Reticulated Organic Photovoltaics

This paper shows how the self‐assembled interlocking of two nanostructured materials can lead to increased photovoltaic performance. A detailed picture of the reticulated 6‐DBTTC/C₆₀ organic photovoltaic (OPV) heterojunction, which produces devices approaching the theoretical maximum for these materials, is presented from near edge X‐ray absorption spectroscopy (NEXAFS), X‐ray photoelectron spectroscopy (XPS), Grazing Incidence X‐ray diffraction (GIXD) and transmission electron microscopy (TEM). The complementary suite of techniques shows how self‐assembly can be exploited to engineer the interface and morphology between the cables of donor (6‐DBTTC) material and a polycrystalline acceptor (C₆₀) to create an interpenetrating network of pure phases expected to be optimal for OPV device design. Moreover, we find that there is also a structural and electronic interaction between the two materials at the molecular interface. The data show how molecular self‐assembly can facilitate 3‐D nanostructured photovoltaic cells that are made with the simplicity and control of bilayer device fabrication. The significant improvement in photovoltaic performance of the reticulated heterojunction over the flat analog highlights the potential of these strategies to improve the efficiency of organic solar cells.     

Electronic Transport Properties of Ensembles of Perylene‐Substituted Poly‐isocyanopeptide Arrays

The electronic transport properties of stacks of perylene‐bis(dicarboximide) (PDI) chromophores, covalently fixed to the side arms of rigid, helical polyisocyanopeptides, are studied using thin‐film transistors. In device architectures where the transistor channel lengths are somewhat greater than the average polymer chain length, carrier mobilities of order 10^?3 cm² V^?1 s^?1 at 350 K are found, which are limited by inter‐chain transport processes. The influence of π–π interactions on the material properties is studied by using PDIs with and without bulky substituents in the bay area. In order to attain a deeper understanding of both the electronic and the electronic‐transport properties of these systems, studies of self‐assembly on surfaces are combined with electronic characterization using Kelvin probe force microscopy, and also a theoretical study of electronic coupling. The use of a rigid polymer backbone as a scaffold to achieve a full control over the position and orientation of functional groups is of general applicability and interest in the design of building blocks for technologically important functional materials, as well as in more fundamental studies of chromophoric interactions.     

Hybrid ZnO–Dye Hollow Spheres with New Optical Properties by a Self‐Assembly Process Based on Evans Blue Dye and Cetyltrimethylammonium Bromide

A facile one‐step process for the fabrication of hybrid ZnO–dye hollow spheres with novel optical properties has been discovered. Addition of Evans blue (EB) dye to cetyltrimethylammonium bromide (CTAB) results in the formation of CTAB‐EB micelles through an ionic self‐assembly process, and the resulting material acts as a soft template for the crystallization of ZnO upon addition of a zinc salt and ammonia under mild refluxing conditions. The formation mechanism of such hollow spheres has been investigated. These new hybrid ZnO–dye hollow spheres display distinct optical properties that differ from properties observed for the pure ZnO and dye components. This approach is a new and effective method for fabricating novel semiconductor–dye hybrids with unique electronic and optical properties and is expected to provide access to additional inorganic–organic materials with novel structures and unusual functionalities.     

Interface Doping for Ohmic Organic Semiconductor Contacts Using Self‐Aligned Polyelectrolyte Counterion Monolayer

Contact resistance limits the performance of organic field‐effect transistors, especially those based on high‐mobility semiconductors. Despite intensive research, the nature of this phenomenon is not well understood and mitigation strategies are largely limited to complex schemes often involving co‐evaporated doped interlayers. Here, this study shows that solution self‐assembly of a polyelectrolyte monolayer on a metal electrode can induce carrier doping at the contact of an organic semiconductor overlayer, which can be augmented by dopant ion‐exchange in the monolayer, to provide ohmic contacts for both p‐ and n‐type organic field‐effect transistors. The resultant 2D‐doped profile at the semiconductor interface is furthermore self‐aligned to the contact and stabilized against counterion migration. This study shows that Coulomb potential disordering by the polyelectrolyte shifts the semiconductor density‐of‐states into the gap to promote extrinsic doping and cascade carrier injection. Contact resistivities of the order of 0.1–1 Ω cm² or less have been attained. This will likely also provide a platform for ohmic injection into other advanced semiconductors, including 2D and other nanomaterials.     

