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A cyano-based electron-accepting building block to design n-type conjugated polymers with ultra-narrow optical gap.

Quasi-two-dimensional (quasi-2D) perovskites are promising for the realization of spectrally stable pure red perovskite light-emitting diodes (PeLEDs) with a single iodide component, because they avoid the halide separation that red three-dimensional perovskites of mixed halides have faced. However, the distribution of high-order phases in solution-processed quasi-2D perovskite films causes the spectral shift away from the pure red region. Here, we introduced a simple approach of adding excessive ligand combinations to redistribute the phase distribution of quasi-2D perovskite and to inhibit the high-order phase. Appropriate excess organic ligands will not affect charge injection but will keep the efficient energy funneling and passivate the defect. The narrowed phase distribution reduced the band tail state and restrained reverse charge transfer, resulting in enhanced radiation recombination. We obtained efficient and spectrally stable pure red PeLEDs at 638 nm (approaching the Rec. 2020 specification) with a peak EQE of 11.8% and maximum luminance of 1688 cd/cm

Solution-processed quasi-two-dimensional (quasi-2D) perovskites with self-assembled multiple quantum well (QW) structures exhibit enhanced exciton binding energy, which is ideal for use as light emitters. Here, we have found that postannealing is important to promoting the QWs' composition transfer, and we explored the correlation among the annealing time, the external quantum efficiency (EQE), and the operational stability of the device. During thermal annealing, the low-n QWs will gradually convert to high-n phases, accompanied by an increase in grain size. The EQE and working stability of the device exhibit different annealing-time dependences; that is, with the extension of the annealing time, the EQE gradually decreases while the working stability improves. By introducing trimethylolpropane trimethacrylate (TPTA) to passivate the emitting-region defects, the annealing-time dependence of the EQE was effectively eliminated due to the reduction of the nonradiative recombination rate, wherefore high efficiency and stability can be achieved simultaneously. Our research provides an effective way to develop highly efficiency and stable perovskite light-emitting diodes.

Quasi-2D perovskites have demonstrated great application potential in light-emitting diodes (LEDs). Defect passivation with chemicals plays a critical role to achieve high efficiency. However, there are still challenges in comprehensively passivating the defects distributed at surface, bulk, and buried interface of quasi-2D perovskite emitting films, hindering the further improvement of device performance. Herein, 9,9-substituted fluorene derivatives with different terminal functional groups are developed tactfully to realize comprehensive passivation, which greatly contributes to reducing nonradiative recombination at surface, suppressing ion migration in bulk, and filling interfacial charge traps at buried interface, respectively. Eventually, quasi-2D perovskite LEDs have an increased external quantum efficiency from 18.2% to 23.2%, improved operation lifetime by more than six times and lower turn-on voltage simultaneously. Here the importance of comprehensive passivation is highlighted and guidelines for the design and application of passivators for perovskite optoelectronics are provided.

Continuous-wave (CW) lasing is still difficult to realize in organic laser dyes, one reason being the thermal degradation caused by intense photoexcitation. A decrease in laser threshold suppresses...

Quasi two-dimensional (2D) lead halide perovskite materials have shown outstanding performance in various photoelectric devices, including perovskite light-emitting diodes (LEDs) and perovskite optical pumping lasers. Due to the structure diversity of bulky organic cation, the photoelectric property for quasi-2D perovskite materials is flexible to be tuned. The spontaneously formed quantum-well structures allow rapid and efficient energy funneling from low-n domains to high-n domains, contributing to high exciton utilization for perovskite LEDs and low threshold for amplified spontaneous emission (ASE) and optical pumping perovskite lasers. Moreover, the hydrophobic bulky organic cations benefit to improve the environmental and operating stability owning to the better moisture tolerance and defects passivation ability. In this review, we will primarily introduce the quasi-2D lead halide perovskite materials from the structure to their optical and electrical properties. Then, we will focus on the advances of optical pumping lasers based on quasi-2D lead halide perovskite materials as gain mediums. Especially, more attention will be paid to perovskite lasers using distributed feedback (DFB) and distributed Bragg reflector (DBR) cavities. Furthermore, the key issues to realize quasi-2D perovskite-based electrical pumping lasers will be discussed.

