Interfacial phenomena between conjugated organic molecules and noble metals

Understanding interfacial interaction between conjugated organic molecules and noble metals is important not only for surface science, but also in relation to organic epitaxy, the architecture of intermolecular networks or nanostructures, and organic electronics. Particularly, properties of interfacial geometric and electronic structures and their related phenomena have attracted much interest for their potential in various electronic and optoelectronic applications, and thus extensive efforts have been devoted to understand and control organic/metal interfaces. We provide an overview of interfacial phenomena between conjugated organic molecules and noble metals via various interactions at the organic/metal interfaces such as surface-molecule and intermolecular interactions, as well as recent progress achieved in this area.     

In situ–Directed Growth of Organic Nanofibers and Nanoflakes: Electrical and Morphological Properties

Organic nanostructures made from organic molecules such as para-hexaphenylene (p-6P) could form nanoscale components in future electronic and optoelectronic devices. However, the integration of such fragile nanostructures with the necessary interface circuitry such as metal electrodes for electrical connection continues to be a significant hindrance toward their large-scale implementation. Here, we demonstrate in situ–directed growth of such organic nanostructures between pre-fabricated contacts, which are source–drain gold electrodes on a transistor platform (bottom-gate) on silicon dioxide patterned by a combination of optical lithography and electron beam lithography. The dimensions of the gold electrodes strongly influence the morphology of the resulting structures leading to notably different electrical properties. The ability to control such nanofiber or nanoflake growth opens the possibility for large-scale optoelectronic device fabrication.     

Different interface orientations of pentacene and PTCDA induce different degrees of disorder

ABSTRACT: Organic polymers or crystals are commonly used in manufacturing of today's electronically functional devices (OLEDs, organic solar cells, etc). Understanding the morphology in general and at the interface in particular is of paramount importance. Proper knowledge of molecular orientation at interfaces is essential for predicting optoelectronic properties such as exciton diffusion length, charge carrier mobility and molecular quadrupole moments. Two promising candidates are pentacene and PTCDA. Different orientations of pentacene on PTCDA have been investigated using an atomistic molecular dynamics approach. Here, we show that the degree of disorder at the interface depends largely on the crystal orientation and that more ordered interfaces generally suffer from large vacancy formation.     

Metallo-organic Conjugated Systems for Organic Electronics

Polymer/organic optoelectronic devices have been the center of attention for the last two decades for both the academic and industrial research communities, due to their potential as a a low-cost, large-area, solution-processable technology alternative to their conventional, inorganic counterparts. There are several issues, such as the lower efficiencies, lower stabilities, and higher resistances of organic/polymer-based optoelectronic devices. To address these obstacles, significant research activity has been devoted to π-conjugated organics. One of the approaches includes the incorporation of metal complexes in the main conjugation or as a pendant substitution on that. Metallo-organic compounds with transition row elements have been extensively studied in organic electronics due to the easy tunability of their electronic properties, amenable redox matching, and the extended life-time of the triplet state. This has successfully resulted in some high performance electronic devices containing metallo-organic π-conjugated small molecules and polymers. Herein, we review the recent advances made in metallo-organic materials (small molecules and polymers) for organic electronics.     

Recent Advances in Hybrid Optoelectronics

Polymer/organic optoelectronic devices have drawn the attention of both the academic and industrial research communities due to the potential for a low-cost, large-area, solution-processable technology alternative to conventional inorganic optoelectronics. Issues related to the stability and degradation of the organic/polymer-based optoelectronics are hampering the progress in the field. The use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT : PSS) as the anode and reactive metals as the cathode, as well as the degradation of organic semiconductors in ambient atmosphere, are some of the stability issues to be addressed. To resolve these issues, in the past decade, there has been a growing interest in research of hybrid optoelectronic devices which employ metal oxides as air-stable charge injecting/extracting layers that sandwich the photo-responsive organic active layer and protect it from the ambient oxygen and moisture and prevent photo-oxidation by absorbing UV light. Herein, we review the recent advances made in hybrid optoelectronics and discuss the tremendous potential of these devices.     

