Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.

Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1-4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620-650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m-2.

Quantum barriers engineering toward radiative and stable perovskite photovoltaic devices.

Efficient photovoltaic devices must be efficient light emitters to reach the thermodynamic efficiency limit. Here, we present a promising prospect of perovskite photovoltaics as bright emitters by harnessing the significant benefits of photon recycling, which can be practically achieved by suppressing interfacial quenching. We have achieved radiative and stable perovskite photovoltaic devices by the design of a multiple quantum well structure with long (∼3 nm) organic spacers with oleylammonium molecules at perovskite top interfaces. Our L-site exchange process (L: barrier molecule cation) enables the formation of stable interfacial structures with moderate conductivity despite the thick barriers. Compared to popular short (∼1 nm) Ls, our approach results in enhanced radiation efficiency through the recursive process of photon recycling. This leads to the realization of radiative perovskite photovoltaics with both high photovoltaic efficiency (in-lab 26.0%, certified to 25.2%) and electroluminescence quantum efficiency (19.7 % at peak, 17.8% at 1-sun equivalent condition). Furthermore, the stable crystallinity of oleylammonium-based quantum wells enables our devices to maintain high efficiencies for over 1000 h of operation and >2 years of storage.

Bright and stable perovskite light-emitting diodes in the near-infrared range.

Perovskite light-emitting diodes (LEDs) have attracted broad attention due to their rapidly increasing external quantum efficiencies (EQEs)1-15. However, most high EQEs of perovskite LEDs are reported at low current densities (<1 mA cm-2) and low brightness. Decrease in efficiency and rapid degradation at high brightness inhibit their practical applications. Here, we demonstrate perovskite LEDs with exceptional performance at high brightness, achieved by the introduction of a multifunctional molecule that simultaneously removes non-radiative regions in the perovskite films and suppresses luminescence quenching of perovskites at the interface with charge-transport layers. The resulting LEDs emit near-infrared light at 800 nm, show a peak EQE of 23.8% at 33 mA cm-2 and retain EQEs more than 10% at high current densities of up to 1,000 mA cm-2. In pulsed operation, they retain EQE of 16% at an ultrahigh current density of 4,000 mA cm-2, along with a high radiance of more than 3,200 W s-1 m-2. Notably, an operational half-lifetime of 32 h at an initial radiance of 107 W s-1 m-2 has been achieved, representing the best stability for perovskite LEDs having EQEs exceeding 20% at high brightness levels. The demonstration of efficient and stable perovskite LEDs at high brightness is an important step towards commercialization and opens up new opportunities beyond conventional LED technologies, such as perovskite electrically pumped lasers.

Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers.

Fast diffusion of charge carriers is crucial for efficient charge collection in perovskite solar cells. While lateral transient photoluminescence microscopies have been popularly used to characterize charge diffusion in perovskites, there exists a discrepancy between low diffusion coefficients measured and near-unity charge collection efficiencies achieved in practical solar cells. Here, we reveal hidden microscopic dynamics in halide perovskites through four-dimensional (directions x, y and z and time t) tracking of charge carriers by characterizing out-of-plane diffusion of charge carriers. By combining this approach with confocal microscopy, we discover a strong local heterogeneity of vertical charge diffusivities in a three-dimensional perovskite film, arising from the difference between intragrain and intergrain diffusion. We visualize that most charge carriers are efficiently transported through the direct intragrain pathways or via indirect detours through nearby areas with fast diffusion. The observed anisotropy and heterogeneity of charge carrier diffusion in perovskites rationalize their high performance as shown in real devices. Our work also foresees that further control of polycrystal growth will enable solar cells with micrometres-thick perovskites to achieve both long optical path length and efficient charge collection simultaneously.

Ultra-bright, efficient and stable perovskite light-emitting diodes.

