Pentacene Single Crystals Research Articles

Charge transport calculations by a wave-packet dynamical approach using maximally localized Wannier functions based on density functional theory: Application to high-mobility organic semiconductors

We present a wave-packet dynamical approach to charge transport using maximally localized Wannier functions based on density functional theory including van der Waals interactions. We apply it to the transport properties of pentacene and rubrene single crystals and show the temperature-dependent natures from bandlike to thermally activated behaviors as a function of the magnitude of external static disorder. We compare the results with those obtained by the conventional band and hopping models and experiments.

Crystallinity of the epitaxial heterojunction of C60 on single crystal pentacene

The structure of pn heterojunctions is an important subject in the field of organic semiconductor devices. In this work, the crystallinity of an epitaxial pn heterojunction of C60 on single crystal pentacene is investigated by non-contact mode atomic force microscopy and high-resolution grazing incidence x-ray diffraction. Analysis shows that the C60 molecules assemble into grains consisting of single crystallites on the pentacene single crystal surface. The in-plane mean crystallite size exceeds 0.1µm, which is at least five time larger than the size of crystallites deposited onto polycrystalline pentacene thin films grown on SiO2. The results indicate that improvement in the crystal quality of the underlying molecular substrate leads to drastic promotion of the crystallinity at the organic semiconductor heterojunction.

Arrays of Pentacene Single Crystals by Stencil Evaporation

In order to realize high-performance organic thin-film transistors (TFT), two parameters of the organic semiconducting layer are desired: single crystallinity for high mobility and patterning for low off currents. High-quality single crystals can be fabricated using vapor techniques such as physical vapor transport (PVT), but they require high temperatures close to thermodynamic equilibrium, for example, 240 °C for pentacene. Such high temperatures are not ideal for TFT fabrication on plastic substrates and limit the use of PVT in flexible electronics applications. In this work arrays of pentacene single crystals were directly deposited at low temperature of 40 °C by vacuum thermal evaporation through microfabricated stencil masks (stencil lithography). By decreasing the stencil aperture size down to 1 μm × 1 μm, we were able to limit the nucleation area until only one grain per aperture is nucleated and grown. We studied systematically scaling effects for large singe crystal growth and discuss details of...

Enhanced mobility in organic field-effect transistors due to semiconductor/dielectric interface control and very thin single crystal

A perfect organic crystal while keeping high quality semiconductor/dielectric interface with minimal defects and disorder is crucial for the realization of high performance organic single crystal field-effect transistors (OSCFETs). However, in most reported OSCFET devices, the crystal transfer processes is extensively used. Therefore, the semiconductor/dielectric interface is inevitably damaged. Carrier traps and scattering centers are brought into the conduction channel, so that the intrinsic high mobility of OSCFET devices is entirely disguised. Here, very thin pentacene single crystal is grown directly on bare SiO2 by developing a ‘seed-controlled’ pentacene single crystal method. The interface quality is controlled by an in situ fabrication of OSCFETs. The interface is kept intact without any transfer process. Furthermore, we quantitatively analyze the influence of crystal thickness on device performance. With a pristine interface and very thin crystal, we have achieved the highest mobility: 5.7 cm2 V−1 s−1—more than twice the highest ever reported pentacene OSCFET mobility on bare SiO2. This study may provide a universal route for the use of small organic molecules to achieve high performance in lamellar single crystal field-effect devices.

Epitaxial Growth of an Organic p-n Heterojunction: C60 on Single-Crystal Pentacene.

Designing molecular p-n heterojunction structures, i.e., electron donor-acceptor contacts, is one of the central challenges for further development of organic electronic devices. In the present study, a well-defined p-n heterojunction of two representative molecular semiconductors, pentacene and C60, formed on the single-crystal surface of pentacene is precisely investigated in terms of its growth behavior and crystallographic structure. C60 assembles into a (111)-oriented face-centered-cubic crystal structure with a specific epitaxial orientation on the (001) surface of the pentacene single crystal. The present experimental findings provide molecular scale insights into the formation mechanisms of the organic p-n heterojunction through an accurate structural analysis of the single-crystalline molecular contact.

