Characterization of Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> Thin Films Prepared by RF Magnetron Sputtering

Zn₂SnO₄ (ZTO) is a stable semiconductor in ZnO–SnO₂ system and important transparent conducting oxide (TCO) predominantly used in optoelectronic devices. ZTO thin films were prepared by RF magnetron sputtering using Zn₂SnO₄ ceramic target in this paper. The effects of annealing temperatures and oxygen contents on characterization of ZTO thin films were studied. The results show that ZTO thin films prepared by RF magnetron sputtering are amorphous with an optical band gap of 3.22 eV. After annealing at 650°C in Ar atmosphere for 40 min, ZTO films possess a spinel structure with an optical band gap of 3.62 eV. The atomic force microscope (AFM) data of morphology reveals that the surface roughness of films is about 2 nm. The results of energy dispersive spectrometer (EDS) show that the concentration ratio of Zn to Sn is in the range from 1.44 to 1.57. The results of Hall-effect-measurement system reveal that the resistivity of films varies from 102 to 10–1 Ωcm, carrier concentration is about 10¹⁷ cm^–3, and mobility ranges from 10⁰ to 10¹ cm² v^–1 s^–1.     

Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Characteristics of filtered vacuum arc deposited ZnO-SnO2 thin films on room temperature substrates

ZnO, SnO₂ and zinc stannate thin films were deposited using filtered vacuum arc deposition (FVAD) system on commercial microscope glass and UV fused silica substrates (UVFS) at room temperature (RT). The structural and morphological analyses were performed using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM), respectively. XRD patterns of ZnO films deposited at RT had strongly c-axis orientation, whereas SnO₂ and zinc stannate films had amorphous structure as they did not have any defined patterns. Average crystalline size and surface grain size of ZnO films were ∼16 nm, as determined from diffraction line broadening and AFM images, respectively. Optical constants in the 250-1100 nm wavelength range were determined by variable angle spectroscopic ellipsometry and transmission measurements. The transmission of the deposited films in the VIS was 80-90%, affected by interference. The refractive indices and the extinction coefficients of deposited ZnO, SnO₂ and zinc stannate films were in the range 1.87-2.15 and 0.02-0.04, depending on wavelengths and deposition parameters. The optical band gap (E_g) was determined by the dependence of the absorption coefficient on the photon energy at short wavelengths. Its values for ZnO, SnO₂ and zinc stannate were in the range 3.25-3.30 eV, 3.60-3.98 eV and 3.43-3.52 eV, respectively, depending on the deposition pressure.     

Selective fabrication of n‐ and p‐type SnO films without doping

Undoped n‐ and p‐type tin monoxide (SnO) films have been selectively fabricated by pulsed laser deposition with a Sn target and careful control of oxygen partial pressure. The films are epitaxially grown in optimal growth conditions on yttria‐stabilized zirconia (YSZ) substrates with out‐of‐plane and in‐plane orientation relationships of (001)_SnO//(001)_YSZ and [110]_SnO//[100]_YSZ, respectively. Both Seebeck and Hall measurements show consistent results on the carrier types of the films. The electron Hall mobility is approximately 11 cm²/Vs at room temperature and the carrier activation energy is 0.14 eV for the n‐type film. The growth at increased oxygen partial pressure yields p‐type films, demonstrating the selective fabrication of both n‐ and p‐type SnO films without doping. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Volume of precursor solution effect on the properties of SnO<Subscript>2</Subscript> thin films prepared by nebulized spray pyrolysis technique

