Ammonium Sulfate to Modulate Crystallization for High-Performance Rigid and Flexible Perovskite Solar Cells.

Perovskite solar cells (PSCs) are attracting widespread research and attention as highly promising candidates in the field of electronic photovoltaics owing to their exceptional power conversion efficiency (PCE). However, rigid or flexible PSCs still face challenges in preparing full-coverage and low-defect perovskite films, as well as achieving highly reproducible and highly stable devices. Herein, a multifunctional additive 2-aminoethyl hydrogen sulfate (AES) is designed to regulate the film crystallization and thereby form flat and pinhole-free perovskite films. It is found that the introduction of AES can effectively passivate defects, restrain charge carrier recombination, and then achieve a higher fill factor. As seen with grazing incidence wide-angle X-ray scattering (GIWAXS), this approach does not affect the crystal orientation distribution. It is observed that AES addition shows a universality across different perovskite components since the PCE is improved up to 20.7% for FA0.97MA0.03Pb(I0.97Br0.03)3-AES, 22.85% for Cs0.05FA0.95PbI3-AES, 22.23% for FAPbI2.7Br0.3-AES, and 23.32% for FAPI-AES rigid devices. Remarkably, the non-encapsulated flexible Cs0.05 (FA0.85MA0.15)0.95Pb(I0.85Br0.15)3 device with AES additive delivers a PCE of 20.1% and maintains over 97% of its initial efficiency under ambient conditions (25 ± 5% relative humidity) over 2280 h of aging.

Multidentate Molecule Anchoring Halide Perovskite Surface and Regulating Crystallization Kinetics toward Efficient Light-Emitting Diodes.

Functional passivators are conventionally utilized in modifying the crystallization properties of perovskites to minimize the non-radiative recombination losses in perovskite light-emitting diodes (PeLEDs). However, the weak anchor ability of some commonly adopted molecules has limited passivation ability to perovskites and even may desorb from the passivated defects in a short period of time, which bring about plenty of challenges for further development of high-performance PeLEDs. Here, a multidentate molecule, formamidine sulfinic acid (FSA), is introduced as a novel passivator to perovskites. FSA has multifunctional groups (S≐O, C≐N and NH2 ) where the S≐O and C≐N groups enable coordination with the lead ions and the NH2 interacts with the bromide ions, thus providing the most effective chemical passivation for defects and in turn the formation of highly stable perovskite emitters. Moreover, the interaction between the FSA and octahedral [PbBr6 ]4- can inhibit the formation of unfavorable low-n domains to further minimize the inefficient energy transfer inside the perovskite emitters. Therefore, the FSA passivated green-emitting PeLED exhibits a high external quantum efficiency (EQE) of 26.5% with fourfold enhancement in operating lifetime as compared to the control device, consolidating that the multidentate molecule is a promising strategy to effectively and sustainably passivate the perovskites.

Highly Efficient Luminescence from a Red Thermally Activated Delayed Fluorescence Emitter with Flexible Conformation of Ancillary Groups.

Robust scaffolds were typically applied in thermally activated delayed fluorescence (TADF) molecules to suppress the non-radiative decay, trigger the fast spin-flipping, and enhance the light out-coupling efficiency. Herein, we disclosed for the first time the positive effect of flexible conformation of ancillary groups on the photophysical properties of TADF emitter. The red TADF emitter Ph-TPA with flexible conformation demonstrated small excited-state structural distortion and low reorganization energy compared to the counterpart Mc-TPA with a rigid macrocycle. Consequently, Ph-TPA showed an excellent photoluminescent quantum yield (PLQY) of 92 % and a state-of-the-art external quantum efficiency (EQE) of 30.6 % at 630 nm. This work could deepen our understanding of structure-property relationships of organic luminophores and help us to rationalize the design of efficient TADF materials.

Hybrid Passivated Red Organic LEDs with Prolonged Operation and Storage Lifetime.