Organic Thin Film Transistor with Carbon Nanotube Electrodes

The contact resistance between organic semiconductors and metallic electrodesaffectsthe performance of the organic thin film transistor (OTFT) negatively so that it may make thefield effect mobility of charge carrier seem small. In order to reduce the contact resistance weused conducting Carbon Nanotube (CNT) films, which consist of the same element as the basicmaterial of the organic semiconductors, as source or drain electrodes. The measurements oftransistor properties based on pentacene single crystals have been carried out by using both CNTfilm electrodes and metal electrodes

High-resolution core-level photoemission measurements on the pentacene single crystal surface assisted by photoconduction

Upon charge carrier transport behaviors of high-mobility organic field effect transistors of pentacene single crystal, effects of ambient gases and resultant probable ‘impurities’ at the crystal surface have been controversial. Definite knowledge on the surface stoichiometry and chemical composites is indispensable to solve this question. In the present study, high-resolution x-ray photoelectron spectroscopy (XPS) measurements on the pentacene single crystal samples successfully demonstrated a presence of a few atomic-percent of (photo-)oxidized species at the first molecular layer of the crystal surface through accurate analyses of the excitation energy (i.e. probing depth) dependence of the C1s peak profiles. Particular methodologies to conduct XPS on organic single crystal samples, without any charging nor damage of the sample in spite of its electric insulating character and fragility against x-ray irradiation, is also described in detail.

Electronic Structures of a Well-Defined Organic Hetero-Interface: C<sub>60 </sub>on Pentacene Single Crystal

Electronic structures of donor-acceptor hetero-interfaces are crucial for performance of organic solar cell devices. In the present study, a well-defined organic molecular interface of pentacene single crystal and C60 overlayer is elucidated by x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and photoelectron yield spectroscopy (PYS). An energy level diagram at this hetero-molecular contact in the “head-on” orientation is derived, which reveals the vacuum level alignment and flat-band conditions. [DOI: 10.1380/ejssnt.2015.59]

Electric-field-assisted position and orientation control of organic single crystals.

We have investigated the motion of growing pentacene single crystals in solution under various electric fields. The pentacene single crystals in 1,2,4-trichlorobenzene responded to the electric field as if they were positively charged. By optimizing the strength and frequency of an alternating electric field, the pentacene crystals automatically bridged the electrodes on SiO2. The pentacene crystal with a large aspect ratio tended to direct the [1̅10] orientation parallel to the conduction direction, which will be suitable from a viewpoint of anisotropy in mobility. The present result shows a possibility of controlling the position and orientation of organic single crystals by the use of an electric field, which leads to high throughput and low cost industrial manufacturing of the single crystal array from solution.

Determination of the highest occupied molecular orbital energy of pentacene single crystals by ultraviolet photoelectron and photoelectron yield spectroscopies

The electronic structures of pentacene single crystals (SCs) were elucidated by ultraviolet photoelectron spectroscopy (UPS) and photoelectron yield spectroscopy (PYS). An asymmetric HOMO peak profile of the pentacene SCs obtained by UPS exhibits a close similarity to the k-projected density-of-states of the valence band that has been predicted by a theoretical calculation [H. Yoshida and N. Sato, Phys. Rev. B 77, 235205 (2008)]. The ionization energy of the pentacene SCs is successfully determined to be 4.95 (± 0.03) eV which is evidently greater than that of the bulk films of pentacene [4.90 (± 0.02) eV].

Observation of Frenkel and charge transfer excitons in pentacene single crystals using spectroscopic generalized ellipsometry

We report on the emerging and admixture of Frenkel and charge transfer (CT) excitons near the absorption onset in pentacene single crystals. Using high energy-resolution spectroscopic generalized ellipsometry with in-plane polarization dependence, the excitonic nature of three lowest lying excitations is discussed. Their distinct polarization dependence strongly indicates the presence of both Frenkel and CT types of excitons near the excitation onset. In particular, the peculiar polarization behavior of the second excitation can only be rationalized by taking into account the inherent CT transition dipole moment. This observation has important implications for the pentacene-based optoelectronic devices.

