Organic Semiconductor Single Crystals Research Articles

Isotropic transport in an oligothiophene derivative for single-crystal field-effect transistor applications

Single-crystal organic semiconductors have proven invaluable tools in the exploration of charge transport in molecular materials. We employ the elastomeric, photolithographically patterned single-crystal field-effect transistor in the study of an alpha-substituted oligothiophene. The terminal units specify a symmetric layered motif, while allowing the oligothiophene cores to pack closely. Angle-resolved measurements of the field-effect mobility reflect the symmetric edge/face interactions and isotropic mobility. These measurements are supported by electronic structure calculations that show nearly equivalent intermolecular interactions along cell diagonals. These results reveal that the transport is diffusive and a minimum of fourfold symmetry is required for in-plane mobility isotropy.

Crystal structure and charge-transport properties of N-trimethyltriindole: Novel p-type organic semiconductor single crystals

We report on a new p-type organic semiconductor single crystal, 5,10,15-trimethyl-10,15-dihydro-5 H-diindolo[3,2- a:3’,2’- c]carbazole ( N-trimethyltriindole). This molecule crystallizes forming a highly ordered columnar structure in which stacked molecules are situated at two alternating distances (3.53 Å and 3.68 Å) along the column as determined by single crystal X-ray diffraction analysis. These short intermolecular distances between adjacent units, make this system an ideal candidate for charge-transport processes along the stacks. Relevant parameters for transport (i.e. internal reorganization energies, transfer integral) have been estimated by DFT calculations at a 6-311G(d,p)/B3LYP level of theory. As a double check for the transfer integral, the electronic band structure of a one-dimensional stack of molecules has been computed. The electronic properties of this material have been studied both theoretically and experimentally. Its HOMO value is found to coincide with Au work function ( Φ Au = 5.1 eV), thus low barriers are expected for hole injection from gold electrodes. The hole mobility of this material has been predicted theoretically considering a hopping-type mechanism for the charge-transport and determined experimentally at the space charge limited current (SCLC) regime of the current–voltage measurements. Both theoretical and experimental values are in good agreement. The high hole mobility ( μ min = 0.4 cm 2 V −1 s −1) of this material points towards its useful application in the organic electronics arena. N-Trimethyltriindole single crystals constitute an essential model to study transport properties of triindole-based materials and to design new derivatives with improved electronic performance.

Nanomechanical Motions of Cantilevers: Direct Imaging in Real Space and Time with 4D Electron Microscopy

The function of many nano- and microscale systems is revealed when they are visualized in both space and time. Here, we report our first observation, using four-dimensional (4D) electron microscopy, of the nanomechanical motions of cantilevers. From the observed oscillations of nanometer displacements as a function of time, for free-standing beams, we are able to measure the frequency of modes of motion and determine Young's elastic modulus and the force and energy stored during the optomechanical expansions. The motion of the cantilever is triggered by molecular charge redistribution as the material, single-crystal organic semiconductor, switches from the equilibrium to the expanded structure. For these material structures, the expansion is colossal, typically reaching the micrometer scale, the modulus is 2 GPa, the force is 600 microN, and the energy is 200 pJ. These values translate to a large optomechanical efficiency (minimum of 1% and up to 10% or more) and a pressure of nearly 1,500 atm. We note that the observables here are real material changes in time, in contrast to those based on changes of optical/contrast intensity or diffraction.

Monolithic vertical microcavities based on tetracene single crystals

The authors report on monolithic, light-emitting vertical microcavities based on an organic semiconductor single crystal. The devices are realized by reactive electron-beam deposition of dielectric mirrors and growth of tetracene crystals by physical vapor transport. The microcavities exhibit optical cavity modes in the visible range (550–580nm) with full width at half maximum down to 2–3nm, corresponding to a Q factor of about 200, and polarization-induced modal splitting up to 20meV. These results open perspectives for the realization of polarized-emitting optoelectronic devices based on organic crystals.

Electronic properties of perfect single crystals of organic semiconductors prepared by crystallization from solutions

Electronic properties of perfect single crystals of organic semiconductors prepared by crystallization from solutions

Large-domain Organic Crystalline Films for Field-effect Transistors

AbstractWe report a method to fabricate thin films of large-domain organic semiconductor single crystals dispersed over the whole surface of centimeter-scale substrates for field-effect transistors. Growing less than 500-nm thick film-like organic crystals of sub-millimeter sizes densely in a furnace independently of substrates by physical vapor transport, the collection of the single crystals is mechanically attached to the surface of gate dielectric layers. The organic transistors made of large-domain benzo-annulated pentathienoacene crystals exhibited pronounced transistor performances with mobility values of ∼ 0.2-2 cm2/Vs, which is as high as devices of one-piece crystals. The result demonstrates that the above technique provides a method to apply high performance of organic single crystal transistors to real circuitry devices on large-area substrates.