Undoped SnO₂ thin films have been deposited on amorphous glass substrates with different precursor solution volume (10, 15, 20 and 25 ml) using simple and cost-effective nebulized spray pyrolysis technique. The influence of precursor solution on structural, optical, photoluminescence and electrical properties had been studied. The X-ray diffraction spectra prove the polycrystalline nature of SnO₂ with tetragonal structure. All the films show a preferred growth orientation along (110) diffraction plane. The average transmittance of SnO₂ thin films varied between 82 and 75% in the visible as well as IR region. The band gap energy decreases from 3.74 to 3.64 eV corresponding to direct transitions with the precursor solution volume had increased from 10 to 20 ml and then increased as 3.72 eV for 25 ml. SEM pictures demonstrated polyhedrons like grains. EDX confirmed the existence of Sn and O elements in all the prepared SnO₂ thin films. Photoluminescence spectra at room temperature revealed that the four emission bands in all the samples such as sharp dominant peak at 361 nm with shoulder peak at 377 nm (UV region), a broad and low intensity peak at 492 nm (blue region) and 519 nm (green region). The electrical parameters were examined by Hall effect measurements, which demonstrated that the film prepared at 20 ml precursor solution volume possess minimum resistivity 2.76?×?10^?3 Ω-cm with activation energy 0.10 eV and maximum figure of merit 1.54?×?10^?2 (Ω/sq)^?1.     

First-principle calculations of structural and electronic properties of rutile-phase dioxides (MO<Subscript>2</Subscript>), M = Ti,V, Ru,Ir and Sn

First principle calculations using density functional theory (DFT) and full-potential linearized augmented plane waves (FP-LAPW) method are performed to investigate the structural and electronic properties of rutile phase titanium, vanadium, ruthenium, iridium and tin dioxides, TiO₂, VO₂, RuO₂, IrO₂, and SnO₂, respectively. The exchange correlation function is described using the local density approximation (LDA) and the generalized gradient approximation (GGA). The structural parameters of the dioxides are found to be in a fair agreement with experimental values and previous calculations. TiO₂ exhibits the maximum cohesive energy and RuO₂ exhibits the minimum, which is opposite to the trend of pure bulk metals. Titanium dioxide in the left of the periodic table exhibits an insulating behavior with an underestimated bandgap of 2 eV. As the d-band filling increases in VO₂, the energy bands shift by 3 eV from those of TiO₂ to cross the Fermi level and exhibit a metallic behavior with a pseudo gap to the right of the Fermi level. The energy bands coalescence in RuO₂ and IrO₂ exhibiting metallic behaviors. However, for a complete filled d-band SnO₂, the insulating behavior is retrieved. The distortion of the octahedrons in the rutile structure lifts the degeneracy of the e_g orbitals causing further splittings.     

Modification of electronic properties during adsorption of conjugate organic molecules on the surface of polycrystalline SnO<Subscript>2</Subscript>

The modification of the electronic structure during adsorption of ultrathin copper phthalocyanine (CuPc) and 3, 4, 9, 10 perylene-tetracarboxylic-dianhydride (PTCDA) coatings on the surface of polycrystalline tin dioxide is traced. Auger electron spectroscopy is employed to find changes in the atomic composition of the surface. It is found with the help of low-energy electron total current spectroscopy using a testing beam of electrons with energies up to 30 eV that the total current spectra typical of organic films are formed when the thickness of the coating being deposited is 2–7 nm. The formation of an interface layer 1.5–2.0 nm in thickness is detected, in which the intensity of the structure of the total current spectra decreases and the effect of interaction of PTCDA molecules with the SnO₂ surface is manifested.     

Highly conducting and crystalline doubly doped tin oxide films fabricated using a low-cost and simplified spray technique

Doubly doped (simultaneous doping of antimony and fluorine) tin oxide films (SnO₂:Sb:F) have been fabricated by employing an inexpensive and simplified spray technique using perfume atomizer from aqueous solution of SnCl₂ precursor. The structural studies revealed that the films are highly crystalline in nature with preferential orientation along the (2 0 0) plane. It is found that the size of the crystallites of the doubly doped tin oxide films is larger (69 nm) than that (27 nm) of their undoped counterparts. The dislocation density of the doubly doped film is lesser (2.08×10¹⁴ lines/m²) when compared with that of the undoped film (13.2×10¹⁴ lines/m²), indicating the higher degree of crystallinity of the doubly doped films. The SEM images depict that the films are homogeneous and uniform. The optical transmittance in the visible range and the optical band gap of the doubly doped films are 71% and 3.56 eV respectively. The sheet resistance (4.13 Ω/□) attained for the doubly doped film in this study is lower than the values reported for spray deposited fluorine or antimony doped tin oxide films prepared from aqueous solution of SnCl₂ precursor (without using methanol or ethanol).     

