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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 (

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.

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.

Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

Funder: Academy of Finland : Flagship Programme “Photonics Research and Innovation”; Grant(s): 320166, Funder: Osk. Huttunen Foundation; Id: http://dx.doi.org/10.13039/501100013507, A series of gold‐centered carbene‐metal‐amide (CMA) complexes are synthesized with the carbazole donor ligand modified by substitution with nitrogen atoms in varying positions. The luminescence of new aza‐CMA complexes shows a significant blueshift depending on the position of the N atom, to provide bright blue‐green (500 nm), sky‐blue (478 nm), blue (450 nm) and deep‐blue (419 nm) light‐emitters. The impact of the electron‐withdrawing aza‐group on the nature of the luminescence and the excited state energies of the locally excited (LE) or charge transfer (CT) states have been interpreted with the help of transient absorption, in‐depth photoluminescence experiments and theoretical calculations. By considering the orbital characters of the lowest CT and LE states, we develop a new concept for simultaneous energy tuning for both of these states with a single aza‐substitution, allowing for fast and blue CT emission. This concept allows the interference of 3LE phosphorescence to be avoided at room temperature. The approach is extended to two N substitutions at the optimal location in the 3‐ and 6‐positions of the carbazole skeleton. These results suggest a practical molecular design towards the development of bright and deep‐blue emitting CMA materials to tackle the stability problem of energy‐efficient deep‐blue OLEDs.

Hybrid small-molecule/quantum dot films have the potential to reduce thermalization losses in single-junction photovoltaics as photon multiplication devices. Here grazing incidence X-ray scattering, optical microscopy and IR fluorescence microscopy (probing materials at two distinct wavelengths), provide new insight into highly complex morphologies across nm and mu m lengthscales to provide direct links between morphologies and photon multiplication performance. Results show that within the small molecule crystallites three different QD morphologies may be identified; (i) large quantum dot aggregates at the crystallite nucleus, (ii) relatively well-dispersed quantum dots and (iii) as aggregated quantum dots "swept" from the growing crystallite and that regions containing aggregate quantum dot features lead to relatively poor photon multiplication performance. These results establish how combinations of scattering and microscopy may be employed to reveal new insights into the structure and function of small molecule:quantum dot blends.

Triplet energy transfer between inorganic quantum dots (QDs) and organic materials plays a fundamental role in many optoelectronic applications based on these nanocomposites. Attaching organic molecules to the QD as transmitter ligands has been shown to facilitate transfer both to and from QDs. Here we show that the often disregarded thiol anchoring group can achieve quantitative triplet energy transfer yields in a PbS QD system with 6,11-bis[(triisopropylsilyl)ethynyl]tetracene-2-methylthiol (TET-SH) ligands. We demonstrate efficient triplet transfer in a singlet fission-based photon multiplication system with 5,12-bis[(triisopropylsilyl)ethynyl]tetracene generating triplets in solution that transfer to the PbS QDs via the thiol ligand TET-SH. Importantly, we demonstrate the increased thermal stability of the PbS/TET-SH system, compared to the traditional carboxylic acid counterpart, allowing for higher photoluminescence quantum yields.

Colloidal lead-halide perovskite nanocrystals (LHP NCs) have emerged over the past decade as leading candidates for efficient next-generation optoelectronic devices, but their properties and performance critically depend on how they are purified. While antisolvents are widely used for purification, a detailed understanding of how the polarity of the antisolvent influences the surface chemistry and composition of the NCs is missing in the field. Here, we fill this knowledge gap by studying the surface chemistry of purified CsPbBr

