Studies on PEO-based sodium ion conducting composite polymer films

A sodium ion conducting composite polymer electrolyte (CPE) prepared by solution-caste technique by dispersion of an electrochemically inert ceramic filler (SnO₂) in the PEO–salt complex matrix is reported. The effect of filler concentration on morphological, electrical, electrochemical, and mechanical stability of the CPE films has been investigated and analyzed. Composite nature of the films has been confirmed from X-ray diffraction and scanning electron microscopy patterns. Room temperature d.c. conductivity observed as a function of filler concentration indicates an enhancement (maximum) at 1–2 wt% filler concentration followed by another maximum at ∼10 wt% SnO₂. This two-maxima feature of electrical conductivity as a function of filler concentration remains unaltered in the CPE films even at 100 °C (i.e., after crystalline melting), suggesting an active role of the filler particles in governing electrical transport. Substantial enhancement in the voltage stability and mechanical properties of the CPE films has been noticed on filler dispersion. The composite polymer films have been observed to be predominantly ionic in nature with t _ion ∼ 0.99 for 1–2 wt% SnO₂. However, this value gets lowered on increasing addition of SnO₂ with t _ion ∼ 0.90 for 25 wt% SnO₂. A calculation of ionic and electronic conductivity for 25 wt% of SnO₂ film works out to be ∼2.34 × 10⁻⁶ and 2.6 × 10⁻⁷ S/cm, respectively.     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Synthesis and characterization of electron beam evaporated LiCoO<Subscript>2</Subscript> thin films

LiCoO₂ thin films were prepared by electron beam evaporation technique using LiCoO₂ target with Li/Co ratio 1.1 in an oxygen partial pressure of 5 × 10⁻⁴ mbar. The films prepared at substrate temperature T _s < 573 K were amorphous in nature, and the films prepared at T _s > 573 K exhibited well defined (104), (101), and (003) peaks among which the (104) orientation predominates. The X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) data revealed that the films prepared in the substrate temperature range 673–773 K are nearly stoichiometric. The grain size increases with an increase of substrate temperature. The Co–e_g absorption bands, are empty and their peak position lies at around 1.7 eV above the top to the Co–t_2g bands. The fundamental absorption edge was observed at 2.32 eV. The films annealed at 1,023 K in a controlled oxygen environment exhibit (104) out plane texture with large grains. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

Determination of the optimal parameters for the fabrication of ZnO thin films prepared by spray pyrolysis method

In this work, ZnO thin films have been prepared by spray pyrolysis deposition method on the glass substrates. The effect of deposition parameters, such as deposition rate, substrate temperature and solution volume has been studied by X-ray diffraction (XRD) method, UV–Vis–NIR spectroscopy, scanning electron microscopy (SEM), and electrical measurements. The XRD patterns indicate polycrystalline wurtzite structure with preferred direction along (0 0 2) planes. Thin films have transparency around 90% in the visible range. The optical band gap was determined at 3.27 eV which did not change significantly. Evolution of electrical results containing the carriers’ density, sheet resistance and resistivity are in agreement with structural results. All the results suggest the best deposition parameters are: deposition rate, R = 3 ml/min, substrate temperature, T _s = 450°C and thickness of the thin films t = 110–130 nm.     

Application of MEH-PPV/SnO<Subscript>2</Subscript> bilayer as hybrid solar cell

The effects of oxygen content in the sputtering gas on the crystallographic and optoelectronic properties of 210 nm-thick Zr–doped In₂O₃ (Zr–In₂O₃) films by rf magnetron sputtering were initially studied. The results of X-ray diffraction show that the Zr–In₂O₃ films grown on glass substrates exhibit mixed crystallographic orientations. Moreover, the Zr–In₂O₃ film grown in an Ar atmosphere promotes the appearance of crystallographic orientation of (222). The surface of the Zr–In₂O₃ film becomes rougher as the oxygen content in the sputtering gas decreases; the current images obtained by conductive atomic force microscopy reveal that the surfaces of the Zr–In₂O₃ films exhibit a distribution of coexisting conducting and nonconducting regions, and that the area of the nonconducting surface increases with the oxygen content in the sputtering gas. The resistivity is minimized to 3.51×10⁻⁴ Ω cm when the Zr–In₂O₃ film is grown in an Ar atmosphere and the average transmittance in the visible light region is ∼85%. The optical band gap decreases as the oxygen content in the sputtering gas increases.     

