Interfacial Strain Gradients Control Nanoscale Domain Morphology in Epitaxial BiFeO3 Multiferroic Films

Domain switching pathways fundamentally control performance in ferroelectric thin film devices. In epitaxial bismuth ferrite (BiFeO₃) films, the domain morphology is known to influence the multiferroic orders. While both striped and mosaic domains have been observed, the origins of the latter have remained unclear. Here, it is shown that domain morphology is defined by the strain profile across the film–substrate interface. In samples with mosaic domains, X‐ray diffraction analysis reveals strong strain gradients, while geometric phase analysis using scanning transmission electron microscopy finds that within 5 nm of the film–substrate interface, the out‐of‐plane strain shows an anomalous dip while the in‐plane strain is constant. Conversely, if uniform strain is maintained across the interface with zero strain gradient, striped domains are formed. Critically, an ex situ thermal treatment, which eliminates the interfacial strain gradient, converts the domains from mosaic to striped. The antiferromagnetic state of the BiFeO₃ is also influenced by the domain structure, whereby the mosaic domains disrupt the long‐range spin cycloid. This work demonstrates that atomic scale tuning of interfacial strain gradients is a powerful route to manipulate the global multiferroic orders in epitaxial films.     

Influence of Dielectric Surface Chemistry on the Microstructure and Carrier Mobility of an n‐Type Organic Semiconductor

This paper examines the microstructure evolution of 3,4,9,10‐perylene‐tetracarboxylic bis‐benzimidazole (PTCBI) thin films resulting from conditions imposed during film deposition. Modification of the silicon dioxide interface with a hydrophobic monolayer (octadecyltrichlorosilane (OTS‐18)) alters the PTCBI growth habit by changing the unit cell contact plane. PTCBI films deposited on oxide surface have an orientation of (011), while films atop OTS‐treated oxide surface have a preferred orientation of (001). The quality of the self assembled monolayer does not appear to influence the PTCBI growth preference significantly yet it enhances the carrier mobility, suggesting that charge traps are adequately passivated due to uniform monolayer coverage. High‐quality monolayers result in n‐type carrier mobility values of 0.05 cm²V^–1s^–1 Increasing the substrate temperature during PTCBI film deposition correlates with an increase in mobility that is most significant for films deposited on OTS‐treated surface.     

Synthesis,Properties, and Photopolymerization of Liquid‐Crystalline Oxetanes: Application in Transflective Liquid‐Crystal Displays

Mixtures of liquid‐crystalline di‐oxetanes and mono‐oxetanes are made for the purpose of making birefringent films by photopolymerization. The composition of a di‐oxetane mixture that forms spin‐coated films of planarly aligned nematic monomers is reported. These films are photopolymerized in air. The molecular order of the monomers can be changed on the microscale to form thin films with alternating birefringent and isotropic parts by using a combination of photopolymerization and heating. The interface observed between the birefringent and isotropic 10 μm × 10 μm domains is very sharp and the films show hardly any surface corrugation. In addition, the polymerized films are thermally stable, making them very suitable for use as patterned thin‐film retarders in high‐performance transflective liquid‐crystal displays (LCDs) which satisfy customer demand for displays that are brighter and thinner and that deliver better optical performance than conventional LCDs with an external non‐patterned retarder.     

Direct Growth of Nanopatterned Graphene on Sapphire and Its Application in Light Emitting Diodes

