Size dependent optical characteristics of chemically deposited nanostructured ZnS thin films

ZnS thin films of different thicknesses were prepared by chemical bath deposition using thiourea and zinc acetate as S²⁻ and Zn²⁺ source. The effect of film thickness on the optical and structural properties was studied. The optical absorption studies in the wavelength range 250–750 nm show that band gap energy of ZnS increases from 3·68–4·10 eV as thickness varied from 332–76 nm. The structural estimation shows variation in grain size from 6·9–17·8 nm with thickness. The thermoemf measurement indicates that films prepared by this method are of n-type.     

Ammonia-free chemical bath deposition of nanocrystalline ZnS thin film buffer layer for solar cells

In this work, we prepared zinc sulfide thin films on glass substrates by ammonia-free chemical bath deposition method using thioacetamide as the sulfide source and Ethylene Diamine Tetra Acetic Acid disodium salt as the complexing agent in a solution of pH = 6.0. Thin films of ZnS with different thicknesses of 18–450 nm were prepared. The effect of film thickness and annealing temperature in atmospheric air, on optical properties, band gap energy and grain size of nanocrystals were studied. The X-ray diffraction analysis showed a cubic zinc blend structure and a diameter of about 2–5 nm for ZnS nanocrystals. The Fourier Transform Infrared spectrum of films revealed no peaks due to impurities. The as-deposited ZnS films had more than 70% transmittance in the visible region. The direct band gap of as-deposited films ranged from 3.68 to 3.78 eV and those of annealed films varied from 3.60 to 3.70 eV.     

Substrate temperature influence on ZnS thin films prepared by ultrasonic spray

ZnS thin films were deposited by ultrasonic spray technique. The starting solution is a mixture of 0.1 M zinc chloride as source of Zn and 0.05 M thiourea as source of S. The glass substrate temperature was varied in the range of 250 °C-400 °C to investigate the influence of substrate temperature on the structure, chemical composition and optical properties of ZnS films. The DRX analyses indicated that ZnS films have nanocrystalline hexagonal structure with (002) preferential orientation and grain size varied from 20 to 50 nm, increasing with substrate temperature. The optical films characterization was carried out by the UV-visible transmission. The optical gap and films disorder were deduced from the absorption spectra and the refractive indices of the films were determined by ellipsometric measurements. It is shown that the obtained films are generally composed of ZnO and ZnS phases with varied proportion, while at deposition temperature of 400 °C, they are near stoichiometric ZnS.     

Effect of thickness on structural,optical, electrical and morphological properties of nanocrystalline CdSe thin films for optoelectronic applications

This paper presents effect of thickness on the physical properties of thermally evaporated cadmium selenide thin films. The films of thickness 445 nm, 631 nm and 810 nm were deposited employing thermal evaporation technique on glass and ITO coated glass substrates followed by thermal annealing in air atmosphere at temperature 300 °C. The as-deposited and annealed films were subjected to the XRD, UV–Vis spectrophotometer, source meter, SEM and EDS to find the structural, optical, electrical, morphological and compositional analysis respectively. The structural analysis shows that the films have cubic phase with preferred orientation (1 1 1) and nanocrystalline nature. The structural parameters like inter-planner spacing, lattice constant, grain size, number of crystallites per unit area, internal strain, dislocation density and texture coefficient are calculated. The optical band gap is found in the range 1.69–1.84 eV and observed to decrease with thickness. The electrical resistivity is found to increase with thickness for as-deposited films and decrease for annealed films. The morphological studies show that the as-deposited and annealed films are homogeneous, smooth, fully covered and free from crystal defects like pin holes and voids. The grains in the as-deposited films are densely packed, well defined and found to be increased with thickness.     

Effect of doping concentration on UV accelerated chemically deposited ZnS:Mn thin films

Pure and Mn alloyed ZnS thin films have been prepared by UV accelerated chemical deposition technique which is simple, economic and easy to monitor. Influence of doping concentration on ZnS thin films was investigated through the structural, compositional, morphological, optical and luminescent studies. The XRD studies confirmed the formation of crystalline films with hexagonal structure. In doped samples the intensities of the prominent peaks increased up to 0.5 wt% Mn and then decreased. The optimum concentration means the amount required to get most suitable characteristics for photovoltaic application. The thickness of the films and the sizes of the crystallites varied in consistent with the structural results. Crystallites became larger in size on doping and appeared to be denser than undoped film. Various structural parameters like stress and micro strain were calculated. The observed strain is compressive in nature which rapidly increased with doping and then remained almost same with doping concentration. The SEM studies revealed the formation of films with almost similar morphology of spherical architectures. All the films exhibited uniform transmission in the high visible region, with a maximum of 80 % for the sample with optimum Mn concentration. Both direct and indirect band gap decreased due to the incorporation of Mn, but showed a blue shift in the fundamental absorption edge with doping concentration up to the optimum dopant content. Undoped and doped films exhibit five distinct luminescence peaks located around 391, 451, 458, 482 and 492 nm. The observed variation in the intensity of the luminescence in doped films clearly indicated the influence of thickness of the films which varied on doping.     

