Room temperature novel chemical synthesis of Cu2ZnSnS4 (CZTS) absorbing layer for photovoltaic application

Cu₂ZnSnS₄ (CZTS) thin films have been prepared by a novel chemical successive ionic layer adsorption and reaction (SILAR) method. These films were annealed in vacuum at 673 K and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectroscopy, electrical, and wettability studies. The X-ray diffraction studies showed the formation of kesterite structure of CZTS films. Scanning electron micrograph revealed the formation of densely packed, compact and large grained CZTS films. The CZTS films showed high optical absorption (10⁴ cm^?1) exhibiting band gap energy of 1.55 eV. Wettability test revealed the hydrophilic nature of CZTS films. The CZTS thin films showed semiconducting behavior with p-type electrical conductivity. Further photovoltaic activity of these films was studied by forming the photoelectrochemical cell.     

Crystallization of amorphous indium zinc oxide thin films produced by radio-frequency magnetron sputtering

In this work we studied indium zinc oxide (IZO) thin films deposited by r.f. magnetron sputtering at room temperature. The films were annealed at high temperature (1100 K) in vacuum, and the oxygen exodiffusion was monitored in-situ. The results showed three main peaks, one at approximately 600 K, other at approximately 850 K and the last one at 940 K, which are probably from oxygen bonded in the film surface and in the bulk, respectively. The initial amorphous structure becomes microcrystalline, according to the X-ray diffraction. The electrical conductivity of the films decreases (about 3 orders of magnitude), after the annealing treatment.This behavior could be explained by the crystallization of the structure, which affects the transport mechanism. Apart from the changes in the material structure, a small variation was observed on the absorption coefficient.     

Low cost CuInSe2 thin films production by stacked elemental layers process for large area fabrication of solar cell application

Low cost deposition of large area CuInSe₂ (CIS) thin films have been grown on Mo-coated glass substrate by simple and economic stacked elemental layer deposition technique in vacuum. The grown parameters such as concentration of Cu, In and Se elements have been optimized to achieve uniform thin film in vacuum chamber. The as-grown Cu/In/Se stacked layers have been annealed at 200 °C and 350 °C for 1 h in air ambient. The as-grown and annealed films have been further subjected to characterization by X-ray diffraction (XRD), optical absorption, atomic force microscopy (AFM) and I-V measurement techniques. XRD patterns revealed that as-grown Cu/In/Se stacked layers represent amorphous nature while annealed CIS film reproduces nano-polycrystalline nature with chalcopyrite structure. The optical band gap of annealed films increases with respect to air annealing which confirms the reduction of crystallite size. Surface morphology of as-grown Cu/In/Se stacked layers and annealed CIS thin films have been confirmed by AFM images. The electrical measurements show enhancement of conductivity which is useful for solar cell application.     

Effect of vacuum annealing and hydrogenation on ZnSe/Mn multilayer diluted magnetic semiconductor thin films

Multilayer thin films of ZnSe/Mn diluted magnetic semiconductor have been physically deposited onto a glass substrate using thermal evaporation technique and vacuum annealed at 333 K for 1 h at base pressure of 10⁻⁵ Torr. These thin films have been hydrogenated at different pressures (15-45 psi) for half an hour at room temperature. Hydrogenation process has been performed for as- grown as well as annealed thin films and named as-grown hydrogenated and annealed hydrogenated DMS thin films respectively. Structural characteristics of as-grown and vacuum annealed thin films have been performed by X-ray diffractometer. Current-voltage measurement has been studied for both as- grown hydrogenated and annealed hydrogenated DMS thin films by Keithly electrometer. X-ray diffraction pattern has been revealed nanocrystalline single phase of cubic zinc blende structure of film. Due to the annealing the conductivity has been found to be increased indicating the mixing of multilayer whereas the conductivity for as-grown hydrogenated and annealed hydrogenated ZnSe/Mn DMS thin films was found to be reduced indicating the electronic passivation effect of hydrogenation. Raman spectra of as-grown and annealed hydrogenated samples have been taken to see the presence of hydrogen in these samples. Surface topography of as-grown and annealed multilayer thin films has been confirmed by optical microscopy. Surface topography of annealed hydrogenated samples clearly shows the effect of hydrogenation at the surface.     