Direct growth of graphene films on functional substrates is immensely beneficial for the large‐scale applications of graphene by avoiding the transfer‐induced issues. Notably, the selective growth of patterned graphene will further boost the development of graphene‐based devices. Here, the direct growth of patterned graphene on the c‐plane of nanopatterned sapphire substrate (NPSS) is realized and the superiority of the patterned graphene for high‐performance ultraviolet light‐emitting diodes (UV‐LED) is demonstrated. As confirmed by density functional theory calculations and analog simulations, compared to the concave r‐plane the flat c‐plane of NPSS is characterized by a lower active barrier for methane decomposition and carbon species diffusion, as well as a greater supply of carbon precursor for graphene growth. The synthesized patterned graphene on the c‐plane of NPSS is verified to be monolayer and high quality. The patterned graphene enables the selective and well‐aligned nucleation of aluminium nitride (AlN) to promote rapid epitaxial lateral overgrowth of single‐crystal AlN films with low dislocation density. Consequently, the fabricated UV‐LED demonstrates high luminescence intensity and stability. The method is suitable for obtaining various patterned graphene by substrate design, which will allow for greater progress in the cutting‐edge applications of graphene.     

Phase‐Separation‐Induced Micropatterned Polymer Surfaces and Their Applications

We report a route to fabricate micropatterned polymer films with micro‐ or nanometer‐scale surface concavities by spreading polymer solutions on a non‐solvent surface. The route is simple, versatile, highly efficient, low‐cost, and easily accessible. The concavity density of the patterned films is tuned from 10⁶ to 10⁹ features cm^–2, and the concavity size is controlled in the range from several micrometers to less than 100 nm, by changing the film‐forming parameters including the polymer concentration, the temperature of the non‐solvent and the interactions between polymer, solvent, and non‐solvent. We further demonstrate that these concavity‐patterned films have significantly enhanced hydrophobicity, owing to the existence of the surface concavities, and their hydrophobicity could be controlled by the concavity density. These films have been used as templates to successfully fabricate convex‐patterned polymer films, inorganic TiO₂ microparticles, and NaCl nanocrystals. Their other potential applications are also discussed.     

Mimicking Biological Phenol Reaction Cascades to Confer Mechanical Function

Phenol reaction cascades are commonly used in nature to create crosslinked materials that perform mechanical functions. These processes are mimicked by electrochemically initiating a reaction cascade to examine if the mechanical properties of a biopolymer film can be predictably altered. Specifically, thin films (≈ 30–45 μm) of the polysaccharide chitosan are cast onto gold‐coated silicon wafers, the chitosan‐coated wafers are immersed in catechol‐containing solutions, and the phenol is anodically oxidized. The product of this oxidation is highly reactive and undergoes reaction with chitosan chains adjacent to the anode. After reaction, the flexible chitosan film can be peeled from the wafer. Chemical and physical evidence support the conclusion that electrochemically initiated reactions crosslink chitosan. When gold is patterned onto the wafer, the electrochemical crosslinking reactions are spatially localized and impart anisotropic mechanical properties to the chitosan film. Further, deswelling of chitosan films can reversibly transduce environmental stimuli into contractile forces. Films patterned to have spatial variations in crosslinking respond to such environmental stimuli by undergoing reversible changes in shape. These results suggest the potential to enlist electrochemically initiated reaction cascades to engineer chitosan films for actuator functions.     

Novel Direct Nanopatterning Approach to Fabricate Periodically Nanostructured Perovskite for Optoelectronic Applications

While indirectly patterned organic–inorganic hybrid perovskite nanostructures have been extensively studied for use in perovskite optoelectronic devices, it is still challenging to directly pattern perovskite thin films because perovskite is very sensitive to polar solvents and high‐temperature environments. Here, a simple and low‐cost approach is proposed to directly pattern perovskite solid‐state films into periodic nanostructures. The approach is basically perovskite recrystallization through phase transformation with the presence of a periodic mold on an as‐prepared solid‐state perovskite film. Interestingly, this study simultaneously achieves not only periodically patterned perovskite nanostructures but also better crystallized perovskites and improved optical properties, as compared to its thin film counterpart. The improved optical properties can be attributed to the light extraction and increased spontaneous emission rate of perovskite gratings. By fabricating light‐emitting diodes using the periodic perovskite nanostructure as the emission layers, approximately twofold higher radiance and lower threshold than the reference planar devices are achieved. This work opens up a new and simple way to fabricate highly crystalline and large‐area perovskite periodic nanostructures for low‐cost production of high‐performance optoelectronic devices.     

