Surface‐Mounted Metal–Organic Frameworks: Crystalline and Porous Molecular Assemblies for Fundamental Insights and Advanced Applications

Metal–organic frameworks (MOFs) are crystalline coordination polymers, assembled from inorganic nodes connected by organic linker molecules. An enormous surface area, huge compositional variety, regular structure, and favorable mechanical properties are among their outstanding properties. Monolithic MOF thin films, i.e., surface‐mounted metal–organic frameworks (SURMOFs), with high degree of structural order and adjustable defect density, can be prepared on solid substrates using layer‐by‐layer techniques. Recent studies where SURMOFs served as model systems for quantitative studies of molecular interactions in porous media, including diffusion, are reviewed. Moreover, SURMOFs are ideally suited for the incorporation of photoactive molecules as well as to study electrical transport through crystalline molecular assemblies. Recent work has demonstrated that the realization of crystalline chromophore assemblies via the SURMOF approach allows the study of fundamental aspects of exciton transport, exciton channeling, and photon upconversion at internal interfaces in organic semiconductor materials. Due to their crystalline nature, MOF materials are well suited for quantitative comparisons with theoretical results; especially, since defect densities and types can be characterized and varied in a straightforward fashion. The active role of these nanoporous films in advanced applications, like for remote‐controlled release of molecules, membranes with photoswitchable selectivity, and ion‐conductors with adjustable conductivity, are also emphasized.     

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.     

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

Abstract

We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO) thin films via dip-coating. Two poly(isobutylene)-b-poly(ethyleneoxide) (PIB-PEO) copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000) are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.     

Synthesis and tailored properties of covalent organic framework thin films and heterostructures

Porous polymeric covalent organic frameworks (COFs) have been under intense synthetic investigation with over 100 unique structural motifs known. In order to realize the true potential of these materials, converting the powders into thin films with strict control of thickness and morphology is necessary and accomplished through techniques including interfacial synthesis, chemical exfoliation and mechanical delamination. Recent progress in the construction and tailored properties of thin film COFs are highlighted in this review, addressing mechanical properties as well as application-focused properties in filtration, electronics, sensors, electrochemistry, magnetics, optoelectronics and beyond. Additionally, heterogeneous integration of these thin films with other inorganic and organic materials is discussed, revealing exciting opportunities to integrate COF thin films with other state of the art material and device systems.     

Ultrafast large-area micropattern generation in nonabsorbing polymer thin films by pulsed laser diffraction

An ultrafast, parallel, and beyond-the-master micropatterning technique for ultrathin (30-400 nm) nonabsorbing polymer films by diffraction of laser light through a 2D periodic aperture is reported. The redistribution of laser energy absorbed by the substrate causes self-organization of polymer thin films in the form of wrinklelike surface relief structures caused by localized melting and freezing of the thin film. Unlike conventional laser ablation and laser writing processes, low laser fluence is employed to only passively swell the polymer as a pre-ablative process without loss of material, and without absorption/reaction with incident radiation. Self-organization in the thin polymer film, aided by the diffraction pattern, produces microstructures made up of thin raised lines. These regular microstructures have far more complex morphologies than the mask geometry and very narrow line widths that can be an order of magnitude smaller than the openings in the mask. The microstructure morphology is easily modulated by changing the film thickness, aperture size, and geometry, and by changing the diffraction pattern.     

Evolution of diffraction and self-diffraction phenomena in thin films of Gelite Bloom/Hibiscus Sabdariffa

In this work, we present a study of non-linear optical response in thin films elaborated with Gelite Bloom and extract of Hibiscus Sabdariffa. Non-linear refraction and absorption effects were studied experimentally (Z-scan technique) and numerically, by considering the transmittance as non-linear absorption and refraction contribution. We observe large phase shifts to far field, and diffraction due to self-phase modulation of the sample. Diffraction and self-diffraction effects were observed as time function. The aim of studying non-linear optical properties in thin films is to eliminate thermal vortex effects that occur in liquids. This is desirable in applications such as non-linear phase contrast, optical limiting, optics switches, etc. Finally, we find good agreement between experimental and theoretical results.     

