Kinetics characterization of the oxidation of Cu thin films at low temperature by using sheet resistance measurement

Film sheet resistance measurement was developed to obtain the oxidation kinetics of Cu thin films in the nanometer range. Cu thin films with smooth and homogenous surfaces were prepared by vacuum evaporation. Oxidation behaviour of Cu thin films at low temperatures from 180 °C to 260 °C in dry air has been studied. The results show that oxidation of Cu thin film follows a parabolic rate law with a considerable low activation energy of 0.57 eV, which is much lower than that reported for bulk Cu and the thick film. The observed rapid oxidation phenomenon may be attributed to the fast diffusion mechanism dominated by the defect-related grain boundary diffusion in thin films. PACS 07.50.-e; 73.61.-r; 82.65.+r     

Properties of Eu-doped zinc oxide thin films grown on glass substrates by radio-frequency magnetron sputtering

Eu-doped ZnO (EZO) thin films were prepared on glass substrates at various growth temperatures by radio-frequency magnetron sputtering. The properties of deposited thin films showed a significant dependence on the growth temperature. The preferential growth orientation of all the thin films was occurred along the ZnO (002) plane. The maximum crystallite size and the minimum average transmittance in the wavelength range of 450–1100 nm were observed for the EZO thin film deposited at 25 °C. A red shift of the optical band gap was observed in the growth temperature range of 25–300 °C. The highest figure of merit, an index for evaluating the performance of transparent conducting thin films, was obtained at 200 °C of growth temperature. These results indicated that the high-quality EZO film was obtained at a growth temperature of 200 °C.     

Crystallization behaviour of PZT in multilayer heterostructures

Microstructural and electrical properties of PZT (lead zirconate titanate) thin films prepared by sol-gel techniques at annealing temperatures in the range from 550°C to 900°C are studied. Perovskite (Pe) grain nucleation in PZT film starts but not completes at 550°C. Along with formation of round Pe (111) grains on the Pt (111) interface, the film contains small Pe and pyrochlore (Py) grains. Films annealed at the temperatures higher than 600°C demonstrate column structure of Pe grains, the amount of Py inclusions reduces with the annealing temperature and practically disappears at 700°C. An increase of annealing temperature leads to enhancement of (100) Pe orientation as a result of Ti diffusion on the Pt surface. Polarization decreases with the annealing temperature (maximum at 600°C), whereas permittivity increases up to the annealing temperature of 750°C.     

Low-temperature performance of thin solid electrolyte cell based on MoO3-doped Bi2O3

Improvement of low-temperature performance of oxygen sensor was studied by preparing a thin film of 15 μm thickness. Melt-quenched Bi₂O₃ film doped with 16 mol% MoO₃ was used as an electrolyte after HF treatment. Impedance measurements were carried out in the frequency range DC-100 KHz. Resistance of electrolyte in the form of thin film (110ω) was negligibly small compared with the overall resistance of the cell (287 Kω) at 350°C. Oxygen/air concentration cell was constructed and the cell performance was measured at 350 and 300°C. Transference number close to unity and rapid response were observed at 350°C, however the cell showed a long response time of about 3 min at 300°C.     

Diffusion of nickel in single- and polycrystalline Cr2O3

Chromia protective layers are formed on many industrial alloys to prevent corrosion by oxidation. Their role is to limit the inward diffusion of oxygen and the outward diffusion of cations. A number of chromia-forming alloys contain nickel as a component, such as steels, FeNiCr and NiCr alloys. To ascertain if chromia is a barrier to outward diffusion, nickel diffusion in chromia was studied in both single crystals and polycrystals in the temperature range 900–1100°C at an oxygen pressure of 10^?4 atm (argon + 100 ppm O₂). A nickel film of ～35 nm thick was deposited on the chromia surface and, after diffusing treatment, nickel penetration profiles were established by secondary ion mass spectrometry (SIMS). Two diffusion domains appear in polycrystals, the first domain is assigned to bulk diffusion and the second is due to diffusion along grain boundaries. For the bulk diffusion domain and diffusion in single crystals, using a solution of Fick's second law for diffusion from a thick film, bulk diffusion coefficients were determined at 900 and 1000°C. At the higher temperature, a solution of Fick's second law for diffusion from a thin film could be used. For the second domain in polycrystals, Le Claire's model allowed the grain boundary diffusion parameter (αD _gb δ) to be established. Nickel bulk diffusion does not vary significantly according to the microstructure of chromia. The activation energy of grain boundary diffusion is slightly greater than the activation energy of bulk diffusion, probably on account of segregation phenomena. Nickel diffusion was compared with cationic self-diffusion and with literature data on Fe and Mn heterodiffusion in the bulk and along grain boundaries. All results were analyzed in relation to the oxidation process of stainless steel.     