Al2O3 thin films by plasma-enhanced chemical vapour deposition using trimethyl-amine alane (TMAA) as the Al precursor

2 O₃ thin films by plasma-enhanced chemical vapour deposition (PECVD) using trimethyl-amine alane (TMAA) as the Al precursor. The thin films were deposited on both Si and quartz silica (SiO₂) substrates. Deposition rates were typically 60 Å min^-1 keeping the TMAA temperature constant at 45 °C. The deposited Al₂O₃ thin films were stoichiometric alumina with low carbon contamination (0.7–1.3 At%). The refractive index ranged from 1.54 to 1.62 depending on the deposition conditions. The deposition rate was studied as a function of both the RF power and the substrate temperature. The structure and the surface of the deposited Al₂O₃ thin films were studied using X-ray diffraction, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Received: 20 May 1997/Accepted: 12 June 1997     

An extreme change in structural and optical properties of indium oxynitride deposited by reactive gas-timing RF magnetron sputtering

The indium oxynitride (InON) films were achieved by reactive RF magnetron sputtering indium target which has the purity of 99.999% with a novel reactive gas-timing technique. The structural, optical and electrical properties in a series of polycrystalline InON films affected by gas-timing of reactive N₂ and O₂ gases introduced to the chamber were observed. The X-ray photoelectron spectroscopy revealed that the oxygen content in thin films that compounded to indium and nitrogen, which increased from 10% in indium nitride (InN) to 66% in indium oxide (In₂O₃) films. The X-ray diffraction peaks show that the phase of deposited films changes from InN to InON and to In₂O₃ with an increasing oxygen timing. The hexagonal structure of InN films with predominant (0 0 2) and (0 0 4) orientation was observed when pure nitrogen is only used as sputtering gas, while InON and In₂O₃ seem to demonstrate body-center cubic polycrystalline structures depending on gas-timing. The surface morphologies investigated from atomic force microscope of deposited films with varying gas-timing of O₂:N₂ show indifferent. The numerical algorithm method was used to define the optical bandgap of films from transmittance results. The increasing oxygen gas-timing affects extremely to the change of crystallinity phase from InN to InON and to In₂O₃, the increase of optical bandgap from 1.4 to 3.4 eV and the rise of sheet resistance from 15 Ω/□ to insulator.     

Characteristics of nitrogen-incorporated silicon oxycarbide films and plasmas for plasma enhanced chemical vapor deposition with TMOS/N2/NH3

Plasma enhanced chemical vapor deposition of nitrogen-incorporated silicon oxycarbide thin films obtained from the gas mixture of TMOS (tetramethoxysilane), N₂, and NH₃ is studied. The effects of the TMOS to N₂ pressure ratio on the properties of the film and the plasma are investigated. The deposited films are analyzed by in situ ellipsometry, ex situ Fourier transform infrared spectroscopy (FTIR), and by X-ray photoelectron spectroscopy (XPS). The plasma is characterized by using optical emission spectroscopy (OES). The mass spectra of the constituents in the plasma are obtained by quadrupole mass spectroscopy. The correlation between the film properties and the plasma characteristics is explained wherever possible. As the partial pressure of N₂ is decreased, the refractive index begins to decrease, reaches a minimum, and then saturates. The FTIR absorption bands are observed from about 850 to 1000 cm⁻¹ and from 1000 to 1250 cm⁻¹, and can be attributed to the formation of a nitrogen-incorporated silicon oxycarbide thin film. The variation of the refractive index is discussed in relationship with the deposition rate, the OES spectra, the mass spectra of the plasma, the film composition obtained by XPS, and FTIR spectra.     

