Chiroptical Resolution and Thermal Switching of Chirality in Conjugated Polymer Luminescence via Selective Reflection using a Double‐Layered Cell of Chiral Nematic Liquid Crystal

An optically resolvable and thermally chiral‐switchable device for circularly polarized luminescence (CPL) is first constructed using a light‐emitting conjugated polymer film and a double‐layered chiral nematic liquid crystal (N*‐LC) cell. The double‐layered N*‐LC cell with opposite handedness at each layer is fabricated by adding each of two types of N*‐LCs into each of the cells, and the N*‐LCs consist of nematic LCs and chiral dopants with opposite chirality and different mole concentrations. The selective reflection band due to the N*‐LC is thermally shifted so that the band wavelength is close to the luminescence band of the racemic conjugated polymer, such as disubstituted polyacetylene (diPA), yielding CPL with opposite handedness and high dissymmetry factor values (|g_lum|) of 1.1–1.6 at low and high temperatures. The double‐layered N*‐LC cell bearing the temperature‐controlled selective reflection is useful for generating CPLs from racemic fluorescent materials and for allowing thermal chirality‐switching in CPLs, which present new possibilities for optoelectronic and photochemical applications.     

2D Chiroptical Nanostructures for High‐Performance Photooxidants

Modulation of the chirality of solid‐like nanoscale membranous structures used as selective photooxidants is an important goal of chemical and materials science. Here, the fabrication of a chiral plasmonic nanoparticle monolayer film which is a highly selective photooxidant under circularly polarized light (CPL) in the visible‐light region is reported. The chiroptical activity of the film can be controlled by altering the amount and stereochemistry of amino acids. The experiments disclose that this stable and reusable catalyst is active in the selective oxidation of glucose enantiomers and CPL of opposite polarization gives around 10.3‐fold increase in conversion rates. The results reveal that the handedness of polarized light dominates the catalytic activity of the chiral film. It is demonstrated that the specific chiral binding of the amino acid ligands and the local field enhancement in the light‐limited regime regulates the selective photocatalytic performance, as confirmed by first‐principles density functional theory and physical field simulations. With the catalyst's signature ability for chiral recognition and switching of handedness of polarized light, the discovery provides a foundation for designing and tailoring chiral inorganic photooxidants. This research also sets an example for the development of light–matter interactions and polarized optics.     

Double Charge Transfer Dominates in Carrier Localization in Low Bandgap Sites of Heterogeneous Lead Halide Perovskites

Heterogeneous organic-inorganic halide perovskites possess inherent non-uniformities in bandgap that are sometimes engineered and exploited on purpose, like in quasi-2D perovskites. In these systems, charge carrier and excitation energy migration to lower-bandgap sites are key processes governing luminescence. The question, which of them dominates in particular materials and under specific experimental conditions, still remains unanswered, especially when charge carriers comprise excitons. In this study transient absorption (TA) and transient photoluminescence (PL) techniques are combined to address the excited state dynamics in quasi-2D and other heterogeneous perovskite structures in broad temperature range, from room temperature down to 15 K. The data provide clear evidence that charge carrier transfer rather than energy migration dominates in heterogeneous quasi-2D perovskite films.     

4D Chiral Photonic Actuators with Switchable Hyper-Reflectivity

Cholesteric liquid crystals (CLCs) are chiral photonic materials reflecting only circularly polarized light with the same handedness as the helical polymer structure. Concurrent shape and color changes can be achieved using CLCs, but the fabrication of CLCs with switchable 3D shape, structural color, and hyper-reflectivity, that is, reflecting both left- and right-handed circularly polarized light simultaneously, has not yet been achieved. Here, CLC elastomer (CLCE) actuators are reported to reflect equal amounts of left- and right-handed circularly polarized light. Hyper-reflectivity is achieved by uniaxially stretching the partially crosslinked film to induce helix deformation which is then fully crosslinked to fix the deformed helical structure. The shape, structural color, and hyper-reflectivity of the polymer film are switchable with temperature. At high temperatures, only right-handed circularly polarized light is reflected and the color is redshifted. The film can be shaped in three dimensions: a structural colored 3D shaped beetle is fabricated using molding, which reflects both left- and right-handed circularly polarized light and shows reversible, temperature responsive structural color and 3D shape changes. Hence, 4D engineered bioinspired multifunctional materials are fabricated, which are interesting for applications ranging from sensing actuators to switchable hyper-reflective films and objects.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Highly efficient quasi-two dimensional perovskite light-emitting diodes by phase tuning

