arXiv subjects

Richard H. Friend

Publications and source records attributed to Richard H. Friend.

49 records · Page 3Linked to original sources

arXiv2017

Maximising and Stabilising Luminescence in Metal Halide Perovskite Device Structures

Metal halide perovskites are attracting tremendous interest for a variety of optoelectronic applications. The ability to tune the perovskite bandgap by tweaking the chemical compositions opens up new applications as coloured emitters and as components of tandem photovoltaics. Nevertheless, non-radiative losses are still limiting performance, with luminescence yields in state-of-the-art perovskite solar cells still far from 100% under solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps ~1.7-1.9 eV), photo-induced ion segregation leads to bandgap instabilities. Here, we substantially mitigate both non-radiative losses and photo-induced ion migration in perovskite structures by decorating the surfaces and grain boundaries with passivating potassium-halide interlayers. We demonstrate external photo-luminescence quantum yields of 66%, translating to internal yields exceeding 95%. The high luminescence yields are achieved while maintaining high mobilities over 40 cm2V-1s-1, giving the elusive combination of both high luminescence and excellent charge transport. We find that the external luminescence yield when interfaced with electrodes in a solar cell device stack, a quantity that must be maximized to approach the efficiency limits, remains as high as 15%, indicating very clean interfaces. We also demonstrate the inhibition of photo-induced ion migration processes across a wide range of mixed halide perovskite bandgaps that otherwise show bandgap instabilities. We validate these results in full operating solar cells, highlighting the importance of stabilising luminescence in device structures. Our work represents a critical breakthrough in the construction of tunable halide perovskite films and interfaces that can approach the efficiency limits in tandem solar cells and coloured LEDs.

cond-mat.mtrl-sci↗

arXiv2017

Ultrafast carrier thermalization in lead iodide perovskite probed with two-dimensional electronic spectroscopy

In band-like semiconductors, charge carriers form a thermal energy distribution rapidly after optical excitation. In hybrid lead halide perovskites, the cooling of such thermal carrier distributions occurs on timescales of ~300 fs via carrier-phonon scattering. However, the initial build-up of the thermal distribution proved difficult to resolve with pump-probe techniques due to the requirement of high resolution, both in time and in energy. Here, we use two-dimensional electronic spectroscopy with sub-10fs resolution to directly observe the carrier interactions that lead to the formation of a thermal carrier distribution. We find that thermalization occurs dominantly via carrier-carrier scattering under the investigated fluences and report the dependence of carrier scattering rates on excess energy and carrier density. We extract characteristic carrier thermalization times from below 10 fs to 85 fs. These values allow for mobilities of up to 500 cm^2 V^(-1) s^(-1) at carrier densities lower than 2x10^19 cm^(-3) and limit the time for carrier extraction in hot carrier solar cells.

cond-mat.mtrl-sci↗

arXiv2017

Energy Efficient Dissociation of Excitons to Free Charges

In photovoltaics (PVs) and artificial photosynthetic systems based on excitons, the question of how energy must be lost in overcoming the Coulomb barrier, converting excitons to free charges, is fundamental, as it determines the achievable open-circuit voltage or over-potential1-3. Here, using transient and steady-state optical spectroscopy we study a model system, pentacene/C60, where pentacene triplet excitons are dissociated to form charge transfer states, which we show to be degenerate in energy with the triplet excitons. We directly track these charge transfer states undergoing efficient long-range separation to free charges within 50 ps, despite a significant Coulomb barrier that we measure to be 220 meV. We model this endothermic charge separation to be driven by entropic gain. Our results demonstrate that endothermic charge separation can proceed rapidly with near unity efficiency, overcoming Coulomb barriers greater than 200meV via a gain in entropy, thus minimising loss of open-circuit voltage or over-potential. In the pentacene/C60 system this leads here to an effective VOC loss of only 400meV with respect to the energy of the triplet exciton. This suggests that excitonic photoconversion systems have no fundamental disadvantage compared to systems which generate free changes directly upon photoexcitation.

cond-mat.mes-hall↗

arXiv2017

Ultrafast Triplet Pair Formation and Subsequent Thermally Activated Dissociation Control Efficient Endothermic Singlet Exciton Fission

Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature even when the energy of S1 is as much as 200 meV less than 2T1. Here, we study films of TIPS-tetracene using transient optical spectroscopy and show that the initial rise of the triplet pair state (TT) occurs in 300 fs, matched by rapid loss of S1 stimulated emission, and that this process is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower 10 ps morphology-dependent phase of S1 decay and TT growth. We observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for "temperature independent", efficient TT formation and thermally activated TT separation.

physics.chem-ph↗

arXiv2016

Highly efficient light-emitting diodes based on intramolecular rotation

The efficiency of an organic light-emitting diode (OLED) is fundamentally governed by the spin of recombining electron-hole pairs (singlet and triplet excitons), since triplets cannot usually emit light. The singlet-triplet energy gap, a key factor for efficient utilization of triplets, is normally positive. Here we show that in a family of materials with amide donor and carbene acceptor moieties linked by a metal, this energy gap for singlet and triplet excitons with charge-transfer character can be tuned from positive to negative values via the rotation of donor and acceptor about the metal-amide bond. When the gap is close to zero, facile intersystem crossing is possible, enabling efficient emission from singlet excitons. We demonstrate solution-processed LEDs with exceptionally high quantum efficiencies (near-100% internal and >27% external quantum efficiencies), and current and power efficiencies (87 cd/A and 75 lm/W) comparable to, or exceeding, those of state-of-the-art vacuum-processed OLEDs and quantum dot LEDs.

cond-mat.mtrl-sci↗

arXiv2016

Mapping Morphological and Structural Properties of Lead Halide Perovskites by Scanning Nanofocus XRD

Scanning nanofocus X-ray diffraction (nXRD) performed at a synchrotron is used for the first time to simultaneously probe the morphology and the structural properties of spin-coated CH3NH3PbI3 (MAPI) perovskite films for photovoltaic devices. MAPI films are spin-coated on a Si/SiO2/PEDOT:PSS substrate held at different temperatures during the deposition in order to tune the perovskite film coverage, and then investigated by nXRD, scanning electron microscopy (SEM) and grazing incidence wide angle X-ray scatter-ing (GI-WAXS). The advantages of nXRD over SEM and GI-WAXS are dis-cussed. A method to visualize, selectively isolate, and structurally charac-terize single perovskite grains buried within a complex, polycrystalline film is developed. The results of nXRD measurements are correlated with solar cell device measurements, and it is shown that spin-coating the perovskite precursor solution at elevated temperatures leads to improved surface coverage and enhanced solar cell performance.

cond-mat.mtrl-sci↗

arXiv2015

A Silicon-Singlet Fission Parallel Tandem Solar Cell Exceeding 100 % External Quantum Efficiency

Silicon solar cells dominate the solar cell market with record lab efficiencies reaching almost 26%. However, after 60 years of research, this efficiency saturated close to the theoretical limit for silicon, and radically new approaches are needed to further improve the efficiency. Here we present parallel-connected tandem solar cells based on down-conversion via singlet fission. This design allows raising the theoretical power conversion efficiency limit to 45% with far superior stability under changing sunlight conditions in comparison to traditional series tandems. We experimentally demonstrate a silicon/pentacene parallel tandem solar cell that exceeds 100% external quantum efficiency at the main absorption peak of pentacene, showing efficient photocurrent addition and proving this design as a realistic prospect for real-world applications.

cond-mat.other↗

arXiv2013

Charge-Transfer State Dynamics Following Hole and Electron Transfer in Organic Photovoltaic Devices

The formation of bound electron-hole pairs, also called charge-transfer (CT) states, in organic-based photovoltaic devices is one of the dominant loss mechanisms hindering performance. While CT state dynamics following electron transfer from donor to acceptor have been widely studied, there is not much known about the dynamics of bound CT states produced by hole transfer from the acceptor to the donor. In this letter, we compare the dynamics of CT states formed in the different charge-transfer pathways in a range of model systems. We show that the nature and dynamics of the generated CT states are similar in the case of electron and hole transfer. However the yield of bound and free charges is observed to be strongly dependent on the HOMOD-HOMOA and LUMOD-LUMOA energy differences of the material system. We propose a qualitative model in which the effects of static disorder and sampling of states during the relaxation determine the probability of accessing CT states favourable for charge separation.

