Impact of vacuum and nitrogen annealing on HVE SnS photoabsorber films

Researchers worldwide focus on new earth abundant and cheap absorber materials for use in thin film solar cells that allow wider use of photovoltaics in energy production. SnS is one of such promising absorber materials that comprises earth abundant elements (Sn, S). We describe here the effect of annealing of high vacuum evaporated (HVE) SnS thin films in vacuum and nitrogen atmosphere with relatively high pressures of nitrogen. SnS thin films with a thickness of 500 nm were deposited onto the surface of glass by HVE at a substrate temperature of 300 °C. The as-deposited SnS thin films were annealed at 500 °C and 550 °C for 1 h in vacuum as well as in nitrogen with respect to ambient (N₂) pressure that varied in the range of 500–2000 mbar. We analyze crystalline quality, crystal structure, elemental and phase compositions, and electrical properties of SnS films before and after the annealing process and their changes. Our results show that the use of pressurized inert ambient, such as nitrogen, improves the crystalline quality as well as the electrical properties of SnS thin films. The enhanced growth of crystals and modification of microstructural properties of SnS thin films as a function of annealing conditions (type of ambient, annealing temperature and ambient pressure) are discussed in detail.     

Effect of doping concentration on the properties of bismuth doped tin sulfide thin films prepared by spray pyrolysis

Bismuth doped tin sulfide (SnS:Bi) thin films were deposited onto glass substrates by the spray pyrolysis technique at the substrate temperature of 350 °C. The effect of doping concentration [Bi/Sn] on their structural, optical and electrical properties was investigated as a function of bismuth doping between 0 and 8 at%. The XRD results showed that the films were polycrystalline SnS with orthorhombic structure and the crystallites in the films were oriented along (111) direction. Atomic force microscopy revealed that the particle size and surface roughness of the films increased due to Bi-doping. Optical analysis exhibited the band gap value of 1.40 eV for SnS:Bi (6 at%) which was lower than the band gap value for 0 at% of Bi (1.60 eV). The film has low resistivity of 4.788×10⁻¹ Ω-cm and higher carrier concentration of 3.625×10¹⁸ cm⁻³ was obtained at a doping ratio of 6 at%.     

Structural and optoelectronic properties of nanostructured TiO2 thin films with annealing

About 480 nm thick titanium oxide (TiO₂) thin films have been deposited by electron beam evaporation followed by annealing in air at 300–600 °C with a step of 100 °C for a period of 2 h. Optical, electrical and structural properties are studied as a function of annealing temperature. All the films are crystalline (having tetragonal anatase structure) with small amount of amorphous phase. Crystallinity of the films improves with annealing at elevated temperatures. XRD and FESEM results suggest that the films are composed of nanoparticles of 25–35 nm. Raman analysis and optical measurements suggest quantum confinement effects since Raman peaks of the as-deposited films are blue-shifted as compared to those for bulk TiO₂ Optical band gap energy of the as-deposited TiO₂ film is 3.24 eV, which decreases to about 3.09 eV after annealing at 600 °C. Refractive index of the as-deposited TiO₂ film is 2.26, which increases to about 2.32 after annealing at 600 °C. However the films annealed at 500 °C present peculiar behavior as their band gap increases to the highest value of 3.27 eV whereas refractive index, RMS roughness and dc-resistance illustrate a drop as compared to all other films. Illumination to sunlight decreases the dc-resistance of the as-deposited and annealed films as compared to dark measurements possibly due to charge carrier enhancement by photon absorption.     

Properties of CuAlO2 thin films deposited by polyacrylamide gel route

CuAlO₂ films were deposited on clean glass substrates by the acrylamide sol–gel dip coating technique. The coated films were dried in air oven for 30 min followed by heat treatment in air at different temperatures in the range of 350–500 °C. The films annealed at low temperatures exhibited weak x-ray diffraction (XRD) peaks. As the post anneal temperature increased beyond 375 °C, the XRD pattern exhibited the diffraction peaks of rhombohedral CuAlO₂. Surface morphology of the films indicated that the films annealed at low temperatures exhibit small grains. As the annealing temperature increases larger grains are observed. The root mean square (rms) value of the surface roughness increases with annealing temperature. The films exhibited optical transmission above 75%. The films post annealed at low temperature exhibited lower transmission. Optical band gap in the range of 3.43–3.75 eV was obtained for the films annealed at different temperature. Hall measurements indicated p-type conductivity. Resistivity of the films decreased from 25.0 to 2.0 Ω cm as the anneal temperature increased. Mobility and carrier density increased with annealing temperature.     

