Long‐Range Domain Structure and Symmetry Engineering by Interfacial Oxygen Octahedral Coupling at Heterostructure Interface

In epitaxial thin film systems, the crystal structure and its symmetry deviate from the bulk counterpart due to various mechanisms such as epitaxial strain and interfacial structural coupling, which is accompanyed by a change in their properties. In perovskite materials, the crystal symmetry can be described by rotations of sixfold coordinated transition metal oxygen octahedra, which are found to be altered at interfaces. Here, it is unraveled how the local oxygen octahedral coupling at perovskite heterostructural interfaces strongly influences the domain structure and symmetry of the epitaxial films resulting in design rules to induce various structures in thin films using carefully selected combinations of substrate/buffer/film. Very interestingly it is discovered that these combinations lead to structure changes throughout the full thickness of the film. The results provide a deep insight into understanding the origin of induced structures in a perovskite heterostructure and an intelligent route to achieve unique functional properties.     

Skin-like Omnidirectional Stretchable Platform with Negative Poisson's Ratio for Wearable Strain–Pressure Simultaneous Sensor

Conventional elastomeric polymers used as substrates for wearable platforms have large positive Poisson's ratios (≈0.5) that cause a deformation mismatch with human skin that is multidirectionally elongated under bending of joints. This causes practical problems in elastomer-based wearable devices, such as delamination and detachment, leading to poorly reliable functionality. To overcome this issue, auxetic-structured mechanical reinforcement with glass fibers is applied to the elastomeric film, resulting in a negative Poisson's ratio (NPR), which is a skin-like stretchable substrate (SLSS). Several parameters for determining the materials and geometrical dimensions of the auxetic-structured reinforcing fillers are considered to maximize the NPR. Based on numerical simulation and digital image correlation analysis, the deformation tendencies and strain distribution of the SLSS are investigated and compared with those of the pristine elastomeric substrate. Owing to the strain-localization characteristics, an independent strain-pressure sensing system is fabricated using SLSS with a Ag-based elastomeric ink and a carbon nanotube-based force-sensitive resistor. Finally, it is demonstrated that the SLSS-based sensor platform can be applied as a wearable device to monitor the physical burden on the wrist in real time.     

Environmental protection of inkjet-printed Ag conductors

Electrically conductive silver nanoparticle ink patterns were fabricated using the inkjet printing method. Two different polymer films were used as the substrate materials. The patterns were exposed to humidity and salt fog and the electrical performance (sheet resistance and RF performance) as well as mechanical endurance (adhesion) were measured before and after the environmental tests. The electrical properties of the printed structures remained good in all the measurable samples. The adhesion between the ink and a substrate material appeared to be a greater challenge in harsh environments. Protection capabilities of one dip coated and one hot laminated barrier materials were evaluated during the environmental tests. The results showed that there is a need for environmental protection in printed electronics. Especially the laminated barrier films can offer a potential solution for shielding printed electronics in harsh environments as they can provide good mechanical protection, and can easily be integrated in roll-to-roll process.     

Electromechanical properties of printed copper ink film using a white flash light annealing process for flexible electronics

We report on a systematic study of the electromechanical properties of flexible copper (Cu) thin film for flexible electronics. Cu ink is synthesized with chemical reduction process. Cu ink film spin-coated on a polyimide substrate is annealed with white flash light, also known as intense pulsed light (IPL), which guarantees a room temperature and sub-second process in ambient conditions. IPL annealed Cu film shows the electrical resistivity of 4.8 μΩ cm and thickness of 200 nm. The electromechanical properties of IPL annealed Cu film are investigated via outer/inner bending, stretching, and adhesion tests, and it is compared with conventional electron-beam evaporated Cu film. IPL annealed Cu film shows a constant electrical resistance within a bending radius of 6 mm. The bending fatigue test shows that the Cu film can withstand 10,000 bending cycles. In the stretching test, the Cu film shows a 50% increase in resistance when a strain of 2.4% was induced. At 4% strain, the resistance increases more than 200%. Meanwhile, the electron-beam evaporated film shows a constant resistance up to a strain of 4%. Lower stretchability of IPL annealed Cu film is attributed to its inherent cracks and porous film morphologies. IPL annealing induces the local melting at the interface between the substrate and Cu film, which increases the adhesion strength of the Cu film. These results provide useful information regarding the mechanical flexibility and durability of the nanoparticle films for the development of flexible electronics.     

