Frenkel and Charge-Transfer Excitonic Couplings Strengthened by Thiophene-Type Solvent Enables Binary Organic Solar Cells with 19.8% Efficiency.

Overcoming the trade-off between short-circuited current (Jsc) and open-circuited voltage (Voc) is important to achieving high-efficiency organic solar cells (OSCs). Previous works modulated energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which is served as driving force of exciton splitting. Differently, our current work focuses on modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent is utilized in treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates the tighter intermolecular interactions with non-fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over-aggregation and retarding the acceptor crystallization with reduced trap. Importantly, the resulted shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes the exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8% (small-area) with a superior operational reliability (T80: 586 hours) and 17.0% (large-area) were yielded in 2Cl-Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade-off between Jsc and Voc, which can productively promote the development of OSC field.

The origins of dual-peak emission and anomalous exciton decay in 2D Sn-based perovskites.

Two-dimensional (2D) Sn-based perovskites exhibit significant potential in diverse optoelectronic applications, such as on-chip lasers and photodetectors. Yet, the underlying mechanism behind the frequently observed dual-peak emission in 2D Sn-based perovskites remains a subject of intense debate, and there is a lack of research on the carrier dynamics in these materials. In this study, we investigate these issues in a representative 2D Sn-based perovskite, namely, PEA2SnI4, through temperature-, excitation intensity-, angle-, and time-dependent photoluminescence studies. The results indicate that the high- and low-energy peaks originate from in-face and out-of-face dipole transitions, respectively. In addition, we observe an anomalous increase in the non-radiative recombination rate as temperature decreases. After ruling out enhanced electron-phonon coupling and Auger recombination as potential causes of the anomalous carrier dynamics, we propose that the significantly increased exciton binding energy (Eb) plays a decisive role. The increased Eb arises from enhanced electronic localization, a consequence of weakened lattice distortion at low temperatures, as confirmed by first-principles calculations and temperature-dependent x-ray diffraction measurements. These findings offer valuable insights into the electronic processes in the unique 2D Sn-based perovskites.

Spectrally Stable and Bright Red Perovskite Light-Emitting Diodes.

Mixing iodide and bromide in three-dimensional metal-halide perovskites is a facile strategy for achieving red light-emitting diodes (LEDs). However, these devices often face challenges such as instability in electroluminescence spectra and low brightness due to phase segregation in mixed-halide perovskites. Here, we demonstrate spectrally stable and bright red perovskite LEDs by substituting some of the halide ions with pseudohalogen thiocyanate ions (SCN-). We find that SCN- can occupy halogen vacancies, thereby releasing microstrain and passivating defects in the perovskite crystals. This leads to the suppression of mixed-halide phase segregation under electrical bias. As a result, the red perovskite LEDs exhibit a high brightness of >35 000 cd m-2 with stable Commission Internationale de l'Eclairage (CIE) coordinates of (0.713, 0.282). This brightness surpasses that of the best-performing red perovskite LEDs, showing great promise for advancing perovskite LEDs in display and lighting applications.

Self-Powered Visible-Blind Ultraviolet Photodetector Based on Organic-Inorganic Hybrid Copper Halide [N(C2H5)4]2[Cu2Br4].

Organic-inorganic hybrid ternary copper halides offer a broader spectrum of structural possibilities for finely tuning their optoelectronic properties. Herein, we demonstrate for the first time the potential of [N(C2H5)4]2[Cu2Br4], a zero-dimensional hybrid copper halide [(TEA)2Cu2Br4], for ultraviolet (UV) photodetection. A self-powered, visible-blind UV photodetector based on a (TEA)2Cu2Br4/GaN heterojunction architecture is developed, exhibiting a high responsivity, a high detectivity, and fast response speeds. The device demonstrates exceptional stability against environmental oxygen/moisture, heat, and UV light illumination, surpassing the stability of reported copper-based UV photodetectors. Our work highlights the significant potential of (TEA)2Cu2Br4 as a lead-free, stable, and efficient material for next-generation UV photodetection technology.

Elevating Charge Transport Layer for Stable Perovskite Light-Emitting Diodes.

Ion migration is a major factor affecting the long term stability of perovskite light-emitting diodes (LEDs), which limits their commercialization potential. The accumulation of excess halide ions at the grain boundaries of perovskite films is a primary cause of ion migration in these devices. Here, it is demonstrated that the channels of ion migrations can be effectively impeded by elevating the hole transport layer between the perovskite grain boundaries, resulting in highly stable perovskite LEDs. The unique structure is achieved by reducing the wettability of the perovskites, which prevents infiltration of the upper hole-transporting layer into the spaces of perovskite grain boundaries. Consequently, nanosized gaps are formed between the excess halide ions and the hole transport layer, effectively suppressing ion migration. With this structure, perovskite LEDs with operational half-lifetimes of 256 and 1774 h under current densities of 100 and 20 mA cm-2 respectively are achieved. These lifetimes surpass those of organic LEDs at high brightness. It is further found that this approach can be extended to various perovskite LEDs, showing great promise for promoting perovskite LEDs toward commercial applications.

