Tailoring Phase Distribution of Quasi-2D Perovskites via Taurine-Assistance Enables Efficient Blue Light-Emitting Diodes.

Quasi-2D (Q-2D) perovskites with typical varied n-phase structures deserve promising candidates in pursuing high-performance perovskite light-emitting diodes (PeLEDs). Whereas their weakness in precise n-phase distribution control disables the optical property of PeLEDs since the n = 1 phase is dominated by severe nonradiative recombination. Here, an effective phase distribution tailoring strategy is developed for pure blue PeLEDs by introducing taurine (TAU) into mixed halide Q-2D perovskites. The sulfonic acid group in TAU can coordinate with Pb2+ to suppress the formation of the n = 1 phase while promoting the growth of Q-2D perovskites into domains with the graded distribution of n = 2 and 3. The amino group in TAU forms hydrogen bonds with electronegative halide ions, suppressing the formation of halide vacancies and reducing the defect density in the Q-2D perovskite films. As a result, optimized blue Q-2D perovskite films boosted PLQY to 92%. Target blue PeLED  was endowed with a peak EQE of 14.82% (average 12.6%) at 475 nm and a maximum luminance of 1937 cd m-2 , which is among the reported high-level pure blue PeLEDs. This work demonstrates a feasible approach to regulate the phase distribution of Q-2D perovskites for high-performance blue PeLEDs.

Rational Design of Coumarin-Based Hybridized Local and Charge-Transfer Blue Emitters for Solution-Processed Organic Light-Emitting Diodes.

Hybridized local and charge-transfer (HLCT) with the utilization of both singlet and triplet excitons through the "hot excitons" channel have great application potential in highly efficient blue organic light-emitting diodes (OLEDs). The proportion of charge-transfer (CT) and locally excited (LE) components in the relevant singlet and triplet states makes a big difference for the high-lying reverse intersystem crossing process. Herein, three novel donor (D)-acceptor (A) type HLCT materials, 7-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-phenyl-1H-isochromen-1-one (pPh-7P), 7-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-methyl-1H-isochromen-1-one (pPh-7M), and 6-([1,1'-biphenyl]-4-yl(9,9-dimethyl-9H-fluoren-2-yl)amino)-3-methyl-1H-isochromen-1-one (pPh-6M), were rationally designed and synthesized with diphenylamine derivative as donor and oxygen heterocyclic coumarin moiety as acceptors. The proportions of CT and LE components were fine controlled by changing the connection site of diphenylamine derivative at C6/C7-position and the substituent at C3-position of coumarin moiety. The HLCT characteristics of pPh-7P, pPh-7M, and pPh-6M were systematically demonstrated through photophysical properties and density functional theory calculations. The solution-processed doped OLEDs based on pPh-6M exhibited deep-blue electroluminescence with the maximum emission wavelength of 446 nm, maximum luminance of 8755 cd m-2, maximum current efficiency of 5.83 cd A-1, and maximum external quantum efficiency of 6.54 %. The results reveal that pPh-6M with dominant 1LE and 3CT components has better OLED performance.

Synergistic Effect of Fluorinated Passivator and Hole Transport Dopant Enables Stable Perovskite Solar Cells with an Efficiency Near 24.

Long-term durability is critically important for the commercialization of perovskite solar cells (PSCs). The ionic character of the perovskite and the hydrophilicity of commonly used additives for the hole-transporting layer (HTL), such as lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and tert-butylpyridine (tBP), render PSCs prone to moisture attack, compromising their long-term stability. Here we introduce a trifluoromethylation strategy to overcome this drawback and to boost the PSC's solar to electric power conversion efficiency (PCE). We employ 4-(trifluoromethyl)benzylammonium iodide (TFMBAI) as an amphiphilic modifier for interfacial defect mitigation and 4-(trifluoromethyl)pyridine (TFP) as an additive to enhance the HTL's hydrophobicity. Surface treatment of the triple-cation perovskite with TFMBAI largely suppressed the nonradiative charge carrier recombination, boosting the PCE from 20.9% to 23.9% and suppressing hysteresis, while adding TFP to the HTL enhanced the PCS's resistance to moisture while maintaining its high PCE. Taking advantage of the synergistic effects resulting from the combination of both fluoromethylated modifiers, we realize TFMBAI/TFP-based highly efficient PSCs with excellent operational stability and resistance to moisture, retaining over 96% of their initial efficiency after 500 h maximum power point tracking (MPPT) under simulated 1 sun irradiation and 97% of their initial efficiency after 1100 h of exposure under ambient conditions to a relative humidity of 60-70%.