Synthesis,surface characterization and optical properties of 3-thiopropionic acid capped ZnS:Cu nanocrystals

3-Thiopropionic acid (TPA) capped ZnS:Cu nanocrystals have been successfully synthesized by simple aqueous method. Powder X-ray diffraction (XRD) studies revealed the particle size to be 4·2 nm. Surface characterization of the nanocrystals by FTIR spectroscopy has been done and the structure for surface bound TPA based on spectral analysis was proposed. The optical studies were done using UV-VIS spectroscopy and particle size and diameter polydispersity index (DPI) were calculated. Photoluminescence (PL) spectrum reveals emission related to the transition from conduction band of ZnS to t ₂ level of Cu^2 +. Electron microscopy was also done by scanning electron microscopy (SEM).     

Nanocrystalline grain size in ZnS thin films deposited by chemical bath technique

Thin films of Zinc Sulfide (ZnS) are prepared by Chemical Bath Deposition Technique using aqueous solution of Zinc acetate (Zn (CH₃COO)₂) and thiourea on glass Substrates. The Structural, Surface morphology and Optical properties of these films are investigated. The crystallinity of the thin films was characterized by means of X-ray diffraction and they all turned out to be polycrystalline. SEM studies gives the average grain size to be small (08–130 nm) with an uneven surface feature. From FTIR analysis, films show an optical transmittance more than 70% in the visible range. Optical band gap found from the absorption study is about 3.7 eV. The physical conditions were kept identical while growing all the samples. The investigation of the effect of the synthesis method on the grain size and the effect of grain size on the properties of semiconductor is under consideration.     

Thickness dependence of structural, electrical and optical properties of sprayed ZnO:Cu films

ZnO:Cu thin films have been deposited by spray pyrolysis techniques within two different (450 °C and 500 °C) substrate temperatures. The structural properties of ZnO:Cu thin films have been investigated by X-ray diffraction techniques. The X-ray diffraction spectra showed that ZnO:Cu thin films are polycrystalline with the hexagonal structure and show a good c-axis orientation perpendicular to the substrate. The most preferential orientation is along the (002) direction for all spray deposited ZnO:Cu films together with orientations in the (100) and (101) planes also being abundant. Some parameters of the films were calculated and correlated with the film thickness for two different substrate temperatures. The optical properties of ZnO:Cu thin films have been investigated by UV/VIS spectrometer and the band gap values were found to be ranging from 3.29 eV to 3.46 eV.     

Preparation and characterization of ZnS nanocrystalline thin films by low cost dip technique

Nanocrystalline ZnS semiconducting nanopowder and thin films have been deposited by simple low cost technique based on combination of dip coating and thermal reaction process. The deposited films and the prepared nanopowder have been characterized in the structurally, optically and electrically point of views. The effect of preparation conditions has been also optimized for good quality films. X-ray diffraction analysis performed the ZnS cubic phase in the reaction temperatures in the range 473–593 K. Above 593 K mixed cubic and hexagonal crystallographic phases have been resolved. Crystallite size and micro strain have been calculated to be 2.65 and 0.011 nm, respectively. The deposited film surface and cross section morphologies show that neither cracks nor peels have been observed and good film adhesion with the substrate was performed. Energy dispersive X-ray measurements of the film agree well with the calculated concentrations of the precursor components. Optical measurements confirm the optical characteristics of nanocrystalline ZnS film such as absorption and dispersion properties. Copper doped ZnS reduces the band gap while indium doped ZnS increases the band gap. Electrical characterization shows that copper doped ZnS increases the resistivity by one order of magnitude due to electron compensation process while indium doped ZnS decreases the resistivity three orders of magnitude due to increase of the carriers concentration. Hot probe thermoelectric quick test of ZnS:Cu and ZnS:In show opposite sign of thermoelectric voltage due to bipolar p and n types, respectively.     

