Highly Oriented Nanofibrils of Regioregular Poly(3‐hexylthiophene) Formed via Block Copolymer Self‐Assembly in Liquid Crystals

A novel method making use of block copolymer self‐assembly in nematic liquid crystals (LCs) is described for preparing macroscopically oriented nanofibrils of π‐conjugated semiconducting polymers. Upon cooling, a diblock copolymer composed of regioregular poly(3‐hexylthiophene) (P3HT) and a liquid crystalline polymer (LCP) in a block‐selective LC solvent can self‐assemble into oriented nanofibrils exhibiting highly anisotropic absorption and polarized photoluminescence emission. An unusual feature of the nanofibrils is that P3HT chains are oriented along the fibrils' long axis. This general method makes it possible to use LCs as an anisotropic medium to grow oriented nanofibrils of many semiconducting polymers insoluble in LCs.     

Very Large Photoconduction Enhancement Upon Self‐Assembly of a New Triindole Derivative in Solution‐Processed Films

A new carbazole‐related small molecule exhibiting self‐assembly into ordered nanostructures in solution‐processed cast films has been synthesized and its charge‐photogeneration and ‐transport properties have been investigated. Large photoconductivity was measured in the amorphous state while an enormous improvement in the photoconduction properties was observed when the molecules spontaneously organized. Photocurrents increased upon self‐assembly by up to four orders of magnitude, mostly due to the drastic enhancement of the charge photogeneration. A greatly favorable arrangement of the aromatic cores in the resulting nanostructures, which were characterized by X‐ray analysis, may explain these improvements. Photocurrents of mA cm^?2, on/off ratios of 10⁴ and quantum efficiencies of unity at low field and light intensity, which are among the best values reported to date, along with the simplicity of fabrication, give this readily‐available organic system great potential for use in plastic optoelectronic devices.     

Highly Fluorescent and Color‐Tunable Exciplex Emission from Poly(N‐vinylcarbazole) Film Containing Nanostructured Supramolecular Acceptors

Highly fluorescent excited‐state charge‐transfer complexes (exciplexes) formed at the interfacial region between a polymeric donor matrix, here, poly(N‐vinylcarbazole), and embedded nanostructured acceptors are characterized for their photophysical properties. Exciplex‐to‐exciton emission switching is observed after solvent vapor annealing (SVA) due to the size evolution of the nanostructures beyond the exciton diffusion length. Color‐tunable exiplex emission (sky blue, green, and orange) is demonstrated for three different nanostructured acceptors with the same HOMO–LUMO gap (i.e., the same blue excitonic emission) but with different electron affinity. White‐emitting poly(N‐vinylcarbazole) film is also fabricated, simply by incorporating mixed supramolecular acceptors, which provide independent exciplex emissions. This study presents important insights into the excited‐state intermolecular interaction at the well‐defined nanoscale interface and suggests an efficient way to obtain multicolored exciplex emissions.     

Donor–Acceptor Poly(3‐hexylthiophene)‐block‐Pendent Poly(isoindigo) with Dual Roles of Charge Transporting and Storage Layer for High‐Performance Transistor‐Type Memory Applications

Field‐effect transistor memories usually require one additional charge storage layer between the gate contact and organic semiconductor channel. To avoid such complication, new donor–acceptor rod–coil diblock copolymers (P3HT₄₄‐b‐Piso_n) of poly(3‐hexylthiophene) (P3HT)‐block‐poly(pendent isoindigo) (Piso) are designed, which exhibit high performance transistor memory characteristics without additional charge storage layer. The P3HT and Piso blocks are acted as the charge transporting and storage elements, respectively. The prepared P3HT₄₄‐b‐Piso_n can be self‐assembled into fibrillar‐like nanostructures after the thermal annealing process, confirmed by atomic force microscopy and grazing‐incidence X‐ray diffraction. The lowest‐unoccupied molecular orbital levels of the studied polymers are significantly lowered as the block length of Piso increases, leading to a stronger electron affinity as well as charge storage capability. The field‐effect transistors (FETs) fabricated from P3HT₄₄‐b‐Piso_n possess p‐type mobilities up to 4.56 × 10^?2 cm² V^?1 s^?1, similar to that of the regioregular P3HT. More interestingly, the FET memory devices fabricated from P3HT₄₄‐b‐Piso_n exhibit a memory window ranging from 26 to 79 V by manipulating the block length of Piso, and showed stable long‐term data endurance. The results suggest that the FET characteristics and data storage capability can be effectively tuned simultaneously through donor/acceptor ratio and thin film morphology in the block copolymer system.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

Embedded Shape‐Memory Alloy Wires for Improved Performance of Self‐Healing Polymers

We report the first measurements of self‐healing polymers with embedded shape‐memory alloy (SMA) wires. The addition of SMA wires shows improvements of healed peak fracture loads by up to a factor of 1.6, approaching the performance of the virgin material. Moreover, the repairs can be achieved with reduced amounts of healing agent. The improvements in performance are due to two main effects: (i) crack closure, which reduces the total crack volume and increases the crack fill factor for a given amount of healing agent and (ii) heating of the healing agent during polymerization, which increases the degree of cure of the polymerized healing agent.     

