Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements.

Impressive performance of hybrid perovskite solar cells reported in recent years still awaits a comprehensive understanding of its microscopic origins. In this work, the intrinsic Hall mobility and photocarrier recombination coefficient are directly measured in these materials in steady-state transport studies. The results show that electron-hole recombination and carrier trapping rates in hybrid perovskites are very low. The bimolecular recombination coefficient (10(-11) to 10(-10) cm(3) s(-1)) is found to be on par with that in the best direct-band inorganic semiconductors, even though the intrinsic Hall mobility in hybrid perovskites is considerably lower (up to 60 cm(2) V(-1) s(-1)). Measured here, steady-state carrier lifetimes (of up to 3 ms) and diffusion lengths (as long as 650 µm) are significantly longer than those in high-purity crystalline inorganic semiconductors. We suggest that these experimental findings are consistent with the polaronic nature of charge carriers, resulting from an interaction of charges with methylammonium dipoles.

Charge carrier coherence and Hall effect in organic semiconductors.

Hall effect measurements are important for elucidating the fundamental charge transport mechanisms and intrinsic mobility in organic semiconductors. However, Hall effect studies frequently reveal an unconventional behavior that cannot be readily explained with the simple band-semiconductor Hall effect model. Here, we develop an analytical model of Hall effect in organic field-effect transistors in a regime of coexisting band and hopping carriers. The model, which is supported by the experiments, is based on a partial Hall voltage compensation effect, occurring because hopping carriers respond to the transverse Hall electric field and drift in the direction opposite to the Lorentz force acting on band carriers. We show that this can lead in particular to an underdeveloped Hall effect observed in organic semiconductors with substantial off-diagonal thermal disorder. Our model captures the main features of Hall effect in a variety of organic semiconductors and provides an analytical description of Hall mobility, carrier density and carrier coherence factor.

Steady-state photoconductivity and multi-particle interactions in high-mobility organic semiconductors.

Fundamental understanding of photocarrier generation, transport and recombination under a steady-state photoexcitation has been an important goal of organic electronics and photonics, since these processes govern such electronic properties of organic semiconductors as, for instance, photoconductivity. Here, we discovered that photoconductivity of a highly ordered organic semiconductor rubrene exhibits several distinct regimes, in which photocurrent as a function of cw (continuous wave) excitation intensity is described by a power law with exponents sequentially taking values 1, 1/3 and ». We show that in pristine crystals this photocurrent is generated at the very surface of the crystals, while the bulk photocurrent is drastically smaller and follows a different sequence of exponents, 1 and ½. We describe a simple experimental procedure, based on an application of "gauge effect" in high vacuum, that allows to disentangle the surface and bulk contributions to photoconductivity. A model based on singlet exciton fission, triplet fusion and triplet-charge quenching that can describe these non-trivial effects in photoconductivity of highly ordered organic semiconductors is proposed. Observation of these effects in photoconductivity and modeling of the underlying microscopic mechanisms described in this work represent a significant step forward in our understanding of electronic properties of organic semiconductors.

Trap healing and ultralow-noise Hall effect at the surface of organic semiconductors.

Fundamental studies of intrinsic charge transport properties of organic semiconductors are often hindered by charge traps associated with static disorder present even in optimized single-crystal devices. Here, we report a method of surface functionalization using an inert non-conjugated polymer, perfluoropolyether (PFPE), deposited at the surface of organic molecular crystals, which results in accumulation of mobile holes and a 'trap healing' effect at the crystal/PFPE interface. As a consequence, a remarkable ultralow-noise, trp-free conduction regime characterized by intrinsic mobility and transport anisotropy emerges in organic single crystals, and Hall effect measurements with an unprecedented signal-to-noise ratio are demonstrated. This general method to convert trap-dominated organic semiconductors to intrinsic systems may enable the determination of intrinsic transport parameters with high accuracy and make Hall effect measurements in molecular crystals ubiquitous.

Dynamic character of charge transport parameters in disordered organic semiconductor field-effect transistors.

