Control of Molecular Orientation in Organic Semiconductor Films using Weak Hydrogen Bonds

Use of the intrinsic optoelectronic functions of organic semiconductor films has not yet reached its full potential, mainly because of the primitive methodology used to control the molecular aggregation state in amorphous films during vapor deposition. Here, a universal molecular engineering methodology is presented to control molecular orientation; this methodology strategically uses noncovalent, intermolecular weak hydrogen bonds in a series of oligopyridine derivatives. A key is to use two bipyridin‐3‐ylphenyl moieties, which form self‐complementary intermolecular weak hydrogen bonds, and which do not induce unfavorable crystallization. Another key is to incorporate a planar anisotropic molecular shape by reducing the steric hindrance of the core structure for inducing π–π interactions. These synergetic effects enhance horizontal orientation in amorphous organic semiconductor films and significantly increasing electron mobility. Through this evaluation process, an oligopyridine derivative is selected as an electron‐transporter, and successfully develops highly efficient and stable deep‐red organic light‐emitting devices as a proof‐of‐concept.     

Ordered‐Assembly Conductive Nanowires Array with Tunable Polymeric Structure for Specific Organic Vapor Detection

An artificial organic vapor sensor based on a finite number of 1D nanowires arrays can provide a strategy to allow classification and identification of different analytes with high efficiency, but fabricating a 1D nanowires array is challenging. Here, a coaxial Ag/polymer nanowires array is prepared as an organic vapor sensor with specific recognition, using a strategy combining superwettability‐based nanofabrication and polymeric swelling‐induced resistance change. Such organic vapor sensor containing commercial polymers can successfully classify and identify various organic vapors with good separation efficiency. An Ag/polymer nanowires array with synthetic polyethersulfone polymers is also fabricated, through molecular structure modification of the polymers, to distinguish the similar organic vapors of methanol and ethanol. Theoretical simulation results demonstrate introduction of specific molecular interaction between the designed polymers and organic vapors can improve the specific recognition performance of the sensors.     

Polymeric nanolayers as actuators for ultrasensitive thermal bimorphs

Polymeric nanolayers are introduced here as active, thermal-stress mediating structures facilitating extremely sensitive thermal detection based upon the thermomechanical response of a bimaterial polymer-silicon microcantilever. To maximize the bimaterial bending effect, the microcantilever bimorph is composed of stiff polysilicon, with a strongly adhered polymer deposited via plasma-enhanced chemical vapor deposition. The polymer layers with thickness ranging from 20 to 200 nm possess a rapid and pronounced response to temperature fluctuations due to intrinsic sensitive thermal behavior. We show that by taking advantage of the thermal stresses generated by the huge mismatch of material properties in the polymer-silicon bimorph, unprecedented thermal sensitivities can be achieved. In fact, the temperature resolution of our bimaterial microcantilevers approaches 0.2 mK with thermal sensitivity reaching 2 nm/mK; both parameters are more than an order of magnitude better than the current metal-ceramic design. This new hybrid platform overcomes the inherently limited sensitivity of current sensor designs and provides the basis to develop the ultimate uncooled IR microsensor with unsurpassable sensitivity.     

Kinking of an interface crack in an orthotropic bimaterial

We investigated the asymptotic problem of a kinked interface crack in an orthotropic bimaterial under in‐plane loading conditions. The stress intensity factors at the tip of the kinked interface crack are described in terms of the stress intensity factors of the interface crack prior to the kink combined with a dimensionless matrix function. Using a modified Stroh formalism and an orthotropy rescaling technique, the matrix function was obtained from the solutions of the corresponding problem in transformed bimaterial. The effects of orthotropic and bimaterial parameters on the matrix function were examined. A reduction in the number of dependent material parameters on the matrix function was made using the modified Stroh formalism. Moreover, the explicit dependence of one orthotropic parameter on the matrix function was determined using an orthotropic rescaling technique. The effects of the other material parameters on the matrix function were numerically examined. The energy release rate was obtained for a kinked interface crack in an orthotropic bimaterial.     

A Highly Responsive Organic Image Sensor Based on a Two‐Terminal Organic Photodetector with Photomultiplication

Highly responsive organic image sensors are crucial for medical imaging applications. To enhance the pixelwise photoresponse in an organic image sensor, the integration of an organic photodetector with amplifiers, or the use of a highly responsive organic photodetector without an additional amplifying component, is required. The use of vertically stacked, two‐terminal organic photodetectors with photomultiplication is a promising approach for highly responsive organic image sensors owing to their simple two‐terminal structure and intrinsically large responsivity. However, there are no demonstrations of an imaging sensor array using organic photomultiplication photodetectors. The main obstacle to a sensor array is the weak‐light sensitivity, which is limited by a relatively large dark current. Herein, a highly responsive organic image sensor based on monolithic, vertically stacked two‐terminal pixels is presented. This is achieved using pixels of a vertically stacked diode‐type organic photodetector with photomultiplication. Furthermore, applying an optimized injection electrode and additionally stacked rectifying layers, this two‐terminal device simultaneously demonstrates a high responsivity (>40 A W^?1), low dark current, and high rectification under illumination. An organic image sensor based on this device with an extremely simple architecture exhibits a high pixel photoresponse, demonstrating a weak‐light imaging capability even at 1 µW cm^?2.     