Recent advances in heterojunction and interfacial engineering of perovskite solar cells (PSCs) have enabled great progress in developing highly efficient and stable devices. Nevertheless, the effect of halide choice on the formation mechanism, crystallography, and photoelectric properties of the low-dimensional phase still requires further detailed study. In this work, we present key insights into the significance of halide choice when designing passivation strategies comprising large organic spacer salts, clarifying the effect of anions on the formation of quasi-2D/3D heterojunctions. To demonstrate the importance of halide influences, we employ novel neo-pentylammonium halide salts with different halide anions (neoPAX, X=I, Br, or Cl). We find that regardless of halide selection, iodide-based (neoPA)2(FA)(n-1)PbnI(3n+1) phases are formed above the perovskite substrate, while the added halide anions diffuse and passivate the perovskite bulk. In addition, we also find the halide choice has an influence on the degree of dimensionality (n). Comparing the three halides, we find that chloride-based salts exhibit superior crystallographic, enhanced carrier transport, and extraction compared to the iodide and bromide analogs. As a result, we report high power conversion efficiency in quasi-2D/3D PSCs, which are optimal when using chloride salts, reaching up to 23.35%, and improving long-term stability.

Funder: Cambridge Commonwealth European and International Trust, Controlling the dispersibility of crystalline inorganic quantum dots (QD) within organic‐QD nanocomposite films is critical for a wide range of optoelectronic devices. A promising way to control nanoscale structure in these nanocomposites is via the use of appropriate organic ligands on the QD, which help to compatibilize them with the organic host, both electronically and structurally. Here, using combined small‐angle X‐ray and neutron scattering, the authors demonstrate and quantify the incorporation of such a compatibilizing, electronically active, organic semiconductor ligand species into the native oleic acid ligand envelope of lead sulphide, QDs, and how this ligand loading may be easily controlled. Further more, in situ grazing incidence wide/small angle X‐ray scattering demonstrate how QD ligand surface chemistry has a pronounced effect on the self‐assembly of the nanocomposite film in terms of both small‐molecule crystallization and QD dispersion versus ordering/aggregation. The approach demonstrated here shows the important role which the degree of incorporation of an active ligand, closely related in chemical structure to the host small‐molecule organic matrix, plays in both the self‐assembly of the QD and small‐molecule components and in determining the final optoelectronic properties of the system.

Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm−1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 μs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters., A low singlet-triplet energy gap, necessary for delayed fluorescence organic semiconductors, results in a small radiative rate that limits performance in OLEDs. Here, the authors show that it is possible to reconcile these conflicting requirements in materials that can access both high oscillator strength intramolecular excitations and intermolecular charge transfer states.

Nanocrystal quantum dots (QD) functionalised with active organic ligands hold significant promise as solar energy conversion materials, capable of multiexcitonic processes that could improve the efficiencies of single-junction photovoltaic devices. Small-angle X-ray and neutron scattering (SAXS and SANS) were used to characterize the structure of lead sulphide QDs post ligand-exchange with model acene-carboxylic acid ligands (benzoic acid, hydrocinnamic acid and naphthoic acid). Results demonstrate that hydrocinnamic acid and naphthoic acid ligated QDs form monolayer ligand shells, whilst benzoic acid ligated QDs possess ligand shells thicker than a monolayer. Further, the formation of a range of nanocomposite materials through the self-assembly of such acene-ligated QDs with an organic small-molecule semiconductor [5,12-bis((triisopropylsilyl)ethynyl)tetracene (TIPS-Tc)] is investigated. These materials are representative of a wider set of functional solar energy materials; here the focus is on structural studies, and their optoelectronic function is not investigated. As TIPS-Tc concentrations are increased, approaching the solubility limit, SANS data show that QD fractal-like features form, with structures possibly consistent with a diffusion limited aggregation mechanism. These, it is likely, act as heterogeneous nucleation agents for TIPS-Tc crystallization, generating agglomerates containing both QDs and TIPS-Tc. Within the TIPS-Tc crystals there seem to be three distinct QD morphologies: (i) at the crystallite centre (fractal-like QD aggregates acting as nucleating agents), (ii) trapped within the growing crystallite (giving rise to QD features ordered as sticky hard spheres), and (iii) a population of aggregate QDs at the periphery of the crystalline interface that were expelled from the growing TIPS-Tc crystal. Exposure of the QD:TIPS-Tc crystals to DMF vapour, a solvent known to be able to strip ligands from QDs, alters the spacing between PbS-hydrocinnamic acid and PbS-naphthoic acid ligated QD aggregate features. In contrast, for PbS-benzoic acid ligated QDs, DMF vapour exposure promotes the formation of ordered QD colloidal crystal type phases. This work thus demonstrates how different QD ligand chemistries control the interactions between QDs and an organic small molecule, leading to widely differing self-assembly processes. It highlights the unique capabilities of multiscale X-ray and neutron scattering in characterising such composite materials.

