In situ optical microspectroscopy of the growth and oxidation of silver nanoparticles in silica thin films on soda-lime glass

An in situ optical microspectroscopy investigation of the growth and oxidation of silver nanoparticles (NPs) embedded in SiO₂ thin films deposited on soda-lime glass has been conducted in real time during thermal processing in air. Variation of Ag NP size is followed by fitting of surface plasmon resonance (SPR) with spectra calculated by Mie theory, and analysed concurrently with the time evolution of SPR peak intensity. The NP transformations appeared to be temperature and time dependent. Silver NPs were indicated to grow at relatively high temperatures (e.g. 600 °C) due to Ostwald ripening, followed by a plateau and a gradual decrease in size resulting in SPR vanishing due to oxidation. The three phases were well separated in time. Oxidation appeared dominant at lower temperatures (e.g. 400 °C) as indicated by a continuous decrease in Ag particle size. The product of Ag NP oxidation was revealed by photoluminescence spectroscopy as single Ag⁺ ions. Furthermore, the data indicated that: (i) Ag⁺ ions are formed during heat treatment under an Ag/Ag⁺ redox equilibrium; (ii) the ions diffuse from the SiO₂ matrix towards the soda-lime substrate where they stabilize; and (iii) the continuous removal of these ions from the matrix is necessary in order for the equilibrium to be displaced towards oxidation.     

VO2 thin films deposited on silicon substrates from V2O5 target: Limits in optical switching properties and modeling

Thermochromic VO₂ thin films presenting a phase change at T_c = 68 °C and having variable thickness were deposited on silicon substrates (Si-001) by radio-frequency sputtering. These thin films were obtained from optimized reduction of low cost V₂O₅ targets. Depending on deposition conditions, a non-thermochromic metastable VO₂ phase might also be obtained. The thermochromic thin films were characterized by X-ray diffraction, atomic force microscopy, ellipsometry techniques, Fourier transform infrared spectrometry and optical emissivity analyses. In the wavelength range 0.3 to 25 μm, the optical transmittance of the thermochromic films exhibited a large variation between 25 and 100 °C due to the phase transition at T_c: the contrast in transmittance (difference between the transmittance values to 25 °C and 100 °C) first increased with film thickness, then reached a maximum value. A model taking into account the optical properties of both types of VO₂ film fully justified such a maximum value. The n and k optical indexes were calculated from transmittance and reflectance spectra. A significant contrast in emissivity due to the phase transition was also observed between 25 and 100 °C.     

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.     

Optical properties of Ag8In14Sb55Te23 phase-change films

Ag₈In₁₄Sb₅₅Te₂₃ phase-change films were deposited on K9 glass substrates by RF magnetron sputtering technology using an Ag–In–Sb–Te alloy target. The optical properties and short-wavelength optical storage properties of Ag₈In₁₄Sb₅₅Te₂₃ films were studied. X-Ray diffraction results indicate that the crystallized compounds consist mainly of AgSbTe₂, with small amounts of Sb and AgInTe₂. Comparatively large absorbance was observed in the wavelength range of visible light. The optical storage characteristics of Ag₈In₁₄Sb₅₅Te₂₃ thin films indicate that larger reflectivity contrast can be obtained at lower writing power and shorter writing pulse width.     

Role of substrate temperature on the structural, morphological and optical properties of CuGaSe2 thin films grown by Pulsed Electron Deposition technique

CuGaSe₂ (CGS) thin films were grown on uncoated and Mo-coated soda lime glass by Pulsed Electron Deposition (PED) technique at substrate temperatures comprised between 25 °C and 475 °C. X-ray diffraction analysis reveals that CGS samples exhibit a noteworthy crystal quality even at low growth temperature, T_g = 100 °C, whereas the out-of-plane preferential orientation of CGS chalcopyrite phase switches from < 220 > to < 112 > by increasing the substrate temperature. Annealing treatments seem to enhance the crystallinity of the film and to release the residual strain energy. Visible/near-infrared absorbance spectra show a monotonic decrease of CGS optical bandgap (from 1.75 to 1.65 eV) by enhancing the substrate temperature. Yet the morphology of CGS films strongly depends on T_g, which promotes the formation of larger columnar grains perpendicular to the growth plane. Grain dimensions of ~ 2 μm are achieved when CGS films are grown at high temperature (> 400 °C) on Mo-coated glass. The results indicate that PED is a promising growth technique for achieving good-quality CGS that can be useful as absorber layers in thin film solar cells.     