Improvement of physical properties of IGZO thin films prepared by excimer laser annealing of sol–gel derived precursor films

Indium gallium zinc oxide (IGZO) transparent semiconductor thin films were prepared by KrF excimer laser annealing of sol–gel derived precursor films. Each as-coated film was dried at 150 °C in air and then annealed using excimer laser irradiation. The influence of laser irradiation energy density on surface conditions, optical transmittances, and electrical properties of laser annealed IGZO thin films were investigated, and the physical properties of the excimer laser annealed (ELA) and the thermally annealed (TA) thin films were compared. Experimental results showed that two kinds of surface morphology resulted from excimer laser annealing. Irradiation with a lower energy density (≤250 mJ cm⁻²) produced wavy and irregular surfaces, while irradiation with a higher energy density (≥350 mJ cm⁻²) produced flat and dense surfaces consisting of uniform nano-sized amorphous particles. The explanation for the differences in surface features and film quality is that using laser irradiation energy to form IGZO thin films improves the film density and removes organic constituents. The dried IGZO sol–gel films irradiated with a laser energy density of 350 mJ/cm² had the best physical properties of all the ELA IGZO thin films. The mean resistivity of the ELA 350 thin films (4.48 × 10³ Ω cm) was lower than that of TA thin films (1.39 × 10⁴ Ω cm), and the average optical transmittance in the visible range (90.2%) of the ELA 350 thin films was slightly higher than that of TA thin films (89.7%).     

Annealing effect on properties of transparent and conducting ZnO thin films

This work presents the effect of postdeposition annealing on the structural, electrical and optical properties of undoped ZnO (zinc oxide) thin films, prepared by radio-frequency sputtering method. Two samples, 0.17 and 0.32 µm-thick, were annealed in vacuum from room temperature to 350 °C while another 0.32 µm-thick sample was annealed in air at 300 °C for 1 h. X-ray diffraction analysis revealed that all the films had a c-axis orientation of the wurtzite structure normal to the substrate. Electrical measurements showed that the resistivity of samples annealed in vacuum decreased gradually with the increase of annealing temperature. For the 0.32 µm-thick sample, the gradual decrease of the resistivity was essentially due to a gradual increase in the mobility. On the other hand, the resistivity of the sample annealed in air increased strongly. The average transmission within the visible wavelength region for all films was higher than 80%. The band gap of samples annealed in vacuum increased whereas the band gap of the one annealed in air decreased. The main changes observed in all samples of this study were explained in terms of the effect of oxygen chemisorption and microstructural properties.     

Solution grown nanocrystalline ZnO thin films for UV emission and LPG sensing

Nanocrystalline ZnO thin films were successfully deposited by a simple and inexpensive solution growth technique. Photoluminescence (PL) and liquefied petroleum gas (LPG) sensing properties were investigated. Films were found to be uniform, pinhole free, and well adherent. As deposited and heat treated (at 673 K for 2 h) films were characterized by XRD, SEM, and EDAX. The dc electrical resistivity and LPG sensing property were measured. The change in morphology, from spherical particle to rod-like, was observed after air annealing. XRD results revealed that the obtained films were nanocrystalline and had a hexagonal wurtzite structure. The absorption edge was found to be at around 366 nm for the as-deposited film and 374 nm for the annealed film. The band gaps were found to be 3.29 and 2.9 eV for the as-deposited and annealed films, respectively. PL spectra of ZnO thin films showed strong peak at 384 nm, which corresponds to near band edge emission (UV emission) and a relatively weak peak at 471 nm. Further, the annealed film was used for detection of LPG in air. Maximum response was observed at 673 K. The maximum sensitivity of sensor was found to be 4.5 for 0.6 vol.% LPG. Sensing response got saturated after 0.6 vol.% of gas concentration. A possible mechanism of LPG sensing has been explained.     

