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With the development of novel semiconductors for optoelectronic applications, new device functionalities utilizing unique characteristics of emerging materials can be particularly appealing. Here, we demonstrate a reversible control of photoluminescence (PL) emission from lead-halide perovskites achieved in perovskite electric-double-layer transistors. PL in several prototypical lead-halide perovskite compounds is shown to be reversibly tuned by a small gate voltage in the range ±1.2 V applied to the ionic-liquid gel on the perovskite surface, with the intensity modulation that can reach one to two orders of magnitude. This effect may be mediated by a reversible migration of oxygen ions affecting the crystal region near the interface with the ion gel. The resulting passivation (or activation) of non-radiative recombination centers (traps) by oxygen ions would then modulate the population of mobile photogenerated electrons and holes that give rise to PL, which is thus tuned with an electric “knob” (the gate) in these devices. more...

The first experimental realization of the intrinsic (not dominated by defects) charge conduction regime in lead-halide perovskite field-effect transistors (FETs) is reported. The advance is enabled by: i) a new vapor-phase epitaxy technique that results in large-area single-crystalline cesium lead bromide (CsPbBr more...

Doping is one of the most fundamental building blocks for semiconductor processing, and enables adaptation to both charge concentration and electrical conductivity. Despite attempts to investigate various doping and de-doping methods for organic semiconductors over many years, their use has been limited to date. Here, we present a method to precisely control the degree of doping in dopant-implanted thiophene-based polymeric conductors. A simple post annealing at a relatively low temperature of approximately 110 °C can significantly diminish the charge carrier concentration with precision, where the controllability is evaluated comprehensively using electron spin resonance and optical absorption techniques. At higher doping regimes, a band-like charge transport with an ideal Hall effect and weak localization is confirmed. more...

There has been increased interest in organic semiconductors over the last decade because of their unique properties. Of these, 5, 6, 11, 12-tetraphenylnaphthacene (rubrene) has generated the most interest because of its high charge carrier mobility. In this work, large single crystals with a volume of ~1 cm3 were grown from solution by a temperature reduction technique. The faceted crystals had flat surfaces and cm-scale, visually defect-free areas suitable for physical characterization. X-ray diffraction analysis indicates that solvent does not incorporate into the crystals and photoluminescence spectra are consistent with pristine, high-crystallinity rubrene. Furthermore, the response curve to pulsed optical illumination indicates that the solution grown crystals are of similar quality to those grown by physical vapor transport, albeit larger. The good quality of these crystals in combination with the improvement of electrical contacts by application of conductive polymer on the graphite electrodes have led to the clear observation of alpha particles with these rubrene detectors. Preliminary results with a 252Cf source generate a small signal with the rubrene detector and may demonstrate that rubrene can also be used for detecting high-energy neutrons. more...

Organic Electronics is one of the most active areas of interdisciplinary research, targeting implementation of organic semiconductors in electronic applications ranging from low-cost, light-weight, fl exible and wearable electronics, to light-emitting diodes, sensors, and solar cells. [ 1 ] In order to provide a stronger fundamental support to this thriving applications-driven fi eld, a deeper understanding of the basic principles governing the operation of organic materials and devices is necessary. Such understanding would help to design better semiconductors, improve device performance, and invent novel device concepts and prototypes. However, this task is very challenging because of the complexity and enormous variety of organic-molecule semiconductors, as well as the multitude of factors and microscopic phenomena that defi ne their electronic properties. more...

