Mixed conductivity in nanocrystalline highly acceptor doped cerium oxide thin films under oxidizing conditions

We report on the investigation of 10 mol% gadolinium-doped cerium oxide thin films of various microstructures prepared by pulsed laser deposition. Depending on substrate, growth conditions and hence microstructure, the electric conductivity values vary considerably by several orders of magnitude. Remarkably, in the sample with the highest grain boundary density, we even have evidence of substantial electronic conductance under oxidizing conditions despite the large acceptor level. This possibly surprising result can be explained by an increased space charge potential at the grain boundaries in combination with the small grain size of 10 nm that leads to an enrichment of excess electrons while the ion conduction is simultaneously blocked by vacancy-depleted regions.     

On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide

Conductivity measurements were performed on microcrystalline and nanocrystalline ceria (undoped and doped) in dry as well as wet atmosphere. Below 200-250 °C, the nanocrystalline samples exhibit an enhanced total conductivity under wet conditions, which increases with decreasing temperature. In addition, thermo-gravimetric analysis revealed a strong water uptake below 200 °C. DC-polarization measurements confirm the ionic character of conductivity in the nanocrystalline samples at low temperatures. The role of both grain boundaries and residual porosity on the enhanced conductivity below 200 °C is discussed.     

Rh-promoted methanol decomposition on cerium oxide thin films

Methanol adsorption and reaction have been studied on Rh-deposited cerium oxide thin films under UHV conditions using temperature-programmed desorption and synchrotron soft X-ray photoelectron spectroscopy. The methanol behavior was examined as a function of the Ce oxidation state, methanol exposure, and Rh particle size and coverage. When Rh nanoparticles were deposited on the ceria films, methanol decomposed on Rh to CO and H below 200 K. H atoms recombined and desorbed between 200 and 300 K. CO evolved from Rh deposited on fully oxidized ceria between 400 and 500 K. However, on reduced ceria films, the CO on Rh further decomposed to atomic C. Methanol adsorbed on the ceria films deprotonated to form methoxy as the only intermediate on the surface. This methoxy decomposed and desorbed as CO and H2 at higher temperatures regardless of the ceria oxidation state. Compared with the methanol reaction on Rh-free ceria thin films, formaldehyde formation from methoxy was completely suppressed after Rh deposition. Our results indicate that Rh can promote the decomposition of methoxy adsorbed on the ceria and that decomposition of methoxy intermediates occurred at the metal/oxide interfaces. On the other hand, the reduced ceria can promote total methanol decomposition on Rh.     

Unusual enhancement in electrical conductivity of tin oxide thin films with zinc doping

Electrical conductivity of SnO(2)-based oxides is of great importance for their application as transparent conducting oxides (TCO) and gas sensors. In this paper, for the first time, an unusual enhancement in electrical conductivity was observed for SnO(2) films upon zinc doping. Films with Zn/(Zn + Sn) reaching 0.48 were grown by pulsed spray-evaporation chemical vapor deposition. X-Ray diffraction (XRD) shows that pure and zinc-doped SnO(2) films grow in the tetragonal rutile-type structure. Within the low doping concentration range, Zn leads to a significant decrease of the crystallite size and electrical resistivity. Increasing Zn doping concentration above Zn/(Zn + Sn) = 0.12 leads to an XRD-amorphous film with electrical resistivity below 0.015 ? cm at room temperature. Optical measurements show transparencies above 80% in the visible spectral range for all films, and doping was shown to be efficient for the band gap tuning.     

Sol-gel processing and properties of cerium doped Barium Strontium Titanate thin films

A stock solution sol-gel based method for making Barium Strontium Titanate (BST) thin films has been developed. A modified titanium alkoxide was combined with a barium and/or strontium inorganic salt in methoxyethanol and ethylene glycol to form the solution. The effect of chemistry on the stability of this BST solution is discussed. The crystallization temperature of 700–725°C for rapid thermally processed films dropped by 100°C using cerium doping. The permittivity for undoped films was 250 and doping by 3 at. % Ce increased the dielectric constant by 20%. A remanent polarization of approximately 0.5 C/cm² and coercive field of 28 kV/cm were measured for the undoped films. The leakage current densities were <10 nA/cm² at E=60 kV/cm and improved for cerium concentrations up to 3 at. %. The charge storage density was 50 fF/m² at 200 kV/cm and the DC breakdown voltage was 300 kV/cm for Ce doped films.     

