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1.
Blue light emitting two dimensional (2D) and quasi‐2D layered halide perovskites (LHPs) are gaining attention in solid‐state lighting applications but their fragile stability in humid condition is one of the most pressing issues for their practical applications. Though water is much greener and cost effective, organic solvents must be used during synthesis as well as the device fabrication process for these LHPs due to their water‐sensitivity/instability and consequently, water‐stable blue‐light emitting 2D and quasi‐2D LHPs have not been documented yet. Here, water‐mediated facile and cost‐effective syntheses, characterizations, and optical properties of 16 organic–inorganic hybrid compounds are reported including 2D (A′)2PbX4 (A′ = butylammonium, X = Cl/Br/I) (8 compounds), 3D perovskites (4), and quasi‐2D (A′)pAx?1BxX3x+1 LHPs (A = methylammonium) (4) in water. Here, both composition and dimension of LHPs are tuned in water, which has never been explored yet. Furthermore, the dual emissive nature is observed in quasi‐2D perovskites, where the intensity of two photoluminescence (PL) peaks are governed by 2D and 3D inorganic layers. The Pb(OH)2‐coated 2D and quasi‐2D perovskites are highly stable in water even after several months. In addition, single particle imaging is performed to correlate structural–optical property of these LHPs.  相似文献   

2.
Metal halide perovskites are maturing as materials for efficient, yet low cost solar cells and light‐emitting diodes, with improving operational stability and reliability. To date however, most perovskite‐based devices contain Pb, which poses environmental concerns due to its toxicity; lead‐free alternatives are of importance to facilitate the development of perovskite‐based devices. Here, the germanium‐based Ruddledsen–Popper series (CH3(CH2)3NH3)2(CH3NH3)n?1GenBr3n+1 is investigated, derived from the parent 3D (n = ∞) CH3NH3GeBr3 perovskite. Divalent germanium is a promising, nontoxic alternative to Pb2+ and the layered, 2D structure appears promising to bolster light emission, long‐term durability, and moisture tolerance. The work, which combines experiments and first principle calculations, highlights that in germanium bromide perovskites the optical bandgap is weakly affected by 2D confinement and the highly stereochemically active 4s2 lone pair preludes to possible ferroelectricity, a topic still debated in Pb‐containing compounds.  相似文献   

3.
Tin‐based perovskites have exhibited high potential for efficient photovoltaics application due to their outstanding optoelectrical properties. However, the extremely undesired instabilities significantly hinders their development and further commercialization process. A novel tin‐based reduced‐dimensional (quasi‐2D) perovskites is reported here by using 5‐ammoniumvaleric acid (5‐AVA+) as the organic spacer. It is demonstrated that by introducing appropriate amount of ammonium chloride (NH4Cl) as additive, highly vertically oriented tin‐based quasi‐2D perovskite films are obtained, which is proved through the grazing incidence wide‐angle X‐ray scattering characterization. In particular, this approach is confirmed to be a universal method to deliver highly vertically oriented tin‐based quasi‐2D perovskites with various spacers. The highly ordered vertically oriented perovskite films significantly improve the charge collection efficiency between two electrodes. With the optimized NH4Cl concentration, the solar cells employing quasi‐2D perovskite, AVA2FAn?1SnnI3n+1 (<n> = 5), as light absorbers deliver a power conversion efficiency up to 8.71%. The work paves the way for further employing highly vertically oriented tin‐based quasi‐2D perovskite films for highly efficient and stable photovoltaics.  相似文献   

4.
2D Ruddlesden–Popper perovskites (RPPs) are a class of quantum‐well (QW) materials, composed of layered perovskite QWs encapsulated between two hydrophobic organic layers. Different from widely investigated 3D‐perovskites with free carriers at room temperature, 2D‐RPPs exhibit strongly bound electron–hole pairs (excitons) for high‐performance solar cells and light emitting diodes (LEDs). Herein, it is reported that self‐organized multiple QWs in 2D‐RPP thin films naturally form an energy cascade, which enables an ultrafast energy transfer process from higher energy‐bandgap QWs to lower energy‐bandgap QWs. Therefore, photoexcitations are concentrated on lower‐bandgap QWs, facilitating the build‐up of population inversion. Room‐temperature amplified spontaneous emission (ASE) from 2D‐RPP thin films is achieved at dramatically low thresholds, with gain coefficients as high as >300 cm?1, and stoichiometrically tunable ASE wavelengths from visible to near‐infrared spectral range (530–810 nm). In view of the high efficiency reported for LEDs, these solution‐processed 2D‐RPP thin films may hold the key to realize electrically driven lasers.  相似文献   