Evolution of nanocrystallinity in periodic mesoporous anatase thin films

Herein we report the first kinetic study of the intrachannel wall phase-transition of amorphous titania to nanocrystalline anatase for periodic mesoporous titania thin films, monitored by time-resolved in situ high-temperature X-ray diffraction. Structural transformations associated with the phase transition are further probed by high-resolution scanning electron microscopy and transmission electron microscopy. The model found to be most consistent with the kinetic data involves 1D diffusion-controlled growth of nanocrystalline anatase within the spatial confines of the channel walls of the mesostructure. The observation of anisotropic, rod-shaped anatase nanocrystals preferentially aligned along the channel axis implies that the framework of the liquid-crystal-templated mesostructure guides the crystal growth.     

溶胶-凝胶法制备c轴取向生长ZnO薄膜

采用sol-gel法,在普通载玻片上使用旋转涂覆技术生长了具有c轴择优取向生长的ZnO薄膜.采用热分析、XRD、SEM等手段对薄膜样品进行了表征.热分析结果表明,二水醋酸锌-乙醇胺-乙二醇甲醚体系sol-gel的热分解过程与纯二水合乙酸锌的分解过程大相径庭.ZnO薄膜的sol-gel分解趋于在较窄的温度范围内一步完成.样品在XRD图谱中表现出明显的c轴择优取向.此外,SEM照片也表明:ZnO薄膜样品中间区域和边缘区域的表面形貌相差甚远.探讨了预热处理温度、退火温度等工艺条件对ZnO薄膜的结构性能的影响,最佳的预热处理温度被认为在ZnO相完全生成温度附近.     

光学材料和光学薄膜的光热表征(英文)

光热技术用来测量样品的光学和热特性。简要介绍了光热技术及其在光学薄膜测量和钛蓝宝石激光晶体表征中的应用。光热技术可以提供纯光学光谱学所无法提供的、类似光-热能量转换效率之类的信息。光热技术已被用作质量测试和改善现代光学制造的有用工具。     

Self diffusion studies on cobalt thin films

The study of lateral diffusion in thin metallic films is important from the application point of view, especially in electromigration reliability studies. Lateral self diffusion in cobalt thin films is studied using a non-destructive tracer scanning method. Neutron irradiation is employed to make a well-defined radioactive (⁶⁰Co) region in the middle of a continuous cobalt thin film stripe of width 3 mm. The experimental data are fitted to the appropriate solution of the diffusion equations by means of a non-linear least square fitting procedure using a computer. The diffusion experiments are conducted in the temperature range 300–600°C in argon atmosphere. This thin film data are compared with the diffusion data available on bulk cobalt. The activation energy for surface diffusion obtained (0·14 eV) is very much smaller than the reported activation energy for grain boundary diffusion in cobalt.     

PZT薄膜厚度对BMT/PZT复合薄膜结构及介电性能的影响

采用液相旋涂法制备了Ba(Mg1/3Ta2/3)O3(BMT)/Pb(Zr0.52Ti0.48)O3(PZT)复合薄膜,研究了PZT薄膜厚度对BMT/PZT复合薄膜结构及介电性能的影响。随着PZT薄膜厚度的增加,BMT/PZT复合薄膜的介电常数呈线性增加。当PZT薄膜的厚度较小时,会明显地增加BMT/PZT复合薄膜的介电损耗;当继续增加PZT薄膜的厚度,介电损耗反而下降直到与BMT薄膜的介电损耗值接近。这是由于PZT的介电常数与介电损耗均明显高于BMT薄膜所致,而异质界面的存在抑制了PZT薄膜中畴壁的运动,使其对复合薄膜介电损耗的影响减弱。研究结果表明,PZT薄膜的引入可以提升BMT薄膜的介电常数而对介电损耗的影响不大。     