In addition to mobile and TV displays, there is a trend of organic LEDs being applied in niche markets, such as microdisplays, automobile taillights, and photobiomodulation therapy. These applications mostly do not require to be flexible in form but need to have long operation lifetimes and storage lifespans. Using traditional glass encapsulation may not be able to fulfill the rigorous product specification, and a hybrid encapsulation method by combining glass and thin-film encapsulation will be the solution. Conventional thin-film encapsulation technology generally involves organic and inorganic multilayer films that are thick and have considerable stress. As a result, when subjected to extreme heat and stress, the film easily peels off. Herein, the water vapor transmission rate (WVTR) of a 2 µm silicon nitride film prepared at 85 °C is less than 5 × 10-5 g/m2/day and its stress is optimized to be 23 MPa. Red organic LEDs are passivated with the hybrid encapsulation, and the T95 lifetime reaches nearly 10 years if the LED is continuously driven at an initial luminance of 1000 cd/m2. In addition, a storage lifespan of over 17 years is achieved.

All-Inorganic Quantum-Dot LEDs Based on a Phase-Stabilized α-CsPbI3 Perovskite.

The all-inorganic nature of CsPbI3 perovskites allows to enhance stability in perovskite devices. Research efforts have led to improved stability of the black phase in CsPbI3 films; however, these strategies-including strain and doping-are based on organic-ligand-capped perovskites, which prevent perovskites from forming the close-packed quantum dot (QD) solids necessary to achieve high charge and thermal transport. We developed an inorganic ligand exchange that leads to CsPbI3 QD films with superior phase stability and increased thermal transport. The atomic-ligand-exchanged QD films, once mechanically coupled, exhibit improved phase stability, and we link this to distributing strain across the film. Operando measurements of the temperature of the LEDs indicate that KI-exchanged QD films exhibit increased thermal transport compared to controls that rely on organic ligands. The LEDs exhibit a maximum EQE of 23 % with an electroluminescence emission centered at 640 nm (FWHM: ≈31 nm). These red LEDs provide an operating half-lifetime of 10 h (luminance of 200 cd m-2 ) and an operating stability that is 6× higher than that of control devices.

Dispirocycles: Platforms for the Construction of High-Performance Host Materials for Phosphorescent Organic Light-Emitting Diodes.

Spirocyclic compounds such as 9,9'-spirobifluorene (SBF) are becoming more and more attractive for use as host materials in organic optoelectronic devices. Herein, two dispirocycles, namely, dispiro[fluorene-9,9'-anthracene-10',9''-fluorene] and 10,10''-diphenyl-10H,10''H-dispiro[acridine-9,9'-anthracene-10',9''-acridine], were used for the construction of host materials 1-4. The attached triphenylamino group determines the thermal, photophysical, electrochemical, and charge-transport properties, and therefore they have different electroluminescent performances. The device based on dispiro[fluorene-9,9'-anthracene-10',9''-fluorene] (2) and 10,10''-diphenyl-10H,10''H-dispiro[acridine-9,9'-anthracene-10',9''-acridine] (3) molecular platforms exhibited external quantum efficiencies of greater than 21 % with a very high power efficiency (≈100 lm W-1 ). These results demonstrate the potential of extending the application of dispirocyclic molecular platforms with inherent rigidity for developing highly efficient host materials for organic light-emitting diodes.

Deep-Blue and Hybrid-White Organic Light Emitting Diodes Based on a Twisting Carbazole-Benzofuro[2,3-b]Pyrazine Fluorescent Emitter.

A novel deep-blue fluorescent emitter was designed and synthesized. The external quantum efficiency (ηEQE) of the blue-emitting, doped, organic light-emitting diode (OLED) was as high as 4.34%. The device also exhibited an excellent color purity with Commission Internationale de l'Eclairage (CIE) coordinates of x = 0.15 and y = 0.05. In addition, the triplet energy had a value of 2.7 eV, which is rare for an emitter with deep-blue emission, which makes it a preferred choice for high-performance white OLEDs. By optimizing the device architectures, the color of hybrid-white OLEDs could be tunable from warm white to cool white using the aforementioned material as a bifunctional material. That is, the ηEQE of the hybrid warm-white OLED is 20.1% with a CIE x and y of 0.46 and 0.48 and the ηEQE of the hybrid cool-white OLED is 9% with a CIE x and y of 0.34 and 0.33.

Management of Exciton for Highly-Efficient Hybrid White Organic Light-Emitting Diodes with a Non-Doped Blue Emissive Layer.