Electrodeposition of SmS optical thin films on ITO glass substrate

SmS optical thin films were deposited on the surface of ITO glass with an electrodeposition method using aqueous solution containing SmCl₃·6H₂O and Na₂S₂O₃·5H₂O. The phase composition was analyzed by X-ray diffraction (XRD) and microstructure of the film was characterized by atomic force microscope (AFM). It is showed that SmS thin film could be obtained in the solution with n(Sm)/n(S) = 1:4, pH = 4.0 and annealing in Ar atmosphere at 200 °C for 0.5 h. The as-prepared thin films on the ITO glass exhibit a dense microstructure. The band gap of the thin film has been found to be 3.6 eV.     

Effects of hydrogen annealing on the microstructure and optical properties of single-phased Ag2O film deposited using direct-current reactive magnetron sputtering

Single-phased and (111)-oriented Ag₂O film deposited using direct-current reactive magnetron sputtering is annealed using different annealing temperatures (T_a) for 1 h in Ar and H₂ mixture. After hydrogen annealing, a very weak but clear Ag(200) diffraction peak begins to appear, and the Ag₂O diffraction peak weakens at T_a = 175 °C. However, the Ag diffraction peak becomes discernable at T_a = 190 °C. No Ag₂O diffraction peaks but rather Ag diffraction peaks are discerned at T_a = 200 °C. The hydrogen reduction effect can reduce the film's critical thermal decomposition temperature to 175 °C. After hydrogen annealing, the surface of the film evolutes from compact and uniform to osteoporosis, and then to a porous structure. Moreover, the optical properties of the film obviously change at T_a over 190 °C, indicating that the hydrogen reduction can significantly enhance the decomposition of Ag₂O due to H₂ dissociation on the surface followed by gaseous H₂O molecule formation and desorption.     

Characterization of phase transition in silver photo-diffused Ge2Sb2Te5 thin films

Surface activity of thermally evaporated amorphous chalcogenide films of Ge₂Sb₂Te₅ has been investigated. Silver (Ag) is readily deposited on such films from appropriate aqueous ionic solution and Ag diffuses into the films upon irradiation with energetic photons. The composition of Ge₂Sb₂Te₅ thin films and the amount of Ag photo-diffused has been gathered from electron probe micro-analyzer having a wavelength dispersive spectrometer. The composition of the films was found to be very close to the bulk used to deposit films and the amount of Ag photo-diffused was ∼ 0.38 at. %. X-ray diffraction and temperature dependent sheet resistance studies have been used for the structural analysis of the bulk alloy, as-deposited, Ag photo-diffused and annealed films at different temperatures. The films remain amorphous after Ag photo-diffusion into the amorphous Ge₂Sb₂Te₅ films. The reflectivity, reflectivity contrast and extinction coefficient of the crystalline and amorphous photo-diffused thin films are presented. The optical band gaps of the amorphous and crystalline photo-diffused (Ge₂Sb₂Te₅)_100−xAg_x=0.38 phase change thin films have also been calculated from absorption data using UV-VIS spectroscopy.     

