Structural,morphological, compositional,and optical properties of single step electrodeposited Cu2ZnSnS4 (CZTS) thin films for solar cell application

We fabricate a Cu₂ZnSnS₄ (CZTS) absorber layer, by using single step electrodeposition of CZTS precursor, deposited at −1.05 V, followed by high temperature annealing in a sulfur atmosphere. X-ray diffraction pattern indicates that the as-grown sample is amorphous in nature, and polycrystalline CZTS thin films with kesterite crystal structure have been obtained by sulfurization from 450 to 580 °C. Surface morphologies of the as-grown sample show some voids with agglomerated particles. After sulfurization, the morphologies of the annealed samples become more uniform, and dense. EDAX study reveals that the sulfurized samples are nearly stoichiometric, being Cu-rich and S-deficient in composition. The band gaps of the annealed samples are found to be in the range from 1.9 to 1.5 eV.     

Influence of solvent on solution processed Cu2ZnSnS4 nanocrystals and annealing induced changes in the optical,structural properties of CZTS film

The well-known quaternary Cu₂ZnSnS₄ (CZTS) chalcogenide thin films are playing an important role in modern technology. The CZTS nanocrystal were successfully prepared by solution method using water, ethylene glycol and ethylenediamine as different solvent. The pure phase material was used for thin film coating by thermal evaporation method. The prepared CZTS thin films were characterized by XRD, Raman spectroscopy, FESEM, XPS and FT-IR spectroscopy. The XRD and Raman spectroscopy analysis revealed the formation of polycrystalline CZTS thin film with tetragonal crystal structure after annealing at 450 ^°C. The oxidation state of the annealed film was studied by XPS. A direct band gap about 1.36 eV was estimated for the film from FT-IR studies, which is nearly close to the optimum value of band gap energy of CZTS materials for best solar cell efficiency. The CZTS annealed thin films are more suitable for using as a p-type absorber layer in a low-cost solar cell.     

Influence of argon ambience on the structural,morphological and optical properties of pulsed laser ablated zinc sulfide thin films

Nanostructured zinc suplhide thin films are successfully deposited on quartz substrates using pulsed laser deposition (PLD) under different argon pressures (0, 5, 10, 15 and 20 Pa). The influence of argon ambience on the microstructural, optical and luminescence properties of zinc sulfide (ZnS) thin films is systematically investigated. The GIXRD data suggests rhombohedral structure for ZnS films prepared under different argon ambience. Self-assembly of grains into well-defined patterns along the y direction is observed in the AFM image of the film deposited under argon pressure 20 Pa. All the films show a blue shift in optical band gap. This can be due to the quantum confinement effect and less widening of conduction and valence band for the films with less thickness and smaller grain size. The PL spectra of the different films are recorded at excitation wavelengths 250 nm and 325 nm and the spectra are interpreted. The PL spectra of the films recorded at excitation wavelength 325 nm show intense yellow emission. The film deposited under an argon pressure of 15 Pa shows the highest PL intensity for excitation wavelength 325 nm. For the PL spectra (excitation at 250 nm), the highest PL intensity is observed for the film prepared under argon free ambience. In our study, 15 Pa is the optimum argon pressure for better crystallinity and intense yellow emission when excited at 325 nm.     

Enhancement of photosensitivity in bismuth doped Cu2ZnSnS4 thin films

In this paper, the effect of bismuth doping on the structural, morphological, optical and electrical properties of Cu₂ZnSnS₄ (CZTS) films has been investigated. The undoped and bismuth doped CZTS films (0, 0.5, 1, 1.5 and 2 mol%) were deposited on glass substrates by solution based method. The XRD result shows a significant improvement in the crystallinity of the films with increase in bismuth concentration. The Raman spectra of the films show the dominant peak at 334 cm^–1 corresponding to A₁ vibrational mode of CZTS kesterite phase. The FESEM micrographs of the films show an enhancement in the grain size and densification with the addition of bismuth ion concentration. The optical bandgap of the films was found to vary (1.59–1.40 eV) with the doping of bismuth ions. The I –V characteristics indicate twofold increment in the photoconductivity for the bismuth doped CZTS films under 100 mW/cm² illumination suggesting their potential application in photovoltaic devices. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Synthesis and characterization of Cu2ZnSnS4 thin films by SILAR method

Semiconducting Cu₂ZnSnS₄ (CZTS) material has been receiving a great technological interest in the photovoltaic industry because of its low-cost non-toxic constituents, ideal direct band gap as a absorber layer and high absorption coefficient. CZTS thin films have been successfully deposited onto the fluorine-doped tin oxide/glass (glass/FTO) substrates coated glass substrates using successive ionic layer adsorption and reaction (SILAR) method and investigated for photoelectrochemical conversion (PEC) of light into electricity. The best solar cell sample showed an open-circuit voltage of 390 mV, a short-circuit current density of 636.9 μA/cm², a fill factor of 0.62 and an efficiency of 0.396% under irradiation of 30 mW/cm². Preliminary results obtained for solar cells fabricated with this material are promising.     