Photoconduction: Very Large Photoconduction Enhancement Upon Self‐Assembly of a New Triindole Derivative in Solution‐Processed Films (Adv. Funct. Mater. 4/2011)

A new carbazole‐related small molecule exhibiting self‐assembly into ordered nanostructures in solution‐processed cast films has been synthesized and its charge‐photogeneration and ‐transport properties have been investigated. Large photoconductivity was measured in the amorphous state while an enormous improvement in the photoconduction properties was observed when the molecules spontaneously organized. Photocurrents increased upon self‐assembly by up to four orders of magnitude, mostly due to the drastic enhancement of the charge photogeneration. A greatly favorable arrangement of the aromatic cores in the resulting nanostructures, which were characterized by X‐ray analysis, may explain these improvements. Photocurrents of mA cm^?2, on/off ratios of 10⁴ and quantum efficiencies of unity at low field and light intensity, which are among the best values reported to date, along with the simplicity of fabrication, give this readily‐available organic system great potential for use in plastic optoelectronic devices.     

High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly

Highly ordered, homogeneous polymer nanocomposites of layered graphene oxide are prepared using a vacuum‐assisted self‐assembly (VASA) technique. In VASA, all components (nanofiller and polymer) are pre‐mixed prior to assembly under a flow, making it compatible with either hydrophilic poly(vinyl alcohol) (PVA) or hydrophobic poly(methyl methacrylate) (PMMA) for the preparation of composites with over 50 wt% filler. This process is complimentary to layer‐by‐layer assembly, where the assembling components are required to interact strongly (e.g., via Coulombic attraction). The nanosheets within the VASA‐assembled composites exhibit a high degree of order with tunable intersheet spacing, depending on the polymer content. Graphene oxide–PVA nanocomposites, prepared from water, exhibit greatly improved modulus values in comparison to films of either pure PVA or pure graphene oxide. Modulus values for graphene oxide–PMMA nanocomposites, prepared from dimethylformamide, are intermediate to those of the pure components. The differences in structure, modulus, and strength can be attributed to the gallery composition, specifically the hydrogen bonding ability of the intercalating species     

Fabrication of a Memory Chip by a Complete Self‐Assembly Process Using State‐of‐the‐Art Multilevel Cell (MLC) Technology

Using a two bit molecular switch, an ultra‐dense memory chip has been built following a fully automated fabrication process. Well‐ordered templates are grown naturally using a well‐defined protocol of temperature variation. This template is so designed that molecules are adsorbed selectively only into particular sites whenever they are bombarded on the template through an e‐beam evaporator for a particular time. The technique is a generalized protocol that has been used to grow atomic‐scale templates by proper tuning of basic global parameters like temperature and evaporation time. Tuning of the basic template parameters is also demonstrated here, and has been used to scale down parameter values following the same route. Tuning the junction profile should allow selective adsorption of more complicated multi‐level switches in future. Therefore, a fairly simple technology has been established that addresses one of the most fundamental issues of continuous miniaturization, i.e., simultaneous automated growth of thousands of atomically precise single molecular devices.     

Control of the Morphology and Structural Development of Solution‐Processed Functionalized Acenes for High‐Performance Organic Transistors

Solution‐processable functionalized acenes have received special attention as promising organic semiconductors in recent years because of their superior intermolecular interactions and solution‐processability, and provide useful benchmarks for organic field‐effect transistors (OFETs). Charge‐carrier transport in organic semiconductor thin films is governed by their morphologies and molecular orientation, so self‐assembly of these functionalized acenes during solution processing is an important challenge. This article discusses the charge‐carrier transport characteristics of solution‐processed functionalized acene transistors and, in particular, focuses on the fine control of the films' morphologies and structural evolution during film‐deposition processes such as inkjet printing and post‐deposition annealing. We discuss strategies for controlling morphologies and crystalline microstructure of soluble acenes with a view to fabricating high‐performance OFETs.     

Large Area Self‐Assembly of Nematic Liquid‐Crystal‐Functionalized Gold Nanorods

Fascinating nematic‐ and smectic‐like self‐assembled arrays are observed for gold nanorods partially capped with either laterally or terminally attached nematic liquid crystals upon slow evaporation of an organic solvent on TEM grids. These arrays can be manipulated and reoriented by applying an external magnetic field from quasi‐planar to vertical similar to a Fréedericksz transition of common organic nematic liquid crystals. Birefringence and thin film textures of these self‐assembled gold nanorod arrays observed by polarized optical microscopy are strongly reminiscent of common organic nematic liquid crystal textures between crossed polarizers and, additionally, support the formation of ordered liquid crystal‐like anisotropic superstructures. The ordering within these arrays is also confirmed in bulk samples using small angle X‐ray scattering (SAXS).     

Alkyl‐Chain‐Length‐Independent Hole Mobility via Morphological Control with Poly(3‐alkylthiophene) Nanofibers

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO₂ gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.     