Strategies for Drug Encapsulation and Controlled Delivery Based on Vapor‐Phase Deposited Thin Films

Vapor‐phase deposition methods allow the synthesis and engineering of organic and inorganic thin films, with high control on the chemical composition, physical properties, and conformality. In this review, the recent applications of vapor‐phase deposition methods such as initiated chemical vapor deposition (iCVD), plasma enhanced chemical vapor deposition (PE‐CVD), and atomic layer deposition (ALD), for the encapsulation of active pharmaceutical drugs are reported. The strategies and emergent routes for the application of vapor‐deposited thin films on the drug controlled release and for the engineering of advanced release nanostructured devices are presented.

     

Thermal Exfoliation of Layered Metal–Organic Frameworks into Ultrahydrophilic Graphene Stacks and Their Applications in Li–S Batteries

2D nanocarbon‐based materials with controllable pore structures and hydrophilic surface show great potential in electrochemical energy storage systems including lithium sulfur (Li–S) batteries. This paper reports a thermal exfoliation of metal–organic framework crystals with intrinsic 2D structure into multilayer graphene stacks. This family of nanocarbon stacks is composed of well‐preserved 2D sheets with highly accessible interlayer macropores, narrowly distributed 7 Å micropores, and ever most polar pore walls. The surface polarity is quantified both by its ultrahigh water vapor uptake of 14.3 mmol g^?1 at low relative pressure of P /P ₀ = 0.4 and ultrafast water wetting capability in less than 10.0 s. Based on the structural merits, this series hydrophilic multilayer graphene stack is showcased as suitable model cathode host for unveiling the challenging surface chemistry issue in Li–S batteries.     

Molecular Structure‐Dependent Charge Injection and Doping Efficiencies of Organic Semiconductors: Impact of Side Chain Substitution

Due to the highly anisotropic nature of π ‐conjugated molecules, the molecular structure of organic semiconductors can significantly affect the device performance of organic optoelectronics. Here, the molecular structure dependence on charge injection and doping efficiencies is investigated by characterizing the typical hole transport material of N,N′‐bis(naphthalen‐1‐yl)‐N,N′‐bis(phenyl)‐benzidine (NPB) and its derivatives N,N′‐bis(naphthalen‐1‐yl)‐N,N′‐bis(phenyl)‐9,9‐dimethyl‐fluorene (DMFL‐NPB) and N,N′‐bis(naphthalen‐1‐yl)‐N,N′‐bis(phenyl)‐9,9‐diphenyl‐fluorene (DPFL‐NPB)]. Using photoelectron spectroscopy data and density functional theory calculation, it is identified that the side chain substitution in NPB and its derivatives plays a crucial role in the intrinsic injection and transport properties, and doping efficiency. The inner twist of the two main benzene rings in NPB is changed from out‐of‐plane to in‐plane due to the alkyl or phenyl side chains of DMFL‐NPB or DPFL‐NPB, which reduces the ionization energies and thus decreases the hole injection barriers at the indium tin oxide/organic interface. The doping efficiency in 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F₄‐TCNQ) doped systems is also highly dependent on the degree of intermolecular orbital energy hybridization with respect to the side chain substitution. These findings show that the rational design of molecular structures with suitable side chains is crucial for achieving high‐performance organic devices.     

炭气凝胶及其有机气凝胶前驱体的吸附性能

间苯二酚和糠醛的醇溶液在六次甲基四胺催化下经溶胶-凝胶过程合成醇凝胶,常压干燥后得到有机气凝胶,经炭化获得炭气凝胶.利用TEM和N2吸附表征了炭气凝胶及其有机气凝胶前驱体的结构,并通过有机蒸汽吸附实验研究了气凝胶的结构-吸附性能关系.实验结果表明：有机气凝胶和炭气凝胶对极性有机蒸汽的静态饱和吸附量高于对非极性有机蒸汽的静态饱和吸附量;提高热处理温度,有利于气凝胶对低浓度极性有机蒸汽和各种浓度非极性有机蒸汽的吸附,但不利于对高浓度极性有机蒸汽的吸附;随着有机蒸汽浓度的提高,气凝胶对极性有机蒸汽的吸附量明显增大,但对非极性有机蒸汽的吸附量影响不大,仅略微上升.此外,气凝胶的室温脱附率高达60 %～85 %.     

