Solution-Processed Graphene-Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation.

Sensitization of graphene with inorganic semiconducting nanostructures has been demonstrated as a powerful strategy to boost its optoelectronic performance. However, the limited tunability of optical properties and toxicity of metal cations in the inorganic sensitizers prohibits their widespread applications, and the in-depth understanding of the essential interfacial charge-transfer process within such hybrid systems remains elusive. Here, we design and develop high-quality nanographene (NG) dispersions with a large-scale production using high-shear mixing exfoliation. The physisorption of these NG molecules onto graphene gives rise to the formation of graphene-NG van der Waals heterostructures (VDWHs), characterized by strong interlayer coupling through π-π interactions. As a proof of concept, photodetectors fabricated on the basis of such VDWHs show ultrahigh responsivity up to 4.5 × 107 A/W and a specific detectivity reaching 4.6 × 1013 Jones, being competitive with the highest values obtained for graphene-based photodetectors. The outstanding device characteristics are attributed to the efficient transfer of photogenerated holes from NGs to graphene and the long-lived charge separation at graphene-NG interfaces (beyond 1 ns), as elucidated by ultrafast terahertz (THz) spectroscopy. These results demonstrate the great potential of such graphene-NG VDWHs as prototypical building blocks for high-performance, low-toxicity optoelectronics.

Effect of water layer at the SiO2/graphene interface on pentacene morphology.

Atomic force microscopy has been used to examine early stages of pentacene growth on exfoliated single-layer graphene transferred to SiO2 substrates. We have observed 2D growth with mean height of 1.5 ± 0.2 nm on as-transferred graphene. Three-dimensional islands of pentacene with an average height of 11 ± 2 nm were observed on graphene that was annealed at 350 °C prior to pentacene growth. Compellingly similar 3D morphology has been observed on graphene transferred onto SiO2 that was treated with hexamethyldisilazane prior to the transfer of graphene. On multilayer graphene we have observed 2D growth, regardless of the treatment of SiO2. We interpret this behavior of pentacene molecules in terms of the influence of the dipolar field that emerges from the water monolayer at the graphene/SiO2 interface on the surface energy of graphene.

Role of Graphene Topography in the Initial Stages of Pentacene Layer Growth.

Using atomic force microscopy, we probed the growth of pentacene molecules on graphene that was fabricated by chemical vapor deposition and transferred onto 300 nm-thick SiO2 substrates. The topography of such graphene has two important properties. First, its surface is comprised of folds that have different orientations, and second, it has several multilayer-graphene regions distributed over the monolayer-graphene surface. On such folded graphene features, we vacuum evaporated pentacene and observed three-dimensional islands with an average height of ∼15 nm. They are oriented either parallel or perpendicular to the folds, and they are also predominantly oriented along the symmetry axes of graphene. Orientation of pentacene islands on graphene evaporated at room temperature has a wide distribution. On the contrary, most of the pentacene islands evaporated at 60 °C are oriented at 30° with respect to the fold direction. We observed that the folds act as a potential barrier for the surface transport of pentacene molecules. In addition, we interpret the 3D growth of pentacene islands on graphene in terms of reduced polar components of the surface energy on graphene investigated with contact angle measurements.

Influence of P3HT:PCBM Ratio on Thermal and Transport Properties of Bulk Heterojunction Solar Cells.

The influence of P3HT:PCBM ratio on thermal and transport properties of solar cells were determined by photothermal beam deflection spectrometry, which is advantageous tool for non-destructively study of bulk heterojunction layers of organic solar cells. P3HT:PCBM layers of different P3HT:PCBM ratios were deposited on top of PEDOT:PSS/ITO layers which were included in organic bulk-heterojunction solar cells. The thermal diffusivity, energy gap and charge carrier lifetime were measured at different illumination conditions and with a different P3HT:PCBM ratios. As expected, it was found that the energy band gap depends on the P3HT:PCBM ratio. Thermal diffusivity is decreasing, while charge carrier lifetime is increasing with PCBM concentration. Energy band gap was found to be independent on illumination intensity, while thermal diffusivity was increasing and carrier lifetime was decreasing with illumination intensity. The carrier lifetime exhibits qualitatively similar dependence on the PCBM concentration when compared to the open-circuit voltage of operating solar cells under AM1.5 illumination. BDS and standard I-V measurement yielded comparable results arguing that the former is suitable for characterization of organic solar cells.

Conjugated Polymer Mesocrystals with Structural and Optoelectronic Coherence and Anisotropy in Three Dimensions.

