Dan Credgington

Insights from Transient Optoelectronic Analyses on the Open-Circuit Voltage of Organic Solar Cells

In this Perspective, we review recent progress on the use of transient optoelectronic techniques to quantify the processes determining the open-circuit voltage (VOC) of organic solar cells. Most theoretical treatments of VOC include the effects of both material energetics and recombination dynamics, yet most experimental approaches are based on materials energetics alone. We show that by direct measurement of charge carrier dynamics and densities, the rate of nongeminate charge recombination may be determined within working cells and its impact on achievable VOC determined. A simple fit-free device model utilizing these measurements is shown to agree (to within ±5 mV) with experimentally observed open-circuit voltages for devices comprised of a range of different photoactive layer materials and different processing conditions, and utilizing both bulk and bilayer heterojunctions. This agreement is significantly better than that obtainable from analyzing materials energetics alone, even when employing an in situ analysis of effective electronic band gap. We go on to argue that the precision of our VOC calculations derives from implicitly including the impact of film microstructure on open-circuit voltage. We show that this can modulate VOC by up to 200 mV, and thereby account for the limits of energy-based models in accurately predicting achievable performance.

Enhanced Performance in Fluorene-Free Organometal Halide Perovskite Light-Emitting Diodes using Tunable, Low Electron Affinity Oxide Electron Injectors

Fluorene-free perovskite light-emitting diodes (LEDs) with low turn-on voltages, higher luminance and sharp, color-pure electroluminescence are obtained by replacing the F8 electron injector with ZnO, which is directly deposited onto the CH3NH3PbBr3 perovskite using spatial atmospheric atomic layer deposition. The electron injection barrier can also be reduced by decreasing the ZnO electron affinity through Mg incorporation, leading to lower turn-on voltages.

Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals

Metal halide perovskite crystal structures have emerged as a class of optoelectronic materials, which combine the ease of solution processability with excellent optical absorption and emission qualities. Restricting the physical dimensions of the perovskite crystallites to a few nanometers can also unlock spatial confinement effects, which allow large spectral tunability and high luminescence quantum yields at low excitation densities. However, the most promising perovskite structures rely on lead as a cationic species, thereby hindering commercial application. The replacement of lead with nontoxic alternatives such as tin has been demonstrated in bulk films, but not in spatially confined nanocrystals. Here, we synthesize CsSnX3 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, I) perovskite nanocrystals and provide evidence of their spectral tunability through both quantum confinement effects and control of the anionic composition. We show that luminescence from Sn-based perovskite nanocrystals occurs on pico- to nanosecond time scales via two spectrally distinct radiative decay processes, which we assign to band-to-band emission and radiative recombination at shallow intrinsic defect sites.

Quantification of Geminate and Non‐Geminate Recombination Losses within a Solution‐Processed Small‐Molecule Bulk Heterojunction Solar Cell

Direct measurements of the field-dependent efficiency with which electron-hole pairs are dissociated (1) can be combined with direct measurement of the carrier-density dependent rate at which they subsequently recombine (2) to determine the proportion of carriers which may be usefully extracted (3) for a class of solution-processed organic small-molecule bulk-heterojunction solar cells.

Thermochemical nanopatterning of organic semiconductors

Patterning of semiconducting polymers on surfaces is important for various applications in nanoelectronics and nanophotonics. However, many of the approaches to nanolithography that are used to pattern inorganic materials are too harsh for organic semiconductors, so research has focused on optical patterning and various soft lithographies. Surprisingly little attention has been paid to thermal, thermomechanical and thermochemical patterning. Here, we demonstrate thermochemical nanopatterning of poly(p-phenylene vinylene), a widely used electroluminescent polymer, by a scanning probe. We produce patterned structures with dimensions below 28 nm, although the tip of the probe has a diameter of 5 microm, and achieve write speeds of 100 microm s(-1). Experiments show that a resolution of 28 nm is possible when the tip-sample contact region has dimensions of approximately 100 nm and, on the basis of finite-element modelling, we predict that the resolution could be improved by using a thinner resist layer and an optimized probe. Thermochemical lithography offers a versatile, reliable and general nanopatterning technique because a large number of optical materials, including many commercial crosslinker additives and photoresists, rely on chemical mechanisms that can also be thermally activated.