Effects of Ag contents and deposition temperatures on the electrical and optical behaviors of Ag-doped Cu2O thin films

Cu₂O-Ag thin films were co-deposited by reactive sputtering on glass substrates. During deposition, Ag contents and deposited temperatures were varied. After deposition, a UV-VIS-NIR photometer and a Hall measurement system were used to characterize the optical and electrical properties of these films. The results showed that the Cu₂O-Ag thin films had a decreased optical transmittance with the increase of Ag contents. The resistivity was also decreased, which is most likely due to the formation of Ag phase. Through the measurement of photo-induced conductivity, it was found that, when Ag concentration was at 4 at.%, the film had the highest increase in conductivity under light irradiation. This is due to the co-existence of Ag₂O and Cu₂O. However, when deposited at a temperature higher than room temperature, the photo-induced conductivity of this film became less obvious, apparently due to the dissociation of Ag₂O. The results of Photoluminescence (PL) measurement confirmed that the Cu₂O-Ag(4 at.%) sample might produce more electron-hole pairs than other samples, which caused the increase of conductivity.     

X-ray diffraction and compositional studies of AgInS2 thin films obtained by spray pyrolysis

Silver indium sulfide (AgInS₂) thin films have been prepared by the spray pyrolysis technique using silver acetate, indium acetate, and N,N-dimethylthiourea as precursor compounds. Depending on the film preparation conditions, AgInS₂ thin films are obtained which could be candidates to be used in photovoltaic devices. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) compositional studies were done on films formed at different substrate temperatures (T _s) and Ag:In:S ratios in the starting solutions. When Ag:In:S ratios are 1:1:1, 1:0.25:2, and 1:1:2, XRD patterns of the thin films indicated that the crystallographic structure is mainly chalcopyrite AgInS₂. An additional phase, acanthite Ag₂S, appeared when the depositions where done at low T _s. EDS analysis showed that AgInS₂ films near stoichiometric composition were obtained by using an atomic ratio of Ag:In:S = 1:1:2 in the starting solution and T _s = 400 °C.     

Reversible transformations of silver oxide and metallic silver nanoparticles inside SiO2 films

Reversible transformation of silver oxide and metallic nanoparticles inside a relatively porous silica film has been established. Annealing of Ag-doped films in oxidizing (air) atmosphere at 450 °C yielded colorless films containing AgO_x. These films were turned yellow when heated in H₂-N₂ (reducing atmosphere) due to the formation of Ag nanoparticles. This yellow coloration (due to nano Ag⁰) and bleaching (conversion of Ag⁰ → Ag⁺) are reversible. Optical and photoluminescence spectra are well consistent with this coloration and bleaching. The soaking test of the air-annealed film in Na₂S₂O₃ solution supports the presence of Ag⁺. Grazing incidence X-ray diffraction and transmission electron microscopy studies reveal the formation of Ag-oxides and Ag nanoparticles in the oxidized and reduced films, respectively.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

Structural, morphological and optical properties of thermal annealed TiO thin films

Structural, morphological and optical properties of TiO thin films grown by single source thermal evaporation method were studied. The films were annealed from 300 to 520 °C in air after evaporation. Qualitative film analysis was performed with X-ray diffraction, atomic force microscopy and optical transmittance and reflectance spectra. A correlation was established between the optical properties, surface roughness and growth morphology of the evaporated TiO thin films. The X-ray diffraction spectra indicated the presence of the TiO₂ phase for the annealing temperature above 400 °C.     

Percolation threshold for electrical resistivity of Ag-nanoparticle/titania composite thin films fabricated using molecular precursor method

To find the percolation threshold for the electrical resistivity of metallic Ag-nanoparticle/titania composite thin films, Ag-NP/titania composite thin films, with different volumetric fractions of silver (0.26 ≤ φ_Ag ≤ 0.68) to titania, were fabricated on a quartz glass substrate at 600 °C using the molecular precursor method. Respective precursor solutions for Ag-nanoparticles and titania were prepared from Ag salt and a titanium complex. The resistivity of the films was of the order of 10⁻² to 10⁻⁵ Ω cm with film thicknesses in the range 100–260 nm. The percolation threshold was identified at a φ_Ag value of 0.30. The lowest electrical resistivity of 10⁻⁵ Ω cm at 25 °C was recorded for the composite with the Ag fraction, φ_Ag, of 0.55. X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), and transmission electron microscopic (TEM) evaluation of the effect of the morphology and the nanostructures of the Ag nanoparticles in the composite thin films on the electrical resistivity of the film revealed that the films consist of rutile, anatase, and metallic Ag nanoparticles homogeneously distributed in the titania matrix. It could be deduced that the electrical resistivity of the thin films formed at 600 °C was unaffected by the anatase/rutile content within the thin film, whereas the shape, size, and separation distance of the Ag nanoparticles strongly influenced the electrical resistivity of the Ag-nanoparticle/titania composite thin films.     