Luminescent semiconductor quantum dots (QDs) have recently been suggested as novel probes for imaging and sensing cell membrane voltages. However, a key bottleneck for their development is a lack of techniques to assess QD responses to voltages generated in the aqueous electrolytic environments typical of biological systems. Even more generally, there have been relatively few efforts to assess the response of QDs to voltage changes in live cells. Here, we develop a platform for monitoring the photoluminescence (PL) response of QDs under AC and DC voltage changes within aqueous ionic environments. We evaluate both traditional CdSe/CdS and more biologically compatible InP/ZnS QDs at a range of ion concentrations to establish their PL/voltage characteristics on chip. Wide-field, few-particle PL measurements with neuronal cells show the QDs can be used to track local voltage changes with greater sensitivity (ΔPL up to twice as large) than state-of-the-art calcium imaging dyes, making them particularly appealing for tracking subthreshold events. Additional physiological observation studies showed that while CdSe/CdS dots have greater PL responses on membrane depolarization, their lower cytotoxicity makes InP/ZnS far more suitable for voltage sensing in living systems. Our results provide a methodology for the rational development of QD voltage sensors and highlight their potential for imaging changes in cell membrane voltage.

Perovskite colloidal nanocrystals have emerged as important new optical materials, with tuneable light emission across the visible spectrum, narrow linewidths for high colour purity, and quantum efficiencies approaching unity. These materials can be solution processed in large volumes at low cost making them promising for optoelectronic devices. The structure of nanocrystals influences the radiative and non-radiative recombination of carriers within them through trap states and Auger recombination. To optimise the emission properties it is vital to understand the relationship between the optical emission of individual nanocrystals and their structure, size, and composition. Here, we use nano-cathodoluminescence to relate the nanoscale optical emission of individual inorganic perovskite nanocrystals to their size. This approach reveals that larger nanocrystals exhibit brighter luminescence, indicating lower non-radiative losses compared to smaller nanocrystals. We also show nanoscale colour mixing with bright red and blue emission from individual CsPbI3 and CsPbCl3 nanocrystals respectively in mixed films. The optical and structural characterisation serve as a powerful approach to the study of colloidal semiconductor nanocrystals that improves the fundamental understanding of quantum structures leading to improved optoelectronic devices.

Recently, there has been an increase in research relating to the search for new optoelectronic materials for photovoltaic devices and light-emitting diodes. This research focuses on developing mate...

Despite extensive research on near-infrared organic light-emitting diodes (OLEDs), the external quantum efficiency (EQE) of these devices are far lower than devices with visible light emission. Recently, doublet fluorescent emission from organic radicals has emerged as a new route to more efficient light-emitting devices than those using established non-radical organic emitters. Charge recombination in radical devices results in doublet excitons with nanosecond emission and avoids the efficiency limit usually associated with singlets and triplets. For the application of the organic radicals to near-infrared electroluminescence, the novel near-infrared radical emitter showing around 800 nm emission was designed. Using the organic radical, not only higher than 5% EQE was attained but also the efficiency roll-off and operational lifetime were substantially improved in addition to decreasing turn-on and driving voltage significantly.