Metal halide perovskites are attracting a lot of attention as next-generation light-emitting materials owing to their excellent emission properties, with narrow band emission1-4. However, perovskite light-emitting diodes (PeLEDs), irrespective of their material type (polycrystals or nanocrystals), have not realized high luminance, high efficiency and long lifetime simultaneously, as they are influenced by intrinsic limitations related to the trade-off of properties between charge transport and confinement in each type of perovskite material5-8. Here, we report an ultra-bright, efficient and stable PeLED made of core/shell perovskite nanocrystals with a size of approximately 10 nm, obtained using a simple in situ reaction of benzylphosphonic acid (BPA) additive with three-dimensional (3D) polycrystalline perovskite films, without separate synthesis processes. During the reaction, large 3D crystals are split into nanocrystals and the BPA surrounds the nanocrystals, achieving strong carrier confinement. The BPA shell passivates the undercoordinated lead atoms by forming covalent bonds, and thereby greatly reduces the trap density while maintaining good charge-transport properties for the 3D perovskites. We demonstrate simultaneously efficient, bright and stable PeLEDs that have a maximum brightness of approximately 470,000 cd m-2, maximum external quantum efficiency of 28.9% (average = 25.2 ± 1.6% over 40 devices), maximum current efficiency of 151 cd A-1 and half-lifetime of 520 h at 1,000 cd m-2 (estimated half-lifetime >30,000 h at 100 cd m-2). Our work sheds light on the possibility that PeLEDs can be commercialized in the future display industry.

Optical Properties of Perovskite-Organic Multiple Quantum Wells.

A comprehensive study of the optical properties of CsPbBr3 perovskite multiple quantum wells (MQW) with organic barrier layers is presented. Quantum confinement is observed by a blue-shift in absorption and emission spectra with decreasing well width and agrees well with simulations of the confinement energies. A large increase of emission intensity with thinner layers is observed, with a photoluminescence quantum yield up to 32 times higher than that of bulk layers. Amplified spontaneous emission (ASE) measurements show very low thresholds down to 7.3 µJ cm-2 for a perovskite thickness of 8.7 nm, significantly lower than previously observed for CsPbBr3 thin-films. With their increased photoluminescence efficiency and low ASE thresholds, MQW structures with CsPbBr3 are excellent candidates for high-efficiency perovskite-based LEDs and lasers.

23.7% Efficient inverted perovskite solar cells by dual interfacial modification.

Despite remarkable progress, the performance of lead halide perovskite solar cells fabricated in an inverted structure lags behind that of standard architecture devices. Here, we report on a dual interfacial modification approach based on the incorporation of large organic cations at both the bottom and top interfaces of the perovskite active layer. Together, this leads to a simultaneous improvement in both the open-circuit voltage and fill factor of the devices, reaching maximum values of 1.184 V and 85%, respectively, resulting in a champion device efficiency of 23.7%. This dual interfacial modification is fully compatible with a bulk modification of the perovskite active layer by ionic liquids, leading to both efficient and stable inverted architecture devices.

Effects of photon recycling and scattering in high-performance perovskite solar cells.

Efficient external radiation is essential for solar cells to achieve high power conversion efficiency (PCE). The classical limit of 1/2n2 (n, refractive index) for electroluminescence quantum efficiency (ELQE) has recently been approached by perovskite solar cells (PSCs). Photon recycling (PR) and light scattering can provide an opportunity to surpass this limit. We investigate the role of PR and scattering in practical device operation using a radiative PSC with an ELQE (13.7% at 1 sun) that significantly surpasses the classical limit (7.4%). We experimentally analyze the contributions of PR and scattering to this strong radiation. A novel optical model reveals an increase of 39 mV in the voltage of our PSC. This analysis can provide design principles for future PSCs to approach the Shockley-Queisser efficiency limit.

Electrical Pumping of Perovskite Diodes: Toward Stimulated Emission.

