Topological Design of Highly Anisotropic Aligned Hole Transporting Molecular Bottlebrushes for Solution-Processed OLEDs.

Polyvinyl polymers bearing pendant hole transport functionalities have been extensively explored for solution-processed hole transport layer (HTL) technologies, yet there are only rare examples of high anisotropic packing of the HT moieties of these polymers into substrate-parallel orientations within HTL films. For small molecules, substrate-parallel alignment of HT moieties is a well-established approach to improve overall device performance. To address the longstanding challenge of extension from vapor-deposited small molecules to solution-processable polymer systems, a fundamental chemistry tactic is reported here, involving the positioning of HT side chains within macromolecular frameworks by the construction of HT polymers having bottlebrush topologies. Applying state-of-the-art polymer synthetic techniques, various functional subunits, including triphenylamine (TPA) for hole transport and adhesion to the substrate, and perfluoro alkyl-substituted benzyloxy styrene for migration to the air interface, were organized with exquisite control over the composition and placement throughout the bottlebrush topology. Upon assembling the HT bottlebrush (HTB) polymers into monolayered HTL films on various substrates through spin-casting and thermal annealing, the backbones of HTBs were vertically aligned while the grafts with pendant TPAs were extended parallel to the substrate. The overall design realized high TPA π-stacking along the out-of-plane direction of the substrate in the HTLs, which doubled the efficiency of organic light-emitting diodes compared with linear poly(vinyl triphenylamine)s.

Charged Polaron Polaritons in an Organic Semiconductor Microcavity.

We report strong coupling between light and polaron optical excitations in a doped organic semiconductor microcavity at room temperature. Codepositing MoO_{3} and the hole transport material 4, 4^{'}-cyclohexylidenebis[N, N-bis(4-methylphenyl)benzenamine] introduces a large hole density with a narrow linewidth optical transition centered at 1.8 eV and an absorption coefficient exceeding 10^{4} cm^{-1}. Coupling this transition to a Fabry-Pérot cavity mode yields upper and lower polaron polariton branches that are clearly resolved in angle-dependent reflectivity with a vacuum Rabi splitting ℏΩ_{R}>0.3 eV. This result establishes a path to electrically control polaritons in organic semiconductors and may lead to increased polariton-polariton Coulombic interactions that lower the threshold for nonlinear phenomena such as polariton condensation and lasing.

Large bipolaron density at organic semiconductor/electrode interfaces.

Bipolaron states, in which two electrons or two holes occupy a single molecule or conjugated polymer segment, are typically considered to be negligible in organic semiconductor devices due to Coulomb repulsion between the two charges. Here we use charge modulation spectroscopy to reveal a bipolaron sheet density >1010 cm-2 at the interface between an indium tin oxide anode and the common small molecule organic semiconductor N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine. We find that the magnetocurrent response of hole-only devices correlates closely with changes in the bipolaron concentration, supporting the bipolaron model of unipolar organic magnetoresistance and suggesting that it may be more of an interface than a bulk phenomenon. These results are understood on the basis of a quantitative interface energy level alignment model, which indicates that bipolarons are generally expected to be significant near contacts in the Fermi level pinning regime and thus may be more prevalent in organic electronic devices than previously thought.

Novel Strategy for Photopatterning Emissive Polymer Brushes for Organic Light Emitting Diode Applications.

A light-mediated methodology to grow patterned, emissive polymer brushes with micron feature resolution is reported and applied to organic light emitting diode (OLED) displays. Light is used for both initiator functionalization of indium tin oxide and subsequent atom transfer radical polymerization of methacrylate-based fluorescent and phosphorescent iridium monomers. The iridium centers play key roles in photocatalyzing and mediating polymer growth while also emitting light in the final OLED structure. The scope of the presented procedure enables the synthesis of a library of polymers with emissive colors spanning the visible spectrum where the dopant incorporation, position of brush growth, and brush thickness are readily controlled. The chain-ends of the polymer brushes remain intact, affording subsequent chain extension and formation of well-defined diblock architectures. This high level of structure and function control allows for the facile preparation of random ternary copolymers and red-green-blue arrays to yield white emission.

Mechanisms of Energy Transfer and Enhanced Stability of Carbidonitride Phosphors for Solid-State Lighting.