The ultimate goal for singlet fission is that each photo-excited singlet exciton, S1, will result in two triplet excitons with unity yield. However, the singlet fission is now recognized to be complicated, involving bright/dark excited states of different spin multiplicity. Identifying the role of such states is vital to optimize singlet fission yield but difficult due to their elusive spectral signature. Here, we develop an experimental protocol based on a refined magneto-optical probe to access the fast time evolution of various excited states. In diphenylhexatriene crystal, the S1 is found to undergo two competing processes?to form one of the two dark triplet pair intermediates having different exchange energies or to form a bright state, Sx, exhibiting excimer-like delayed photoluminescence. Our result provides a clear picture of a competition event in singlet fission, which is beneficial for the development and tailoring of singlet fission materials with high yield. Funding agencies: Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR-2017-05285]; Linkoping University; Knut and Alice Wallenberg Foundation (KAW)Knut & Alice Wallenberg Foundation; Royal Thai Government Scholarship under the Development and Promotion of Science and Technology Talents Project (DPST); EPSRCUK Research & Innovation (UKRI)Engineering & Physical Sciences Research Council (EPSRC) [EP/M005143/1, EP/P027741/1, EP/L011972/1]; Spanish Government MINECO/FEDERSpanish Government [PID2019109555GB-l00]; Basque governmentBasque Government [PIBA19-0004]; CONACYT-MexicoConsejo Nacional de Ciencia y Tecnologia (CONACyT) [591700]

A wide-gap host matrix is a major obstacle detrimentally influencing the performance of hyperfluorescent organic light-emitting diodes since it substantially increases driving voltage. Moreover, these hyperfluorescent devices typically require at least three components in their emitting layer, which is unfavorable for mass production. To tackle the issue, we report hyperfluorescent organic light-emitting diodes based on a two-component emissive system of carbene-metal-amide donors and conventional fluorescent acceptors. We demonstrate a significant reduction of the driving voltage versus three-component hyperfluorescent devices at practical brightness (1000 cdm-2), leading to a doubling of power conversion efficiency for some composites. From an analysis of thin-film photophysics, it is shown that operational efficiency is limited by Dexter energy transfer between donors and acceptors, which may be reduced by tert-butyl steric substituents, providing new targets for molecular design. While reducing driving voltage, matrix-free hyperfluorescent devices also achieve a maximum external quantum efficiency of 16.5%.

The effect of the heavy metal atom on the photophysics of carbene-metal-amide (CMA) photoemitters is explored, where the metal bridge is either Au, Ag, or Cu. Spectroscopic investigations reveal the coupling mechanism responsible for communication between the singlet and triplet manifolds. The photophysical properties do not reflect expected trends based upon the heavy atom effect, as both direct coupling between charge-transfer states and spin-vibronic coupling via a ligand-centered triplet state are present. Direct coupling is weakest for CMA(Ag), increasing the importance of the spin-vibronic pathway and rendering its properties more sensitive to inter-state energy gaps than for the Au and Cu-bridged analogues. The measured activation energy correlates with the expected exchange energy of the charge-transfer state, which is also closely related to the length of the bonds joining the carbene and amide ligands, and decreases in the order CMA(Cu) > CMA(Au) > CMA(Ag). These findings reveal that reducing interference between charge-transfer and ligand-centers excited, and minimizing exchange energy, are required for developing efficient luminescent CMA complexes.

The conversion efficiency of solar energy in semiconductors is fundamentally limited by ultrafast hot-carrier relaxation processes, and slowing down these processes is critical for improved energy harvesting. Here we report formamidinium tin iodide (FASnI3) nanocrystals where quantum confinement effects yield an evolution from a continuous band structure to separate energy states with decreasing nanocrystal size, as observed by transient absorption spectroscopy. The appearance of separate energy levels slows down the relaxation of hot carriers by two orders of magnitude at low injected carrier densities (

