The nature of the photochromism arising in the nanosized MoO3 films

We carried out the experiments which show unambiguously that not one, as it was commonly accepted, but three optical absorption bands corresponding to different color centers arise in the nanosized MoO₃ films due to hydrogen atoms. Varying the conditions for the photoinjection of hydrogen into the MoO₃ films, it is possible to change drastically the correlation between the concentrations of different arising centers, which in turn yields the great difference in the optical absorption spectra. Our findings are crucial for understanding of the nature of electrochromism and photochromism not only in MoO₃ films but also in the series of the transition metal oxide films.     

Hydrogen annealing induced physical properties of ZnTe thin films

The ZnTe material has an unprecedented role in the fabrication of high efficiency CdTe thin film solar cells and optimization of hydrogen annealing induced physical properties of ZnTe films is next required step. Consequently, in the present work, the impact of Hydrogen annealing temperature on the structural, optical, electrical, topographical, morphological, and compositional properties of ZnTe films is explored. The ZnTe thin films (having 300 nm thickness) are grown via electron-beam evaporation technique on glass and ITO substrates followed by annealing at different temperatures under a Hydrogen atmosphere. The ZnTe films are found to crystallize in cubic phase with (111) predominant peak having crystallite size in the range of 19–28 nm, whereas annealed films demonstrated lower optical transmittance vis-à-vis to pristine films. The PL spectra exhibit two luminescence peaks with a stronger band at ～351 nm and a weaker band at ～450 nm. Ohmic behavior of ZnTe films is assured through I–V characteristics, while the AFM images revealed hill-like surface topographies. The FESEM image of pristine films demonstrated a homogeneous surface comprising spherical grains whereas annealed films have spherical, stone, and blisters like morphologies. The EDS patterns assured the Te element richness as well as successful ZnTe films deposition. The observed findings signify that the Hydrogen annealing at different temperatures notably modified the physical properties of ZnTe films.     

Characterization of co-sputtered Cu-In alloy precursors for CuInSe2 thin films fabrication by close-spaced selenization

Sputtering technique for Cu–In precursor films fabrication using different Cu and In layer sequences have been widely investigated for CuInSe₂ production. But the CuInSe₂ films fabricated from these precursors using H₂Se or Se vapour selenization mostly exhibited poor microstructural properties. The co-sputtering technique for producing Cu–In alloy films and selenization within a close-spaced graphite box resulting in quality CuInSe₂ films was developed. All films were analysed using SEM, EDX, XRD and four-point probe measurements. Alloy films with a broad range of compositions were fabricated and XRD showed mainly In, CuIn₂ and Cu₁₁In₉ phases which were found to vary in intensities as the composition changes. Different morphological properties were displayed as the alloy composition changes. The selenized CuInSe₂ films exhibited different microstructural properties. Very In-rich films yielded the ODC compound with small crystal sizes whilst slightly In-rich or Cu-rich alloys yielded single phase CuInSe₂ films with dense crystals and sizes of about 5 μm. Film resistivities varied from 10⁻²–10⁸ Ω cm. The films had compositions with Cu/In of 0.40–2.3 and Se/(Cu+In) of 0.74–1.35. All CuInSe₂ films with the exception of very Cu-rich ones contained high amount of Se (>50%).     

Electrochromic behaviour of Nb2O5 thin films with different morphologies obtained by spray pyrolysis

Two different procedures to stabilize the precursor NbCl₅ have been applied to obtain Nb₂O₅ thin films by spray pyrolysis. Depending on the procedure used, determined by the way in which the precursor solution was injected into the air stream of the spray nozzle, niobium oxide thin films with different surface morphologies can be obtained. The structural properties of the Nb₂O₅ thin films depend on the post-annealing temperature because as-deposited films are amorphous, independently of the synthesis procedure used. The electrochromic behaviour has been estimated for all films, where monochromatic colouration efficiency (at 660 nm) of 25.5 cm²/C and a cathodic charge density close to 24 mC/cm² were found to give the best results to date for niobium oxide thin films obtained by spray pyrolysis.     

The effects of Si and expanded PTFE substrates on formation and hydrogenation of Mg and Mg–Ti films

In this work, we investigated how DC and pulsed DC Ar gas plasma treatment changes surface topography and chemical composition of silicon and expanded Polytetrafluoroethylene (ePTFE) substrates and how different surface pretreatment techniques can affect the formation and hydrogenation of Mg and Mg–Ti films. It is observed that pre-treating Si and ePTFE substrates with different plasma modes results in significant changes of microstructures of as-deposited Mg and Mg–Ti films. After the hydrogenation of Mg films at 20 bar H₂ pressure and 180 °C temperature the formation of crystalline MgH₂ phase is observed only for the films deposited on plasma non-treated Si substrates which had the films with smallest dimensions of its columnar structure. It is known that, usually, Ti additives has positive effect on hydrogenation properties of Mg, but in this study independently of the used substrate pre-treatment technique after the hydrogenation of Mg–Ti films their XRD analysis showed no peaks of the crystalline hydride phase. However, depending on the surface properties of the substrate after hydrogenation Mg–Ti films also have several disparities which are discussed and attributed to the potentially related substrate features.     