Acceleration of radiative recombination for efficient perovskite LEDs.

The increasing demands for more efficient and brighter thin-film light-emitting diodes (LEDs) in flat-panel display and solid-state lighting applications have promoted research into three-dimensional (3D) perovskites. These materials exhibit high charge mobilities and low quantum efficiency droop1-6, making them promising candidates for achieving efficient LEDs with enhanced brightness. To improve the efficiency of LEDs, it is crucial to minimize nonradiative recombination while promoting radiative recombination. Various passivation strategies have been used to reduce defect densities in 3D perovskite films, approaching levels close to those of single crystals3. However, the slow radiative (bimolecular) recombination has limited the photoluminescence quantum efficiencies (PLQEs) of 3D perovskites to less than 80% (refs. 1,3), resulting in external quantum efficiencies (EQEs) of LED devices of less than 25%. Here we present a dual-additive crystallization method that enables the formation of highly efficient 3D perovskites, achieving an exceptional PLQE of 96%. This approach promotes the formation of tetragonal FAPbI3 perovskite, known for its high exciton binding energy, which effectively accelerates the radiative recombination. As a result, we achieve perovskite LEDs with a record peak EQE of 32.0%, with the efficiency remaining greater than 30.0% even at a high current density of 100 mA cm-2. These findings provide valuable insights for advancing the development of high-efficiency and high-brightness perovskite LEDs.

The Role of Solution Aggregation Property toward High-Efficiency Non-Fullerene Organic Photovoltaic Cells.

In organic photovoltaic cells, the solution-aggregation effect (SAE) is long considered a critical factor in achieving high power-conversion efficiencies for polymer donor (PD)/non-fullerene acceptor (NFA) blend systems. However, the underlying mechanism has yet to be fully understood. Herein, based on an extensive study of blends consisting of the representative 2D-benzodithiophene-based PDs and acceptor-donor-acceptor-type NFAs, it is demonstrated that SAE shows a strong correlation with the aggregation kinetics during solidification, and the aggregation competition between PD and NFA determines the phase separation of blend film and thus the photovoltaic performance. PDs with strong SAEs enable earlier aggregation evolutions than NFAs, resulting in well-known polymer-templated fibrillar network structures and superior PCEs. With the weakening of PDs' aggregation effects, NFAs, showing stronger tendencies to aggregate, tend to form oversized domains, leading to significantly reduced external quantum efficiencies and fill factors. These trends reveal the importance of matching SAE between PD and NFA. The aggregation abilities of various materials are further evaluated and the aggregation ability/photovoltaic parameter diagrams of 64 PD/NFA combinations are provided. This work proposes a guiding criteria and facile approach to match efficient PD/NFA systems.

Kornblum Oxidation Reaction-Induced Collective Transformation of Lead Polyhalides for Stable Perovskite Photovoltaics.

The iodide vacancy defects generated during the perovskite crystallization process are a common issue that limits the efficiency and stability of perovskite solar cells (PSCs). Although excessive ionic iodides have been used to compensate for these vacancies, they are not effective in reducing defects through modulating the perovskite crystallization. Moreover, these iodide ions present in the perovskite films can act as interstitial defects, which are detrimental to the stability of the perovskite. Here, an effective approach to suppress the formation of vacancy defects by manipulating the coordination chemistry of lead polyhalides during perovskite crystallization is demonstrated. To achieve this suppression, an α-iodo ketone is introduced to undergo a process of Kornblum oxidation reaction that releases halide ions. This process induces a rapid collective transformation of lead polyhalides during the nucleation process and significantly reduces iodide vacancy defects. As a result, the ion mobility is decreased by one order of magnitude in perovskite film and the PSC achieves significantly improved thermal stability, maintaining 82% of its initial power conversion efficiency at 85 °C for 2800 h. These findings highlight the potential of halide ions released by the Kornblum oxidation reaction, which can be widely used for achieving high-performance perovskite optoelectronics.

Enhancing Light Out-coupling in Perovskite Light-Emitting Diodes through Plasmonic Nanostructures.

