The role of photon recycling in perovskite light-emitting diodes

Abstract: Perovskite light-emitting diodes have recently broken the 20% barrier for external quantum efficiency. These values cannot be explained with classical models for optical outcoupling. Here, we analyse the role of photon recycling (PR) in assisting light extraction from perovskite light-emitting diodes. Spatially-resolved photoluminescence and electroluminescence measurements combined with optical modelling show that repetitive re-absorption and re-emission of photons trapped in substrate and waveguide modes significantly enhance light extraction when the radiation efficiency is sufficiently high. In this manner, PR can contribute more than 70% to the overall emission, in agreement with recently-reported high efficiencies. While an outcoupling efficiency of 100% is theoretically possible with PR, parasitic absorption losses due to absorption from the electrodes are shown to limit practical efficiencies in current device architectures. To overcome the present limits, we propose a future configuration with a reduced injection electrode area to drive the efficiency toward 100%

Photodoping through local charge carrier accumulation in alloyed hybrid perovskites for highly efficient luminescence

Metal halide perovskites have emerged as exceptional semiconductors for optoelectronic applications. Substitution of the monovalent cations has advanced luminescence yields and device efficiencies. Here, we control the cation alloying to enhance optoelectronic performance through alteration of the charge carrier dynamics in mixed-halide perovskites. In contrast to single-halide perovskites, we find high luminescence yields for photoexcited carrier densities far below solar illumination conditions. Using time-resolved spectroscopy we show that the charge carrier recombination regime changes from second to first order within the first tens of nanoseconds after excitation. Supported by microscale mapping of the optical bandgap, electrically gated transport measurements and first-principles calculations, we demonstrate that spatially varying energetic disorder in the electronic states causes local charge accumulation, creating p- and n-type photodoped regions, which unearths a strategy for efficient light emission at low charge-injection in solar cells and light-emitting diodes

Engineering the Photoresponse of InAs Nanowires

We report on individual-InAs nanowire optoelectronic devices which can be tailored to exhibit either negative or positive photoconductivity (NPC or PPC). The NPC photoresponse time and magnitude is found to be highly tunable by varying the nanowire diameter under controlled growth conditions. Using hysteresis characterization, we decouple the observed photoexcitation-induced hot electron trapping from conventional electric field-induced trapping to gain a fundamental insight into the interface trap states responsible for NPC. Furthermore, we demonstrate surface passivation without chemical etching which both enhances the field-effect mobility of the nanowires by approximately an order of magnitude and effectively eliminates the hot carrier trapping found to be responsible for NPC, thus restoring an "intrinsic" positive photoresponse. This opens pathways toward engineering semiconductor nanowires for novel optical-memory and photodetector applications.We acknowledge funding from the EPSRC (Grant No. EP/ M009505/1) and the ERC (Grant No. 716471, ACrossWire). S.H. acknowledges funding from the EPSRC (Grant No. EP/ P005152/1). This work was also supported by the Australian Research Council, Australian National Fabrication Facility and Australian Microscopy & Microanalysis Research Facility. J.A.A.-W. acknowledges the support of his Research Fellowships from the Royal Commission for the Exhibition of 1851 and Churchill College, Cambridge. C.K.G acknowledges the support of her scholarship from The Winston Churchill Foundation of the United States

Engineering the Photoresponse of InAs Nanowires.

We report on individual-InAs nanowire optoelectronic devices which can be tailored to exhibit either negative or positive photoconductivity (NPC or PPC). The NPC photoresponse time and magnitude is found to be highly tunable by varying the nanowire diameter under controlled growth conditions. Using hysteresis characterization, we decouple the observed photoexcitation-induced hot electron trapping from conventional electric field-induced trapping to gain a fundamental insight into the interface trap states responsible for NPC. Furthermore, we demonstrate surface passivation without chemical etching which both enhances the field-effect mobility of the nanowires by approximately an order of magnitude and effectively eliminates the hot carrier trapping found to be responsible for NPC, thus restoring an "intrinsic" positive photoresponse. This opens pathways toward engineering semiconductor nanowires for novel optical-memory and photodetector applications

Spatially Resolved Charge Transport and Recombination in Metal-Halide Perovskite Films and Solar Cells

Metal-halide perovskites show great promise as solution-processable semiconductors for efficient solar cells and LEDs. In particular, the diffusion range of photogenerated carriers is unexpectedly long and the luminescence yield is remarkably high. While much effort has been made to improve device performance, the barriers to improving charge transport and recombination properties remain unidentified. I first explore charge transport by investigating a back-contact architecture for measurement. In collaboration with the Snaith group at Oxford, we develop a new architecture to isolate charge carriers. We prepare thin films of perovskite semiconductors over laterally-separated electron- and hole-selective materials of SnO$_{x}$ and NiO$_{x}$, respectively. Upon illumination, electrons (holes) generated over SnO$_{x}$ (NiO$_{x}$) rapidly transfer to the buried collection electrode, leaving holes (electrons) to diffuse laterally as majority carriers in the perovskite layer. We characterise charge transport parameters of electrons and holes, separately, and demonstrate that grain boundaries do not prevent charge transport. Our results show that the low mobilities found in applied-field techniques do not reflect charge diffusivity in perovskite solar cells at operating conditions. We then use the back-contact architecture to investigate recombination under large excess of one charge carrier type. Recombination velocities under these conditions are found to be below 2 cm s$^{-1}$, approaching values of high quality silicon and an order of magnitude lower than under common bipolar conditions. Similarly, diffusion lengths of electrons and holes exceed 12 $\mu$m, an order of magnitude higher than reported in perovskite devices to date. We report back-contact solar cells with short-circuit currents as high as 18.4 mA cm$^{-2}$, giving 70% external charge-collection efficiency. We then explore the behaviour of charge carriers in continuously illuminated metal-halide perovskite devices. We show that continuous illumination of perovskite devices gives rise to a segregated charge carrier population, and we find that the distance photo-induced charges travel increases significantly under these conditions. Finally, we examine intermittancy in the photoluminescence intensity of metal-halide perovskite films.I principally benefited from joint funding between the Nanotechnology Doctoral Training Centre and the Cambridge Overseas Trusts. In addition, I received some support from Robinson College and my supervisor, Dr Hannah Joyce

The role of photon recycling in perovskite light-emitting diodes.