The success of metal halide perovskites in photovoltaic and light-emitting diodes (LEDs) motivates their application as a solid-state thin-film laser. Various perovskites have shown optically pumped stimulated emission of lasing and amplified spontaneous emission (ASE), yet the ultimate goal of electrically pumped stimulated emission has not been achieved. As an essential step toward this goal, here, a perovskite diode structure that simultaneously exhibits stable operation at high current density (≈1 kA cm-2 ) and optically excited ASE (with a threshold of 180 µJ cm-2 ) is reported. This diode structure achieves an electroluminescence quantum efficiency of 0.8% at 850 A cm-2 , which is estimated to be ≈3% of the charge carrier population required to reach ASE in the same device. It is shown that the formation of a large angle waveguide mode and the reduction of parasitic absorption losses are two major design principles for diodes to obtain a positive gain for stimulated emission. In addition to its prospect as a perovskite laser, a new application of electrically pumped ASE is proposed as an ideal perovskite LED architecture allowing 100% external radiation efficiency.

Computational Study of Dipole Radiation in Re-Absorbing Perovskite Semiconductors for Optoelectronics.

Compared to organic emitters, perovskite materials generally have a small Stokes shift and correspondingly large re-absorption of dipole emission. Classical optical modelling methods ignoring re-absorption do not provide an adequate description of the observed light emission properties. Here, optical modelling methods and design rules for perovskite light-emitting diodes are presented. The transfer-matrix formalism is used to quantify the Poynting vectors generated by a dipole radiating inside a perovskite optoelectronic device. A strategy is presented to deal with non-radiative coupling to nearby emissive material that can otherwise lead to non-physical divergence in the calculation. Stability issues are also investigated regarding coherence of the light propagating in the substrate and the absence of a light absorber in the system. The benefit of the photon recycling effect is taken into account by recursive calculation of the dipole generation profile. The simulation results predict that a high external quantum efficiency of ≈40% is achievable in formamidinium lead triiodide-based perovskite light-emitting diodes, by optimization of microcavity, dipole orientation, and photon recycling effects. Contrary to conventional device structures currently reported, this work highlights the benefits of thick charge transport layers and thick perovskite with small Stokes shift.

Controlling and Optimizing Amplified Spontaneous Emission in Perovskites.

Perovskites are currently attracting extensive research interest as a wavelength-tunable lasing material. As a first step toward electrically pumped lasers, numerous investigations have recently reported amplified spontaneous emission (ASE) of optically pumped perovskites with remarkably low thresholds. Here, we investigate the optical aspects of perovskite ASE, to establish the design principle of materials and devices. We show that compared to solution-processed CsPbBr3, vacuum deposition yields superior ASE characteristics with a threshold of 35 µJ/cm2. The optical loss (Rloss) during lateral photon propagation in the waveguide mode is identified as a key parameter to determine the ASE quality. With spatially resolved photoluminescence, we determine Rloss as 40 and >1000 cm-1 for vacuum and solution-processed perovskites, respectively. We present a comprehensive model that relates ASE, gain length, optical loss, temperature, and density of states. Finally, we succeed in demonstrating ASE in perovskite samples with metal electrodes, mimicking a diode architecture for electrical pumping. Optical spacer layers are shown to play a crucial role in preventing metal absorption loss in waveguide modes.

Enhanced bendability of nanostructured metal electrodes: effect of nanoholes and their arrangement.

Metallic thin films often exhibit poor mechanical robustness, which makes them unsuitable for use as electrodes in flexible and stretchable electronic devices. This prompted us to investigate the effect of creating a pattern of nanoholes in a metallic thin film to its mechanical and electrical properties. The adoption of nanonetwork structures is shown to confer significantly improved bendability to the films, with a change in electrical resistance of only 21% after 10 000 bending cycles, under a bending strain of 6.3%. In contrast to the planar silver (Ag) films in which large cracks are formed, structures that contain nanoholes act as barriers that block the growth of cracks; consequently, only short cracks are formed in these films and therefore changes in their resistance are much lower. In this paper, we suggest a novel model based on random grain boundaries to simulate the behavior of various nanopattern arrangements when the film is subjected to mechanical stress. Our modeling studies revealed that nanoholes secure the electrical current pathways by effectively blocking crack propagation, and that optimizing orientation, size, and coverage of these nanoholes can further improve the mechanical properties. Although diamond patterns exhibit superior characteristics to those of rectangular ones, their directional dependence is shown to be reduced by adopting randomly dispersed nanostructures. We additionally verified experimentally that an array of holes (rectangular, diamond-shaped, and randomly patterned) significantly affects crack propagation and resistance change.