Metal–Insulator–Semiconductor Coaxial Microfibers Based on Self‐Organization of Organic Semiconductor:Polymer Blend for Weavable,Fibriform Organic Field‐Effect Transistors

With the increasing importance of electronic textiles as an ideal platform for wearable electronic devices, requirements for the development of functional electronic fibers with multilayered structures are increasing. In this paper, metal–polymer insulator–organic semiconductor (MIS) coaxial microfibers using the self‐organization of organic semiconductor:insulating polymer blends for weavable, fibriform organic field‐effect transistors (FETs) are demonstrated. A holistic process for MIS coaxial microfiber fabrication, including surface modification of gold microfiber thin‐film coating on the microfiber using a die‐coating system, and the self‐organization of organic semiconductor–insulator polymer blend is presented. Vertical phase‐separation of the organic semiconductor:insulating polymer blend film wrapping the metal microfibers provides a coaxial bilayer structure of gate dielectric (inside) and organic semiconductor (outside) with intimate interfacial contact. It is determined that the fibriform FETs based on MIS coaxial microfiber exhibit good charge carrier mobilities that approach the values of typical devices with planar substrate. It additionally exhibits electrical property uniformity over the entire fiber surface and improved bending durability. Fibriform organic FET embedded in a textile is demonstrated by weaving MIS coaxial microfibers with cotton and conducting threads, which verifies the feasibility of MIS coaxial microfiber for use in electronic textile applications.     

Interface Engineering for Organic Electronics

The field of organic electronics has been developed vastly in the past two decades due to its promise for low cost, lightweight, mechanical flexibility, versatility of chemical design and synthesis, and ease of processing. The performance and lifetime of these devices, such as organic light‐emitting diodes (OLEDs), photovoltaics (OPVs), and field‐effect transistors (OFETs), are critically dependent on the properties of both active materials and their interfaces. Interfacial properties can be controlled ranging from simple wettability or adhesion between different materials to direct modifications of the electronic structure of the materials. In this Feature Article, the strategies of utilizing surfactant‐modified cathodes, hole‐transporting buffer layers, and self‐assembled monolayer (SAM)‐modified anodes are highlighted. In addition to enabling the production of high‐efficiency OLEDs, control of interfaces in both conventional and inverted polymer solar cells is shown to enhance their efficiency and stability; and the tailoring of source–drain electrode–semiconductor interfaces, dielectric–semiconductor interfaces, and ultrathin dielectrics is shown to allow for high‐performance OFETs.     

Rational Design of Organic Semiconductors for Texture Control and Self‐Patterning on Halogenated Surfaces

Understanding the interactions at interfaces between the materials constituting consecutive layers within organic thin‐film transistors (OTFTs) is vital for optimizing charge injection and transport, tuning thin‐film microstructure, and designing new materials. Here, the influence of the interactions at the interface between a halogenated organic semiconductor (OSC) thin film and a halogenated self‐assembled monolayer on the formation of the crystalline texture directly affecting the performance of OTFTs is explored. By correlating the results from microbeam grazing incidence wide angle X‐ray scattering (μGIWAXS) measurements of structure and texture with OTFT characteristics, two or more interaction paths between the terminating atoms of the semiconductor and the halogenated surface are found to be vital to templating a highly ordered morphology in the first layer. These interactions are effective when the separating distance is lower than 2.5 d_w, where d_w represents the van der Waals distance. The ability to modulate charge carrier transport by several orders of magnitude by promoting “edge‐on” versus “face‐on” molecular orientation and crystallographic textures in OSCs is demonstrated. It is found that the “edge‐on” self‐assembly of molecules forms uniform, (001) lamellar‐textured crystallites which promote high charge carrier mobility, and that charge transport suffers as the fraction of the “face‐on” oriented crystallites increases.     

Formation of Functionalized Nanowires by Control of Self‐Assembly Using Multiple Modified Amyloid Peptides

Amyloid peptides have great potential as building blocks in the creation of functional nanowires due to their natural ability to self‐assemble into nanofibrillar structures and because they can be easily modified with various functional groups. However, significant modifications of an amyloid peptide generally alter its self‐assembly property, making it difficult to construct functionalized fibrils with a desired structure and function. In this study, a very effective method to overcome this problem is demonstrated by using our structure‐controllable amyloid peptides (SCAPs) terminated with a three‐amino‐acid‐residue cap. The method consists on mixing two or more structurally related amyloid peptides with a fraction of modified SCAPs which co‐assemble into a fibril. This SCAP‐mixing method provides remarkable control over the self‐assembly process both on the small oligomers level and the macroscopic fibrils level. Furthermore, it is shown that the modified peptides imbedded in the resulting fibril can subsequently be functionalized to generate nanowires with the desired properties, highlighting the importance of this SCAP method for nanotechnology applications.     

