Structural, compositional, and optical properties of electrochemically deposited stoichiometric CdSe thin films from non-aqueous bath

In the recent years, cadmium chalcogenide compounds have been extensively investigated because of their potential applications in solar energy conversion. Thin films of CdSe have been deposited onto the stainless steel and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive electrodeposition technique. The non-aqueous solvent ethylene glycol (CH₂OHCH₂OH) containing precursors of Cd and Se with ethylenediaminetetraacetic acid (EDTA) tetra sodium salt as a complexing agent is used to obtain stoichiometric deposits. Deposition potential was estimated from polarization curves and other preparative parameters such as bath temperature and concentration of solution were optimized. X-ray diffraction (XRD) analysis reveals that the films are polycrystalline with cubic structure. PEC study shows the CdSe films are photoactive. Optical absorption study shows the presence of direct transition with band gap energy 1.72 eV. The energy dispersive analysis by X-rays (EDAX) reveals that the substrate is well covered with large number of grains indicating compact structure. The average ratio of the atomic percentage of Cd:Se is 50.31:49.69, showing that the deposited films are almost stoichiometric.     

Structural and optical characterization of hot wall deposited CdSexTe1−x films

CdSe_0.3Te_0.7 alloy was prepared from the individual components and its composition and structural analysis were done. Films were prepared by hot wall deposition technique using 0.15 m length tube under a vacuum of 5×10⁻⁵ Torr on well cleaned glass substrates. The composition, structural, morphological, and optical properties of hot wall deposited films were investigated. The XRD analysis revealed that the films are like amorphous in nature for lower thicknesses but with increasing thickness a more preferred orientation along (1 0 1) direction was observed. The crystallite size (D), dislocation density (δ) and strain () were evaluated. From the EDX composition analysis, the individual concentrations of Se and Te in the films were estimated. An analysis of optical measurements shows that all the films have fairly good transparency above 850 nm. The optical band gap was found to be around 1.55 eV and decreases with increasing thickness. Also comparison of band gap with corresponding values for CdSe and CdTe are made.     

Structural phase change and optical band gap bowing in hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on glass substrates by hot wall deposition method under conditions very close to thermodynamical equilibrium with minimum loss of material. The structural studies carried out on the deposited films revealed that they are crystalline in nature and exhibit either cubic zinc blende or hexagonal phase or both depending on the composition of the material. The lattice parameter values for both cubic and hexagonal phases have been determined and are observed to vary with composition according to Vegard’s law. The optical properties of the deposited CdSe_xTe_1−x thin films have been studied using transmittance spectra. The spectra shows a sharp fall in transmittance at wavelength corresponding to the band gap of the material. The optical band gap has been determined and found to be direct allowed. The band gap has been observed to strongly depend on film composition. The variation of band gap with composition has been observed to be quadratic in nature exhibiting a bowing behaviour.     

Dielectric and conduction studies on hot-wall deposited CdSe films

CdSe films are deposited using hot-wall deposition technique on glass and ITO substrates. From the XRD analysis, the structural parameters like crystallite size, dislocation density and strain were calculated. Films had preferential orientation along (0 0 2) and the structure of the film corresponded to wurtzite nature. From the EDAX analysis a slight increase in the cadmium content is observed as thickness increases. The dielectric study has been carried out on the stoichiometric films at different frequencies and temperatures to study their effect on capacitance, dielectric constant and dielectric loss. To explore the effect of illumination on these fundamental dielectric parameters, measurements are taken in dark as well as under an illumination of 1000 lx. and observed slight variation in these parameters. The temperature coefficient of capacitance, relative permittivity and linear expansion coefficient are evaluated. From the AC conduction studies the conduction was found to be due to hopping. Variation of conductivity with temperature reveals the presence of two activation energies. The Mott–Schottky plot for the films yields the value for carrier concentration in the range 10¹⁷–10¹⁸ cm⁻³ and the conduction was found to be n-type.     