Electrochemical synthesis and characterization of CdSnSe thin films

The effects of deposition potentials on the electrochemical, structural, morphological and optical properties of the CdSnSe films are studied. X-ray diffraction patterns revealed a mix of cubic and orthogonal phases for the grown CdSnSe thin films. The refractive index, extinction coefficient, dielectric constant and thereby the optical band gap of the films are calculated from transmittance spectral data recorded in the range 400–1,200 nm by UV–Vis–NIR Spectrometer. The optical band gap energy of CdSnSe thin films is found to be in the range of 1.23–1.25 eV. Morphological studies revealed nano-rod shaped grains occupied over the entire surface of the film with average grain size of 150 nm. The influence of deposition potential on the microstructural properties of CdSnSe is also explained in the paper.     

Optical and structural characteristics of ZnO thin films grown by rf magnetron sputtering

Nanostructured ZnO thin films on Pyrex glass substrates were deposited by rf magnetron sputtering at different substrate temperatures. Structural features and surface morphology were studied by X-ray diffraction and atomic force microscopy analyses. Films were found to be transparent in the visible range above 400 nm, having transparency above 90%. Sharp ultraviolet absorption edges around 370 nm were used to extract the optical band gap for samples of different particle sizes. Optical band gap energy for the films varied from 3.24 to 3.32 eV and the electronic transition was of the direct in nature. A correlation of the band gap of nanocrystalline ZnO films with particle size and strain was discussed. Photoluminescence emission in UV range, which is due to near band edge emission is more intense in comparison with the green band emission (due to defect state) was observed in all samples, indicating a good optical quality of the deposited films.     

Effect of cobalt doping on the structural and optical properties of TiO2 films prepared by sol-gel process

Pure and cobalt doped titanium dioxide thin films have been prepared on glass and Si (100) substrates by sol-gel spin coating method. The structural and optical properties of the films as a function of cobalt concentration (up to 15 wt.%) have been systematically studied by Rutherford backscattering spectroscopy, X-ray diffraction, Raman spectroscopy, scanning electron microscopy, optical spectroscopy and spectroscopic ellipsometry methods. Rutherford backscattering studies show the presence of cobalt dopant in the films is almost equal to the precursor stoichiometry. Grazing incidence X-ray diffraction and Raman spectroscopy studies confirm the amorphous phase of the as-deposited films and crystalline anatase phase for the films annealed at 600 °C. The optical spectroscopy measurements show that the films are fully transparent in the visible region and there is a band gap narrowing upon increasing cobalt dopant concentration. The refractive index, band gap (E_g) and thickness of the films were determined from spectroscopic ellipsometry measurements. The refractive index of the films was found to increase from 2.2 to 2.7 with the increase in cobalt concentration with a simultaneous decrease of band gap from 3.1 to 2.8, which is favorable for photocatalytic applications. The packing density of the films was calculated by Clausius-Mossotti relation and is found to increase with cobalt concentration.     

Role of precursors on morphology and optical properties of ZnS thin films prepared by chemical spray pyrolysis

This study investigates the effect of different growth parameters on the structural and optical properties of ZnS thin films, prepared using spray pyrolysis. The films were prepared using different Zn:S ratios (between 1:1 and 1:6) and in different growth solutions: (A), zinc chloride and thiourea and (B) dehydrated zinc acetate and thiourea, both in distilled water.By varying the Zn:S ratio in the films, the optical properties (absorption and photoluminescence) show that different species are created during film growth. This was deduced from the wide emission band appearing in the green region of the photoluminescence spectra, and from the change in band gap, which varies between 3.2 and 3.5 eV. Films formed from solution (A) with a Zn:S ratio of 1:3 or 1:4 show the best morphology and transmission. ZnS has a wider band gap than other conventional II-VI semiconductors utilized in various electronic and optical devices and can be expected to provide a useful window layer of solar cells which leads to an improvement in overall efficiency by decreasing absorption loss.     

A non-vacuum method for synthesis of ZnO films by thermal oxidation of ZnS films in air

A non-vacuum method for preparation of ZnO films via thermal oxidation of ZnS films deposited by thin layer thermolysis is described. Transmission electron microscopic studies reveals that the films are polycrystalline with preferentially oriented along (100) direction and grain size of 5-10 nm. The films have about 95% transmission in the visible-near infrared (VIS-NIR) region and an energy band gap of 3.22 eV.     