Optical and electrical measurement of FeSe2 thin films obtained at low temperature

FeSe₂ thin films were prepared at low temperature by thermal annealing at 350 °C during 6 h of sequentially evaporated iron and selenium films under selenium atmosphere. The structural, optical and electrical characteristics were investigated. The roughness of films (~76 nm) was confirmed by AFM images. Moreover, optical band gap of FeSe₂, which was evaluated as nearly 1.11 eV and confirmed by the electrical study which yielded a value in the order of 1.08 eV. The electrical conductivity, conduction mechanism, dielectric properties and relaxation model of theses thin films were studied using impedance spectroscopy technique in the frequency range 5 Hz–13 MHz under various temperatures (180–300 °C). Besides, complex impedance and AC conductivity have been investigated on the basis of frequency and temperature dependence.     

Influence of annealing temperature on the phase composition and optical properties of CuInS2 films

We studied the growth of CuInS₂ thin films by single-source evaporation of CuInS₂ powder in a high-vacuum system with a base pressure of 10^?3 Pa. After evaporation, the films were annealed in a sulfur atmosphere at temperatures from 200 to 500 °C for 1 h. XRD curves and Raman spectra of the films demonstrated that chalcopyrite CuInS₂ was the major crystalline phase. The morphology of Cu_xS exhibited a star-like structure, which we report for the first time. The phase composition and optical properties of our polycrystalline thin films were effectively modified by annealing in S. For films annealed at 200 and 350 °C, a secondary CuIn₁₁S₁₇ phase appeared, which may be related to solid-state reaction in the S atmosphere. This secondary CuIn₁₁S₁₇ phase has not been widely reported in previous studies. After annealing at 500 °C, only a chalcopyrite phase was detected, with bandgap energy of 1.46 eV, which is nearly identical to the optimal bandgap energy (1.5 eV) of single-crystal CuInS₂. This indicates that the composition of the CuInS₂ film annealed at 500 °C was nearly stoichiometric. The bandgap of the samples first increased and then decreased with increasing annealing temperature, which may be attributed to an increase in grain size, the secondary CuIn₁₁S₁₇ phase, and deviation from stoichiometry.     

Effect of rapid thermal annealing on properties of thermally evaporated nanostructured CdTe thin film treated with CdCl2

The effects of rapid thermal annealing on properties of crystalline nanostructured CdTe films treated with CdCl₂ and prepared by vacuum evaporation are described. X-ray diffraction confirmed the crystalline nature of post-treated films with high preferential orientation around 23.7°, corresponding to a (1 1 1) diffracted plane of cubic phase. Optical band gap of CdTe films increased from 1.4 eV to 1.48 eV after annealing at 500 °C for 90 s. Atomic force microscopy of annealed films revealed an increase in root mean square roughness and grain size with increased annealing time. Electrical measurements of as-grown and annealed films are consistent with p-type; film resistivity has decreased significantly with increased annealing time.     

Quantum confinement and size effects in Cu2ZnSnS4 thin films produced using solution processed ultrafine nanoparticles

Copper–zinc–tin-sulfide (Cu₂ZnSnS₄, abbreviated as CZTS) is a direct band gap p-type semiconductor material with high absorption coefficient. Using oleylamine as solvent/stabilizing agent and metal chlorides and sulfur particles as chemical precursors, CZTS based nanoparticles were produced and subsequently deposited as thin films on glass substrates via spin coating of the nanoinks. The effect of temperature on crystallite size and phase composition was assessed after the solution mixture was undercooled by 30, 70 or 90 °C. Upon cooling the solution from 230 to 140 °C i.e. by 90 °C, maximum refinement in the nanoparticles size was noticed with average size on the order of few nanometers. The morphological and compositional studies of the nanoparticles were performed by means of scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscopy techniques. Phase-pure CZTS formation was confirmed from fast Fourier transform (FFT) patterns and lattice fringes observed during HR-TEM examination. Characterization of the annealed spin coated films, made from nanoink containing ultrafine nanoparticles, indicated morphological changes in the film surface during air annealing at 350°C that can be attributed to depression of CZTS phase decomposition temperature. Spectrophotometric studies of the annealed films suggested quantum confinement effect through an associated increase in the band gap value from 1.34 to 2.04 eV upon reduction in the nanoparticle size caused by increasing the degree of undercooling to 90 °C.     