Gamma-irradiation effects on the electrical conductivity of pure and Co-doped MgAl2O4 spinel

The electrical conductivity of pure and Co-doped MgAl₂O₄ spinels was measured at 700–1100 K. The results of both pure and doped spinels were found to be fitted with an exponential expression with two different activation-energy parameters, in two ranges of temperature. The effect of -irradiation on the electrical conductivity of pure and doped spinels was also studied. The kinetic parameters of the isothermal annealing of the induced irradiation damages in the spinels were determined. All the results were found to be consistent with the ionic conduction which was suggested to be due to the motion of the cation vacancy.     

Gamma-irradiation effects on the electrical conductivity of pure and Cu-doped Fe3O4 spinel

The electrical conductivity and IR-spectra of pure and Cu-doped Fe₃O₄ spinels were measured at 300–1000 K. Two breaks in the conductivity-temperature curves have been observed for all investigated pure and doped samples. One of these two breaks were found near the Curie point of the investigated spinel. The electrical conduction in -irradiated and non-irradiated pure and Cu-doped Fe₃O₄ occurred by a hopping mechanism due to a fast electron exchange between Fe²⁺ and Fe³⁺-ions present on octahedral sites. The Seebeck-voltage of the irradiated and non-irradiated pure and Cu-doped samples has been measured. The effect of -irradiation on the conductivity values //, activation energy and type of defects was discussed.     

GISAXS view of vanadium/cerium oxide thin films and influence of lithium intercalation

An examination of structural modifications, induced by mixing vanadium and cerium oxides and by the introduction of lithium in vanadium and mixed vanadium/cerium oxide films, was performed using synchrotron sourced grazing incidence small-angle X-ray scattering. Samples were sol-gel-derived films, deposited by a dip-coating technique. An analysis of the scattering data, acquired by a two-dimensional detection system, is based on the comparison of the surface and bulk characteristics of the film. The trend of estimated structural modifications is supported by the results of previous investigations on a different length scale, performed by atomic force microscopy.     

Enhancement of optical conductivity in the ultra-violet region of Cs doped ZnO sol gel thin films

Nano crystalline cesium (Cs) doped ZnO thin films were deposited on glass substrate by sol gel spin coating method with 1–3 mol.% doping concentration and different annealing temperatures. The deposited films were characterized by X-ray diffraction (XRD), Hall Effect, Photoluminescence (PL) and UV–Visible studies. XRD measurements reveal that all the samples abound in the wurtzite structure with polycrystalline nature. An increase in crystalline size from 19.60 to 44.54 nm is observed with the increase of doping concentration. Electrical conductivity of Cs doped ZnO films were observed from Hall effect measurements and the maximum carrier concentration obtained is 7.35 × 10¹⁸ cm^?3. The near band emission (384 nm) peak intensity increases with the increase of Cs doping concentration and a maximum intensity 55,280 was observed for CZ3 film from PL spectrum. Also a low energy near infrared (NIR) emission peak centered at 1.62 eV appears for the Cs doped ZnO films. The average transmission of CZ film is 88 % and the absorption edge is red shifted with the increase of Cs doping concentration and also the optical conductivity increases in the UV region.     

Speciation of activators in electroluminescent thin films: an EXAFS study of cerium and terbium doped strontium sulfide

Extended X-ray absorption fine structure (EXAFS) was used to determine the local structure of the luminescent centers in Tb³⁺ and Ce³⁺ -doped strontium sulfide thin films deposited by Atomic Layer Epitaxy (ALE). The rare earths were observed to enter mainly the substitutional sites but at the same time a part of the atoms form RES clusters (RE = rare earth). The presence of both substitutional sites and RES clusters has been observed for the first time in this study for rare earths in II–VI compounds. Received: 9 February 1998 / Revised: 22 May 1998 / Accepted: 29 May 1998     

Speciation of activators in electroluminescent thin films: an EXAFS study of cerium and terbium doped strontium sulfide

Extended X-ray absorption fine structure (EXAFS) was used to determine the local structure of the luminescent centers in Tb³⁺ and Ce³⁺ -doped strontium sulfide thin films deposited by Atomic Layer Epitaxy (ALE). The rare earths were observed to enter mainly the substitutional sites but at the same time a part of the atoms form RES clusters (RE = rare earth). The presence of both substitutional sites and RES clusters has been observed for the first time in this study for rare earths in II–VI compounds.     

CO-sensing properties of undoped and doped tin oxide thin films prepared by electron beam evaporation

Undoped thin films of tin oxide and those doped with indium oxide and nickel oxides were deposited by electron beam evaporation. The effects of the film thickness and preparation conditions (films prepared with or without the presence of oxygen environment during deposition) on the optical and carbon monoxide sensing properties of the films were studied. The films were characterized using X-ray diffraction and X-ray photoelectron spectroscopy and optical spectroscopy techniques. All the films were found to be amorphous. It was found that the sensitivity of the films to CO increased with the thickness and the porosity of the films. It was found that their selectivity to CO gas relative to CO₂ and SO₂ gases could be improved upon doping the films with indium (or nickel) oxide.     