Tetraphenylphosphonium chloride (TPPCl) is used as an additive in the antisolvent for preparing the quasi-two Dimensional (quasi-2D) perovskite film. This strategy is not only beneficial for the morphology formation but also the phase tuning of the quasi-2D perovskite film. Highly efficient and stable perovskite light-emitting diodes (PeLEDs) were achieved with the maximum luminance of 35,000 cd/m², the maximum current efficiency of 48.0 cd/A and the maximum external quantum efficiency (EQE) of 12.42%. Due to the reduced exciton quenching rate, improved charge carrier injection and transport ability, the electroluminescent performance of the TPPCl-based PeLEDs has been enhanced.     

Fully Chiral Light Emission from CsPbX3 Perovskite Nanocrystals Enabled by Cholesteric Superstructure Stacks

Halide perovskites have received tremendous attention due to their fantastic optical and electrical properties. Here, circularly polarized light emission is successfully demonstrated using a simple configuration consisting of inorganic perovskite nanocrystals embedded within a predefined handedness cholesteric superstructure stack. The helical structured cholesteric liquid crystal film acts as a selective filter to transform the unpolarized light emission from perovskite nanocrystals into circularly polarized luminescence. The transformation is accompanied by an extraordinary dissymmetry factor (|g_lum|) up to 1.6, well‐defined handedness, high photoluminescence quantum yield, and full‐color availability. Furthermore, the circularly polarized luminescence is angular dependent and can easily be modulated by shifting the overlap of the reflection band and the emission band. The proposed method is more straightforward and powerful than the previous approaches, offering new opportunities in optoelectronic and photonic devices.     

Photoinduced Chiral Nematic Organization in an Achiral Glassy Nematic Azopolymer

A liquid crystalline homopolymer that has photoisomerizable methoxyazobenzene groups in the side chain has been synthesized and characterized. Thin films of the nematic glassy phase of this polymer have been processed in order to study the absorption spectra and the vibrational and electronic circular dichroism responses by irradiation with 488 nm circularly polarized light (CPL). Selective reflection of visible light demonstrates that the irradiation of this glassy nematic azopolymer induces a helix as a consequence of the chiral arrangement of the azobenzene units. Moreover, a wedge cell with an aligning layer for planar orientation was filled with the polymer with the aim of investigating the change in the macroscopic optical properties and optical textures of the azopolymer on irradiation with CPL. The transfer of chirality from CPL to azopolymer through chiral conformations is proposed as a model for explaining the supramolecular chirality.     

Chiral Thermally Activated Delayed Fluorescence Materials Based on R/S-N2,N2′-Diphenyl-[1,1′-binaphthalene]-2,2′-diamine Donor with Narrow Emission Spectra for Highly Efficient Circularly Polarized Electroluminescence

In this study, two pairs of chiral thermally activated delayed fluorescence (TADF) materials enabling circularly polarized luminescence (CPL) named R/S-p- BAMCN (rod-shape) and R/S-o- BAMCN (helix-shape) are prepared based on a new pair of chiral donor (D*), R/S-N²,N²′-diphenyl-[1,1′-binaphthalene]-2,2′-diamine (R/S- BAM ), and two cyano (CN) acceptors. Due to the rigid molecular structure and special intramolecular arrangement, the chiral TADF materials show high photoluminescence quantum efficiency (up to 0.86) with narrow full-width at half-maximum (38 nm in cyclohexane, 51 nm in toluene) and photoluminescence dissymmetry factor (|g_PL|) up to 5.3 × 10⁻³. Particularly, the circularly polarized OLEDs (CP-OLEDs) with rod-shaped R/S-p- BAMCN as the emitter show high device performances with the maximum external quantum efficiency nearing 28%. Meanwhile, the semi-transparent CP-OLEDs based on helix-shaped R/S-o- BAMCN exhibit obvious circularly polarized electroluminescence (CPEL) properties with the electroluminescence |g_EL| factors around 4.6 × 10⁻³. The strategy of rigid D*-A-D* structure with special arrangement of chiral donor provides a direct way to obtain efficient CP-TADF materials with narrow emission spectra and promising CPL properties for better CPEL performance.     