Electrical conduction studies of hot wall deposited CdSexTe1−x thin films

CdSe_xTe_1−x thin films of different compositions have been deposited on cleaned glass substrates using the hot wall deposition technique under conditions very close to thermodynamical equilibrium with minimum loss of material. The electrical conductivity of the deposited films has been studied as a function of temperature. All the films showed a transition from phonon-assisted hopping conduction through the impurity band to grain-boundary-limited conduction in the conduction/valence band at temperature around 325 K. The conductivity has been found to vary with composition; it varied from 0.0027 to 0.0198 Ω⁻¹ cm⁻¹ when x changed from 0 to 1. The activation energies of the films of different compositions determined at 225 and 400 K have been observed to lie in the range 0.0031–0.0098 and 0.0285–0.0750 eV, respectively. The Hall-effect studies carried out on the deposited films revealed that the nature of conductivity (p or n-type) was dependent on film composition; films with composition x=0 and 0.15 have been found to be p-type and the ones with composition x=0.4, 0.6, 0.7, 0.85 and 1 have been observed to exhibit n-type conductivity. The carrier concentration has been determined and is of the order of 10¹⁷ cm⁻³. The majority of carrier mobilities of the films have been observed to vary from 0.032 to 0.183 cm² V⁻¹ s⁻¹ depending on film composition. The study of the mobility of the charge carriers with temperature in the range of 300–450 K showed that the mobility increased with power of temperature indicating that the type of scattering mechanism in the studied temperature range is the ionized impurity scattering mechanism.     

Photoelectrochemical investigations on electrochemically deposited CdSe and Fe-doped CdSe thin films

Thin films of CdSe and Fe-doped CdSe (Fe:CdSe) were deposited onto stainless steel substrates by electrodeposition technique. The photoelectrochemical investigations have been carried out using the cell configurations CdSe/1 M (Na₂S–S–NaOH)/C and Fe:CdSe/1 M (Na₂S–S–NaOH)/C for studying the current–voltage (I–V) characteristics in dark and under illumination, photovoltaic output, spectral response, photovoltaic rise and decay characteristics. The studies reveal that films are n-type conductivity. The junction quality factor in light (n_l), series and shunt resistance (R_s and R_sh), fill factor (FF) and efficiency (η) for the cell have been estimated. After Fe doping, efficiency and FF of PEC solar cell is found to be improved from 0.34% and 31.12 to 1.80% and 35.78, respectively.     

Analysis of semiconductor thin films deposited using a hollow cathode plasma torch

The hollow cathode plasma torch has been used for several years. One of the major applications has been the deposition of dielectric thin films. However, this technique has also been used to deposit metals where high-speed deposition is needed. It has proven to be useful in deposition of coatings onto the inside of substrates of complex shape, high-speed etching, and deposition of thin films at atmospheric pressure. In recent years, we have adapted the technique to deposit high-quality amorphous and polycrystalline semiconducting films. A large variety of measurement techniques have been employed to determine the film properties and the results are reported here.     

Structural, morphological, optical and electrochromic properties of Ti-doped MoO3 thin films

Thin films of molybdenum trioxide (MoO₃) doped with titanium were prepared using a spray pyrolysis technique. Increasing Ti doping concentration was found to hamper the polycrystalline nature of undoped orthorhombic MoO₃ and undergo transformation from polycrystalline to amorphous structure with decrease in grain size. This was also reflected in scanning electron microscopy wherein transformation of thread-like reticulated morphology to spongy structures could be observed at higher Ti concentration (9 at% Ti). With increasing Ti concentration, the charge capacity, coloration efficiency, reversibility and electrochemical stability increased. This improvement could be ascribed to the amorphous spongy morphology of the doped samples that offers easy pathway for intercalation and deintercalation of the ions. Hence, 9 at% Ti-doped MoO₃ can act as an adequate host for electrochromic devices.     

Electrodeposition of ZnO thin films by using molecular oxygen and hydrogen peroxide as oxygen precursors: Structural and optical properties

Zinc oxide thin films were potentiostatically electrodeposited from a ZnCl₂+LiCl bath using two different oxygen precursors: molecular oxygen and hydrogen peroxide. X-ray diffraction (XRD) studies confirmed the presence of the ZnO wurtzite structure with marked preferential orientation along the (0 0 2) axis. The optical transmittance shows a clear absorption edge in the ultraviolet (UV) region which corresponds to an energy band gap of 3.41±0.03 eV. As a general rule the higher band gap energies are related to the more transparent films.     

Influence of silane flow on structural, optical and electrical properties of a-Si:H thin films deposited by hot wire chemical vapor deposition (HW-CVD) technique