Hybrid white organic light-emitting diodes (WOLEDs) have drawn great attention both for display and solid-state lighting purposes because of the combined advantages of desirable stability of fluorescent dyes and high efficiency of phosphorescent materials. However, in most WOLEDs, obtaining high efficiency often requires complex device structures. Herein, we achieved high-efficiency hybrid WOLEDs using a simple but efficacious structure, which included a non-doped blue emissive layer (EML) to separate the exciton recombination zone from the light emission region. After optimization of the device structure, the WOLEDs showed a maximum power efficiency (PE), current efficiency (CE), and external quantum efficiency (EQE) of 82.3 lm/W, 70.0 cd/A, and 22.2%, respectively. Our results presented here provided a new option for promoting simple-structure hybrid WOLEDs with superior performance.

A Novel Linking Strategy of Using 9,10-Dihydroacridine to Construct Efficient Host Materials for Red Phosphorescent Organic Light-Emitting Diodes.

Three novel 9,10-dihydroacridine derivatives, 4'-(10-methyl-9,9-diphenyl-9,10-dihydroacridin-4-yl)[1,1'-biphenyl]-4-carbonitrile (MeAcPhCN), 4'-(9,9,10-triphenyl-9,10-dihydroacridin-4-yl)[1,1'-biphenyl]-4-carbonitrile (PhAcPhCN), and 5-[4-(9,9,10-triphenyl-9,10-dihydroacridin-4-yl)phenyl]picolinonitrile (MeAcPyCN), were prepared by the attachment of [1,1'-biphenyl]-4-carbonitrile or 5-phenylpicolinonitrile to the 4-position of 9,10-dihydroacridine. This special linking strategy limited the conjugation length, maintained the triplet energy, and inhibited the intermolecular charge-transfer (ICT) characteristics of these compounds. Notably, the enhanced accepting strength of the picolinonitrile segment relative to that of benzonitrile led to relatively strong ICT characteristics, a low energy gap, and a low triplet energy for MeAcPyCN. The thermal, photophysical, electrochemical, and electroluminescent properties of these host materials were studied systematically. Consequently, (acetylacetonato)bis(2-methyldibenzo[f,h]quinoxaline)iridium(III) [Ir(MDQ)2 (acac)]-based red phosphorescent organic light-emitting diodes (PHOLEDs) were fabricated with these three host materials. As a result, the device hosted by MeAcPhCN showed good device performance with a maximum external quantum efficiency of 20.5 %.

Stable Enantiomers Displaying Thermally Activated Delayed Fluorescence: Efficient OLEDs with Circularly Polarized Electroluminescence.

Aromatic-imide-based thermally activated delayed fluorescent (TADF) enantiomers, (+)-(S,S)-CAI-Cz and (-)-(R,R)-CAI-Cz, were efficiently synthesized by introducing a chiral 1,2-diaminocyclohexane to the achiral TADF unit. The TADF enantiomers exhibited high PLQYs of up to 98 %, small ΔEST  values of 0.06 eV, as well as obvious temperature-dependent transient PL spectra, thus demonstrating their excellent TADF properties. Moreover, the TADF enantiomers showed mirror-image CD and CPL activities. Notably, the CP-OLEDs with CPEL properties based on the TADF enantiomers not only achieved high EQE values of up to 19.7 and 19.8 %, but also displayed opposite CPEL signals with gEL  values of -1.7×10-3 and 2.3×10-3 , which represents the first CP-OLEDs, based on the enantiomerically pure TADF materials, having both high efficiencies and intense CPEL.

Charge transport dependent high open circuit voltage tandem organic photovoltaic cells with low temperature deposited HATCN-based charge recombination layers.

Mechanisms of charge transport between the interconnector and its neighboring layers in tandem organic photovoltaic cells have been systematically investigated by studying electronic properties of the involving interfaces with photoelectron spectroscopies and performance of the corresponding devices. The results show that charge recombination occurs at HATCN and its neighboring hole transport layers which can be deposited at low temperature. The hole transport layer plays an equal role to the interconnector itself. These insights provide guidance for the identification of new materials and the device architecture for high performance devices.