有机场效应晶体管导电机制及其稳定性研究

The research of pentacene thin-film transistors (TFTs) and pentacene single crystal has been the research focus recently. In this paper, we have performed both experimental and theoretical studies for the influence of morphology of the first pentacene layer on the electronic properties of TFTs. We proposed a two-dimensional grain boundary model to interpret the relationship of the mobility as well as threshold voltage shift under gate bias-stress and the first-layered grain size. We obtained several meaningful parameters, such as mobility in single grain, trap density in grain boundary and the height of potential barrier. This is meaningful to optimize the performance of organic thin-film transistors. Meanwhile, we raised a new strategy to prepare pentacene single crystal, which starts from pentacene monolayer film and the process can be defined as two step growth of high quality, large pentacene single crystals. We systematically studied the molecular dynamics in this process, which may make essential preparation for device fabrication in the future.

Two-Step Growth of Large Pentacene Single Crystals Based on Crystallization of Pentacene Monolayer Film

A two-step growth method, namely, initial crystallization from pentacene monolayer grains to nanosized single crystals (nanocrystals) and subsequent physical vapor transport (PVT) growth on the nanocrystals as seeds, is demonstrated to fabricate larger microsized pentacene single crystals. The pentacene monolayer film deposited on a bare SiO2 substrate was found to self-assemble to nanoparticles during a post-annealing process. Selected area electron difffraction demonstrates unambiguously the nanoparticles and the microsized particles grown by the following PVT are both single crystals but with different crystal phases. Such a two-step growth technology maintains the intrinsic interface states between the SiO2 dielectric and the pentacene active layer and provides a more flexible way to in-situ prepare oraganic single crystals for device fabrication. The detailed investigation of morphology evolution and the discussion of formation mechanism of nanocrystal seeds indicate that the pentacene molecular tran...

Organic single crystal transistor characteristics of single-crystal phase pentacene grown by ionic liquid-assisted vacuum deposition

Organic transistor characteristics of single-crystal phase pentacene were investigated. Ionic liquids (ILs) were used as not only a gate dielectric material in the transistors but also a crystallization solvent in vacuum deposition of pentacene. The crystal sizes reached 200 μm and their surface exhibits a molecularly step-and-terrace structure. There was no sign of IL molecules inside the crystal, and the impurity level of 6,13-pentacenequinone was also reduced. The average value of the field-effect mobility was not so inferior to those for the conventional pentacene single crystals, and the highest value exceeded 5 cm2/Vs, with the on/off current ratio of 104.

Wave-packet approach to transport properties of carrier coupled with intermolecular and intramolecular vibrations of organic semiconductors

We present a methodology to study the charge-transport properties of organic semiconductors by the time-dependent wave-packet diffusion method, taking the polaron effects into account. As an example, we investigate the transport properties of single-crystal pentacene organic semiconductors coupled with inter- and intramolecular vibrations within the mixed Holstein and Peierls model, which describes both hopping and bandlike transport behaviors due to small and large polaron formations. Taking into account static disorders, which inevitably exist in the molecular crystals, we present the temperature dependence of charge-transport properties in competition among the thermal fluctuation of molecular motions, the polaron formation, and the static disorders.

High‐Performance Transistors and Complementary Inverters Based on Solution‐Grown Aligned Organic Single‐Crystals

Constructing a complementary inverter is technically more complex because both pand n-channel transistors are required to be patterned onto a common substrate. Here, we report a simple solution processing method to fabricate complementary inverters based on n-channel C 60 single crystals and p-channel 6,13-bis(triisopropyl-silylethynyl) pentacene (TIPS-pentacene) single crystals. We achieved a signal gain as high as 155. Hence, this work provides a platform to study high-performance complementary circuits based on organic single-crystals. Organic FETs have been widely used for electronic applications such as displays [ 5 , 6 ] and sensors. [ 7–9 ] Organic single-crystals show the best FET performance with the highest charge mobility among organic materials. The p-channel organic single-crystal FETs have exhibited hole mobility as high as 40 cm 2 V − 1 s − 1 , [ 10–14 ]

