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1.
    
Pulsed Laser Deposition (PLD) was used to prepare thin films with the nominal composition La0.58Sr0.4Co0.2Fe0.8O3‐δ (LSCF). The thin film microstructure was investigated as a function of PLD deposition parameters such as: substrate temperature, ambient gas pressure, target‐to‐substrate distance, laser fluence and frequency. It was found that the ambient gas pressure and the substrate temperature are the key PLD process parameters determining the thin film micro‐ and nanostructure. A map of the LSCF film nanostructures is presented as a function of substrate temperature (25–700 °C) and oxygen background pressure (0.013–0.4 mbar), with film structures ranging from fully dense to highly porous. Fully crystalline, dense, and crack‐free LSCF films with a thickness of 300 nm were obtained at an oxygen pressure lower than 0.13 mbar at a temperature of 600 °C. The obtained knowledge on the structure allows for tailoring of perovskite thin film nanostructure, e.g., for solid oxide fuel cell cathodes. A simple geometrical model is proposed, allowing estimation of the catalytic active surface area of the prepared thin films. It is shown that voids at columnar grain boundaries can result in an increase of the surface area by approximately 25 times, when compared to dense flat films.  相似文献   

2.
    
Micro‐solid oxide fuel cells (μ‐SOFCs) are fabricated on nanoporous anodic aluminum oxide (AAO) templates with a cell structure composed of a 600‐nm‐thick AAO free‐standing membrane embedded on a Si substrate, sputter‐deposited Pt electrodes (cathode and anode) and an yttria‐stabilized zirconia (YSZ) electrolyte deposited by pulsed laser deposition (PLD). Initially, the open circuit voltages (OCVs) of the AAO‐supported μ‐SOFCs are in the range of 0.05 V to 0.78 V, which is much lower than the ideal value, depending on the average pore size of the AAO template and the thickness of the YSZ electrolyte. Transmission electron microscopy (TEM) analysis reveals the formation of pinholes in the electrolyte layer that originate from the porous nature of the underlying AAO membrane. In order to clog these pinholes, a 20‐nm thick Al2O3 layer is deposited by atomic layer deposition (ALD) on top of the 300‐nm thick YSZ layer and another 600‐nm thick YSZ layer is deposited after removing the top intermittent Al2O3 layer. Fuel cell devices fabricated in this way manifest OCVs of 1.02 V, and a maximum power density of 350 mW cm?2 at 500 °C.  相似文献   

3.
    
Crystallization and phase segregation during thermal annealing lead to the increase of power‐conversion efficiency in poly(3‐hexylthiophene) (P3HT):[6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) bulk‐heterojunction solar cells. An understanding of the length and time scale on which crystallization and phase segregation occur is important to improve control of the nanomorphology. Crystallization is monitored by means of grazing incidence X‐ray diffraction in real time during thermal annealing. Furthermore, the change in film density is monitored by means of ellipsometry and the evolution of carrier mobilities by means of field effect transistors, both during annealing. From the combination of such measurements with those of device performance as a function of annealing time, it is concluded that the evolution of microstructure involves two important time windows: i) A first one of about 5 minutes duration wherein crystallization of the polymer correlates with a major increase of photocurrent; ii) a second window of about 30 minutes during which the aggregation of PCBM continues, accompanied by an increase in the fill factor.  相似文献   

4.
    
Mixed ionic and electronic conducting (MIEC) films can be applied in solid state electrochemical devices such as oxygen separation membranes for producing pure oxygen, gas sensors or as cathode in solid oxide fuel cells. The current interest in layered perovskite‐related phases, like Sr4Fe6O13 (SFO), arises from their significant oxygen permeability as predicted from theoretical studies. Nevertheless, before any practical application further fundamental study on this fairly unknown oxide is required mainly to assess the mechanisms affecting the transport properties. Epitaxial Sr4Fe6O12+δ (SFO) films of b‐axis orientation with different thicknesses have been prepared by the pulsed laser deposition technique onto different perovskite substrates: SrTiO3, NdGaO3 and LaAlO3. The strain accommodation has been found to vary as a function of film thickness as well as the substrate material causing different type of defects in the film microstructure, as well as variations in the oxygen anion content and ordering. Correspondingly, the total electrical conductivity of the films has been also found to vary significantly as a function of thickness and substrate type showing an unexpected enhancement for strained thin films. The variations in the transport properties are discussed in terms of the different strain accommodation mechanisms and the variation of the modulated structure observed for this compound.  相似文献   

5.
    