Fully Printed Foldable Integrated Logic Gates with Tunable Performance Using Semiconducting Carbon Nanotubes

The realization of large‐area and low‐cost flexible macroelectronics relies on both the advancements in materials science and the innovations in manufacturing techniques. In this study, extremely bendable and foldable carbon nanotube thin film transistors and integrated logic gates are fabricated on a piece of ultrathin polyimide substrate through an ink‐jet‐like printing process. The adoption of a hybrid gate dielectric layer consisting of barium titanate nanoparticles and poly(methyl methacrylate) has led to not only excellent gating effect but also superior mechanical compliance. The device characteristics show negligible amount of change after up to 1000 cycles of bending tests with curvature radii down to 1 mm, as well as very aggressive folding tests. Additionally, the electrical characteristics of each integrated logic gate can be tuned and optimized individually by using different numbers of carbon nanotube printing passes for different devices, manifesting the unique adaptability of ink‐jet printing as a digital, additive, and maskless method. This report on fully printed and foldable integrated logic gates represents an inspiring advancement toward the practical applications of carbon nanotubes for high‐performance and low‐cost ubiquitous flexible electronics.     

Preliminary Works of Contact via Formation of LCD Backplanes Using Silver Printing

The fabrication of a thin‐film transistor backplane and a liquid‐crystal display using printing processes can eliminate the need for photolithography and offers the potential to reduce the manufacturing costs. In this study, we prepare contact via structures through a poly(methyl methacrylate) polymer insulator layer using inkjet printing. When droplets of silver ink composed of a polymer solvent are placed onto the polymer insulator and annealed at high temperatures, the silver ink penetrates the interior of the polymer and generates conducting paths between the top and bottom metal lines through the partial dissolution and swelling of the polymer. The electrical property of various contact via‐hole interconnections is investigated using a semiconductor characterization system.     

Universally applicable small-molecule co-host ink formulation for inkjet printing red,green, and blue phosphorescent organic light-emitting diodes

For organic light-emitting diodes (OLEDs), inkjet printing technology is being developed as an alternative to the traditional vacuum evaporation, because of its precise patterning, high-efficient material utilization, large-area compatibility and low-cost. In this work, we report a universal ink formulation of small-molecule co-host and binary solvents for red, green and blue phosphorescent OLEDs. Moreover, the effect of hole-transporting layers on the ink spreading, film uniformity and exciton confinement ability is investigated. Furthermore, a large-area (170 mm × 170 mm) and homogeneous light-emitting film is inkjet-printed. Finally, red, green and blue OLEDs are successfully constructed using these optimized ink formulations on the solvent resistance hole-transporting layer. This work can reduce the complexity to adjust the host materials and solvents for different color inks, and could be applied in large-area and low-cost OLED displays with high resolution.     

3D Printing of Multifunctional Conductive Polymer Composite Hydrogels

Functional conductive hydrogels are widely used in various application scenarios, such as artificial skin, cell scaffolds, and implantable bioelectronics. However, their novel designs and technological innovations are severely hampered by traditional manufacturing approaches. Direct ink writing (DIW) is considered a viable industrial-production 3D-printing technology for the custom production of hydrogels according to the intended applications. Unfortunately, creating functional conductive hydrogels by DIW has long been plagued by complicated ink formulation and printing processes. In this study, a highly 3D printable poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)-based ink made from fully commercially accessible raw materials is demonstrated. It is shown that complex structures can be directly printed with this ink and then precisely converted into high-performance hydrogels via a post-printing freeze–thawing treatment. The 3D-printed hydrogel exhibits high electrical conductivity of ≈2000 S m⁻¹, outstanding elasticity, high stability and durability in water, electromagnetic interference shielding, and sensing capabilities. Moreover, the hydrogel is biocompatible, showing great potential for implantable and tissue engineering applications. With significant advantages, the fabrication strategy is expected to open up a new route to create multifunctional hydrogels with custom features, and can bring new opportunities to broaden the applications of hydrogel materials.     