π‐Conjugated Oligothiophene‐Based Polycatenar Liquid Crystals: Self‐Organization and Photoconductive,Luminescent, and Redox Properties

A series of liquid‐crystalline (LC) π‐ ‐conjugated oligothiophenes bearing three or two alkoxy chains at their extremities has been designed and synthesized. These polycatenar oligothiophenes form various LC nanostructures including smectic, columnar, and micellar cubic phases. These properties depend on the number and length of the terminal alkoxy chains. The hole mobilities for the oligothiophenes have been measured. The layered smectic and columnar structures are capable of transporting holes, leading to mobilities of up to 0.01 cm² V^?1 s^?1. The columnar LC assemblies have also been explored to produce linearly polarized light‐emission. Fine red polarized fluorescence is observed from a uniaxially aligned film of the oligothiophenes. The redox properties of the oligothiophenes both in solutions and in films have been examined. The oligothiophenes exhibit electrochromism upon applying an oxidative potential. The present design strategy is useful for fabricating a variety of functional electro‐active molecular assemblies.     

Self‐Assembly of Nanostructured,Complex, Multication Films via Spontaneous Phase Separation and Strain‐Driven Ordering

Spontaneous self‐assembly of a multication nanophase in another multication matrix phase is a promising bottom‐up approach to fabricate novel, nanocomposite structures for a range of applications. In an effort to understand the mechanisms for such self‐assembly, complimentary experimental and theoretical studies are reported to first understand and then control or guide the self‐assembly of insulating BaZrO₃ (BZO) nanodots within REBa₂Cu₃O_7–δ (RE = rare earth elements including Y, REBCO) superconducting films. The strain field developed around BZO nanodots embedded in the REBCO matrix is a key driving force dictating the self‐assembly of BZO nanodots along REBCO c‐axis. The size selection and spatial ordering of BZO self‐assembly are simulated using thermodynamic and kinetic models. The BZO self‐assembly is controllable by tuning the interphase strain field. REBCO superconducting films with BZO defect arrays self‐assembled to align in both vertical (REBCO c‐axis) and horizontal (REBCO ab‐planes) directions result in the maximized pinning and J_c performance for all field angles with smaller angular J_c anisotropy. The work has broad implications for the fabrication of controlled self‐assembled nanostructures for a range of applications via strain‐tuning.     

Halogen Bonding versus Hydrogen Bonding in Driving Self‐Assembly and Performance of Light‐Responsive Supramolecular Polymers

Halogen bonding is arguably the least exploited among the many non‐covalent interactions used in dictating molecular self‐assembly. However, its directionality renders it unique compared to ubiquitous hydrogen bonding. Here, the role of this directionality in controlling the performance of light‐responsive supramolecular polymers is highlighted. In particular, it is shown that light‐induced surface patterning, a unique phenomenon occurring in azobenzene‐containing polymers, is more efficient in halogen‐bonded polymer–azobenzene complexes than in the analogous hydrogen‐bonded complexes. A systematic study is performed on a series of azo dyes containing different halogen or hydrogen bonding donor moieties, complexed to poly(4‐vinylpyridine) backbone. Through single‐atom substitution of the bond‐donor, control of both the strength and the nature of the noncovalent interaction between the azobenzene units and the polymer backbone is achieved. Importantly, such substitution does not significantly alter the electronic properties of the azobenzene units, hence providing us with unique tools in studying the structure–performance relationships in the light‐induced surface deformation process. The results represent the first demonstration of light‐responsive halogen‐bonded polymer systems and also highlight the remarkable potential of halogen bonding in fundamental studies of photoresponsive azobenzene‐containing polymers.     

Hierarchical Self‐Assembly of a Dandelion‐Like Supramolecular Polymer into Nanotubes for use as Highly Efficient Aqueous Light‐Harvesting Systems

A dandelion‐like supramolecular polymer (DSP) with a “sphere‐star‐parachute” topological structure consisting of a spherical hyperbranched core and many parachute‐like arms is constructed by the non‐covalent host–guest coupling between a cyclodextrin‐endcapped hyperbranched multi‐arm copolymer (host) and many functionalized adamantanes with each having three alkyl chain arms (guests). The obtained DSPs can further self‐assemble into nanotubes in water in a hierarchical way from vesicles to nanotubes through sequential vesicle aggregation and fusion steps. The nanotubes have a bilayer structure consisting of multiple “hydrophobic‐hyperbranched‐hydrophilic” layers. Such a structure is very useful for constructing a chlorosome‐like artificial aqueous light‐harvesting system, as demonstrated here, via the incorporation of hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole as donors inside the hyperbranched cores of the nanotubes and the hydrophilic Rhodamine B as the acceptors immobilized on the nanotube surfaces. This as‐prepared nanotube light harvesting system demonstrates unexpectedly high energy transfer efficiency (above 90%) in water. This extends supramolecular polymers with more complex topological structure, special self‐assembly behavior, and new functionality.