Evolution‐Based Design of an Injectable Hydrogel

A new class of simple, linear, amphiphilic peptides are developed that have the ability to undergo triggered self‐assembly into self‐supporting hydrogels. Under non‐gelling aqueous conditions, these peptides exist in a random coil conformation and peptide solutions have the viscosity of water. On the addition of a buffered saline solution, the peptides assemble into a β‐sheet rich network of fibrils, ultimately leading to hydrogelation. A family of nine peptides is prepared to study the influence of peptide length and amino acid composition on the rate of self‐assembly and hydrogel material properties. The amino acid composition is modulated by varying residue hydrophobicity and hydrophilicity on the two opposing faces of the amphiphile. The conformation of peptides in their soluble and gel state is studied by circular dichroism (CD), while the resultant material properties of their gels is investigated using oscillatory sheer rheology. One weight percent gels formed under physiological conditions have storage modulus (G′) values that vary from ≈20 to ≈800 Pa, with sequence length and hydrophobic character playing a dominant roll in defining hydrogel rigidity. Based on the structural and functional data provided by the nine‐peptide family members, an optimal sequence, namely LK13, is evolved. LK13 (LKLKLKLKLKLKL‐NH₂) undergoes triggered self‐assembly, affording the most rigid gel of those studied (G′=797 ± 105). It displays shear thin‐recovery behavior, allowing its delivery by syringe and is cytocompatibile as assessed with murine C3H10t1/2 mesenchymal stem cells.     

3D2 Self‐Assembling Janus Peptide Dendrimers with Tailorable Supermultivalency

The self‐assembly of peptides enables the construction of self‐assembled peptide nanostructures (SPNs) with chemical composition similar to those of natural proteins; however, the structural complexity and functional properties of SPNs are far beneath those of natural proteins. One of the most fundamental challenges in fabricating more elaborate SPNs lies in developing building blocks that are simultaneously more complex and relatively easy to synthesize. Here, the development of self‐assembling Janus peptide dendrimers (JPDs) is reported, which have fully 3D structures similar to those of globular proteins. For the reliable and convenient synthesis of JPDs, a solid‐phase bifurcation synthesis method is devised. The self‐assembly behavior of JPDs is unique because only the dendrimer generation and not the weight fraction dictates the morphology of SPNs. The coassembly of two JPD building blocks provides an opportunity not only to enlarge the morphological repertoire in a predictable manner but also to discover SPNs with unusual and interesting morphologies. Because JPD assemblies have dual multivalency, i.e., supramolecular and unimolecular multivalency, the JPD system enables the statistical selection of materials with high avidity for the desired cell types and possibly any target receptors.     

Organized Nanostructured Complexes of Polyoxometalates and Surfactants that Exhibit Photoluminescence and Electrochromism

A variety of functional nanostructured organic/inorganic hybrid materials from the europium‐exchanged derivative of a Preyssler‐type polyoxometalate (POM), [EuP₅W₃₀O₁₁₀]^12?, and functional organic surfactants were prepared by the ionic self‐assembly (ISA) route. The effect of organic surfactants on the structure, photoluminescent, electrochemical and electrochromic properties of the POM anions was investigated in detail. All obtained hybrid materials are amphotropic, i.e., exhibit both thermotropic and lyotropic liquid‐crystalline phase behaviour. Investigations of their photophysical properties have shown that the interactions of the various surfactants with the polyanions influence the coordination environments and site symmetry of Eu³⁺ in different ways. The functional groups in the organic surfactants significantly influence the electrochromic properties and photoluminescence of POMs. Different from normal and pyridine‐containing complexes, no photoluminescence and no electrochromism were observed from the ferrocene‐containing complexes. This may be explained in view of charge transfer between the POM anion and the ferrocenyl group.     

Low‐k Insulators as the Choice of Dielectrics in Organic Field‐Effect Transistors

In this paper, we present a new effect influencing the operation of organic field‐effect transistors resulting from the choice of gate insulator material. In a series of studies it was found that the interaction between the insulator and the semiconductor materials plays an important role in carrier transport. The insulator is not only capable of affecting the morphology of the semiconductor layer, but can also change the density of states by local polarization effects. Carrier localization is enhanced by insulators with large permittivities, due to the random dipole field present at the interface. We have investigated this effect on a number of disordered organic semiconductor materials, and show here that significant benefits are achievable by the use of low‐k dielectrics as opposed to the existing trend of increasing the permittivity for low operational voltage. We also discuss fundamental differences in the case of field‐effect transistors with band‐like semiconductors.     

