Optical and structural properties of CuSbS2 thin films grown by thermal evaporation method

Structural, optical and electrical properties of CuSbS₂ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuSbS₂ thin films were carried out at substrate temperatures in the temperature range 100-200 °C. The structure and composition were characterized by XRD, SEM and EDX. X-ray diffraction revealed that the films are (111) oriented upon substrate temperature 170 °C and amorphous for the substrate temperatures below 170 °C. No secondary phases are observed for all the films. The optical absorption coefficients and band gaps of the films were estimated by optical transmission and reflection measurements at room temperature. Strong absorption coefficients in the range 10⁵-10⁶ cm^− 1 at 500 nm were found. The direct gaps Eg lie between 0.91-1.89 eV range. It is observed that there is a decrease in optical band gap Eg with increasing the substrate temperature. Resistivity of 0.03-0.96 Ω cm, in dependence on substrate temperature was characterized. The all unheated films exhibit p-type conductivity. The characteristics reported here also offer perspective for CuSbS₂ as an absorber material in solar cells applications.     

Microstructure and physical properties of nanofaceted antimony doped tin oxide thin films deposited by chemical vapor deposition on different substrates

Antimony doped tin oxide SnO₂: Sb thin films have been fabricated by atmospheric pressure chemical vapour deposition at substrate temperature varying between 350 °C and 420 °C in a horizontal reactor, from a mixture of hydrated SnCl₂, SbCl₃ and O₂ gas. The films were grown on glass substrates and onto polished and porous n-type silicon. Doped films fabricated with various Sb (Sb/Sn %) contents ranging from undoped 0% to 4% were characterised employing different optical characterisation techniques, like X-ray diffraction, transmittance and reflectance in the wavelength range of 300 to 2500 nm and ellipsometry. The films exhibit the usual cassiterite diffraction pattern with high crystalline structure. Examination of the surface by scanning electron microscopy (SEM) showed that the films are textured made up of many pyramidal crystallites with nanofaceted surfaces, indicating highly stabilised material. The presence of inverted pyramids indicates that the crystallites grown by coalescence. The surface morphology was found to be independent on the kind of the substrate. From X-Ray spectra and SEM observations we get the texture the lattice constant and the grain size. The optical results provide information on film thickness, optical parameters and transmittance upon antimony concentration. The microstructure of the films, the grain growth topics (nucleation, coalescence…) depend strongly on deposition conditions and doping concentration. The observed variations of both the resistivity ρ and transmittance T are correlated to antimony atoms concentration which induced variation in the microstructure and in the size of SnO₂ nanograins (typically 20-40 nm). In this work, we have determined the feasibility of incorporating the correct amount of Sb atoms in tin oxide film by means of resistivity and transmission. SEM observations showed that the substrate do not affect the morphology.     

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.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Structural and optical studies of nanocrystalline V2O5 thin films

We report the structural and optical properties of nanocrystalline thin films of vanadium oxide prepared via evaporation technique on amorphous glass substrates. The crystallinity of the films was studied using X-ray diffraction and surface morphology of the films was studied using scanning electron microscopy and atomic force microscopy. Deposition temperature was found to have a great impact on the optical and structural properties of these films. The films deposited at room temperature show homogeneous, uniform and smooth texture but were amorphous in nature. These films remain amorphous even after postannealing at 300 °C. On the other hand the films deposited at substrate temperature T_S > 200 °C were well textured and c-axis oriented with good crystalline properties. Moreover colour of the films changes from pale yellow to light brown to black corresponding to deposition at room temperature, 300 °C and 500 °C respectively. The investigation revealed that nanocrystalline V₂O₅ films with preferred 001 orientation and with crystalline size of 17.67 nm can be grown with a layered structure onto amorphous glass substrates at temperature as low as 300 °C. The photograph of V₂O₅ films deposited at room temperature taken by scanning electron microscopy shows regular dot like features of nm size.     

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.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

The structure and optical properties of ZnO films on various LiNbO3 substrates

ZnO films thin films have been deposited on glass and three different LiNbO₃ (LNO) substrates at room temperature using radio frequency magnetron sputtering. The structure and optical properties of the films were investigated by X-ray diffraction (XRD), optical transmission spectroscopy and spectro-photometry. XRD analysis shows that all the films are hexagonal wurtzite structure, and there is compressive strain in the films. Typical optical transmittance values in the order of 80% were obtained for all the films, and the band gaps are in the range of 3.273-3.282 eV. The Photo-Luminescence (PL) spectra results indicate that the type of substrate affects the photoluminecence of ZnO films significantly, and the films on rotated Y-cut 128° LNO substrates have strong UV emission at room temperature.     