Impact of various irradiation photon energies and gamma doses on the optical properties of ZnSe nanostructure thin film

ZnSe thin films were prepared by thermal evaporation technique under high vacuum (10⁻⁶ Torr) at 300 K and different film thickness. The structure of thin films was measured using grazing incident in-plane X-ray diffraction (GIIXD) and shows single phase zinc blende structure. The particle sizes of the deposited films were estimated for low film thickness by TEM and high film thickness by GIIXD. The particle size of ZnSe films was decreased from ~8.53 to 3.93 nm as film thickness lowered from 200 to 20 nm which ensures the nanocrystalline structure. The optical transmission (T) and reflection (R) in the wavelength range 190–2,500 nm for irradiated and unirradiated ZnSe thin films under investigation were measured. The effect of irradiation of different energies in range (0.1–1.25 MeV) from X-ray, ¹³⁷Cs and ⁶⁰Co irradiation sources were studied for ZnSe thin films of 100 and 200 nm thicknesses. The dependence of the absorption spectra and refractive index were investigated for different energies irradiation sources. The ZnSe films show direct allowed interband transition. The effect of particle size of nanocrystalline ZnSe thin films for unirradiated and irradiated by gamma (γ) doses from ¹³⁷Cs on the optical properties was studied. Both the optical energy bandwidth and absorption coefficient (α) were found to be (γ) dose dependent.     

Effect of Thickness on the Properties of Ga-doped Nano-ZnO Thin Films Prepared by RF Magnetron Sputtering

Nano transparent conductive oxide (TCO) Ga-doped ZnO (GZO) thin films with thickness from 260 nm to 620 nm were prepared on glass substrates by RF magnetron sputtering from a powder target with 3 at.% Ga₂O₃. The substrate temperature was kept at 300 °C. The effect of thickness on the structural, electrical, and optical properties of GZO thin films was investigated. It shows that the nano-GZO films are dense and flat, and have polycrystalline structure with preferentially in the (002) orientation. With the increase of thickness, the crystallinity and the grain sizes of the films are improved, meanwhile the carrier concentration increases and the lowest resistivity of 3.685×10⁻³ Ω cm occurs in the 620 nm thick GZO film. The average optical transmittance of all the films is over 80% in the visible range. Decreasing the thickness, the optical transmission of the films increase, and the absorption edge shifts to shorter wavelength, which means the optical band gap is broadened.     

Effects of aluminum on the properties of p-type Cu-Al-O transparent oxide semiconductor prepared by reactive co-sputtering

p-Type Cu-Al-O films are successfully prepared by using radio frequency magnetron reactive co-sputtering deposition with Cu and Al metallic targets. Stoichiometric Cu/Al atomic percentage ratio has been achieved. The films show good transmittance in the range of 20-80% with an average thickness of 250 nm. The optical direct band gaps of the films are found in the range of 2.9-3.3 eV depending on the aluminum content. Blue-shift in absorption edge and optical band gap broadening effect are found with the increase of Al content in the films.     

Thickness dependence of structural and optical properties of indium tin oxide nanofiber thin films prepared by electron beam evaporation onto quartz substrates

Indium tin oxide (ITO) thin films, produced by electron beam evaporation technique onto quartz substrates maintained at room temperature, are grown as nanofibers. The dependence of structural and optical properties of ITO thin films on the film thickness (99-662 nm) has been reported. The crystal structure and morphology of the films are investigated by X-ray diffraction and scanning electron microscope techniques, respectively. The particle size is found to increase with increasing film thickness without changing the preferred orientation along (2 2 2) direction. The optical properties of the films are investigated in terms of the measurements of the transmittance and reflectance determined at the normal incidence of the light in the wavelength range (250-2500 nm). The absorption coefficient and refractive index are calculated and the related optical parameters are evaluated. The optical band gap is found to decrease with the increase of the film thickness, whereas the refractive index is found to increase. The optical dielectric constant and the ratio of the free carrier concentration to its effective mass are estimated for the films.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

Characterization on pulsed laser deposited nanocrystalline ZnO thin films

Nanocrystalline zinc oxide thin films were deposited on glass and silicon substrates by using pulsed laser deposition at different laser energy densities (1.5, 2, and 3 J/cm²). The film thickness, surface roughness, composition, optical and structural properties of the deposited films were studied using an α-step surface profilometer, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), optical transmittance, and X-ray diffraction (XRD), respectively. The film thickness was calculated as 244 nm. AFM analysis shows that the root-mean-square roughness increases with increasing laser energy density. XPS analysis shows that the interaction of zinc with oxygen atoms is greatly increased at high laser energy density. In the optical transmittance spectra, a shift of the absorption edge towards higher wavelength region confirms that the optical band gap increases with an increase in laser energy density. The particle size of the deposited films was measured by XRD, it is found to be in the range from 7.87 to 11.81 nm. It reveals that the particle size increases with an increase in laser energy density.