Effect of the pH on the physical properties of ZnO : In thin films deposited by spray pyrolysis

The optical, electrical and structural properties of polycrystalline ZnO : In thin films grown from starting solutions with different pH values are reported. The films were deposited on glass substrates by spray pyrolysis at temperatures below 500°C. Zinc acetate dissolved in an aqueous solution was used as a precursor. Different amounts of acetic acid were added to change the pH of the solution to two different values. The average optical transmission of the films was above 85% and the film thickness was about 0.65 μm. The resistivity of the films decreased as the pH of the solution decreased. Concentration and mobility values, measured from Hall effect, were slightly lower for pH=3.2 grown films. pH=3.8 grown films showed textured surfaces with the texture changing from rounded to rough and angular uniform grains as the substrate temperature increased. pH=3.2 grown films had smooth surfaces. X-ray diffraction spectra showed a 0 0 2 preferential orientation for pH=3.2 grown films, and 0 0 2 and 1 0 1 orientations for pH=3.8 grown films. These results have been discussed on the basis of the chemical species involved in the solution. A two-dimensional predominance zone diagram was constructed in order to define the thermodynamic distribution of chemical species in both systems.     

Influence of sputtering conditions on the solar and luminous optical properties of amorphous LixWoy thin films

Thin films of amorphous tungsten oxide were deposited by sputtering onto glass substrates coated by conductive indium–tin oxide. The films were sputtered at different oxygen-to-argon flow ratios with different pressure and power. Elastic recoil detection analysis determined the density and the stoichiometry. X-ray diffraction measurements showed that the films were amorphous. The films were electrochemically intercalated with lithium ions. At several intercalation levels of each film, the optical reflectance and transmittance were measured in the wavelength range 0.3–2.5 μm. We study the effect of various sputtering conditions on the coloration efficiency of the films and on the luminous and solar optical properties. The O₂/Ar ratio and the sputter pressure determine to a large extent the optical absorption. As-deposited sputtered tungsten oxide with sufficiently little oxygen exhibits an absorption peak similar to the case of lithium intercalation.     

Electrical and optical properties of Al doped cadmium oxide thin films deposited by radio frequency magnetron sputtering

Cadmium oxide thin films with different percentages of aluminum doping have been synthesized via radio frequency magnetron sputtering technique. Thin films were deposited on glass and silicon substrates with different percentages of aluminum at a substrate temperature of 573 K and pressure of 0.1 mbar in Ar+O₂ atmosphere. The deposited films were characterized by studying their structural, electrical and optical properties. The X-ray diffraction pattern revealed good crystallinity with preferred (1 1 1) orientation in the films. Aluminum doping in CdO thin films were confirmed by X-ray photoelectron spectroscopic studies and actual doping percentages were also measured from it. The optical band gap was found to decrease first and then increase with increasing percentages of aluminum concentrations. The electrical conductivity was found to increase with increase of aluminum doping concentration up to 5% but for higher doping concentration (>5%) the conductivity was found to decrease.     

Influence of substrate temperature on the properties of laser ablated indium tin oxide films

Nanocrystalline indium tin oxide films are deposited in a reactive oxygen atmosphere with background pressure at 0.02 mbar on glass substrate at different substrate temperatures (T_s) ranging from 300 to 573 K using pulsed laser deposition technique. The films are characterized using GIXRD, AFM and UV–visible spectroscopy to study the effect of substrate temperature on the structural and optical properties of films. The XRD patterns suggest that the films deposited at room temperature are amorphous in nature and the crystalline nature of the films increases with increase in substrate temperature. The thickness of the film decreases with increase in substrate temperature. The AFM data show that substrate temperature plays a dominant role on the surface morphology of the films. UV–visible spectra show that all the deposited ITO films exhibit a direct allowed transition. The higher value of optical band gap obtained for the films may be attributed to quantum confinement effect. The films deposited at higher substrate temperatures show higher value of transmittance.     