5.
While perovskite light‐emitting diodes typically made with high work function anodes and low work function cathodes have recently gained intense interests. Perovskite light‐emitting devices with two high work function electrodes with interesting features are demonstrated here. Firstly, electroluminescence can be easily obtained from both forward and reverse biases. Secondly, the results of impedance spectroscopy indicate that the ionic conductivity in the iodide perovskite (CH3NH3PbI3) is large with a value of ≈10?8 S cm?1. Thirdly, the shift of the emission spectrum in the mixed halide perovskite (CH3NH3PbI3?xBrx) light‐emitting devices indicates that I? ions are mobile in the perovskites. Fourthly, this work shows that the accumulated ions at the interfaces result in a large capacitance (≈100 μF cm?2). The above results conclusively prove that the organic–inorganic halide perovskites are solid electrolytes with mixed ionic and electronic conductivity and the light‐emitting device is a light‐emitting electrochemical cell. The work also suggests that the organic–inorganic halide perovskites are potential energy‐storage materials, which may be applicable in the field of solid‐state supercapacitors and batteries.  相似文献   

6.
The recent rise of low‐dimensional Ruddlesden–Popper (RP) perovskites is notable for superior humidity stability, however they suffer from low power conversion efficiency (PCE). Suitable organic spacer cations with special properties display a critical effect on the performance and stability of perovskite solar cells (PSCs). Herein, a new strategy of designing self‐additive low‐dimensional RP perovskites is first proposed by employing a glycine salt (Gly+) with outstanding additive effect to improve the photovoltaic performance. Due to the strong interaction between C?O and Pb2+, the Gly+ can become a nucleation center and be beneficial to uniform and fast growth of the Gly‐based RP perovskites with larger grain sizes, leading to reduced grain boundary and increased carrier transport. As a result, the Gly‐based self‐additive low‐dimensional RP perovskites exhibit remarkable photoelectric properties, yielding the highest PCE of 18.06% for Gly (n = 8) devices and 15.61% for Gly (n = 4) devices with negligible hysteresis. Furthermore, the Gly‐based devices without encapsulation show excellent long‐term stability against humidity, heat, and UV light in comparison to BA‐based low‐dimensional PSCs. This approach provides a feasible design strategy of new‐type low‐dimensional RP perovskites to obtain highly efficient and stable devices for next‐generation photovoltaic applications.  相似文献   

7.
With respect to three‐dimensional (3D) perovskites, quasi‐two‐dimensional (quasi‐2D) perovskites have unique advantages in light‐emitting devices (LEDs), such as strong exciton binding energy and good phase stability. Interlayer ligand engineering is a key issue to endow them with these properties. Rational design principles for interlayer materials and their processing techniques remain open to investigation. A co‐interlayer engineering strategy is developed to give efficient quasi‐2D perovskites by employing phenylbutylammonium bromide (PBABr) and propylammonium bromide (PABr) as the ligand materials. Preparation of these co‐interlayer quasi‐2D perovskite films is simple and highly controllable without using antisolvent treatment. Crystallization and morphology are readily manipulated by tuning the ratio of co‐interlayer components. Various optical techniques, including steady and ultrafast transient absorption and photoluminescence spectroscopies, are used to investigate their excitonic properties. Photoluminescence quantum yield (PLQY) of the perovskite film is dramatically improved to 89% due to the combined optimization of exciton binding energy and suppression of trap state formation. Accordingly, a high current efficiency of 66.1 cd A?1 and an external quantum efficiency of 15.1% are achieved for green co‐interlayer quasi‐2D perovskite LEDs without using any light out‐coupling techniques, indicating that co‐interlayer engineering is a simple and effective approach to develop high‐performance perovskite electroluminescence devices.  相似文献   

8.
Lead halide perovskites show excellent optoelectronic properties but are unsatisfactory in terms of stability and toxicity. Herein, bismuth (Bi)‐doped lead‐free inorganic perovskites Cs2SnCl6:Bi are reported as blue emissive phosphors. Upon Bi doping, the originally nonluminous Cs2SnCl6 exhibits a highly efficient deep‐blue emission at 455 nm, with a Stokes shift of 106 nm and a high photoluminescence quantum yield (PLQY) close to 80%. Hybrid density functional theory calculations suggest the preferred formation of [BiSn+VCl] defect complex, which is believed to be responsible for the optical absorption and the associated blue emission. The Cs2SnCl6:Bi also shows impressive thermal and water stability due to its inorganic nature and the formation of protective BiOCl layer. White light‐emitting diodes (LEDs) are constructed using Cs2SnCl6:Bi and commercial yellow phosphors combined with commercial UV LED chips, giving the Commission Internationale de I'Eclairage (CIE) color coordinates of (0.36, 0.37). This work represents a significant step toward the realization of highly efficient, stable, and environmentally benign next‐generation solid‐state lighting.  相似文献   

