On Proton Conductivity in Porous and Dense Yttria Stabilized Zirconia at Low Temperature

The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.     

近距离升华法制备Bi催化纳米晶CdTe薄膜的表征

采用近距离升华法(Close-Spaced-Sublimation,CSS)引入Bi催化剂成功制备出了具有纳米线、近阵列排布的纳米棒等形貌的纳米晶CdTe薄膜.并利用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见分光光度计等研究了薄膜的结构、表面形貌和光学性能.讨论了CdTe纳米结构可能的生长机制.

Abstract：

Bi-catalyzed nanocrystalline CdTe films were prepared by close spaced sublimation (CSS) technique successfully.These nanocrystalline CdTe films had surface appearance of nanowires or a similar array arrangement nanorod.The structure,the surface topograph and the optical properties of these films were studied using X-ray diffraction(XRD),scanning electron microscopy(SEM) and ultroviolet-visible (UV-VIS) spectrophotometer.And the possible growth mechanisms of these nanostructures were discussed.     

纳米晶体TiO2多孔膜的制备

采用电子束蒸发方法成功制备了用于光电变色器件的纳晶多孔结构TiO2薄膜，借助于俄歇仪(AES)和原子力显微镜(AFM)分析了制备条件对薄膜的表面形貌、粒径大小及化学计量比的影响。最终给出了制备光电变色器件用纳晶多孔结构TiO2薄膜的工艺参数。     

Crystallization and Grain Growth Kinetics for Precipitation‐Based Ceramics: A Case Study on Amorphous Ceria Thin Films from Spray Pyrolysis

The introductory part reviews the impact of thin film fabrication, precipitation versus vacuum‐based methods, on the initial defect state of the material and microstructure evolution to amorphous, biphasic amorphous‐nanocrystalline, and fully nanocrystalline metal oxides. In this study, general rules for the kinetics of nucleation, crystallization, and grain growth of a pure single‐phase metal oxide thin film made by a precipitation‐based technique from a precursor with one single organic solvent are discussed. For this a complete case study on the isothermal and non‐isothermal microstructure evolution of dense amorphous ceria thin films fabricated by spray pyrolysis is conducted. A general model is established and comparison of these thin film microstructure evolution to kinetics of classical glass‐ceramics or metallic glasses is presented. Knowledge on thermal microstructure evolution of originally amorphous precipitation‐based metal oxide thin films allows for their introduction and distinctive microstructure engineering in devices‐based on microelectromechanical (MEMS) technology such as solar cells, capacitors, sensors, micro‐solid oxide fuel cells, or oxygen separation membranes on Si‐chips.     

Co基磁性薄膜的快速循环纳米晶化

采用独特的快速循环纳米晶化技术(RRTA)对直流磁控溅射制备的非晶CoNbZr软磁膜进行纳米晶化。研究了不同的纳米晶化工艺条件下,薄膜的微观结构和软磁性能。结果表明,CoNbZr软磁薄膜晶粒细化到30 nm,RRTA晶化方法可有效地控制CoNbZr薄膜的软磁性能。     

Careful Choices in Low Temperature Ceramic Processing and Slow Hydration Kinetics Can Affect Proton Conduction in Ceria

Low-temperature ceramic proton conductors such as ceria are important for applications ranging from sensors and resistive switches to new devices like implantable solid-oxide glucose fuel cells. Spray pyrolysis offers a promising fabrication route for proton-conducting ceria, with direct liquid-to-solid synthesis and control over crystallinity and grain size. To date, there are conflicting reports on ceria's proton conduction mechanism, particularly whether the interior contributes to proton conduction or transport occurs exclusively along a surface water layer. In this work, proton conductivity is observed in sprayed ceria thin films at 125 °C and below. Post-annealed films exhibit higher conductivity than as-deposited films of 3.3 × 10⁻⁵ S cm⁻¹ at 25 °C, which is comparable to previous reports and ascribed to the increase in crystallinity and grain size by post-annealing. This indicates that the interior of ceria in fact contributes to proton conduction. Remarkably slow hydration kinetics of ceria are observed, with time-dependent conductivity equilibrating to 9.53 × 10⁻⁶ S cm⁻¹ after up to 76 h. This implies kinetics may have suppressed proton conduction in previous studies, explaining the strong fluctuations in reports to date. Slow protonation kinetics must be considered when designing functional ceria ceramics, for example, in electrochemical bio-energy conversion, sensing or neuromorphic computing.     

Band-Like Charge Transport in Phytic Acid-Doped Polyaniline Thin Films

We explore the charge transport properties of phytic acid (PA) doped polyaniline thin films prepared by the surfactant monolayer-assisted interfacial synthesis (SMAIS). Structural and elemental analysis confirms the inclusion of PA in the thin films and reveals a progressive loss of crystallinity with the increase of PA doping content. Charge transport properties are interrogated by time-resolved terahertz (THz) spectroscopy. Notably, independently of doping content and hence crystallinity, the frequency-resolved complex conductivity spectra in the THz region can be properly described by the Drude model, demonstrating band-like charge transport in the samples and state-of-the-art charge carrier mobilities of ≈1 cm²V⁻¹s⁻¹. A temperature-dependent analysis for the conductivity further supports band-like charge transport and suggest that charge carrier mobility is primarily limited by impurity scattering. This work highlights the potential of PA doped polyaniline for organic electronics.     