Temperature dependence of the Hall effect in pentacene field-effect transistors: Possibility of charge decoherence induced by molecular fluctuations

Temperature dependence of the Hall effect is measured for both single-crystal and thin-film field-effect transistors of pentacene. At room temperature, the inverse Hall coefficient $1/{R}_{H}$ exceeds field-induced charge density $Q$ by a factor of 2 at each gate-electric field for all the samples, regardless of their charge-carrier mobility and detailed subthreshold properties. Violating the band-transport model that $1/{R}_{H}$ equals to $Q$, the excess $1/{R}_{H}$ does not measure the charge amount anymore so that the result possibly indicates insufficient electromagnetic coupling due to somewhat reduced charge coherence. At lower temperatures, the deviation of $1/{R}_{H}$ from $Q$ gradually diminishes to approach the band-transport behavior. Interestingly, the degree of the deviation has been universal for the measured five samples, including both polycrystal and single-crystal pentacene films. The result suggests that significant molecular fluctuation near room temperature can affect the fundamental electronic state.

Effect of dynamic disorder on charge transport along a pentacene chain

The lattice equation of motion and a numerical solution of the time-dependent Schr\"odinger equation provide us with a microscopic picture of charge transport in highly ordered molecular crystals. We have chosen the pentacene single crystal as a model system, and we study charge transport as a function of phonon-mode time-dependent fluctuations in the intermolecular electron transfer integral. For comparison, we include similar fluctuations also in the intramolecular potentials. The variance in these energy quantities is closely related to the temperature of the system. The pentacene system is shown to be very sensitive to fluctuation in the intermolecular transfer integral, revealing a transition from adiabatic to nonadiabatic polaron transport for increasing temperatures. The extension of the polaron at temperatures above 200 K is limited by the electron localization length rather than the interplay between the electron transfer integral and the electron-phonon coupling strength.

Theoretical Characterization of the Air-Stable, High-Mobility Dinaphtho[2,3-b:2′3′-f]thieno[3,2-b]-thiophene Organic Semiconductor

Recently, an optimum mobility of 8.3 cm2/(Vs) has been measured for single-crystal organic field-effect transistors based on the dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) molecule. Here, on the basis of quantum chemistry calculations and molecular dynamics simulations, we investigate the microscopic charge transport parameters of the DNTT molecule and crystal. Our findings confirm that the moderate anisotropy of the hole mobility in DNTT is highly dependent on the presence of in-plane herringbonelike intermolecular interactions with large electronic coupling (transfer integral) values (ca. 0.1 eV). Also, we demonstrate that the π-extended heteroaromatic structure leads to strong electronic coupling interactions among neighboring molecules and to a decrease of the intramolecular reorganization energy. In DNTT, thermal modulations of the electronic couplings at 300 K remain small when compared to those exhibited by the pentacene single crystal. This theoretical study suggests that heteroacenes are a promising route toward high-mobility organic semiconductor materials. Charge transport is discussed in the framework of both band and hopping models.

Electronic Properties of the 2,6-Diiododithieno[3,2-b:2′,3′-d]thiophene Molecule and Crystal: A Joint Experimental and Theoretical Study

The electronic properties of the 2,6-diiododithieno[3,2-b:2',3'-d] thiophene molecule and crystal are investigated by means of UV-vis spectroscopy, cyclic voltammetry, X-ray crystallography, and density functional theory. The experimental and calculated properties of the compound are compared to those exhibited by the parent molecule, dithieno[3,2-b:2',3'-d]thiophene. Quantum-chemical studies of the 2,6-diiododithieno[3,2-b:2',3'-d]thiophene crystal suggest uniaxial hole-transport character with an effective mass of about 2m(0), comparable to that in the pentacene single crystal.