The impact of etching during microfabrication on the microstructure and the electrical conductivity of gadolinia-doped ceria thin films

Gadolinia-doped ceria, Ce_0.8Gd_0.2O_1.9−x (CGO), thin films deposited by spray pyrolysis and annealed to different degree of crystallinity between 0% and 95% are exposed to different etchants and etching methods. The attack of the etchants on the CGO thin films is analyzed with respect to changes in microstructure and in-plane electrical conductivity. It is found that amorphous CGO films are dissolved in hydrochloric acid after elongated etching times. Hydrofluoric acid severely attacks CGO thin films after already short times of exposure (1 min), more intense the less crystalline the thin film is. Ar ion etching smoothens the surface of the CGO thin films without considerable removal of material. No microstructural attack of NaOH, CHF₃/O₂ and SF₆/Ar is found. The electrical conductivity is in general only affected when microstructural changes are severe. Therefore, it is concluded that CGO thin films can be well used as functional layers in micro-fabricated devices and that micro-fabrication is, with the exception of hydrofluoric, not harmful for the electrical properties of crystalline CGO thin films.     

Comparative study of Cu2ZnSnS4 film growth

We fabricated Cu₂ZnSnS₄ (CZTS) thin films using two different methods, spray pyrolysis and sulfurization of Cu-Zn-Sn metallic films. Spray pyrolysis was carried out under air ambient with modified ultrasonic spray system. Sulfurizations of metallic Cu-Zn-Sn films were done for stacked metallic films, Cu/Sn/Zn/glass, Cu/Sn/Cu/Zn/glass and Sn/Cu/Zn/glass, which were prepared by sputtering method in high vacuum chamber. The sprayed films were not observed to be grown well with good crystallinity, compared with CZTS films made by sulfurization of stacked metallic films. However, it was found that application of additional sulfurization to sprayed CZTS films induced great improvement of crystallinity to the level of the sulfurized metallic films. This implicates that spray pyrolysis with additional sulfurization is a good method for fabrication of CZTS films, especially as a low-cost fabrication technique. All CZTS films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy measurements.     

Sprayed CuInS2 thin films for solar cells: The effect of solution composition and post-deposition treatments

CuInS₂ thin films were prepared by spray pyrolysis from solutions with different compositions. Etching in KCN solution and thermal treatments in vacuum and hydrogen were applied to as-deposited films. KCN etching removes conductive copper sulfide from the surface of Cu-rich films but has no effect on matrix composition. Vacuum annealing at 500°C and hydrogen treatment at 400–500°C purifies the films, prepared from the solutions with the Cu/In=1, from secondary phases, reduces chlorine content and improves crystallinity. Vacuum annealing results in n-type films due to the formation of In₂O₃ phase. Treatment in hydrogen reduces oxygen-containing residues and results in p-type CuInS₂ films with resistivity close to 10 Ω cm.     

Observation of the growth process of CuInSe2 thin films

In order to observe the growth process of CuInSe₂ thin films by a usual vacuum evaporation method with two sources, thin films of the compound were grown on different substrates: glass slides, SnO₂, Al₂O₃, and molybdenum. During deposition, the shutter was moved stepwise to obtain layers for different evaporation times, and crystallographical, compositional, optical and electrical properties were investigated. In general, in the initial stage of evaporation, the films are In-rich, and then move toward the stoichiometrical composition. The grain size grows larger, and the film quality becomes better with time. The detailed variations of the properties of the films are presented.     

Comparison of electrochromic amorphous and crystalline tungsten oxide films

A detailed systematic study of the tungsten oxide thin films has been carried out using WO₃ films after they were annealed at progressively increasing temperatures ranging from 350°C to 450°C in oxygen environments. The structural properties of the films were characterized using X-ray diffraction and Raman spectroscopy. The amorphous WO₃ films remain as an amorphous phase up to 385°C and begin to crystallize at 390°C and then are completely crystallized at 450°C. Absorption peaks of the films are found to shift to a higher energy side with increasing annealing temperature up to 385°C and then shift abruptly to a lower energy as the films begin to crystallize at 390°C. Deconvolution of the absorption spectra shows that there are two different polaron transitions in the amorphous WO₃ films.     

Photoelectrochemical properties of CdSxSe1−x films

CdS_xSe_1−x films of different composition (0 < x < 1) were deposited by pulse plating technique at different duty cycles in the range of 10-50%. The films were polycrystalline and exhibited hexagonal structure. The band gap of the films varies from 1.68 to 2.39 eV as the concentration of CdS increases. Energy Dispersive analysis of X-rays (EDAX) measurements indicate that the composition of the films are nearly the same as that of the precursors considered for the deposition. Atomic force microscopy studies indicated that the grain size increased from 20 to 200 nm as the concentration of CdSe increased. Photoelectrochemical (PEC) cell studies indicated that the films of composition CdS_0.9Se_0.1 exhibited maximum photoactivity. Mott-Schottky studies indicated that the films exhibit n-type behaviour. Spectral response measurements indicated that the photocurrent maxima occurred at the wavelength value corresponding to the band gap of the films.     