Synthesis and characterization of a polyaniline-modified SnO<Subscript>2</Subscript> nanocomposite

Polyaniline-modified tin oxide and tin oxide nanoparticles were synthesized using a solution route technique. The obtained pristine products were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and optical absorption spectroscopy. Thermogravimetric analysis results showed that the polyaniline-modified SnO₂ nanoparticles exhibit higher thermal stability than the SnO₂ nanoparticles. Scanning electron microscopy analysis on the as-synthesized powders showed spherical particle in the range of 50–100 nm.     

Effect of balanced and unbalanced magnetron sputtering processes on the properties of SnO2 thin films

A comparative study has been carried on the role of balanced magnetron (BM) and unbalanced magnetron (UBM) sputtering processes on the properties of SnO₂ thin films. The oxygen partial pressure, substrate temperature and deposition pressure were kept 20%, 700 °C and 30 mTorr, respectively and the applied RF power varied in the range of 150–250 W. It is observed that the UBM deposition causes significant effect on the structural, electrical and optical properties of SnO₂ thin films than BM as evidenced by X-ray diffraction, C-V, Spectroscopic Ellipsometer and Photoluminescence measurements. The value of band gap (E_g) of the films deposited at 150 W in UBM is found as E_g = 3.83 eV which is much higher than the value of E_g = 3.69 eV as observed in BM sputtering indicating that UBM sputtering results in good crystalline quality. Further, the C-V measurements of SnO₂ thin films deposited using UBM at high power 250 W show hysteresis with large flat band shift indicating that these thin films can be used for the fabrication of memory device. The observed results have been attributed to different mechanisms which exist simultaneously under unbalanced magnetron sputtering due to ion bombardment of growing SnO₂ thin film by energetic Ar+ ions.     

Studies on Structural,Morphological and Optical Properties of Chemically Deposited CdS<Subscript>1-x</Subscript>Se<Subscript>x</Subscript> Thin Films

The thin films of CdS_1-xSe_x were successfully deposited over glass substrates by chemical bath deposition technique. Cadmium acetate, thiourea and sodium selenosulfate were used as source materials for Cd²⁺, S^2? and Se^2? ions, while 2-mercaptoethanol was used as capping agent. The various deposition conditions such as precursor concentration, deposition temperature, pH and deposition time were optimized for the deposition of CdS_1-xSe_x thin films of good quality and the films were annealed at 200° and 300 °C. The structural, morphological, chemical and optical properties were examined by various characterization techniques and discussed in detail. The optical band gap of CdS_1-xSe_x thin film samples were estimated and found in the range from 2.11 to 1.79 eV for as-deposited and annealed thin films.     

Influence of Si substrate preparation on surface chemistry and morphology of L-CVD SnO2 thin films studied by XPS and AFM

Results of experimental studies of the influence of substrate preparation on the surface chemistry and surface morphology of the laser-assisted chemical vapour deposition (L-CVD) SnO₂ thin films are presented in this paper. The native Si(1 0 0) substrate cleaned by UHV thermal annealing (TA) as well as thermally oxidized Si(1 0 0) substrate cleaned by ion bombardment (IBA) have been used as the substrates. X-ray photoemission spectroscopy (XPS) has been used for the control of surface chemistry of the substrates as well as of deposited films. Atomic force microscopy (AFM) has been used to control the surface morphology of the L-CVD SnO₂ thin films deposited on differently prepared substrates. Our XPS shows that the L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit the same stoichiometry, i.e. ratio [O]/[Sn] = 1.30 as that of the layers deposited on Si(1 0 0) substrate previously cleaned by UHV prolonged heating. AFM shows that L-CVD SnO₂ thin films deposited on thermally oxidized Si(1 0 0) substrate after cleaning with ion bombardment exhibit evidently increasing rough surface topography with respect to roughness, grain size range and maximum grain height as the L-CVD SnO₂ thin films deposited on atomically clean Si substrate at the same surface chemistry (nonstoichiometry) reflect the higher substrate roughness after cleaning with ion bombardment.     

