properties of CdO and Mn: CdO films were investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), UV–vis and Hall measurement. X-ray diffraction study reveals that the CdO and Mn: CdO films are possessing cubic crystal structures. SEM and AFM studies reveal that the grain size and roughness of the films are increased with increasing Mn doping concentration. Optical transmittance spectra of the CdO film decreases with increasing doping concentration of manganese. The optical band gap of the films decreases from 2.42 eV to 2.08 eV with increasing concentration of manganese. A minimum resistivity of 1.11×10⁻³ Ω cm and maximum mobility of 20.77 cm² V⁻¹ s⁻¹ is achieved for 1 wt% of manganese doping.     

Effect of annealing on structural,optical and electrical properties of pulse electrodeposited tin sulfide films

Polycrystalline tin sulfide (SnS) thin films were grown on conducting glass substrates by pulse electrodeposition. The effect of annealing on the physical properties such as structure, morphology, optical, and opto-electronic properties were evaluated to understand the effect of post-deposition treatment for SnS films. Annealing at temperatures higher than 250 °°C resulted in the formation of SnS₂ as a second phase, however, no significant grain growth or morphological changes were observed for films after annealing at 350 °C. A small change in band gap of 0.1 eV observed for films annealed at 350 °C was interpreted as due to the formation of SnS₂ rather than due to morphological changes. This interpretation was supported by X-ray diffractometry, scanning electron microscopy, and Raman spectral data. The electric conduction in the films is controlled by three shallow trap levels with activation energies 0.1, 0.05, and 0.03 eV. The trap with energy 0.03 eV disappeared after annealing at higher temperature, however, the other two traps were unaffected by annealing.     

Structural, optical and electrical properties of zinc oxide thin films deposited by a spray pyrolysis technique

Zinc oxide (ZnO) thin films were deposited on glass substrates by spray pyrolysis technique decomposition of zinc acetate dihydrate in an ethanol solution with 30 mL of deposition rate, the ZnO thin films were deposited at two different temperatures: 300 and 350 ℃. The substrates were heated using the solar cells method. The substrate was R217102 glass, whose size was 30 × 17.5 × 1 mm³. The films exhibit a hexagonal wurtzite structure with a strong (002) preferred orientation. The higher value of crystallite size is attained for sprayed films at 350 ℃, which is probably due to an improvement of the crystallinity of the films at this point. The average trans mittance of obtain films is about 90%-95%, as measured by a UV-vis analyzer. The band gap energy varies from 3.265 to 3.294 eV for the deposited ZnO thin film at 300 and 350 ℃, respectively. The electrical resistivity measured of our films are in the order 0.36 Ω·cm.     

Antimony sulfide (Sb2S3) thin films by pulse electrodeposition: Effect of thermal treatment on structural,optical and electrical properties

Antimony sulfide films have been deposited by pulse electrodeposition on Fluorine doped SnO₂ coated glass substrates from aqueous solutions containing SbCl₃ and Na₂S₂O₃. The crystalline structure of the films was characterized by X-ray diffraction, Raman spectroscopy and TEM analysis. The deposited films were amorphous and upon annealing in nitrogen/sulfur atmosphere at 250 °C for 30 min, the films started to become crystalline with X-ray diffraction pattern matching that of stibnite, Sb₂S₃, (JCPDS 6-0474). AFM images revealed that Sb₂S₃ films have uniformly distributed grains on the surface and the grain agglomeration occurs with annealing. The optical band gap calculated from the transmittance and the reflectance studies were 2.2 and 1.65 eV for as deposited and 300 °C annealed films, respectively. The annealed films were photosensitive and exhibited photo-to-dark current ratio of two orders of magnitude at 1 kW/m² tungsten halogen radiation.     