Pyromellitic diimides (PyDIs) are π-conjugated electron-transport materials based on an unusually small aromatic core (benzene), which provides low temperature processing and transparency in much of the visible range. We synthesized PyDI derivatives with a systematic series of fluoroalkyl side chains and investigated their film structures and electrical performances in thin-film transistors. The effect of the length of the fluorinated segment in fluoroalkylmethylene side chains was examined. Shorter side chains within this series induce higher electron mobilities, with a maximum of 0.026 cm2 V−1 s−1 achieved with the perfluorobutylmethyl side chain. Atomic force microscopy images and X-ray diffraction peak widths were used as indications of crystallinity correlating with the mobility trend. The perfluorobutylmethyl side chain, when attached to 3,6-dibromo PyDI using a total of three synthetic steps, allowed nearly parallel PyDI cores and an exceptional mobility of 0.2 cm2 V−1 s−1, accompanied by a correspondingly excellent morphology and effective intermolecular packing illustrated by a single crystal X-ray structure. This is the highest PyDI mobility yet reported, and is an unusually high mobility for a compound with such a small core, having such low visible range absorbance, and requiring so few synthetic steps. more...

Fundamental studies of intrinsic charge transport properties of organic semiconductors are often hindered by charge traps associated with static disorder present even in optimized single-crystal devices. Here, we report a method of surface functionalization using an inert non-conjugated polymer, perfluoropolyether (PFPE), deposited at the surface of organic molecular crystals, which results in accumulation of mobile holes and a 'trap healing' effect at the crystal/PFPE interface. As a consequence, a remarkable ultralow-noise, trp-free conduction regime characterized by intrinsic mobility and transport anisotropy emerges in organic single crystals, and Hall effect measurements with an unprecedented signal-to-noise ratio are demonstrated. This general method to convert trap-dominated organic semiconductors to intrinsic systems may enable the determination of intrinsic transport parameters with high accuracy and make Hall effect measurements in molecular crystals ubiquitous. more...

The origin of the bias stress effect related only to semiconductor properties is investigated in "air-gap" organic field-effect transistors (OFETs) in the absence of a material gate dielectric. The effect becomes stronger as the density of trap states in the semiconductor increases. A theoretical model based on carrier trapping and relaxation in localized tail states is formulated. Polar molecular vapors in the gap of "air-gap" OFETs also have a significant impact on the bias stress effect via the formation of bound states between the charge carriers and molecular dipoles at the semiconductor surface. more...

Commonly observed variations in photoluminescence (PL) spectra of crystalline organic semiconductors, including the appearance or enhancement of certain PL bands, are shown to originate from a small amount of structural disorder (e.g., amorphous inclusions embedded in a crystal), rather than be necessarily related to chemical impurities or material oxidation. For instance, in rubrene, a minute amount of such disorder can lead to the appearance of a dominant PL band at 650 nm as a result of triplet excitons captured and fused at these sites, with a subsequent emission from the amorphous phase. more...

We describe new Rutherford Backscattering Spectroscopy (RBS) measurements to explore the surface chemistry associated with the growth of self-assembled monolayer (SAM) molecules on conducting organic films. The report includes a description of the optimization of both substrates and RBS scattering parameters to appropriately analyze these novel and damage susceptible structures. Our RBS measurements reveal that the final surface stoichiometry is consistent with a specific model of hydrolyzed and crosslinked trichlorosilanes that form a dense two-dimensional network (a monolayer) at the surface of small-molecule organic semiconductors and a bulk SAM network in the case of conjugated polymer films. Organic semiconductors used in this study are thin films of rubrene (a small molecule semiconductor (C42H28)) and poly(3-hexyl)thiophene (P3HT) (a conjugated polymer (C10H18S)n). As a substrate we used a thick (1 μm) film of parylene (a non-conjugated polymer (C8H8)n) deposited on Si (1 0 0) wafers. The SAM molecules used to functionalize the organic semiconductor films are fluoroalkyl trichlorosilane (FTS) (C8(H4F13)SiCl3) and octyltrichlorosilane (OTS) (C8H17SiCl3). Quantitative detection of medium and small-mass elements, such as O, F, Si, S and residual Cl is demonstrated and used to elucidate the surface chemistry in these novel organic systems. more...