Tribological behavior of radio-frequency sputtering WS2 thin films with vacuum annealing

Thin films of tungsten disulfide (WS₂) were deposited on 3Cr13 martensitic stain less steel substrate by radio-frequency (RF) sputtering. The as-deposited films were annealed at 473, 673 and 873 K respectively for 2 h in 5 × 10^− 4 Pa vacuum. Composition of the films was inspected by energy dispersive spectroscopy. Surface morphology and structure properties were studied by scanning electron microscopy and X-ray diffraction techniques. Tribological behavior was also examined using tribometer. At 473 K, the films exhibited low crystallization structure and no significant improvement in the tribological performance. At 673 K, the tribological performance was improved and a transition from non-crystalline to hexagonal structure took in place. When the annealing temperature rose up to 873 K, the films cracked and fell off from the substrate. The results suggested that with suitable technical parameters vacuum annealing could promote crystallization and improve tribological performance of RF sputtering WS₂ films.     

Influence of annealing temperature on the properties of ZnO:Zr films deposited by direct current magnetron sputtering

Transparent conducting zirconium-doped zinc oxide (ZnO:Zr) films were deposited on quartz substrates by direct current (DC) magnetron sputtering at room temperature. The influence of post-annealing temperature on the structural, morphological, electrical and optical properties of ZnO:Zr films were investigated. When annealing temperature increases from room temperature to 573 K, the resistivity decreases obviously due to an improvement of the crystallinity. However, with further increase in annealing temperature, the crystallinity deteriorates leading to an increase in resistivity. The films annealed at the optimum annealing temperature of 573 K in vacuum have the lowest resistivity of 9.8 × 10⁻⁴ Ω cm and a high transmittance of above 92% in the visible range.     

Growth and vacuum post-annealing effect on the properties of the new absorber CuSbS2 thin films

Post-growth treatments in vacuum atmosphere were performed on CuSbS₂ films prepared by the single-source thermal evaporation method on glass substrates. The films were annealed in vacuum atmosphere for 2 h in temperature range 130-200 °C. The effect of this thermal treatment on the structural, optical and electrical properties of the films was studied. X-ray diffraction (XRD) patterns indicated that the films exhibited an amorphous structure for annealing temperature below 200 °C and a polycrystalline structure with CuSbS₂ principal phase. For the films annealed at temperatures below 200 °C one direct optical transition in range 1.8-2 eV was found. For the films annealed at 200 °C, two optical direct transitions emerged at 1.3 and 1.79 eV corresponding to the CuSbS₂ and Sb₂S₃ values respectively. The electrical measurements showed a conversion from low resistivities (3.10^− 2-9.10^− 2) Ω cm for the samples annealed at temperatures below 200 °C to relatively high resistivities (2 Ω cm) for the samples annealed at 200 °C. In all cases the samples exhibited p-Ztype conductivity.     

Preparation and optical properties of Bi doped ZnO thin films with (100) orientation by rf magnetron sputtering

Bi doped ZnO films with (100) orientation have been grown on glass substrates by rf magnetron sputtering followed by vacuum annealing at 400 °C for 3 h. X-ray diffraction (XRD) revealed that the film first growth along (002) direction was suppressed to form (100) plane with c-axis parallel to the substrate. After annealed at 400 °C for 3 h under vacuum, transmittance about 80% in visible region and near 100% absorption in UV region for (100) oriented Bi doped ZnO films are confirmed by the optical transmission spectra. The optical band gap is evaluated to be around 3.13 eV which is lower than (002) oriented films.     