The electrical, structural and optical properties of hydrogenated amorphous silicon (a-Si:H) films deposited from pure silane (SiH₄) using hot wire chemical vapor deposition (HW-CVD) technique are systematically studied as a function of silane flow rate between 5 and 30 sccm. We found that the properties are greatly affected by the silane flow rate over the range we studied. The device quality a-Si:H films with a photosensitivity >10⁵ were deposited by HW-CVD at a deposition rate >10 Å s⁻¹ using low silane flow rate. However, a-Si:H films deposited at higher silane flow rate and/or higher deposition rates show degradation in their structural and electrical properties. The FTIR studies indicate that the hydrogen bonding in a-Si:H films shifts from mono-hydrogen (Si–H) to di-hydrogen (Si–H₂) and (Si–H₂)_n complexes when films were deposited at higher silane flow rate. The hydrogen content in the a-Si:H films increases with increase in silane flow rate and was found to be less than 10 at.%. The Raman spectra show increase in disorder and the Rayleigh scattering with increase in silane flow rate. The optical band gap also shows an increasing trend with silane flow rate. Therefore, only the hydrogen content cannot be accounted for the increase in the optical band gap. We think that the increase in the optical band gap may be due to the increase in the voids. These voids reduce the effective density of material and increase the average Si–Si distance, which is responsible for the increase in the band gap. Silane flow rate of 5 sccm, appears to be an optimum flow rate for the growth of mono-hydrogen (Si–H) bonded species having low hydrogen content (4.25 at%) in a-Si:H films at high deposition rate (12.5 Å s⁻¹), high photosensitivity (10⁵) and small structural disorder.     

Some physical properties of ZnO thin films prepared by RF sputtering technique

ZnO thin films were deposited with RF sputtering using pure Zn target. In order to generate oxidation process of Zn, Ar:O₂ gas mixing in (9:1), (7:3) and (5:5) ratios of Ar:O₂ was used. To characterize ZnO thin films thickness and transparency were measured using optical method, and refractive index and band gap energies were calculated. Electrical conductivity of the ZnO thin films was also determined. AFM images were used to determine surface morphology of produced ZnO thin films.     

Effect of substrate temperature on the structure and optical properties of CdTe thin film

The present work deals with the preparation, structure and optical characterization of cadmium telluride (CdTe) thin films. These films are formed by vacuum evaporation on the well-cleaned glass substrates. The compositional analyses are made by energy dispersive analysis by X-ray. The thicknesses of the samples are measured by multiple beam interferometry. The samples are prepared at different substrate temperatures. The X-ray diffraction has been employed to study the structure of the film. The structures of the samples are found to be crystalline and the crystallite size increases with the increase of substrate temperature. The d-spacing and lattice parameters of the samples are calculated and the results are also discussed. Optical characteristics of the CdTe samples have been analyzed using spectrophotometer in the wavelength range of 400–800 nm. The transmittance is found to decrease with the increase of film thickness. The transmittance falls steeply with decreasing wavelength. It reveals that CdTe films are having considerable absorption throughout the wavelength region (400–800 nm). The optical band gap energy has been evaluated from the plot of α² vs. hν. Two possible direct transitions have been observed for all the CdTe films in visible region. The observed allowed transition may be attributed due to the spin orbit splitting of the valence band.     

Optical properties of electrodeposited CdTe thin films

The absorption coefficient spectra of the elctrodeposited CdTe thin films were analyzed and compared with that of the single crystal. Pinhole-free thin films facilitated the analysis of the high-energy regions of the absorption coefficient spectra. The various allowed direct and indirect transitions were detected successively by subtracting the extrapolated values of the lower-energy transitions. The effect of heat treatment on the optical transitions were analyzed with films annealed at 300°C in air, argon and CdCl₂.The direct band gap of the electrodeposited films decreased with increasing film thickness and approaches the value of the single crystal. The films annealed at different environments show slightly lower value for the band gap. Annealing in argon caused significant change in the optical transition spectra.     

Improvement of the optical properties of electrodeposited CuInSe2 thin films by thermal and chemical treatments

Cu, In and Se have been codeposited in thin films by potentiostatic one-step electrodeposition. The as-deposited material has shown direct optical transitions attributable to the CuInSe₂ semiconductor, but also additional absorption corresponding to another semimetallic phase. The secondary phases are selenium and copper selenide compounds which have been determined by composition measurements. In order to eliminate the semimetallic phases and to improve the semiconductor behaviour of the electrodeposited material, thermal and chemical treatments have been performed. After heat-treatment of the samples at 400°C in flowing argon, elemental selenium loss has been detected together with an enhancement of the allowed direct optical transition. The subsequent chemical etching of the layers in a KCN solution has showed to be successful in eliminating the copper selenide phases which were responsible of the remaining sub-bandgap absorption.     

Physical properties of chemical bath deposited CdS thin films

Cadmium sulfide films of different thicknesses were deposited by chemical bath deposition (CBD) from a bath containing cadmium chloride, ammonium chloride, ammonium hydroxide and thiourea. The XRD patterns show that the films have a hexagonal phase with a preferential (0 0 2) orientation. The photoluminescence spectra show a defect structure, characteristics of the CdS films obtained by CBD. The electrical behavior in dark and under illumination, the optical properties and the band gap value reported in this work is in agreement with that reported in the literature.     