Effect of temperature on structural, optical and photoluminescence properties of antimony (Sb) doped polycrystalline CuInS2 thin films prepared by spray pyrolysis

Copper indium disulphide (CuInS₂) is an absorber material for solar cell and photovoltaic applications. By suitably doping CuInS₂ thin films with dopants such as Zn, Cd, Na, Bi, Sn, N, P and As its structural, optical, photoluminescence properties and electrical conductivities could be controlled and modified. In this work, Sb (0.01 mole (M)) doped CuInS₂ thin films are grown in the temperature range 300-400 °C on heated glass substrates. It is observed that the film growth temperature, the ion ratio (Cu/In = 1.25) and Sb-doping affects the structural, optical and photoluminescence properties of sprayed CuInS₂ films.The XRD patterns confirm that the Sb-doping suppresses the growth of CuInS₂ polycrystalline thin films along (1 1 2) preferred plane and in other characteristic planes. The EDAX results confirm the presence of Cu, In, S and Sb. About 60% of light transmission occurs in the wavelength range 350-1100 nm. The absorption coefficient (α) is found to be in the order of 10⁵ cm⁻¹. The band gap energy increases as the temperature increases from 300-400 °C (1.35-1.40 eV). SEM photographs depict that large sized crystals of Sb-doped CuInS₂ (1 μm) are formed on the surface of the films. Well defined sharp blue and green band emissions are exhibited by Sb-doped CuInS₂ thin films. Defects-related photoluminescence emissions are discussed. These Sb-doped CuInS₂ thin films are prepared by the cost effective method of spray pyrolysis from the aqueous solutions of CuCl₂, InCl₃, SC(NH₂)₂ and SbCl₃ on heated glass substrates.     

Influence of oxygen pressure on the structural, electrical and optical properties of VO2 thin films deposited on ZnO/glass substrates by pulsed laser deposition

The influence of oxygen pressure on the structural and electrical properties of vanadium oxide thin films deposited on glass substrates by pulsed laser deposition, via a 5-nm thick ZnO buffer, was investigated. For the purposes of comparison, VO₂ thin films were also deposited on c-cut sapphire and glass substrates. During laser ablation of the V metal target, the oxygen pressure was varied between 1.33 and 6.67 Pa at 500 °C, and the interaction and reaction of the VO₂ and the ZnO buffer were studied. X-ray diffraction studies showed that the VO₂ thin film deposited on a c-axis oriented ZnO buffer layer under 1.33 Pa oxygen had (020) preferential orientation. However, VO₂ thin films deposited under 5.33 and 6.67 Pa were randomly oriented and showed (011) peaks. Crystalline orientation controlled VO₂ thin films were prepared without such expensive single crystal substrates as c-cut sapphire. The metal-insulator transition properties of the VO₂/ZnO/glass samples were investigated in terms of electrical conductivity and infrared reflectance with varying temperatures, and the surface composition was investigated by X-ray photoelectron spectroscopy.     