Calcination‐ and Etching‐Free Photolithography of Inorganic Phosphor Films Consisting of Rare Earth Ion Doped Nanoparticles on Plastic Sheets

It is demonstrated that patterned inorganic phosphor films consisting of rare earth ion doped nanoparticles (RE‐NPs) can be fabricated on plastic sheets using calcination‐ and etching‐free photolithography. Green up‐conversion luminescence and near‐infrared (NIR) fluorescence appears from the RE‐NPs that are prepared from Y₂O₃ doped with 1 mol% Er³⁺ and 0.85 mol% Yb³⁺. The diameter of the RE‐NPs is estimated to be about 300 nm using dynamic light scattering. Visible transmittance of the RE‐NP film fabricated by dip‐coating is more than 90%. Patterned RE‐NP films are obtained by dip‐coating the RE‐NPs on patterned photoresist films fabricated by UV exposure through a photomask, followed by selective removal of the photoresist. Optical, fluorescence, scanning electron, atomic force, and Kelvin probe force microscopies are used for the characterization of the patterned RE‐NP films. The present methodology enables fabrication of patterned RE‐NP films, not only on inorganic substrates but also on plastic sheets, with low cost and material consumption.     

Control of the crystalline phase and morphology of CdS deposited on microstructured surfaces by chemical bath deposition

Chemical bath deposition (CBD) has been used extensively to deposit thin films of CdS for window layers in solar cells. The microtopography or roughness of the surface, however, can affect the quality of the film by influencing the morphology, uniformity, or crystal phase of the CdS film. Here, we have demonstrated that thin films of CdS can be successfully patterned on surfaces bearing micropillars as a model surface for roughness. The phase purity of CdS deposited on the micropillar surfaces is uniform and conformal with the formation of packed clusters on the micropillars at pH 10 that form flower-like structures at long deposition times. Smaller crystallites were observed on micropillar arrays at pH 8 with “network” like structures observed at long deposition times. Additionally, by controlling the pH of the chemical bath, the hexagonal and cubic crystal phases of CdS were both accessible in high purity at temperatures as low as 85 °C.     

Microcrystalline Structure and Luminescence of ZnS Thin Films

The electroluminescence thin films doped with erbium, fabricated by thermal evaporation with two boats, are analyzed by X-ray diffraction(XRD).The relationship between electroluminescence brightness and microstructure of the thin films is obtained.The results reveal that the large grain size in high index plane of deposited microcrystalline film has an effect on electroluminescence characteristics of the film devices.     

Biomimetic Carbon Nanotube Films with Gradient Structure and Locally Tunable Mechanical Property

Naturally existing materials often acquire unique functions by adopting a gradient structure with gradual change in their microstructure and related properties. Imparting such an elegant structural control into synthetic materials has been a grand challenge in the field. Here, the concept of gradient structure into macroscopic carbon nanotube (CNT) films is employed and the CNT arrangement from well‐aligned array to completely random distribution, in a continuous and smooth way, is changed. Gradient films with tailored aligned‐to‐random transition rate or multilevel hierarchical structures with repeated transition have been fabricated. Local deformation and mechanical properties are directly related to the arrangement of CNTs and can be tailored by Herman's orientation factor; in particular, the elastic modulus and stiffness span over several orders of magnitude from aligned to random regions within a single monolithic film. Controlled synthesis of macroscopic CNT gradient structures with tunable mechanical properties opens a potential route toward manufacturing biomimetic functional materials with locally optimized design.     

Multivalent‐Ion‐Mediated Stabilization of Hydrogen‐Bonded Multilayers

Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce⁴⁺ or Fe³⁺) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce⁴⁺‐ and Fe³⁺‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe³⁺‐treated films to iodide solutions.     

