Electronic Transport Properties of Pentacene Single Crystals upon Exposure to Air

We report the effect of air exposure on the electronic properties of pentacene single crystals. Air can diffuse reversibly in and out of the crystals and controls the physical properties. We discern two competing mechanisms that modulate the electronic transport. The presence of oxygen increases the hole conduction, as in dark four O2 molecules introduce one charge carrier. This effect is enhanced by the presence of visible light. Contrarily, water, present in ambient air, is incorporated in the crystal lattice and forms trapping sites for injected charges.Comment: 16 pages, 3 figure

Structure–function relations in diF-TES-ADT blend organic field effect transistors studied by scanning probe microscopy

We develop structure–property relations for organic field effect transistors using a polymer/small-molecule blend active layer. An array of bottom gate, bottom contact devices using a polymeric dielectric and a semiconductor layer of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT) is described and shown to have good device-to-device uniformity. We describe the nucleation and growth processes that lead to the formation of four structurally distinct regimes of the diF-TES-ADT semiconductor film, including evidence of layer-by-layer growth when spin-coated onto silver electrodes and an organic dielectric as part of a polymer blend. Devices exhibiting a maximum saturation mobility of 1.5 cm2 V−1 s−1 and maximum current modulation ratio (Ion/Ioff) of 1.20 × 105 are visualised by atomic force microscopy and appear to have excellent domain connectivity and aligned crystallography across the channel. In contrast, poorly performing devices tend to show a phase change in semiconductor crystallinity in the channel centre. These observations are enhanced by direct visualisation of the potential drop across the channel using Kelvin probe microscopy, which confirms the importance of large, well-aligned and well-connected semiconductor domains across the transistor channel

Pentacene islands grown on ultra-thin SiO2

Ultra-thin oxide (UTO) films were grown on Si(111) in ultrahigh vacuum at room temperature and characterized by scanning tunneling microscopy. The ultra-thin oxide films were then used as substrates for room temperature growth of pentacene. The apparent height of the first layer is 1.57 +/- 0.05 nm, indicating standing up pentacene grains in the thin-film phase were formed. Pentacene is molecularly resolved in the second and subsequent molecular layers. The measured in-plane unit cell for the pentacene (001) plane (ab plane) is a=0.76+/-0.01 nm, b=0.59+/-0.01 nm, and gamma=87.5+/-0.4 degrees. The films are unperturbed by the UTO's short-range spatial variation in tunneling probability, and reduce its corresponding effective roughness and correlation exponent with increasing thickness. The pentacene surface morphology follows that of the UTO substrate, preserving step structure, the long range surface rms roughness of ~0.1 nm, and the structural correlation exponent of ~1.Comment: 15 pages, 4 figure

Fluorinated benzalkylsilane molecular rectifiers

We report on the synthesis and electrical properties of nine new alkylated silane self-assembled monolayers (SAMs) – (EtO)3Si(CH2)nN = CHPhX where n = 3 or 11 and X = 4-CF[subscript 3], 3,5-CF[subscript 3], 3-F-4-CF[subscript 3], 4-F, or 2,3,4,5,6-F, and explore their rectification behavior in relation to their molecular structure. The electrical properties of the films were examined in a metal/insulator/metal configuration, with a highly-doped silicon bottom contact and a eutectic gallium-indium liquid metal (EGaIn) top contact. The junctions exhibit high yields (>90%), a remarkable resistance to bias stress, and current rectification ratios (R) between 20 and 200 depending on the structure, degree of order, and internal dipole of each molecule. We found that the rectification ratio correlates positively with the strength of the molecular dipole moment and it is reduced with increasing molecular length.National Science Foundation (U.S.) (Award ECCS 1254757)Wake Forest University (Pilot Research Grant

A 2-D π–π dimer model system to investigate structure-charge transfer relationships in rubrene

© The Royal Society of Chemistry 2019Rubrene (5,6,11,12-tetraphenyltetracene) is undoubtedly one of the best performing organic charge transfer mediating materials, with experimentally determined mobilities up to 40 cm2 V−1 s−1. Consequently, there has been increasing interest by means of crystal engineering in trying to generate rubrene-based materials with analogous or even superior conducting properties. Often, experimental measurements are carried out in thin film architectures of these materials, where measured properties can be detrimentally impacted by device manufacture rather than intrinsic charge transfer properties of the material. The latter results in discarding potential good performers. To address these concerns, we report a two-dimensional model system that will allow researchers to predict charge transfer properties of their materials solely requiring the coordinates of the π–π stacking motifs. We envisaged this study to be of significant interest to the increasingly large community of materials scientists devoted to the realisation of improved organic charge mediating materials and particularly to those engaged in exploiting rubrene-based architectures.Peer reviewedFinal Accepted Versio

Impact of regioregularity on thin-film transistor and photovoltaic cell performances of pentacene-containing polymers

Regioregular pentacene-containing polymers were synthesized with alkylated bithiophene (BT) and cyclopentadithiophene (CPDT) as comonomers. Among them, 2,9-conjugated polymers PnBT-2,9 and PnCPDT-2,9 achieved the best performance in transistor and photovoltaic devices respectively. The former achieved the most highly ordered structures in thin films, yielding ambipolar transistor behavior with hole and electron mobilities up to 0.03 and 0.02 cm(2) V-1 s(-1) on octadecylsilane-treated substrates. The latter achieved photovoltaic power conversion efficiencies up to 0.33%. The impact of regioregularity and direction of conjugation-extension (2,9 vs. 2,10), on thin-film order and device performance has been demonstrated for the pentacene-containing polymers for the first time, providing insight towards future functional material design.close101

Highly Efficient Rubrene–Graphene Charge-Transfer Interfaces as Phototransistors in the Visible Regime

This is the final version of the article. Available from Wiley via the DOI in this record.Atomically thin materials such as graphene are uniquely responsive to charge transfer from adjacent materials, making them ideal charge-transport layers in phototransistor devices. Effective implementation of organic semiconductors as a photoactive layer would open up a multitude of applications in biomimetic circuitry and ultra-broadband imaging but polycrystalline and amorphous thin films have shown inferior performance compared to inorganic semiconductors. Here, the long-range order in rubrene single crystals is utilized to engineer organic-semiconductor–graphene phototransistors surpassing previously reported photogating efficiencies by one order of magnitude. Phototransistors based upon these interfaces are spectrally selective to visible wavelengths and, through photoconductive gain mechanisms, achieve responsivity as large as 10^7 A/W and a detectivity of 9 × 10^11 Jones at room temperature. These findings point toward implementing low-cost, flexible materials for amplified imaging at ultralow light levels.S.R. and M.F.C. acknowledge financial support from EPSRC (Grant 464 Nos. EP/J000396/1, EP/K017160/1, EP/K010050/1, EP/G036101/1, EP/M001024/1, and 465 EP/M002438/1), from Royal Society international Exchanges Scheme 2012/R3 and 466 2013/R2 and from European Commission (No. FP7-ICT-2013-613024-GRASP)