Semiconducting mesocrystalline bulk polymer specimens that exhibit near-intrinsic properties using channel-die pressing are demonstrated. A predominant edge-on orientation is obtained for poly(3-hexylthiophene-2,5-diyl) (P3HT) throughout 2 mm-thick/wide samples. This persistent mesocrystalline arrangement at macroscopic scales allows reliable evaluation of the electronic charge-transport anisotropy along all three crystallographic axes, with high mobilities found along the π-stacking. Indeed, charge-carrier mobilities of up to 2.3 cm2 V-1 s-1 are measured along the π-stack, which are some of the highest mobilities reported for polymers at low charge-carrier densities (drop-cast films display mobilities of maximum ≈10-3 cm2 V-1 s-1 ). The structural coherence also leads to an unusually well-defined photoluminescence line-shape characteristic of an H-aggregate (measured from the surface perpendicular to the materials flow), rather than the typical HJ-aggregate feature usually found for P3HT. The approach is widely applicable: to electrical conductors and materials used in n-type devices, such as poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200) where the mesocrystalline structure leads to high electron transport along the polymer backbones (≈1.3 cm2 V-1 s-1 ). This versatility and the broad applicability of channel-die pressing signifies its promise as a straightforward, readily scalable method to fabricate bulk semiconducting polymer structures at macroscopic scales with properties typically accessible only by the tedious growth of single crystals.

Ionization energy and energy gap structure of MoSI molecular wires: Kelvin probe, ultraviolet photoelectron spectroscopy, and cyclic voltammetry measurements.

The work function W of Mo(6)S(3)I(6) molecular nanowires is determined by Kelvin probe (KP) measurements, UV photoelectron spectroscopy (UPS), and cyclic voltammetry (CV). The values obtained by all three methods agree well, giving W = 4.8 ± 0.1 eV. CV measurements also give a gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of E(g) = 1.2 ± 0.1 eV, in agreement with recent optical measurements, but in disagreement with theoretical calculations, which predict the material to be a metal. The electronic structure of Mo(6)S(3)I(6) suggests use of the material in applications such as bulk heterostructure photovoltaics and transparent electrodes and for molecular electronics devices.

Multiresponsive Nonvolatile Memories Based on Optically Switchable Ferroelectric Organic Field-Effect Transistors.

Organic transistors are key elements for flexible, wearable, and biocompatible logic applications. Multiresponsivity is highly sought-after in organic electronics to enable sophisticated operations and functions. Such a challenge can be pursued by integrating more components in a single device, each one responding to a specific external stimulus. Here, the first multiresponsive organic device based on a photochromic-ferroelectric organic field-effect transistor, which is capable of operating as nonvolatile memory with 11 bit memory storage capacity in a single device, is reported. The memory elements can be written and erased independently by means of light or an electric field, with accurate control over the readout signal, excellent repeatability, fast response, and high retention time. Such a proof of concept paves the way toward enhanced functional complexity in optoelectronics via the interfacing of multiple components in a single device, in a fully integrated low-cost technology compatible with flexible substrates.

Enhancement of Charge Transport in Polythiophene Semiconducting Polymer by Blending with Graphene Nanoparticles.

This paper describes a study on the charge transport in a composite of liquid-exfoliated graphene nanoparticles (GNPs) and a polythiophene semiconducting polymer. While the former component is highly conducting, although it consists of isolated nanostructures, the latter offers an efficient charge transport path between the individual GNPs within the film, overall yielding enhanced charge transport properties of the resulting bi-component system. The electrical characteristics of the composite layers were investigated by means of measurements of time-of-flight photoconductivity and transconductance in field-effect transistors. In order to analyze both phenomena separately, charge density and charge mobility contributions to the conductivity were singled out. With the increasing GNP concentration, the charge mobility was found to increase, thereby reducing the time spent by the carriers on the polymer chains. In addition, for GNP loading above 0.2 % (wt.), an increase of free charge density was observed that highlights an additional key role played by doping. Variable-range hopping model of a mixed two- and three-dimensional transport is explained using temperature dependence of mobility and free charge density. The temperature variation of free charge density was related to the electron transfer from polythiophene to GNP, with an energy barrier of 24 meV.

Self-Suspended Nanomesh Scaffold for Ultrafast Flexible Photodetectors Based on Organic Semiconducting Crystals.

Self-standing nanostructures are of fundamental interest in materials science and nanoscience and are widely used in (opto-)electronic and photonic devices as well as in micro-electromechanical systems. To date, large-area and self-standing nanoelectrode arrays assembled on flexible substrates have not been reported. Here the fabrication of a hollow nanomesh scaffold on glass and plastic substrates with a large surface area over 1 mm2 and ultralow leakage current density (≈1-10 pA mm-2 @ 2 V) across the empty scaffold is demonstrated. Thanks to the continuous sub-micrometer space formed in between the nanomesh and the bottom electrode, highly crystalline and dendritic domains of 6,13-bis(triisopropylsilylethinyl)pentacene growing within the hollow cavity can be observed. The high degree of order at the supramolecular level leads to efficient charge and exciton transport; the photovoltaic detector supported on flexible polyethylene terephthalate substrates exhibits an ultrafast photoresponse time as short as 8 ns and a signal-to-noise ratio approaching 105 . Such a hollow scaffold holds great potential as a novel device architecture toward flexible (opto-)electronic applications based on self-assembled micro/nanocrystals.