SnS?Sno2 conversion of chemically deposited SnS thin films

The thermal decomposition of chemically deposited SnS thin films to SnO₂ films by air annealing at temperatures up to 400°C is discussed. The conversion of a 0.7 μm thick SnS thin film to an SnO₂ film involves the creation of non-stoichiometric SnS, SnS + SnS₂ mixed phase and non-stoichiometric SnO₂ (i.e. SnO_{2 ? x}), as concluded from X-ray diffraction patterns, optical transmission spectra and electrical characteristics. The SnO₂ thin films obtained in this manner are photoconductive, with a lowest sheet resistance (in the dark) of about 10⁵ Ω/□ and an activation energy (E_a) of 0.1 eV for the electrical conductivity observed for the SnS films annealed at 325°C. This was found as the onset temperature for conversion of the SnS + SnS₂ phase to the non-stoichiometric SnO_{2 – x} film. Elevation of the annealing temperature to 400°C results in an elevation of the sheet resistance to about 10⁹ Ω/□ with the value of E_a at 1.3 eV, indicating an improvement in the degree of stoichiometry.     

Evaporated iron disulfide thin films with sulfurated annealing treatments

FeS₂ thin films were grown on a glass substrate using a physical vapor deposition technique at room temperature. Subsequently, the thin films were annealed in two different atmospheres: vacuum and vacuum-sulfur. In the vacuum-sulfur atmosphere a graphite box was used as sulfur container and the films were sulfurated successfully at 200–350 ºC. It was found that annealing in a vacuum-sulfur atmosphere was indispensable in order to obtain polycrystalline FeS₂ thin films. The polycrystalline nature and pure phase were determined by XRD and Raman techniques and the electrical properties by the Hall effect. Using the sulfurating technique, the n-type semiconductor was prepared at 200–350 °C and a p-type at 500 °C. The carrier concentrations were between 1.19×10²⁰ and 2.1×10²⁰ cm⁻³. The mobility was 9.96–5.25 cm² V⁻¹ s⁻¹ and the resistivity was 6.31×10⁻² to 1.089×10⁻² Ω cm. The results obtained from EDS showed that the films prepared in the vacuum-sulfur atmosphere were close to stoichiometric and that the indirect band gap varied between 1.03 and 0.945 eV.     

Investigation of structural and optoelectronic properties of annealed nickel phthalocyanine thin films

Thin films of nickel phthalocyanine (NiPc) were prepared by thermal evaporation and the effects of annealing temperature on the structural and optical properties of the samples were studied using different analytical methods. Structural analysis showed that the grain size and crystallinity of NiPc films improved as annealing temperature increased from 25 to 150 °C. Also, maximum grain size (71.3 nm) was obtained at 150 °C annealing temperature. In addition, NiPc films annealed at 150 °C had a very smooth surface with an RMS roughness of 0.41 nm. Optical analysis indicated that band gap energy of films at different annealing temperatures varied in the range of 3.22–3.28 eV. Schottky diode solar cells with a structure of ITO/PEDOT:PSS/NiPc/Al were fabricated. Measurement of the dark current density–voltage (J–V) characteristics of diodes showed that the current density of films annealed at 150 °C for a given bias was greater than that of other films. Furthermore, the films revealed the highest rectification ratio (23.1) and lowest barrier height (0.84 eV) demonstrating, respectively, 23% and 11% increase compared with those of the deposited NiPc films. Meanwhile, photoconversion behavior of films annealed at 150 °C under illumination showed the highest short circuit current density (0.070 mA/cm²) and open circuit voltage of (0.55 V).     

Epitaxial growth of Ge thin film on Si (001) by DC magnetron sputtering

We have demonstrated that sub-10 nm-thick heteroepitaxial Ge films on Si (001) having smooth surfaces can be obtained by DC magnetron sputtering. Ge films grown at 350 °C preserve the smooth surfaces with a roughness root mean square (RMS) of 0.39 nm, whereas, the Ge films grown at 500 °C show significant roughness with an island-like morphology. In samples grown at 350 °C, it is confirmed that the Ge films are grown epitaxially by cross-section transmission electron microscopy (TEM) and X-ray diffraction (XRD) rocking curve measurements. Rapid thermal annealing (RTA) at 720 °C is effective in improving the crystalline quality and the degradation in the roughness is negligible. Raman spectra and an XRD reciprocal space map reveal that the epitaxial Ge grown at 350 °C show an in-plane compressive strain and that the strain continues to remain after a 720 °C RTA.     