Study of field emission and dielectric properties of AlN films prepared by DC sputtering technique at different substrate temperatures

Nanocrystalline AlN thin films were prepared via DC sputtering technique at different substrate temperature. The crystal orientation and particle size of aluminum nitride thin films were investigated by XRD analysis. Study indicated that the sample contained pure phase hexagonal AlN nanoparticles with a single peak corresponding to the (100) planes. The peak at 665 cm⁻¹ in the FTIR spectrum of film was assigned to the LO phonon of hexagonal AlN. The particle size of the film, prepared at substrate temperature 200°C was about 9.5 nm, as investigated by atomic force microscope. Field emission study indicated that it can be used as a good field emitter. Turn-on field (E_to) of 15.02 V/μm was observed for the AlN films synthesized at substrate temperature 200°C. Dielectric constant of the AlN film was found nearly independent of frequencies in the measured frequency range 1 KHz to 1 MHz, i.e. in the audio frequency range. The values of dielectric constant (ε) were 10.07, 9.46 and 8.65 for the film prepared at 70°C, 150°C and 200°C, respectively, at frequency 1 KHz.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Modelling the voltammetric study of intercalation in a host structure: application to lithium intercalation in RuO2

Intercalation process kinetics have been studied theoretically for the case of potential sweep voltammetry. The influence of the thickness (or the particle radius) of the “host” material and the potential sweep rate has been determined between the limits of thin film diffusion and semi-infinite diffusion for a reversible process. Experimental data have been obtained with the cell: RuO₂/LiClO₄-PEO/Li. The theoretical results have been used to calculate the diffusion coefficient of lithium in the “host” structure RuO₂ at 80°C, giving an approximate value of 1.6 × 10^?11 cm² s^?1     

Highly frequency-, temperature-, and bias-stable dielectric properties of 500 °C processed Bi2SiO5 thin films with low dielectric loss

Excellent dielectric frequency, bias, and temperature stability of bismuth silicate (Bi₂SiO₅, BSO) thin films with a low dielectric loss has been obtained in this study. The thin films were prepared on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method at a relatively low annealing temperature of 500 °C. The BSO films have a preferred growth along (200) orientation with dense fine-grained surface morphology. The dielectric constant and dielectric loss of the thin film annealed at 500 °C are 57 and 0.01, respectively, at 100 kHz, with little change between 1 kHz and 100 kHz and in the bias electric field range between −250 kV/cm and 250 kV/cm, indicating that the thin film exhibits a low dielectric loss as well as excellent frequency and bias field stability. The dielectric-temperature measurements confirmed that the BSO thin film annealed at 500 °C also has good temperature stability between 150 K and 450 K. Our results suggest that the BSO thin films have potential applications in the next-generation integrated capacitors.     

In-process ZnO thin films alloying during pulsed laser deposition

Alloyed ZnO:Al thin films were prepared by a pulsed laser deposition by the altering of two pure targets (ZnO and Al) during the deposition process. Two deposition temperatures (?197 °C and 400 °C) were applied and differences of diffusion dynamics were compared. As-grown layered films were annealed and aluminium distribution was homogenized. The results revealed that the amorphous structure (samples grown at ?197 °C) of ZnO provide more positive conditions for efficient Al diffusion in comparison with crystalline structure (samples grown at 400 °C). A detailed investigation by SIMS depth profiling confirmed a homogeneous chemical composition of annealed and recrystallized films which exhibited a porous nature and wurtzite crystalline structure.     

