Vitaly Podzorov

Intrinsic charge transport on the surface of organic semiconductors.

The air-gap field-effect technique enabled realization of the intrinsic (not limited by static disorder) polaronic transport on the surface of rubrene (C42H28) crystals over a wide temperature range. The signatures of this intrinsic transport are the anisotropy of the carrier mobility, mu, and the growth of mu with cooling. Anisotropy of mu vanishes in the activation regime at low temperatures, where the transport is dominated by shallow traps. The deep traps, introduced by x-ray radiation, increase the field-effect threshold without affecting mu, an indication that the filled traps do not scatter polarons.

Organic single-crystal field-effect transistors

Organic electronics constitute an innovative field, with interesting applications complementary to the silicon semiconductor technology. From a scientific perspective, there is large interest in the fundamental understanding of electrical transport in organic semiconductors. However, a well-developed microscopic description is still lacking, due to the complicated character of the many-body polaronic-type of charge carriers in molecular compounds. In this Thesis, we have experimentally studied the intrinsic charge transport properties of organic semiconductors by using organic single-crystal field-effect transistors. The electric field-effect has been frequently used to investigate thin films of organic compounds. Unfortunately, thin-film transistors are not suitable for the study of intrinsic electronic properties of organic conductors, because their characteristics are often strongly affected by imperfections of the film structure and by insufficient purity of organic materials. Thus, for a higher degree of molecular ordering and an improved quality of the FET, we fabricate devices on the surface of a free-standing single crystal of organic molecules. In short, in this work we have achieved successful fabrication of high-quality single-crystal FETs, exhibiting high mobilities and signs of intrinsic transport. Herewith, we have identified new aspects that influence charge transport in organic semiconductor FETs, and we have performed exploratory measurements in the charge density regime approaching one carrier per molecule.

Field-effect transistors on rubrene single crystals with parylene gate insulator

We report on the fabrication and characterization of the organic field-effect transistors (OFETs) on the surface of single crystals of rubrene. The parylene polymer film has been used as the gate insulator. At room temperature, these OFETs exhibit the p-type conductivity with the field-effect mobility 0.1–1 cm2/V s and the on/off ratio⩾104. The temperature dependence of the mobility is discussed.

Single-crystal organic field effect transistors with the hole mobility ∼8 cm2/V s

We report on the fabrication and characterization of single-crystal organic p-type field-effect transistors (OFETs) with the field-effect mobility μ∼8 cm2/V s, substantially higher than that observed in thin-film OFETs. The single-crystal devices compare favorably with thin-film OFETs not only in this respect: the mobility for the single-crystal devices is nearly independent of the gate voltage and the field effect onset is very sharp. The subthreshold slope as small as S=0.85 V/decade has been observed for a gate insulator capacitance Ci=2±0.2 nF/cm2. This corresponds to the intrinsic subthreshold slope Si≡SCi at least one order of magnitude smaller than that for the best thin-film OFETs and amorphous hydrogenated silicon (α-Si:H) devices.

High-mobility field-effect transistors based on transition metal dichalcogenides

We report on fabrication of field-effect transistors (FETs) based on transition metal dichalcogenides. The unique structure of single crystals of these layered inorganic semiconductors enables fabrication of FETs with intrinsically low field-effect threshold and high charge carrier mobility, comparable to that in the best single-crystal Si FETs (up to 500 cm2/V s for the p-type conductivity in the WSe2-based FETs at room temperature). These FETs demonstrate ambipolar operation. Owing to mechanical flexibility, they hold potential for applications in “flexible” electronics.

Observation of long-range exciton diffusion in highly ordered organic semiconductors

Excitons in polycrystalline and disordered films of organic semiconductors have been shown to diffuse over distances of 10-50 nm. Here, using polarization- and wavelength-dependent photoconductivity in the highly ordered organic semiconductor rubrene, we show that the diffusion of triplet excitons in this material occurs over macroscopic distances (2-8 μm), comparable to the light absorption length. Dissociation of these excitons at the surface of the crystal is found to be the main source of photoconductivity in rubrene. In addition, we observe strong photoluminescence quenching and a simultaneous enhancement of photoconductivity when the crystal surface is functionalized with exciton splitters. In combination with time-resolved measurements, these observations strongly suggest that long-lived triplet excitons are indeed generated in molecular crystals by fission of singlets, and these triplets provide a significant contribution to the surface photocurrent generated in organic materials. Our findings indicate that the exciton diffusion bottleneck is not an intrinsic limitation of organic semiconductors.

Chromophore Fluorination Enhances Crystallization and Stability of Soluble Anthradithiophene Semiconductors

We report dramatic improvements in the stability and crystallinity arising from partial fluorination of soluble anthradithiophene derivatives. These fluorinated materials still behave as p-type semiconductors but with dramatic increases in thermal and photostability compared to the non-fluorinated derivatives. The triethylsilyl-substituted material forms highly crystalline films even from spin-cast solutions, leading to devices with maximum hole mobility greater than 1.0 cm(2)/V s. In contrast, the triisopropylsilyl derivative forms large, high-quality crystals that could serve as the substrate for transistor fabrication. For this compound, mobility as high as 0.1 cm(2)/V s was measured on the free-standing crystal.

Hall Effect in the Accumulation Layers on the Surface of Organic Semiconductors

We have observed the Hall effect in the field-induced accumulation layer on the surface of single-crystal samples of a small-molecule organic semiconductor rubrene. The Hall mobility muH increases with decreasing temperature in both the intrinsic (high-temperature) and trap-dominated (low-temperature) conduction regimes. In the intrinsic regime, the density of mobile field-induced charge carriers extracted from the Hall measurements, nH, coincides with the density n calculated using the gate-channel capacitance and becomes smaller than n in the trap-dominated regime. The Hall data are consistent with the diffusive bandlike motion of field-induced charge carriers between trapping events.

Ultra-flexible solution-processed organic field-effect transistors

Organic semiconductors might enable new applications in low-cost, light-weight, flexible electronics. To build a solid foundation for these technologies, more fundamental studies of electro-mechanical properties of various types of organic semiconductors are necessary. Here we perform basic studies of charge transport in highly crystalline solution-processed organic semiconductors as a function of applied mechanical strain. As a test bed, we use small molecules crystallized on thin plastic sheets, resulting in high-performance flexible field-effect transistors. These devices can be bent multiple times without degradation to a radius as small as ~200 μm, demonstrating that crystalline solution-processed organic semiconductors are intrinsically highly flexible. This study of electro-mechanical properties suggests that solution-processable organic semiconductors are suitable for applications in flexible electronics, provided that integration with other important technological advances, such as device scalability and low-voltage operation, is achieved in the future.

Electronic functionalization of the surface of organic semiconductors with self-assembled monolayers

Self-assembled monolayers (SAMs) are widely used in a variety of emerging applications for surface modification of metals and oxides. Here, we demonstrate a new type of molecular self-assembly: the growth of organosilane SAMs at the surface of organic semiconductors. Remarkably, SAM growth results in a pronounced increase of the surface conductivity of organic materials, which can be very large for SAMs with a strong electron-withdrawing ability. For example, the conductivity induced by perfluorinated alkyl silanes in organic molecular crystals approaches 10(-5) S per square, two orders of magnitude greater than the maximum conductivity typically achieved in organic field-effect transistors. The observed large electronic effect opens new opportunities for nanoscale surface functionalization of organic semiconductors with molecular self-assembly. In particular, SAM-induced conductivity shows sensitivity to different molecular species present in the environment, which makes this system very attractive for chemical sensing applications.