干涉在喷墨打印文件中朱墨时序的应用研究

朱墨时序检验是文件形成时间检验技术的重要组成部分之一,随着涉及喷墨打印文件的案件增多,为有效解决在喷墨打印文件中朱墨时序检验难、难检验的问题,将薄膜干涉原理应用在朱墨时序文件检验中,探索研究一种朱墨时序检验中的新特征。针对打印机的类型、印章印油的种类、印文材料、光线等方面,寻找薄膜干涉现象对朱墨时序的影响,分析朱墨时序现象形成的原因。通过显微镜检验法观察不同条件下黄绿干涉条纹的表现,进行综合比较分析。结果表明,先墨后朱比先朱后墨的薄膜干涉现象更为明显,以此可以判断薄膜干涉现象对朱墨时序检验具有应用价值,可为印刷文件和印章的先后顺序判断提供参考和借鉴。     

Design of color tunable thin film polymer solar cells for photovoltaics printing

Color tunable thin film polymer solar cells have demonstrated the potentials of a wide applications in photovoltaics printing, which is significant for ink pollution reduction and energy saving. This work presents a new effective approach to realize color-tuning photovoltaic cells with optical microcavity structures. Aluminum-doped zinc oxide is utilized as electron transport layer material. With its high electrical conductivity, the thickness tuning range can be quite large, which means the cavity length has a wide variation range. It thus provides sufficient space for optical thin film design to obtain multi colors. By the transfer matrix method, device reflection and absorption spectra are numerically investigated. Based on that, the optical principles for color tunability are explored. In further step, the relationship between device photovoltaics performance and reflective colors are also discussed. Finally, the color coordinates and luminosities are calculated. As results, the colors of the devices designed are capable to cover a relatively large region in Commission Internationale de l′Eclairage(CIE) 1931 x, y chromaticity diagram, which is available to be integrated into the advertisement poster boards, building wall printing and other display applications.     

Study of nano-mechanical properties for thin porous films through instrumented indentation: SiO2 low dielectric constant films as an example

Much research has been focused on the mechanical properties of porous materials such as films of silica xerogels because of their potential for application to microelectronic interconnects. To accurately probe the film properties, one has to challenge with the porosity as well as the large differences between film and substrate properties. In this paper, a study is presented for the investigation of Young’s modulus and yield stress of these porous films by instrumented indentation under complete consideration of the substrate influence by using the approach of the ‘effectively shaped indenter concept’. This concept provides the basis of a more appropriate analysis for thin films in case of elastic-plastic contact situations as given for porous low-k films. It was found that the ratio of yield stress to Young’s modulus, which equals the yield strain of the stress-strain curve, is not constant and changes with porosity.     

基于纳米颗粒的铜锌锡硫硒薄膜制备

采用热注入法制备了Cu2ZnSnS4(CZTS)纳米颗粒,并形成高分散、稳定的"墨水",采用滴注方法形成CZTS前驱体薄膜。利用X射线衍射(XRD)、拉曼光谱(Raman)、透射电子显微镜(TEM)和紫外-可见光谱(UV-VIS)对CZTS纳米颗粒的晶体结构、表面形貌和带隙进行了表征。Raman数据显示合成的纳米颗粒为纯的CZTS,不存在ZnS和Cu2SnS3等杂相。傅里叶红外光谱(FTIR)和UV-VIS表明合成的CZTS纳米颗粒表面被油胺(OLA)包覆,并且其带隙为1.52 eV。对CZTS前驱体薄膜在硫化氢气氛和固态硒气氛中退火处理,得到铜锌锡硫硒(CZTSSe)薄膜。结果表明,经硫化氢处理后薄膜表面平整但CZTS晶粒并没长大,而经过固态硒处理后得到了结晶质量较好的CZTSSe薄膜。     

