Bi_(1.5)Mg_(1.0)Nb_(1.5)O_7薄膜的介电损耗机理研究

采用射频磁控溅射法在Al2O3基片上沉积了铌酸铋镁(Bi1.5Mg1.0Nb1.5O7,BMN)薄膜,研究了不同退火条件下BMN薄膜的介电损耗机理。结果表明,充分的退火能够减小氧空位缺陷密度,并降低介电损耗。氧气气氛下退火能够有效补偿BMN薄膜中的氧空位,使得介电损耗进一步降低。这说明氧空位导致的带电缺陷损耗是BMN薄膜材料主要的介电损耗机制。此外,BMN薄膜中也存在晶界损耗机制。     

Nondestructive Characterization of Graphene Defects

An effective method is reported for oxidizing graphene/copper film in which air oxidation of the underlying copper film occurs through the grain boundary lines of graphene without oxidizing graphene. This oxidation is realized by partially immersing the graphene/copper film in sodium chloride solution. Electrons generated during etching of the graphene/copper film in electrolyte diffuse into the film in contact with air, which eventually enhances air oxidation of copper through the graphene layer. While the graphene layer acts as a protective layer against oxidation of the copper film, oxidation of the underlying Cu film near graphene grain boundary lines is observed by optical microscopy. This observation could be attributed to the selective diffusion of oxygen radicals through isolated defects and graphene grain boundaries. The process involves no appreciable oxidation of the graphene layer including the graphene grain boundary, as confirmed by use of detailed Raman and X‐ray photoelectron spectroscopy.     

TA17钛合金板材对接焊缝显微组织表征研究

利用电子背散射衍射（EBSD）取向成像技术,对TA17钛合金板材对接焊缝的显微组织、晶界特征和晶体学取向进行表征研究。结果表明其母材呈典型的轧制变形组织,且由α相和少量晶间分布的β相组成,大部分为小角度晶界,为基面织构。热影响区晶粒呈梯度长大分布。在焊接热传导下,热影响区晶粒得到回复和长大,大角度晶界逐渐增多。其织构继承了母材织构的特点,只是织构密度有所减弱。熔区为粗大的α＇马氏体相交织成的网篮状组织,大部分为大角度晶界,织构比较漫散。     

Bi_2Cu_(0.1)V_(0.9)O_(5.35-δ)固态电解质化学溶液法的合成与性能

用化学溶液法合成了Bi2Cu0.1V0.9O5.35-δ(BICUVOX.10)材料,研究了材料的物相、表面形貌和电学特性.BICUVOX.10薄膜具有室温稳定的高电导γ相.在LaNiO3/Si衬底上,BICUVOX.10薄膜具有(001)择优取向,平均晶粒大小约为200nm.低频范围的介电损耗来源于氧空位的短程扩散,BICUVOX.10薄膜主要表现为晶粒电导特性.BICUVOX.10薄膜中氧离子电导激活能约为0.3 eV,氧离子电导率约为5×10-2S.cm-1.     

An investigation of band profile around the grain boundary of Cu(InGa)Se2 solar cell material by scanning probe microscopy

We performed scanning tunneling spectroscopy on an as‐grown Cu(InGa)Se₂ (CIGS) thin film and photo‐assisted Kelvin probe force microscopy on a CIGS solar cell. From these measurements, we estimated the band profile around the grain boundaries (GBs). The results indicate both downward bending of the conduction band edge and broadening of the band gap near GBs. We can therefore conclude that photo‐generated electrons and holes are easily separated by the built‐in field near GBs, and consequently their recombination at the GBs should be suppressed. Copyright © 2011 John Wiley & Sons, Ltd.     