Quasi-two dimensional perovskites demonstrate unique excitonic properties due to their multilayer structure making them attractive for various optoelectronic applications. However, the thickness of individual perovskite sheets in wet cast quasi-2D layers tends to randomly fluctuate giving rise to a specific type of disorder, which impacts on the carrier dynamics and is rather complex and remains understudied. Here, we present a study of carrier transport in Ruddlesden–Popper type (PEA)2FAn−1PbnBr3n+1 layers of order n from one to four, and in the bulk FAPbBr3 layer. We use a light induced transient grating technique to measure the carrier diffusion coefficient directly, and the transient absorption via photoluminescence to investigate the energy relaxation pathways. We observe two distinct energy transfer processes on different time scales. Fast energy funnelling in thicker (n ≥ 3) layers is observed up to 10 ps after excitation; we attribute this to short-distance transfer of excitons to neighbouring perovskite sheets of higher order. On the longer timescale of hundreds of picoseconds, carrier in-plane transport is governed by exciton diffusion in n = 1 and 2 layers and by free carrier plasma in thicker ones. Within the carrier density range of (0.5–4) × 1019 cm−3, the exciton diffusion coefficient in n = 1, 2 increases slowly from 1 to 2.8 cm2 s−1, whereas in thicker layers the dependence is much stronger and the diffusivity grows from 0.09 to 1.9 cm2 s−1. We explain these dependencies by a higher structural order in the thinner samples and the stronger localization of carriers in thicker ones. Also, amplified spontaneous emission (ASE) is observed in thicker (n ≥ 3) layers in electron–hole plasma, as evidenced by the typical ASE line redshift upon excitation.

Organic–inorganic lead halide quasi-two-dimensional (2D) perovskites are promising gain media for lasing applications because of their low cost, tunable colour, excellent stability and solution processability1–3. Optically pumped continuous-wave (CW) lasing is highly desired for practical applications in high-density integrated optoelectronics devices and constitutes a key step towards electrically pumped lasers4–6. However, CW lasing has not yet been realized at room temperature because of the ‘lasing death’ phenomenon (the abrupt termination of lasing under CW optical pumping), the cause of which remains unknown. Here we study lead halide-based quasi-2D perovskite films with different organic cations and observe that long-lived triplet excitons considerably impede population inversion during amplified spontaneous emission and optically pumped pulsed and CW lasing. Our results indicate that singlet–triplet exciton annihilation is a possible intrinsic mechanism causing lasing death. By using a distributed-feedback cavity with a high quality factor and applying triplet management strategies, we achieve stable green quasi-2D perovskite lasers under CW optical pumping in air at room temperature. We expect that our findings will pave the way to the realization of future current-injection perovskite lasers. Lead halide-based quasi-two-dimensional perovskite films with different organic cations are used to create stable green lasers under continuous-wave optical pumping in air at room temperature.

Perovskites show exciting potential for photoelectric applications, especially for light-emitting diodes (LEDs), owing to their intrinsically high photoluminescence efficiency and color purity. Wit...

Halide perovskites are currently intensively being investigated for applications in light-emitting diodes for next-generation lighting and display technology. A recent report shows that the control...

Additives play a critical role for efficient perovskite light-emitting diodes (PeLEDs). Here, we report a novel phosphonate/phosphine oxide dyad molecular additive (PE-TPPO), with unique dual roles of passivating defects and enhancing carrier radiative recombination, to boost the device efficiency of metal-halide perovskites. In addition to the defect passivation effect of the phosphine oxide group to enhance the photoluminescence intensity and homogeneity of perovskite film, the phosphonate group with strong electron affinity can capture the injected electrons to increase local carrier concentration and accelerate the carrier radiative recombination in the electroluminescence process. Owing to their synergistic enhancement on device efficiency, quasi-two-dimensional green PeLEDs modified by this dyad additive exhibit a maximum external quantum efficiency, current efficiency, and power efficiency of 25.1 %, 100.5 cd A

Emission thermal quenching is commonly observed in quasi-2D perovskite emitters, which causes the severe drop in luminescence efficiency for the quasi-2D perovskite light-emitting diodes (PeLEDs) during practical operations. However, this issue is often neglected and rarely studied, and the root cause of the thermal quenching has not been completely revealed now. Here, we develop a passivation strategy via the 2,7-dibromo-9,9-bis (3′-diethoxylphosphorylpropyl)-fluorene to investigate and suppress the thermal quenching. The agent can effectively passivate coordination-unsaturated Pb2+ defects of both surface and bulk of the film without affecting the perovskite crystallization, which helps to more truly demonstrate the important role of defects in thermal quenching. And our results reveal the root cause that the quenching will be strengthened by the defect-promoted exciton-phonon coupling. Ultimately, the PeLEDs with defect passivation achieve an improved external quantum efficiency (EQE) over 22% and doubled operation lifetime at room temperature, and can maintain about 85% of the initial EQE at 85 °C, much higher than 17% of the control device. These findings provide an important basis for fabricating practical PeLEDs for lighting and displays.

