Organic light-emitting devices (OLEDs) are already widely used for common applications like OLED TVs or smartphone displays. Nevertheless, it is still a challenge for both science and industry to develop OLED systems for lighting applications that combine true-color white light, high efficiencies and high brightness at the same time. Since white emission in OLEDs is usually a combination of two or more different emitters with individual colors it is necessary that all included systems are efficient. It has been shown that the concept of thermally activated delayed fluorescence (TADF) allows to synthesize very efficient light-emitting molecules with various emission colors.
In our work, we use the sky-blue TADF emitter 9-[2,3,4,5-tetra(carbazol-9-yl)-6-(trifluoromethyl)phenyl]carbazole (5CzCF3Ph) with an emission maximum at a wavelength of 495 nm in thin films, reaching a photoluminescence quantum yield of 70 %. In an OLED, the emitter delivered up to 18 % external quantum efficiency (EQE). This is beyond the theoretical limit of conventional fluorescent OLEDs. To achieve warm-white emission, we combine the sky-blue emission of 5CzCF3Ph with the red emission of the common phosphorescent emitter Ir(MDQ)2(acac) within one emission layer. Due to the very broad blue emission (FWHM ~ 95 nm), a dedicated deep blue emitter becomes obsolete and it is possible to tune the combined two-color spectrum in such a way, that a high color rendering index of over 80 and correlated color temperatures about 2800 K can be obtained by this strategy. EQEs of up to 17 % and luminous efficacies of 16 lm/W have been measured for the hybrid white OLEDs. This two-color concept paves the way towards future utilization of TADF emitters in lighting applications by simplifying the required sequence of organic layers inside the OLED.
In our approach, the excitons are formed mostly on the TADF emitter itself. To achieve a suitable amount of red light for the white emission, it is necessary to enable efficient exciton transition pathways between 5CzCF3Ph and Ir(MDQ)2(acac). Due to the variety of potential local and charge-transfer excited states in the emitter system, there are several probable scenarios for the energy transfer. Utilizing time-correlated single photon counting (TCSPC) with a wavelength-sensitive detection, we study the exciton decay of both the TADF prompt and delayed fluorescence as well as the phosphorescent emission channel in detail. With this technique, we deliver a thorough investigation of the exciton transfer and exchange mechanisms in the emitter system of our warm-white hybrid OLEDs.
Organic field-effect transistors (OFET) are important elements in thin-film electronics, being considered for
flat-panel or flexible displays, radio frequency identification systems, and sensor arrays. To optimize the
devices for high-frequency operation, the channel length, defined as the horizontal distance between the
source and the drain contact, can be scaled down. Here, an architecture with a vertical current flow, in particular the
Organic Permeable-Base Transistors (OPBT), opens up new opportunities, because the effective transit
length in vertical direction is precisely tunable in the nanometer range by the thickness of the semiconductor
layer. We present an advanced OPBT, competing with best OFETs while a low-cost, OLED-like fabrication
with low-resolution shadow masks is used (Klinger et al., Adv. Mater. 27, 2015). Its design consists of a stack
of three parallel electrodes separated by two semiconductor layers of C60 . The vertical current flow is
controlled by the middle base electrode with nano-sized openings passivated by an native oxide.
Using insulated layers to structure the active area, devices show an on/off ratio of 10⁶ , drive 11 A/cm² at an
operation voltage of 1 V, and have a low subthreshold slope of 102 mV/decade. These OPBTs show a unity
current-gain transit frequency of 2.2 MHz and off-state break-down fields above 1 MV/cm. Thus, our
optimized setup does not only set a benchmark for vertical organic transistors, but also outperforms best
lateral OFETs using similar low-cost structuring techniques in terms of power efficiency at high frequencies.