Thickness‐Dependent Structural Evolutions and Growth Models in Relation to Carrier Transport Properties in Polycrystalline Pentacene Thin Films

Thickness‐dependent crystal structure, surface morphology, surface energy, and molecular structure and microstructure of a series of polycrystalline pentacene films with different film thickness ranging from several monolayers to the several hundred nanometers have been investigated using X‐ray diffraction (XRD), atomic force microscopy (AFM), contact angle meter, and Raman spectroscopy. XRD studies indicate that thin film polymorphs transformation behaviours are from the orthorhombic phase to the thin‐film phase and then to the triclinic bulk phase as measured by the increased tilt angle (θ_tilt) of the pentacene molecule from the c‐axis toward the a‐axis. We propose a growth model that rationalizes the θ_tilt increased along with increasing film thickness in terms of grain size and surface energy varying with film growth using AFM combined with contact angle measurements. The vibrational characterizations of pentacene molecules in different thickness films were investigated by Raman spectroscopy compared to density functional theory calculations of an isolated molecule. In combination with XRD and AFM the method enables us to distinguish the molecular microstructures in different thin film polymorphs. We proposed a methodology to probe the microscopic parameters determining the carrier transport properties based on Davydov splitting and the characteristics of aromatic C–C stretching modes in Raman spectra. When compared to the triclinic bulk phase at a high thickness, we suggest that the first few monolayer structures located at the dielectric surface could have inferior carrier transport properties due to weak intermolecular interactions, large molecular relaxation energy, and more grain boundaries.     

Structure of [110] tilt grain boundaries in zirconia bicrystals

Cubic stabilized zirconia bicrystals with [110] symmetric tilt grain boundaries were fabricated by diffusion bonding of two single crystals with the composition of ZrO2-9.6mol%Y2O3. The structures of symmetric tilt small angle grain boundary and two types of symmetric tilt sigma3 grain boundaries with different grain boundary planes were observed by transmission electron microscopy (TEM). High-resolution transmission electron microscopy (HREM) observations clarified that the [110] small angle tilt grain boundary consists of periodic array of b = a/2[110] type edge dislocations. This result is consistent with Frank's dislocation model for small angle grain boundary. HREM observation also revealed that the 70.5 degrees sigma3 grain boundary shows atomically coherent grain boundary structure with the boundary plane of [111], while the 109.5 degrees sigma3 grain boundary accompanies grain boundary facets taking [111]/[115] asymmetric grain boundary plane. Because of the very low surface energy of [111] plane and/or high lattice matching of [111] and [115] type planes, the grain boundary faceting may be preferred in spite of increasing grain boundary area to about 6%. TEM-energy-dispersive X-ray spectroscopy (EDS) analyses were performed on both sigma3 grain boundaries, and the segregation of yttrium ions to the boundaries was detected in both cases. The amount of segregation is about the same in both sigma3 boundaries. It can be concluded that the segregation of yttrium ions to sigma3 grain boundary exists in cubic zirconia.     

Grain boundary diffusion mechanisms in metals

In recent years it has become well established that fast diffusion along grain boundaries plays a key role in many important metallurgical processes including cases where net mass is transported along boundaries which act as sources and/or sinks for the fluxes of atoms. In addition, considerable advances have been made in understanding grain boundary structure, and new techniques have become available for studying kinetic phenomena in grain boundaries. This lecture will attempt to review our current knowledge of the atomistic mechanisms responsible for these grain boundary diffusion phenomena. Relevant aspects of the structure of grain boundaries and the point and line defects which may exist in grain boundaries are described first. The important experimental observations are then discussed. Diffusion models are then taken up, and it is concluded that the atomic migration occurs by a point defect exchange mechanism which, in at least the vast majority of boundaries in simple metals, most likely involves grain boundary vacancies. The grain boundary sources and/or sinks required to support divergences in the atomic (vacancy) fluxes are grain boundary dislocations. Phenomena therefore occur which resemblethe Kirkendall Effect in the bulk lattice in certain respects. Additional topics are discussed which include effects of boundary structure on boundary diffusion and the question of whether or not boundary diffusion is faster along migrating than stationary boundaries.     