Effects of heat treatment on properties of ITO films prepared by rf magnetron sputtering

Indium tin oxide (ITO) films were deposited on glass substrates by rf magnetron sputtering using a ceramic target (In₂O₃-SnO₂, 90-10 wt%) without extra heating. The post annealing was done in air and in vacuum, respectively. The effects of annealing on the structure, surface morphology, optical and electrical properties of the ITO films were studied. The results show that the increase of the annealing temperature improves the crystallinity of the films, increases the surface roughness, and improves the optical and electrical properties. The transmittance of the films in visible region is increased over 90% after the annealing process in air or in vacuum. The resistivity of the films deposited is about 8.125×10⁻⁴ Ω cm and falls down to 2.34×10⁻⁴ Ω cm as the annealing temperature is increased to 500°C in vacuum. Compared with the results of the ITO films annealed in air, the properties of the films annealed in vacuum is better.     

Effect of oxygen on the surface morphology of CuGaS2 thin films

Since the effect of oxygen is very significant during the heat treatment of the thin films, we study the effect of this during the annealing of CuGaS₂ thin films by two different types. In this study, CuGaS₂ thin films were deposited by vacuum thermal evaporation of CuGaS₂ powder on heated glass substrates at 200 °C submitted to a thermal gradient. The films are annealed in air and under nitrogen atmosphere at 400 °C for 2 h. In order to improve our understanding of the influence of oxygen during two annealing types on device performance, we have investigated our CuGaS₂ material by X-ray diffraction, scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDX) and spectrophotometry. A correlation was established between the surface roughness, growth morphology and optical properties, of the annealed CuGaS₂ thin films. It was found that annealing of CuGaS₂ film in nitrogen atmosphere leads to a decrease of the mean grain size and to an evolution of a (112) preferred film orientation. Annealing in air results in the growth of oxide phases such as CuO and modifies the films structure and their surface morphology.     

Electrochemical etching of copper indium diselenide surface

CuInSe₂ thin films were grown onto ITO surface by electrodeposition and annealed in the hydrogen atmosphere at 400 °C. The influence of traditional chemical etching (KCN etchant) and electrochemical etching at various potentials and values of solution pH (0.8-13) on the surface composition and morphology was studied using the EDX and SEM methods. The mechanism of CuInSe₂ decomposition at various pH values was examined by cycling voltammetry. The influence of chemical and electrochemical etchings on electrical and optical characteristics of thin films was analyzed.     

Effect of air annealing on structural, optical, microscopic, electrical properties of cadmium selenide thin films

Cadmium selenide films have been deposited on glass substrate dip method. The resultant films were annealed upto 473 K temperature. The structural properties of cadmium selenide thin films have been investigated by X-ray diffraction techniques. The X-ray diffraction spectra showed that cadmium selenide thin films are polycrystalline. As deposited sample shows cubic phase whereas sample annealed at 473 K shows hexagonal phase. The optical properties showed direct band gap values were found to be in the region of 1.82–1.55 eV. The electrical studies shows conductivity increases with increase in annealing temperature. The optoelectric and structural data are discussed from the point of applications based on achieving high performance devices.     

Annealing effect of ZnO/Au/ZnO transparent conductive films

Au intermediate ZnO (ZAZ) thin films were prepared by radio frequency and direct current magnetron sputtering on glass substrates and then vacuum annealed. The thickness of each layer of the ZAZ films was set at 50 nm, 3 nm, and 47 nm, respectively. The structural, electrical, and optical properties of ZAZ films were investigated with respect to the variation of annealing temperature.As-deposited AZO films showed X-ray diffraction peaks corresponding to ZnO (002) and Au (111) planes and those peak intensities increased with post-deposition vacuum annealing. The optical and electrical properties of the films were strongly influenced by post-deposition annealing. Although the optical transmittance of the films deteriorated with an Au interlayer, as-deposited ZAZ films showed a low resistivity of 2.0 × 10⁻⁴ Ω cm, and the films annealed at 300 °C had a lower resistivity of 9.8 × 10⁻⁵ Ω cm. The work function of the films increased with annealing temperature, and the films annealed at 300 °C had a higher work function of 4.1 eV than the films annealed at 150 °C. The experimental results indicate that vacuum-annealed ZAZ films are attractive candidates for use as transparent electrodes in large area electronic applications such as solar cells and large area displays.     