Structural and optoelectronic properties of amorphous GaN thin films

Amorphous gallium nitride (a-GaN) thin films were deposited on glass substrate by electron beam evaporation technique at room temperature and high vacuum using N ₂ as carrier gas. The structural properties of the films was studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was clear from XRD spectra and SEM study that the GaN thin films were amorphous. The absorbance, transmittance and reflectance spectra of these films were measured in the wavelength range of 300–2200 nm. The absorption coefficient spectral analysis in the sharp absorption region revealed a direct band gap of E _g = 3:1 eV. The data analysis allowed the determination of the dispersive optical parameters by calculating the refractive index. The oscillator energy E ₀ and the dispersion energy E _d, which is a measure of the average strength of inter-band optical transition or the oscillator strength, were determined. Electrical conductivity of a-GaN was measured in a different range of temperatures. Then, activation energy of a-GaN thin films was calculated which equalled E _a = 0:434 eV.     

Optical properties of the HfO2 ? x N x and TiO2 ? x N x films prepared by ion beam sputtering

Optical characteristics of the HfO_{2 − x} N _x and TiO_{2 − x} N _x films obtained by reactive ion beam sputtering have been investigated by spectral ellipsometry. The chemical composition of the films was determined using X-ray photoelectron spectroscopy. The nitrogen content in the oxynitride films (determined by the N₂/O₂ ratio in the gas mixture during synthesis) reached ≈9 at % for TiO_{2 − x} N _x and ≈ 6 at % for HfO_{2 − x} N _x . It is found that the dispersion relations n(λ) and k(λ) for the TiO_{2 − x} N _x films change from those characteristic of titanium dioxide to those typical of titanium nitride with an increase in the nitrogen content from 0 to ≈9 at %. The optical parameters of the HfO_{2 − x} N _x films depend weakly on the nitrogen content in the range 0–6 at %. Original Russian Text ? V.V. Atuchin, V.N. Kruchinin, A.V. Kalinkin, V.Sh. Aliev, S.V. Rykhlitskiĭ, V.A. Shvets, E.V. Spesivtsev, 2009, published in Optika i Spektroskopiya, 2009, Vol. 106, No. 1, pp. 77–82.     

The development of the physical and electrical characteristics of multi-layer TiO<Subscript>2</Subscript>–W–TiO<Subscript>2</Subscript> thin films

In this study, two different thin films, TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films (W, tungsten), are prepared by RF magnetron sputtering onto glass substrates. The crystal structure, morphology, and transmittance of TiO₂ and TiO₂–W–TiO₂ multi-layer thin films are investigated by X-ray diffraction, SEM, and UV-Vis spectrometer, respectively. The amorphous, rutile, and anatase TiO₂ phases are observed in the TiO₂ thin film and in the TiO₂–W–TiO₂ multi-layer thin films. The deposition of tungsten as the inter-layer will have large effect on the transmittance and phase ratios of rutile and anatase phases in the TiO₂–W–TiO₂ multi-layer thin films. The crystal intensities of amorous TiO₂ will decrease as the tungsten is used as the middle layer in the multi-layer structure. The band gap energy values of TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films are evaluated from (αhν)^1/2 versus energy plots, and the calculated results show that the energy gap decreases from 3.21 eV (TiO₂ thin film) to 3.08∼3.03 EV (TiO₂–W–TiO₂ multi-layer thin films).     

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.     