Organic light-emitting diode (OLED) technology is promising for applications in next-generation displays and lighting. However, it is difficult-especially in large-area mass production-to cover a large substrate uniformly with organic layers, and variations in thickness cause the formation of shunting paths between electrodes1,2, thereby lowering device production yield. To overcome this issue, thicker organic transport layers are desirable because they can cover particles and residue on substrates, but increasing their thickness increases the driving voltage because of the intrinsically low charge-carrier mobilities of organics. Chemical doping of organic layers increases their electrical conductivity and enables fabrication of thicker OLEDs3,4, but additional absorption bands originating from charge transfer appear5, reducing electroluminescence efficiency because of light absorption. Thick OLEDs made with organic single crystals have been demonstrated6, but are not practical for mass production. Therefore, an alternative method of fabricating thicker OLEDs is needed. Here we show that extraordinarily thick OLEDs can be fabricated by using the organic-inorganic perovskite methylammonium lead chloride, CH3NH3PbCl3 (MAPbCl3), instead of organics as the transport layers. Because MAPbCl3 films have high carrier mobilities and are transparent to visible light, we were able to increase the total thickness of MAPbCl3 transport layers to 2,000 nanometres-more than ten times the thickness of standard OLEDs-without requiring high voltage or reducing either internal electroluminescence quantum efficiency or operational durability. These findings will contribute towards a higher production yield of high-quality OLEDs, which may be used for other organic devices, such as lasers, solar cells, memory devices and sensors.

Tin iodide perovskite CH3NH3SnI3 is often considered as a replacement for toxic lead halide perovskites. Tin iodide is not only suitable for production of solar cells, but also it emits in the near...

Heat management of optoelectronic devices is of critical significance in lead halide perovskites due to the intrinsically low thermal conductivity of this material. Despite its importance, thermal conductivity remains understudied, particularly in polycrystalline perovskite layers with different halides. Here, we employ a novel method for investigation of thermal properties in perovskite layers, which is based on a light-induced transient diffraction grating technique. We demonstrate the applicability of thermal grating technique by determining in an all-optical way the thermo-optic coefficient, speed of sound, and thermal conductivity in vapor-deposited polycrystalline layers of MAPbX3 (X = Cl, Br, I), MAPbBr2I, and MAPbCl2Br perovskites. We reveal the spatial anisotropy of thermal conductivity, which is noticeably lower in the direction along the layer surface (0.2–0.5 W/(m K)) if compared to that across the layer (0.3–1.1 W/(m K)). Finally, we demonstrate that for both directions the thermal conductivi...

This work investigates the feasibility of using low-dimensional perovskites for electrically driven lasers given the current status of perovskite light-emitting diodes and optically pumped lasers. ...

The current status of electrochemical impedance spectroscopy (EIS) and related analysis on perovskite solar cells (PSC) is still unsatisfactory. The provided models are still vague and not really helpful for guiding the efforts to develop more efficient and stable devices. Due to the slow and complex dynamics of these devices, the obtained spectra need to be validated, which is hardly ever done. This study may be the first to provide fully validated impedance spectra and presents reproducible EIS time series at open circuit voltage (VOC) for more than 20 hours, with a total of 140 analysed spectra. We conclude that the observed changes stem from a temporary reduction of the electronically active area of the devices, as can be deduced from the inverse behaviour of resistance and capacitance. The changes in these values are almost 100% reversible if the devices are kept in the dark for only one day, while the time constant of the high-frequency process remains unchanged throughout the whole characterization procedure. The tested devices are full PSC devices that have proven to be stable over more than 500 hours, and the non-steady impedance measurements shine a critical light on previously published EIS data. With the results of this study, it can be rationalized that the high-frequency semicircle can serve as a good indicator for ionic migration by monitoring its consequences. The results presented here are helpful to quantify ionic migration on the device level in order to derive new stability criteria and countermeasures against degradation.