Atmospheric pressure chemical vapour deposition of thermochromic tungsten doped vanadium dioxide thin films for use in architectural glazing

Atmospheric pressure chemical vapour deposition of VCl₄, WCl₆ and water at 550 °C lead to the production of high quality tungsten doped vanadium dioxide thin films. Careful control of the gas phase precursors allowed for tungsten doping up to 8 at.%. The transition temperature of the thermochromic switch was tunable in the range 55 °C to − 23 °C. The films were analysed using X-ray diffraction, scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Their optical properties were examined using variable-temperature transmission and reflectance spectroscopy. It was found that incorporation of tungsten into the films led to an improvement in the colour from yellow/brown to green/blue depending on the level of tungsten incorporation. The films were optimized for optical transmission, thermochromic switching temperature, magnitude of the switching behaviour and colour to produce films that are suitable for use as an energy saving environmental glass product.     

Structural, optical and electrical properties of thermally evaporated Ag2S thin films

Thin films of Ag₂S are prepared on glass and quartz substrates by a thermal evaporation method. The structural studies show that the films are well crystallized with an acanthite structure. The optical properties of the films are investigated using spectrophotometric measurements of transmittance and reflectance at normal incidence in the wavelength range 500-2200 nm. The refractive index, n, and the absorption index, k, of Ag₂S are determined from the absolute values of the measured transmittance and reflectance. The dispersion of refractive index in Ag₂S is analyzed using the concept of the single oscillator. Within this concept the oscillator energy, E₀, and the dispersion energy, E_d, can be determined as 5 and 32.5 eV, respectively. It is interesting to note that Ag₂S appears to fall into the ionic class. The values of the lattice dielectric constant and the ratio of the carrier concentration to the effective mass are also determined as 7.77 and 1.7×10⁴⁷ kg⁻¹ m⁻³, respectively. The analysis of the spectral behavior of the absorption coefficient in the intrinsic absorption region reveals an indirect allowed transition with a band gap of 0.96 eV and associated phonons of 0.05 eV. Measurements of the dark electrical resistivity is studied as a function of film thickness and temperature. The dark electrical resistivity decreases with increasing film thickness. Graphical representation of log ρ as a function of reciprocal temperature yields two distinct linear parts indicating the existence of two activation energies ΔE₁ and ΔE₂ as 0.18 and 0.28 eV respectively. Discussion on the obtained results and their comparison with the previous published data is also given.     

Structural, chemical, and optical properties of tin sulfide thin films as controlled by the growth temperature during co-evaporation and subsequent annealing

Tin sulfide thin films on soda-lime glass substrate were prepared by co-evaporation. This technique uses a vapor phase procedure involving chemical reactions between the precursor species evaporated simultaneously. The influence of the substrate temperature in the crystal structure and chemical composition were determined by X-ray diffraction and energy dispersive analysis of X-rays, showing that thin films crystallized in SnS, SnS₂, and Sn₂S₃ phases. Scanning electron microscope shows thin films with homogenous and uniform surface. Some of the samples were annealed to study the variation of structural, chemical, and optical properties. The variation of refractive index (n), extinction coefficient (k), and dielectric constant (ε) with wavelength and photon energy are reported. The energy band gap was calculated from optical transmittance and reflectance measurements in the range 300–1500 nm. The calculated energy band gap values were between 1.75 and 2.3 eV, depending on the phase in which crystallized the different thin films.     

CuInS2 thin films obtained by spray pyrolysis for photovoltaic applications

Copper indium disulphide, CuInS₂, is a promising absorber material for thin film photovoltaic which has recently attracted considerable attention due to its suitability to reach high efficiency solar cells by using low-cost techniques. In this work CuInS₂ thin films have been deposited by chemical spray pyrolysis onto glass substrates at ambient atmosphere, using different composition solutions at various substrate temperatures. Structural, chemical composition and optical properties of CIS films were analysed by X-ray diffraction, energy dispersive X-ray spectroscopy and optical spectroscopy. Sprayed CIS films are polycrystalline with a chalcopyrite structure with a preferential orientation along the <112> direction and no remains of oxides were found after spraying in suitable conditions. X-ray microanalysis shows that a chemical composition near to stochiometry can be obtained. An optical gap of about 1.51 eV was found for sprayed CIS thin films.