Perovskite light-emitting diodes have recently broken the 20% barrier for external quantum efficiency. These values cannot be explained with classical models for optical outcoupling. Here, we analyse the role of photon recycling (PR) in assisting light extraction from perovskite light-emitting diodes. Spatially-resolved photoluminescence and electroluminescence measurements combined with optical modelling show that repetitive re-absorption and re-emission of photons trapped in substrate and waveguide modes significantly enhance light extraction when the radiation efficiency is sufficiently high. In this manner, PR can contribute more than 70% to the overall emission, in agreement with recently-reported high efficiencies. While an outcoupling efficiency of 100% is theoretically possible with PR, parasitic absorption losses due to absorption from the electrodes are shown to limit practical efficiencies in current device architectures. To overcome the present limits, we propose a future configuration with a reduced injection electrode area to drive the efficiency toward 100%

Data supporting "The Role of Photon Recycling in Perovskite Light-Emitting Diodes"

Data underlying each of the graphical figures in the associated publication regarding photon recycling in perovskite LEDs. These include: Figure 1: absorption and emissions spectra; PLE spectra; intensity dependence of luminescence. Figure 2: spatial PL intensity, and PL spectra at various positions. Figure 3: Output of optical model

Solvent–Morphology–Property Relationship of PTB7:PC71\mathrm{PTB7:PC_{71}}BM Polymer Solar Cells

The influence of three different solvents and a solvent additive on the morphology and photovoltaic performance of bulk heterojunction films made of the copolymer based on thieno[3,4-b]thiophene-alt-benzodithiophene unit PTB7-F40 blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC$_{71}$BM) is investigated. Optical microscopy and atomic force microscopy are combined with X-ray reflectivity and grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively), enabling the characterization of the morphology of the whole photoactive film. The detailed study reveals that different length scales of PCBM clusters are observed using different solvents, while adding a solvent additive results in the PCBM clusters being selectively dissolved. Vertical and lateral phase separation occurs during spin coating and depends on the solvent used. A hierarchical morphology is detected within the bulk film through GISAXS measurements. Furthermore, GIWAXS shows that a rather amorphous film with low crystallinity was probed, which substantiates that high crystallinity is not necessarily required for high performance organic solar cells. Different models for the morphology are proposed through the combination of all the findings and correlated with the corresponding device properties. Consequently, the solvent-induced different device performance is mainly ascribed to the varied lateral structure sizes, whereas the highest device performance is a result of the smallest average multilength scale lateral structure sizes with the smallest length scale matching the exciton diffusion length

The role of photon recycling in perovskite light-emitting diodes

Abstract: Perovskite light-emitting diodes have recently broken the 20% barrier for external quantum efficiency. These values cannot be explained with classical models for optical outcoupling. Here, we analyse the role of photon recycling (PR) in assisting light extraction from perovskite light-emitting diodes. Spatially-resolved photoluminescence and electroluminescence measurements combined with optical modelling show that repetitive re-absorption and re-emission of photons trapped in substrate and waveguide modes significantly enhance light extraction when the radiation efficiency is sufficiently high. In this manner, PR can contribute more than 70% to the overall emission, in agreement with recently-reported high efficiencies. While an outcoupling efficiency of 100% is theoretically possible with PR, parasitic absorption losses due to absorption from the electrodes are shown to limit practical efficiencies in current device architectures. To overcome the present limits, we propose a future configuration with a reduced injection electrode area to drive the efficiency toward 100%

Solvent–Morphology–Property Relationship of PTB7:PC₇₁BM Polymer Solar Cells

The influence of three different solvents and a solvent additive on the morphology and photovoltaic performance of bulk heterojunction films made of the copolymer based on thieno­[3,4-<i>b</i>]­thiophene-<i>alt</i>-benzodithiophene unit PTB7-F40 blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) is investigated. Optical microscopy and atomic force microscopy are combined with X-ray reflectivity and grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively), enabling the characterization of the morphology of the whole photoactive film. The detailed study reveals that different length scales of PCBM clusters are observed using different solvents, while adding a solvent additive results in the PCBM clusters being selectively dissolved. Vertical and lateral phase separation occurs during spin coating and depends on the solvent used. A hierarchical morphology is detected within the bulk film through GISAXS measurements. Furthermore, GIWAXS shows that a rather amorphous film with low crystallinity was probed, which substantiates that high crystallinity is not necessarily required for high performance organic solar cells. Different models for the morphology are proposed through the combination of all the findings and correlated with the corresponding device properties. Consequently, the solvent-induced different device performance is mainly ascribed to the varied lateral structure sizes, whereas the highest device performance is a result of the smallest average multilength scale lateral structure sizes with the smallest length scale matching the exciton diffusion length