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%.

Multi-bandgap Solar Energy Conversion via Combination of Microalgal Photosynthesis and Spectrally Selective Photovoltaic Cell.

Microalgal photosynthesis is a promising solar energy conversion process to produce high concentration biomass, which can be utilized in the various fields including bioenergy, food resources, and medicine. In this research, we study the optical design rule for microalgal cultivation systems, to efficiently utilize the solar energy and improve the photosynthesis efficiency. First, an organic luminescent dye of 3,6-Bis(4'-(diphenylamino)-1,1'-biphenyl-4-yl)-2,5-dihexyl-2,5-dihydropyrrolo3,4-c pyrrole -1,4-dione (D1) was coated on a photobioreactor (PBR) for microalgal cultivation. Unlike previous reports, there was no enhancement in the biomass productivities under artificial solar illuminations of 0.2 and 0.6 sun. We analyze the limitations and future design principles of the PBRs using photoluminescence under strong illumination. Second, as a multiple-bandgaps-scheme to maximize the conversion efficiency of solar energy, we propose a dual-energy generator that combines microalgal cultivation with spectrally selective photovoltaic cells (PVs). In the proposed system, the blue and green photons, of which high energy is not efficiently utilized in photosynthesis, are absorbed by a large-bandgap PV, generating electricity with a high open-circuit voltage (Voc) in reward for narrowing the absorption spectrum. Then, the unabsorbed red photons are guided into PBR and utilized for photosynthesis with high efficiency. Under an illumination of 7.2 kWh m-2 d-1, we experimentally verified that our dual-energy generator with C60-based PV can simultaneously produce 20.3 g m-2 d-1 of biomass and 220 Wh m-2 d-1 of electricity by utilizing multiple bandgaps in a single system.

Highly Efficient (>10%) Flexible Organic Solar Cells on PEDOT-Free and ITO-Free Transparent Electrodes.

A novel approach to fabricate flexible organic solar cells is proposed without indium tin oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) using junction-free metal nanonetworks (NNs) as transparent electrodes. The metal NNs are monolithically etched using nanoscale shadow masks, and they exhibit excellent optoelectronic performance. Furthermore, the optoelectrical properties of the NNs can be controlled by both the initial metal layer thickness and NN density. Hence, with an extremely thin silver layer, the appropriate density control of the networks can lead to high transmittance and low sheet resistance. Such NNs can be utilized for thin-film devices without planarization by conductive materials such as PEDOT:PSS. A highly efficient flexible organic solar cell with a power conversion efficiency (PCE) of 10.6% and high device yield (93.8%) is fabricated on PEDOT-free and ITO-free transparent electrodes. Furthermore, the flexible solar cell retains 94.3% of the initial PCE even after 3000 bending stress tests (strain: 3.13%).

Study of Optical Configurations for Multiple Enhancement of Microalgal Biomass Production.

Microalga is a promising biomass feedstock to restore the global carbon balance and produce sustainable bioenergy. However, the present biomass productivity of microalgae is not high enough to be marketable mainly because of the inefficient utilization of solar energy. Here, we study optical engineering strategies to lead to a breakthrough in the biomass productivity and photosynthesis efficiency of a microalgae cultivation system. Our innovative optical system modelling reveals the theoretical potential (>100 g m-2 day-1) of the biomass productivity and it is used to compare the optical aspects of various photobioreactor designs previously proposed. Based on the optical analysis, the optimized V-shaped configuration experimentally demonstrates an enhancement of biomass productivity from 20.7 m-2 day-1 to 52.0 g m-2 day-1, under the solar-simulating illumination of 7.2 kWh m-2 day-1, through the dilution and trapping of incident energy. The importance of quantitative optical study for microalgal photosynthesis is clearly exhibited with practical demonstration of the doubled light utilization efficiencies.

