Sulfurization temperature effects on the growth of Cu2ZnSnS4 thin film

We made Cu₂ZnSnS₄ (CZTS) thin films by sulfurization of Cu/Sn/Cu/Zn metallic films. Sulfurizations were carried out under different thermal annealing conditions, where maximum temperatures were 440 °C (LT-CZTS) and 550 °C (HT-CZTS). For LT-CZTS films, secondary phases such as SnS₂ and Cu_2?xS were observed, whereas for HT-CZTS films secondary impurities were not detected. Chemical composition of LT-CZTS film was observed to be very non-uniform. Highly Sn-rich and Zn-rich regions were found on the film surface of LT-CZTS. However, averaged chemical composition for larger area was close to stoichiometry. The HT-CZTS film showed homogeneous structural and chemical composition features. But, for HT-CZTS film, the Sn composition was observed to be decreased, which was due to the Sn-loss. By UV–Visible spectroscopy, optical band gaps of LT- and HT-CZTS films were measured to be ～1.33 eV and ～1.42 eV, respectively. The band gap of LT-CZTS film was also observed to be smaller by photoluminescence measurement. The depressed band gap of LT-CZTS film may be ascribed to some defects and low band gap impurities such as Cu₂SnS₃ and Cu_2-xS in the LT-CZTS film.     

Study on the structure and optical property of Zn1−xCuxO sol–gel thin films on quartz substrate

Zn_1−xCu_xO thin films (x=0, 1.0, 3.0, 5.0%) are prepared on quartz substrate by sol–gel method. The structure and morphology of the samples are investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The results show that Cu ions were effectively penetrated into the ZnO crystal lattices with substitutional and interstitial impurities to form stable solid solutions without changing the polycrystalline wurtzite structure. Two peaks at 420 nm (2.95 eV, violet), 485 nm (2.56 eV, blue) have been observed from the photoluminescence (PL) spectra of the samples. It is concluded that the violet peak may correspond to the exciton emission; the blue emission corresponds to the electron transition from the bottom of the conduction band to the acceptor level of zinc vacancy. The optical test shows that the optical band gap E_g is decreased with the increase amount of Cu doping in ZnO. The band gap decrease from 3.40 eV to 3.25 eV gradually. It is also found that the transmission rate is increased rapidly with the increase of Cu ions concentration.     

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.     

Swift heavy ion induced modifications in cobalt doped ZnO thin films: Structural and optical studies

Modifications in the structural and optical properties of 100 MeV Ni⁷⁺ ions irradiated cobalt doped ZnO thin films (Zn_1−xCo_xO, x = 0.05) prepared by sol-gel route were studied. The films irradiated with a fluence of 1 × 10¹³ ions/cm² were single phase and show improved crystalline structure with preferred C-axis orientation as revealed from XRD analysis. Effects of irradiation on bond structure of thin films were studied by FTIR spectroscopy. The spectrum shows no change in bonding structure of Zn-O after irradiation. Improved quality of films is further supported by FTIR studies. Optical properties of the pristine and irradiated samples have been determined by using UV-vis spectroscopic technique. Optical absorption spectra show an appreciable red shift in the band gap of irradiated Zn_1−xCo_xO thin film due to sp-d interaction between Co²⁺ ions and ZnO band electrons. Transmission spectra show absorption band edges at 1.8 eV, 2.05 eV and 2.18 eV corresponding to d-d transition of Co²⁺ ions in tetrahedral field of ZnO. The AFM study shows a slight increase in grain size and surface roughness of the thin films after irradiation.     

Annealing effect on the structural and optical properties of a Cd1−xZnxS thin film for photovoltaic applications

Herein is a report of a study on a Cd_1−xZn_xS thin film grown on an ITO substrate using a chemical bath deposition technique. The as-deposited films were annealed in air at 400 °C for 30 min. The composition, surface morphology and structural properties of the as-deposited and annealed Cd_1−xZn_xS thin films were studied using EDX, SEM and X-ray diffraction techniques. The annealed films have been observed to possess a crystalline nature with a hexagonal structure. The optical absorption spectra were recorded within the range of 350-800 nm. The band gap of the as-deposited thin films varied from 2.46 to 2.62 eV, whereas in the annealed film these varied from 2.42 to 2.59 eV. The decreased band gap of the films after annealing was due to the improved crystalline nature of the material.     