利用EBSD技术对690合金不同类型晶界处碳化物形貌的研究

利用扫描电子显微镜（SEM）、电子背散射衍射（EBSD）技术和取向成像显微（OIM）软件研究了Ni基690合金中不同类型晶界处碳化物的形貌。不同类型晶界处析出碳化物的形貌有很大区别,在孪晶的非共格界面（Σ3i）附近,棒状碳化物向两侧晶粒内部生长,而类似的棒状碳化物只向Σ9晶界一侧的晶粒内部生长。Σ3i与Σ9晶界附近的棒状碳化物的生长方向与基体晶粒的{111}面平行。晶界上析出的碳化物尺寸随着Σ值的升高而明显增大。在相同的腐蚀条件下,晶间腐蚀的痕迹随着Σ值的升高变得严重。     

Sb掺杂SnO2/SiO2纳米光学气敏薄膜的制备及其性质

采用溶胶凝胶(sol-gel)工艺制备了Sb掺杂SnO2/SiO2复合膜。通过X射线衍射(XRD)、傅立叶变换红外谱(FT-IR)及原子力显微镜(AFM)表征了薄膜样品的物相结构与表面形貌,利用紫外-可见光谱研究了复合薄膜光学特性．利用p-偏振光双面反射法对薄膜的气敏特性进行了测试。实验结果表明,薄膜中的晶粒具有纳米尺寸(～35nm)的大小．比表面积大,孔隙率高;薄膜的透光率高,可见光波段近95％;纳米Sb：SnO2：SiO2复合膜的气敏灵敏度高于纯SnO2薄膜及Sb掺杂的SnO2薄膜。     

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.     

Anomalous Oxidation States in Multilayers for Fuel Cell Applications

Significant recent interest has been directed towards the relationship between interfaces and reports of enhanced ionic conductivity. To gain a greater understanding of the effects of hetero‐interfaces on ionic conductivity, advanced analytical techniques including electron microscopy (TEM/STEM), electron energy loss spectroscopy (EELS), and secondary ion mass spectrometry (SIMS) are used to characterize CeO₂/Ce_0.85Sm_0.15O₂ multilayer thin films grown by pulsed laser deposition. High quality growth is observed, but ionic conductivity measured by impedance spectroscopy and ¹⁸O tracer experiments is consistent with bulk materials. EELS analysis reveals the unusual situation of layers containing only Ce(IV) adjacent to layers containing both Ce(III) and Ce(IV). Post oxygen annealing induced oxygen diffusion and mixed oxidation states in both layers, but only in the vicinity of low angle grain boundaries perpendicular to the layers. The implications of the anomalous behavior of the Ce oxidation states on the design of novel electrolytes for solid oxide fuel cells is discussed.     

Applications of STEM-EELS to complex oxides

In this chapter we will review a few examples of applications of atomic resolution aberration corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to complex oxide materials. These are most challenging systems where subtle changes in structure or chemistry may result in colossal responses in macroscopic physical behavior. Here, we will review how atomic resolution compositional mapping can be achieved in manganite thin films and single crystals, highlighting the importance of considering artifacts during quantification. Besides, minor changes in near edge fine structure may take place when the crystalline environment, and hence nearest neighbor configuration, is modified. These can also be tracked by atomic resolution EELS, as will be shown through the study of binary Fe oxides. Also, examples regarding the study of distributions of point defects such as O vacancies in cobaltite thin films will be discussed. In these materials, a combination of epitaxial strain and defects may promote physical behaviors not present in bulk, such as the stabilization of unexpected spin state superlattices. Last, a study of extended defects such as dislocation lines will be reviewed. In particular, we will show how chemical segregation at dislocation cores in yttria-stabilized zirconia grain boundaries results in the generation of static O vacancies that affect the local electrostatic potential and hence, the macroscopic ionic conduction properties.     

Electronic properties of defects in polycrystalline dielectric materials

Grain boundaries have been implicated in current leakage and dielectric breakdown of CMOS devices. We calculate the electronic properties of oxygen vacancy defects near grain boundaries in the dielectric insulators MgO and HfO₂ using first principles methods. In both materials we find that oxygen vacancies favourably segregate to grain boundaries, in various charge states. Their electronic properties are different from their counterparts in the bulk. At increased concentrations, such defects at grain boundaries may play a key role in processes such as electron tunneling, charge trapping and dielectric breakdown in electronic devices.     