Ionic Space‐Charge Depletion in Lithium Fluoride Thin Films on Sapphire (0001) Substrates

Lithium fluoride thin films with various thicknesses have been grown on c‐plane sapphire substrates by radio‐frequency sputtering. The thin films are granular with a preferential [111] orientation of the grains. Thickness‐dependent measurements allow the separation of bulk and interface conductions. The normalized conductance decreases linearly with decreasing LiF layer thickness with a negative extrapolated intercept. DC polarization, AC impedance spectroscopy and electromotive force measurement indicate depletion of lithium ion vacancies as majority charge carriers and hence a negative space‐charge potential. A generalized Mott–Schottky approach within the model of heterogeneous doping fully explains the entire boundary defect chemistry.     

RF反应磁控溅射纳米晶ZnO薄膜的XRD和XPS研究

采用RF反应磁控溅射沉积ZnO薄膜,沉积完成后对薄膜进行氧气氛下的原位退火处理。薄膜的结晶状况和化学成分分别采用XRD和XPS进行分析。结果表明,该薄膜为结晶性能良好的纳米晶薄膜,具有高度的C轴取向性。薄膜的主要成分为ZnO,不存在金属态Zn。采用文中的工艺方法可获得较高质量的纳米晶ZnO薄膜。     

N-Al共掺ZnO薄膜的p型传导特性

利用直流反应磁控溅射技术制得N-Al共掺的p型ZnO薄膜，N2O为生长气氛．利用X射线衍射（XRD），Hall实验，X射线光电子能谱（XPS）和光学透射谱对共掺ZnO薄膜的性能进行研究．结果表明，薄膜中Al的存在显著提高了N的掺杂量，N以N-Al键的形式存在．N-Al共掺ZnO薄膜具有优良的p型传导特性.当Al含量为0.15wt%时，共掺ZnO薄膜的电学性能取得最优值，载流子浓度为2.52e17cm－3，电阻率为57.3Ω·cm，Hall迁移率为0.43cm2/(V·s)．N-Al共掺p型ZnO薄膜具有高度c轴取向，在可见光区域透射率高达90%．     

BST溶胶及其纳米晶铁电薄膜特性研究

考察了在溶胶-凝胶(Sol-Gel)工艺中化学添加剂对钛酸锶钡(BST)溶胶的粒度分布的影响。通过对化学添加剂的优选,制备出具有优异电性能的BST薄膜。X-射线衍射(XRD)表明在Pt/Cr/SiO2/Si衬底上制备的BST薄膜具有完整的钙钛矿结构,AFM表面形貌显示BST薄膜表面致密、平整、无裂纹,平均晶粒尺寸约50 nm。漏电流测试表明BST薄膜在0~9 V的外加偏压下始终保持着较低的漏电流,在外加偏压为8.8 V时,漏电流密度为2.9×10-6A/cm2。     

Assessing Antisite Defect and Impurity Concentrations in Bi2Te3 Based Thin Films by High‐Accuracy Chemical Analysis

In Bi₂Te₃‐based materials charge‐carrier densities are determined by antisite defects and controlling these defects is a key issue for thermoelectric and topological insulator materials. Bi‐Te thin films with high‐quality thermoelectric properties are deposited using a nano‐alloying approach by molecular beam epitaxy (MBE) and sputtering. The in‐plane transport properties are measured at room temperature as a function of charge‐carrier density. High‐accuracy chemical analysis by wavelength‐dispersive X‐ray spectrometry (WDX) is applied for the first time to these Bi₂Te₃‐based thin films. The acquisition conditions for WDX spectrometry are established using Monte Carlo simulations for the electron trajectories, which guarantees a high lateral resolution and rules out stray radiation generated in the substrate of the films. In contrast to energy‐dispersive X‐ray spectrometry (EDX), which is usually applied, WDX offers unprecedented accuracy for measuring antisite defect concentrations and thus has a high impact on improving the quality of thin films. The charge‐carrier densities are calculated from the WDX results according to the point‐defect model of Miller and Li and the thermopower and electrical conductivity are calculated for different charge‐carrier densities by solving the linearized Boltzmann transport equation. A good quantitative agreement is found for the dependence of the thermopower on stoichiometry, whereas the electrical conductivity is sensitively affected by contaminants.     