Microstructures of yttria‐stabilized zirconia (YSZ) thin films deposited by spray pyrolysis at 370 °C on sapphire are investigated. The as‐deposited films are predominantly amorphous and crystallize upon heating at temperatures above 370 °C, developing grains in the range of 5 nm to several 100 nm. During post‐deposition heat treatment up to 800 °C, ～ 50 vol% porosity develops in the center of the films with gradients towards almost dense interfaces to the air and substrate. The reason for this porosity is the decomposition of residues from the precursor and the free volume liberated due to crystallization. Dense YSZ thin films consisting of one monolayer of grains are obtained with annealing temperatures exceeding 1200 °C. In gadolinium‐doped‐ceria (CGO) thin films similar microstructures and porosity are found after low‐temperature heat treatments indicating that the precursor residues due to the deposition method are the main cause of the porosity. Grain growth stagnation in annealed thin films is observed in both the YSZ and in CGO thin films. Stagnating grain growth in the thin films is rather caused by reduced grain boundary mobility, here predominately due to a “secondary phase”, i.e., pores, than to other effects. The stagnation ceases at higher annealing temperatures after densification has taken place.  相似文献   

6.
    
Composite cathodes of solid oxide fuel cells (SOFCs) are normally fabricated by mechanical mixing of electronic‐ and ionic‐conducting phases. Here, a dual‐phase SOFC cathode, composed of perovskite PrNi0.5Mn0.5O3 (PNM) and exsoluted fluorite PrOx particles, produced in situ through a glycine–nitrate solution combustion process, is reported. When applied as the cathode for a BaZr0.1Ce0.7Y0.1Yb0.1O3‐based protonic ceramic fuel cell, the hybrid cathode displays excellent electrocatalytic activity (area‐specific resistance of 0.052 Ω cm2 at 700 °C) and remarkable long‐term stability when operated at a cell voltage of 0.7 V for ≈500 h using H2 as fuel and ambient air as oxidant. The excellent performance is attributed to the proton‐conducting BaPrO3‐based coating and high‐concentration oxygen vacancies of a Ba‐doped PNM surface coating, produced by the reaction between the cathode and Ba from the electrolyte (via evaporation or diffusion), as confirmed by detailed X‐ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory‐based calculations.  相似文献   

7.
    
Fabrication of hierarchical materials, with highly optimized features from the millimeter to the nanometer scale, is crucial for applications in diverse areas including biosensing, energy storage, photovoltaics, and tissue engineering. In the past, complex material architectures have been achieved using a combination of top‐down and bottom‐up fabrication approaches. A remaining challenge, however, is the rapid, inexpensive, and simple fabrication of such materials systems using bench‐top prototyping methods. To address this challenge, the properties of hierarchically structured electrodes are developed and investigated by combining three bench‐top techniques: top‐down electrode patterning using vinyl masks created by a computer‐aided design (CAD)‐driven cutter, thin film micro/nanostructuring using a shrinkable polymer substrate, and tunable electrodeposition of conductive materials. By combining these methods, controllable electrode arrays are created with features in three distinct length scales: 40 μm to 1 mm, 50 nm to 10 μm, and 20 nm to 2 μm. The electrical and electrochemical properties of these electrodes are analyzed and it is demonstrated that they are excellent candidates for next generation low‐cost electrochemical and electronic devices.  相似文献   

8.
    
