Designing molecules to bypass the singlet-triplet bottleneck in the electroluminescence of organic light-emitting-diode materials

Electroluminescence in organic light emitting diode (OLED) materials occurs via the recombination of excitonic electrons-hole pairs Only the singlet excitons of commonly used OLED materials, e.g., Aluminum trihydroxyquinoline (AlQ$_3$), decay radiatively, limiting the external quantum efficiency to a maximum 25%. Thus 75% of the energy is lost due to the triplet bottleneck for radiative recombination. We consider molecules derived from AlQ$_3$ which bypass the triplet bottleneck by designing structures which contain strong spin-orbit coupling. As a first stage of this work, groundstate energies and vertical excitation energies of Al-arsenoquinolines and Al-boroarsenoquinolines are calculated. It is found that the substitution of N by As leads to very favourable results, while the boron substitution leads to no advantage.Comment: 4 pages, 4 figue

Effects of boundary roughness on a Q-factor of whispering-gallery-mode lasing microdisk cavities

We perform numerical studies of the effect of sidewall imperfections on the resonant state broadening of the optical microdisk cavities for lasing applications. We demonstrate that even small edge roughness causes a drastic degradation of high-Q whispering gallery (WG) mode resonances reducing their Q-values by many orders of magnitude. At the same time, low-Q WG resonances are rather insensitive to the surface roughness. The results of numerical simulation obtained using the scattering matrix technique, are analyzed and explained in terms of wave reflection at a curved dielectric interface combined with the examination of Poincare surface of sections in the classical ray picture.Comment: 4 pages, 3 figure

Ambipolar charge injection and transport in a single pentacene monolayer island

Electrons and holes are locally injected in a single pentacene monolayer island. The two-dimensional distribution and concentration of the injected carriers are measured by electrical force microscopy. In crystalline monolayer islands, both carriers are delocalized over the whole island. On disordered monolayer, carriers stay localized at their injection point. These results provide insight into the electronic properties, at the nanometer scale, of organic monolayers governing performances of organic transistors and molecular devices.Comment: To be published in Nano Letter

Flat photonic bands in guided modes of textured metallic microcavities

M. G. Salt and William L. Barnes, Physical Review B, Vol. 61, pp. 11125-11135 (2000). "Copyright © 2000 by the American Physical Society."A detailed experimental study of how wavelength-scale periodic texture modifies the dispersion of the guided modes of λ/2 metal-clad microcavities is presented. We first examine the case of a solid-state microcavity textured with a single, periodic corrugation. We explore how the depth of the corrugation and the waveguide thickness affect the width of the band gap produced in the dispersion of the guided modes by Bragg scattering off the periodic structure. We demonstrate that the majority of the corrugation depths studied dramatically modify the dispersion of the lowest-order cavity mode to produce a series of substantially flat bands. From measurements of how the central frequency of the band gap varies with direction of propagation of the guided modes, we determine a suitable two-dimensional texture profile for the production of a complete band gap in all directions of propagation. We then experimentally examine band gaps produced in the guided modes of such a two-dimensionally textured microcavity and demonstrate the existence of a complete band gap for all directions of propagation of the lowest-order TE-polarized mode. We compare our experimental results with those from a theoretical model and find good agreement. Implications of these results for emissive microcavity devices such as light-emitting diodes are discussed

Nonexponetial relaxation of photoinduced conductance in organic field effect transistor

We report detailed studies of the slow relaxation of the photoinduced excess charge carriers in organic metal-insulator-semiconductor field effect transistors consisting of poly(3-hexylthiophene) as the active layer. The relaxation process cannot be physically explained by processes, which lead to a simple or a stretched-exponential decay behavior. Models based on serial relaxation dynamics due to a hierarchy of systems with increasing spatial separation of the photo-generated negative and positive charges are used to explain the results. In order to explain the observed trend, the model is further modified by introducing a gate voltage dependent coulombic distribution manifested by the trapped negative charge carriers.Comment: 17 pages, 3 Figure