Effect of high-temperature annealing on lanthanum aluminate thin films grown by ALD on Si(1 0 0)

Amorphous lanthanum aluminate thin films were deposited by atomic layer deposition on Si(1 0 0) using La(ⁱPrCp)₃, Al(CH₃)₃ and O₃ species. The effects of post-deposition rapid thermal annealing on the physical and electrical properties of the films were investigated. High-temperature annealing at 900 °C in N₂ atmosphere leads to the formation of amorphous La-aluminosilicate due to Si diffusion from the substrate. The annealed oxide exhibits a uniform composition through the film thickness, a large band gap of 7.0 ± 0.1 eV, and relatively high dielectric constant (κ) of 18 ± 1.     

Effects of Cu/In ratio and annealing temperature on physical properties of dip-coated CuInS2 thin films

CuInS₂ thin films were prepared by sol–gel dip-coating method on glass substrates using 0.75, 1 and 1.25 ratios of Cu/In in the solution. The prepared films were annealed at 380 °C, 420 °C and 460 °C for 30 min under argon environment. The structural, optical, morphological and composition properties of those were investigated by X-ray diffraction (XRD), UV–vis transmittance spectroscopy and scanning electron microscopy with an energy dispersive X-ray spectrometer. The XRD results showed that the films exhibit polycrystalline tetragonal CuInS₂ phase with (112) orientation. According to the EDX results the Cu/In ratios of the films were respectively 0.65, 0.92 and 1.35 for the Cu/In ratios of 0.75, 1 and 1.25 in the solutions. The optical band gap was found to be between 1.30 eV and 1.43 eV, depending on Cu/In ratio.     

Effect of thermal annealing on physical properties of vacuum evaporated In2S3 buffer layer for eco-friendly photovoltaic applications

The present communication reports the effect of thermal annealing on the physical properties of In₂S₃ thin films for eco-friendly buffer layer photovoltaic applications. The thin films of thickness 150 nm were deposited on glass and indium tin oxide (ITO) coated glass substrates employing thermal vacuum evaporation technique followed by post-deposition thermal annealing in air atmosphere within a low temperature range 150–450 °C. These as-deposited and annealed films were subjected to the X-ray diffraction (XRD), UV–vis spectrophotometer, current–voltage tests and scanning electron microscopy (SEM) for structural, optical, electrical and surface morphological analysis respectively. The compositional analysis of as-deposited film is also carried out using energy dispersive spectroscopy (EDS). The XRD patterns reveal that the as-deposited and annealed films (≤300 °C) have amorphous nature while films annealed at 450 °C show tetragonal phase of β-In₂S₃ with preferred orientation (109) and polycrystalline in nature. The crystallographic parameters like lattice constant, inter-planner spacing, grain size, internal strain, dislocation density and number of crystallites per unit area are calculated for thermally annealed (450 °C) thin films. The optical band gap was found in the range 2.84–3.04 eV and observed to increase with annealing temperature. The current–voltage characteristics show that the as-deposited and annealed films exhibit linear ohmic behavior. The SEM studies show that the as-deposited and annealed films are uniform, homogeneous and free from crystal defects and voids. The grains in the thin films are similar in size and densely packed and observed to increase with thermal annealing. The experimental results reveal that the thermal annealing play significant role in the structural, optical, electrical and morphological properties of deposited In₂S₃ thin films and may be used as cadmium-free eco-friendly buffer layer for thin films solar cells applications.     

Behavior of chemically deposited PbS thin films subjected to two different routes of post deposition annealing

Lead sulfide (PbS) thin films were prepared on soda lime glass substrates at room temperature by Chemical Bath Deposition (CBD) technique. This paper reports a comparative study of characteristic properties of as-prepared PbS thin films after thermal treatment through two different routes. Studies were carried out for as-prepared as well as rapidly and gradually annealed samples at 100, 200 and 300 °C. The characterizations of the films were carried out using X-ray diffraction, scanning electron microscopy and optical measurement techniques. The structural studies confirmed the polycrystalline nature and the cubic structure of the films. As-deposited films partly transformed to Pb₂O₃ when gradually annealed to 300 °C. The presence of nano crystallites was revealed by structural and optical absorption measurements. The values of average crystallite size were found to be in the range 18–20 nm. The variation in the microstructure, thickness, grain size, micro strain and optical band gap on two types of annealing were compared and analyzed. Data showed that post deposition parameters and thermal treatment strongly influence the optical properties of PbS films. Optical band gap of the film gets modified remarkably on annealing. Direct band gap energy values for rapidly and gradually annealed samples varied in the range of 1.68–2.01 eV and 1.68–2.12 eV respectively. Thus we were succeeded in tailoring direct band gap energies by post deposition annealing method.     