It has been previously found that through an established synthesis of the macrocycle boron subnaphthalocyanine (BsubNc) that random bay-position chlorination occurs and results in a mixed alloyed composition that cannot be separated; called chloro-(chloron)-boron subnaphthalocyanines (Cl-ClnBsubNcs). Through modifications of the synthetic method, amounts of the average bay-position chlorination can be varied. Cl-ClnBsubNcs are fluorescent and therefore here we explore the effect of the amount of bay-position chlorination on the photoluminescent and electroluminescent properties of Cl-ClnBsubNcs. Distinct from previous reports detailing the positive impact of higher average bay-position chlorination, we find that the photophysical processes important to OLEDs improve with lower average bay-position chlorination. A higher degree of bay-position chlorine shows higher nonradiative recombination rates, lower photoluminescence quantum efficiencies and a basic OLEDs exhibits a greater host emission fraction, implying less effective energy transfer. These results advance the consideration of subnaphthalocyanines for light-emitting and optoelectronic applications.

Luminescent colloidal CdSe nanorings are a new type of semiconductor structure that have attracted interest due to the potential for unique physics arising from their non-trivial toroidal shape. However, the exciton properties and dynamics of these materials with complex topology are not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and single particle measurements to study these materials. We find that on transformation of CdSe nanoplatelets to nanorings, by perforating the center of platelets, the emission lifetime decreases and the emission spectrum broadens due to ensemble variations in the ring size and thickness. The reduced PL quantum yield of nanorings (~10%) compared to platelets (~30%) is attributed to an enhanced coupling between: (i) excitons and CdSe LO-phonons at 200 cm-1 and (ii) negatively charged selenium-rich traps which give nanorings a high surface charge (~-50 mV). Population of these weakly emissive trap sites dominates the emission properties with an increased trap emission at low temperatures relative to excitonic emission. Our results provide a detailed picture of the nature of excitons in nanorings and the influence of phonons and surface charge in explaining the broad shape of the PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that the excitonic properties of nanorings are not solely a consequence of the toroidal shape but are also a result of traps introduced by puncturing the platelet center., Comment: 38 pages, 10 figures

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., The methodology for optical modelling of perovskite light‐emitting diodes is investigated. Reabsorption in the perovskite causes divergence in classical methods of optical modelling. Here, the divergence is resolved by exploring the physical meaning of non‐radiative nearfield coupling to nearby emissive material. This enables the quantitative analysis of light emission in perovskites, including the contribution of photon recycling.

Polymer–Fullerene photovoltaics have potential in small-scale power production, but low open-circuit voltages limit their efficiency. Understanding the processes affecting the charge recombination rate is key to increasing device efficiency through optimizing open-circuit voltage. Most of the polymer–fullerene systems have an intramolecular triplet exciton state lower in energy than the interfacial charge-transfer state, and its formation can provide a terminal recombination pathway that may limit device performance. We used magnetic fields to modulate intersystem crossing in a prototypical system and monitored the effect on the open-circuit voltage to infer changes in the steady-state carrier density and hence in the net recombination rate constant. We analyzed these effects using density matrix modeling and quantified the various recombination rate constants for a working device.

Near-infrared light-emitting diodes (LEDs) show potential for telecommunication and medical applications. Quantum dot nanocrystals (QDs), specifically lead chalcogenides, are candidate LED materials since they exhibit tuneable luminescence across the whole near-infrared region, but their surface structure must be carefully controlled to achieve efficient emission. We demonstrate an efficient donor–acceptor QD system by embedding low-energy QDs with high photoluminescence quantum efficiency (PLQE) into a matrix of higher-energy QDs with lower PLQE. We find that the overall PLQE of densely packed cross-linked QD films can be improved by the incorporation of a relatively small fraction of well-passivated acceptor QDs, also leading to improved LED performance. Excitations are transferred into the isolated low-energy acceptor QDs, where they recombine with high radiative efficiency.