<Superscript>119</Superscript>Sn CEMS study of Sb doped SnO<Subscript>2</Subscript> film

Sb doped SnO₂ films prepared by DC sputtering and heating were characterized by ¹¹⁹Sn conversion electron Mössbauer spectrometry (CEMS). An asymmetric doublet was observed in the Mössbauer spectra of 1 %, 3 %, and 10 % Sb doped SnO₂ films. The peak ratios of doublets are considered to be due to the columnar crystal growth on the substrate. With the doping level of Sb, both the isomer shift (δ) and the quadrupole splitting (Δ) increased. After annealing, δ increased and Δ decreased for each sample. These results suggest the followings. The electron doping of the SnO₂ lattice by pentavalent Sb induces the increase of the electron density at the Sn^IV nucleus. The annealing process leads to more complete accommodation of the Sb dopant that results in more effective electron doping and therefore increasing isomer shift for tin. Simultaneously, the distortion of the lattice caused by Sb is relaxed and the quadrupole splitting decreases.     

Effect of solvent volume on the physical properties of undoped and fluorine doped tin oxide films deposited using a low-cost spray technique

Undoped and fluorine doped tin oxide films were deposited from starting solutions having different values of solvent volume (10-50 ml) by employing a low cost and simplified spray technique using perfume atomizer. X-ray diffraction studies showed that there was a change in the preferential orientation from (2 1 1) plane to (1 1 0) plane as the volume of the solvent was increased. The sheet resistance (R_sh) of undoped SnO₂ film was found to be minimum (13.58 KΩ/□) when the solvent volume was lesser (10 ml) and there was a sharp increase in R_sh for higher values of solvent volume. Interestingly, it was observed that while the R_sh increases sharply with the increase in solvent volume for undoped SnO₂ films, it decreases gradually in the case of fluorine doped SnO₂ films. The quantitative analysis of EDAX confirmed that the electrical resistivity of the sprayed tin oxide film was mainly governed by the number of oxygen vacancies and the interstitial incorporation of Sn atoms which in turn was governed by the impinging flux on the hot substrate. The films were found to have good optical characteristics suitable for opto-electronic devices.     

Electron microscopic investigation of the kinetics of the layer and island crystallization of amorphous V<Subscript>2</Subscript>O<Subscript>3</Subscript> films deposited by pulsed laser evaporation

An electron microscopic investigation was performed on the kinetics of the layer and island crystallization of amorphous V₂O₃ films deposited by pulsed laser evaporation of vanadium in an oxygen atmosphere. The crystallization was initiated by the action of an electron beam on an amorphous film in the column of a transmission electron microscope. The kinetic curves were plotted on the basis of a frame-by-frame analysis of the video recorded during the crystallization of the film. It was found that the layer crystallization of amorphous films is characterized by a quadratic dependence of the fraction of the crystalline phase x on the time t, whereas the island crystallization is described by an exponential dependence of x on t. The kinetic curves of island crystallization of amorphous films were analyzed on the basis of the α-version of the Kolmogorov model. For each type of crystallization, there are specific values of the dimensionless relative length unit δ₀, which is equal to the ratio of the characteristic length unit to the parameter characterizing the unit cell of the crystal. It was established that, for the layer crystallization, the relative length unit lies in the range δ₀ ~ 4300–4700, whereas for the fine-grained island crystallization, it amounts to δ₀ ~ 110.     

The study of optical properties of amorphous thin films of mixed oxides In<Subscript>2</Subscript>O<Subscript>3</Subscript>—SnO<Subscript>2</Subscript> system,deposited by co-evaporation

A discussion of optical properties of mixed oxides In₂O₃—SnO₂ system is presented. Film thickness, substrate temperature, composition (in molar %) and annealing have a profound effect on the structure and optical properties of these films. Initially the increase in band gap with the increase of SnO₂ content in In₂O₃ is due to the increase in carrier density as a result of donor electrons from tin. The decrease in band gap above the critical Sn content is caused by the defects formed by Sn atoms, which act as carrier traps rather than electron donors. The increase in band gap with film thickness is caused by the increase in free carrier density which is generated by (i) Sn atom substitution of In atom, giving out one extra electron and (ii) oxygen vacancy acting as two electrons donor. The decrease in band gap with substrate temperature and annealing is due either to the severe deficiency of oxygen, which deteriorate the film properties and reduce the mobility of the carriers, or to the formation of indium species of lower oxidation state (In²⁺).     