Effect of laser treatment on the optical properties of poly(methyl methacrylate) thin films

In this work, the effect of laser pulse treatment on the optical properties of poly(methyl methacrylate) (PMMA) films has been studied experimentally. The second harmonic of a pulsed Nd:YAG laser at 532 nm and 6 ns pulse width with 10 Hz repetition rate was used to modify the surface of red-BS-dye-doped PMMA films. Samples were ablated with 50 and 100 laser pulses. Optical reflectance and transmittance spectra were obtained in the range of 200–2000 nm. The optical properties of the films were influenced by the pulse number significantly. The oscillator and dispersion energies of the films were determined using the Wemple-Didomenico model. The optical band gap energy was extracted using the Tauc method. Results show that the optical parameters of the films were changed significantly after laser treatment.     

Effect of Al doping on structural,optical and electrical properties of SnO2 thin films synthesized by pulsed laser deposition

Aluminium-doped (Al = 0–5?wt.%) SnO₂ thin films with low-electrical resistivity and high optical transparency have been successfully synthesized by pulsed laser deposition technique at 500 °C. Structural, optical and electrical properties of the as-deposited and post-annealed thin films were investigated. X-ray diffraction patterns suggest that the films transform from crystalline to amorphous state with increasing aluminium content. The root mean square (R_q) surface roughness parameter, determined by atomic force microscopy decreases upon annealing of the as-deposited film. While resistivity of the film is the lowest (9.49 × 10^?4 Ω-cm) at a critical doping level of 1?wt.% Al, optical transparency is the highest (nearly 90%) in the as-deposited condition. Temperature dependence of the electrical resistivity suggests that the Mott’s variable range hopping process is the dominant carrier transport mechanism in the lower temperature range (40–135 K) for all the films whereas, thermally activated band conduction mechanism seems to account for conduction in the higher temperature region (200–300 K).     

Improving Cu2ZnSnS4 (CZTS) solar cell performance by an ultrathin ZnO intermediate layer between CZTS absorber and Mo back contact

The effects of an ultrathin ZnO intermediate layer deposited at the CZTS/Mo interface on CZTS solar cell performance have been investigated in this work. The ZnO layer inhibits the generation of MoS₂ layer and the formation of voids in the CZTS absorber. Consequently, the incorporation of this layer reduces the series resistance and increases the shunt resistance, which boosts photovoltaic conversion efficiency from 1.13% to 4.3%. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of K-doping on structural and optical properties of ZnO thin films

In this work, K-doped ZnO thin films were prepared by a sol–gel method on Si(111) and glass substrates. The effect of different K-doping concentrations on structural and optical properties of the ZnO thin films was studied. The results showed that the 1 at.% K-doped ZnO thin film had the best crystallization quality and the strongest ultraviolet emission ability. When the concentration of K was above 1 at.%, the crystallization quality and ultraviolet emission ability dropped. For the K-doped ZnO thin films, there was not only ultraviolet emission, but also a blue emission signal in their photoluminescent spectra. The blue emission might be connected with K impurity or/and the intrinsic defects (Zn interstitial and Zn vacancy) of the ZnO thin films.     

Effect of thickness on the structural,optical and electrical properties of thermally evaporated PbI2 thin films

This work describes the physical properties of lead iodide (PbI₂) thin films with different thicknesses that were deposited on ultrasonically cleaned glass substrates using a thermal evaporation technique at 5×10^-6 torr. The initial material was purified by the zone refining technique under an atmosphere of argon gas. XRD analysis of the material demonstrates that the thin films were preferably oriented along the (001) direction. The size of the crystallites was calculated from the Scherer relation and found to be in the range of ～5–10 nm, with higher values being observed for increasing film thicknesses. The optical energy band gaps were evaluated and determined to belong to direct transitions. Because the band gap increased with decreasing film thickness, a systematic blue shift was observed. The surface morphologies of PbI₂ films exhibited a clear increase in grain size with increasing film thickness. The photoluminescence and dc conductivity of the thin films are also discussed.     