In current organic photovoltaic devices, the loss in energy caused by the inevitable charge transfer step leads to a low open circuit voltage, which is one of the main reasons for rather low power conversion efficiencies. A possible approach to avoid these losses is to tune the exciton binding energy below 25 meV, which would lead to free charges upon absorption of a photon, and therefore increase the power conversion efficiency towards the Shockley Queisser limit for inorganic solar cells. We determine the size of the excitons for different one-dimensional organic small molecules or polymers by electron energy loss spectroscopy (EELS) measurements and by DFT calculations. Using the measured dielectric constant and exciton extension, the exciton binding energy is calculated for the investigated molecules, leading to a lower limit of the exciton binding energy for ladder-type polymers. We discuss and propose potential ways to increase the ionic and electronic part of the dielectric function in order to further lower the limit of the exciton binding energy in organic materials. Furthermore, the influence of charge transfer states on the exciton size and its binding energy is calculated with DFT methods for the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) in a dimer configuration.
Axel Fischer, Thomas Koprucki, Annegret Glitzky, Matthias Liero, Klaus Gärtner, Jacqueline Hauptmann, Sebastian Reineke, Daniel Kasemann, Björn Lüssem, Karl Leo, Reinhard Scholz
Large area OLEDs show pronounced Joule self-heating at high brightness. This heating induces brightness inhomogeneities, drastically increasing beyond a certain current level. We discuss this behavior considering 'S'-shaped negative differential resistance upon self-heating, even allowing for 'switched-back' regions where the luminance finally decreases (Fischer et al., Adv. Funct. Mater. 2014, 24, 3367). By using a multi-physics simulation the device characteristics can be modeled, resulting in a comprehensive understanding of the problem. Here, we present results for an OLED lighting panel considered for commercial application. It turns out that the strong electrothermal feedback in OLEDs prevents high luminance combined with a high degree of homogeneity unless new optimization strategies are considered.
We report on the enhanced light outcoupling efficiency of monochrome top-emitting organic light-emitting diodes (OLEDs). These OLEDs incorporate a hole transport layer (HTL) material with a substantially lower refractive index (∼ 1.5) than the emitter material or the standard HTL material (∼ 1.8) of a reference device. This low-index HTL is situated between the opaque bottom metal contact (anode) and the active emission layer. Compared to an HTL with common refractive index, the dispersion relation of the surface plasmon polariton (SPP) mode from the opaque metal contact is shifted to smaller in-plane wavenumbers. This shift enhances the outcoupling efficiency as it reduces the total dissipated power of the emitter. Furthermore, the excitation of the coupled SPPs at the thin transparent metal top contact (cathode) is avoided by using an ultrathin top electrode. Hence, the coupling of the electroluminescence from the emitter molecules to all non-radiative evanescent modes, with respect to the emitter material, is reduced by at least a factor of two, additionally increasing the outcoupling efficiency. Furthermore, for sufficiently high refractive index contrast the shift of the SPP at the anode/organic interface can lead to in-plane wavenumbers smaller than the wavenumber within the organic emitter layer and outcoupling of all excited modes by high index light extraction structures, e.g. microlens, seems feasible. In accordance to optical simulations, the external quantum efficiency is enhanced by about 20 % for monochrome green emitting OLEDs with low refractive index HTL compared to a reference sample.
Bragg scattering by one dimensional periodic structures is investigated in order to enhance the outcoupling effciency of optically optimized planar top-emitting OLEDs. Using a soft imprint process, we fabricate extremely homogeneous gratings with sub- m period. These gratings are integrated beneath the bottom contact of topemitting OLEDs, without affecting the electrical device performance. The reflective contacts of the top emission geometry introduce pronounced micro-cavity effects for directly outcoupled and internally trapped light modes. Bragg scattering of the trapped waveguided and surface plasmon modes into the air cone, i.e. the forward direction, leads to interference with the directly outcoupled mode. As a result, constructive and destructive interference of the modes is detected and analyzed. Overall, we find that the introduction of shallow one dimensional sub- m periodic grating structures underneath top-emitting OLEDs leads to an EQE and luminous efficacy enhancement by up to 42%.
During the deposition of Pentacene on a Si-SiO2 gate structure with Au bottom contacts for source and drain, the film growth was monitored with simultaneous in situ macro Raman spectroscopy and drain current measurements of the OFET device. The deposition of the active layer was carried out under UHV conditions at a growth rate of 0.65 Å/min. The purpose of the in situ characterization was to determine the minimum nominal thickness of the Pentacene layer required for efficient charge transport through the OFET circuit. At a thickness around 1.5 nm nominal coverage, the first percolation paths through the first organic monolayer develop, resulting in a sharp rise of the drain current. Up to a nominal film thickness of 30 nm, a subsequent slower increase of the drain current can be observed, revealing that the percolation of the first monolayer continues on a slower pace up to rather thick organic layers. These in situ measurements were complemented by ex situ isothermal deep level transient spectroscopy (charge QTS).