Engineering the metal–organic interface by transferring a high-quality single layer graphene on top of organic materials

We present a new method for transferring chemical vapor deposition (CVD)-grown graphene onto the surfaces of organic materials directly. Raman and near edge X-ray absorption fine structure measurements prove that high-quality and single layer graphene/organic thin films can be obtained with minimized impurity introduction. In-situ synchrotron radiation photoemission spectroscopy combined with ultraviolet photoelectron spectroscopy experiments demonstrate that the inserted graphene can not only act as a buffer layer to reduce the interfacial chemical reactions between the deposited Al and organic materials, but also tune the metal/organic interface electronic structure significantly. This new graphene transfer technique may have a great potential in the application of engineering the metal–organic interface properties, which is one of the key technologies for the optimal design and fabrication of organic electronic and optoelectronic devices.     

Phosphonate-functionalized polyfluorene and its application in organic optoelectronic devices

Conjugated polar polymers, in which the conjugated backbones are chemically anchored with functional polar side groups, can be processed with water/alcohol solvents, and thus multilayered device architectures can be easily realized via sequential solution processing of the toluene-soluble emissive polymer and alcohol-soluble electron-transporting polymer without intermixing. Regarding their use in organic optoelectronic devices, the success in achieving efficient charge injection and intimate contact between metal electrodes and organic semiconductors is very vital for enhancing the device performance. In this short review, it gives a brief review to neutral alcohol-soluble phosphonate-functionalized polyfluorene, mainly concerning the electronic structure at the phosphonate-functionalized polyfluorene/aluminum cathode interface and its successful application in multilayered polymer optoelectronic devices including polymer light-emitting diodes and polymer solar cells.     

Enhanced light extraction in ITO-free OLEDs using double-sided printed electrodes

We show how nanoimprint lithographic techniques are particularly suited for the realization of OLED device structures. We tested them to realize nanopatterned metallic electrodes containing photonic crystals to couple the light out and plasmonic crystals showing extraordinary transmission. At similar current densities, a two-fold electroluminescence is achieved with devices having double-sided structured metallic electrodes as compared to a control OLED with an ITO anode. The use of combined nanoimprint lithography processes has the potential to expand the performance range of various organic optoelectronic devices.     

Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics

Polyfluorenes have emerged as versatile semiconducting materials with applications in various polymer optoelectronic devices, such as light-emitting devices, lasers, solar cells, memories, field-effect transistors and sensors. Organic syntheses and polymerizations allow for the powerful introduction of various periodic table elements and their building blocks into π-conjugated polymers to meet the requirements of organic devices. In this review, a soccer-team-like framework with 11 nodes is initially proposed to illustrate the structure-property relationships at three levels: chain structures, thin films and devices. Second, the modelling of hydrocarbon polyfluorenes (CPFs) is summarized within the framework of a four-element design principle, in which we have highlighted polymorphic poly(9,9-dialkylfluorene)s with unique supramolecular interactions, various hydrocarbon-based monomers with different electronic structures, functional bulky groups with steric hindrance effects and ladder-type, kinked, hyperbranched and dendritic conformations. Finally, the detailed electronic structure designs of main-chain-type heteroatomic copolyfluorenes (HPFs) and metallopolyfluorenes (MPFs) are described in the third and fourth sections. Supramolecular, nano and soft semiconductors are the future of polyfluorenes in the fields of optoelectronics, spintronics and electromechanics.     