Optical characterization of nano-structured Cu2ZnSnS4 thin films deposited by GLAD technique

In this paper, Cu₂ZnSnS₄ (CZTS) thin films were elaborated at room temperature by thermal evaporation method using Glancing Angle Deposition (GLAD) technique at different incident angles γ = 00°, 20°, 40°, 60°, 75° and 85°. XRD, Raman scattering analysis, (SEM) and UV-Visible-NIR spectroscopy were used to characterize the crystalline structure, morphology and optical properties of CZTS samples. The results have showed that the ellipsometric analysis leaded to an optical anisotropy due to the structural anisotropy for CZTS samples deposited at γ = 85°. All Cu₂ZnSnS₄ samples exhibited a high absorption coefficient (α > 10⁴ cm⁻¹) and a direct optical transition varied between 1.48 eV and 2.05 eV for CZTS thin films deposited at γ = 00° and 85°, respectively. The value of the Urbach energy increased with incident angle, indeed, its value increased from 58 meV (γ = 00°) to 604 meV (γ = 75°) and decrease to be 368 meV for γ = 85°. This result is correlated with the Raman analysis. From transmittance data of CZTS thin films deposited at γ = 00°, 20° and 40° Swanepoel's method was used, to estimate the refractive index n. It allows us, using the Wemple-DiDomenico and Spitzer-Fan models, to calculate other optical parameters such as the oscillator energy E₀, dispersion energy E_d, zero frequency refractive index n₀, high frequency dielectric constant ε_∞ and the electric susceptibility χ_e. On the other hand, to have an idea about the evolution of the nonlinear optical character, the nonlinear susceptibility χ⁽³⁾ and the nonlinear refractive index n₂ of CZTS thin films deposited at γ = 00°, 20° and 40° were investigated. Ellipsometric measurements of CZTS thin films has leaded to an optical anisotropy for γ = 85°. In addition, the generalized ellipsometry in Jones formalism have proved this property, which can be related to the nano-columnar slanted structure as revealed by (SEM) analysis.     

Effect of complexing agent on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films

The Cu₂ZnSnS₄ (CZTS) thin films have been electrochemically deposited on Mo-coated glass substrate from weak acidic medium (pH 4.5-5) at room temperature. The effect of complexing agent (tri-sodium citrate) on the structural, morphological and compositional properties of CZTS thin films has been investigated. The as-deposited and annealed thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM),EDAX and X-ray photoelectron spectroscopy (XPS) techniques for their structural, morphological, compositional and chemical properties, respectively. XRD studies reveal that the amorphous nature of as-deposited thin film changes into polycrystalline with kesterite crystal structure after annealing in Ar atmosphere. The film prepared without complexing agent showed well-covered surface morphology on the substrate with some cracks on the surface of the film whereas those prepared using complexing agent, exhibited uneven and slightly porous and some overgrown particles on the surface of the films. After annealing, morphology changes into the flat grains, uniformly distributed over the entire surface of the substrate. The EDAX and XPS study reveals that the films deposited using 0.2 M tri-sodium citrate are nearly stoichiometric.     

Influence of air annealing on the structural, morphological, optical and electrical properties of chemically deposited ZnSe thin films

Zinc selenide nanocrystalline thin films are grown onto amorphous glass substrate from an aqueous alkaline medium, using chemical bath deposition (CBD) method. The ZnSe thin films are annealed in air for 4 h at various temperatures and characterized by structural, morphological, optical and electrical properties. The as-deposited ZnSe film grew with nanocrystalline cubic phase alongwith some amorphous phase present in it. After annealing metastable nanocrystalline cubic phase was transformed into stable polycrystalline hexagonal phase with partial conversion of ZnSe into ZnO. The optical band gap, E_g, of as-deposited film is 2.85 eV and electrical resistivity of the order of 10⁶-10⁷ Ω cm. Depending upon annealing temperature, decrease up to 0.15 eV and 10² Ω cm were observed in the optical band gap, E_g, and electrical resistivity, respectively.     

Effect of Al incorporation on the structural,morphological, optoelectronic and transport properties of PbS thin films

Doping of PbS thin films with different metal atoms produce considerable changes in structural and material properties that make them useful in the technology of thin film devices. The goal of this work is to study the effects of doping on the structural, morphological, optoelectronic and transport properties of PbS thin films as a function of Al³⁺ concentration. Thin films of pure and Al doped PbS nanoparticles are prepared on soda lime glass substrates by chemical bath deposition technique. The Al content in aqueous solution is varied from 0 to 20 mg. XRD analysis of the films revealed significant enhancement in crystallinity and crystallite size up to an optimum concentration of doping. Films are polycrystalline with crystallite size 19–32 nm, having face centered cubic structure. The optical band gap energy exhibits a decreasing trend and is shifted from 2.41 to 1.34 eV with increasing Al content. The room temperature conductivity of the as-deposited PbS films is in the range of 0.78×10⁻⁸ to 0.67×10⁻⁶(Ω cm)⁻¹ with a maximum for optimum Al content. The Al doped PbS thin film, which we synthesize with optimum Al concentration of 15 mg is found to be a most suitable material for solar control coating applications.     