Columnar-Structured Low-Concentration Donor Molecules in Bulk Heterojunction Organic Solar Cells.

We investigate the arrangement of donor molecules in vacuum-deposited bulk heterojunction (BHJ) 1,1-bis-(4-bis(4-methyl-phenyl)-amino-phenyl)-cyclohexane (TAPC):C70-based organic solar cells (OSCs). Even a low dose of donors (∼10%) forms columnar structures that provide pathways for efficient hole transport in the BHJ layer; however, these structures disappear at donor concentrations below 10%, generating disconnected and isolated hole pathways. The formation of columnar donor structures is confirmed by the contrast of the contact potential difference, measured by Kelvin probe force microscopy, and by the trap-assisted charge injection at low donor concentrations. The mobility of electrons and holes is well balanced in OSCs owing to the preservation of the hole mobility at such low donor concentrations, consequently maximizing the internal quantum efficiency of the OSCs. A high power conversion efficiency of 6.24% was achieved in inverted TAPC:C70 (1:9) OSCs.

Broadband light trapping strategies for quantum-dot photovoltaic cells (>10%) and their issues with the measurement of photovoltaic characteristics.

Bandgap tunability and broadband absorption make quantum-dot (QD) photovoltaic cells (PVs) a promising candidate for future solar energy conversion systems. Approaches to improving the electrical properties of the active layer increase efficiency in part. The present study focuses on optical room for enhancement in QD PVs over wide spectrum in the near-infrared (NIR) region. We find that ray-optical light trapping schemes rather than the nanophotonics approach may be the best solution for enhancing broadband QD PVs by suppressing the escape probability of internal photons without spectral dependency. Based on the theoretical study of diverse schemes for various bandgaps, we apply a V-groove structure and a V-groove textured compound parabolic trapper (VCPT) to PbS-based QD PVs along with the measurement issues for PVs with a light scattering layer. The efficiency of the best device is improved from 10.3% to 11.0% (certified to 10.8%) by a V-groove structure despite the possibility of underestimation caused by light scattering in small-area devices (aperture area: 0.0625 cm2). By minimizing such underestimation, even greater enhancements of 13.6% and 15.6% in short circuit current are demonstrated for finger-type devices (0.167 cm2 without aperture) and large-area devices (2.10 cm2 with an aperture of 0.350 cm2), respectively, using VCPT.

Improved Internal Quantum Efficiency and Light-Extraction Efficiency of Organic Light-Emitting Diodes via Synergistic Doping with Au and Ag Nanoparticles.

This paper reports the distinct roles of Au and Ag nanoparticles (NPs) in organic light-emitting diodes (OLEDs) depending on their sizes. Au and Ag NPs that are 40 and 50 nm in size, respectively, are the most effective for enhancing the performance of green OLEDs. The external quantum efficiencies (EQEs) of green OLEDs doped with Au and Ag NPs (40 and 50 nm, respectively) are improved by 29.5% and 36.1%, respectively, while the power efficiencies (PEs) are enhanced by 47.9% and 37.5%, respectively. Furthermore, combining the Au and Ag NPs produces greater enhancements. The EQE and PE of the codoped OLEDs are improved by 63.9% and 68.8%, respectively, through the synergistic behavior of the different NPs. Finite-difference time-domain simulations confirm that the localized surface-plasmon resonance of the Au NPs near 580 nm improves the radiative recombination rate (krad) of green-light emitters locally (<50 nm), while the Ag NPs cause relatively long-range and broadband enhancements in krad. The simulations of various domain sizes verify that the light-extraction efficiency (LEE) can be enhanced by more than 4.2% by applying Ag NPs. Thus, size-controlled Au and Ag NPs can synergistically enhance OLEDs by improving both the internal quantum efficiency and LEE.