In this perspective article, we discuss the dynamic instability of charge carrier transport in a range of popular organic semiconductors. We observe that in many cases field-effect mobility, an important parameter used to characterize the performance of organic field-effect transistors (OFETs), strongly depends on the rate of the gate voltage sweep during the measurement. Some molecular systems are so dynamic that their nominal mobility can vary by more than one order of magnitude, depending on how fast the measurements are performed, making an assignment of a single mobility value to devices meaningless. It appears that dispersive transport in OFETs based on disordered semiconductors, those with a high density of localized trap states distributed over a wide energy range, is responsible for the gate voltage sweep rate dependence of nominal mobility. We compare such rate dependence in different materials and across different device architectures, including pristine and trap-dominated single-crystal OFETs, as well as solution-processed polycrystalline thin-film OFETs. The paramount significance given to a single mobility value in the organic electronics community and the practical importance of OFETs for applications thus suggest that such an issue, previously either overlooked or ignored, is in fact a very important point to consider when engaging in fundamental studies of charge carrier mobility in organic semiconductors or designing applied circuits with organic semiconductors.

Bias stress effect in "air-gap" organic field-effect transistors.

The origin of the bias stress effect related only to semiconductor properties is investigated in "air-gap" organic field-effect transistors (OFETs) in the absence of a material gate dielectric. The effect becomes stronger as the density of trap states in the semiconductor increases. A theoretical model based on carrier trapping and relaxation in localized tail states is formulated. Polar molecular vapors in the gap of "air-gap" OFETs also have a significant impact on the bias stress effect via the formation of bound states between the charge carriers and molecular dipoles at the semiconductor surface.

Vacuum lamination approach to fabrication of high-performance single-crystal organic field-effect transistors.

A novel vacuum lamination approach to fabrication of high-performance single-crystal organic field-effect transistors has been developed. The non-destructive nature of this method allows a direct comparison of field-effect mobilities achieved with various gate dielectrics using the same single-crystal sample. The method also allows gating delicate systems, such as n -type crystals and SAM-coated surfaces, without perturbation.

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.

Modification of electronic properties of graphene with self-assembled monolayers.

Integration of organic and inorganic electronic materials is one of the emerging approaches to achieve novel material functionalities. Here, we demonstrate a stable self-assembled monolayer of an alkylsilane grown at the surface of graphite and graphene. Detailed characterization of the system using scanning probe microscopy, X-ray photoelectron spectroscopy, and transport measurements reveals the monolayer structure and its effect on the electronic properties of graphene. The monolayer induces a strong surface doping with a high density of mobile holes (n > 10(13) cm(-2)). The ability to tune electronic properties of graphene via stable molecular self-assembly, including selective doping of steps, edges, and other defects, may have important implications in future graphene electronics.

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.

Light quasiparticles dominate electronic transport in molecular crystal field-effect transistors.

We report on an infrared spectroscopy study of mobile holes in the accumulation layer of organic field-effect transistors based on rubrene single crystals. Our data indicate that both transport and infrared properties of these transistors at room temperature are governed by light quasiparticles in molecular orbital bands with the effective masses m* comparable to free electron mass. Furthermore, the m* values inferred from our experiments are in agreement with those determined from band structure calculations. These findings reveal no evidence for prominent polaronic effects, which is at variance with the common beliefs of polaron formation in molecular solids.

Effect of interfacial shallow traps on polaron transport at the surface of organic semiconductors.

The photo-induced electron and hole transfer across the semiconductor-dielectric interface in trap-dominated p-type organic field-effect transistors has been investigated. It has been observed that the transfer of electrons into the dielectric results in a decrease of the field-effect mobility of polarons, suggesting that additional shallow traps are generated in the conduction channel. Using this effect, the dependence of the field-effect mobility on the density of shallow traps, mu(N), has been measured, which allowed us to estimate the average polaron trapping time, tau_{tr}=50+/-10 ps, and the density of shallow traps, N0=(3+/-0.5) x 10(11) cm(-2), in the channel of single-crystal tetracene devices.

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.

Photoinduced charge transfer across the interface between organic molecular crystals and polymers.

Photoinduced charge transfer of positive and negative charges across the interface between a single-crystal organic semiconductor and a polymeric insulator is observed in electric field-effect experiments. Immobilization of the transferred charge by deep traps in the polymer results in a shift of the threshold of field-induced conductivity along the semiconductor-polymer interface, which allows for direct measurements of the charge transfer rate. The transfer occurs when the photon energy exceeds the absorption edge of the semiconductor. The direction of the transverse electric field at the interface determines the sign of the transferred charge; the transfer rate is controlled by the field magnitude and light intensity.

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.