Martijn Kuik

Unification of trap-limited electron transport in semiconducting polymers

Electron transport in semiconducting polymers is usually inferior to hole transport, which is ascribed to charge trapping on isolated defect sites situated within the energy bandgap. However, a general understanding of the origin of these omnipresent charge traps, as well as their energetic position, distribution and concentration, is lacking. Here we investigate electron transport in a wide range of semiconducting polymers by current-voltage measurements of single-carrier devices. We observe for this materials class that electron transport is limited by traps that exhibit a gaussian energy distribution in the bandgap. Remarkably, the electron-trap distribution is identical for all polymers considered: the number of traps amounts to 3 × 10(23) traps per m(3) centred at an energy of ~3.6 eV below the vacuum level, with a typical distribution width of ~0.1 eV. This indicates that the electron traps have a common origin that, we suggest, is most likely related to hydrated oxygen complexes. A consequence of this finding is that the trap-limited electron current can be predicted for any polymer.

Origin of the dark-current ideality factor in polymer: fullerene bulk heterojunction solar cells

In organic bulk heterojunction solar cells, a deviation of the ideality factor of the dark current from unity is commonly put forward as evidence for the presence of trap-assisted recombination. We demonstrate that the non-ideality of the dark characteristics is determined by deeply trapped carriers in the transport-dominating constituent of the donor:acceptor blend, rather than a trap-assisted recombination mechanism. The light-intensity dependence of the open-circuit voltage confirms the absence of trap-assisted recombination and demonstrates that the dominant recombination mechanism in the investigated polymer:fullerene solar cells is bimolecular.

Tri‐Diketopyrrolopyrrole Molecular Donor Materials for High‐Performance Solution‐Processed Bulk Heterojunction Solar Cells

Two new high-performance DPP-containing donor molecules employing a molecular architecture with three DPP chromorphores (tri-DPP) in conjugated backbones are synthesized and characterized. The two tri-DPP molecules with only a structural difference on alkyl substitutions, when blended with PC71 BM, lead to power conversion efficiencies up to 4.8 and 5.5%, respectively.

25th Anniversary Article: Charge Transport and Recombination in Polymer Light‐Emitting Diodes

This article reviews the basic physical processes of charge transport and recombination in organic semiconductors. As a workhorse, LEDs based on a single layer of poly(p-phenylene vinylene) (PPV) derivatives are used. The hole transport in these PPV derivatives is governed by trap-free space-charge-limited conduction, with the mobility depending on the electric field and charge-carrier density. These dependencies are generally described in the framework of hopping transport in a Gaussian density of states distribution. The electron transport on the other hand is orders of magnitude lower than the hole transport. The reason is that electron transport is hindered by the presence of a universal electron trap, located at 3.6 eV below vacuum with a typical density of ca. 3 × 10¹⁷ cm⁻³. The trapped electrons recombine with free holes via a non-radiative trap-assisted recombination process, which is a competing loss process with respect to the emissive bimolecular Langevin recombination. The trap-assisted recombination in disordered organic semiconductors is governed by the diffusion of the free carrier (hole) towards the trapped carrier (electron), similar to the Langevin recombination of free carriers where both carriers are mobile. As a result, with the charge-carrier mobilities and amount of trapping centers known from charge-transport measurements, the radiative recombination as well as loss processes in disordered organic semiconductors can be fully predicted. Evidently, future work should focus on the identification and removing of electron traps. This will not only eliminate the non-radiative trap-assisted recombination, but, in addition, will shift the recombination zone towards the center of the device, leading to an efficiency improvement of more than a factor of two in single-layer polymer LEDs.

