Rubrene single crystal solar cells and the effect of crystallinity on interfacial recombination.

Single crystal studies provide a better understanding of the basic properties of organic photovoltaic devices. Therefore, in this work, rubrene single crystals with a thickness of 250 nm to 1000 nm were used to produce an inverted bilayer organic solar cell. Subsequently, polycrystalline rubrene (orthorhombic, triclinic) and amorphous bilayer solar cells of the same thickness as single crystals were studied to make comparisons across platforms. To investigate how single crystal, polycrystalline (triclinic-orthorhombic) and amorphous forms alter the charge carrier recombination mechanism at the rubrene/PCBM interface, light intensity measurements were carried out. The light intensity dependency of the JSC, VOC and FF parameters in organic solar cells with different forms of rubrene was determined. Monomolecular (Shockley Read Hall) recombination is observed in devices employing amorphous and polycrystalline rubrene in addition to bimolecular recombination, whereas the single crystal device is weakly affected by trap assisted SRH recombination due to reduced trap states at the donor acceptor interface. To date, the proposed work is the only systematic study examining transport and interface recombination mechanisms in organic solar cells produced by different structure forms of rubrene.

Efficient Electron Mobility in an All-Acceptor Napthalenediimide-Bithiazole Polymer Semiconductor with Large Backbone Torsion.

An all-acceptor napthalenediimide-bithiazole-based co-polymer, P(NDI2OD-BiTz), was synthesized and characterized for application in thin-film transistors. Density functional theory calculations point to an optimal perpendicular dihedral angle of 90° between acceptor units along isolated polymer chains; yet optimized transistors yield electron mobility of 0.11 cm2/(V s) with the use of a zwitterionic naphthalene diimide interlayer. Grazing incidence X-ray diffraction measurements of annealed films reveal that P(NDI2OD-BiTz) adopts a highly ordered edge-on orientation, exactly opposite to similar bithiophene analogs. This report highlights an NDI and thiazole all-acceptor polymer and demonstrates high electron mobility despite its nonplanar backbone conformation.

Enhanced Device Efficiency and Long-Term Stability via Boronic Acid-Based Self-Assembled Monolayer Modification of Indium Tin Oxide in a Planar Perovskite Solar Cell.

Interfacial engineering is essential for the development of highly efficient and stable solar cells through minimizing energetic losses at interfaces. Self-assembled monolayers (SAMs) have been shown as a handle to tune the work function (WF) of indium tin oxide (ITO), improving photovoltaic cell performance and device stability. In this study, we utilize a new class of boronic acid-based fluorine-terminated SAMs to modify ITO surfaces in planar perovskite solar cells. The SAM treatment demonstrates an increase of the WF of ITO, an enhancement of the short-circuit current, and a passivation of trap states at the ITO/[poly(3,4ethylenedioxylenethiophene):poly(styrenesulfonic acid)] interface. Device stability improves upon SAM modification, with efficiency decreasing only 20% after one month. Our work highlights a simple treatment route to achieve hysteresis-free, reproducible, stable, and highly efficient (16%) planar perovskite solar cells.

Gecko-Inspired Biocidal Organic Nanocrystals Initiated from a Pencil-Drawn Graphite Template.

The biocidal properties of gecko skin and cicada wings have inspired the synthesis of synthetic surfaces decorated with high aspect ratio nanostructures that inactivate microorganisms. Here, we investigate the bactericidal activity of oriented zinc phthalocyanine (ZnPc) nanopillars grown using a simple pencil-drawn graphite templating technique. By varying the evaporation time, nanopillars initiated from graphite that was scribbled using a pencil onto silicon substrates were optimized to yield a high inactivation of the Gram-negative bacteria, Escherichia coli. We next adapted the procedure so that analogous nanopillars could be grown from pencil-drawn graphite scribbled onto stainless steel, flexible polyimide foil, and glass substrates. Time-dependent bacterial cytotoxicity studies indicate that the oriented nanopillars grown on all four substrates inactivated up to 97% of the E. coli quickly, in 15 min or less. These results suggest that organic nanostructures, which can be easily grown on a broad range of substrates hold potential as a new class of biocidal surfaces that kill microbes quickly and potentially, without spreading antibiotic-resistance genes.

Correlating Crystal Thickness, Surface Morphology, and Charge Transport in Pristine and Doped Rubrene Single Crystals.