Influence of ultrsonification in CdS thin film deposition in PCD technique

CdS thin films are successfully deposited from aqueous solutions by photochemical reactions. CdS thin films are deposited on a glass substrate only in the UV illuminated region by heterogeneous nucleation. Ultrasonic vibrations are used to stir the solution because ultrasonic waves can drive chemical reactions such as oxidation, reduction and decomposition. The nature of the as-deposited and annealed CdS thin films was studied using XRD, Hall measurements and AES. The surface morphology of the film has been studied using a scanning electron microscope. AES and SEM analysis on as-deposited CdS thin film showed that the surface contains less impurity and change in morphology under the influence of ultrosonic vibrations.     

Structures and properties of titania thin films annealed under different atmosphere

The effects of crystallinity, phase and oxygen vacancies on optical and photocatalytic properties of titania (TiO₂) thin films were systematically studied. The as-deposited amorphous titania films were prepared by reactive sputtering titanium metal targets in argon–oxygen plasma at 100 °C and subsequently annealed at various temperatures of 400–800 °C in air, vacuum and H₂ atmosphere. The results indicate that in general the crystallinity of the annealed films is enhanced with the increasing annealing temperature. At the same temperature, the H₂ annealed films achieve better crystallinity but containing more oxygen vacancies than the films annealed in air and in vacuum. In H₂ or in vacuum, the concentration of oxygen vacancies in the annealed films increases with increasing temperature, while in air it remains constant. Oxygen vacancies in titania film not only facilitate phase transformation but also lower the band gap of titania, and make the film visible-light responsive. Photocatalytic properties of the TiO₂ films were characterized in UV and visible light irradiation by following the Ag reduction and degradation of methylene blue. The films annealed at 600–700 °C in H₂ possess the best film crystallinity and the proper concentration of oxygen vacancies and exhibit the best photocatalytic performance under both UV and visible light.     

Study of the properties of CuInSe2 materials prepared from nanoparticle powder

This work studies the properties of CuInSe₂ (CIS) thin films obtained from nanoparticle powder. The samples were prepared by direct thermal evaporation of ball milled powder from a tungsten crucible onto precleaned glass substrates, using a BALZERS coating unit. The as deposited films were annealed in a vacuum at different temperatures. The composition, structure, morphology and optical properties of these samples have been investigated. X-ray diffraction (XRD) results showed that the CuInSe₂ phase may be prepared by mechanical alloying method. The crystallites of the CIS powder were found to be partially copper-rich. The as-deposited film was polycrystalline in nature having chalcopyrite structure as a mainly phase. The surface morphology is homogeneous across the surface. Expected optical properties (E_g = 1.04 eV, α ≈ 10⁴ cm^? 1) and near stoichiometric composition (Cu: 23.62 at.%, In: 24.35 at.% and Se: 52.03 at.%) were determined.     

Structural and electrical characteristics of chemical solution derived (Bi3.2La0.4Nd0.4)Ti3O12 thin films

(Bi_3.2La_0.4Nd_0.4)Ti₃O₁₂ (BLNT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by using chemical solution deposition technique, and the effects of annealing temperatures in the range of 550-750 °C on structure and electrical properties of the thin films were investigated. X-ray diffraction analysis shows that the thin films have a bismuth-layered perovskite structure with preferred (117) orientation. The surface morphology observation by field-emission scanning electron microscopy confirms that films are dense and smooth with uniformly distributed grains. The grain size of the thin films increases with increasing annealing temperature; meanwhile, the structural distortion of the thin films also increases. It was demonstrated that the thin films show good electrical properties. The dielectric constant and dielectric loss are 191 and 0.028, respectively, at 10 kHz for the thin film annealed at 600 °C, and the 2Pr value of the thin film annealed at 700 °C is 20.5 μC/cm² at an electric field of 500 kV/cm.