Circularly Polarized Luminescence Induced by Chiral Super Nanospaces

A simple methodology is developed to realize chiroptical function induced through superstructural chirality of a matrix of helical nanofilaments formed by achiral molecules. In this work, circularly polarized luminescence is demonstrated in nanosegregated mesophase comprising only achiral molecules. An achiral molecular mixture of a bent‐core host and a rod‐like guest blended with a fluorescent dye is prepared. Circularly polarized luminescence confirms that the chiral superstructure consisting only of achiral molecules may serve as a chiral super nanospace for inducing chiral emissions from the fluorescent dye that exhibits rod‐like molecular ordering. In other words, the formation of a chiral superstructure by the segregated rod‐like molecules embedded in helical nanofilaments (bent‐core molecules) is confirmed. The results provide a novel strategy for constructing dissymmetric circularly polarized luminescence materials based on achiral molecules, which is potentially applicable in future information and display technologies.     

Triptycene-derived TADF enantiomers displaying circularly polarized luminescence and high-efficiency electroluminescence

A pair of novel circularly polarized thermally activated delayed fluorescence (CP-TADF) enantiomers (+)-(S,S)-CTRI-Cz and (−)-(R,R)-CTRI-Cz based on chiral triptycene scaffold were designed and synthesized. The obtained triptycene-derived enantiomers displayed obvious TADF activities with small singlet-triplet energy gap value (ΔE_ST) of 0.20 eV and characteristic microsecond delayed lifetime of 15.4 μs. Moreover, the TADF enantiomers showed mirror-image circular dichroism (CD) and circularly polarized luminescence (CPL) activities, and their luminescence dissymmetry factors (g_lum) were about ±0.9 × 10⁻³. Finally, by using the TADF enantiomers as emitters, the optimized organic light-emitting diodes (OLEDs) achieved maximum external quantum efficiency (EQE_max), current efficiency (CE_max) and power efficiency (PE_max) of 15.0%, 48.8 cd/A and 46.9 lm/W, respectively.     

Solution-Processed and Room-Temperature Spin Light-Emitting Diode Based on Quantum Dots/Chiral Metal-Organic Framework Heterostructure

Spin optoelectronics is an indispensable key for the future development of spintronics. In conventional spin light emitting diodes (LEDs), spin-polarized carrier pairs are injected electrically into the light emitting layer and create circularly polarized light (CPL). Generally, spin-polarized carriers are accomplished using ferromagnetic contacts or applying an external magnetic field, which will produce several drawbacks, including low temperature operation, low spin-polarized carriers injection efficiency, etc. To circumvent the existing shortcomings, here, an alternative approach is proposed and achieves spin-polarized LEDs at room temperature based on quantum dots (QDs)/chiral metal-organic framework heterojunction without using ferromagnetic contacts or magnetic fields. The spin-polarized injected layer composed of self-assembled monolayer (SAM)/Chiral-MOF ([Sr(9,10-adc)(DMAc)2]n)) film, which produces spin-polarized holes with spin orientation, determining the polarization and strength of circularly polarized electroluminescence (CP-EL). The spin-QLED emits CP-EL at a rate of 12.24% efficiency, which provides an excellent alternative to generate new functionality for conventional QLEDs. The approach is anticipated to be very useful, enabling to offer a general methodology for generating not yet realized spin optoelectronic devices.     

Mixed Ruddlesden–Popper and Dion–Jacobson Phase Perovskites for Stable and Efficient Blue Perovskite LEDs

Producing efficient blue and deep blue perovskite LEDs (PeLEDs) still represents a significant challenge in optoelectronics. Blue PeLEDs still have problems relating to color, luminance, and structural and electrical stability so new materials are needed to achieve better performance. Recent reports suggest using low n states (n = 1, 2, 3) to achieve blue electroluminescence in Ruddlesden–Popper (RP) perovskite films. However, there are fewer reports on the other quasi-2D structure, Dion–Jacobson (DJ) perovksites, despite their highly desirable optical properties, due to the difficulty in achieving charge injection. To resolve this issue, herein, w e have mixed DJ phase precursors, propane-1,3-diammonium (PDA) bromide into RP phase perovskites and fabricated low-dimensional PeLEDs. It is found that these specific precursors aid in suppressing both the low n (n = 1) and high n (n ≥ 4) quasi-2D RP phases and is an effective strategy in blue-shifting sky-blue RP perovskites into the sub-470 nm region. With optimization of the PDA concentration and device layers, it is achieved an external quantum efficiency of 1.5% at 469 nm and stable electroluminescence for the first deep blue PeLED to be reported using DJ perovskites.     