Blue emissive dimethylmethylene-bridged triphenylamine derivatives appending cross-linkable groups.

Five new dimethylmethylene-bridged triphenylamine (DTPA) derivatives 4a-e bearing peripheral cross-linkable vinyl and trifluorovinyl groups were synthesized. The chemical structure of these compounds was characterized by 1H NMR, 13C NMR and HRMS. Their optical properties were studied by UV/Vis spectroscopy and fluorescence spectroscopy. Based on these studies, blue-coloured fluorescence and high fluorescence quantum yields were obtained for 4a-e. The electrochemical properties of these compounds were studied by cyclic voltammetry and the results were further elucidated by DFT calculations. Furthermore, the thermotropic properties of the new DTPAs were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds 4a-d exhibit high thermal stability and thermal cross-linkable properties. These results provide an effective strategy for the design and synthesis of thermally stable and cross-linkable DTPA derivatives with tunable optical and electrochemical properties.

A Chiral Organic Field-Effect Transistor with a Cyclodextrin Modulated Copper Hexadecafluorophthalocyanine Semiconductive Layer as the Sensing Unit.

This work reported the construction of a chiral sensor based on an organic field-effect transistor  to probe the subtle change of weak interactions in the chiral discrimination process, with the ability to achieve fast, sensitive, and quantitative real-time chiral analysis for various racemic pairs, where a ß-cyclodextrin (ß-CD) sensitized copper hexadecafluorophthalocyanine (F16CuPc) semiconductive layer was employed as the sensing unit. Physical adsorptive assembly of ß-CD on the semiconductive layer guarantees the impressive field-effect-amplified chiral sensitivity. The enantiomer induced aggregation pattern diversification of the sensing layer resulted in enhanced or weakened surface-dipole interactions to various degrees and hence brought about the drain current fluctuation. A fast and real-time detection of the enantiomer pairs in aqueous solution at 10-9 M was achieved. This chiral organic field-effect transistor (COFET) afforded reliable ability for quantitative determination of the pure isomer content in enantiomer pairs and was further proven to have great potential for the resolution of "real-world" pharmaceutical drugs.

Amplification of Circularly Polarized Luminescence through Triplet-Triplet Annihilation-Based Photon Upconversion.

Amplification of circularly polarized luminescence (CPL) is demonstrated in a triplet-triplet annihilation-based photon upconversion (TTA-UC) system. When chiral binaphthyldiamine acceptors are sensitized with an achiral Pt(II) octaethylporphine (PtOEP) in solution, upconverted circularly polarized luminescence (UC-CPL) were observed for the first time, in which the positive or negative circularly polarized emission could be obtained respectively, following the molecular chirality of the acceptors (R/S). More interestingly, one order of magnitude amplification of the dissymmetry factor glum in UC-CPL was obtained in comparison with the normal promoted CPL. The multistep photophysical process of TTA-UC including triplet-triplet energy transfer (TTET) and triplet-triplet annihilation (TTA) have been suggested to enhance the UC-CPL, which provided a new strategy to design CPL materials with a higher dissymmetry factor.

The first transition metal phthalocyanines: sensitizing rubrene emission based on triplet-triplet annihilation.

Metallophthalocyanines (MPc-o-Cou, M = Fe, Co, Ni, and Cu) with fourth period metal ions have been successfully applied as a sensitizer coupled with rubrene (Rub) in photon upconversion based on triplet-triplet annihilation. An upconversion quantum yield (ϕPUC) of up to 4.82% was observed in the CoPc-o-Cou : Rub couple. The absorption and phosphorescence emission spectra showed that the Q bands and phosphorescence emission peaks were dramatically dependent on the number of d-electrons of the metal ions in MPc-o-Cou. These results suggested that the photon upconversion behavior of MPc-o-Cou : Rub systems could be managed by altering the metal ions in MPc-o-Cou.

Highly Efficient p-i-n Perovskite Solar Cells Utilizing Novel Low-Temperature Solution-Processed Hole Transport Materials with Linear π-Conjugated Structure.