Influences of post-annealing temperature on the structural and electrical properties of mixed oxides (CuFeO2 and CuFe2O4) thin films prepared by spray pyrolysis technique

P-type mixed oxides (CuFeO₂ and CuFe₂O₄) transparent conducting thin films have been successfully deposited on p-type Si (111) substrates at 450 °C by spray pyrolysis deposition (SPD) and annealed at 800 °C for 2 h. The crystal structure, surface morphology and electrical property have been investigated. It is observed that the CuFeO₂ and CuFe₂O₄ thin films as deposited and annealed, have polycrystalline hexagonal structure and the crystallite size increases by annealing processes. The electrical property of the Ni/CuFeO₂/Si Metal–Semiconductor–Metal (MSM) photo detectors was investigated using the current–voltage (I–V) measurements. The barrier heights ϕ_Β of Ni/CuFeO₂/Ni MSM thin films of as deposited and annealed on Si substrates were calculated and its values are 0.478, 0.345 eV, respectively with an applied bias voltage of 3 V.     

Influence of thermal annealing on electrical and optical properties of indium tin oxide thin films

Transparent conducting indium tin oxide (ITO) thin films with the thickness of 300 nm were deposited on quartz substrates via electron beam evaporation, and five of them post-annealed in air atmosphere for 10 min at five selected temperature points from 200 °C to 600 °C, respectively. An UV–vis spectrophotometer and Hall measurement system were adopted to characterize the ITO thin films. Influence of thermal annealing in air atmosphere on electrical and optical properties was investigated in detail. The sheet resistance reached the minimum of 6.67 Ω/sq after annealed at 300 °C. It increased dramatically at even higher annealing temperature. The mean transmittance over the range from 400 nm to 800 nm reached the maximum of 89.03% after annealed at 400 °C, and the figure of merit reached the maximum of 17.79 (Unit: 10⁻³ Ω⁻¹) under the same annealing condition. With the annealing temperature increased from 400 °C to 600 °C, the variations of transmittance were negligible, but the figure of merit decreased significantly due to the deterioration of electrical conductivity. With increasing the annealing temperature, the absorption edge shifted towards longer wavelength. It could be explained on the basis of Burstein–Moss shift. The values of optical band gap varied in the range of 3.866–4.392 eV.     

Structural properties of FeTe2 thin films synthesized by tellurization of amorphous iron oxide thin films

This paper deals with the structural properties of FeTe₂ thin films obtained using a simple and non-toxic experimental procedure. First, iron oxide thin films have been prepared by the spray pyrolysis technique from an aqueous solution containing FeCl₃6H₂O (0.03 M) as a precursor onto glass substrates heated at 623 K. Second, these films were subjected to a heat treatment under tellurium atmosphere at various temperatures (723–803 K) for 24 h. XRD analysis revealed that FeTe₂-ortorombic phase films were obtained at a heat treatment of the order of 773 K. This film has a good crystalline state with a preferential orientation of the crystallites along (111) direction. Moreover, AFM as well as SEM morphological observations show a relatively perturbed surface state.To date, this simple and low cost route process to obtained FeTe₂ thin films has not yet been used.     

Structural and opto-electrical properties of pyrolized ZnO-CdO crystalline thin films

A series of ZnO-CdO thin films of different molar ratios of Zn and Cd have been deposited on glass substrate at substrate temperature ~ 360 ℃ by the spray pyrolysis technique at an ambient atmosphere. X-ray diffraction (XRD) studies confirmed the polycrystalline nature of the film and modulated crystal structures of wurtzite (ZnO) and cubic (CdO) are formed. The evaluated lattice parameters, and crystallite size are consistent with literature. Dislocation density and strain increased in the film as the grain sizes of ZnO and CdO are decreased. The band gap energy varies from 3.20 to 2.21 eV depending on the Zn/Cd ratios in the film. An incident photon intensity dependent I-V study confirmed that the films are highly photosensitive. Current increased with the increase of the intensity of the light beam. The optical conductivity and the optical constants, such as extinction coefficient, refractive index and complex dielectric constants are evaluated from transmittance and reflectance spectra of the films and these parameters are found to be sensitive to photon energy and displayed intermediate optical properties between ZnO and CdO, making it preferable for applications as the buffer and window layers in solar cells.     