Enhancing Light Outcoupling Efficiency via Anisotropic Low Refractive Index Electron Transporting Materials for Efficient Perovskite Light-Emitting Diodes.

Thanks to the extensive efforts toward optimizing perovskite crystallization properties, high-quality perovskite films with near-unity photoluminescence quantum yield are successfully achieved. However, the light outcoupling efficiency of perovskite light-emitting diodes (PeLEDs) is impeded by insufficient light extraction, which poses a challenge to the further advancement of PeLEDs. Here, an anisotropic multifunctional electron transporting material, 9,10-bis(4-(2-phenyl-1H-benzo[d]imidazole-1-yl)phenyl) anthracene (BPBiPA), with a low extraordinary refractive index (ne) and high electron mobility is developed for fabricating high-efficiency PeLEDs. The anisotropic molecular orientations of BPBiPA can result in a low ne of 1.59 along the z-axis direction. Optical simulations show that the low ne of BPBiPA can effectively mitigate the surface plasmon polariton loss and enhance the photon extraction efficiency in waveguide mode, thereby improving the light outcoupling efficiency of PeLEDs. In addition, the high electron mobility of BPBiPA can facilitate balanced carrier injection in PeLEDs. As a result, high-efficiency green PeLEDs with a record external quantum efficiency of 32.1% and a current efficiency of 111.7 cd A-1 are obtained, which provides new inspirations for the design of electron transporting materials for high-performance PeLEDs.

Using azaacene as an acceptor unit to construct an ultraefficient red fluorophore with an EQE over 40.

Azaacenes, which have been known for a long time, are of scientific and practical importance in organic electronics. Azaacenes once shone as the luminophore in organic light-emitting diodes (OLEDs). However, due to the low exciton utilization efficiency and/or the aggregation induced quenching (ACQ) effect, N-heteroacene based OLEDs generally showed inferior device performance. In this work, azaacene has been revisited and applied as an acceptor for a red fluorophore (AZA-TPA), where the judicious connection pattern between donor and acceptor maximized the harvest of singlet and triplet excitons, resulting in a high photoluminescence efficiency of 94.6% in doped films (3 wt%). In addition, the linearly-fused polycyclic structure contributed to a high horizontal emitting dipole ratio (Θ‖ = 90%). As a result, an AZA-TPA-based OLED achieved an unprecedented external quantum efficiency of 41.30% at 610 nm. This work will pave a new path for the development of efficient N-heteroacene-based fluorophores.

Intramolecular charge transfer effect for highly efficient deep red and near infrared thermally activated delayed fluorescence.

Thermally activated delayed fluorescence (TADF) materials with emission in the deep red and near infrared (DR/NIR) region are underresearched due to the limited choice of strong donor/acceptor units. The current mainstream strategy for the design of DR/NIR TADFs is to increase the acceptor strength via the introduction of multiple sub-acceptor units, thereby narrowing the bandgap. In this work, the intramolecular charge transfer (ICT) effect was applied for the development of acceptor units to achieve efficient DR/NIR TADFs. The ICT effect within the acceptor unit enhanced the π-electron delocalization, lowered the LUMO and redshifted the emission wavelength. In addition, the fusion of the donor unit into the planar acceptor skeleton rigidified the molecular structure and reduced the non-radiative decay. This proof-of-concept study demonstrated that ICT is an undoubtedly effective strategy for the rational design of efficient DR/NIR TADFs.

In Situ Inorganic Ligand Replenishment Enables Bandgap Stability in Mixed-Halide Perovskite Quantum Dot Solids.

Instability in mixed-halide perovskites (MHPs) is a key issue limiting perovskite solar cells and light-emitting diodes (LEDs). One form of instability arises during the processing of MHP quantum dots using an antisolvent to precipitate and purify the dots forming surface traps that lead to decreased luminescence, compromised colloidal stability, and emission broadening. Here, the introduction of inorganic ligands in the antisolvents used in dot purification is reported in order to overcome this problem. MHPs that are colloidally stable for over 1 year at 25 °C and 40% humidity are demonstrated and films that are stable under 100 W cm-2 photoirradiation, 4× longer than the best previously reported MHPs, are reported. In LEDs, the materials enable an EQE of 24.4% (average 22.5 ± 1.3%) and narrow emission (full-width at half maximum of 30 nm). Sixfold-enhanced operating stability relative to the most stable prior red perovskite LEDs having external quantum efficiency >20% is reported.