Preliminary studies on molybdenum-doped indium oxide thin films deposited by radio-frequency magnetron sputtering at room temperature

Thin films of molybdenum-doped indium oxide (IMO) were prepared by a 3-source, cylindrical radio-frequency magnetron sputtering at room temperature. The films were post-annealed and were characterized by their structural (X-ray diffraction) and optical (UV-VIS-NIR spectrophotometer) properties. The films were studied as a function of oxygen volume percentage (O₂ vol.%) ranging from 3.5 to 17.5. The structural studies revealed that the as-deposited amorphous films become crystalline on annealing. In most cases, the (222) reflection emerged as high intensive peak. The poor visible transmittance of the films as-deposited without oxygen was increased from ∼ 12% to over 80% on introducing oxygen (3.5 O₂ vol.%). For the films annealed in open air, the average visible transmittance in the wavelength ranging 400-800 nm was varied between 77 and 84%. The films annealed at high temperatures (> 300 °C) decreased the transmittance to as low as < 1%. The optical band gap of the as-deposited films increased from the range 3.83-3.90 to 3.85-3.98 eV on annealing at different conditions.     

Influence of substrate temperature and bias voltage on the optical transmittance of TiN films

Titanium nitride (TiN) thin films were prepared by means of reactive DC sputtering on quartz and sapphire substrates. Structural, electrical and optical effects of deposition parameters such as thickness, substrate temperature, substrate bias voltage were studied. The effect of substrate temperature variations in the 100-300°C range and substrate bias voltage variations in the 0-200 V DC range for 45-180 nm thick TiN films were investigated. Temperature-dependent electrical resistivity in the 100-350 K range and optical transmission in the 300-1500 nm range were measured for the samples. In addition, structural and morphological properties were studied by means of XRD and STM techniques.The smoothest surface and the lowest electrical resistivity was recorded for the optimal samples that were biased at about V_s=−120 V DC. Unbiased films exhibited a narrow optical transmission window between 300 and 600 nm. However, the transmission became much greater with increasing bias voltage for the same substrate temperature. Furthermore, it was found that lower substrate temperatures produced optically more transparent films.Application of single layers of MgF₂ antireflecting coating on optimally prepared TiN films helped increase the optical transmission in the visible region to more than 40% for 45 nm thick samples.     

Role of oxygen in enhancing N-type conductivity of CuInS2 thin films

Post-growth treatments in air atmosphere were performed on CuInS₂ films prepared by the single-source thermal evaporation method. Their effect on the structural, optical and electrical properties of the films was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical reflection and transmission and resistance measurements. The films were annealed from 100 to 350 °C in air. The stability of the observed N-type conductivity after annealing depends strongly on the annealing temperature. Indeed it is shown that for annealing temperatures above 200 °C the N-type conductivity is stable. The resistance of the N-CuInS₂ thin films correlates well with the corresponding annealing temperature. The samples after annealing have direct bandgap energies of 1.45-1.50 eV.     

Effect of annealing on the electrical, optical and structural properties of cadmium stannate thin films prepared by spray pyrolysis technique

Polycrystalline thin films of cadmium stannate (Cd₂SnO₄) were deposited by spray pyrolysis method on the Corning substrates at substrate temperature of 525 °C. Further, the films were annealed at 600 °C in vacuum for 30 min. These films were characterized for their structural, electrical and optical properties. The experimental results showed that the post-deposition annealing in vacuum has a significant influence on the properties of the films. The average grain size of the film was increased from 27.3 to 35.0 nm on heat treatment. The average optical transmittance in the visible region (500-850 nm) is decreased from 81.4% to 73.4% after annealing in vacuum. The minimum resistivity achieved in the present study for the vacuum annealed films is the lowest among the reported values for the Cd₂SnO₄ thin films prepared by spray pyrolysis method.     

Synthesis and electrochromic study of sol-gel cuprous oxide nanoparticles accumulated on silica thin film

In this study, electrochromic properties of cuprous oxide nanoparticles, self-accumulated on the surface of a sol-gel silica thin film, have been investigated by using UV-visible spectrophotometry in a lithium-based electrolyte cell. The cuprous oxide nanoparticles showed a reversible electrochromic process with a thin film transmission reduction of about 50% in a narrow wavelength range of 400-500 nm, as compared to the bleached state of the film. Using optical transmission measurement, we have found that the band gap energy of the films reduced from 2.7 eV for Cu₂O to 1.3 eV for CuO by increasing the annealing temperature from 220 to 300 °C in an N₂ environment for 1 h. Study of the band gaps of the as-deposited, colored and bleached states of the nanoparticles showed that the electrochromic process corresponded to a reversible red-ox conversion of Cu₂O to CuO on the film surface, in addition to the reversible red-ox reaction of the Cu₂O film. X-ray photoelectron spectroscopy indicated that the copper oxide nanoparticles accumulated on the film surface, after annealing the samples at 200 °C. Surface morphology of the films and particle size of the surface copper oxides have also been studied by atomic force microscopy analysis. The copper oxide nanoparticles with average size of about 100 nm increased the surface area ratio and surface roughness of the silica films from 2.2% and 0.8 nm to 51% and 21 nm, respectively.     