Organic-inorganic lead halide quasi-two-dimensional (2D) perovskites are promising gain media for lasing applications because of their low cost, tunable colour, excellent stability and solution processability

Carrier mobility is one of the crucial parameters determining the electronic device performance. We apply the light-induced transient grating technique to measure independently the carrier diffusion coefficient and lifetime, and to reveal the impact of additives on carrier transport properties in wet-cast CH3NH3PbI3 (MAPbI3) perovskite films. We use the high excitation regime, where diffusion length of carriers is controlled purely by carrier diffusion and not by the lifetime. We demonstrate a four-fold increase in diffusion coefficient due to the reduction of localization center density by additives; however, the density dependence analysis shows the dominance of localization-limited diffusion regime. The presented approach allows us to estimate the limits of technological improvement—carrier diffusion coefficient in wet-cast layers can be expected to be enhanced by up to one order of magnitude.

In this study, we investigate the nanoscale effects of photochemically active additives of benzoquinone (BQ), hydroquinone (HQ), and tetracyanoquinodimethane (TCNQ) on grain boundaries in CH3NH3PbI3 solar cells. We employ scanning probe microscopy under light illumination, in particular Kelvin probe force microscopy, to study surface potential changes under laser light illumination. The recently found improvement in the efficiency of BQ added solar cells can be clearly seen in vanishing contact potential differences at grain boundaries under illumination, rendering the material more uniform under solar cell operating conditions. These effects are observed for BQ, but not for HQ and TCNQ. Our findings shed light onto halide perovskite materials and the functional additive design for improved solar cell performance.

Dye sensitized solar cells (DSSCs) were co-sensitized with three custom molecularly engineered organic dyes containing butyloxyl chain induced dye (Y1), boron dipyrromethene (bodipy) dye (TP2A), and squaraine (SQ) ring configured dye (HSQ4). The individual power conversion efficiencies of the DSSCs sensitized with Y1, TP2A and HSQ4 sensitizers were 3.44%, 4.26% and 5.78%, respectively. Co-sensitized TP2A + HSQ4 dyes at a 2 : 1 molar ratio showed an efficiency of 7.02%. Further addition of Y1 dye with optimal TP2A + HSQ4 increased the VOC from 0.580 V to 0.605 V. The co-sensitized Y1 + TP2A + HSQ4 based DSSCs showed a new optimal efficiency (η) of 7.48%. This is the highest efficiency recorded for DSSCs based on co-sensitization of triple organic dyes. Intensity modulated photovoltage spectroscopy further confirms the longer lifetime of co-sensitized Y1 + TP2A + HSQ4 compared to that of each individual TP2A and HSQ4 and co-sensitized TP2A + HSQ4 dye.

Organo-metal-halide perovskites are a promising set of materials for optoelectronic applications such as solar cells, light emitting diodes and lasers. Perovskite thin films have demonstrated amplified spontaneous emission thresholds as low as 1.6 μJ cm-2 and lasing thresholds as low as 0.2 μJ cm-2. Recently the performance of perovskite light emitting diodes has rapidly risen due to the formation of quasi 2D films using bulky ligands such as phenylethylammonium. Despite the high photoluminescent yield and external quantum efficiency of quasi 2D perovskites, few reports exist on amplified spontaneous emission. We show within this report that the threshold for amplified spontaneous emission of quasi 2D perovskite films increases with the concentration of phenylethylammonium. We attribute this increasing threshold to a charge transfer state at the PEA interface that competes for excitons with the ASE process. Additionally, the comparatively slow inter-grain charge transfer process cannot significantly contribute to the fast radiative recombination in amplified spontaneous emission. These results suggest that relatively low order PEA based perovskite films that are suitable for LED applications are not well suited for lasing applications. However high order films were able to maintain their low threshold values and may still benefit from improved stability.

The optical, structural, and electroluminescent (EL) characteristics of pure quasi-2D CsPb2Br5 were reported. We fabricated continuous, compact, well-crystallized CsPb2Br5 films by centrifugal coating from a colloidal solution containing CsPb2Br5 nanoparticles. The centrifugal-coated CsPb2Br5 films have a photoluminescence quantum yield (PLQY) of ∼35% because of its low-dimensional structure. Taking advantage of the high PLQY, we fabricated perovskite light-emitting diodes (PeLEDs) with a centrifugal-coated CsPb2Br5 emitting layer exhibiting bright green EL, a maximum luminance of 7317 cd m–2, an and external quantum efficiency of 1.1%. Additionally, the EL color could be changed easily from green to red using a halogen exchange method. The half lifetime of our CsPb2Br5 PeLEDs reached around 6 h under continuous operation at 10 mA cm–2.