Controlled Deposition of Crystalline Organic Semiconductors for Field‐Effect‐Transistor Applications

The search for low‐cost, large‐area, flexible devices has led to a remarkable increase in the research and development of organic semiconductors, which serve as one of the most important components for organic field‐effect transistors (OFETs). In the current review, we highlight deposition techniques that offer precise control over the location or in‐plane orientation of organic semiconductors. We focus on various vapor‐ and solution‐processing techniques for patterning organic single crystals in desired locations. Furthermore, the alignment of organic semiconductors via different methods relying on mechanical forces, alignment layers, epitaxial growth, and external magnetic and electric fields are surveyed. The advantages, limitations, and applications of these techniques in OFETs are also discussed.     

Material‐dependent crack‐tip enrichment functions in XFEM for modeling interfacial cracks in bimaterials

A novel set of enrichment functions within the framework of the extended finite element method is proposed for linear elastic fracture analysis of interface cracks in bimaterials. The motivation for the new enrichment set stems from the revelation that the accuracy and conditioning of the widely accepted 12‐fold bimaterial enrichment functions significantly deteriorates with the increase in material mismatch. To this end, we propose an 8‐fold material‐dependent enrichment set, derived from the analytical asymptotic displacement field, that well captures the near‐tip oscillating singular fields of interface cracks, including the transition to weak discontinuities of bimaterials. The performance of the proposed material‐dependent enrichment functions is studied on 2 benchmark examples. Comparisons are made with the 12‐fold bimaterial enrichment as well as the classical 4‐fold homogeneous branch functions, which have also been used for bimaterials. The numerical studies clearly demonstrate the superiority of the new enrichment functions, which yield the most accurate results but with less number of degrees of freedom and significantly improved conditioning than the 12‐fold functions.     

An analytical expression for the J2‐integral of an interfacial crack in orthotropic bimaterials

This paper presents a new analytical expression relating the J₂‐integral and stress intensity factors (SIF) in an in‐plane traction‐free crack between two orthotropic elastic solids using the complex function method. The singular oscillatory near tip field of a bimaterial interfacial crack is usually characterized by a pair of SIFs. In linear elastic interfacial fracture mechanics, the majority of numerical and experimental methods rely on the analytical equations relating J_k‐integrals and SIFs. Although an analytical equation relating J₁‐integral or strain energy release rate and SIFs is available, a similar relation for J₂‐integral in debonded anisotropic solids is non‐existent. Using this new analytical expression, in conjunction with the values of J_k, the SIFs can be computed without the need for an auxiliary relation. An example with known analytical solutions for SIFs is presented to show the variation of the J₂‐integral near the crack tip of a bimaterial orthotropic plate. Different bimaterial combinations are considered, and the effect of material mismatch on J_k is demonstrated.     

General size effect on strength of bimaterial quasibrittle structures

This paper presents a general size effect equation for the strength of hybrid structures, which are made of two dissimilar quasibrittle materials with a thin and weak bimaterial interface. Depending on the material mismatch and structure geometry, a singular stress field could occur at the bimaterial corner. For structures with strong stress singularities, an energetic size effect is derived based on the equivalent linear elastic fracture mechanics and asymptotic matching. For structures without stress singularities, a finite weakest link model is adopted to derive the size effect. A general scaling equation that bridges the limits of strong and zero stress singularities is formulated by combining the energetic scaling of fracture of the bimaterial corner and the finite weakest link model.     

Structural study of single-walled carbon nanotube films doped by a solution method

Herein, we have studied a structure of SWNT films doped by organic molecules. In this study, we reacted organic molecules with SWNT films by a vapor phase and a liquid phase, respectively. The structure of doped SWNT films was investigated using synchrotron X-ray powder diffraction measurements, and we found the clear difference between the vapor phase reaction (v-doped) and the liquid phase reaction (I-doped). In v-doped SWNT films, organic molecules are predominantly encapsulated inside SWNTs, although molecules adsorbed on the surface of SWNT bundles in l-doped SWNT films.     

Effect of ultraviolet illumination and ambient gases on the photoluminescence and electrical properties of nanoporous silicon layer for organic vapor sensor

The purpose of this research, the nanoporous silicon layer were fabricated and investigated the physical properties such as photoluminescence and the electrical properties in order to develop organic vapor sensor by using nanoporous silicon. The Changes in the photoluminescence intensity of nanoporous silicon samples are studied during ultraviolet illumination in various ambient gases such as nitrogen, oxigen and vacuum. In this paper, the nanoporous silicon layer was used as organic vapor adsorption and sensing element. The advantage of this device are simple process compatible in silicon technology and usable in room temperature. The structure of this device consists of nanoporous silicon layer which is formed by anodization of silicon wafer in hydrofluoric acid solution and aluminum electrode which deposited on the top of nanoporous silicon layer by evaporator. The nanoporous silicon sensors were placed in a gas chamber with various organic vapor such as ethanol, methanol and isopropyl alcohol. From studying on electrical characteristics of this device, it is found that the nanoporous silicon layer can detect the different organic vapor. Therefore, the nanoporous silicon is important material for organic vapor sensor and it can develop to other applications about gas sensors in the future.     