Phosphor-converted light emitting diodes (pcLEDs) produce white light through the use of phosphors that convert blue light emitted from the LED chip into green and red wavelengths. Understanding the mechanisms of degradation of the emission spectra and quantum yields of the phosphors used in pcLEDs is of critical importance to fully realize the potential of solid-state lighting as an energy efficient technology. Toward this end, time-resolved photoluminescence spectroscopy was used to identify the mechanistic origins of enhanced stability and luminescence efficiency that can be obtained from a series of carbidonitride red phosphors with varying degrees of substitutional carbon. The increasing substitution of carbon and oxygen in nitrogen positions of the carbidonitride phosphor (Sr2Si5N8-[(4x/3)+z]CxO3z/2:Eu2+) systematically changed the dimensions of the crystalline lattice. These structural changes caused a red shift and broadening of the emission spectra of the phosphors due to faster energy transfer from higher to lower energy emission sites. Surprisingly, in spite of broadening of the emission spectra, the quantum yield was maintained or increased with carbon substitution. Aging phosphors with lowered carbon content under conditions that accurately reflected thermal and optical stresses found in functioning pcLED packages led to spectral changes that were dependent on substitutional carbon content. Importantly, phosphors that contained optimal amounts of carbon and oxygen possessed luminescence spectra and quantum yields that did not undergo changes associated with aging and therefore provided a more stable color point for superior control of the emission properties of pcLED packages. These findings provide insights to guide continued development of phosphors for efficient and stable solid-state lighting materials and devices.

Large-scale production of graphene nanoribbons from electrospun polymers.

Graphene nanoribbons (GNRs) are promising building blocks for high-performance electronics due to their high electron mobility and dimensionality-induced bandgap. Despite many past efforts, direct synthesis of GNRs with controlled dimensions and scalability remains challenging. Here we report the scalable synthesis of GNRs using electrospun polymer nanofiber templates. Palladium-incorporated poly(4-vinylphenol) nanofibers were prepared by electrospinning with controlled diameter and orientation. Highly graphitized GNRs as narrow as 10 nm were then synthesized from these templates by chemical vapor deposition. A transport gap can be observed in 30 nm-wide GNRs, enabling them to function as field-effect transistors at room temperature. Our results represent the first success on the scalable synthesis of highly graphitized GNRs from polymer templates. Furthermore, the generality of this method allows various polymers to be explored, which will lead to understanding of growth mechanism and rational control over crystallinity, feature size and bandgap to enable a new pathway for graphene electronics.

Direct growth of aligned graphitic nanoribbons from a DNA template by chemical vapour deposition.

Graphene, laterally confined within narrow ribbons, exhibits a bandgap and is envisioned as a next-generation material for high-performance electronics. To take advantage of this phenomenon, there is a critical need to develop methodologies that result in graphene ribbons <10 nm in width. Here we report the use of metal salts infused within stretched DNA as catalysts to grow nanoscopic graphitic nanoribbons. The nanoribbons are termed graphitic as they have been determined to consist of regions of sp(2) and sp(3) character. The nanoscopic graphitic nanoribbons are micrometres in length, <10 nm in width, and take on the shape of the DNA template. The DNA strand is converted to a graphitic nanoribbon by utilizing chemical vapour deposition conditions. Depending on the growth conditions, metallic or semiconducting graphitic nanoribbons are formed. Improvements in the growth method have potential to lead to bottom-up synthesis of pristine single-layer graphene nanoribbons.

Scalable and selective dispersion of semiconducting arc-discharged carbon nanotubes by dithiafulvalene/thiophene copolymers for thin film transistors.

We report a simple and scalable method to enrich large quantities of semiconducting arc-discharged single-walled carbon nanotubes (SWNTs) with diameters of 1.1-1.8 nm using dithiafulvalene/thiophene copolymers. Stable solutions of highly individualized and highly enriched semiconducting SWNTs were obtained after a simple sonication and centrifuge process. Molecular dynamics (MD) simulations of polymer backbone interactions with and without side chains indicated that the presence of long alkyl side chains gave rise to the selectivity toward semiconducting tubes, indicating the importance of the roles of the side chains to both solubilize and confer selectivity to the polymers. We found that, by increasing the ratio of thiophene to dithiafulvalene units in the polymer backbone (from pDTFF-1T to pDTFF-3T), we can slightly improve the selectivity toward semiconducting SWNTs. This is likely due to the more flexible backbone of pDTFF-3T that allows the favorable wrapping of SWNTs with certain chirality as characterized by small-angle X-ray scattering. However, the dispersion yield was reduced from pDTFF-1T to pDTFF-3T. MD simulations showed that the reduction is due to the smaller polymer/SWNT contact area, which reduces the dispersion ability of pDTFF-3T. These experimental and modeling results provide a better understanding for future rational design of polymers for sorting SWNTs. Finally, high on/off ratio solution-processed thin film transistors were fabricated from the sorted SWNTs to confirm the selective dispersion of semiconducting arc-discharge SWNTs.