XPS and SIMS characterisation of TiOxNy solar absorber films

Solar thermal collectors have been prepared with thin TiO_xN_y films deposited using ion beam assisted deposition, on Si and Cu substrates. The films are amorphous and x and y were controlled by altering the O₂/N₂ ratio in the gas source. After annealing at temperatures of 200 – 400 °C, films have been depth profiled using Secondary Ion Mass Spectrometry. Profiles reveal the degradation of the film, particularly for films on Cu substrates, by migration of the substrate atoms through the films, to the sample surface. In general, films with x<1 and y>1 show improved temperature stability, ultimately at the expense of a reduced transmission window. Contrary to previous suggestions in the literature, the degradation mechanism initially involves the formation of a nitrogen rich phase, rather than an oxide at the film surface. On copper substrates, the nature of the films and of this phase, formed by diffusion of the substrate atoms, have been investigated by X-ray photoelectron spectroscopy (XPS). These investigations reveal complex behaviour in the early stages of film failure, with the suggestion that the initial films, at least near the surface, are two phase, and the reaction layer mixes the TiO_xN_y with some Ti replacement by ions from the Cu substrate.     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000     

Sol–gel derived ferroelectric Bi3.15Nd0.85Ti3O12 thin films of predominant 100/010/119 orientation deposited both on Nb-doped (011)SrTiO3 and on (011)SrRuO3/(011)SrTiO3

Ferroelectric Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films of predominant 100/010/119 orientation were grown through a cheap and simple sol–gel process both on Nb-doped (011)SrTiO₃ and on (011)SrRuO₃/(011)SrTiO₃. Using rapid heating rates during crystallization, films containing 28% (100)/(010)-oriented grains plus 19% (119)-oriented grains were obtained on SrRuO₃/SrTiO₃, while 30% (100)/(010)- and 18% (119)-oriented grains were obtained on Nb:SrTiO₃. The films consist of columnar grains and 90° a–b domains exist in large BNdT grains. The BNdT thin films exhibit excellent ferroelectric and dielectric properties with a remanent polarization 2P_r=39.2 μC/cm² and a dielectric constant ε_r=184.5. PACS 77.80.Fm; 77.80.Dj; 68.60.Wm; 68.55.Jk; 68.37.Lp     

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.     

Probing the effect of nitrogen gas on electrical conduction phenomena of ZnO and Cu-doped ZnO thin films prepared by spray pyrolysis

Zinc oxide (ZnO) and Cu-doped ZnO (CZO) thin films were prepared on borosilicate glass substrates by spray pyrolysis technique. The X-ray diffraction study revealed that Cu doping caused a reduction in crystallite size. AFM study showed an increase in roughness with doping. This is attributed to the aggregation of particles to form clusters. From transmission electron microscopy analysis, the particle size is measured to be in the range 30–65 nm (average particle size 48 nm) for undoped ZnO, whereas it is in the range 24–56 nm (average particle size 40 nm) for CZO film. The electrical resistivity of the thin films was investigated in the presence of air as well as N₂ mixed air at different temperatures in the range 30–270 °C. The change in resistivity properties was explained on the basis of conduction phenomena within the grain along with the grain boundaries as well as Cu- and N₂-induced defect states. The thermal activation energy of ZnO was found to be in the range 0.04–0.7 eV and dependent on Cu doping and N₂ level in air.     

Optical and electronic properties of NiFe2O4 and CoFe2O4 thin films

We report the optical and electronic properties of the inverse spinel ferrite NiFe₂O₄ and CoFe₂O₄ thin films deposited on single crystal sapphire by electron beam deposition. We carried out variable temperature (78–500 K) transmittance measurements on the thin films to investigate the optical properties and electronic structures of these ferrites. The absorption spectra of both NiFe₂O₄ and CoFe₂O₄ thin films show insulating characters with Ni (Co) d to d on-site transitions below 3 eV. The energy bands above 3 eV are mainly due to the O 2p to Fe 3d charge transfer transitions. The observed electronic transitions have been assigned based on the first principles calculations and comparisons with structurally similar Ni and Co-containing compounds. The Co²⁺ d to d transition in the CoFe₂O₄ thin film shows a strong temperature dependence, likely due to the spin-charge coupling effect.