Positive impact of chromophore flexibility on the efficiency of red thermally activated delayed fluorescence materials.

Rigid electron donors (D) and acceptors (A) have been widely used in recent years for the construction of D-A type thermally activated delayed fluorescence (TADF) materials. However, the chromophore robustness does not always make a positive contribution to the high efficiency of TADF materials. Here, the comparison study of two D-A type red TADF compounds (PT-TPA and PT-Az) demonstrated, for the first time, the positive impact of chromophore flexibility on the efficiency of TADF materials. In PT-Az, the rotation of terminal phenyl groups is restrained by an ethylene linker, leading to its inferior photoluminescence quantum yield (PLQY). In contrast, PT-TPA with free rotation of the phenyl groups showed a low reorganization energy and a large transition dipole moment for the S1→ S0 transition, which resulted in a high fluorescence radiative decay rate. As a result, the optimized devices based on PT-TPA gave a maximum external quantum efficiency (EQE) of 29.7% (632 nm) when doped in a single host and an EQE of 28.8% (648 nm) in an exciplex host. This study provided an insight into the impact of chromophore flexibility on the photophysical properties and device efficiency of TADF materials, and these results may provide valuable guidance for the molecular design of efficient emitters.

Four-Coordinate Organoboron Platforms for Efficient Red Phosphorescent Organic Light-Emitting Diodes.

So far both three- and four-coordinate organoboron compounds have been widely applied in organic light-emitting diode (OLED) materials. However, the use of four-coordinate organoboron compounds as host materials is rarely reported. In this work, two new four-coordinate organoboron compounds, namely 8-(4-(9H-carbazol-9-yl)phenyl)-6,6-difluoro-6H-6λ4 ,7λ4 -benzo[4',5']imidazo[1',2':3,4][1,3,2]diazaborolo[1,5-a]pyridine (B1PCz) and 8-(3-(9H-carbazol-9-yl)phenyl)-6,6-difluoro-6H-6λ4 ,7λ4 -benzo[4',5']imidazo[1',2':3,4][1,3,2]diazaborolo[1,5-a]pyridine (B1MCz), were successfully designed, synthesized, and fully characterized. The red OLEDs using B1PCz and B1MCz as host materials achieved relatively high device performance with a maximum external quantum efficiency of 14.8 % and 11.8 %, respectively. These results will expand the scope of organoboron compounds for OLED materials and reveal the great potential of four-coordinate organoboron materials.

Design and Synthesis of Donor-σ-π-σ-Acceptor-Type Dispiro Molecules.

Two novel donor-σ-π-σ-acceptor-type dispiro molecules-10-phenyl-10H-dispiro-acridine-9,9'-anthracene-10',9''-fluorene-2'',7''-dicarbo-nitrile (DiSAAF) and dispiro-fluorene-9,9'-anthracene-10',9''-quinolino[3,2,1-kl]phenoxazine-2,7-dicarbonitrile (DiSFAQ)-with excellent thermal stability are designed and synthesized. Both materials exhibit blocked long-range intramolecular charge transfer but show intermolecular charge-transfer emission in the film state. Their photophysical and thermal properties then are fully investigated and a maximum external quantum efficiency of 21.7% of the red phosphorescent device is achieved by DiSAAF.

Donor-σ-Acceptor Molecules for Green Thermally Activated Delayed Fluorescence by Spatially Approaching Spiro Conformation.

By separating donor/acceptor with a σ linker while keeping them in contact through space interactions, new oxygen-bridged triphenylamine/fluorene-based donor-σ-acceptor (D-σ-A) type thermally activated delayed fluorescence (TADF) emitters are developed. X-ray structural analyses and time-dependent density functional theory reveal that tilted configuration of spiro skeleton, extended delocalization of the highest occupied molecular orbital (HOMO), and lowest triplet state of charge transfer property (3CT) play key roles in the TADF mechanism. OLEDs fabricated with these D-σ-A emitters achieved good external quantum efficiency of 20.4% and long operating durability of 18000 h at 100 cd m-2.