Solid‐State Photovoltaic Thin Films using TiO2, Organic Dyes,and Layer‐by‐Layer Polyelectrolyte Nanocomposites

We report photovoltaic devices consisting of patterned TiO₂, porphyrin dyes, and layer‐by‐layer (LBL) polyelectrolyte multilayer/oligoethylene glycol dicarboxylic acid (OEGDA) composite films. A composite polyelectrolyte LBL/OEGDA film was fabricated by formation of an alternating multilayer of linear polyethyleneimine (LPEI) and polyacrylic acid (PAA), followed by immersion of the LBL film into an OEGDA aqueous solution. The ionic conductivity attained in this LBL LPEI/PAA and OEGDA composite film was approximately 10^–5 S cm^–1 at room temperature and humidity. Investigations of dye‐sensitized photovoltaic devices constructed with the LBL (LPEI/PAA)/OEGDA composite films, TiO₂, and four types of porphyrin dyes resulted in optimization of the dye molecule and its orientation at the interface with the ionically conductive composite. The photocurrent value of photovoltaic devices constructed with the composite LBL/OEGDA film from illumination of a xenon white light source exhibited a nearly 1.5 times enhancement over the device without OEGDA. This enhancement of the photocurrent was due to the high room‐temperature ionic conductivity of the multilayer composite film. Further marked improvements of the photovoltaic performance were achieved by patterning the TiO₂ electrode using polymer stamping as a template for TiO₂ deposition. The device with patterned TiO₂ electrodes exhibited almost 10 times larger conversion efficiencies than a similar device without patterning.     

Cover Picture: Self‐Organization of Ink‐jet‐Printed Triisopropylsilylethynyl Pentacene via Evaporation‐Induced Flows in a Drying Droplet (Adv. Funct. Mater. 2/2008)

Charge carrier transport in organic electronic devices is influenced by the crystalline microstructure and morphology of the organic semiconductor film. Evaporation behavior during drying plays a vital role in controlling the film morphology and the distribution of solute in inkjet‐printed films. On p. 229, Kilwon Cho and co‐workers demonstrate the influence of the evaporation‐induced flow in a single droplet on the crystalline microstructure and film morphology of inkjet‐printed 6,13‐bis((triisopropylsilylethynyl) pentacene. The results provide an excellent method for direct‐write fabrication of high‐performance organic electronics. We have demonstrated the influence of evaporation‐induced flow in a single droplet on the crystalline microstructure and film morphology of an ink‐jet‐printed organic semiconductor, 6,13‐bis((triisopropylsilylethynyl) pentacene (TIPS_PEN), by varying the composition of the solvent mixture. The ringlike deposits induced by outward convective flow in the droplets have a randomly oriented crystalline structure. The addition of dichlorobenzene as an evaporation control agent results in a homogeneous film morphology due to slow evaporation, but the molecular orientation of the film is undesirable in that it is similar to that of the ring‐deposited films. However, self‐aligned TIPS_PEN crystals with highly ordered crystalline structures were successfully produced when dodecane was added. Dodecane has a high boiling point and a low surface tension, and its addition to the solvent results in a recirculation flow in the droplets that is induced by a Marangoni flow (surface‐tension‐driven flow), which arises during the drying processes in the direction opposite to the convective flow. The field‐effect transistors fabricated with these self‐aligned crystals via ink‐jet printing exhibit significantly improved performance with an average effective field‐effect mobility of 0.12 cm² V^–1 s^–1. These results demonstrate that with the choice of appropriate solvent ink‐jet printing is an excellent method for the production of organic semiconductor films with uniform morphology and desired molecular orientation for the direct‐write fabrication of high‐performance organic electronics.     

Capillary instabilities in thin films

Very thin films, less than 100 nm-thick, are used in a variety of applications, including as catalysts and for thin film reactions to form patterned silicides in electronic devices. Because of their high surface to volume ratio, these very thin films are subject to cap-illary instability and can agglomerate well below their melting temperatures. In order to develop a general understanding of agglomeration in very thin films, we have studied initially continuous and patterned films of gold on fused silica substrates. Two in situ techniques were used to monitor agglomeration: 1) heating and video recording in a transmission electron microscope, and 2) measurement of the intensity of laser light transmitted through a sample heated in a furnace. Electron microscopy allowed inves-tigation of the role of the microstructure of the Au film and analysis of light transmis-sion during heating allowed determination of temperature-dependent and film-thick-ness-dependent agglomeration rates. These results will be described along with models for the agglomeration process.     