Alternative low-temperature solution-processed hole-transporting materials (HTMs) without dopant are critical for highly efficient perovskite solar cells (PSCs). Here, two novel small molecule HTMs with linear π-conjugated structure, 4,4'-bis(4-(di-p-toyl)aminostyryl)biphenyl (TPASBP) and 1,4'-bis(4-(di-p-toyl)aminostyryl)benzene (TPASB), are applied as hole-transporting layer (HTL) by low-temperature (sub-100 °C) solution-processed method in p-i-n PSCs. Compared with standard poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT:PSS) HTL, both TPASBP and TPASB HTLs can promote the growth of perovskite (CH3 NH3 PbI3 ) film consisting of large grains and less grain boundaries. Furthermore, the hole extraction at HTL/CH3 NH3 PbI3 interface and the hole transport in HTL are also more efficient under the conditions of using TPASBP or TPASB as HTL. Hence, the photovoltaic performance of the PSCs is dramatically enhanced, leading to the high efficiencies of 17.4% and 17.6% for the PSCs using TPASBP and TPASB as HTL, respectively, which are ≈40% higher than that of the standard PSC using PEDOT:PSS HTL.

Microencapsulated Perovskite Crystals via In Situ Permeation Growth from Polymer Microencapsulation-Expansion-Contraction Strategy: Advancing a Record Long-Term Stability beyond 10 000 h for Perovskite Solar Cells.

Organic metal halide perovskite solar cells (PSCs) bearing both high efficiency and durability are predominantly challenged by inadequate crystallinity of perovskite. Herein, a polymer microencapsulation-expansion-contraction strategy is proposed for the first time to optimize the crystallization behavior of perovskite, typically by adeptly harnessing the swelling and deswelling characteristics of poly(4-acryloylmorpholine) (poly(4-AcM)) network on PbI2 surface. It can effectively retard the crystallization rate of perovskite, permitting meliorative crystallinity featured by increased grain size from 0.74 to 1.32 µm and reduced trap density from 1.12 × 1016 to 2.56 × 1015 cm-3. Moreover, profiting from the protection of poly(4-AcM) microencapsulation layer, the degradation of the perovskite is markedly suppressed. Resultant PSCs gain a robust power conversion efficiency (PCE) of 24.04%. Typically, they maintain 91% of their initial PCE for 13 008 h in a desiccated ambient environment and retain 92% PCE after storage for 4000 h with a relative humidity of 50 ± 10%, which is the state-of-the-art long-term stability among the reported contributions.

Preventing lead leakage in perovskite solar cells and modules with a low-cost and stable chemisorption coating.

Despite the promising commercial prospects of perovskite solar cells, the issue of lead toxicity continues to hinder their future industrial applications. Here, we report a low-cost and rapidly degraded sulfosuccinic acid-modified polyvinyl alcohol (SMP) coating that prevents lead leakage and enhances device stability without compromising device performance. Even under different strict conditions (simulated heavy rain, acid rain, high temperatures, and competing ions), the coatings effectively prevent lead leakage by over 99%. After 75 days of outdoor exposure, the coating still demonstrates similar lead sequestration efficiency (SQE). In addition, it can be applied to different device structures (n-i-p and p-i-n) and modules, with over 99% SQE, making it a general method for preventing lead leakage.

Correction: Preventing lead leakage in perovskite solar cells and modules with a low-cost and stable chemisorption coating.

Correction for 'Preventing lead leakage in perovskite solar cells and modules with a low-cost and stable chemisorption coating' by Zongxu Zhang et al., Mater. Horiz., 2024, 11, 2449-2456, https://doi.org/10.1039/D4MH00033A.

Seeding Agents in Metal Halide Perovskite Solar Cells: From Material to Mechanism.

Metal halide perovskite solar cells (PSCs) have been showing up in the commercial field, with an inspiring power conversion efficiency (PCE) of over 26 % in the laboratory. The quality of perovskite films is still a bottleneck due to the random and fast crystallization of ionic perovskite materials. Seeding agent-mediated crystallization has consistently been recognized as an efficient method for preparing bulk single crystals and high-quality films. Herein, we summarized the seeding mechanism, characterization techniques, and seeding agents working in different locations during PSC device fabrication. This Review could further facilitate researchers with a deeper understanding of seeding agents and enhance more choices for seeding crystallization to improve the performance further and the device's large-scale fabrication toward commercialization.

A Breakthrough in Solution-Processed Ultra-Deep-Blue HLCT OLEDs: A Record External Quantum Efficiency Exceeding 10% Based on Novel V-Shaped Emitters.