Metal halide perovskites are attractive materials for the realization of cheap and effective solar cells, thin film transistors, and light emitters. Carrier diffusion at high excitations, however, is poorly addressed in perovskites, even though it governs the diffusion length and determines the efficiency of photonic devices. To fully understand the dependence of diffusion length on carrier density, we performed direct and independent measurements of the carrier diffusion coefficient and recombination rate in several methylammonium lead-halide perovskite layers by applying the light-induced transient grating technique. We demonstrate the existence of two distinct carrier diffusion regimes within the density range of 1018–1020 cm–3. In the perovskite films of high compositional quality, diffusion is governed by a bandlike transport of free carriers. The diffusivity is high (0.28–0.7 cm2/s) in these samples, even at low carrier density, and further increases with excitation due to carrier degeneracy. The op...

Organo-lead-halide perovskites are promising materials for optoelectronic applications. Perovskite solar cells have reached power conversion efficiencies of over 22%, and perovskite light-emitting diodes have recently achieved over 11% external quantum efficiency. To date, most research on perovskite light-emitting diodes has focused on solution-processed films. There are many advantages of a vapor-based growth process to prepare perovskites, including ease of patterning, ability to batch process, and material compatibility. We investigated an all-vapor perovskite growth process by chemical vapor deposition and demonstrated luminance up to 560 cd/m2.

Perovskite light-emitting diodes are promising for next-generation lighting and displays because of their high colour purity and performance1. Although the management of singlet and triplet excitons is fundamental to the design of efficient organic light-emitting diodes, the nature of how excitons affect performance is still not clear in perovskite2–4 and quasi-two-dimensional (2D) perovskite-based devices5–9. Here, we show that triplet excitons are key to efficient emission in green quasi-2D perovskite devices and that quenching of triplets by the organic cation is a major loss path. Employing an organic cation with a high triplet energy level (phenylethylammonium) in a quasi-2D perovskite based on formamidinium lead bromide yields efficient harvesting of triplets. Furthermore, we show that upconversion of triplets to singlets can occur, making 100% harvesting of electrically generated excitons potentially possible. The external quantum and current efficiencies of our green (527 nm) devices reached 12.4% and 52.1 cd A−1, respectively. Careful harvesting of triplet excitons allows the realization of efficient green-emitting quasi-2D perovskite LEDs.

Excess/unreacted lead iodide (PbI

In article number 1801079, Chuanjiang Qin, Chihaya Adachi, and co‐workers adopt thermally stimulated current and electrochemical impedance spectroscopy measurements to reveal that carrier traps are generated in solar cells with CH3NH3PbI3 as a light absorber after operation at 85°C, which is higher than its phase transition temperature. Perovskite alloys‐based solar cells with improved thermal stability under a standard thermal cycling test are demonstrated.

A very high hole mobility of 15 cm2 V-1 s-1 along with negligible hysteresis are demonstrated in transistors with an organic-inorganic perovskite semiconductor. This high mobility results from the well-developed perovskite crystallites, improved conversion to perovskite, reduced hole trap density, and improved hole injection by employing a top-contact/top-gate structure with surface treatment and MoOx hole-injection layers.

We demonstrate that double spin coating, where a perovskite film is covered with another perovskite film, can increase substrate coverage from 81% to 97% along with an increase of film thickness from 151 ± 17 to 246 ± 18 nm. The increased substrate coverage by double coating improves the solar power conversion efficiency from 7.1 ± 0.6 to 10.3 ± 1.0%, an approximate 1.5-fold increase. Additionally, a double-coated film of higher substrate coverage exhibits amplified spontaneous emission (ASE) while a single-coated film of lower substrate coverage does not exhibit ASE. Double coating is an attractive method for increasing substrate coverage and improving solar power conversion and ASE.

Excess/unreacted lead iodide (PbI2 ) has been commonly used in perovskite films for the state-of-the-art solar cell applications. However, an understanding of intrinsic degradation mechanisms of perovskite solar cells (PSCs) containing unreacted PbI2 has been still insufficient and, therefore, needs to be clarified for better operational durability. Here, it is shown that degradation of PSCs is hastened by unreacted PbI2 crystals under continuous light illumination. Unreacted PbI2 undergoes photodecomposition under illumination, resulting in the formation of lead and iodine in films. Thus, this photodecomposition of PbI2 is one of the main reasons for accelerated device degradation. Therefore, this work reveals that carefully controlling the formation of unreacted PbI2 crystals in perovskite films is very important to improve device operational stability for diverse opto-electronic applications in the future.