Effect of deposition time on structural and physical properties of Cu<Subscript>2</Subscript>CdSnS<Subscript>4</Subscript> thin films prepared by spray pyrolysis technique: experimental and ab initio study

Cu₂CdSnS₄ (CCdTS) thin films were synthesized using chemical spray pyrolysis deposition technique. The effect of various deposition times (20, 40, 60 min) on growth of these films was investigated. The as-synthesized Cu₂CdSnS₄ thin films were characterized by X-ray diffraction (XRD), ultraviolet–visible (UV–Vis) spectroscopy, Raman spectroscopy and Hall Effect measurements. The XRD pattern of Cu₂CdSnS₄ structured in stannite phase with preferential orientations along (112) planes. Raman spectrum revealed very strong peak at about 333 cm^?1. The films have the direct optical band gaps of 1.39–1.5 eV. The optimum hole mobility was found to be 3.212 × 10¹ cm² v^?1 s^?1 for the film deposited on 60 min. The electronic structure and optical properties of the stannite structure Cu₂CdSnS₄ were obtained by ab initio calculations using the Korringa–Kohn–Rostoker method combined with the Coherent Potential Approximation (CPA), as well as CPA confirms our results.     

Effect of process parameters on surface morphology and characterization of PE-ALD SnO2 thin films for gas sensing

Tin dioxide (SnO₂) thin films were deposited by plasma enhanced-atomic layer deposition (PE-ALD) on Si(1 0 0) substrate using dibutyl tin diacetate (DBTA) ((CH₃CO₂)₂Sn[(CH₂)₃-CH₃]₂) as precursor. The process parameters were optimized as a function of substrate temperature, source temperature and purging time. It is observed that the surface phenomenon of the thin films was changed with film thickness. Atomic force microscopy (AFM) images and X-ray diffraction (XRD) pattern were used to observe the texture and crystallanity of the films. The films deposited for 100, 200 and 400 cycles were characterized by XPS to determine the chemical bonding properties. XPS results reveal that the surface dominant oxygen species for 100, 200 and 400 cycles deposited films are O₂⁻, O⁻ and O²⁻, respectively. The 200 cycles film has exhibited highest concentration of oxygen (O⁻) species before and after annealing. Conductivity studies revel that this film has best adsorption strength to the oxygen ions forming on the surface. The sensor with 200 cycles SnO₂ thin film has shown highest sensitivity to CO gas than other films. A correlation between the characteristics of Sn3d_5/2 and O1s XPS spectra before and after annealing and the electrical behavior of the SnO₂ thin films is established.     

Work function of sol-gel indium tin oxide (ITO) films on glass

Indium tin oxide (ITO) films (physical thickness, 250-560 ± 25 nm) were deposited on soda lime silica (SLS) glass and silica layer coated (∼200 nm physical thickness) SLS glass substrates by sol-gel technique using alcohol based precursors containing different In:Sn atomic percentages, namely, 90:10, 70:30, 50:50, 30:70. Cubic phase of In₂O₃ was observed up to 50 at.% Sn while cassiterite SnO₂ phase was observed for 70 at.% Sn. Work function of the films was evaluated from inelastic secondary electron cutoff of ultraviolet photoelectron spectroscopy (UPS) energy distribution curve (EDC) obtained under two experimental conditions (i) as-introduced (ii) after the cleaning of the surface by sputtering. Elemental distribution and the presence of oxygen containing contaminant and carbon contaminant of the samples were done by XPS analysis under same conditions. The work function changed little due to the presence of surface contaminants. It was in the range, 3.9-4.2 eV (±0.1 eV).