9.
Blue fluorescent materials based on silicone end‐capped 2‐diphenylaminofluorene derivatives are synthesized and characterized. These materials are doped into a 2‐methyl‐9,10‐di‐[2‐naphthyl]anthracene host as blue dopant materials in the emitting layer of organic light‐emitting diode devices bearing a structure of ITO/DNTPD (60 nm)/NPB (30 nm)/emitting layer (30 nm)/Alq3 (20 nm)/LiF (1.0 nm)/Al (200 nm). All devices exhibit highly efficient blue electroluminescence with high external quantum efficiencies (3.47%–7.34% at 20 mA cm?2). The best luminous efficiency of 11.2 cd A?1 and highest quantum efficiency of 7.34% at 20 mA cm?2 are obtained in a device with CIE coordinates (0.15, 0.25). A deep‐blue OLED with CIE coordinates (0.15, 0.14) exhibits a luminous efficiency of 3.70 cd A?1 and quantum efficiency of 3.47% at 20 mA cm?2.  相似文献   

10.
Through first‐principles calculations, it is found that two lattice‐matched halide double‐perovskites, Cs2NaBiBr6 and Cs2AgBiBr6, have a type‐I band alignment and can form highly miscible alloys in which the disordering makes the bandgaps become direct and activates the direct transition from the valence to conduction band edge, leading to a strong optical absorption and high radiative recombination rate. The bandgaps of the alloys are tunable in a wide range of 1.93–3.24 eV, while the lattice constants remain unchanged. This advantage inspires the design of a coherent crystalline matrix based on Cs2(Na,Ag)BiBr6 alloys, in which the Ag‐rich and narrower‐bandgap regions are embedded in the Na‐rich and wide‐bandgap region with lattice‐matched and coherent interfaces. The type‐I band alignment drives the photogenerated excitons into the narrower‐bandgap Ag‐rich regions, so the regions become light‐emitting centers with a high photoluminescence quantum yield (PLQY). The bandgaps of the Ag‐rich regions are tunable, so the color of emitted light can be adjusted, making a broadband emission possible. Such kind of coherent crystalline matrix with high‐PLQY and broadband emission can also be fabricated based on the alloys of other lattice‐matched halide double‐perovskites, demonstrating the flexibility of band structure engineering in the coherent heterostructures of various halide double‐perovskites.  相似文献   

11.
Quasi‐2D metal halide perovskite films are promising for efficient light‐emitting diodes (LEDs), because of their efficient radiative recombination and suppressed trap‐assisted quenching compared with pure 3D perovskites. However, because of the multidomain polycrystalline nature of solution‐processed quasi‐2D perovskite films, the composition engineering always impacts the emitting properties with complicated mechanisms. Here, defect passivation and domain distribution of quasi‐2D perovskite films prepared with various precursor compositions are systematically studied. As a result, in perovskite films prepared from stoichiometric quasi‐2D precursor compositions, large organic ammonium cations function well as passivators. In comparison, precursor compositions of simply adding large organic halide salt into a 3D perovskite precursor ensure not only the defect passivation but also the effective formation of quasi‐2D perovskite domains, avoiding unfavorable appearance of low‐order domains. Quasi‐2D perovskite films fabricated with a well‐designed precursor composition achieve a high photoluminescence quantum yield of 95.3% and an external quantum efficiency of 14.7% in LEDs.  相似文献   

12.
A novel blue‐emitting material, 2‐tert‐butyl‐9,10‐bis[4‐(1,2,2‐triphenylvinyl)phenyl]anthracene ( TPVAn ), which contains an anthracene core and two tetraphenylethylene end‐capped groups, has been synthesized and characterized. Owing to the presence of its sterically congested terminal groups, TPVAn possesses a high glass transition temperature (155 °C) and is morphologically stable. Organic light‐emitting diodes (OLEDs) utilizing TPVAn as the emitter exhibit bright saturated‐blue emissions (Commission Internationale de L'Eclairage (CIE) chromaticity coordinates of x = 0.14 and y = 0.12) with efficiencies as high as 5.3 % (5.3 cd A–1)—the best performance of non‐doped deep blue‐emitting OLEDs reported to date. In addition, TPVAn doped with an orange fluorophore served as an authentic host for the construction of a white‐light‐emitting device that displayed promising electroluminescent characteristics: the maximum external quantum efficiency reached 4.9 % (13.1 cd A–1) with CIE coordinates located at (0.33, 0.39).  相似文献   