Perovskite light-emitting diodes (PeLEDs) have emerged as promising candidates for lighting and display technologies owing to their high photoluminescence quantum efficiency and high carrier mobility. However, the performance of planar PeLEDs is limited by the out-coupling efficiency, predominantly governed by photonic losses at device interfaces. Most notably, the plasmonic loss at the metal electrode interfaces can account for up to 60% of the total loss. Here, we investigate the use of plasmonic nanostructures to improve the light out-coupling in PeLEDs. By integrating these nanostructures with PeLEDs, we have demonstrated an effectively reduced plasmonic loss and enhanced light out-coupling. As a result, the nanostructured PeLEDs exhibit an average 1.5-fold increase in external quantum efficiency and an ∼20-fold improvement in device lifetime. This finding offers a generic approach for enhancing light out-coupling, promising great potential to go beyond existing performance limitations.

Spin coating epitaxial heterodimensional tin perovskites for light-emitting diodes.

Environmentally friendly tin (Sn) perovskites have received considerable attention due to their great potential for replacing their toxic lead counterparts in applications of photovoltaics and light-emitting diodes (LEDs). However, the device performance of Sn perovskites lags far behind that of lead perovskites, and the highest reported external quantum efficiencies of near-infrared Sn perovskite LEDs are below 10%. The poor performance stems mainly from the numerous defects within Sn perovskite crystallites and grain boundaries, leading to serious non-radiative recombination. Various epitaxy methods have been introduced to obtain high-quality perovskites, although their sophisticated processes limit the scalable fabrication of functional devices. Here we demonstrate that epitaxial heterodimensional Sn perovskite films can be fabricated using a spin-coating process, and efficient LEDs with an external quantum efficiency of 11.6% can be achieved based on these films. The film is composed of a two-dimensional perovskite layer and a three-dimensional perovskite layer, which is highly ordered and has a well-defined interface with minimal interfacial areas between the different dimensional perovskites. This unique nanostructure is formed through direct spin coating of the perovskite precursor solution with tryptophan and SnF2 additives onto indium tin oxide glass. We believe that our approach will provide new opportunities for further developing high-performance optoelectronic devices based on heterodimensional perovskites.

Unraveling the Origin of Long-Lifetime Emission in Low-Dimensional Copper Halides via a Magneto-optical Study.

The origin of the long lifetime of self-trapped exciton emission in low-dimensional copper halides is currently the subject of extensive debate. In this study, we address this issue in a prototypical zero-dimensional copper halide, Cs2(C18)2Cu2I4-DMSO, through magneto-optical studies at low temperatures down to 0.2 K. Our results exclude spin-forbidden dark states and indirect phonon-assisted recombination as the origin of the long photoluminescence lifetime. Instead, we propose that the minimal Franck-Condon factor of the radiative transition from excited states to the ground state is the decisive factor, based on the transition probability analysis. Our findings offer insights into the electronic processes in low-dimensional copper halides and have the potential to advance the application of these distinctive materials in optoelectronics.

A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties.

Developing open-shell singlet (OS) diradicals with high luminescent properties and exceptional single-molecule magnetoluminescence (ML) performance is extremely challenging. Herein, we propose a concept to enhance luminescent efficiency by adjusting the donor conjugation of OS diradicals, thereby achieving a highly luminescent diradical, DR1, with outstanding stability and making it a viable option for use in the emitting layer of organic light-emitting diodes (OLEDs). More importantly, the 0.5 wt%-DR1 doped film demonstrates significant single-molecule magnetoluminescence (ML) properties. A giant ML value of 210% is achieved at a magnetic field of 7 T, showing the great potential of DR1 in magneto-optoelectronic devices.

Continuous-Wave Lasing in Perovskite LEDs with an Integrated Distributed Feedback Resonator.

Realization of electrically pumped laser diodes based on solution-processed semiconductors is a long-standing challenge. Metal halide perovskites have shown great potential toward this goal due to their excellent optoelectronic properties. Continuous-wave (CW) optically pumped lasing in a real electroluminescent device represents a key step to current-injection laser diodes, but it has not yet been realized. This is mainly due to the challenge of incorporating a resonant cavity into an efficient light-emitting diode (LED) able to sustain intensive carrier injection. Here, CW lasing is reported in an efficient perovskite LED with an integrated distributed feedback resonator, which shows a low lasing threshold of 220 W cm-2 at 110 K. Importantly, the LED works well at a current density of 330 A cm-2 , indicating the carrier injection rate already exceeds the threshold of optically pumping. The results suggest that electrically pumped perovskite laser diodes can be achieved once the Joule heating issue is overcome.

Spherulitic Crystallization of CsCu2I3 for High Performance Ultraviolet Photodetectors.