Effect of Bi doping on structural,morphological, optical and ethanol vapor response properties of SnO2 nanoparticles

The gas sensing behavior of thick films of Bi doped SnO₂ has been investigated towards ethanol vapor. The screen printing technique was used to prepare the thick films. The films were sintered at 650 °C for 2 h. The structural, surface morphological, optical and gas sensing properties of undoped and Bi doped SnO₂ thick films have been studied. X-ray diffraction and Raman spectroscopy confirmed that the films consisted exclusively of tetragonal tin oxide, without any impurity phases. FE-SEM studies revealed the formation of highly porous microstructure with grain size in few tens of nanometers. From the optical studies, the band gap was found to be decreased with bismuth doping (3.96 eV for undoped, 3.83 eV, 3.71 eV and 3.6 eV for 1 mol%, 2 mol% and 3 mol% Bi, respectively). The 3 mol % Bi doped SnO₂ thick films exhibited the highest sensitivity to 100 ppm of ethanol vapor at 300 °C. The effect of microstructure on sensitivity, response time and recovery time of the sensor was studied and discussed.     

AC conductivity,dielectric relaxation and modulus behavior of Sb2S2O new kermesite alloy for optoelectronic applications

In this work, we present some physical properties of Sb₂S₂O thin films obtained through heat treatment of Sb₂S₃ thin films under an atmospheric pressure at 350 °C. The electrical conductivity, dielectric properties and relaxation model of these thin films were studied using impedance spectroscopy technique in the frequency range from 5 Hz to 13 MHz at various temperatures from 350 °C to 425 °C. Besides, the frequency and temperature dependence of the complex impedance, AC conductivity and complex electric modulus has been investigated.     

Antimony sulfide (Sb2S3) thin films by pulse electrodeposition: Effect of thermal treatment on structural,optical and electrical properties

Antimony sulfide films have been deposited by pulse electrodeposition on Fluorine doped SnO₂ coated glass substrates from aqueous solutions containing SbCl₃ and Na₂S₂O₃. The crystalline structure of the films was characterized by X-ray diffraction, Raman spectroscopy and TEM analysis. The deposited films were amorphous and upon annealing in nitrogen/sulfur atmosphere at 250 °C for 30 min, the films started to become crystalline with X-ray diffraction pattern matching that of stibnite, Sb₂S₃, (JCPDS 6-0474). AFM images revealed that Sb₂S₃ films have uniformly distributed grains on the surface and the grain agglomeration occurs with annealing. The optical band gap calculated from the transmittance and the reflectance studies were 2.2 and 1.65 eV for as deposited and 300 °C annealed films, respectively. The annealed films were photosensitive and exhibited photo-to-dark current ratio of two orders of magnitude at 1 kW/m² tungsten halogen radiation.     

Effect of annealing temperature on optical and electrical properties of lead sulfide thin films

Lead sulfide (PbS) thin films with 150 nm thickness were prepared onto ultra-clean quartz substrate by the RF-sputtering deposition method. Deposited thin films of PbS were annealed at different temperatures 100 °C, 150 °C, 200 °C, 250 °C and 300 °C. X-ray diffraction pattern of thin films revealed that thin films crystallized at 150 °C. Crystalline thin films had cubic phase and rock salt structure. The average crystallite size of crystalline thin films was 22 nm, 28 nm and 29 nm for 150 °C, 200 °C and 250 °C respectively. From 150 °C to 250 °C increase in annealing temperature leads to increase in crystallite arrangement. FESEM images of thin films revealed that crystallite arrangement improved by increasing annealing temperature up to 250 °C. Increase in DC electrical conductivity by increasing temperature confirmed the semiconductor nature of crystalline thin films. Increase in dark current by increasing annealing temperature showed the effect of crystallite arrangement on carrier transport. Photosensitivity decreased by increasing annealing temperature for crystalline thin films that it was explained at the base of thermal quenching of photoconductivity and adsorption of oxygen at the surface of thin films that leads to the formation of PbO at higher temperatures.