Investigation of O7+ swift heavy ion irradiation on molybdenum doped indium oxide thin films

Molybdenum (0.5 at%) doped indium oxide thin films deposited by spray pyrolysis technique were irradiated by 100 MeV O⁷⁺ ions with different fluences of 5×10¹¹, 1×10¹² and 1×10¹³ ions/cm². Intensity of (222) peak of the pristine film was decreased with increase in the ion fluence. Films irradiated with the maximum ion fluence of 1×10¹³ ions/cm² showed a fraction of amorphous nature. The surface microstructures on the surface of the film showed that increase in ion fluence decreases the grain size. Mobility of the pristine molybdenum doped indium oxide films was decreased from ～122 to 48 cm²/V s with increasing ion fluence. Among the irradiated films the film irradiated with the ion fluence of 5×10¹¹ ions/cm² showed relatively low resistivity of 6.7×10^?4 Ω cm with the mobility of 75 cm²/V s. The average transmittance of the as-deposited IMO film is decreased from 89% to 81% due to irradiation with the fluence of 5×10¹¹ ions/cm².     

Non‐contact evaluation of the electrical conductivity of thin metallic films by eddy current microscopy

An eddy current microscopy technique to evaluate the electrical conductivity of thin metallic films in a non‐contact manner is reported. A narrow track formed in an approximately 100 nm thick Au film was prepared, and a Co–Cr coated magnetic tip was driven to oscillate above the track both with and without current passing through the track. Despite the absence of current, the electromagnetic interaction between the tip and the stray magnetic field from the track gave rise to a phase delay in the probe. This was due to an eddy current being induced within part of the track. Moreover, measurements of the phase change in the probe oscillation for different metallic films with thicknesses of about 100 nm found this to be proportional to the electrical conductivity of the film. Finally, the electrical conductivity of an Al film was evaluated using the eddy current microscopy technique. Copyright © 2012 John Wiley & Sons, Ltd.     

n-型掺杂反式聚乙炔导电性能各向异性研究

根据固体能带理论，用量子化学ＥＨＭＯ／ ＣＯ 方法，计算了高取向反式聚乙炔及其ｎ－ 型掺杂态（掺杂Ｌｉ，Ｎａ，Ｋ） 的二维能带结构，首次从能隙与带宽角度讨论了聚乙炔经ｎ－ 型掺杂呈现的导电性能的各向异性．研究表明：平行和垂直于分子链方向的电导率之比（σ∥／σ⊥） 取决于这两个方向上能隙和带宽的大小；掺杂后σ∥／σ⊥下降，其原因是掺杂剂在聚乙炔链间架起了一个“浮桥”，使链间耦合作用增强．理论计算与实验结果一致     

Photocatalysis and hydrophilicity of doped TiO2 thin films

TiO(2) thin films were prepared using the dip-coating method with a polymeric sol including additives such as Al, W, and Al+W to examine two major properties: photocatalysis and hydrophilicity. W-doped films showed the best photocatalytic efficiency, while Al-doped film was poorer than undoped samples. However, good hydrophilicity in terms of saturation contact angle and surface conversion rate was found in Al- and (Al+W)-mixed-doped films. It was found that deep electron-hole traps and high surface acidity of W-doped TiO(2) thin film were the major factors in high photocatalytic efficiency. In addition, low surface acidities of Al- and (Al+W)-doped films provided better hydrophilicity than W-doped ones. However, the amount of [Ti(3+)] point defects on the surface was another major factor, probably the most important, in getting the best hydrophilicity. Conclusively, it seemed that many parts of the photocatalysis mechanism depend more on bulk-related properties than do those of hydrophilicity, which can be defined as an interfacial (surface) or near-surface-restricted process.     

Relaxation phenomena and electrical conductivity of some polymeric films

Electrical conduction in sandwich samples of polyacrylonitrile (PAN) or copolymer of acrylonitrile with butadiene between silver has been studied, measuring the dependence of current on the applied field, temperature and time. The conduction mechanism depends on the polymer type. A polarization contribution is suggested in the conduction mechanism at high temperatures, besides Schottky emission in the case of PAN and the simple carrier jump model in the case of NBR at room temperature. The temporal current variation is explained in terms of dipole orientation. The mobility and charge carrier density are influenced by the applied field, temperature and film thickness.