Potentiometry with a Kelvin probe atomic force microscope is used to investigate the contact resistances of pentacene OFETs, so that the injection of the charges at the source contact and their extraction at the drain contact can be distinguished from the influence of trap
states on the charge transport through the accumulation channel. The
samples consist of Au bottom contacts on a SiO2 gate dielectric with a channel length of L=10- 15 μm and a channel
width of W=100 μm. The gate oxide is first treated by an
oxygen plasma before depositing about 30 nm of pentacene under high
vacuum conditions. The output characteristics are measured as a
function of temperature in an evacuated cryostat, revealing
temperature-activated hole transport. The potentiometry measurements
are performed ex situ under atmospheric conditions after storing
the samples in air for several weeks. At room temperature, the
pentacene OFETs are dominated by the resistance at the injection
contact, so that the mobility in the channel region as deduced from
potentiometry is about one order of magnitude higher than the value
obtained from the output characteristics. The measurements are
interpreted with microscopic model calculations for the
temperature-activated currents.
Raman spectroscopy is capable of distinguishing neutral and charged states of organic molecules due to its sensitivity for charge induced changes in the molecular geometry and the bond strength.Combined with in situ electrical measurements it provides a powerful tool for characterizing charged molecules in the channel of organic field effect transistors OFETs. The active 3nm C60 layer in an OFET structure with bottom gate con figuration was characterized by in situ Raman spectroscopy using the 514.5 nm (2.41 eV)Ar+ laser line as a function of the drain source (Vds) voltage. The Raman spectra show pronounced changes upon application of a drain source Vds voltage. The experimental findings are compared to the vibrational spectra calculated for molecules under external bias fields. Complementary to the Raman characterization,the Id-Vds and Id-Vgs characteristics were recorded and the mobility value of 0.1 cm2/V s was derived from these measurements.
The understanding of metal/organic interfaces is fundamental for achieving high quality contacts in organic based field effect transistors,OFETs. Here the formation of In and Ag interfaces on 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA)and N,N dimethy l3,4,9,10 perylene tetracarboximide (DiMe-PTCDI)is investigated by in situ Raman spectroscopy. Upon metal deposition a significant enhancement of the Raman signals arising
from internal vibrational modes is observed for these two perylene derivatives,clearly indicating the presence of surface enhanced Raman scattering (SERS). Molecules in direct contact with the metal are involved in a weak dynamical charge transfer in the electronic ground state, resulting in a breakdown of the Raman selection rules for the free molecule. Both metals show very weak interactions with the organic thin films. This finding is opposite to previous suggestions of covalent bond formation between In and O atoms in PTCDA. The Raman
scattering of molecules close to the metal interface is enhanced by coupling to the plasmon resonance of small metal clusters,indicating a high roughness of the metallic film. The enhancement factors can be used to extract information on diffusion of the metal atoms into the organic film and on the morphology of the contact layer.
In the present work we investigate the influence of molecular vibrations on the tunneling of electrons through a molecule sandwiched between two metal contacts. The study is confined to the elastic scattering only, but beyond the harmonic approximation. The problem is tackled both from a classical and a quantum-mechanical point of view. The classical approach consists in the computation of the time-dependent current uctuations calculated at each step of a molecular dynamics (MD) simulation. On the other hand, the vibrational modes are treated quantum-mechanically and the tunneling current is computed as an ensemble average over the distribution of
the atomic configurations obtained by a suitable approximation of the density matrix for the normal mode oscillators. We show that the lattice fluctuations modify the electron transmission. At low temperatures the quantum-mechanical treatment is necessary in order to correctly include the zero-point fluctuations. However, for temperatures higher than few hundreds Kelvin the simple harmonic approximation which leads to the phonon modes breaks because the oscillation amplitudes of the lowest energy modes become large.
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