7150铝合金时效时晶界析出行为的研究

本文采用透射电子显微镜(TEM)、能谱分析(EDAX)对人工时效条件下晶界无析出带(PFZ)的演变规律进行研究.实验选用同一投影方向测量PFZ的宽度,结果表明PFZ的宽度对时效温度的敏感性远远高于对时效时间的敏感性.时效温度越高PFZ越宽,而在同一时效温度下PFZ的宽度并不随时效时间的延长而宽化.PFZ的宽度与相邻两个...     

Chemically Stable Pr and Y Co‐Doped Barium Zirconate Electrolytes with High Proton Conductivity for Intermediate‐Temperature Solid Oxide Fuel Cells

A chemically stable and highly proton‐conductive electrolyte is developed by partially substituting the Zr site of Y‐doped barium zirconate (BZY) with 10 mol% of Pr. Compared to BZY, BaZr_0.7Pr_0.1Y_0.2O_3‐δ (BZPY) shows improved sinterability as revealed by dilatometric measurements and scanning electron microscopy (SEM) analysis. Dense samples are obtained after sintering at 1500?C for 8 h. Moreover, BZPY shows good chemical stability in the wide range of fuel‐cell operating conditions. The larger density and the enhanced grain growth, compared to BZY, allow the volume content of grain boundaries, which generally show a high resistance for proton transport, to be reduced and, thus, a high proton conductivity can be achieved in the temperature range of interest for practical applications (above 10^?2 Scm^?1 at 600?C). The good sinterability, chemical stability, and high conductivity of the BZPY electrolyte enabled the fabrication of single‐cell prototypes based on a thin BZPY membrane by a simple and cost‐saving co‐pressing method. Electrochemical impedance spectroscopy (EIS) analysis performed during fuel‐cell tests under open‐circuit conditions confirms the good electrical performance of BZPY as electrolyte material. To improve the present fuel‐cell performance adapted cathode materials for this BZPY electrolyte need to be developed.     

Grain boundary segregation in multicrystalline silicon: correlative characterization by EBSD,EBIC, and atom probe tomography

This study aims to better understand the influence of crystallographic structure and impurity decoration on the recombination activity at grain boundaries in multicrystalline silicon. A sample of the upper part of a multicrystalline silicon ingot with intentional addition of iron and copper has been investigated. Correlative electron‐beam‐induced current, electron backscatter diffraction, and atom probe tomography data for different types of grain boundaries are presented. For a symmetric coherent Σ3 twin boundary, with very low recombination activity, no impurities are detected. In case of a non‐coherent (random) high‐angle grain boundary and higher order twins with pronounced recombination activity, carbon and oxygen impurities are observed to decorate the interface. Copper contamination is detected for the boundary with the highest recombination activity in this study, a random high‐angle grain boundary located in the vicinity of a triple junction. The 3D atom probe tomography study presented here is the first direct atomic scale identification and quantification of impurities decorating grain boundaries in multicrystalline silicon. The observed deviations in chemical decoration and induced current could be directly linked with different crystallographic structures of silicon grain boundaries. Hence, the current work establishes a direct correlation between grain boundary structure, atomic scale segregation information, and electrical activity. It can help to identify interface–property relationships for silicon interfaces that enable grain boundary engineering in multicrystalline silicon. Copyright © 2015 John Wiley & Sons, Ltd.     

Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin‐Film Electrodes on YSZ Electrolyte

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

Thin‐Film Electrodes: Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin Film Electrodes on YSZ Electrolyte (Adv. Funct. Mater. 3/2011)

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

Grain boundary mediated leakage current in polycrystalline HfO2 films

In this work, we combine conductive atomic force microscopy (CAFM) and first principles calculations to investigate leakage current in thin polycrystalline HfO₂ films. A clear correlation between the presence of grain boundaries and increased leakage current through the film is demonstrated. The effect is a result of a number of related factors, including local reduction in the oxide film thickness near grain boundaries, the intrinsic electronic properties of grain boundaries which enhance direct tunnelling relative to the bulk, and segregation of oxygen vacancy defects which increase trap assisted tunnelling currents. These results highlight the important role of grain boundaries in determining the electrical properties of polycrystalline HfO₂ films with relevance to applications in advanced logic and memory devices.