On the preparation of CuInSe<Subscript>2</Subscript> thin films via two‒stage selenization

A two-stage selenization method for preparing CuInSe₂ thin films in a carrier-gas (nitrogen) flow is developed. The dependences between the morphology and structure of CuInSe₂ thin films and the selenization temperature are studied via electron microscopy and X-ray diffraction analysis. It is demonstrated that the film incorporates copper and indium selenides in the temperature range 300°C ≤ T < 400°C and a stoichiometric film with ordered chalcopyrite is formed at Т = 400°С. The possible mechanism whereby a CuInSe₂ thin film is generated with the participation of selenization centers, namely, Cu₂Se and In₂Se₃ grains, is discussed.     

The effect of different ambient gases, pressures, and substrate temperatures on TiO2 thin films grown on Si(100) by laser ablation technique

Pure titanium dioxide (TiO₂) thin films were deposited on single-crystal Si(100) substrates by laser ablation. We investigated the effects of ambient gas (O₂ or Ar), pressures, and substrate temperatures on film quality. From the annealing experiment of the deposited TiO₂ thin film under Ar or O₂ ambient gas, we see the chemical effect of ambient gas on film quality. The crystallinity of the deposited TiO₂ thin film is best at 700 °C in the substrate temperature range attempted, 400-700 °C, and at pressures of 0.1 Torr and below. The rutile phase is dominant under most experimental conditions. Only under very extreme conditions did we obtain a thin film of the anatase phase.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Thermal recrystallization of physical vapor deposition based germanium thin films on bulk silicon (100)

We demonstrate a simple, low‐cost, and scalable process for obtaining uniform, smooth surfaced, high quality mono‐crystalline germanium (100) thin films on silicon (100). The germanium thin films were deposited on a silicon substrate using plasma‐assisted sputtering based physical vapor deposition. They were crystallized by annealing at various temperatures ranging from 700 °C to 1100 °C. We report that the best quality germanium thin films are obtained above the melting point of germanium (937 °C), thus offering a method for in‐situ Czochralski process. We show well‐behaved high‐κ /metal gate metal–oxide–semiconductor capacitors (MOSCAPs) using this film. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thickness dependent optical properties of titanium oxide thin films

TiO₂ thin films of different thickness were prepared by the Electron Beam Evaporation (EBE) method on crystal silicon. A variable angle spectroscopic ellipsometer (VASE) was used to determine the optical constants and thickness of the investigated films in the spectral range from 300 to 800 nm at incident angles of 60°, 70°, and 75°, respectively. The whole spectra have been fitted by Forouhi–Bloomer (FB) model, whose best-fit parameters reveal that both electron lifetime and band gap of TiO₂ thin film have positive correlation to the film thickness. The refractive indices of TiO₂ thin film increase monotonically with an increase in film thickness in the investigated spectral range. The refractive index spectra of TiO₂ thin films have maxima at around 320 nm and the maxima exhibit a marginally blue-shift from 327.9 to 310.0 nm with an increase in film thickness. The evolution of structural disorder in the TiO₂ thin film growth can be used to explain these phenomena.     

Carbon anode thin films for lithium batteries

This paper describes a simple method to create carbon anode films for potential applications to the research field of lithium batteries. Carbon films were prepared using DC magneton sputtering with post-annealing process in the range from room temperature (RT) to 700 °C. Half cells assembled with lithium foils as the counter electrode and 1 M LiPF₆ in EC:DMC (1:1 v/v) electrolytic solution was used to evaluate the discharging capacity of prepared anode thin films. We showed that carbon film deposited at RT can be more suitable for an anode material than that of higher temperature annealed films above 400 °C. A variety of analysis methods including X-ray diffraction spectrometry (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were utilized to evaluate the defect density of the films; for example, the more defects on the film were identified when the carbon film was treated at a low temperature such as RT. It is envisioned that DC magnetron-sputtering with optimized process conditions can be useful for fabricating carbon based film anodes.     