Structural and optical characterization of V- and W-doped SnS2 thin films prepared by spray pyrolysis

Tin(IV) sulfide (SnS₂) doped with V ions are promising intermediate band solar cell materials. In this work, we demonstrate the possibility of preparing thin films of Sn_0.75V_0.25S₂ and Sn_0.75W_0.25S₂ using the spray pyrolysis deposition method. Successful attempts are reported when a water/ethanol mixture at 9:1 ratio was used as a solvent and the deposition temperature was set at 360 °C. The samples were characterized by x-ray diffraction, atomic force microscopy, micro-Raman spectroscopy and UV–Vis–NIR optical transmission measurements. The analysis of the data showed that all the samples are crystalline with no impurities. Optical transmission data revealed that the direct and the indirect band gaps of SnS₂ are found to be 2.25 and 2.15 eV, respectively. These values decrease as the samples were doped with V- and W-ions. The direct band gap values are found to fall within the 1.56–1.75 eV range while the indirect band gap values are found to be within the 1.55–1.70 eV range. Furthermore, the effect of doping caused the optical absorption coefficient to approximately be double of its values in a broad range extending from the visible to the near infrared regions. These findings suggest that Sn_0.75V_0.25S₂ and Sn_0.75W_0.25S₂ can be used as new potential solar energy absorbers in photovoltaic devices.     

Effect of processing parameter on structural,optical and electrical properties of photovoltaic chalcogenide nanostructured RF magnetron sputtered thin absorbing films

The aim of this work was to develop high quality of CuIn_1−xGa_xSe₂ thin absorbing films with x (Ga/In+Ga)<0.3 by sputtering without selenization process. CuIn_0.8Ga_0.2Se₂ (CIGS) thin absorbing films were deposited on soda lime glass substrate by RF magnetron sputtering using single quaternary chalcogenide (CIGS) target. The effect of substrate temperature, sputtering power & working pressure on structural, morphological, optical and electrical properties of deposited films were studied. CIGS thin films were characterised by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Energy dispersive X-ray spectroscopy (EDAX), Atomic force microscopy (AFM), UV–vis–NIR spectroscopy and four probe methods. It was observed that microstructure, surface morphology, elemental composition, transmittance as well as conductivity of thin films were strongly dependent on deposition parameters. The optimum parameters for CIGS thin films were obtained at a power 100 W, pressure 5 mT and substrate temperature 500 °C. XRD revealed that thin film deposited at above said parameters was polycrystalline in nature with larger crystallite size (32 nm) and low dislocation density (0.97×10¹⁵ lines m⁻²). The deposited film also showed preferred orientation along (112) plane. The morphology of the film depicted by FE-SEM was compact and uniform without any micro cracks and pits. The deposited film exhibited good stoichiometry (Ga/In+Ga=0.19 and In/In+Ga=0.8) with desired Cu/In+Ga ratio (0.92), which is essential for high efficiency solar cells. Transmittance of deposited film was found to be very low (1.09%). The absorption coefficient of film was ~10⁵ cm⁻¹ for high energy photon. The band gap of CIGS thin film evaluated from transmission data was found to be 1.13 eV which is optimum for solar cell application. The electrical conductivity (7.87 Ω⁻¹ cm⁻¹) of deposited CIGS thin film at optimum parameters was also high enough for practical purpose.     