On the phase behaviour of organic semiconductors

The physical organisation, from the molecular to the macroscale, of functional organic matter such as polymer semiconductors can profoundly affect the properties and features of the resulting architectures and their consequent performance when used as active layers in organic optoelectronic devices, including organic thin‐film field‐effect transistors, organic light‐emitting diodes or organic photovoltaic cells. Here, we present a survey on the principles of structure development from the liquid phase of this interesting and broad class of materials with focus on how to manipulate their phase transformations and solid‐state order to tailor and manipulate the final ‘morphology’ towards technological and practical applications. Copyright © 2012 Society of Chemical Industry     

Moisture permeability through multilayered barrier films as applied to flexible OLED display

Strict protection of organic light‐emitting diodes (OLEDs) and other optoelectronic materials from direct contact with ambient moisture and oxygen is one of the major challenges in the development of flexible OLED displays and other flexible electronic devices. This problem is typically addressed by the use of polymeric substrates with multilayered barrier coatings comprising alternating organic/inorganic layers. The multilayered barrier approach is critically examined using a numerical model based on a defect‐dominated diffusion process combined with experiments involving face‐to‐face lamination of two barrier films. The modeling results identify two regimes, corresponding to two distinct permeation mechanisms, and provide scaling relationships and general design criteria for multilayered barrier coatings. The results suggest that the most significant gain in barrier performance can be realized when the thickness of the organic/adhesive layer(s) in the multilayered structure is less than the average pinhole (defect) size in the inorganic barrier layer(s). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Failure Mechanisms of Stretchable Perovskite Light-Emitting Devices under Monotonic and Cyclic Deformations

This paper presents the results of experimental and analytical studies of the failure mechanisms of stretchable perovskite light-emitting devices (PeLEDs). The multilayered PeLED structures consist of an anodic layer of poly(3,4-ethylenedioxythiophene):polystyrene-sulfonate (PEDOT:PSS), an emissive layer of methylammonium lead bromide (MAPbBr₃), and a eutectic gallium–indium (EGaIn) cathodic layer, which are deposited onto treated polydimethylsiloxane substrates. The intrinsically nonstretchable MAPbBr₃ and PEDOT:PSS are modified with poly(ethylene oxide). The failure mechanisms of the layered stretchable PeLED structures are then investigated under monotonic and cyclic deformations. The optical and scanning electron microscopy images show the deflection and propagation of cracks and wrinkles under applied strains. Cracking of perovskite crystal and debonding of films are also observed with increased cyclic deformation. The effects of the failure mechanisms on the optoelectronic properties of the devices are then studied. The in situ measured transmittance of the PEDOT:PSS (≈75%) reduces with increasing uniaxial strain, and then is increased close to its initial value when the strain is released. The turn-on voltage of the device increases with increasing number of cycles between 50 and 1000 cycles at 20% strain level. The fatigue lifetimes of the PeLED structures are used to explain the design of stretchable perovskite devices.     

Electronic structures and photophysical properties of carbazole- and thiophene-based organic compounds used as hole-injecting layer for organic light-emitting diodes (OLEDs)

In this study, we have carried out a theoretical study on six organic compounds based on thiophene and carbazole, with the aim of using them as a hole-injecting layer of organic light-emitting diodes (OLEDs). In this study, we have tested two types of structures: D-π-D for MO1, MO2, MO3, and MO4 compounds and D-π-A for MO5 and MO6 compounds. The correlation structure-properties of these studied compounds have been proceeded and discussed by analyzing highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), energy gap, polarization effect, atom transition density matrix, absorption, and photoluminescence (PL). This theoretical study, based on density functional theory (DFT)/TPSSTPSS/aug-cc-pVQZ and the integral-equation-formalism polarizable continuum model/Coulomb attenuated method-Becke, 3-parameter, Lee–Yang–Parr (IEFPCM/TD-CAM-B3LYP)/6-31++G(d,p) is consolidated by experimental data for MO1, MO2, and MO4 compounds, allowing the determination of their structural and optoelectronic properties (HOMO, LUMO, gap [Eg], absorption, and emission parameters). The obtained results appear very conclusive and show that the performance of these compounds in terms of luminescence, absorption, and current–voltage (I–V) characteristics of OLED devices make them a promising candidate for the realization of light-emitting diodes.     