3D-Printed Photoresponsive Liquid Crystal Elastomer Composites for Free-Form Actuation

Direct ink writing of liquid crystal elastomers (LCEs) offers a new opportunity to program geometries for a wide variety of shape transformation modes toward applications such as soft robotics. So far, most 3D-printed LCEs are thermally actuated. Herein, a 3D-printable photoresponsive gold nanorod (AuNR)/LCE composite ink is developed, allowing for photothermal actuation of the 3D-printed structures with AuNR as low as 0.1 wt.%. It is shown that the printed filament has a superior photothermal response with 27% actuation strain upon irradiation to near-infrared (NIR) light (808 nm) at 1.4 W cm⁻² (corresponding to 160 °C) under optimal printing conditions. The 3D-printed composite structures can be globally or locally actuated into different shapes by controlling the area exposed to the NIR laser. Taking advantage of the customized structures enabled by 3D printing and the ability to control locally exposed light, a light-responsive soft robot is demonstrated that can climb on a ratchet surface with a maximum speed of 0.284 mm s⁻¹ (on a flat surface) and 0.216 mm s⁻¹ (on a 30° titled surface), respectively, corresponding to 0.428 and 0.324 body length per min, respectively, with a large body mass (0.23 g) and thickness (1 mm).     

Thickness Dependence of the Mechanical Properties of Free‐Standing Graphene Oxide Papers

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.     

Two-Dimensional Material-Enhanced Flexible and Self-Healable Photodetector for Large-Area Photodetection

Flexible photodetectors are fundamental elements to develop flexible/wearable systems, which can be widely used for in situ health and environmental monitoring, human–machine interacting, flexible displaying, etc. However, the degraded performance or even malfunction under severe mechanical deformation and/or damage remains a key challenge for current flexible photodetectors. In this article, a flexible photodetector is developed with strong self-healing capability and stable performance under large deformation. This photodetector is made of the 2D material self-healing film by mixing 2D materials homogenously with the self-healing polymer of imidazolium-based norbornene polymerized with ionic liquids and counterions. The 2D material self-healing films show enhanced light absorption, and thus, decent photoresponse as compared to the pure self-healing film. The achieved photoresponse remains stable and even increases under small tensile strain within 150%, while decreases slightly under large tensile strain up to 1000%. Moreover, the photodetector not only can be fully recovered from repeated mechanical cuttings, but also presents excellent long-term stability in ambient condition for 500 days without showing any obvious degraded performance. Furthermore, a large-area 2D material self-healing photodetection array is designed with adjustable pixel size, which successfully recognizes the patterns of “T”, “J”, and “U”.     

Ink formulation and low‐temperature incorporation of sodium to yield 12% efficient Cu(In,Ga)(S,Se)2 solar cells from sulfide nanocrystal inks

Solution phase deposition methods offer great potential for low‐cost photovoltaic device fabrication. We have previously developed a method for copper indium gallium disulfoselenide (CIGSSe) device fabrication based on drop‐casting copper indium gallium disulfide (CIGS) nanocrystals in a toluene or hexane‐based ink followed by chalcogen exchange in elemental selenium vapor at 500 °C. By starting with the chalcopyrite or sphaelerite phase of CIGS nanocrystals with controlled stoichiometry, superior composition uniformity can be achieved inherently. Here, we present a dramatic improvement in ink formulation using alkanethiol as the solvent, which enables the ability to create uniform nanocrystal coatings over large areas using a simple knife coating technique. In addition, we show a major improvement in device performance by a simple and low‐temperature method of incorporating sodium into the CIGSSe film based on soaking the films in aqueous NaCl solution. The addition of sodium plays an important role in improving the structural properties of the resulting CIGSSe films, where large and densely packed grain can be obtained. The improved film morphology significantly reduces recombination losses in the resulting device leading to a dramatically enhanced device performance. With the use of standard glass/Mo/CIGSSe/CdS/i‐ZnO/ITO device structure, photovoltaic devices yield total area power conversion efficiency as high as 12.0% under AM1.5 illumination without an anti‐reflection coating. Copyright © 2012 John Wiley & Sons, Ltd.     