Solution‐processed thin polymer films have many applications, such as organic electronics and block‐copolymer nanofabrication. These films are often made by spin coating a solution that contains one or more solids and can show different phase‐separated structures. The formation mechanism of the droplet‐like morphology is studied here by processing polystyrene (PS) and a fullerene derivative ([6,6]‐phenyl‐C71‐butyric acid methyl ester, [70]PCBM) from o‐xylene. The final structure consists of [70]PCBM droplets partially embedded in a PS‐rich matrix showing interdomain distance of 100–1000 nm as determined from transmission electron microscopy and grazing incidence small angle X‐ray scattering (GISAXS). To elucidate the formation of these morphologies in real time, ultrafast in situ GISAXS coupled with laser interferometry and laser scattering is performed during spin coating. In situ thickness measurements and laser scattering show that liquid–liquid phase separation occurs at ≈70 vol% solvent. Subsequently, in only 100–400 ms, almost dry [70]PCBM domains start to protrude from the swollen PS‐rich matrix. These results are used to verify the ternary phase diagram calculated using Flory–Huggins theory. The discussed multitechnique approach can be applied to study fundamental aspects in soft matter such as phase separation in thin films occurring at very short time scales.  相似文献   

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10.
    
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11.
    
Time–temperature–transformation (TTT) diagrams are proposed for the crystallization of amorphous metal oxide thin films and their specific characteristics are discussed in comparison to glass‐based materials, such as glass‐ceramics and metallic glasses. The films crystallize from amorphous to full crystallinity in the solid state. As an example the crystallization kinetics for a single‐phase metal oxide, ceria, and its gadolinia solid solutions are reported made by the precipitation thin‐film method spray pyrolysis. The crystallization of an amorphous metal oxide thin film generally follows the Lijschitz–Sletow–Wagner (LSW) Ostwald ripening theory: Below the percolation threshold of 20 vol% single grains crystallize in the amorphous phase and low crystallization rates are measured. In this state no impact of solute on crystallization is measurable. Once the grains form primary clusters above the threshold the solute slows down crystallization (and grain growth) thus shifting the TTT curves of the doped ceria films to longer times and higher temperatures in comparison to undoped ceria. Current views on crystallization of metal oxide thin films, the impact of solute dragging, and primary TTT diagrams are discussed. Finally, examples on how to use these TTT diagrams for better thermokinetic engineering of metal oxide thin films for MEMS are given, for example, for micro‐Solid Oxide Fuel Cells and resistive sensors. In these examples the electrical properties depend on the degree of crystallinity and, thereby, on the TTT conditions.  相似文献   

12.
利用脉冲激光沉积（ pulsed laser depositon, PLD）方法在YSZ（ Y2 O3 stabilised zirconia）单晶衬底上外延生长了Gd掺杂的CeO2薄膜（gadolinium doped CeO2,GDC）。利用透射电子显微镜（TEM）对GDC／YSZ界面以及GDC薄膜内部的位错结构进行了表征。实验发现,界面处存在周期性分布的失配位错,界面失配主要通过失配位错释放。 GDC薄膜内部存在两种不同的位错,其中一种为纯刃型位错,另外一种为混合型位错。  相似文献   

13.
Miniaturized solid oxide fuel cells are fabricated on a photostructurable glass ceramic substrate (Foturan) by thin film and micromachining techniques. The anode is a sputtered platinum film and the cathode is made of a spray pyrolysis (SP)‐deposited lanthanum strontium cobalt iron oxide (LSCF), a sputtered platinum film and platinum paste. A single‐layer of yttria‐stabilized zirconia (YSZ) made by pulsed laser deposition (PLD) and a bilayer of PLD–YSZ and SP–YSZ are used as electrolytes. The total thickness of all layers is less than 1 µm and the cell is a free‐standing membrane with a diameter up to 200 µm. The electrolyte resistance and the sum of polarization resistances of the anode and cathode are measured between 400 and 600 °C by impedance spectroscopy and direct current (DC) techniques. The contribution of the electrolyte resistance to the total cell resistance is negligible for all cells. The area‐specific polarization resistance of the electrodes decreases for different cathode materials in the order of Pt paste > sputtered Pt > LSCF. The open circuit voltages (OCVs) of the single‐layer electrolyte cells ranges from 0.91 to 0.56 V at 550 °C. No electronic leakage in the PLD–YSZ electrolyte is found by in‐plane and cross‐plane electrical conductivity measurements and the low OCV is attributed to gas leakage through pinholes in the columnar microstructure of the electrolyte. By using a bilayer electrolyte of PLD–YSZ and SP–YSZ, an OCV of 1.06 V is obtained and the maximum power density reaches 152 mW cm−2 at 550 °C.  相似文献   