Design of Novel Dielectric Surface Modifications for Perylene Thin‐Film Transistors

Dielectric surface modifications (DSMs) can improve the performance of organic thin‐film transistors (OTFTs) significantly. In order to gain a deeper understanding of this performance enhancement and to facilitate high‐mobility transistors, perylene based devices utilizing novel dielectric surface modifications have been produced. Novel DSMs, based on derivates of tridecyltrichlorosilane (TTS) with different functional end‐groups as well as polymeric dielectrics have been applied to tailor the adhesion energy of perylene. The resulting samples were characterized by electronic transport measurements, scanning probe microscopy, and X‐ray diffraction (XRD). Measurements of the surface free energy of the modified dielectric enabled the calculation of the adhesion energy of perylene upon these novel DSMs by the equation‐of‐state approach. These calculations demonstrate the successful tailoring of the adhesion energy. With these novel DSMs, perylene thin‐films with a superior film quality were produced, which enabled high‐performance perylene‐based OTFTs with high charge‐carrier mobility.     

Synthesis of Semiconducting Functional Materials in Solution: From II‐VI Semiconductor to Inorganic–Organic Hybrid Semiconductor Nanomaterials

This Feature Article provides a brief overview of the latest development and emerging new synthesis solution strategies for II–VI semiconducting nanomaterials and inorganic‐organic semiconductor hybrid materials. Research on the synthesis of II–VI semiconductor nanomaterials and inorganic–organic hybrid semiconducting materials via solution strategies has made great progress in the past few years. A variety of II–VI semiconductor and a new family of [MQ(L)_0.5] (M = Mn, Zn, Cd; Q = S, Se, Te; L = diamine, deta) hybrid nanostructures can be generated using solution synthetic routes. Recent advances have demonstrated that the solution strategies in pure solvent and a mixed solvent can not only determine the crystal size, shape, composition, structure and assembly properties, but also the crystallization pathway, and act as a matrix for the formation of a variety of different II–VI semiconductor and hybrid nanocomposites with diverse morphologies. These II–VI semiconductor nanostructures and their hybrid nanocomposites display obvious quantum size effects, unique and tunable optical properties.     

Nitrogen‐Dopant‐Induced Organic–Inorganic Hybrid Perovskite Crystal Growth on Carbon Nanotubes

Interfacial engineering of organic–inorganic halide perovskites in conjunction with different functional materials is anticipated to offer novel heterojunction structures with unique functionalities. Unfortunately, complex material compositions and structures of the organic–inorganic hybrid materials make it difficult to tailor a desirable intermolecular interaction at the interface. Spontaneous and highly specific nucleation of perovskite crystals, that is, methylammonium lead iodide perovskite (CH₃NH₃PbI₃, MAPbI₃) at nitrogen‐doped carbon nanotube (NCNT) surfaces for the self‐assembly of MAPbI₃/NCNT hybrids is reported. It is demonstrated that the lone‐pair electrons of pyridinic nitrogen‐dopant sites at NCNTs mediate specific interactions with the cationic component in the perovskite structure and serve as the nucleation sites via coordinate bonding formation, as supported by X‐ray photoelectron spectroscopy and density functional theory calculation. The potential suitability of MAPbI₃/NCNT hybrids is presented for highly sensitive and selective NO₂ sensing layer. This work suggests a reliable self‐assembly route to the molecular level hybridization of organic–inorganic halide perovskites by employing the substitutional dopant sites at graphene‐based nanomaterials.     

Ordered Superparticles with an Enhanced Photoelectric Effect by Sub‐Nanometer Interparticle Distance

As the development in self‐assembly of nanoparticles, a main question is directed to whether the supercrystalline structure can facilitate generation of collective properties, such as coupling between adjacent nanocrystals or delocalization of exciton to achieve band‐like electronic transport in a 3D assembly. The nanocrystal surfaces are generally passivated by insulating organic ligands, which block electronic communication of neighboring building blocks in nanoparticle assemblies. Ligand removal or exchange is an operable strategy for promoting electron transfer, but usually changes the surface states, resulting in performance alteration or uncontrollable aggregation. Here, 3D, supercompact superparticles with well‐defined superlattice domains through a thermally controlled emulsion‐based self‐assembly method is fabricated. The interparticle spacing in the superparticles shrinks to ≈0.3 nm because organic ligands lie prone on the nanoparticle surface, which are sufficient to overcome the electron transfer barrier. The ordered and compressed superstructures promote coupling and electronic energy transfer between CdSSe quantum dots (QDs). Therefore, the acquired QD superparticles exhibit different optical properties and enhanced photoelectric activity compared to individual QDs.     