The authors are grateful to the following programs for the financial support of this work: the National Science Foundation under the grant DMR-1506609, the Rutgers Energy Institute (REI), the Center for Advanced Soft-Electronics funded by the Ministry of Science, ICT and Future Planning as Global Frontier Project (CASE-2011-0031628), and the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST «MISiS» (№ K3-2016-004), implemented by a governmental decree dated 16th of March 2013, N 211. T.D.A., and A.F.P, acknowledge the King Abdullah University of Science and Technology (KAUST) for financial support. more...

Under certain conditions, self-assembling molecules preferentially bind to molecular steps at the surface of crystalline organic semiconductors, inducing a strong local doping effect. This creates macroscopically long conducting paths of nanoscale width (a single crystalline analogue of organic nanowires) that can span distances of up to 1 cm between electrical contacts. The observed effect of molecular step decoration opens intriguing possibilities for visualization, passivation, and selective doping of surface and interfacial defects in organic electronic devices and provides a novel system for research on nanoscale charge transport in organic semiconductors. In addition, this effect sheds light on the microscopic origin of nucleation and growth of self-assembled monolayers at organic surfaces. It can also have implications in electronic patterning, nanoscale chemical sensors, integrated interconnects and charge-transfer interfaces in organic transistors and solar cells. more...

A strong modification of the electronic properties of solution-processable conjugated polythiophenes by self-assembled silane molecules is reported. Upon bulk doping with hydrolized fluoroalkyl trichlorosilane, the electrical conductivity of ultrathin polythiophene films increases by up to six orders of magnitude, reaching record values for polythiophenes: (1.1 ± 0.1) × 103 S cm−1 for poly(2,5-bis(3-tetradecylthiophen -2-yl)thieno[3,2-b]thiophene) (PBTTT) and 50 ± 20 S cm−1 for poly(3-hexyl)thiophene (P3HT). Interband optical absorption of the polymers in the doped state is drastically reduced, making these highly conductive films transparent in the visible range. The dopants within the porous polymer matrix are partially crosslinked via a silane self-polymerization mechanism that makes the samples very stable in vacuum and nonpolar environments. The mechanism of SAM-induced conductivity is believed to be based on protonic doping by the free silanol groups available within the partially crosslinked SAM network incorporated in the polythiophene structure. The SAM-doped polythiophenes exhibit an intrinsic sensing effect: a drastic and reversible change in conductivity in response to ambient polar molecules, which is believed to be due to the interaction of the silanol groups with polar analytes. The reported electronic effects point to a new attractive route for doping conjugated polymers with potential applications in transparent conductors and molecular sensors. more...

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. Here we report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO3. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90–250 K and 70–100 K, respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications. more...

Poorly ordered films of conjugated polymers that show high charge mobility recently challenged the idea that disorder is detrimental for electrical conduction. Systematic studies now reveal that long polymeric chains can bridge small crystalline domains thus supporting charge transport on length scales relevant for device operation. more...

Excitons in rubrene single crystals dissociate into free charge carriers via two mechanisms whose relative importance depends on the illumination wavelength through the optical penetration depth into the crystal. The first mechanism is defect-induced dissociation in less than 10 ns after photoexcitation. For low photoexcitation densities, about 10% of the excitons that survive radiative recombination dissociate through this channel. The second mechanism, affecting the remaining 90% of the excitons, involves a previously reported state localized close to the surface of the crystal that leads to a delayed release of photocarriers a fraction of a millisecond after photoexcitation. more...

We report results of photocurrent studies performed on rubrene single crystal transistors in the air-gap configuration under 405nm irradiation. The phototransistors show a strong photoresponse indicative of photoconduction. Under illumination, the phototransistors show an average threshold voltage shift of 22V and a maximum photosensistivity of 2.65×103. A small persistent photoconductivity effect is observed in the transistors tested under continuous illumination which is explained by delayed recombination aided by spatial separation of the photocarriers. Photocurrent transients measured by applying short pulses on the other hand show a complete recovery in the microsecond regime implying immediate recombination. more...