Self-assembled organic semiconductors for monolayer field-effect transistors

Recent data on the structures and properties of self-organized molecules used for the production of the semiconducting layer in self-assembled organic monolayer field-effect transistors are reviewed. Methods for fabrication of these transistors are presented together with their advantages and shortcomings. Electric characteristics of the produced devices are compared. Major structural regularities for selection of the reactive group in self-organized semiconductor oligomer molecules are elucidated with respect to the type of substrate.     

Functionalized silicon quantum dots by N-vinylcarbazole: synthesis and spectroscopic properties

Silicon quantum dots (Si QDs) attract increasing interest nowadays due to their excellent optical and electronic properties. However, only a few optoelectronic organic molecules were reported as ligands of colloidal Si QDs. In this report, N-vinylcarbazole - a material widely used in the optoelectronics industry - was used for the modification of Si QDs as ligands. This hybrid nanomaterial exhibits different spectroscopic properties from either free ligands or Si QDs alone. Possible mechanisms were discussed. This type of new functional Si QDs may find application potentials in bioimaging, photovoltaic, or optoelectronic devices.     

Synthesis and optical behavior of PLED devices based on (PMMA)/(PAA)/Er(AP)6Cl3 complex and N,N′-didodecyl-3,4,9,10-perylene tetracarboxylic diimide composites

The realization of efficient polymeric light emitting diode (PLEDs) in a double-layered configuration was investigated. The devices are composed by transparent conductive oxide (ITO)/MoO₃/organic layers/aluminum/selenium, conformed by thin film sandwich structures obtained by vacuum evaporation. Two organic layers were developed. First a n-type organic layer of composite based on polymethylmethacrylate (PMMA)/polyacrilic acid (PAA)/Er(AP)₆Cl₃ complex and second a n-type organic semiconductor, N,N′-didodecyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₁₂H₂₅). The rare earth complex composites and the perilenic compound were synthesized and characterized using UV–Visible absorption, XPS, and NMR techniques, respectively. Driving voltage of devices was lowered by applying MoO₃ thin film as buffer layer and high current intensity efficiency was obtained applying a perilenic film. The effect of MoO₃ and PTCDI-C₁₂H₂₅ thin films, on the optical and the physical properties of the electroluminescent devices were discussed. I–V measurements have shown that the structures exhibit diode characteristics and the electroluminescent signal increases when PTCDI-C₁₂H₂₅ thin layer is introduced between the anode and the holes transporting layer. The morphology of the thin films with and without buffer layer indicates that introduction of this layer allows to obtain a homogeneous surface morphology. The results indicate that carrier injection ability and optimized charge balance is obtained to the lowest driving voltage and highest intensities efficiency among the referenced devices.     

基于巴比妥酸衍生物的自组装研究进展

巴比妥酸结构单元作为超分子体系中的重要氢键组件,一直是科学家们关注的焦点。巴比妥酸衍生物在有机纳米材料、太阳能电池、有机光电设备、分子识别等方面都具有广泛的应用前景。综述了具有巴比妥酸结构单元的化合物通过氢键等非共价作用力形成的具有液晶性质的复合物或其他超分子结构。     

Polymer molecular behaviors at buried polymer/metal and polymer/polymer interfaces and their relations to adhesion in packaging

Packaging materials are widely used in modern microelectronics. The interfacial structures of packaging materials determine the adhesion properties of these materials. Weak adhesion or delamination at interfaces involving packaging materials can lead to failure of microelectronic devices. Therefore, it is important to investigate the molecular structures of such interfaces. However, it is difficult to study molecular structures of buried interfaces due to the lack of appropriate analytical techniques. Sum frequency generation (SFG) vibrational spectroscopy has recently been used to probe buried solid/solid interfaces to understand molecular structures and behaviors such as the presence, coverage, ordering, orientation, and diffusion of functional groups at buried interfaces and their relations to adhesion in situ in real time. In this review, we describe our recent progress in the development of nondestructive methodology to examine buried polymer/metal interfaces and summarize how the developed methodology has been used to elucidate adhesion mechanisms at buried polymer/metal interfaces using SFG. We also elucidated the molecular interactions between polymers and various model and commercial epoxy materials, and the correlations between such interactions and the interfacial adhesion, providing in-depth understanding on the adhesion mechanisms of polymer adhesives.     