Device Optimization of Tris-Aluminum (Alq3) Based Bilayer Organic Light Emitting Diode Structures

In this work we present detailed analysis of the emitted radiation spectrum from tris(8-hydroxyquinoline) aluminum (Alq3) based bilayer OLEDs as a function of: the choice of cathode, the thickness of organic layers, and the position of the hole transport layer/Alq3 interface. The calculations fully take into account dispersion in the glass substrate, the indium tin oxide anode, and in the organic layers, as well as the dispersion in the metal cathode. Influence of the incoherent transparent substrate (1 mm glass substrate) is also fully accounted for. Four cathode structures have been considered: Mg/Ag, Ca/Ag, LiF/Al, and Ag. For the hole transport layer, N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD) and N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine (NPB) were considered. As expected, emitted radiation is strongly dependent on the position of the emissive layer inside the cavity and its distance from the metal cathode. Although our optical model for an OLED does not explicitly include exciton quenching in vicinity of the metal cathode, designs placing the emissive layer near the cathode are excluded to avoid unrealistic results. Guidelines for designing devices with optimum emission efficiency are presented. Finally, several different devices were fabricated and characterized and experimental and calculated emission spectra were compared

Efficiency of radiative emission from thin films of a light-emitting conjugated polymer

J. A. E. Wasey, A. Safonov, I. D. W. Samuel, and William L. Barnes, Physical Review B, Vol. 64, article 205201 (2001). "Copyright © 2001 by the American Physical Society."We examine the efficiency of radiative emission from thin layers of light-emitting conjugated polymers. We compare our experimental results for photoluminescence of the conjugated polymer poly(2-methoxy, 5-(2′-ethyl-hexyloxy) 1,4 phenylenevinylene) (MEH-PPV) with those of a theoretical model, finding good agreement between the two. The specially developed model takes into account several factors including absorption in the emissive layer, a spread of emitter sites within the layer, and the broad emission spectrum of the polymer. We find that the photoluminescence quantum efficiency for radiative emission of a bare MEH-PPV film on a glass substrate is ∼25%. We then apply our model to study electroluminescent devices. We show that for these structures the efficiency of radiative emission is ∼10%. There is thus potential for considerable improvement in efficiency for both systems through recovery of some of the wasted waveguided light. Finally we use our model to reexamine some controversial results that indicate the probability of singlet exciton formation to be 0.4±0.05, and thus greater than the 0.25 expected from spin statistics. Our reanalysis supports a probability >0.25. We conclude by discussing the limitations of present models, including our own, in predicting the performance of realistic light-emitting diodes

Nanooptics of molecular-shunted plasmonic nanojunctions.

Gold nanoparticles are separated above a planar gold film by 1.1 nm thick self-assembled molecular monolayers of different conductivities. Incremental replacement of the nonconductive molecules with a chemically equivalent conductive version differing by only one atom produces a strong 50 nm blue-shift of the coupled plasmon. With modeling this gives a conductance of 0.17G(0) per biphenyl-4,4'-dithiol molecule and a total conductance across the plasmonic junction of 30G(0). Our approach provides a reliable tool quantifying the number of molecules in each plasmonic hotspot, here <200.We acknowledge financial support from EPSRC grant EP/ G060649/1, EP/I012060/1, EP/L027151/1, EP/K028510/1, ERC grant LINASS 320503. F.B. acknowledges support from the Winton Programme for the Physics of Sustainability. C.T. and J.A. acknowledge financial support from Project FIS2013- 41184-P from MINECO, ETORTEK 2014-15 of the Basque Department of Industry and IT756-13 from the Basque consolidated groups.This paper was originally published in Nano Letters under a CC-BY licence (F Benz, C Tserkezis, LO Herrmann, B de Nijs, A Sanders, DO Sigle, L Pukenas, SD Evans, J Aizpurua, JJ Baumberg, Nano Letters 2015, 15, 669−674