PECVD法制备纳米晶硅薄膜的研究进展

简要介绍了纳米晶硅薄膜的微结构表征方法,重点讨论了PECVD制备方法中工艺参数对薄膜结构的影响,并探讨了氢在薄膜形成和生长中的作用。通过优化氢稀释率、衬底温度、反应气压、激励功率和激发频率等工艺参数可提高纳米晶硅薄膜的晶化率并改善薄膜质量。结合喇曼光谱、X射线衍射谱、傅里叶红外光谱和高分辨透射电镜等表征方法可深入研究薄膜形成机理,对进一步探索薄膜光电特性有重要意义。分析了等离子体化学气相沉积(PECVD)制备方法中各工艺参数对薄膜质量和沉积速率的影响,指出其存在的问题,并探寻了今后的研究方向。     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

功能薄膜在薄膜电致发光显示技术中的应用

薄膜电致发光(thin film electroluminescence,简称TFEL或EL)显示器件,具有全固化、主动发光、重量轻、视角大、反应速度快、使用温度范围广等诸多优点,有着广泛的应用前景。TFEL器件的结构中包括了多种功能薄膜的应用,器件性能的好坏决定于各种功能薄膜的合理选择及其制备工艺。本文对TFEL器件中的功能薄膜进行了介绍。     

Scalable Oxygen‐Ion Transport Kinetics in Metal‐Oxide Films: Impact of Thermally Induced Lattice Compaction in Acceptor Doped Ceria Films

In this paper, we focus on the effect of processing‐dependent lattice strain on oxygen ion conductivity in ceria based solid electrolyte thin films. This is of importance for technological applications, such as micro‐SOFCs, microbatteries, and resistive RAM memories. The oxygen ion conductivity can be significantly modified by control of lattice strain, to an extent comparable to the effect of doping bulk ceria with cations of different diameters. The interplay of dopant radii, lattice strain, microstrain, anion‐cation near order and oxygen ion transport is analyzed experimentally and interpreted with computational results. Key findings include that films annealed at 600 °C exhibit lattice parameters close to those of their bulk counterparts. With increasing anneal temperature, however, the films exhibited substantial compaction with lattice parameters decreasing by as much as nearly 2% (viz, Δd_{600–1100 °C}: –1.7% (Sc⁺³) > –1.5% (Gd⁺³) > –1.2% (La⁺³)) for the annealing temperature range of 600–1100 °C. Remarkably 2/3^rd of the lattice parameter change obtained in bulk ceria upon changing the acceptor diameter from the smaller Sc to larger La, can be reproduced by post annealing a film with fixed dopant diameter. While the impact of lattice compaction on defect association/ordering cannot be entirely excluded, DFT computation revealed that the main effect appears to result in an increase in migration energy and consequent drop in ionic conductivity. As a consequence, it is clear that annealing procedures should be held to a minimum to maintain the optimum level of oxygen ion conductivity for energy‐related applications. Results reveal also the importance to understand the role of electro‐chemo‐mechanical coupling that is active in thin film materials.     

金刚石薄膜和类金刚石薄膜

本文介绍了金刚石薄膜和类金刚石薄膜的制备与薄膜性能分析方法,也介绍了它们的应用前景。本文给出了华北光电所研究类金刚石薄膜的结果。     

Voltage‐Controlled Nonstoichiometry in Oxide Thin Films: Pr0.1Ce0.9O2−δ Case Study

While the properties of functional oxide thin films often depend strongly on oxygen stoichiometry, there have been few means available for its control in a reliable and in situ fashion. This work describes the use of DC bias as a means of systematically controlling the stoichiometry of oxide thin films deposited onto yttria‐stabilized zirconia substrates. Impedance spectroscopy is performed on the electrochemical cell Pr_0.1Ce_0.9O_2?δ (PCO)/YSZ/Ag for conditions: T = 550 to 700 °C, pO ₂ = 10^?4 to 1 atm, and ΔE = ‐100 to 100 mV. The DC bias ΔE is used to control the effective pO ₂ or oxygen activity at the PCO/YSZ interface. The non‐stoichiometry (δ) of the PCO films is calculated from the measured chemical capacitance (C_chem ). These δ values, when plotted isothermally as a function of effective pO ₂, established, either by the surrounding gas composition alone, or in combination with applied bias, agree well with each other and to predictions based on a previously determined defect model. These results confirm the suitability of using bias to precisely control δ of thin films in an in situ fashion and simultaneously monitor these changes by measurement of C_chem . Of further interest is the ability to reach effective pO ₂s as high as 280 atm.     

Suitability of Raman Spectroscopy for Assessing Anisotropic Strain in Thin Films of Doped Ceria

A protocol for characterizing relaxation of anisotropic strain in thin films of 10 mol% Eu‐ or Sm‐doped ceria is described. The method is based on comparison of Raman spectra and X‐ray diffraction patterns from substrate‐supported films, displaying in‐plane compressive strain (initial state), with analogous data from 2 mm diameter self‐supported films (i.e., membranes), prepared by partial substrate removal (final state). These membranes are found to be relaxed, i.e., approximately unstrained, but with increased unit cell volume. The effective (i.e., 2‐state) Grüneisen parameter of the F_2g Raman active mode for these films is calculated to be 0.4 ± 0.1, which is ≈30% of the literature value for the corresponding ceramics under isostatic pressure. On this basis, it is found that the observed red‐shift of the F_2g mode frequency following isothermal strain relaxation of the doped ceria thin films cannot be determined solely by the increase in average unit cell volume. The study presented here may shed light on the suitability of Raman spectroscopy as a technique for characterizing strain in lanthanide‐doped ceria thin films.