Biodegradable Self‐Folding Polymer Films with Controlled Thermo‐Triggered Folding

Self‐folding films are a unique kind of thin film. They are able to deform in response to a change in environmental conditions or internal stress and form complex 3D structures. They are very promising candidates for the design of bioscaffolds, which resemble different kinds of biological tissues. In this paper, a very simple and cheap approach for the fabrication of fully biodegradable and biocompatible self‐rolled tubes is reported. The tubes' folding can be triggered by temperature. A bilayer approach is used, where one component is active and another one is passive. The passive one can be any biocompatible, biodegradable, hydrophobic polymer. Gelatin is used as an active component: it allows the design of (i) self‐folding polymer films, which fold at room temperature (22 °C) and irreversibly unfold at 37 °C, and (ii) films, which are unfolded at room temperature (22 °C), but irreversibly fold at 37 °C. The possibilities of encapsulation of neural stem cells are also demonstrated using self‐folded tubes.     

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.     

Nanosized Glass Frit as an Adhesion Promoter for Ink‐Jet Printed Conductive Patterns on Glass Substrates Annealed at High Temperatures

Ink‐jet printed metal nanoparticle films have been shown to anneal at high temperatures (above 500 °C) to highly conductive metal films on glass or ceramic substrates, but they suffer from cracking and inadequate substrate adhesion. Here, we report printable conductive materials, with added nanosized glass frit that can be annealed at 500 °C to form a crack‐free dense microstructure that adheres well to glass substrates. This overcomes the previous challenges while still retaining the desired high film conductivity. Controlling the particle characteristics and dispersion behavior plays an important role in successfully incorporating the glass frit into the conductive inks.     

Effects of Confinement on Microstructure and Charge Transport in High Performance Semicrystalline Polymer Semiconductors

The film thickness of one of the most crystalline and highest performing polymer semiconductors, poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT), is varied in order to determine the effects of interfaces and confinement on the microstructure and performance in organic field effect transistors (OFETs). Crystalline texture and overall film crystallinity are found to depend strongly on film thickness and thermal processing. The angular distribution of crystallites narrows upon both a decrease in film thickness and thermal annealing. These changes in the film microstructure are paired with thin‐film transistor characterization and shown to be directly correlated with variations in charge carrier mobility. Charge transport is shown to be governed by film crystallinity in films below 20 nm and by crystalline orientation for thicker films. An optimal thickness is found for PBTTT at which the mobility is maximized in unannealed films and where mobility reaches a plateau at its highest value for annealed films.     

不同制备工艺下氧化硅和氧化铪薄膜的椭偏光谱

椭偏技术是一种分析表面的光学方法,通过测量被测对象(样品)反射出的光线的偏振状态的变化情况来研究被测物质的性质。结合XRD和原子力显微镜等方法,利用椭圆偏振光谱仪测试了单层SiO2薄膜(K9基片)和单层HfO2薄膜(K9基片)的椭偏参数,并用Sellmeier模型和Cauchy模型对两种薄膜进行拟合,获得了SiO2薄膜和HfO2薄膜在300～800 nm波段内的色散关系。用X射线衍射仪确定薄膜结构,用原子力显微镜观察薄膜的微观形貌,分析表明:SiO2薄膜晶相结构呈现无定型结构,HfO2薄膜的晶相结构呈现单斜相结构;薄膜光学常数的大小和薄膜的表面形貌有关;Sellmeier和Cauchy模型较好地描述了该波段内薄膜的光学性能,并得到薄膜的折射率和消光系数等光学常数随波长的变化规律。