Effect of annealing on structural and optical properties of diamond-like nanocomposite thin films

The annealing effect on structural and optical properties of the Diamond-like Nanocomposite (DLN) thin film deposited on glass substrate by Plasma Assisted Chemical Vapor Deposition (PACVD) method has been investigated. The films were annealed at temperature ranging from 300 to 600 °C, with 100 °C interval for 9 minutes by rapid thermal process (RTP) under vacuum. The structural changes of the annealed films have been studied using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Scanning Electron Microscope (SEM), and optical parameters have been determined using transmittance and reflectance spectra in UV-UIS-NIR range. The result shows that the refractive index increases gradually from 1.79 to 2.84 with annealing temperature due to out-diffusion of H by breaking Si–H and C–H bond leads to Si–C bond, i.e. more cross linking structure. In higher temperature range, graphitization also enhanced the refractive index. However, the optical band gap at up to 400 °C initially increases from 3.05 to 3.20 eV and then decreases due to graphitization. The film has a great potential to be used as anti-reflection coating (ARC) on silicon-based solar cell.     

KTN thin films prepared by pulsed laser deposition on transparent single crystal quartz(100)

Using the Sol-Gel method to produce the KTN ultrafine powder and the sintering technique with K2O atmosphere to prepare KTN ceramics as the targets instead of the KTN single crystal, highly oriented KTN thin films were produced on the transparent single crystal quartz (100) by the pulsed laser deposition (PLD). Since the thermal stress sustained by the quartz is relatively small, the limit temperature of the quartz substrates (300℃) is much lower than that of the P-Si substrates (560℃); the prepared thin film is at amorphous state. Increasing the pulsed laser energy density in the process incorporated with annealing the film after deposition at different temperatures converts the amorphous films into crystal. The optimal pulsed laser energy density and annealing temperature were 2.0 J/cm2 and 600℃, respectively. A discussion was made to understand the mechanism of film production at relatively low substrate temperature by PLD and effects of the annealing temperatures on the forming of the perovskite p     

Photoluminescence characteristics of ZnGa2O4 thin films prepared by chemical solution method

Zinc gallate (ZnGa₂O₄) thin film phosphors have been formed on ITO glass substrates by a chemical solution method with starting materials of zinc acetate dihydrate, gallium nitrate hydrate and 2-methoxiethanol as a solution. The thin films were firstly dried at 100 °C and fired at 500 °C for 30 min and then, annealed at 500 °C and 600 °C for 30 min under an annealing atmosphere of 3% H₂/Ar. XRD patterns of the thin film phosphors showed (311) and (220) peak indicating ZnGa₂O₄ crystalline phase in which all the (311) peaks of the film phosphors synthesized on ITO glass and soda-lime glass revealed high intensity with increasing annealing temperature from 500 °C to 600 °C. The ZnGa₂O₄ thin film phosphors represented marked change in AFM surface morphologies according to an annealing temperature under an annealing atmosphere (3% H2/Ar). The film phosphor, annealed at 600 °C, showed the embossed pattern with relatively regular spacing in AFM surface morphology. The ZnGa₂O₄ thin film phosphors formed on ITO glass, which were annealed at different temperatures and showed distinctive spectra with peak wavelengths of 434 nm and 436 nm in the blue emission region.     

Effect of thickness on the stability of transparent conducting impurity‐doped ZnO thin films in a high humidity environment

The resistivity of transparent conducting Al‐ and Ga‐doped ZnO (AZO and GZO) thin films prepared with a thickness in the range from 20 to 200 nm on glass substrates at a temperature below 200 °C was found to increase with exposure time when tested in a high humidity environment (air at 90% relative humidity and 60 °C). The resistivity stability (resistivity increase) was considerably affected by the thin film thickness. In particular, thin films with a thickness below about 50 nm were very unstable. The increase in resistivity is interpreted as carrier transport being dominated by grain boundary scattering resulting from the trapping of free electrons due to oxygen adsorption on the grain boundary surface. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)