It is always a great challenge to achieve high-efficiency solution-processed ultra-deep-blue organic light-emitting diodes (OLEDs) with the Commission Internationale de l'Eclairage (CIE) 1931 chromaticity coordinates matching the blue primary of Rec. International Telecommunication Union-Radiocommunication BT.2100, which specifies high dynamic range television image parameters. Inspired by hybrid local and charge transfer (HLCT) excited state emitters improving exciton utilization through high-lying reverse intersystem crossing, here, a series of high-performance blue emitters by a V-shaped symmetric donor (D)-π-acceptor (A)-π-D design strategy are developed. Here, the large torsions and unstable bonds of D-A structures can be improved through π bridges, and also the conjugation length and donor groups can be easily adjusted. The obtained emitters merit excellent photophysical and electrochemical properties, thermal stability, solution processibility, and HLCT excited state excellence. Results suggest that the OLEDs based on the obtained blue emitters all achieve high maximum external quantum efficiency (EQEmax ) of more than 8% with very low efficiency roll-off. In particular, the device based on 4',5'-bis(4-(9H-carbazol-9-yl)phenyl)spiro[fluorene-9,2'-imidazole] exhibits a satisfactory ultra-deep-blue emission (CIEx , y = 0.1579, 0.0387) and a record-high EQEmax (10.40%) among solution-processed HLCT OLEDs, which is very close to the record EQEmax of devices by vacuum vapor deposition technology.

High-Performance Planar Self-Driven Visible and Near-Infrared Photodetector Based on Pb-Sn Perovskite Single Crystals.

MAPbI3 single crystals (SCs) are promising candidates for self-driven photodetectors due to their spontaneous polarization properties. However, their absorption cutoff wavelength, which is limited to 850 nm, severely hinders their further application in near-infrared photodetectors. In this work, a series of high-quality (MAPbI3)x(FASnI3)1-x (x = 0.8, 0.5 and 0.2) SCs with low defect density and wide absorption range were obtained by employing 1,4-pentanolactone as the solvent at low temperature. Typically, (MAPbI3)0.2(FASnI3)0.8 SCs grown at 32 °C realize absorption in the UV-vis-NIR range from 200 to 1120 nm, which is superior among the absorption wavelengths reported for Pb-Sn perovskite SCs. Resultantly, by merit of the spontaneously polarized built-in electric field, for (MAPbI3)0.2(FASnI3)0.8 SCs based self-driven photodetectors with planar symmetric electrodes exhibiting significant responsivities at 405-1064 nm, the device achieved a maximum responsiveness and detection of 0.247 A/W and 1.17 × 1012 Jones, respectively.

Mixed Cations Enabled Combined Bulk and Interfacial Passivation for Efficient and Stable Perovskite Solar Cells.

Here, we report a mixed GAI and MAI (MGM) treatment method by forming a 2D alternating-cation-interlayer (ACI) phase (n = 2) perovskite layer on the 3D perovskite, modulating the bulk and interfacial defects in the perovskite films simultaneously, leading to the suppressed nonradiative recombination, longer lifetime, higher mobility, and reduced trap density. Consequently, the devices' performance is enhanced to 24.5% and 18.7% for 0.12 and 64 cm2, respectively. In addition, the MGM treatment can be applied to a wide range of perovskite compositions, including MA-, FA-, MAFA-, and CsFAMA-based lead halide perovskites, making it a general method for preparing efficient perovskite solar cells. Without encapsulation, the treated devices show improved stabilities.

Zn2+-Doped Lead-Free CsMnCl3 Nanocrystals Enable Efficient Red Emission with a High Photoluminescence Quantum Yield.

The toxicity of Pb and the instability of lead halide perovskites are the main obstacles to the practical application of lead-based nanocrystals (NCs). In this paper, all-inorganic Zn2+-doped lead-free perovskite (CsMn1-xZnxCl3) NCs were synthesized by a hot-injection method. Mn2+ ions were partially replaced by Zn2+ ions, and the energy transfer between Mn2+ was effectively suppressed. Because of this, excitons are more advantageously confined to the [MnCl6]4- octahedron. Target CsMn0.95Zn0.05Cl3 NCs were endowed with red emission at 654 nm with CIE coordinates of (0.70, 0.30) closing to the standard value of NTSC, and their photoluminescence quantum yield was increased to 77.1%, which is higher than those of Mn-based lead-free perovskites previously reported. Finally, a white light-emitting diode (LED) with adjustable emission from warm to cold white was realized by mixing Cs3MnBr5, CsMn0.95Zn0.05Cl3, and a blue phosphor on a 382 nm ultraviolet LED chip.

How to apply metal halide perovskites to photocatalysis: challenges and development.