14.
    
The efficiencies of a number of electrochemical devices (e.g., fuel cells and metal‐air batteries) are mainly governed by the kinetics of the oxygen reduction reaction (ORR). Among all the good ORR catalysts, the partially substituted double perovskite oxide (AA′B2O5+δ) has the unique layered structure, providing a great flexibility regarding the optimization of its electronic structures and physicochemical properties. Here, it is demonstrated that the double perovskite oxide, i.e., NdBa0.75Ca0.25Co1.5Fe0.5O5+δ, is a good ORR catalyst at both room and elevated temperatures. Under ambient condition, its half‐wave potential of ORR in alkaline media is as low as 0.74 V versus RHE; at 650 °C, the cathodic polarization resistance is merely 0.0276 Ω cm2 according to a symmetric cell measurement, whereas the solid oxide fuel cells using this cathode exhibit a maximum power density of 1982 mW cm?2. From various materials characterizations, it is hypothesized that its excellent ORR activity is strongly correlated with the crystallographic, electronic, and defect structures of the materials.  相似文献   

15.
    
A promising route to increase the performance of hematite (α‐Fe2O3) photoelectrodes for solar hydrogen production through water‐splitting is to use an extremely thin layer of this visible light absorber on a nanostructured scaffold. However, the typically poor performance of ultrathin (ca. 20 nm) films of hematite has been the limiting factor in implementing this approach. Here, the surprising effect of a substrate pretreatment using tetraethoxysilicate (TEOS) is reported; it results in drastic improvements in the photoperformance of 12.5 nm thick films of hematite. These films exhibit a water oxidation photocurrent onset potential at 1.1 V versus the reversible hydrogen electrode (vs. RHE) and a plateau current of 0.63 mA cm?2 at 1.5 V vs. RHE under standard illumination conditions, representing the highest reported performance for ultrathin hematite films. In contrast, almost no photoactivity is observed for the photoanode with the same amount of hematite on an untreated substrate. A detailed study of the effects of the TEOS treatment shows that a monolayer of SiOx is formed, which acts to change the hematite nucleation and growth mechanism, increases its crystallinity, reduces the concentration of carrier trapping states of the ultrathin films, and suggests its further application to quantum‐dot and extremely‐thin‐absorber (ETA)‐type solar cells.  相似文献   

16.
Solution processing of inorganic thin films has become an important thrust in material research community because it offers low‐cost and high‐throughput deposition of various functional coatings and devices. Especially inorganic thin film solar cells – macroelectronic devices that rely on consecutive deposition of layers on large‐area rigid and flexible substrates – could benefit from solution approaches in order to realize their low‐cost nature. This article critically reviews existing deposition approaches of functional layers for chalcogenide solar cells with an extension to other thin film technologies. Only true solutions of readily available metal salts in appropriate solvents are considered without the need of pre‐fabricated nanoparticles. By combining three promising approaches, an air‐stable Cu(In,Ga)Se2 thin film solar cell with efficiency of 13.8% is demonstrated where all constituent layers (except the metal back contact) are processed from solutions. Notably, water is employed as the solvent in all steps, highlighting the potential for safe manufacturing with high utilization rates.  相似文献   

17.
    