Ternary copper halides have become promising materials for UV photodetection due to their stability and eco-friendliness. However, the uncontrollable crystallization induces high-concentration defects in these films, inherently limiting further improvement in device performance. Herein, we reveal the antisolvent-assisted crystallization kinetics mechanism of CsCu2I3 during the film-forming process. The nucleation rate is manipulated by adjusting precursor supersaturation using different antisolvents, resulting in decreased density and preferential orientation of the nuclei within the wet film. Subsequent annealing leads to a homogeneous and low-defect CsCu2I3 film with 40-µm-scale spherulites. A resulting visible-blind ultraviolet photodetector exhibits a responsivity of 8.73 A W-1, a specific detectivity of 5.28 × 1012 jones, and a response speed of 1.12 ms. The unencapsulated photodetector shows negligible degradation of responsivity in ambient air (∼70% humidity) for one month. Moreover, the flexible device with a responsivity of 420.2 mA W-1 and a detectivity of 1.18 × 1012 jones also shows excellent bending stability.

Enhanced Charge Balance for Efficient Electroluminescence from Cesium Copper Halides.

Cesium copper halides have the advantages of high photoluminescence quantum efficiency and good stability, making them attractive for replacing toxic lead halides in the field of perovskite light-emitting diodes (LEDs). However, due to their shallow conduction band and the lack of electron transport layers compatible with it, it remains a great challenge to achieve charge balance in LED devices. This drawback manifests as the accumulation of holes at the interface between the emitting layer and electron transport layer, resulting in nonradiative recombination. Here, we demonstrate an effective approach to address this issue by suppressing hole injection, which is realized through modification of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) layer with polyethylenimine. This leads to cesium-copper-halide LEDs with a high external quantum efficiency of 5.6%, representing an advance in device architecture for efficient electroluminescence from cesium copper halides.

Monolithically-grained perovskite solar cell with Mortise-Tenon structure for charge extraction balance.

Although the power conversion efficiency values of perovskite solar cells continue to be refreshed, it is still far from the theoretical Shockley-Queisser limit. Two major issues need to be addressed, including disorder crystallization of perovskite and unbalanced interface charge extraction, which limit further improvements in device efficiency. Herein, we develop a thermally polymerized additive as the polymer template in the perovskite film, which can form monolithic perovskite grain and a unique "Mortise-Tenon" structure after spin-coating hole-transport layer. Importantly, the suppressed non-radiative recombination and balanced interface charge extraction benefit from high-quality perovskite crystals and Mortise-Tenon structure, resulting in enhanced open-circuit voltage and fill-factor of the device. The PSCs achieve certified efficiency of 24.55% and maintain >95% initial efficiency over 1100 h in accordance with the ISOS-L-2 protocol, as well as excellent endurance according to the ISOS-D-3 accelerated aging test.

Carrier Dynamics Determines the Optimization Strategies of Perovskite LEDs and PVs.

Metal halide perovskites have advanced greatly in both light-emitting diodes (LEDs) and photovoltaics (PVs) through delicate device engineering. The optimization strategies of perovskite LEDs and PVs have been demonstrated to be quite different. Here, we show that this dissimilarity in device fabrications can be well understood based on the analysis of carrier dynamics in LEDs and PVs.

Indirect Bandgap Emission of the Metal Halide Perovskite FAPbI3 at Low Temperatures.

In this work, we provide a picture of the band structure of FAPbI3 by investigating low-temperature spin-related photophysics. When the temperature is lower than 120 K, two photoluminescence peaks can be observed. The lifetime of the newly emerged low-energy emission is much longer than that of the original high-energy one by two orders of magnitude. We propose that Rashba effect-caused spin-dependent band splitting is the reason for the emergence of the low-energy emission and verify this using the magneto-optical measurements.

In Situ Halide Exchange of Cesium Lead Halide Perovskites for Blue Light-Emitting Diodes.

3D perovskites are promising to achieve efficient and bright deep-blue light-emitting diodes (LEDs), which are required for lighting and display applications. However, the efficiency of deep-blue 3D perovskite-based LEDs is limited by high density of defects in perovskites, and their deep-blue emission is not easy to achieve due to the halide phase separation and low solubility of chloride in precursor solutions. Here, an in situ halide exchange method is developed to achieve deep-blue 3D perovskites by spin-coating an organic halide salts solution to treat blue 3D perovskites. It is revealed that the halide-exchange process is mainly determined by halide ion diffusion targeting a concentration equalization, which leads to homogeneous 3D mixed-halide perovskites. By further introducing multifunctional organic ammonium halide salts into the exchange solution to passivate defects, high-quality deep-blue perovskites with reduced trap density can be obtained. This approach leads to efficient deep-blue perovskite LEDs with a peak external quantum efficiency (EQE) of 4.6% and a luminance of 1680 cd m-2 , which show color coordinates of (0.131, 0.055), very close to the Rec. 2020 blue standard. Moreover, the halide exchange method is bidirectional, and blue perovskite LEDs can be achieved with color coordinates of (0.095, 0.160), exhibiting a high EQE of 11.3%.