Effect of exciton diffusion on the triplet-triplet annihilation rate in organic semiconductor host-guest systems

\u3cp\u3eWe study the contribution of triplet exciton diffusion to the efficiency loss resulting from Förster-type triplet-triplet annihilation (TTA) in organic phosphorescent semiconductor host-guest systems, using kinetic Monte Carlo (KMC) simulations. Our study focusses on diffusion due to Förster-type guest-guest transfer, but includes also a comparison with simulation results for the case of Dexter-type guest-guest transfer. The simulations are carried out for a wide range of Förster radii, and for guest concentrations up to 100 mol%, with the purpose to support analyses of time-resolved photoluminescence experiments probing TTA. We find that the relative contribution of diffusion to the TTA-induced efficiency loss may be deduced quite accurately from a quantitative experimental measure for the shape of the time-dependent photoluminescence intensity, the so-called r ratio. For small guest concentrations and Förster radii that are most relevant to organic light-emitting diodes (OLEDs), the diffusion contribution is in general quite small. Under these weak-diffusion conditions, the absolute diffusion contribution to the TTA-induced efficiency loss can be understood quantitatively using a capture radius formalism. The effective guest-guest diffusion coefficient that follows from the TTA simulations, using the capture radius formalism, agrees well with the diffusion coefficient that follows from direct KMC diffusion simulations. The simulations reveal that the diffusion coefficient is strongly affected by the randomness of the distribution of guest molecule locations.\u3c/p\u3

Kinetic Monte Carlo study of triplet-triplet annihilation in organic phosphorescent emitters

The triplet-triplet annihilation (TTA) rate in organic phosphorescent materials such as used in organic light-emitting diodes is determined predominantly either by the rate of single-step Förster-type triplet-triplet interactions, or by multi-step triplet diffusion. We show how kinetic Monte Carlo simulations may be used to analyze the role of both processes. Under steady state conditions, the effective triplet-triplet interaction rate coefficient, k TT, which is often regarded as a constant, is found to depend actually on the number of excitons lost upon a triplet-triplet interaction process and to show a significant higher-order dependence on the triplet volume density. Under the conditions encountered in transient photoluminescence (PL) studies, k TT is found to be effectively constant in the case of diffusion-dominated TTA. However, for the case of single-step TTA, a strongly different decay of the emission intensity is found, which also deviates from an analytic expression proposed in the literature. We discuss how the transient PL response may be used to make a distinction between both mechanisms. The simulations are applied to recently published work on the dye concentration dependence of the TTA rate in materials based on the archetypal green emitter tris[2-phenylpyridine]iridium (Ir(ppy)3)

Förster-type triplet-polaron quenching in disordered organic semiconductors

\u3cp\u3eTriplet-polaron quenching (TPQ) is a major cause of the efficiency loss at large current densities in phosphorescent organic light-emitting diodes. The nature of the interaction process is presently not well understood. In this paper, we study TPQ due to Förster-type triplet-polaron interactions in energetically disordered organic semiconductors with a Gaussian polaron density of states. A continuum theory, which neglects the spatial inhomogeneity and energetic disorder, is from a kinetic Monte Carlo approach shown to correctly predict that the effective steady-state TPQ rate coefficient kTPQ,eff depends only sensitively on the polaron diffusion in a rather narrow range of diffusion coefficients. However, in this regime, significant discrepancies between the two approaches are found, in particular for realistic values of the TPQ-Förster radius, around 3 nm, and for systems with strong energetic disorder. Both approaches show that kTPQ,eff is not constant but can depend on the polaron density and the electric field. Various methods for deducing the TPQ mechanism from experiment are discussed, including an approach which utilizes the shape of the time-dependent photoluminescence after pulsed illumination.\u3c/p\u3

Efficiency loss processes in hyperfluorescent OLEDs:a kinetic Monte Carlo study

\u3cp\u3eIn hyperfluorescent OLEDs, fluorescence emitter molecules are sensitized by molecules utilizing thermally activated delayed fluorescence (TADF). In principle, obtaining an internal quantum efficiency (IQE) approaching 100% combined with a small IQE roll-off should be feasible. However, the actual device performance depends on the balance between the transfer of singlet and triplet excitons from the TADF emitters to the fluorescent molecules and on the role of excitonic loss processes. Here, we study these factors governing the IQE using kinetic Monte Carlo simulations, for prototypical OLEDs based on the green TADF emitter (2s,4r,6s)-2,4,5,6-tetrakis(3,6-dimethyl-9H-carbazol-9-yl)isophthalonitrile (4CzIPN-Me) and the yellow fluorescent emitter 2,8-di-tert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene. Making use of the experimental photophysical interaction rates, the simulated voltage versus current density characteristics and IQE roll-off agree well with experiment. The simulations show that the IQE can be enhanced by carefully avoiding the formation of charge-transfer excitons.\u3c/p\u3