Organic-inorganic perovskite solar cells have attracted significant attention due to their remarkable performance. The use of alternative metal-oxide charge-transport layers is a strategy to improving device reliability for large-scale fabrication and long-term applications. Here, we report solution-processed perovskite solar cells employing nickel oxide hole-extraction layers produced in situ using an atmospheric pressure spatial atomic-layer deposition system, which is compatible with high-throughput processing of electronic devices from solution. Our sub-nanometer smooth (average roughness of ≤0.6 nm) oxide films enable the efficient collection of holes and the formation of perovskite absorbers with high electronic quality. Initial solar-cell experiments show a power-conversion efficiency of 17.1%, near-unity ideality factors, and a fill factor of >80% with negligible hysteresis. Transient measurements reveal that a key contributor to this performance is the reduced luminescence quenching trap density in the perovskite/nickel oxide structure.

Perovskite-based optoelectronic devices are gaining much attention owing to their remarkable performance and low processing cost, particularly for solar cells. However, for perovskite light-emitting diodes, non-radiative charge recombination has limited the electroluminescence efficiency. Here we demonstrate perovskite-polymer bulk heterostructure light-emitting diodes exhibiting external quantum efficiencies of up to 20.1% (at current densities of 0.1-1 mA cm(-2)). The light-emitting diode emissive layer comprises quasi-two-dimensional and three-dimensional (2D/3D) perovskites and an insulating polymer. Photogenerated excitations migrate from quasi-2D to lower-energy sites within 1 ps, followed by radiative bimolecular recombination in the 3D regions. From near-unity external photoluminescence quantum efficiencies and transient kinetics of the emissive layer with and without charge-transport contacts, we find non-radiative recombination pathways to be effectively eliminated, consistent with optical models giving near 100% internal quantum efficiencies. Although the device brightness and stability (T-50 = 46 h in air at peak external quantum efficiency) require further improvement, our results indicate the significant potential of perovskite-based photon sources. Funding Agencies|Cambridge Trust; China Scholarship Council; VINNMER Marie-Curie Fellowship; Royal Society Newton-Bhabha International Fellowship; UAEs Distinguished Student Scholarship Program; UAEs Ministry of Presidential Affairs; Engineering and Physical Sciences Research Council (EPSRC); Thousand Talent Program; EPSRC; European Research Council (ERC) under the European Unions Horizon 2020 research and innovation programme [670405]

CdSe/CdTe core-crown type-II nanoplatelet heterostructures are two-dimensional semiconductors that have attracted interest for use in light-emitting technologies due to their ease of fabrication, outstanding emission yields, and tunable properties. Despite this, the exciton dynamics of these complex materials, and in particular how they are influenced by phonons, is not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and temperature-dependent structural measurements to investigate CdSe/CdTe nanoplatelets with a thickness of four monolayers. We show that charge-transfer (CT) excitons across the CdSe/CdTe interface are formed on two distinct time scales: initially from an ultrafast (∼70 fs) electron transfer and then on longer time scales (∼5 ps) from the diffusion of domain excitons to the interface. We find that the CT excitons are influenced by an interfacial phonon mode at ∼120 cm-1, which localizes them to the interface. Using low-temperature PL spectroscopy we reveal that this same phonon mode is the dominant mechanism in broadening the CT PL. On cooling to 4 K, the total PL quantum yield reaches close to unity, with an ∼85% contribution from CT emission and the remainder from an emissive sub-band-gap state. At room temperature, incomplete diffusion of domain excitons to the interface and scattering between CT excitons and phonons limit the PL quantum yield to ∼50%. Our results provide a detailed picture of the nature of exciton-phonon interactions at the interfaces of 2D heterostructures and explain both the broad shape of the CT PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that to maximize the PL quantum yield both improved engineering of the interfacial crystal structure and diffusion of domain excitons to the interface, e.g., by altering the relative core/crown size, are required.

Metal-halide perovskite-based tandem solar cells show great promise for overcoming the Shockley–Queisser single-junction efficiency limit via low-cost tandem structures, but so far, they employ conventional bottom-cell materials that require stringent processing conditions. Meanwhile, difficulty in achieving low-bandgap ( 11% absolute gain) to the ultimate efficiency via photon recycling. We report an initial experimental demonstration of a solution-processed monolithic perovskite/CQD tandem solar cell, showin...