13.
Green‐emitting iridium dendrimers with rigid hole‐transporting carbazole dendrons are designed, synthesized, and investigated. With second‐generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87 % in solution and 45 % in a film. High‐quality films of the dendrimers are fabricated by spin‐coating, producing highly efficient, non‐doped electrophosphorescent organic light‐emitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonic acid)/neat dendrimer/1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3 % and a maximum luminous efficiency of 34.7 cd A–1 are realized. By doping the dendrimers into a carbazole‐based host, the maximum EQE can be further increased to 16.6 %. The integration of rigid hole‐transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution‐processable dendrimers for OLED applications.  相似文献   

14.
Light‐emitting diodes exhibiting efficient pure‐white‐light electroluminescence have been successfully developed by using a single polymer: polyfluorene derivatives with 1,8‐naphthalimide chromophores chemically doped onto the polyfluorene backbones. By adjusting the emission wavelength of the 1,8‐naphthalimide components and optimizing the relative content of 1,8‐naphthalimide derivatives in the resulting polymers, white‐light electroluminescence from a single polymer, as opposed to a polymer blend, has been obtained in a device with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(100 nm). The device exhibits Commission Internationale de l'Eclairage coordinates of (0.32,0.36), a maximum brightness of 11 900 cd m–2, a current efficiency of 3.8 cd A–1, a power efficiency of 2.0 lm W–1, an external quantum efficiency of 1.50 %, and quite stable color coordinates at different driving voltages, even at high luminances of over 5000 cd m–2.  相似文献   

15.
The synthesis and characterization of two new phosphorescent cationic iridium(III) cyclometalated diimine complexes with formula [Ir( L )2(N‐N)]+(PF6) ( HL = (9,9‐diethyl‐7‐pyridinylfluoren‐2‐yl)diphenylamine); N‐N = 4,4′‐dimethyl‐2,2′‐bipyridine ( 1 ), 4,7‐dimethyl‐1,10‐phenanthroline ( 2 )) are reported. Both complexes are coordinated by cyclometalated ligands consisting of hole‐transporting diphenylamino (DPA)‐ and fluorene‐based 2‐phenylpyridine moieties. Structural information on these heteroleptic complexes has been obtained by using an X‐ray diffraction study of complex 2 . Complexes 1 and 2 are morphologically and thermally stable ionic solids and are good yellow phosphors at room temperature with relatively short lifetimes in both solution and solid phases. These robust iridium complexes can be thermally vacuum‐sublimed and used as phosphorescent dyes for the fabrication of high‐efficiency organic light‐emitting diodes (OLEDs). These devices doped with 5 wt % 1 can produce efficient electrophosphorescence with a maximum brightness of up to 15 610 cd m–2 and a peak external quantum efficiency of ca. 7 % photons per electron that corresponds to a luminance efficiency of ca. 20 cd A–1 and a power efficiency of ca. 19 lm W–1. These results show that charged iridium(III) materials are useful alternative electrophosphors for use in evaporated devices in order to realize highly efficient doped OLEDs.  相似文献   

16.
Perovskite materials serve as promising candidates for display and lighting due to their excellent optical properties, including tunable bandgaps and efficient luminescence. However, their efficiency and stability must be improved for further application. In this work, quasi‐two‐dimensional (quasi‐2D) perovskites embedded in different polymers are prepared by inkjet printing to construct any luminescent patterns/pictures on the polymer substrates. The optimized quantum yield reaches over 65% by polyvinyl‐chloride‐based quasi‐2D perovskite composites. In addition, as‐fabricated perovskite?polymer composites with patterns show excellent resistance to abrasion, moisture, light irradiation, and chemical erosion by various solvents. Both quantum yield and lifetime are superior to those reported to date. These achievements are attributed to the introduction of the PEA+ cations to improve the luminance and stability of perovskite. This patterned composite can be useful for color‐conversion films with low cost and large‐scale fabrication.  相似文献   