Semiconductor photocatalysts are widely used in environmental remediation and energy conversion processes that affect social development. These processes involve, for example, hydrogen production from water splitting, carbon dioxide reduction, pollutant degradation, and the conversion of raw organic chemical materials into high-value-added chemicals. Metal halide perovskites (MHPs) have become a new class of promising cheap and easy to manufacture candidate materials for use in photocatalytic semiconductors due to their advantages of high extinction coefficients, optimal band gaps, high photoluminescence quantum yields, and long electron-hole diffusion lengths. However, their unstable ion-bonded crystal structures (very low theoretical decomposition energy barriers) limit their widespread application. In this review, we introduce the physical properties of MHP materials suitable for photocatalysis, and MHP-based photocatalytic particle suspension systems, photoelectrode thin film systems, and photovoltaic-photo(electro)chemical systems. Then, numerous studies realizing efficient and stable photocatalytic water splitting, carbon dioxide reduction, organic conversion, and other reactions involving MHP materials were highlighted. In addition, we conducted rigorous analysis of the potential problems that could hinder progress in this new scientific research field, such as Pb element toxicity and material instability. Finally, we outline the potential opportunities and directions for photocatalysis research based on MHPs.

Blue nanocomposites coated with an ionic liquid polymer for electrophoretic displays.

Electrophoretic display (EPD) is a type of flexible display which has attracted wide attention. In this work, blue nanosized crystals of cobalt aluminum oxide (CoAl2O4) were precipitated on silica nanoparticles, and then the nanocomposites were coated with an ionic liquid polymer (PIL) to give blue electrophoretic particles. The blue nanocomposites (SCAs) formed possess an excellent spherical structure, and the average diameter is about 188 nm. The porous silica matrix presents a relative light density, and the blue CoAl2O4 pigment offers excellent color. The outside ionic liquid polymer supplies the PIL/SCAs with a light density of 1.7915 g cm-3, excellent hydrophobicity and dispersion stability in the electrophoretic liquid. The fabricated single-particle EPD prototypes show a response time of 165 ms in the EPD cell with a 0.2 mm thickness, which is much faster than the commercial EPDs, and this is probably because of the unique composite structure.

Tunable White Light-Emitting Devices Based on Unilaminar High-Efficiency Zn2+-Doped Blue CsPbBr3 Quantum Dots.

Perovskite-based white-light-emitting devices (WLEDs) are expected to be the potential candidate for the next-generation lighting field due to their scalability and low-cost process. However, simple and adjustable WLED fabrication technology is in urgent need. Here, WLEDs with a single layer of perovskite quantum dots (PQDs) were constructed by combining Zn2+-doped CsPbBr3 PQDs with exciplex emission between poly(9-vinylcarbazole) (PVK) and ((1-phenyl-1H-benzimidazol-2-yl)benzene)) (TPBi). Zn2+-doped CsPbBr3 PQDs with polar ion shells were prepared by means of low temperature and post-treatment. The photoluminescence quantum yield (PLQY) can reach as high as 95.9% at the emission wavelength of 456 nm. The blue shift of its PL (∼60 nm) is much greater than that of other reported Zn2+-doped CsPbBr3 PQDs (5-10 nm), thus realizing the true blue-emission Zn2+-doped CsPbBr3 PQDs. As a result, just by controlling the thickness of TPBi, the adjustment of cold (CIE (0.2531, 0.2502)) and warm WLEDs (CIE (0.3561, 0.3562)) is realized for the first time.

Electronic Coordination Effect of the Regulator on Perovskite Crystal Growth and Its High-Performance Solar Cells.

The rapid growth of perovskite crystals leads to excessive grain boundaries and surface defects, which have a negative effect on the performance of solar cells (PSCs). Passivating defects by controlling the crystal growth rate becomes a crucial research hotspot for preparing high-crystallinity perovskite films. In this work, phenylacetonitrile (PA) and 2-naphthylacetonitrile (2-NA) serving as crystal growth regulators are introduced into the perovskite precursor. The coordination effect of lone-pair electrons (n-electrons) and π-electrons in the regulator molecule with Pb2+ on the nucleation and growth of FA0.80MA0.15Cs0.05Pb(I0.85Br0.15)3 perovskite crystal along with the passivation of surface defects and grain boundaries are systematically investigated. The n-electrons of N atom form a coordination bond with Pb2+, and the π-electrons in the aromatic ring generate a cation-π interaction with Pb2+. This combined effect efficiently delays the crystallization rate of the perovskite crystal and then promotes the grain growth and reduces the grain boundaries, which is favorable for the dissociation of more excitons to carriers. The PA-optimized PSCs shows an increase of power conversion efficiency (PCE) from 18.01 to 21.09%, with an unencapsulated device retaining 91.2% of its initial efficiency for 60 days in 40 ± 5% relative humidity under dark conditions.