Direct Formation of Thin Single Crystals of Organic Semiconductors onto a Substrate

We have developed a novel and convenient method of crystal growth in a liquid phase. This method produces directly onto a substrate well-defined polygon organic thin crystals with uniform thickness. The thin crystals are found to be single crystals of high quality. We show various illustrations including thiophene/phenylene co-oligomers and an oligophenylene. The organic crystal transistors based on these crystals showed good device performance. These thin single crystals are expected to be suitably applied to electronic devices.

Ambipolar Light‐Emitting Transistors of a Tetracene Single Crystal

AbstractThe first ambipolar light‐emitting transistor of an organic molecular semiconductor single crystal, tetracene, is demonstrated. In the device configuration, electrons and holes injected from separate magnesium and gold electrodes recombined radiatively within the channel. By varying the applied voltages, the position of the recombination/emission zone could be moved to any position along the channel. Because of the changes made to the device structure, including the use of single crystals and polymer dielectric layers and the adoption of an inert‐atmosphere fabrication process, the set of materials that can be used for light‐emitting transistors has been expanded to include monomeric molecular semiconductors.

Crystal clear

Controlling the growth of single-crystal organic semiconductors has implications for flexible large-area electronic devices

Organic crystals at large

Fabricating large-scale semiconducting surfaces for the flexible screens of the future is a bothersome business. A simple technique for growing single-crystal organic semiconductors brings new vision to the field.

Nanoscale Surface Morphology and Rectifying Behavior of a Bulk Single‐Crystal Organic Semiconductor

Local surface measurements of rubrene single crystals reveal interesting insights on carrier transport mechanisms at the active interface of high-performance field-effect “air-gap stamp” transistors. Scanning tunnelling microscopy (STM) images, combined with atomic force microscopy and X-ray diffraction, reveal directly the position and orientation of individual molecules in the a–b plane (see figure and inside cover). Local current–voltage curves recorded using STM in the dark and under light indicate a rectifying p-type behavior.

Photopumped laser oscillation and charge-injected luminescence from organic semiconductor single crystals of a thiophene/phenylene co-oligomer

We have demonstrated that single crystals of a thiophene/phenylene co-oligomer [α,ω-bis-biphenyl-4-yl-terthiophene (BP3T)] show interesting photonic aspects: (1) the self-waveguided amplified spontaneous light emissions with a comparable low threshold of 8μJ∕cm2 to other optimized organic solid-state laser systems, and (2) the laser oscillation based on the optical self-confinement effect in the crystals. We have also presented electroluminescence from the crystals based on bipolar injection and the crystals’ tolerance for intense current driving. These achievements strongly imply that BP3T crystals are a promising candidate for organic laser diodes.

SAMs Serve as Templates for Patterned Growth of Large Oriented Organic Semiconductor Single Crystals

SAMs Serve as Templates for Patterned Growth of Large Oriented Organic Semiconductor Single Crystals

Patterned Growth of Large Oriented Organic Semiconductor Single Crystals on Self-Assembled Monolayer Templates

This work demonstrates a method for inducing site-specific nucleation and subsequent growth of large oriented organic semiconductor single crystals using micropatterned self-assembled monolayers (SAMs). We demonstrate growth of oriented, patterned, and large organic semiconductor single crystals for potential use in organic electronic devices. The control over multiple parameters in a single system has not yet been reported. The ability to control various aspects of crystal growth in one system provides a powerful technique for the bottom-up fabrication of organic single-crystal semiconductor devices.

Organic thin-film electronics from vitreous solution-processed rubrene hypereutectics

Electronic devices based on single crystals of organic semiconductors provide powerful means for studying intrinsic charge-transport phenomena and their fundamental electronic limits. However, for technological exploitation, it is imperative not to be confined to the tedious growth and cumbersome manipulation of molecular crystals-which generally show notoriously poor mechanical properties-but to be able to process such materials into robust architectures by simple and efficient means. Here, we advance a general route for facile fabrication of thin-film devices from solution. The key beneficial feature of our process-and the principal difference from existing vapour deposition and solution-processing schemes-is the incorporation of a glass-inducing diluent that enables controlled crystallization from an initial vitreous state of the organic semiconductor, formed in a selected area of the phase diagram of the two constituents. We find that the vitrifying diluent does not adversely affect device performance. Indeed, our environmentally stable, discrete rubrene-based transistors rival amorphous silicon devices, reaching saturated mobilities of up to 0.7 cm2 V-1 s-1, ON-OFF ratios of >or=10(6) and subthreshold slopes as steep as 0.5 V per decade. A nearly temperature-independent device mobility, indicative of a high crystalline quality of our solution-processed, rubrene-based films, corroborates these findings. Inverter and ring-oscillator structures are also demonstrated.