The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. 'Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C(8)-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm(2) V(-1) s(-1). This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.

We demonstrate controllable shift of the threshold voltage and the turn-on voltage in pentacene thin film transistors and rubrene single crystal field effect transistors (FET) by the use of nine organosilanes with different functional groups. Prior to depositing the organic semiconductors, the organosilanes were applied to the SiO2 gate insulator from solution and form a self assembled monolayer (SAM). The observed shift of the transfer characteristics range from -2 to 50 V and can be related to the surface potential of the layer next to the transistor channel. Concomitantly the mobile charge carrier concentration at zero gate bias reaches up to 4 × 10 12 /cm 2 . In the single crystal FETs the measured transfer characteristics are also shifted, while essentially maintaining the high quality of the subthreshold swing. The shift of the transfer characteristics is governed by the built-in electric field of the SAM and can be explained using a simple energy level diagram. In the thin film devices, the subthreshold region is broadened, indicating that the SAM creates additional trap states, whose density is estimated to be of order 1 × 10 12 /cm 2 .

We report on organic field-effect transistors with unprecedented resistance against gate bias stress. The single crystal and thin-film transistors employ the organic gate dielectric Cytop TM . This fluoropolymer is highly water repellent and shows a remarkable electrical breakdown strength. The single crystal transistors are consistently of very high electrical quality: near zero onset, very steep subthreshold swing (average: 1.3 nF V/(dec cm 2 )) and negligible current hysteresis. Furthermore, extended gate bias stress only leads to marginal changes in the transfer characteristics. It appears that there is no conceptual limitation for the stability of organic semiconductors in contrast to hydrogenated amorphous silicon.

We show that it is possible to reach one of the ultimate goals of organic electronics: producing organic field-effect transistors with trap densities as low as in the bulk of single crystals. We studied the spectral density of localized states in the band gap (trap DOS) of small molecule organic semiconductors as derived from electrical characteristics of organic field-effect transistors or from space-charge-limited-current measurements. This was done by comparing data from a large number of samples including thin-film transistors (TFT's), single crystal field-effect transistors (SC-FET's) and bulk samples. The compilation of all data strongly suggests that structural defects associated with grain boundaries are the main cause of "fast" hole traps in TFT's made with vacuum-evaporated pentacene. For high-performance transistors made with small molecule semiconductors such as rubrene it is essential to reduce the dipolar disorder caused by water adsorbed on the gate dielectric surface. In samples with very low trap densities, we sometimes observe a steep increase of the trap DOS very close (< 0.15 eV) to the mobility edge with a characteristic slope of 10 − 20 meV. It is discussed to what degree band broadening due to the thermal fluctuation of the intermolecular transfer integral is reflected in this steep increase of the trap DOS. Moreover, we show that the trap DOS in TFT's with small molecule semiconductors is very similar to the trap DOS in hydrogenated amorphous silicon even though polycrystalline films of small molecules with van der Waals-type interaction on the one hand are compared with covalently bound amorphous silicon on the other hand. Although important conclusions can already be drawn from the existing data, more experiments are needed to complete the understanding of the trap DOS near the band edge in small molecule organic semiconductors.

-We report on single crystal high mobility organic field-effect transistors (OFETs) prepared on prefabricated substrates using a "flip-crystal" approach. This method minimizes technique employed in this study shows potential as a general method for studying charge transport in field-accumulated carrier channels near the surface of organic single crystals.2

Influence of surface states on the two-dimensional electron gas in AlGaN/GaN heterojunction field-effect transistorsA method has been developed to inject mobile charges at the surface of organic molecular crystals, and the dc transport of field-induced holes has been measured at the surface of pentacene single crystals. To minimize damage to the soft and fragile surface, the crystals are attached to a prefabricated substrate which incorporates a gate dielectric (SiO 2 ) and four probe pads. The surface mobility of the pentacene crystals ranges from 0.1 to 0.5 cm 2 /V s and is nearly temperature independent above ϳ150 K, while it becomes thermally activated at lower temperatures when the induced charges become localized. Ruling out the influence of electric contacts and crystal grain boundaries, the results contribute to the microscopic understanding of trapping and detrapping mechanisms in organic molecular crystals.

A well‐defined structural phase transformation is observed in bulk single crystals of pentacene, whereas pentacene powders heated above the phase‐transformation temperature do not always fully convert, and upon cooling, coexistence of the two polymorphs is observed down to room temperature. The first‐order phase transformation is isostructural: the close‐packed herringbone‐type layers shift against each other, keeping the same symmetry.

The density of trap states in the bandgap of semiconducting organic single crystals has been measured quantitatively and with high energy resolution by means of the experimental method of temperature-dependent space-charge-limited-current spectroscopy (TDSCLC). This spectroscopy has been applied to study bulk rubrene single crystals, which are shown by this technique to be of high chemical and structural quality. A density of deep trap states as low as ∼ 10 15 cm −3 is measured in the purest crystals, and the exponentially varying shallow trap density near the band edge could be identified (one decade in the density of states per ∼ 25 meV). Furthermore, we have induced and spectroscopically identified an oxygen-related sharp hole bulk trap state at 0.27 eV above the valence band.