17.
Lead-free 2D perovskites based on tin halide octahedron slabs with Dion–Jacobson (DJ) phases have drawn attention due to their improved stability; still, reports on light-emitting DJ lead-free perovskites are scarce. Herein, a room-temperature ligand assisted re-precipitation method is used to produce ODASnBr4 perovskite microcrystals (ODA denotes protonated 1,8-octanediamine). After incorporating molecular dopants chloroform and dichloromethane, not only the crystallinity of the DJ perovskite phase improves, but their emission becomes much stronger due to the formation of hydrogen bonds between [SnBr6]4− octahedra and acidic C H proton donors. ODASnBr4 microcrystals doped with these molecules show a high photoluminescence quantum yield (PLQY) approaching 90%, and their emission remains stable under a continuous UV irradiation, with less than 10% loss in intensity over 6 h. Moreover, by tuning the pristine ODASnBr4 with various degrees of exposure to the molecular dopants, the maximum of their self-trapped exciton emission can be fine-tuned over a spectral range of 570–608 nm while maintaining high PLQYs of 83–88%. This provides a convenient way to adjust the spectral position of DJ perovskite emission without changing halides or A-site spacers. Thus, stable and strongly emitting lead-free DJ perovskite materials have been developed.  相似文献   

18.
3D organic–inorganic and all‐inorganic lead halide perovskites have been intensively pursued for resistive switching memories in recent years. Unfortunately, instability and lead toxicity are two foremost challenges for their large‐scale commercial applications. Dimensional reduction and composition engineering are effective means to overcome these challenges. Herein, low‐dimensional inorganic lead‐free Cs3Bi2I9 and CsBi3I10 perovskite‐like films are exploited for resistive switching memory applications. Both devices demonstrate stable switching with ultrahigh on/off ratios (≈106), ultralow operation voltages (as low as 0.12 V), and self‐compliance characteristics. 0D Cs3Bi2I9‐based device shows better retention time and larger reset voltage than the 2D CsBi3I10‐based device. Multilevel resistive switching behavior is also observed by modulating the current compliance, contributing to the device tunability. The resistive switching mechanism is hinged on the formation and rupture of conductive filaments of halide vacancies in the perovskite films, which is correlated with the formation of AgIx layers at the electrode/perovskite interface. This study enriches the library of switching materials with all‐inorganic lead‐free halide perovskites and offers new insights on tuning the operation of solution‐processed memory devices.  相似文献   

19.
X‐Ray magnetic circular dichroism (XMCD) experiments on diluted magnetic semiconductor nanocrystals (2–7 nm) are reported in order to study their local electronic structure and magnetic properties. ZnSe nanoparticles containing either single manganese ions (Mn2+) distributed in the lattice of the entire particle or a MnSe core in the center are prepared using high temperature approaches. The Mn2+ concentration is varied between less than one to several tens of manganese ions per nanocrystal. For all samples it is shown that the Mn2+ is exclusively present in the bulk of ZnSe nanoparticles with no evidence for oxidation to higher Mn‐oxidation states. The magnetic ions are highly polarized inside the nanocrystals reaching about 80% of the theoretical value of a pure d5 state under identical conditions for the case of isolated manganese ions. Nanocrystals with a MnSe core ZnSe shell structure reach <50% of this value. Thus, their polarization is significantly more hindered, which is due to the significantly enhanced Mn–Mn interactions and a more distorted crystalline lattice. In contrast, no coupling between the manganese centers is observed in the nanoparticles doped samples with low concentrations of Mn2+, indicating that these ions are isolated in the bulk of the nanoparticles.  相似文献   

20.
For resolving toxicity issues of Pb-based perovskites, Sn-based perovskites have been widely studied as a promising alternative due to similar valence electron configuration between Sn2+ and Pb2+. However, desired Sn2+ in the precursor solution and film is easily oxidized to Sn4+, causing detrimental Sn vacancies and impurities in the films. Unfortunately, dimethyl sulfoxide, a ubiquitously used Lewis base for the fabrication of high-quality perovskite thin films via the adduct approach, further accelerates the oxidation of Sn2+ in the precursor solution. Herein, N,N′-dimethylpropyleneurea (DMPU) is proposed as an alternative Lewis base for the fabrication of high-quality Sn-based perovskite thin films. The strongly coordinating Lewis base DMPU is shown to suppress the oxidation of Sn2+ in the precursor solution while promoting growth of uniform and highly crystalline thin films. The PEA2SnI4 perovskite light emitting diode (PeLED) based on DMPU demonstrates dramatically improves luminance (L): a more than sixfold enhanced external quantum efficiency (EQE) and better operational stability than those of the device fabricated without DMPU. The optimum PeLED based on DMPU achieves a maximum L and EQE of 68.84 cd m−2 and 0.361%, respectively. This study provides an important methodological base for studying Sn perovskites for development of high-performance and eco-friendly PeLEDs.  相似文献   

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