Trap-Limited Exciton Diffusion in Organic Semiconductors

Excited states in organic semiconductors, imposed either by electroor by photoexcitation, are referred to as excitons, and are known to migrate throughout the organic material. [ 1 ] In an organic semiconductor singlet excitons migrate between conjugated segments via Förster energy transfer. [ 2 ] Due to the disordered nature of the polymers such hopping can be regarded as diffusion. The exciton diffusion length, the average distance an excitation can migrate in a material during its lifetime, is generally used as a quantitative characterization of this process. The exciton diffusion length has been determined using a variety of measurement techniques such as fl uorescence quenching in thin fi lms of organic semiconductors, in which one or both interfaces act as an exciton quenching wall, [ 3–13 ] exciton density modulation due to light absorption, [ 14–16 ] exciton-exciton annihilation, [ 17–19 ] photocurrent modeling in solar cells, [ 20–24 ] and fl uorescence quenching in thin fi lms with randomly distributed quenchers. [ 25–31 ] For a large number of (disordered) organic semiconductors, exciton diffusion lengths of typically 5–10 nm have been reported. The dynamics of exciton migration in organic semiconductors is governed by the exciton diffusion coeffi cient. Knowledge of the exciton diffusion coeffi cient is therefore required in order to describe the spatialand temporal evolution of the exciton population in organic semiconductors. Experimentally, it can be determined by modeling the photoluminescence (PL) decay curves. [ 5,25,30,32,33 ]

Space-charge-limited hole current in poly(9,9-dioctylfluorene) diodes

Characterization of the hole transport in blue-emitting polymers as poly(9,9-dioctylfluorene) (PFO) is strongly hindered by their large ionization potential of ∼6 eV. Using common anodes as poly(3,4-ethylenedioxythiophene)/poly(styrenesulphonic acid) leads to a strongly injection limited current. We demonstrate that molybdenum trioxide forms an Ohmic hole contact on PFO, enabling the observation of a space-charge-limited current(SCLC). This allows a direct determination of the hole mobility PFO of 1.3×10−9 m2/V s at room temperature, in good agreement with previously reported mobility values determined by time-of-flight measurements.

Determination of the trap-assisted recombination strength in polymer light emitting diodes

The recombination processes in poly(p-phenylene vinylene) based polymer light-emitting diodes (PLEDs) are investigated. Photogenerated current measurements on PLED device structures reveal that next to the known Langevin recombination also trap-assisted recombination is an important recombination channel in PLEDs, which has not been considered until now. The dependence of the open-circuit voltage on light intensity enables us to determine the strength of this process. Numerical modeling of the current-voltage characteristics incorporating both Langevin and trap-assisted recombination yields a correct and consistent description of the PLED, without the traditional correction of the Langevin prefactor. At low bias voltage the trap-assisted recombination rate is found to be dominant over the free carrier recombination rate.

Understanding the Charge‐Transfer State and Singlet Exciton Emission from Solution‐Processed Small‐Molecule Organic Solar Cells

Electroluminescence (EL) from the charge-transfer state and singlet excitons is observed at low applied voltages from high-performing small-molecule bulk-heterojunction solar cells. Singlet emission from the blends emerges upon altering the processing conditions, such as thermal annealing and processing with a solvent additive, and correlates with improved photovoltaic performance. Low-temperature EL measurements are utilized to access the physics behind the singlet emission.

Increased Mobility Induced by Addition of a Lewis Acid to a Lewis Basic Conjugated Polymer

Through simple addition of a Lewis acid to a conjugated polymer bearing a Lewis basic heteroatom, the hole transport of the polymer can be effectively p-doped resulting in a two-orders increase in hole mobility. The temperature dependent hole transport of a variety of Lewis acid concentrations are explored.

Hysteresis-free electron currents in poly(p-phenylene vinylene) derivatives

The interpretation of electron currents in conjugated polymers is strongly hindered by the occurrence of hysteresis. We investigate the transport of electrons in electron-only devices based on derivatives of poly(p-phenylene vinylene) (PPV) for various hole-blocking bottom electrodes as well as purification of the polymer. The use of a variety of hole blocking bottom contacts, as metallic electrodes and n-type doped polymers, did not give any improvement in the observed hysteresis. By purification of the PPV, hysteresis free electron-only currents can be obtained. The deep traps responsible for hysteresis, with a concentration in the 10 16 cm -3 range, are not responsible for the trap-limited electron transport as observed in purified PPV.