Routes for efficiency enhancement in fluorescent TADF exciplex host OLEDs gained from an electro‐optical device model

Fluorescence-based organic light-emitting diodes (OLEDs) using thermally activated delayed fluorescence (TADF) have increasingly attracted attention in research and industry. One method to implement TADF is based on an emitter layer composed of an exciplex host and a fluorescent dopant. Even though the experimental realization of this concept has demonstrated promising external quantum efficiencies, the full potential of this approach has not yet been assessed. To this end, a comprehensive electro-optical device model accounting for the full exciton dynamics including triplet harvesting and exciton quenching is presented. The model parameters are fitted to multiple output characteristics of an OLED comprising a TADF exciplex host with a fluorescent emitter, showing an external quantum efficiency of >10%. With the model at hand, an emission zone analysis and a parameter study are performed, and possible routes for further efficiency enhancement are presented

Field-induced charge transport at the surface of pentacene single crystals: a method to study charge dynamics of 2D electron systems in organic crystals

A 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 pre-fabricated 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/Vs and is nearly temperature-independent above ~150 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.Comment: 14 pages, 4 figures. Submitted to J. Appl. Phy

Hole mobility in organic single crystals measured by a "flip-crystal" field-effect technique

We report on single crystal high mobility organic field-effect transistors (OFETs) prepared on prefabricated substrates using a "flip-crystal" approach. This method minimizes crystal handling and avoids direct processing of the crystal that may degrade the FET electrical characteristics. A chemical treatment process for the substrate ensures a reproducible device quality. With limited purification of the starting materials, hole mobilities of 10.7, 1.3, and 1.4 cm^2/Vs have been measured on rubrene, tetracene, and pentacene single crystals, respectively. Four-terminal measurements allow for the extraction of the "intrinsic" transistor channel resistance and the parasitic series contact resistances. The 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.Comment: 26 pages, 7 figure

Density of bulk trap states in organic semiconductor crystals: discrete levels induced by oxygen in rubrene

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 (TD-SCLC). 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 (1 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.Comment: published in Phys. Rev. B, high quality figures: http://www.cpfs.mpg.de/~krellner

Unusually large enhancement of thermopower in an electric field induced two-dimensional electron gas

Two-dimensionally confined electrons showing unusually large thermopower (S) have attracted attention as a potential approach for developing high performance thermoelectric materials. However, enhanced S has never been observed in electric field induced two-dimensional electron gas (2DEG). Here we demonstrate electric field modulation of S for a field effect transistor (FET) fabricated on a SrTiO3 crystal using a water-infiltrated nanoporous glass as the gate insulator. An electric field application confined carrier electrons up to ~2E15 /cm^2 in an extremely thin (~2 nm) 2DEG. Unusually large enhancement of |S| was observed when the sheet carrier concentration exceeded 2.5E14 /cm^2, and it modulated from ~600 (~2E15 /cm^2) to ~950 {\mu}V/K (~8E14 /cm^2), which were approximately five times larger than those of the bulk, clearly demonstrating that an electric field induced 2DEG provides unusually large enhancement of |S|.Comment: 20 pages including 4 figures and Supporting Information, Advanced Materials (in press

UV/Ozone treatment to reduce metal-graphene contact resistance

We report reduced contact resistance of single-layer graphene devices by using ultraviolet ozone (UVO) treatment to modify the metal/graphene contact interface. The devices were fabricated from mechanically transferred, chemical vapor deposition (CVD) grown, single layer graphene. UVO treatment of graphene in the contact regions as defined by photolithography and prior to metal deposition was found to reduce interface contamination originating from incomplete removal of poly(methyl methacrylate) (PMMA) and photoresist. Our control experiment shows that exposure times up to 10 minutes did not introduce significant disorder in the graphene as characterized by Raman spectroscopy. By using the described approach, contact resistance of less than 200 {\Omega} {\mu}m was achieved, while not significantly altering the electrical properties of the graphene channel region of devices.Comment: 17 pages, 5 figure

Simulations, measurements and optimization of OLEDs with scattering layer

A multi-scale optical model for organic light-emitting devices containing scattering layers is presented. This model describes the radiation of embedded oscillating dipoles and scattering from spherical particles. After successful model validation with experiments on a top-emitting white OLED, we show how this tool can be used for optimization with specific targets