Preparation and investigation of optical, structural, and morphological properties of nanostructured ZnO:Mn thin films

Nanostructured ZnO:Mn thin films have been prepared by sol–gel dip coating method. The content of Mn in the sol was varied from 0 to 12 wt%. The effect of Mn concentration on the optical, structural, and morphological properties of ZnO thin films were studied by using Fourier Transform Infrared (FTIR), UV–visible and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD results showed that the films have hexagonal wurtzite structure at lower content of Mn. The diffraction peaks corresponding to ZnO disappeared and two diffraction peaks of MnO₂ and Mn₃O₄ appeared at the highest value of doping concentration (viz., 12 wt%). SEM results revealed that the surface smoothness of the films improved at higher content of Mn. The optical band gap of the films decreased from 3.89 to 3.15 eV when the Mn concentration increased from 0 to 12 wt%. The PL spectra of the films showed the characteristic peaks linked to band-to-band, green and yellow emissions. Besides, the PL intensity of the samples decreased with increase in Mn concentration.     

Effect of annealing on structural, optical and electrical properties of nanostructured Ge thin films

Ge thin films with a thickness of about 110 nm have been deposited by electron beam evaporation of 99.999% pure Ge powder and annealed in air at 100-500 °C for 2 h. Their optical, electrical and structural properties were studied as a function of annealing temperature. The films are amorphous below an annealing temperature of 400 °C as confirmed by XRD, FESEM and AFM. The films annealed at 400 and 450 °C exhibit X-ray diffraction pattern of Ge with cubic-F structure. The Raman spectrum of the as-deposited film exhibits peak at 298 cm⁻¹, which is left-shifted as compared to that for bulk Ge (i.e. 302 cm⁻¹), indicating nanostructure and quantum confinement in the as-deposited film. The Raman peak shifts further towards lower wavenumbers with annealing temperature. Optical band gap energy of amorphous Ge films changes from 1.1 eV with a substantial increase to ∼1.35 eV on crystallization at 400 and 450 °C and with an abrupt rise to 4.14 eV due to oxidation. The oxidation of Ge has been confirmed by FTIR analysis. The quantum confinement effects cause tailoring of optical band gap energy of Ge thin films making them better absorber of photons for their applications in photo-detectors and solar cells. XRD, FESEM and AFM suggest that the deposited Ge films are composed of nanoparticles in the range of 8-20 nm. The initial surface RMS roughness measured with AFM is 9.56 nm which rises to 12.25 nm with the increase of annealing temperature in the amorphous phase, but reduces to 6.57 nm due to orderedness of the atoms at the surface when crystallization takes place. Electrical resistivity measured as a function of annealing temperature is found to reduce from 460 to 240 Ω-cm in the amorphous phase but drops suddenly to 250 Ω-cm with crystallization at 450 °C. The film shows a steep rise in resistivity to about 22.7 KΩ-cm at 500 °C due to oxidation. RMS roughness and resistivity show almost opposite trends with annealing in the amorphous phase.     

Radio frequency magnetron sputtered epitaxial Cu2ZnSnS4 thin film on ZnS(100)

Heteroepitaxial growth of kesterite Cu₂ZnSnS₄ (CZTS) thin film on cubic ZnS(100) single crystal substrate was achieved by radio frequency magnetron sputtering from a single CZTS target. An optimal substrate temperature in the range of 470–500 °C is found suitable for this epitaxial growth. The growth of CZTS was confirmed to be along a‐axis. The sputtered CZTS thin film is homogeneous throughout the whole film. The band gap of the film is found to be approximately 1.51 eV, i.e., promising for high efficiency thin film solar cells.

     

Effect of Cr implantation on structural and optical properties of AlN thin films

Molecular beam epitaxy (MBE) grown AlN thin layer on sapphire substrates have been implanted with Cr⁺ ions for various dose from 10¹³ to 10¹⁵ cm⁻². The analyses were carried out by an X-ray diffractometer (XRD), Raman spectroscopy, a spectrophotometer and spectroscopic ellipsometry (SE) for structural and optical analyses. E₂(high) and A₁(LO) Raman modes of AlN layer have been observed and analyzed. The behavior of Raman shift and the variation in intensity and in peak width of Raman modes as a function of ions flux are explained on the basis of chromium substituting aluminum atom and implantation-induced lattice damage. Both Raman and X-ray analyses reveal that the incorporation of chromium atoms increases in the host lattice with the increasing of Cr ions fluence. The band gap energy was determined by using transmission spectra. It was found that the band gap energy decreases as the ion dose increases. The band gap of the unimplanted AlN is 6.02 eV and it decreases down to 5.92 eV for the Cr⁺-implanted AlN with a ion dose of 1×10¹⁵ cm⁻². Optical properties such as optical constants of the samples were examined by using a spectroscopic ellipsometer. It was observed that the refractive index (n) decreases with the increasing of ion dose.