Electrically activated thin film optical coatings as functional layers in electrochromic devices

This study presents results on technology and characterization of molybdenum oxide, tungsten oxide and mixed oxide films based on Mo and W. These films were deposited by low-temperature carbonyl CVD process at atmospheric pressure and by simplified sol–gel method using spinning and spraying approaches. The obtained films were structurally and optically investigated. The films show good optical quality with optical transmittance of about 70% in the visible spectral range. Cyclic voltammograms as well as the transmittance modulation at different wavelengths in the visible spectral range were measured to characterize the electrochromic behaviour of the films. The colour efficiencies of the optimized films are in the order of 110–115 cm²/C, in case of spray deposited WO₃-sol–gel films—130 cm²/C.     

Photoelectrochemical characterization of the Cu(In,Ga)S2 thin film prepared by evaporation

Cu(In,Ga)S₂ chalcopyrite thin films have been characterized in order to determine the band edges potential position for photoelectrolysis water splitting. These values are correlated with the atomic composition of the samples. The characterization includes structural and atomic composition of the films. Sputtering/Sulphurization technique was used to prepare the films using different types of Cu–Ga and In targets. According to the capacitance measurements all of the films tested were p-type and the photoresponse technique shows that the band-gap values are between 1.38 and 1.74 eV. We distinguish three type of samples, low, medium and high content of Ga in the films, and the band edges potential position values depend on the amount of Ga in the films and also these values shift more positive when the pH of solution increases.     

Growth, structural and optical properties of copper indium diselenide thin films deposited by thermal evaporation method

Copper indium diselenide (CuInSe₂) compound was synthesized by reacting its constituent’s elements copper, indium and selenium in near stoichiometric proportions (i.e. 1:1:2 with 5% excess selenium) in an evacuated quartz ampoule. Synthesized pulverized compound material was used as an evaporant material to deposit thin films of CuInSe₂ onto organically cleaned sodalime glass substrates, held at different temperatures (300-573 K), by means of single source thermal evaporation method. The phase structure and the composition of chemical constituents present in the synthesized compound and thin films have been investigated using X-ray diffraction and energy dispersive X-ray analysis, respectively. The investigations show that CuInSe₂ thin films grown above 423 K are single phase, having preferred orientation of grains along the (112) direction, and having near stoichiometric composition of elements. The surface morphology of CuInSe₂ films, deposited at different substrate temperatures, has been studied using the atomic force microscopy to estimate its surface roughness. An analysis of the transmission spectra of CuInSe₂ films, recorded in the wavelength range of 500-1500 nm, revealed that the optical absorption coefficient and the energy band gap for CuInSe₂ films, deposited at different substrate temperatures, are ∼10⁴ cm⁻¹ and 1.01-1.06 eV, respectively. The transmission spectrum was analyzed using iterative method to calculate the refractive index and the extinction coefficient of CuInSe₂ thin film deposited at 523 K. The Hall effect measurements and the temperature dependence of the electrical conductivity of CuInSe₂ thin films, deposited at different substrate temperatures, revealed that the films had electrical resistivity in the range of 0.15-20 ohm cm, and the activation energy 82-42 meV, both being influenced by the substrate temperature.     

Structure of PECVD Si:H films for solar cell applications

The structure of undoped SiH films and solar cells deposited under different hydrogen concentration and substrate temperatures were studied. The characterization techniques used were XRD, Raman spectroscopy, TEM, optical absorption, and hydrogen effusion. The high concentration films were amorphous in the as-deposited state but crystallized upon annealing at 700°C. Middle and low concentration films were nanocrystalline (nc) and remained nc up to 800°C annealing. A theoretical explanation is given for the stability of these films. Such films, on glass substrates, had optical absorption spectra close to those of amorphous material. The solar cell samples, showed some nc morphology in all-concentration states.     

Electrical characterization and Poole–Frenkel effect in sol–gel derived ZnO:Al thin films

Electrical properties of ZnO:Al thin films, prepared by sol–gel dip-coating technique were studied in the range of 0.32% to 1.62% Al concentrations in the films. Room temperature electrical conductivity was found in the range of 0.08 to 1.39 S/cm for different aluminium concentrations in the films. I–E characteristics of the films at a constant temperature showed non-linearity, while non-linearity becomes more and more pronounced with increase in temperature and this could be explained by Poole–Frenkel model of thermionic emission. Presence of adsorbed oxygen and excess Al atoms at grain boundaries is assumed to be the cause of this effect. These atoms produce defect levels, which trapped electrons and created a potential barrier across the grain boundaries. In the presence of an external field, the barrier height was attenuated, resulting in the thermionic emission of electrons from the trapped level to the conduction band. The trapped potentials (φ_t) were calculated for different doping concentrations in the films. The thermoelectric power (TEP) measurement confirmed the n-type nature of the films and the room temperature Seebeck coefficient was found to be −91.65 μV/K.