Printable Ultra-Flexible Fluorinated Organic–Inorganic Nanohybrid Sol–Gel Derived Gate Dielectrics for Highly Stable Organic Thin-Film Transistors and Other Practical Applications

A novel fluorinated organic–inorganic (O–I) hybrid sol—gel based material, named FAGPTi, is successfully synthesized and applied as a gate dielectric in flexible organic thin-film transistors (OTFTs). The previously reported three-arm-shaped alkoxysilane-functionalized amphiphilic polymer yields a stable O–I hybrid material consisting of uniformly dispersed nanoparticles in the sol-state. Here, a fluorinated precursor is introduced into the system, making it possible to realize more stable spherical composites. This results in long-term colloidal stability (≈1.5 years) because composite growth is strongly inhibited by the presence of fluorine groups with intrinsically strong repulsive forces. Additionally, the FAGPTi film is easily deposited via thermally annealed sol–gel reactions; the films can be successfully fabricated through the printing method, and exhibit excellent flexibility and enhanced insulating properties compared to existing materials. OTFTs with FAGPTi layers show highly stable driving characteristics under severe bending conditions (1.9% strain). Integrated logic devices are also successfully operated with these OTFTs. Additionally, it can facilely be applied to amorphous indium-gallium-zinc-oxide (a-IGZO) TFT devices other than OTFT. Therefore, this synthetic strategy can provide useful insights into the production of functional O–I hybrid materials, enabling the efficient fabrication of electronic materials and devices exhibiting these properties.     

Strain Effects on Electronic Bandstructures in Nanoscaled Silicon: From Bulk to Nanowire

In this paper, we present a comparative computational study on strain effects in Si nanostructures including bulk, thin film, and nanowire configurations. We employed a first principles calculation to identify the bandstructure parameters such as band splitting energy and transport effective mass. As a result, we found that bulk Si and Si thin film have similar strain effects on the bandstructure parameters under uniaxial $langlehbox{110}rangle$ strain. Particularly, the effective mass reduction of electrons due to uniaxial $langlehbox{110}rangle$ strain is expected even in Si thin film. On the other hand, Si nanowire structure with nanoscale cross section has lighter transport effective mass than the other structures, regardless of the amount of uniaxial strain.      

Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.     

Ferroelectric Materials: Probing Local and Global Ferroelectric Phase Stability and Polarization Switching in Ordered Macroporous PZT (Adv. Funct. Mater. 5/2011)

We describe the characterization, ferroelectric phase stability and polarization switching in strain‐free assemblies of PbZr_0.3Ti_0.7O₃ (PZT) nanostructures. The 3‐dimensionally ordered macroporous structures present uniquely large areas and volumes of PZT where the microstructure is spatially modulated and the composition is homogeneous. Variable temperature powder X‐ray diffraction (XRD) studies show that the global structure is crystalline and tetragonal at room temperature and undergoes a reversible tetragonal to cubic phase transition on heating/cooling. The measured phase‐transition temperature is 50–60 °C lower than bulk PZT of the same composition. The local ferroelectric properties were assessed using piezoresponse force spectroscopy that reveal an enhanced piezoresponse from the nanostructured films and demonstrate that the switching polarization can be spatially mapped across these structures. An enhanced piezoresponse is observed in the nanostructured films which we attribute to the formation of strain free films, thus for the first time we are able to assess the effects of crystallite‐size independently of internal stress. Corresponding polarization distributions have been calculated for the bulk and nanostructured materials using a direct variational method and Landau‐Ginzburg‐Devonshire (LGD) theory. By correlating local and global characterization techniques we have for the first time unambiguously demonstrated the formation of tetragonal and ferroelectric PZT in large volume nanostructured architectures. With the wide range of materials available that can be formed into such controlled architectures we conclude that this study opens a pathway for the effective studies of nanoscale ferroelectrics in uniquely large volumes.