Ellipsometric characterization of PbI2 thin film on glass

The optical properties of polycrystalline lead iodide thin film grown on Corning glass substrate have been investigated by spectroscopic ellipsometry. A structural model is proposed to account for the optical constants of the film and its thickness. The optical properties of the PbI₂ layer were modeled using a modified Cauchy dispersion formula. The optical band gap E_g has been calculated based on the absorption coefficient (α) data above the band edge and from the incident photon energy at the maximum index of refraction. The band gap was also measured directly from the plot of the first derivative of the experimental transmission data with respect to the light wavelength around the transition band edge. The band gap was found to be in the range of 2.385±0.010 eV which agrees with the reported experimental values. Urbach's energy tail was observed in the absorption trend below the band edge and was found to be related to Urbach's energy of 0.08 eV.     

Influence of indium content on the optical, electrical and crystallization kinetics of Se100−xInxthin films deposited by flash evaporation technique

Thin films of Se _100−xIn_x (x=10, 20 and 30 at%) have been prepared by the flash evaporation technique. The effect of the indium content on optical band gap of the Se_100−x In_x films has been investigated by the optical characterization. The optical band gap values of the Se_100−x In_x thin films were determined and are found to decrease with increasing indium content. This indium content changes the width of localized states in the optical band gaps of the thin films. It was found that the optical band gap, E_g, of the Se_100−x In_x films changes from 1.78 to 1.37 eV with increasing indium content from 10 to 30 at%, while the width of localized states in optical band gap changes from 375 to 342 meV. The temperature dependence of the dark electrical conductivity were studied in the temperature range 303-433 K and revealed two activation energies providing two electrical conduction mechanisms. The activation energy of the Se_100−x In_x films in the high temperature region changes from 0.49 to 0.32 eV with increasing indium content from 10 to 30 at%, while the hopping activation energy in the lower temperature region changes from 0.17 to 0.22 meV. The change in the electrical conductivity with time during the amorphous-to-crystalline transformation is recorded for amorphous Se_100−xIn_x films at two points of isothermal temperatures 370 and 400 K. The formal crystallization theory of Avrami has been used to calculate the kinetic parameters of crystallization.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.     

I–V characteristics of ZnO/Cu2O thin film n–i–p heterojunction

ZnO/Cu₂O thin film n–i–p heterojunctions were fabricated by magnetron sputtering. The microstructure, optical, and electrical properties of n-type (n‐) ZnO, insulating (i‐) ZnO, and p-type (p‐) Cu₂O films deposited on glass substrates were characterized by X-Ray diffraction (XRD), spectrophotometer, and the van der Pauw method, respectively. XRD results show that the mean grain size of i-ZnO film is much larger than that of n-ZnO film. The optical band gap energies of n-ZnO, i-ZnO, and p-Cu₂O film are 3.27, 3.47, and 2.00 eV, respectively. The carrier concentration of n-ZnO film is two orders of magnitude larger than that of p-Cu₂O film. The current–voltage (I–V) characteristics of ZnO/Cu₂O thin film n–i–p heterojunctions with different i-ZnO film thicknesses were investigated. Results show that ZnO/Cu₂O n–i–p heterojunctions have well-defined rectifying behavior. All ideality factors of these n–i–p heterojunctions are larger than 2.0. The forward bias threshold voltage and ideality factor increase when i-ZnO layer thickness increases from 100 to 200 nm. An energy band diagram was proposed to analyze the I–V characteristics of these n–i–p heterojunctions.     

Band gap energy and bowing parameter of In-rich InAlN films grown by magnetron sputtering

The crystal structure, band gap energy and bowing parameter of In-rich In_xAl_1−xN (0.7 < x < 1.0) films grown by magnetron sputtering were investigated. Band gap energies of In_xAl_1−xN films were obtained from absorption spectra. Band gap tailing due to compositional fluctuation in the films was observed. The band gap of the as-grown InN measured by optical absorption method is 1.34 eV, which is larger than the reported 0.7 eV for pure InN prepared by molecular beam epitaxy (MBE) method. This could be explained by the Burstein-Moss effect under carrier concentration of 10²⁰ cm⁻³ of our sputtered films. The bowing parameter of 3.68 eV is obtained for our In_xAl_1−xN film which is consistent with the previous experimental reports and theoretical calculations.     

Ferromagnetism in noncompensated (Mn,Ga)-codoped ZnO films

Mn/Ga noncompensated codoped ZnO films were prepared on c-cut sapphire substrates via pulsed laser deposition. The structural, magnetic, transport, and optical properties of the films were then investigated. Addition of the Ga donor increases the electron concentration and enhances the magnetization in these films because of the net negative charge of the special noncompensated codoping, which can adjust the carrier concentration as well as the magnetic moment. Moreover, the Fermi level moves into the conduction band because of the increase in electron concentration, which results in an increase in the optical band gap value, from 3.28 eV for the undoped ZnO film to 3.61 eV for the (Mn,Ga)-codoped ZnO film.     