The transient localization scenario for charge transport in crystalline organic materials

Charge transport in crystalline organic semiconductors is intrinsically limited by the presence of large thermal molecular motions, which are a direct consequence of the weak van der Waals inter-molecular interactions. These lead to an original regime of transport called \textit{transient localization}, sharing features of both localized and itinerant electron systems. After a brief review of experimental observations that pose a challenge to the theory, we concentrate on a commonly studied model which describes the interaction of the charge carriers with inter-molecular vibrations. We present different theoretical approaches that have been applied to the problem in the past, and then turn to more modern approaches that are able to capture the key microscopic phenomenon at the origin of the puzzling experimental observations, i.e. the quantum localization of the electronic wavefuntion at timescales shorter than the typical molecular motions. We describe in particular a relaxation time approximation which clarifies how the transient localization due to dynamical molecular motions relates to the Anderson localization realized for static disorder, and allows us to devise strategies to improve the mobility of actual compounds. The relevance of the transient localization scenario to other classes of systems is briefly discussed.Comment: Accepted for publication in Advanced Functional Materials - Special issue on Organic Single Crystal

High-performance, low-operating-voltage organic field-effect transistors with low pinch-off voltages

Organic field-effect transistors suffer from ultra-high operating voltages in addition to their relative low mobility. A general approach to low-operating-voltage organic field-effect transistors (OFETs) using donor/acceptor buffer layers is demonstrated. P-type OFETs with acceptor molecule buffer layers show reduced operating voltages (from 60–100 V to 10–20 V), with mobility up to 0.19 cm2 V−1 s−1 and an on/off ratio of 3 × 106. The subthreshold slopes of the devices are greatly reduced from 5–12 V/decade to 1.68–3 V/decade. This favorable combination of properties means that such OFETs can be operated successfully at voltages below 20 V (|VDS| ≤ 20 V, |VGS| ≤ 20 V). This method also works for n-type semiconductors. The reduced operating voltage and low pinch-off voltage contribute to the improved ordering of the polycrystalline films, reduced grain boundary resistance, and steeper subthreshold slope

Approaching disorder-free transport in high-mobility conjugated polymers.

Conjugated polymers enable the production of flexible semiconductor devices that can be processed from solution at low temperatures. Over the past 25 years, device performance has improved greatly as a wide variety of molecular structures have been studied. However, one major limitation has not been overcome; transport properties in polymer films are still limited by pervasive conformational and energetic disorder. This not only limits the rational design of materials with higher performance, but also prevents the study of physical phenomena associated with an extended π-electron delocalization along the polymer backbone. Here we report a comparative transport study of several high-mobility conjugated polymers by field-effect-modulated Seebeck, transistor and sub-bandgap optical absorption measurements. We show that in several of these polymers, most notably in a recently reported, indacenodithiophene-based donor-acceptor copolymer with a near-amorphous microstructure, the charge transport properties approach intrinsic disorder-free limits at which all molecular sites are thermally accessible. Molecular dynamics simulations identify the origin of this long sought-after regime as a planar, torsion-free backbone conformation that is surprisingly resilient to side-chain disorder. Our results provide molecular-design guidelines for 'disorder-free' conjugated polymers.We gratefully acknowledge financial support from the Engineering and Physical Sciences Research Council (EPSRC) through a programme grant (EP/G060738/1) and the Technology Strategy Board (TSB) (PORSCHED project). D. Venkateshvaran acknowledges financial support from the Cambridge Commonwealth Trust through a Cambridge International Scholarship. K. Broch acknowledges post-doctoral fellowship support from the German Research Foundation (DFG). Mateusz Zelazny acknowledges funding from the NanoDTC in Cambridge. The work in Mons was supported by the European Commission / Région Wallonne (FEDER – Smartfilm RF project), the Interuniversity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 7/05), Programme d’Excellence de la Région Wallonne (OPTI2MAT project) and FNRS-FRFC. D.B. and J.C. are FNRS Research Fellows.This is the accepted manuscript. The final version's available from Nature at http://www.nature.com/nature/journal/vaop/ncurrent/full/nature13854.html