Optical properties of TiO2 thin films deposited by DC sputtering and their photocatalytic performance in photoinduced process

TiO₂ thin films were deposited by DC Sputtering varying the deposit time. These films were characterized by XRD, AFM, photoluminescence, UV–Vis, ellipsometry and XPS. The optical properties of TiO₂ thin films with different thickness, influenced their photocatalytic behavior in two photoinduced process. When TiO₂ thin films were irradiated with a UV light, midgap states were generated and the electrons were placed in lower energies than its band gap, favoring the photocatalytic hydrogen production and CO₂ photoreduction. From PL technique analyses it was observed that electrons occupied midgap states between the bands, with lower energies than the band gap. With these results it was possible to propose an energy diagram in order to correlate with photoinduced processes results. The presence of Ti³⁺ species was reconfirmed by means of XPS analyses. These species could be found in the midgap states, generated by the interaction between the UV irradiation and the film surface, which contributed to the photocatalytic activity of the films. The hydrogen production was similar for all the thin films studied (33–35 μmol) associated to the presence of similar energy midgap states. In the case of CO₂ photoreduction, all films produced CH₂O (8951 and 6252 μmol/g) and the films with a thickness of 330 and 420 nm generated CH₃OH (970 and 292 μmol/g). The extinction coefficient confirmed the XRD results for the film with greatest deposited time, which exhibited the highest crystallinity. All photocatalytic results did not show any dependence with the thin film thickness.     

Structure–property correlations of polymeric films for transparent insulation wall applications. Part 1: Solar optical properties

In this paper the results of a research project to establish a fundamental understanding of the physical relationships between the material structure and solar optical properties of polymeric transparent insulation (TI) materials are described. First, a systematic characterization of potential materials for TI applications in respect to their relevant physical properties in the solar radiation range was done. Second, based on the investigation of polymer films with different thicknesses model functions for the solar optical properties were established. Third, the solar optical properties were interpreted on base of polymerphysical relations. The characterization in the solar range and the calculation of solar optical film properties have shown, that the solar extinction is dominated by scattering occurring mainly at the surface. A linear relationship between the solar optical thickness and the film thickness was obtained for film thicknesses ranging from 12 to 150 μm. For various amorphous and semi-crystalline films the surface roughness correlated well with the solar optical thickness.     

Structure–property correlations of polymeric films for transparent insulation wall applications. Part 2: Infrared optical properties

In this paper the results of a research project to establish a fundamental understanding of the physical relationships between the material structure and the infrared optical properties of polymeric transparent insulation (TI) materials are described. First, a systematic characterization of potential materials for TI applications in respect to their relevant physical properties in the infrared radiation range was done. Second, based on the investigation of polymer films with different thicknesses model functions for the infrared optical properties were established. Third, the infrared optical properties were interpreted on base of polymerphysical relations. The characterization in the infrared range and the calculation of infrared optical film properties have revealed, that various functional groups of the macromolecular structure are highly absorbing. For polymers with service temperatures of about 100 °C the carbon–oxygen single bond was identified as highly effective. For 50 μm thick films a good correlation between the concentration of the functional carbon–oxygen group and the non-spectral infrared optical thickness as well as the hemispherical emittance was found. An outstanding performance profile for TI wall applications with black absorbers was obtained for cellulose based materials.     

Determination of optical properties of amorphous Ta2O5 films deposited by spin- and dip-coating methods

The optical properties of amorphous Ta₂O₅ films prepared by the sol-gel dip- and spin-coating deposition technique and dried at 60°C have been investigated. Refractive index, extinction coefficient and optical energy gap have been calculated from optical transmission measurements using the Swanepoel method. The films of similar thickness deposited by the two methods were compared. It is shown that the optical properties are dependent on the deposition methods. The energy band gap of the Ta₂O₅ films is 3.75 ± 0.12 eV and is independent of the coating methods.     

Characteristics of nanocrystalline CdSe films

CdSe films have been pulse electrodeposited on evaporated gold substrates with different duty cycles. The deposition of nanocrystalline films was carried out at 100°C for 10 min with precursors of CdSO₄, SeO₂ and H₂SO₄. TEM studies indicated a crystal size in the range 10–50 nm depending upon the duty cycle. The size of the nanoparticle could be controlled by the pulse parameters. Variation of grain size and band gap with duty cycle are in close agreement with the results reported earlier for the films prepared by electrodeposition and chemical bath deposition. Luminescence studies indicated room temperature emission in the wavelength range 520–410 nm depending on the duty cycle, the excitation wavelength was 570 nm.