cond-mat.mes-hall↗

arXiv2013

The Role of Driving Energy and Delocalised States for Charge Separation in Organic Semiconductors

The electron-hole pair created via photon absorption in organic photoconversion systems must overcome the Coulomb attraction to achieve long-range charge separation. We show that this process is facilitated through the formation of excited, delocalized band states. In our experiments on organic photovoltaic cells, these states were accessed for a short time (<1ps) via IR optical excitation of electron-hole pairs bound at the heterojunction. Atomistic modelling showed that the IR photons promote bound charge pairs to delocalised band states, similar to those formed just after singlet exciton dissociation, which indicates that such states act as the gateway for charge separation. Our results suggest that charge separation in efficient organic photoconversion systems, occurs through hot-state charge delocalisation rather than energy-gradient-driven intermolecular hopping.

cond-mat.mes-hall↗

arXiv2013

Kinetic Control of Recombination in Organic Photovoltaics: The Role of Spin

In photovoltaic diodes recombination of photogenerated electrons and holes is a major loss process. Biological light harvesting complexes (LHCs) prevent recombination via the use of cascade structures, which lead to spatial separation of charge-carriers1. In contrast, the nanoscale morphology and high charge densities in organic photovoltaic cells (OPVs) give a high rate of electron-hole encounters, which should result in the formation of spin triplet excitons, as in organic light emitting diodes (OLEDs)2. OPVs would have poor quantum efficiencies if every encounter lead to recombination, but state-of-the-art OPVs demonstrate near-unity quantum efficiency3. Here we show that this suppression of recombination can be engineered through the interplay between spin, energetics and delocalisation of electronic excitations in organic semiconductors. We use time-resolved spectroscopy to study a series of model, high efficiency polymer-fullerene systems in which the lowest lying molecular triplet exciton (T1) (on the polymer) lies below the intermolecular charge transfer state (CT). We observe the formation of T1 states following bimolecular recombination, indicating that encounters of spin-uncorrelated electrons and holes generate CT states with both spin singlet (1CT) and spin triplet (3CT) characters. We show that triplet exciton formation can be the major loss mechanism in OPVs. However, we find that even when energetically favoured, the relaxation of 3CT to T1 can be strongly suppressed, via control over wavefunction delocalisation, allowing for the dissociation of 3CT back to free changes, thereby reducing recombination and enhancing device performance. Our results point towards new design rules for artificial photo-conversion systems, enabling the suppression of electron-hole recombination, and also for OLEDs, avoiding the formation of triplet states and enhancing fluorescence efficiency.

cond-mat.mtrl-sci↗

arXiv2009

Determining exciton bandwidth and film microstructure in polythiophene films using linear absorption spectroscopy

We analyze the linear absorption spectrum of regioregular poly(3-hexylthiophene) films spun from a variety of solvents to probe directly the film microstructure and how it depends on processing conditions. We estimate the exciton bandwidth and the percentage of the film composed of aggregates quantitatively using a weakly interacting H-aggregate model. This provides a description of the degree and quality of crystallites within the film and is in turn correlated with thin-film field-effect transistor characteristics.

cond-mat.mtrl-sci↗

arXiv2007

The role of intermolecular coupling in the photophysics of disordered organic semiconductors: Aggregate emission in regioregular polythiophene

We address the role of excitonic coulping on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By means of temperature-dependent absorption and photoluminescence spectroscopy, we show that optical emission is overwhelmingly dominated by weakly coupled H-aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to extract the magnitude of the intermolecular coupling energy, approximately 5 and 30 meV for films spun from isodurene and chloroform solutions respectively.

cond-mat.mtrl-sci↗

arXiv2004

Exciton Regeneration at Polymeric Semiconductor Heterojunctions

Control of the band-edge offsets at heterojunctions between organic semiconductors allows efficient operation of either photovoltaic or light-emitting diodes. We investigate systems where the exciton is marginally stable against charge separation, and show via E-field-dependent time-resolved photoluminescence spectroscopy that excitons that have undergone charge separation at a heterojunction can be efficiently regenerated. This is because the charge transfer produces a geminate electron-hole pair (separation 2.2-3.1nm) which may collapse into an exciplex and then endothermically (E=100-200meV) back-transfer towards the exciton.

cond-mat.soft↗