Effect of environment and heat treatment on the optical properties of RF-sputtered SnO2 thin films

Thin films of SnO₂ were deposited by RF-magnetron sputtering on quartz substrates at room temperature in an environment of Ar and O₂. The XRD pattern shows amorphous nature of the as-deposited films. The optical properties were studied using the reflectance and transmittance spectra. The estimated optical band gap (E_g) values increase from 4.15 to 4.3 eV as the Ar gas content decreases in the process gas environment. The refractive index exhibits an oscillatory behavior that is strongly dependent on the sputtering gas environment. The Urbach energy is found to decrease with increase in band gap. The band gap is found to decrease on annealing the film. The role of oxygen defects is explored in explaining the variation of optical parameters.     

On the paramagnetic behavior of heavily doped Zn1−xMnxO films fabricated by Pechini’s method

Heavily doped Zn_1−xMn_xO (x = 0.3) films were prepared by polymeric precursor method onto glass substrates and their structural, morphological, optical and magnetic properties carefully studied. Undoped ZnO films were also prepared for the purpose of comparison. The polymeric precursor method consists in preparing a coating solution from the Pechini process followed by a three-step thermal treatment of the as deposited films at temperatures up to 550 °C for 30 min. X-ray diffraction (XRD) analysis reveals the typical hexagonal wurtzite structure of the undoped ZnO film. The addition of Mn ions leads to a dramatic reduction of the crystalline quality of film although no evidence of affectation by secondary phases is found. The affectation of the ZnO structure may be due to the formation of Mn clusters and generation of defects such as vacancies and interstitials. Here, the solubility limit of the Mn ions in ZnO should play an important role and it is discussed in the framework of ionic radius and valence states. The scanning electron microscopy (SEM) analysis shows that the surface of the doped sample was affected by the presence of cracks due, probably, to the expansion of the lattice constant of Zn_0.7Mn_0.3O caused by the Mn incorporation in the ZnO lattice. The existence of cluster-type structures on the surface is corroborated by atomic force microscopy (AFM). The EDX analysis, carried out on some areas in the film, yielded Mn/Zn ratios of about 0.3, which points out to an effective Mn incorporation in the film. On the other hand, the absorption edge of the doped films is red shifted to 2.9 eV (3.24 eV for undoped ZnO film) and the absorption edge is less sharp due, probably, to amorphous states appearing in the band gap. No evidence of dilute magnetic semiconductor mean-field ferromagnetic behavior is observed. The temperature dependence of the magnetization follows a Curie law suggesting pure paramagnetic behavior. The very small s-shape behavior of M versus H (without hysteresis) observed at room temperature on selected areas would stem from Mn clusters which are easily formed in transition metal doped ZnO.     

Microstructure, magnetic and optical properties of sputtered polycrystalline ZnO films with Fe addition

Microstructure, magnetic and optical properties of polycrystalline Fe-doped ZnO films fabricated by cosputtering with different Fe atomic fractions (x_Fe) have been examined systematically. Fe addition could affect the growth of ZnO grains and surface morphology of the films. As x_Fe is larger than 7.0%, ZnFe₂O₄ grains appear in the films. All the films are ferromagnetic. The ferromagnetism comes from the ferromagnetic interaction activated by defects between the Fe ions that replace Zn ions. The average moment per Fe ion reaches a maximum value of 1.61 μ_B at x_Fe = 4.8%. With further increase in x_Fe, the average moment per Fe ion decreases because the antiferromagnetic energy is lower than the ferromagnetic one due to the reduced distance between the adjacent Fe ions. The optical band gap value decreases from 3.245 to 3.010 eV as x_Fe increases from 0% to 10%. Photoluminescence spectra analyses indicate that many defects that affect the optical and magnetic properties exist in the films.     