Expedient vapor probing of organic amines using fluorescent nanofibers fabricated from an n-type organic semiconductor

A new type of fluorescence sensory material with high sensitivity, selectivity, and photostability has been developed for vapor probing of organic amines. The sensory material is primarily based on well-defined nanofibers fabricated from an n-type organic semiconductor molecule, N-(1-hexylheptyl)perylene-3,4,9,10-tetracarboxyl-3,4-anhydride-9,10-imide. Upon deposition onto a substrate, the entangled nanofibers form a meshlike, highly porous film, which enables expedient diffusion of gaseous analyte molecules within the film matrix, leading to milliseconds response for the vapor sensing.     

The boundary finite element method for predicting directions of cracks emerging from notches at bimaterial junctions

The analysis of a bimaterial medium with various notch opening angles has been carried out using boundary finite element method (BFEM) under arbitrary loading conditions. Introduced as novel method for stress concentration problems at geometrical discontinuities, cracks, bimaterial notches etc., the BFEM has been proved as numerically highly efficient. This has become more and more important because wedge type construction creates stress concentrations which may lead to crack initiation in many practical situations where multi-layered composite material is used, e.g. within aerospace, ship or automobile structures. So, the computational prediction of potential directions for crack initiation is essential for the knowledge of weak regions. All the analysis results are based on the hypothesis of Erdogan and Sih and have been verified by the well established finite element method. Results for potential crack initiation angles of both homogeneous and bimaterial media are presented with multiple examples of different wedge angles and different loading combinations.     

Hierarchical Porous SWCNT Stringed Carbon Polyhedrons and PSS Threaded MOF Bilayer Membrane for Efficient Solar Vapor Generation

Interfacial solar vapor generation is considered to be an efficient and eco‐friendly technology for harvesting solar energy and providing freshwater. However, the efficient and long‐term steady evaporation of seawater under 1 sun becomes a critical issue when it comes to practical applications. Based on this issue, a special double‐layer structure, which contains a metal–organic‐framework‐derived hierarchical porous carbon membrane (HPCM) for solar absorption and a polystyrene sulfonate (PSS)@Cu₃(BTC)₃?3H₂O (HKUST‐1)/single‐walled carbon nanotube (SWCNT) (PHS) membrane for water supply and salt blocking, is designed in this work. The converted heat is utilized efficiently in situ to drive the evaporation of water‐trapped HPCM. The PHS membrane with PSS modified channels successfully prevents the deposition of salt. Due to the synergistic combination of the HPCM and PHS membranes, the device exhibits a remarkably high water evaporation rate of 1.38 kg m^?2 h^?1 and solar‐vapor generation efficiency of 90.8% under 1 sun.     

25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

Well‐adhered, conformal, thin (<100 nm) coatings can easily be obtained by chemical vapor deposition (CVD) for a variety of technological applications. Room temperature modification with functional polymers can be achieved on virtually any substrate: organic, inorganic, rigid, flexible, planar, three‐dimensional, dense, or porous. In CVD polymerization, the monomer(s) are delivered to the surface through the vapor phase and then undergo simultaneous polymerization and thin film formation. By eliminating the need to dissolve macromolecules, CVD enables insoluble polymers to be coated and prevents solvent damage to the substrate. CVD film growth proceeds from the substrate up, allowing for interfacial engineering, real‐time monitoring, and thickness control. Initiated‐CVD shows successful results in terms of rationally designed micro‐ and nanoengineered materials to control molecular interactions at material surfaces. The success of oxidative‐CVD is mainly demonstrated for the deposition of organic conducting and semiconducting polymers.     

Partition of unity enrichment for bimaterial interface cracks

Partition of unity enrichment techniques are developed for bimaterial interface cracks. A discontinuous function and the two‐dimensional near‐tip asymptotic displacement functions are added to the finite element approximation using the framework of partition of unity. This enables the domain to be modelled by finite elements without explicitly meshing the crack surfaces. The crack‐tip enrichment functions are chosen as those that span the asymptotic displacement fields for an interfacial crack. The concept of partition of unity facilitates the incorporation of the oscillatory nature of the singularity within a conforming finite element approximation. The mixed‐mode (complex) stress intensity factors for bimaterial interfacial cracks are numerically evaluated using the domain form of the interaction integral. Good agreement between the numerical results and the reference solutions for benchmark interfacial crack problems is realized. Copyright © 2004 John Wiley & Sons, Ltd.