The relationship between charge transport and surface morphology is investigated by utilizing rubrene single crystals of varying thicknesses. In the case of pristine crystals, the surface conductivities decrease exponentially as the crystal thickness increases until ∼4 µm, beyond which the surface conductivity saturates. Investigation of the surface morphology using optical and atomic force microscopy reveals that thicker crystals have a higher number of molecular steps, increasing the overall surface roughness compared with thin crystals. The density of molecular steps as a surface trap is further quantified with the subthreshold slope of rubrene air-gap transistors. This thickness-dependent surface conductivity is rationalized by a shift from in-plane to out-of-plane transport governed by surface roughness. The surface transport is disrupted by roughening of the crystal surface and becomes limited by the slower vertical crystallographic axis on molecular step edges. Separately, we investigate surface-doping of rubrene crystals by using fluoroalkyltrichrolosilane and observe a different mechanism for charge transport which is independent of surface roughness. This work demonstrates that the correlation between crystal thickness, surface morphology, and charge transport must be taken into account when measuring organic single crystals. Considering the fact that these molecular steps are universally observed on organic/inorganic and single/polycrystals, we believe that our findings can be widely applied to improve charge transport understanding.

Phase Transition of Graphene-Templated Vertical Zinc Phthalocyanine Nanopillars.

We report on the graphene-assisted growth, crystallization, and phase transition of zinc phthalocyanine (ZnPc) vertically oriented single crystal nanopillars. Postcrystallization thermal annealing of the nanostructures results in a molecular packing change while maintaining the vertical orientation of the single crystals orthogonal to the underlying substrate. Grazing incidence X-ray diffraction and high-resolution TEM studies characterized this phase transition from a metastable crystal phase to the more stable ß-phase commonly observed in bulk crystals. These vertical arrays of crystalline nanopillars exhibit a high-surface-to-volume ratio, which is advantageous for applications such as gas sensors. We fabricated chemiresistor sensors with ZnPc nanopillars grown on graphene and demonstrated its selectivity for ammonia vapors, and improvement in sensitivity in the ß-phase crystal packing pillars due to their molecular orientation increasing the exposure of the Zn2+ ion to the ammonia analyte. This work highlights the first morphology-retentive phase transition in organic single crystal nanopillars through simple postprocessing thermal annealing. This study opens up the possibility of molecular packing control without large variations in morphology, a necessity for high-performance devices and establishing structure-property relations.

Surface Grafting of Functionalized Poly(thiophene)s Using Thiol-Ene Click Chemistry for Thin Film Stabilization.

Regioregular poly[(3-hexylthiophene)-ran-(3-undecenylthiophene)] (pP3HT) and vinyl terminated poly(3-hexylthiophene) (xP3HT) were synthesized by the McCullough method and surface grafted to thiol modified silicon dioxide wafers using thiol-ene click chemistry. Utilizing this method, semiconducting, solvent impervious films were easily generated. Thiol-ene click chemistry is convenient for film stabilization in electronics because it does not produce side products that could be inimical to charge transport in the active layer. It was found through grazing incidence wide-angle X-ray scattering (GIWAXS) that there is no change in microstructure between as-spun films and thiol-ene grafted films, while there was a change after the thiol-ene grafted film was exposed to solvent. Organic field-effect transistors (oFETs) were fabricated from grafted films that had been swelled with chloroform, and these devices had mobilities on the order of 10-6 cm2 V-1 s-1, which are consistent with poly(thiophene) monolayer devices.

Graphene Ink as a Conductive Templating Interlayer for Enhanced Charge Transport of C60-Based Devices.

We demonstrate conductive templating interlayers of graphene ink, integrating the electronic and chemical properties of graphene in a solution-based process relevant for scalable manufacturing. Thin films of graphene ink are coated onto ITO, following thermal annealing, to form a percolating network used as interlayer. We employ a benchmark n-type semiconductor, C60, to study the interface of the active layer/interlayer. On bare ITO, C60 molecules form films of homogeneously distributed grains; with a graphene interlayer, a preferential orientation of C60 molecules is observed in the individual graphene plates. This leads to crystal growth favoring enhanced charge transport. We fabricate devices to characterize the electron injection and the effect of graphene on the device performance. We observe a significant increase in the current density with the interlayer. Current densities as high as ∼1 mA/cm2 and ∼70 mA/cm2 are realized for C60 deposited with the substrate at 25 °C and 150 °C, respectively.

Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential "edge-on" packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V(-1) s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast, moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.