Sol-gel preparation and characterisation of mixed metal tin oxide thin films

Mixed metal oxide stannates were prepared by sol-gel methods and coated onto solid titanium substrates as thin films using spin and dip coating methods. Metal oxides such as Sb₂O₅, ZrO₂, CuO, MnO_x and PdO were introduced into a SnO₂ host matrix using sol-gel technology. The mixed metal tin oxide materials prepared via the sol-gel route were extensively characterised in terms of surface characterisation and chemical composition. Thermogravimetric analysis was performed to confirm that at 600 °C (the calcination temperature) no further structural changes due to mass loss occur. UV spectroscopy of the liquid gels allowed the determination of the band gap energy. The surface morphology of the thin film electrodes were characterised by atomic force microscopy and scanning electron microscopy and the effect of the coating method employed i.e. spin or dip coating could be clearly seen in the estimated values of surface roughness. These techniques were also able to confirm the thickness of the films in the nano range. Combined nuclear beam techniques such as Rutherford backscattering spectroscopy and particle induced X-ray emission provided some insight into the chemical composition of the mixed metal tin oxides and confirmed the presence of the dopant element in the SnO₂ host material.     

Nanoporous Polymers for Hydrogen Storage

The design of hydrogen storage materials is one of the principal challenges that must be met before the development of a hydrogen economy. While hydrogen has a large specific energy, its volumetric energy density is so low as to require development of materials that can store and release it when needed. While much of the research on hydrogen storage focuses on metal hydrides, these materials are currently limited by slow kinetics and energy inefficiency. Nanostructured materials with high surface areas are actively being developed as another option. These materials avoid some of the kinetic and thermodynamic drawbacks of metal hydrides and other reactive methods of storing hydrogen. In this work, progress towards hydrogen storage with nanoporous materials in general and porous organic polymers in particular is critically reviewed. Mechanisms of formation for crosslinked polymers, hypercrosslinked polymers, polymers of intrinsic microporosity, and covalent organic frameworks are discussed. Strategies for controlling hydrogen storage capacity and adsorption enthalpy via manipulation of surface area, pore size, and pore volume are discussed in detail.

     

非化学计量比SbOx薄膜的结晶动力学研究

利用直流磁控反应溅射法在不同氧分压下制备了SbOx薄膜,对退火前后薄膜的X射线衍射(XRD)分析表明,退火后薄膜结构发生了从非晶态向晶态的转变.利用示差扫描量热法(DSC)测出不同升温速度条件下非晶态薄膜粉末的晶化峰温度,用Kissinger公式计算了材料的结晶活化能计算结果表明,随着溅射时氧分压的增加,薄膜的结晶活化能增加,而相应的非晶态与晶态之间的焓差则呈现出相反的变化趋势.     

A novel high-throughput fatigue testing method for metallic thin films

Abstract

Thin films are used in a wide variety of computing and communication applications although their fatigue behavior and its dependence on alloying elements are not very well known. In this paper, we present an experimental implementation of a novel high-throughput fatigue testing method for metallic thin films. The methodology uses the fact that the surface strain amplitude of a vibrating cantilever decreases linearly from the fixed end to the free end. Therefore, a thin film attached to a vibrating cantilever will experience a gradient of strain and corresponding stress amplitudes along the cantilever. Each cantilever can be used to extract a lifetime diagram by measuring the fatigue-induced damage front that progresses along the cantilever during up to 10⁸ load cycles.     

A novel high-throughput fatigue testing method for metallic thin films

Thin films are used in a wide variety of computing and communication applications although their fatigue behavior and its dependence on alloying elements are not very well known. In this paper, we present an experimental implementation of a novel high-throughput fatigue testing method for metallic thin films. The methodology uses the fact that the surface strain amplitude of a vibrating cantilever decreases linearly from the fixed end to the free end. Therefore, a thin film attached to a vibrating cantilever will experience a gradient of strain and corresponding stress amplitudes along the cantilever. Each cantilever can be used to extract a lifetime diagram by measuring the fatigue-induced damage front that progresses along the cantilever during up to 10⁸ load cycles.