Biomimetic Ultralight,Highly Porous,Shape‐Adjustable,and Biocompatible 3D Graphene Minerals via Incorporation of Self‐Assembled Peptide Nanosheets

Hybrid nanomaterials with tailored functions, consisting of self‐assembled peptides, are intensively applied in nanotechnology, tissue engineering, and biomedical applications due to their unique structures and properties. Herein, a peptide‐mediated biomimetic strategy is adopted to create the multifunctional 3D graphene foam (GF)‐based hybrid minerals. First, 2D peptide nanosheets (PNSs), obtained by self‐assembling a motif‐specific peptide molecule (LLVFGAKMLPHHGA), are expected to exhibit biofunctionality, such as the biomimetic mineralization of hydroxyapatite (HA) minerals. Subsequently, the noncovalent conjugation of PNSs onto GF support is utilized to form 3D GF‐PNSs hybrid scaffolds, which are suitable for the growth of HA minerals. The fabricated biomimetic 3D GF‐PNSs‐HA minerals exhibit adjustable shape, superlow weight (0.017 g cm^?3), high porosity (5.17 m² g^?1), and excellent biocompatibility, proving potential applications in both bone tissue engineering and biomedical engineering. To the best of the authors' knowledge, it is the first time to combine 2D PNSs and GF to fabricate 3D organic–inorganic hybrid scaffold. Further development of these hybrid GF‐PNSs scaffolds can potentially lead to materials used as matrices for drug delivery or bone tissue engineering as proven via successful 3D scaffold formation exhibiting interconnected pore‐size structures suitable for vascularization and medium transport.     

Efficient and Stable Quasi-2D Perovskite Solar Cells Enabled by Thermal-Aged Precursor Solution

Quasi-2D perovskites have received wide attention in photovoltaics owing to their excellent materials robustness and merits in the device stability. However, the highest power conversion efficiency (PCE) reported on quasi-2D perovskite solar cells (PSCs) still lags those of the 3D counterparts, mainly caused by the relatively high voltage loss. Here, a study is presented on the mitigation of voltage loss in quasi-2D PSCs via usage of thermal-aged precursor solutions (TAPSs). Based on the (AA)₂MA₄Pb₅I₁₆ (n = 5) quasi-2D perovskite absorber with a bandgap of ≈1.60 eV, a record-high open-circuit voltage of 1.24 V is obtained, resulting in boosting the PCE to 18.68%. The enhanced photovoltaic performance afforded by TAPS is attributed to the thermal-aged solution processing that triggers colloidal aggregations to reduce the nucleation sites inside the solution. As a result, formation of high-quality perovskite films featuring compact morphology, preferential crystal orientation, and lowered trap density is allowed. Of importance, with the improved film quality, the corrosion of Ag electrode induced by ion migrations is effectively restrained, which leads to a satisfactory storage stability with <2% degradation after 1200 h under nitrogen environment without encapsulation.     

Frontiers in Circularly Polarized Phosphorescent Materials

Circularly polarized luminescence (CPL) materials have received increasing attention in recent years. Amongst various CPL materials, circularly polarized phosphorescence (CPP) materials featuring long life-time represent a novel research frontier and exhibit promising applications in various fields. Herein, the state-of-the-art advances of CPP materials are systematically summarized, as classified into transition metal complexes, organic small molecules, polymers, and organic/inorganic hybrid materials. Besides, the recent applications of CPP materials in organic light-emitting diodes and encryption display are also summarized. Furthermore, the current challenges and future perspectives are put forward. It is expected that this review will offer more inspirations for the future rational design of advanced CPP materials, thus further promoting their future practical applications.     