Fast-Response Photonic Device Based on Organic-Crystal Heterojunctions Assembled into a Vertical-Yet-Open Asymmetric Architecture.

Crystalline dioctyl-3,4,9,10-perylenedicarboximide nanowires and 6,13-bis(triisopropylsilylethynyl) pentacene microplates are integrated into a vertical-yet-open asymmetrical heterojunction for the realization of a high-performance organic photovoltaic detector, which shows fast photoresponse, ultrahigh signal-to-noise ratio, and high sensitivity to weak light.

Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend.

Organic nanomaterials are attracting a great deal of interest for use in flexible electronic applications such as logic circuits, displays and solar cells. These technologies have already demonstrated good performances, but flexible organic memories are yet to deliver on all their promise in terms of volatility, operational voltage, write/erase speed, as well as the number of distinct attainable levels. Here, we report a multilevel non-volatile flexible optical memory thin-film transistor based on a blend of a reference polymer semiconductor, namely poly(3-hexylthiophene), and a photochromic diarylethene, switched with ultraviolet and green light irradiation. A three-terminal device featuring over 256 (8 bit storage) distinct current levels was fabricated, the memory states of which could be switched with 3 ns laser pulses. We also report robustness over 70 write-erase cycles and non-volatility exceeding 500 days. The device was implemented on a flexible polyethylene terephthalate substrate, validating the concept for integration into wearable electronics and smart nanodevices.

A nanomesh scaffold for supramolecular nanowire optoelectronic devices.

Supramolecular organic nanowires are ideal nanostructures for optoelectronics because they exhibit both efficient exciton generation as a result of their high absorption coefficient and remarkable light sensitivity due to the low number of grain boundaries and high surface-to-volume ratio. To harvest photocurrent directly from supramolecular nanowires it is necessary to wire them up with nanoelectrodes that possess different work functions. However, devising strategies that can connect multiple nanowires at the same time has been challenging. Here, we report a general approach to simultaneously integrate hundreds of supramolecular nanowires of N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) in a hexagonal nanomesh scaffold with asymmetric nanoelectrodes. Optimized PTCDI-C8 nanowire photovoltaic devices exhibit a signal-to-noise ratio approaching 107, a photoresponse time as fast as 10 ns and an external quantum efficiency >55%. This nanomesh scaffold can also be used to investigate the fundamental mechanism of photoelectrical conversion in other low-dimensional semiconducting nanostructures.

Highly active photocatalytic coatings prepared by a low-temperature method.

Photocatalytic properties of titanium (IV) oxide (TiO2) in anatase form can be used for various purposes, including photocatalytic purification of water. For such an application, suspended or fixed photocatalytic reactors are used. Those with fixed phase seem to be preferred due to some advantages, one of which is the avoidance of photocatalyst filtration. To avoid leaching and exfoliation of the fixed phase, an immobilization procedure leading to a good adhesion of a catalyst to a substrate is crucial. Within this work, we present physical and photocatalytic characterization results of five commercially available TiO2 photocatalysts (P25, P90, PC500, KRONOClean 7000, VPC-10) and one pigment (Hombitan LO-CR-S-M), which were successfully immobilized on glass slides by a "sol suspension" procedure. Different mechanical tests and characterization methods were used to evaluate the stability and morphology of the layers. Evaluation of photocatalytic activity was done by tests under UVA and UV-vis irradiation, using a method based on the detection of the fluorescent oxidation product of terephthalic acid (TPA), i.e., hydroxyterephthalic acid (HTPA). Aeroxide® P90 incorporated into the silica-titania binder was the most photocatalytically active layer and, unlike the others, showed significant increase of photocatalytic activity through the entire range of tested UVA irradiation intensities (2.3 mW/cm(2)-6.1 mW/cm(2)). The high mechanical stability of some photocatalytic layers allows using them in water photocatalytic purification reactions.

Optically switchable transistor via energy-level phototuning in a bicomponent organic semiconductor.

Organic semiconductors are suitable candidates for printable, flexible and large-area electronics. Alongside attaining an improved device performance, to confer a multifunctional nature to the employed materials is key for organic-based logic applications. Here we report on the engineering of an electronic structure in a semiconducting film by blending two molecular components, a photochromic diarylethene derivative and a poly(3-hexylthiophene) (P3HT) matrix, to attain phototunable and bistable energy levels for the P3HT's hole transport. As a proof-of-concept we exploited this blend as a semiconducting material in organic thin-film transistors. The device illumination at defined wavelengths enabled reversible tuning of the diarylethene's electronic states in the blend, which resulted in modulation of the output current. The device photoresponse was found to be in the microsecond range, and thus on a technologically relevant timescale. This modular blending approach allows for the convenient incorporation of various molecular components, which opens up perspectives on multifunctional devices and logic circuits.