Hierarchical Self‐Organization of Nanomaterials into Two‐Dimensional Arrays Using Functional Polymer Scaffold

Fabrication of two and three‐dimensional nanostructures requires the development of new methodologies for the assembly of molecular/macromolecular objects on substrates in predetermined arrangements. Templated self‐assembly approach is a powerful strategy for the creation of materials from assembly of molecular components or nanoparticles. The present study describes the development of a facile, template directed self‐assembly of (metal/organic) nanomaterials into periodic micro‐ and nanostructures. The positioning and the organization of nanomaterials into spatially well‐defined arrays were achieved using an amphiphilic conjugated polymer‐aided, self‐organization process. Arrays of honeycomb patterns formed from conjugated C₁₂PPPOH film with homogenous distribution of metal/organic nanomaterials. Our approach offers a straightforward and inexpensive method of preparation for hybrid thin films without environmentally controlled chambers or sophisticated instruments as compared to multistep micro‐fabrication techniques.     

Interface Engineering for Solid‐State Dye‐Sensitized Nanocrystalline Solar Cells: The Use of Ion‐Solvating Hole‐Transporting Polymers

The control of interfacial charge transfer is central to the design of photovoltaic devices. This charge transfer is strongly dependent upon the local chemical environment at each interface. In this paper we report a methodology for the fabrication of a novel nanostructured multicomponent film, employing a dual‐function supramolecular organic semiconductor to allow molecular‐level control of the local chemical composition at a nanostructured inorganic/organic semiconductor heterojunction. The multicomponent film comprises a lithium ion doped dual‐functional hole‐transporting material (Li⁺–DFHTM), sandwiched between a dye‐sensitized nanocrystalline TiO₂ film and a mono‐functional organic hole‐transporting material (MFHTM). The DFHTM consists of a conjugated organic semiconductor with ion supporting side chains, designed to allow both electronic and ionic charge transport properties. The Li⁺–DFHTM layers provide a new and versatile way to control the interface electrostatics, and consequently the charge transfer, at a nanostructured dye‐sensitized inorganic/organic semiconductor heterojunction.     

Molecular‐Level Switching of Polymer/Nanocrystal Non‐Covalent Interactions and Application in Hybrid Solar Cells

Hybrid composites obtained upon blending conjugated polymers and colloidal semiconductor nanocrystals are regarded as attractive photo­active materials for optoelectronic applications. Here it is demonstrated that tailoring nanocrystal surface chemistry permits to control non‐covalent and electronic interactions between organic and inorganic components. The pending moieties of organic ligands at the nanocrystal surface are shown to not merely confer colloidal stability while hindering charge separation and transport, but drastically impact morphology of hybrid composites during formation from blend solutions. The relevance of this approach to photovoltaic applications is demonstrated for composites based on poly(3‐hexylthiophene) and lead sulfide nanocrystals, considered as inadequate until this report, which enable the fabrication of hybrid solar cells displaying a power conversion efficiency that reaches 3%. By investigating (quasi)steady‐state and time‐resolved photo‐induced processes in the nanocomposites and their constituents, it is ascertained that electron transfer occurs at the hybrid interface yielding long‐lived separated charge carriers, whereas interfacial hole transfer appears hindered. Here a reliable alternative aiming to gain control over macroscopic optoelectronic properties of polymer/nanocrystal composites by mediating their non‐covalent interactions via ligands' pending moieties is provided, thus opening new possibilities towards efficient solution‐processed hybrid solar cells.     

Energy‐Level Alignment at the Organic/Electrode Interface in Organic Optoelectronic Devices

It is commonly believed that the work‐function reduction effect of the cathode interfacial material in organic electronic devices leads to better energy‐level alignment at the organic/electrode interface, which enhances the device performance. However, there is no agreement on the exact dipole direction in the literature. In this study, a peel‐off method to reveal the buried organic/metal interface to examine the energy‐level alignment is developed. By splitting the device at different interfaces, it is discovered that oppositely oriented dipoles are formed at different surfaces of the interfacial layer. Moreover, the function of the electrode interface differs in different device types. In organic light‐emitting diodes, the vacuum‐level alignment generally occurs at the organic/cathode interface, while in organic photovoltaic devices, the Fermi‐level pinning commonly happens. Both are determined by the integer charge‐transfer levels of the organic materials and the work‐function of the electrode. As a result, the performance enhancement by the cathode interfacial material in organic photovoltaic devices cannot be solely explained by the energy‐level alignment. The clarification of the energy‐level alignment not only helps understand the device operation but also sets up a guideline to design the devices with better performance.