Nanocrystalline SiC films prepared by direct deposition of carbon and silicon ions

The method of direct deposition of carbon and silicon ions was used for preparation of nanocrystalline silicon carbide films. The deposition energy of carbon and silicon ions was 90 eV. The effect of substrate temperature in the range of 500-1150 °C on the structure of SiC films was studied by means of X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). According to XPS data, the films contained heterobonded Si-C atoms and homobonded Si-Si and C-C atoms, the relation between which varied as the function of substrate temperature. The data of XRD showed a noticeable growth of a nanocrystalline phase of cubic silicon carbide in the films at a temperature of about 700 °C. The content of 3C-SiC nanocrystalline phase reached 80 at.% at 950 °C. There was an established change from cubic polytype to rhombohedral polytype of silicon carbide α-SiC-21R at a substrate temperature higher than 1000 °C. The size of SiC crystal grains depended on the substrate temperature and changed from 4-5 up to 8-10 nm over the range of 700-950 °C. Besides, silicon unbonded with carbon also crystallized in nanocrystalline form with similar sizes of crystal grains. A possible model of the change of the polytypic composition of SiC film under the conditions of direct ion deposition was discussed.     

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.     

Non-uniform deposition in the early stage of hot-wire chemical vapor deposition of silicon: The charge effect approach

The deposition behavior in hot-wire chemical vapor deposition (HWCVD) of silicon was investigated, focusing on the thickness uniformity of films deposited on silicon and glass substrates, and based on the previous suggestion that a major depositing flux in HWCVD should be negatively charged nanoparticles. The deposition was performed using a 20%-SiH₄-80%-H₂ gas mixture at a 450 °C substrate temperature under a working pressure of 66.7 Pa (0.5 Torr). Non-uniform depositions for three hot-wire temperatures, 1590 °C, 1670 °C, and 1800 °C, and on the silicon and glass substrates were compared. The non-uniformity was most pronounced at 1800 °C and more pronounced on the glass substrate. On the glass substrate, the deposition rate was highest at the corner and lowest at the center, which was attributed to the fastest charge removal, to a conducting stainless steel substrate holder, at the corner. Once the entire glass substrate was deposited with silicon, the growth rate tended to become uniform, possibly due to the high charge removal rate of silicon. The observed deposition behavior indicated that the major depositing flux is negatively charged.     

Medium-term thermal stability of amorphous Ge2Sb2Te5 flash-evaporated thin films with regards to change in structure and optical properties

The stability of flash-evaporated amorphous Ge₂Sb₂Te₅ thin films has been studied under medium-term temperature treatment (30 - 80 °C, with a step of 10 °C) in ten subsequent heating and cooling cycles. The significant changes in structure and optical properties are reported. The temperature cycling of the films resulted in formation of an isolated 5 - 7 nm nano-crystalline phase in the amorphous phase. The corresponding increase in refractive index and change in optical bandgap energy and sheet resistance are also presented. The formation of Ge₂Sb₂Te₅ nano-crystals (~ 5 - 7 nm) even under temperature below 80 °C could contribute to the explanation of mechanism of resistivity fluctuation (drift) of the “amorphous phase” films. We also show that the optical and electrical properties of flash evaporated Ge₂Sb₂Te₅ thin films are very similar to those reported for sputtered films.     

Thermally stable, highly conductive, and transparent Ga-doped ZnO thin films

Highly conductive and transparent films of Ga-doped ZnO (GZO) have been prepared by pulsed laser deposition using a ZnO target with Ga₂O₃ dopant of 3 wt.% in content added. Films with resistivity as low as 3.3 × 10^− 4 Ω cm and transmittance above 80% at the wavelength between 400 and 800 nm can be produced on glass substrate at room temperature. It is shown that a stable resistivity for use in oxidation ambient at high temperature can be attained for the films. The electrical and optical properties, as well as the thermal stability of resistivity, of GZO films were comparable to those of undoped ZnO films.     

Structural and optical properties of indium tin oxide (ITO) thin films with different compositions prepared by electron beam evaporation

Tin-doped Indium oxide thin films in different compositions (Sn = 0,5,10,15,20 at.wt%) were prepared on glass substrates at the substrate temperature of 250 °C in an oxygen atmosphere by electron beam evaporation. The structural and morphological studies were carried out by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The grain size of the ITO films decreased when increasing the dopant concentration of Sn in the In₂O₃ lattice. Optical properties of the films were studied in the UV-Visible-NIR region (300-1000 nm). The optical energy band gap (E_g), as determined by the dependence of the absorption coefficient on the photon energy at short wavelengths was found to increase from 3.61 to 3.89 eV revealing the ascending loading profile of dopant concentration. Optical Parameters, such as absorption depth, refractive index (n), extinction coefficient (k), packing density, porosity, dispersion energy and single effective oscillator energy were also studied to show the composition dependence of tin-doped indium oxide films.