Effect of Fe-doping on the structural and optical properties of ZnO thin films prepared by spray pyrolysis

Fe-doped ZnO thin films have been prepared by spray pyrolysis on glass substrates and the influence of Fe-doping concentration on the structural and optical properties of the films has been studied.The X-ray diffraction (XRD) analysis shows that Fe doping has a significant effect on crystalline quality,grain size and strain in the thin films.The best crystalline structure is obtained for 3 at%Fe doping as observed from scanning electron microscopy (SEM) and XRD.However,lower or higher Fe-doping degrades the crystalline quality in turn.Moreover,UV spectroscopy demonstrates the influence of Fe-incorporation on visible range transmittance of ZnO where the best transmittance is obtained for 3 at%doping.The results have been illustrated simultaneously focusing previous results obtained from literature.     

衬底温度对Na-Mg共掺ZnO薄膜光学性能的影响

采用超声喷雾热解法,以石英玻璃为衬底,以乙酸 锌(Zn(CH₃COO)₂·2H₂O)、硝酸镁(Mg(NO₃)₂·6H₂O) 和醋酸钠(CH₃COONa·3H₂O)为前驱体溶液,在不同衬底温 度(480～560℃)下制备Na-Mg共掺杂ZnO薄膜。通过X-射线衍射(X RD)、扫描电子显微镜(SEM)、 光致发光(PL)谱和紫外-可见(UV-Vis)分光光度计等表征手段对样品的晶格结构 、表面形貌、PL性能 和透过率进行了研究。结果表明,衬底温度对薄膜结构和光学特性影响显著,当衬底温度为 500 ℃时制备的 Na-Mg共掺杂ZnO薄膜的c轴择优最明显,表面形貌更加致密,结 晶质量最好,PL性能最佳。     

Study of structural,electrical and photoconductive properties of F and P co-doped SnO2 transparent semiconducting thin film deposited by spray pyrolysis

Transparent conducting phosphorus–fluorine co-doped tin oxide (SnO₂:(P, F)) thin films have been deposited onto preheated glass substrates using the spray pyrolysis technique by the various dopant quantity of spray solution. The [F/Sn] atomic concentration ratio (x) in the spray solution is kept at value of 0.7 and the [P/Sn] atomic ratio (y) varied at values of 0, 0.001, 0.005, 0.01, 0.02, 0.04, 0.06, and 0.10. The structural, morphological, X-ray diffraction, electrical, optical and photoconductive properties of these films have been studied. It is found that the films are polycrystalline in nature with a tetragonal crystal structure corresponding to SnO₂ phase having orientation along the (110) plane and polyhedrons like grains appear in the FE-SEM image. The average grain size increases with increasing P-dopant concentration. The compositional analysis of FTO:P thin films were studied using EDAX. The Hall effect measurements have shown n-type conductivity in all deposited films. The lowest sheet resistance and highest the carrier concentration about 6.4 Ω/□ and 7.4×10²², respectively, were obtained for the film deposited with y=[P/Sn]=0.01. The films deposited with y=0.04 phosphorus-doped SnO₂:F shows 68% optical transparency. From the photoconductive studies, the P-doped films exhibited sensitivity to incident light especially in y=0.04. The electrical resistivity and carrier concentration vary in rang 6.2×10⁻⁴ to 21.1×10⁻⁴ Ω cm and 7.4×10²² to 1.3×10²² cm⁻³, respectively.     

Growth and molarity effects on properties of alumina thin films obtained by spray pyrolysis

Various and versatile applications of alumina in materials science and engineering specially in semiconductor and energy conversion technology encouraged us to prepare and investigate its physical properties as much as possible. Hence, after depositing of alumina thin films on glass substrates by a spray pyrolysis technique, structural, morphological, and optical properties of the films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and UV–visible spectrophotometry. Different optical quantities, such as optical band gap, refractive index and extinction coefficient, were determined in this article for different molarities (from 0.10 M to 0.25 M) at two specific substrate temperatures (250 °C and 500 °C). XRD results showed the prevailing amorphous phase in all samples as expected, whereas SEM, XPS, and FTIR presented the presence of molarity effects on alumina properties. Decrease of optical transmittance with molarity increase was notable. Using the transmittance data other optical quantities were obtained by a numerical approximation method.