Organic transistors with ordered nanoparticle arrays as a tailorable platform for selective, in situ detection.

The use of organic transistors as sensing platforms provides a number of distinct advantages over conventional detection technologies, including their tunability, portability, and ability to directly transduce binding events without tedious and expensive labeling procedures. However, detection efforts using organic transistors lack a general method to uniquely specify and detect a target of interest. While highly sensitive liquid- and vapor-phase sensors have been previously reported, detection has been restricted either to the serendipitous interaction of the analyte molecules with the organic semiconductor or to the covalent functionalization of the semiconductor with receptor groups to enhance specificity. However, the former technique cannot be regularly relied upon for tailorable sensing while the latter may result in unpredictable decreases in electronic performance. Thus, a method to provide modular receptor sites on the surface of an organic transistor without damaging the device will significantly advance the field, especially regarding biological species detection. In this work, we utilized a block copolymer to template ordered, large-area arrays of gold nanoparticles, with sub-100 nm center-to-center spacing onto the surface of an organic transistor. This highly modular platform is designed for orthogonal modification with a number of available chemical and biological functional groups by taking advantage of the well-studied gold-thiol linkage. Herein, we demonstrate the functionalization of gold nanoparticles with a mercury-binding oligonucleotide sequence. Finally, we demonstrate the highly selective and robust detection of mercury(II) using this platform in an underwater environment.

Chemical and engineering approaches to enable organic field-effect transistors for electronic skin applications.

Skin is the body's largest organ and is responsible for the transduction of a vast amount of information. This conformable material simultaneously collects signals from external stimuli that translate into information such as pressure, pain, and temperature. The development of an electronic material, inspired by the complexity of this organ is a tremendous, unrealized engineering challenge. However, the advent of carbon-based electronics may offer a potential solution to this long-standing problem. In this Account, we describe the use of an organic field-effect transistor (OFET) architecture to transduce mechanical and chemical stimuli into electrical signals. In developing this mimic of human skin, we thought of the sensory elements of the OFET as analogous to the various layers and constituents of skin. In this fashion, each layer of the OFET can be optimized to carry out a specific recognition function. The separation of multimodal sensing among the components of the OFET may be considered a "divide and conquer" approach, where the electronic skin (e-skin) can take advantage of the optimized chemistry and materials properties of each layer. This design of a novel microstructured gate dielectric has led to unprecedented sensitivity for tactile pressure events. Typically, pressure-sensitive components within electronic configurations have suffered from a lack of sensitivity or long mechanical relaxation times often associated with elastomeric materials. Within our method, these components are directly compatible with OFETs and have achieved the highest reported sensitivity to date. Moreover, the tactile sensors operate on a time scale comparable with human skin, making them ideal candidates for integration as synthetic skin devices. The methodology is compatible with large-scale fabrication and employs simple, commercially available elastomers. The design of materials within the semiconductor layer has led to the incorporation of selectivity and sensitivity within gas-sensing devices and has enabled stable sensor operation within aqueous media. Furthermore, careful tuning of the chemical composition of the dielectric layer has provided a means to operate the sensor in real time within an aqueous environment and without the need for encapsulation layers. The integration of such devices as electronic mimics of skin will require the incorporation of biocompatible or biodegradable components. Toward this goal, OFETs may be fabricated with >99% biodegradable components by weight, and the devices are robust and stable, even in aqueous environments. Collectively, progress to date suggests that OFETs may be integrated within a single substrate to function as an electronic mimic of human skin, which could enable a large range of sensing-related applications from novel prosthetics to robotic surgery.

From computational discovery to experimental characterization of a high hole mobility organic crystal.

For organic semiconductors to find ubiquitous electronics applications, the development of new materials with high mobility and air stability is critical. Despite the versatility of carbon, exploratory chemical synthesis in the vast chemical space can be hindered by synthetic and characterization difficulties. Here we show that in silico screening of novel derivatives of the dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene semiconductor with high hole mobility and air stability can lead to the discovery of a new high-performance semiconductor. On the basis of estimates from the Marcus theory of charge transfer rates, we identified a novel compound expected to demonstrate a theoretic twofold improvement in mobility over the parent molecule. Synthetic and electrical characterization of the compound is reported with single-crystal field-effect transistors, showing a remarkable saturation and linear mobility of 12.3 and 16 cm(2) V(-1) s(-1), respectively. This is one of the very few organic semiconductors with mobility greater than 10 cm(2) V(-1) s(-1) reported to date.