Strategies Toward Efficient Blue Perovskite Light-Emitting Diodes

Substantial progress has been made in blue perovskite light-emitting diodes (PeLEDs). In this review, the strategies for high-performance blue PeLEDs are described, and the main focus is on the optimization of the optical and electrical properties of perovskites. In detail, the fundamental device working principles are first elucidated, followed by a systematical discussion of the key issues for achieving high-quality perovskite nanocrystals (NCs) and quasi-2D perovskites. These involve ligand optimization and metal doping in enhancing the carrier transport and reducing the traps of perovskite NCs, as well as the perovskite phase modulation and defect passivation in improving energy transfer and emission efficiency of quasi-2D perovskites. The strategies for efficient 3D mixed-halide perovskite and lead-free perovskite blue LEDs are then briefly introduced. After that, other strategies, including effective charge transport layer, efficient perovskite emission system, and effective device architecture for high light outcoupling efficiency, are further discussed to boost the blue PeLED performances. Meanwhile, the testing standard of blue PeLED lifetime is suggested to enable the direct comparisons of the device operational stability. Finally, challenges and future directions for blue PeLEDs are addressed.     

Domain Distribution Management of Quasi-2D Perovskites toward High-Performance Blue Light-Emitting Diodes

Quasi-2D perovskites, as one of the promising materials applied in perovskite light-emitting diodes (PeLEDs), have attracted great attention for their superior semiconductor properties. The inherent multiquantum well structure can induce a strong confinement effect, which is especially suitable for blue emission. However, compared to their green counterparts, blue emitters constructed from quasi-2D perovskites are more sensitive to n domain distribution (where n represents the number of PbX₆ inorganic layers). Suffering from inefficient domain distribution management, blue PeLEDs now face a variety of negative issues, including color instability, multipeak emission, and poor fluorescence yield. In this review, the development of blue PeLEDs and the optical properties of quasi-2D perovskites are overviewed. Then, a classification and summary of strategies for domain distribution management are proposed. Finally, the challenges and potential directions of domain distribution management in quasi-2D perovskites are summarized. This review is expected to provide a comprehensive perspective and reference on domain distribution management toward efficient blue quasi-2D PeLEDs.     

A recent advances of blue perovskite light emitting diodes for next generation displays

The halide perovskite blue light emitting diodes (PeLEDs) attracted many researchers because of its fascinating opto-electrical properties.This review introduces the recent progress of blue PeLEDs which focuses on emissive layers and interlay-ers.The emissive layer covers three types of perovskite structures:perovskite nanocrystals (PeNCs),2-dimensional (2D) and quasi-2D perovskites,and bulk (3D) perovskites.We will discuss about the remaining challenges of blue PeLEDs,such as lim-ited performances,device instability issues,which should be solved for blue PeLEDs to realize next generation displays.     

Host-Guest Chemistry of Chiral MOFs for Multicolor Circularly Polarized Luminescence Including Room Temperature Phosphorescence

Exploiting the chirality transfer and amplification in the hierarchical chiral systems by the visible and accurate structures is still a challenge. Herein, a pair of homochiral metal-organic frameworks (MOFs) DCF-12 and LCF-12 with high rigidity and high porosity are synthesized via reticular chemistry. Interestingly, these two enantiomers can act as nano-containers, in which four chromophores, covering acridine, pyrene, 9,10-Bis(phenylvinyl) anthracene (BPEA), and coronene can be introduced by in situ encapsulation. Importantly, the precise single crystal structures of all guest-loaded MOFs by X-ray diffraction technique can be obtained smoothly. It not only clearly reveals the chirality transfer from chiral host framework to achiral guest emitters through space chirality transfer, but also circularly polarized luminescence can be achieved and modulated through the synergistic effect. Extraordinarily, both pyrene@DCF-12 and pyrene@LCF-12 exhibit fascinating multi-color tunable room temperature phosphorescence (RTP) and dynamic circularly polarized luminescence. Besides, the RTP quantum yields of pyrene@DCF-12 and pyrene@LCD-12 are high up to 75.39% and 73.43%, which exceeds most of that of RTP materials. These results demonstrate that chiral MOFs can serve as an accurate platform to investigate the mechanism of chirality transfer and amplification and to prompt the development of CPL-active materials.