Microstructural and optical investigations of sol-gel derived ferroelectric BaTiO3 nanocrystalline films determined by spectroscopic ellipsometry

Ferroelectric BaTiO₃ nanocrystalline films (BTNFs) with the crystalline sizes of about 30 nm were grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. Spectroscopic ellipsometry (SE) was used to characterize the films in the photon energy range of 1.5-5.0 eV with a five-phase layered model (air/surface rough layer/BaTiO₃/interface layer/Pt). The optical properties in the transparent and absorption regions have been investigated with the Forouhi-Bloomer dispersion relation. With the aid of the structural and dielectric function models, the microstructure and electronic structure of the BTNFs can be readily obtained. It was found that the refractive index reaches the value of 2.20 in the transparent region. Based on the Sellmeier dispersion analysis, the single-oscillator energy is about 4.7 eV for the BTNFs. The long wavelength refractive index n(0) can be estimated to about 2.00 at zero point. The direct optical band gap energy approaches approximately 4.2 eV and Urbach band tail energy is 262±2 and 268±1 meV respectively with increasing crystalline size. A higher band gap observed can be owing to the known quantum confinement effect in the nanocrystalline formation and different fraction of amorphous and crystalline components. The theoretical analysis based on the effective mass approximation theory is well used to explain these experimental data.     

Room temperature transparent conducting oxides based on zinc oxide thin films

Doped zinc oxide thin films are grown on glass substrate at room temperature under oxygen atmosphere, using pulsed laser deposition (PLD). O₂ pressure below 1 Pa leads to conductive films. A careful characterization of the film stoichiometry and microstructure using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) concludes on a decrease in crystallinity with Al and Ga additions (≤3%). The progressive loss of the (0 0 2) orientation is associated with a variation of the c parameter value as a function of the film thickness and substrate nature. ZnO:Al and ZnO:Ga thin films show a high optical transmittance (>80%) with an increase in band gap from 3.27 eV (pure ZnO) to 3.88 eV and 3.61 eV for Al and Ga doping, respectively. Optical carrier concentration, optical mobility and optical resistivity are deduced from simulation of the optical data.     

Characterization of ZnO-SnO2 thin film composites prepared by pulsed laser deposition

Thin films of ZnO-SnO₂ composites have been deposited on Si(1 0 0) and glass substrates at 500 °C by pulsed laser ablation using different composite targets with ZnO amount varying between 1 and 50 wt%. The effect of increasing ZnO-content on electrical, optical and structural properties of the ZnO-SnO₂ films has been investigated. X-ray diffraction analysis indicates that the as-deposited ZnO-SnO₂ films can be both crystalline (for ZnO <1 wt%) and amorphous (for ZnO ≥ 10 wt%) in nature. Atomic force microscopy studies of the as-prepared composite films indicate that the surfaces are fairly smooth with rms roughness varying between 3.07 and 2.04 nm. The average optical transmittance of the as-deposited films in the visible range (400-800 nm), decreases from 90% to 72% for increasing ZnO concentration in the film. The band gap energy (E_g) seems to depend on the amount of ZnO addition, with the maximum obtained at 1 wt% ZnO. Assuming that the interband electron transition is direct, the optical band gap has been found to be in the range 3.24-3.69 eV for as-deposited composite films. The lowest electrical resistivity of 7.6 × 10⁻³ Ω cm has been achieved with the 25 wt% ZnO composite film deposited at 500 °C. The photoluminescence spectrum of the composite films shows a decrease in PL intensity with increasing ZnO concentration.     

Optical and structural parameters of the ZnO thin film grown by pulsed filtered cathodic vacuum arc deposition

Transparent conductive ZnO film was deposited on glass substrate by pulsed filtered cathodic vacuum arc deposition (PFCVAD). Optical parameters such as absorption coefficient α, the refractive index n, energy band gap E_g and dielectric constants have been determined using different methods. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. The spectra of the dielectric coefficient were used to calculate the energy band gap and the value was 3.24 eV. The experimental energy band gap was found to be 3.22 eV for 357 nm thick ZnO thin film. The envelope method was also used to calculate the refractive index and the data were consistent with K-K relation results. The structure of the film was analyzed with an x-ray diffractometer and the film was polycrystalline in nature with preferred (002) orientation.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Characterization of flash evaporated Hg1−xZnxTe films

Results of structural, optical and electrical properties of flash-evaporated Hg_1−xZn_xTe films. in the composition range 0.08 ⩽ x ⩽ 1, show that the films are formed by alloying HgTe and ZnTe. The optical band gap of these films increases from 0.04 to 2.26 eV with an increase in Zn concentration from 0.08 to 1.0. The band gap variation is not linear but shows a “bowing effect” familiar to pseudobinary solid solutions. An increase in resistivity with an increase in the substrate temperature can be related to larger grain size at the higher substrate temperatures in these p-type films. The films exhibit higher conductivity for the Hg-rich films which decreases linearly as the Zn concentration is increased.