Applications of hydrogen-bond-acceptor templates to direct 'in-phase' reactivity of a diene diacid in the solid state.

The hydrogen-bond-acceptor (HBA) templates 2,3-bis(4-methylenethiopyridyl)naphthalene (2,3-nap) and 1,8-bis(4-pyridyl)naphthalene (1,8-dpn) are used to assemble (E,E)-2,5-dimethylmuconic acid (dmma) in the solid state for an intermolecular [2 + 2] photocycloaddition. Co-crystallisation of 2,3-nap with dmma affords an 1D hydrogen-bonded polymer that is photostable while 1,8-nap affords a 0D hydrogen-bonded assembly that is photoactive. The diene stacks in-phase and reacts to give a syn monocyclobutane in up to 55% yield.

A solid-state trimerisation of a diene diacid affords a bicyclobutyl: reactant structure from X-ray powder data and product separation and structure determination via co-crystallisation.

A bicyclobutyl that bears six carboxylic acid groups results from a trimerisation of a diene diacid in the solid state. Powder X-ray diffraction and a co-crystallisation are used to solve the structure of the diene and elucidate the stereochemistry of the bicyclobutyl, respectively.

Highly sensitive flexible pressure sensors with microstructured rubber dielectric layers.

The development of an electronic skin is critical to the realization of artificial intelligence that comes into direct contact with humans, and to biomedical applications such as prosthetic skin. To mimic the tactile sensing properties of natural skin, large arrays of pixel pressure sensors on a flexible and stretchable substrate are required. We demonstrate flexible, capacitive pressure sensors with unprecedented sensitivity and very short response times that can be inexpensively fabricated over large areas by microstructuring of thin films of the biocompatible elastomer polydimethylsiloxane. The pressure sensitivity of the microstructured films far surpassed that exhibited by unstructured elastomeric films of similar thickness, and is tunable by using different microstructures. The microstructured films were integrated into organic field-effect transistors as the dielectric layer, forming a new type of active sensor device with similarly excellent sensitivity and response times.

Conformational polymorphism facilitates assignment of trans and cis-conformers of an alpha-substituted oligothiophene via IR spectroscopy.

Conformational polymorphism is exploited as a means to assign cis-trans and trans-trans conformations of an oligothiophene backbone using solid-state IR spectroscopy.

Self-sorted nanotube networks on polymer dielectrics for low-voltage thin-film transistors.

Recent exploitations of the superior mechanical and electronic properties of carbon nanotubes (CNTs) have led to exciting opportunities in low-cost, high performance, carbon-based electronics. In this report, low-voltage thin-film transistors with aligned, semiconducting CNT networks are fabricated on a chemically modified polymer gate dielectric using both rigid and flexible substrates. The multifunctional polymer serves as a thin, flexible gate dielectric film, affords low operating voltages, and provides a platform for chemical functionalization. The introduction of amine functionality to the dielectric surface leads to the adsorption of a network enriched with semiconducting CNTs with tunable density from spin coating a bulk solution of unsorted CNTs. The composition of the deposited CNT networks is verified with Raman spectroscopy and electrical characterization. For transistors at operating biases below 1 V, we observe an effective device mobility as high as 13.4 cm(2)/Vs, a subthreshold swing as low as 130 mV/dec, and typical on-off ratios of greater than 1,000. This demonstration of high performance CNT thin-film transistors operating at voltages below 1 V and deposited using solution methods on polymeric and flexible substrates is an important step toward the realization of low-cost flexible electronics.

General application of mechanochemistry to templated solid-state reactivity: rapid and solvent-free access to crystalline supermolecules.

Supermolecules with olefins organized by hydrogen-bond donor and acceptor templates and that react in the solid state rapidly form co-crystals via solvent-free and liquid-assisted grinding.

Conformational polymorphism in a heteromolecular single crystal leads to concerted movement akin to collective rack-and-pinion gears at the molecular level.

We describe a heteromolecular single crystal that exhibits three reversible and concerted reorganizations upon heating and cooling. The products of the reorganizations are conformational polymorphs. The reorganizations are postulated to proceed through three motions: (i) alkyl translations, (ii) olefin rotations, and (iii) rotational tilts. The motions are akin to rack-and-pinion gears at the molecular level. The rack-like movement is based on expansions and compressions of alkyl chains that are coupled with pinion-like 180 degree rotations of olefins. To accommodate the movements, phenol and thiophene components undergo rotational tilts about intermolecular hydrogen bonds. The movements are collective, being propagated in close-packed repeating units. This discovery marks a step to understanding how organic solids can support the development of crystalline molecular machines and devices through correlated and collective movements.