Effect of polaron diffusion on exciton-polaron quenching in disordered organic semiconductors

\u3cp\u3eExciton-polaron quenching (EPQ) is a major efficiency loss process in organic optoelectronic devices, in particular at high excitation densities. Within commonly used models, the rate is assumed to be given by the product of the exciton density, the polaron density, and a constant EPQ rate coefficient, which is proportional to the polaron diffusion coefficient and an EPQ capture radius. In this work, we study the effects of polaron diffusion on the EPQ rate in energetically disordered materials with a Gaussian density of states using kinetic Monte Carlo simulations, and show that the effective rate coefficient can depend strongly on the polaron concentration and on the electric field. We furthermore find that under realistic conditions, the effective value of the capture radius can exceed the expected value of ∼1 nm by up to two orders of magnitude. To a first approximation, the simulation results can be understood from macroscopic diffusion theory, adapted at finite electric fields to include the observed polaron wind effect. However, for strongly disordered systems we find distinct deviations from that theory, related to the very small time and spatial scales involved in the capture process.\u3c/p\u3

Triple junction polymer solar cells for photoelectrochemical water splitting

A triple junction polymer solar cell in a novel 1 + 2 type configuration provides photoelectrochemical water splitting in its maximum power point at V ˜ 1.70 V with an estimated solar to hydrogen energy conversion efficiency of 3.1%. The triple junction cell consists of a wide bandgap front cell and two identical small bandgap middle and back cells

Clarifying the mechanism of triplet–triplet annihilation in phosphorescent organic host–guest systems:A combined experimental and simulation study

At high brightness, triplet–triplet annihilation (TTA) reduces the efficiency of organic light-emitting diodes. Triplet diffusion may considerably enhance this effect, which is otherwise limited by the rate of long-range interactions. Although its role can be clarified by studying the emissive dye concentration dependence of the TTA loss, we demonstrate here the practical applicability of a more direct method, requiring a study for only a single dye concentration. The method uses transient photoluminescence yield measurements, for a wide initial excitation density range. The analysis is applied to an iridium complex and is supported by the results of kinetic Monte Carlo simulations

Kinetic Monte Carlo simulation of the efficiency roll-off, emission color, and degradation of organic light-emitting diodes

The performance of Organic Light Emitting Diodes (OLEDs) is determined by a complex interplay of the charge transport and excitonic processes in the active layer stack. We have developed a three-dimensional kinetic Monte Carlo (kMC) OLED simulation method which includes all these processes in an integral manner. The method employs a physically transparent mechanistic approach, and is based on measurable parameters. All processes can be followed with molecular-scale spatial resolution and with sub-nanosecond time resolution, for any layer structure and any mixture of materials. In the talk, applications to the efficiency roll-off, emission color and lifetime of white and monochrome phosphorescent OLEDs [1,2] are demonstrated, and a comparison with experimental results is given. The simulations show to which extent the triplet-polaron quenching (TPQ) and triplet-triplet-annihilation (TTA) contribute to the roll-off, and how the microscopic parameters describing these processes can be deduced properly from dedicated experiments. Degradation is treated as a result of the (accelerated) conversion of emitter molecules to non-emissive sites upon a triplet-polaron quenching (TPQ) process. The degradation rate, and hence the device lifetime, is shown to depend on the emitter concentration and on the precise type of TPQ process. Results for both single-doped and co-doped OLEDs are presented, revealing that the kMC simulations enable efficient simulation-assisted layer stack development. [1

Three-dimensional modeling of bipolar charge-carrier transport and recombination in disordered organic semiconductor devices at low voltages

\u3cp\u3eThe electroluminescence from organic light-emitting diodes can be predicted with molecular-scale resolution using three-dimensional kinetic Monte Carlo (3D KMC) simulations [M. Mesta et al., Nat. Mater. 12, 652 (2013)]. However, around and below the built-in voltage KMC simulations are computationally inefficient. 3D master-equation (3D ME) simulation methods, which are fastest for low voltages, are so far mainly available for describing unipolar charge transport. In such simulations, the charge-carrier interactions are treated within a mean-field approach. It is not a priori evident whether such simulations, when applied to bipolar devices, can be extended to include the Coulomb attraction between the individual electrons and holes, so that charge-carrier recombination is sufficiently well described. In this work, we develop a systematic method for extending 3D ME simulations to bipolar devices. The method is applied to devices containing materials with Gaussian energetic disorder, and validated by a comparison with the results of 3D KMC simulations. The comparison shows that the 3D nonuniformity of the molecular-site-resolved carrier concentration and the one-dimensional layer-averaged profile of the recombination rate are fully retained, and that the 3D nonuniformity of the molecular-site-resolved recombination rate is fairly well retained.\u3c/p\u3