Polyfluorene-based light-emitting diodes with an azide photocross-linked poly(3,4-ethylene dioxythiophene):(polystyrene sulfonic acid) hole-injecting layer

We used a water-soluble bis(fluorinated phenyl azide) to cross-link a poly(ethylene dioxythiophene):poly(styrene sulphonic acid) (PEDOT:PSS), hole-injection layer, with a view to its future use with water-soluble emitters. To enable direct comparison with conventional PEDOT:PSS, we studied the cross-linked films in diodes incorporating the organic-solvent soluble polymer poly(9,9′-dioctylfluorene-alt-benzothiadiazole). Kelvin probe characterization of the PEDOT:PSS and electroabsorption measurements of the devices consistently show a 0.2eV increase of the PEDOT:PSS work function upon cross-linking. We also observe a 70-fold reduction in resistivity, an increase of the current above threshold and a decrease of the “leakage” current below threshold.

High-performance light-emitting diodes based on carbene-metal-amides

Adding a twist for enhanced performance The efficiency of organic light-emitting diodes (OLEDs) is fundamentally governed by the ratio of emissive singlet to dark triplet excitons that are formed from spin-polarized electron and hole currents within the material. Typically, this has set an upper limit of 25% internal quantum efficiency for OLEDs. Di et al. manipulated the ratio of spin states through a modification of process chemistry. They introduced a rotation of the molecular structure, which inverted the spin-state energetics and enhanced OLED performance. Science, this issue p. 159 Spin-state inversion via intramolecular rotation can enhance the performance of solution-processed organic light-emitting diodes. Organic light-emitting diodes (OLEDs) promise highly efficient lighting and display technologies. We introduce a new class of linear donor-bridge-acceptor light-emitting molecules, which enable solution-processed OLEDs with near-100% internal quantum efficiency at high brightness. Key to this performance is their rapid and efficient utilization of triplet states. Using time-resolved spectroscopy, we establish that luminescence via triplets occurs within 350 nanoseconds at ambient temperature, after reverse intersystem crossing to singlets. We find that molecular geometries exist at which the singlet-triplet energy gap (exchange energy) is close to zero, so that rapid interconversion is possible. Calculations indicate that exchange energy is tuned by relative rotation of the donor and acceptor moieties about the bridge. Unlike other systems with low exchange energy, substantial oscillator strength is sustained at the singlet-triplet degeneracy point.

Strong Photocurrent from Two-Dimensional Excitons in Solution-Processed Stacked Perovskite Semiconductor Sheets.

Room-temperature photocurrent measurements in two-dimensional (2D) inorganic–organic perovskite devices reveal that excitons strongly contribute to the photocurrents despite possessing binding energies over 10 times larger than the thermal energies. The p-type (C6H9C2H4NH3)2PbI4 liberates photocarriers at metallic Schottky aluminum contacts, but incorporating electron- and hole-transport layers enhances the extracted photocurrents by 100-fold. A further 10-fold gain is found when TiO2 nanoparticles are directly integrated into the perovskite layers, although the 2D exciton semiconducting layers are not significantly disrupted. These results show that strong excitonic materials may be useful as photovoltaic materials despite high exciton binding energies and suggest mechanisms to better understand the photovoltaic properties of the related three-dimensional perovskites.

Charge Dynamics in Solution-Processed Nanocrystalline CuInS2 Solar Cells.

We investigate charge dynamics in solar cells constructed using solution-processed layers of CuInS2 (CIS) nanocrystals (NCs) as the electron donor and CdS as the electron acceptor. By using time-resolved spectroscopic techniques, we are able to observe photoinduced absorptions that we attribute to the mobile hole carriers in the NC film. In combination with transient photocurrent and photovoltage measurements, we monitor charge dynamics on time scales from 300 fs to 1 ms. Carrier dynamics are investigated for devices with CIS layers composed of either colloidally synthesized 1,3-benzenedithiol-capped nanocrystals or in situ sol-gel synthesized thin films as the active layer. We find that deep trapping of holes in the colloidal NC cells is responsible for decreases in the open-circuit voltage and fill factor as compared to those of the sol-gel synthesized CIS/CdS cell.

Efficient Triplet Exciton Fusion in Molecularly Doped Polymer Light-Emitting Diodes

Solution-processed polymer organic light-emitting diodes (OLEDs) doped with triplet-triplet annihilation (TTA)-upconversion molecules, including 9,10-diphenylanthracene, perylene, rubrene and TIPS-pentacene, are reported. The fraction of triplet-generated electroluminescence approaches the theoretical limit. Record-high efficiencies in solution-processed OLEDs based on these materials are achieved. Unprecedented solid-state TTA-upconversion quantum yield of 23% (TTA-upconversion reaction efficiency of 70%) at electrical excitation well below one-sun equivalent is observed.