Reversible solid oxide cells based on ceramic proton conductors have potential to be the most efficient system for large‐scale energy storage. The performance and long‐term durability of these systems, however, are often limited by the ionic conductivity or stability of the proton‐conducting electrolyte. Here new family of solid oxide electrolytes, BaHfxCe0.8?xY0.1Yb0.1O3?δ (BHCYYb), which demonstrate a superior ionic conductivity to stability trade‐off than the state‐of‐the‐art proton conductors, BaZrxCe0.8?xY0.1Yb0.1O3?δ (BZCYYb), at similar Zr/Hf concentrations, as confirmed by thermogravimetric analysis, Raman, and X‐ray diffraction analysis of samples over 500 h of testing are reported. The increase in performance is revealed through thermodynamic arguments and first‐principle calculations. In addition, lab scale full cells are fabricated, demonstrating high peak power densities of 1.1, 1.4, and 1.6 W cm?2 at 600, 650, and 700 °C, respectively. Round‐trip efficiencies for steam electrolysis at 1 A cm?2 are 78%, 72%, and 62% at 700, 650, and 600 °C, respectively. Finally, CO2? H2O electrolysis is carried out for over 700 h with no degradation.  相似文献   

18.
利用真空热蒸发在石英基片上制备了不同厚度的氧化钒薄膜, 研究厚度对薄膜的结构、形貌和光学特性的影响。薄膜的结构由X射线衍射(XRD)仪和拉曼(Raman)光谱仪测得, 表面形貌用原子力显微镜(AFM)观测。利用分光光度计测量薄膜的光学透射率, 并且采用Forouhi-Bloomer模型与修正的德鲁德(Drude)自由电子模型相结合的方法拟合透射率来确定薄膜的折射率、消光系数和带隙。结果表明, 热蒸发的氧化钒薄膜呈非晶态, 薄膜的主要成分为五氧化二钒, 且含有少量的二氧化钒。薄膜表面的颗粒粘结在一起, 随着薄膜厚度的增加, 薄膜表面粗糙度以及颗粒尺寸变小, 膜层表面平整度越来越好, 颗粒之间的空隙变小, 导致折射率随膜厚的增加而增大, 消光系数减小。另外, 随着薄膜厚度从200 nm增加到450 nm, 光学带隙从2.67 eV减小到2.45 eV。  相似文献   

19.
    
Graphene oxide (GO) papers are candidates for structural materials in modern technology due to their high specific strength and stiffness. The relationship between their mechanical properties and structure needs to be systematically investigated before they can be applied to the broad range fields where they have potential. Herein, the mechanical properties of GO papers with various thicknesses (0.5–100 μm) are investigated using bulge and tensile test methods; this includes the Young's modulus, fracture strength, fracture strain, and toughness. The Young's modulus, fracture strength, and toughness are found to decrease with increasing thickness, with the first two exhibiting differences by a factor of four. In contrast, the fracture strain slightly increases with thickness. Transmission electron, scanning electron, and atomic force microscopy indicate that the mechanical properties vary with thickness due to variations in the inner structure and surface morphology, such as crack formation and surface roughness. Thicker GO papers are weaker because they contain more voids that are produced during the fabrication process. Surface wrinkles and residual stress are found to result in increased fracture strain. Determination of this structure–property relationship provide improved guidelines for the use of GO‐based thin‐film materials in mechanical structures.  相似文献   

20.
A significant improvement in the deposition rate of thin films of aluminum oxide, using trimethylaluminum and oxygen at a substrate temperature of 570° C, is demonstrated. Hard, transparent, strongly adherent films of refractive index 1.62–1.63 were consistently achieved with controlled growth rates from 15 Å/sec to 94 Å/sec, depending upon the Al mole fraction. Systematic analysis of the growth rate data offers insight into the complicated kinetics of the deposition process. In comparison, the films produced from the trimethylaluminum and nitrous oxide system were of inferior quality.  相似文献   

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