One-dimensional self-assembly of planar pi-conjugated molecules: adaptable building blocks for organic nanodevices

In general, fabrication of well-defined organic nanowires or nanobelts with controllable size and morphology is not as advanced as for their inorganic counterparts. Whereas inorganic nanowires are widely exploited in optoelectronic nanodevices, there remains considerable untapped potential in the one-dimensional (1D) organic materials. This Account describes our recent progress and discoveries in the field of 1D self-assembly of planar pi-conjugated molecules and their application in various nanodevices including the optical and electrical sensors. The Account is aimed at providing new insights into how to combine elements of molecular design and engineering with materials fabrication to achieve properties and functions that are desirable for nanoscale optoelectronic applications. The goal of our research program is to advance the knowledge and develop a deeper understanding in the frontier area of 1D organic nanomaterials, for which several basic questions will be addressed: (1) How can one control and optimize the molecular arrangement by modifying the molecular structure? (2) What processing factors affect self-assembly and the final morphology of the fabricated nanomaterials; how can these factors be controlled to achieve the desired 1D nanomaterials, for example, nanowires or nanobelts? (3) How do the optoelectronic properties (e.g., emission, exciton migration, and charge transport) of the assembled materials depend on the molecular arrangement and the intermolecular interactions? (4) How can the inherent optoelectronic properties of the nanomaterials be correlated with applications in sensing, switching, and other types of optoelectronic devices? The results presented demonstrate the feasibility of controlling the morphology and molecular organization of 1D organic nanomaterials. Two types of molecules have been employed to explore the 1D self-assembly and the application in optoelectronic sensing: one is perylene tetracarboxylic diimide (PTCDI, n-type) and the other is arylene ethynylene macrocycle (AEM, p-type). The materials described in this project are uniquely multifunctional, combining the properties of nanoporosity, efficient exciton migration and charge transport, and strong interfacial interaction with the guest (target) molecules. We see this combination as enabling a range of important technological applications that demand tightly coupled interaction between matter, photons, and charge. Such applications may include optical sensing, electrical sensing, and polarized emission. Particularly, the well-defined nanowires fabricated in this study represent unique systems for investigating the dimensional confinement of the optoelectronic properties of organic semiconductors, such as linearly polarized emission, dimensionally confined exciton migration, and optimal pi-electronic coupling (favorable for charge transport). Combination of these properties will make the 1D self-assembly ideal for many orientation-sensitive applications, such as polarized light-emitting diodes and flat panel displays.     

Recent Advances in Solution-Processed White Organic Light-Emitting Materials and Devices

Solution-processed white organic light-emitting diodes (WOLEDs) have drawn great attention both in the academic and industrial research communities due to the potential application in low-cost, large-area, solid-state lightings. Issues related to the device efficiencies are largely hampering progress in this field. Alongside the development of new materials and novel device architectures, distinct progress has been made for such white devices. In particular, the all-phosphorescent light-emitting strategy has been intensively developed in recent years, mainly focusing on a host guest, doping-system-based, single-active-layer structure and a solution-processed, multilayer device structure. Novel approaches, including white single polymers and excimer-/exciplex-based white devices, have also appeared as a promising choice and received great attention. As a prerequisite, the issue of the morphology of the emissive layer is also important and has an influence on the optoelectronic behavior of the device. Herein, major advances in solution-processed WOLEDs based on polymers, dendrimers, or solution-processed small molecules are summarized. Special attention is focused on the main progress in high-efficiency, solution-processed WOLEDs with the key strategies mentioned above and the morphology issue in these systems. The remaining challenges in pursuing the development of reliable and energy-saving lighting devices are also discussed.