Efficient Visible-Light-Activated Ultra-Long Room-Temperature Phosphorescence Triggered by Multi-Esterification.

The development of ultra-long room-temperature phosphorescence (UL-RTP) in processable amorphous organic materials is highly desirable for applications in flexible displays, anti-counterfeiting, and bio-imaging. However, achieving efficient UL-RTP from amorphous materials remains a challenging task, especially with activation by visible light and a bright afterglow. Here we report a general and rational molecular-design strategy to enable efficient visible-light-excited UL-RTP by multi-esterification of a rigid large-plane phosphorescence core. Notably, multi-esterification minimizes the aggregation-induced quenching and accomplishes a 'four birds with one stone' possibility in the generation and radiation process of UL-RTP: i) shifting the excitation from ultraviolet light to blue-light through enhancing the transition dipole moment of low-lying singlet-states, ii) facilitating the intersystem crossing process through the incorporation of lone-pair electrons, iii) boosting the decay process of long-lived triplet excitons resulting from a significantly increased transition dipole moment, and iv) reducing the intrinsic triplet nonradiative decay by substitution of high-frequency vibrating hydrogen atoms. All these factors synergistically contribute to the most efficient and stable visible-light-stimulated UL-RTP (lifetime up to 2.01 s and efficiency up to 35.4 % upon excitation at 450 nm) in flexible films using multi-esterified coronene, which allows high-tech applications in single-component time-delayed white light-emitting diodes and information technology based on flashlight-activated afterglow encryption.

Light-Reconfiguring Inhomogeneous Soft Helical Pitch with Fatigue Resistance and Reversibility.

Active engineering and modulation of optical spectra in a remote and fully reversible light is urgently desired in photonics, chemistry, and materials. However, the real-time regulation of multiple optical information such as wavelength, bandwidth, reflectance, and polarization is still a longstanding issue due to the lack of an appropriate photoresponsive candidate. Herein, we propose an additional "degree-of-freedom (DOF)" in a photo-modulated soft helix, and build up an unprecedented inhomogeneous helical pitch length with light-reconfiguring property, fatigue resistance, and reversibility. For the working model, the intrinsic chiral photoswitch LBC5 is employed as an actuator to modulate the helical pitch length, which is proportional to the irradiation intensity, and the unique broadband absorbance photo-modulator BTA-C5 is incorporated as an attenuator of the transmitted light to decrease its intensity along the sample thickness, therefore successfully adding another controlled DOF on the pitch length distribution (i.e., homogeneous or inhomogeneous) apart from the common soft helix with only a single DOF on the pitch length. The absorbance photo-modulator BTA-C5 with a unique variable broadband absorption enables the light to reconfigure the helical pitch from homogeneous to inhomogeneous, thereby achieving the robust fatigue-resistance establishment of reversible spectral programming. The established light-reconfigurable inhomogeneous helical pitch with the photoresponsive modulator BTA-C5 can provide a breakthrough to control absorbance and chirality, especially for dynamically broadening and narrowing the bandwidth on demand, and further enable the ever-desired broadband NIR circularly polarized luminescence (CPL) with a high dissymmetry factor glum of up to 1.88. The cutting-edge photoswitchable inhomogeneous soft helical pitch provides access to multi-freedom control in soft materials, optics, biophotonics, and other relevant fields.

Light-regulating chirality of metallacages featuring dithienylethene switches.

Dynamic chiral superstructures are of vital importance for understanding the organization and function of chirality in biological systems. However, achieving high conversion efficiency for photoswitches in nanoconfined architectures remains challenging but fascinating. Herein, we report a series of dynamic chiral photoswitches based on supramolecular metallacages through the coordination-driven self-assembly of dithienylethene (DTE) units and octahedral zinc ions, thereby successfully achieving an ultrahigh photoconversion yield of 91.3% in nanosized cavities with a stepwise isomerization mechanism. Interestingly, the chiral inequality phenomenon is observed in metallacages, resulting from the intrinsic photoresponsive chirality in the closed form of the dithienylethene unit. Upon hierarchical organization, we establish a dynamic chiral system at the supramolecular level, featuring chiral transfer, amplification, induction, and manipulation. This study provides an intriguing idea to simplify and understand chiral science.

Programmable Jigsaw Puzzles of Soft Materials Enabled by Pixelated Holographic Surface Reliefs.

Manual intervention in the self-organization of soft matter to obtain a desired superstructure is a complex but significant project. Specifically, optical components made fully or partially from reconfigurable and stimuli-responsive soft materials, referred to as soft photonics, are poised to form versatile platforms in various areas; however, a limited scale, narrow spectral adaptability, and poor stability are still formidable challenges. Herein, a facile way is developed to program the optical jigsaw puzzle of nematic liquid crystals via pixelated holographic surface reliefs, leading to an era of manufacturing for programmable soft materials with tailored functions. Multiscale jigsaw puzzles are established and endowed with unprecedented stability and durability, further sketching a prospective framework toward customized adaptive photonic architectures. This work demonstrates a reliable and efficient approach for directly assembling soft matter, unlocking the long-sought full potential of stimuli-responsive soft systems, and providing opportunities to inspire the next generation of soft photonics and relevant areas.

Immobilizing Surface Halide in Perovskite Solar Cells via Calix[4]pyrrole.

Halide diffusion across the charge-transporting layer followed by a reaction with metal electrode represents a critical factor limiting the long-term stability of perovskite solar cells (PSCs). In this work, a supramolecular strategy with surface anion complexation is reported for enhancing the light and thermal stability of perovskite films, as well as devices. Calix[4]pyrrole (C[4]P) is demonstrated as a unique anion-binding agent for stabilizing the structure of perovskite by anchoring surface halides, which increases the activation energy for halide migration, thus effectively suppressing the halide-metal electrode reactions. The C[4]P-stabilized perovskite films preserve their initial morphology after ageing at 85 °C or under 1 sun illumination in humid air over 50 h, significantly outperforming the control samples. This strategy radically tackles the halide outward-diffusion issue without sacrificing charge extraction. Inverted-structured PSCs based on C[4]P modified formamidinium-cesium perovskite exhibit a champion power conversion efficiency of over 23%. The lifespans of unsealed PSCs are unprecedentedly prolonged from dozens of hours to over 2000 h under operation (ISOS-L-1) and 85 °C ageing (ISOS-D-2). When subjected to a harsher protocol of ISOS-L-2 with both light and thermal stresses, the C[4]P-based PSCs maintain 87% of original efficiency after ageing for 500 h.

Neglected acidity pitfall: boric acid-anchoring hole-selective contact for perovskite solar cells.

The spontaneous formation of self-assembly monolayer (SAM) on various substrates represents an effective strategy for interfacial engineering of optoelectronic devices. Hole-selective SAM is becoming popular among high-performance inverted perovskite solar cells (PSCs), but the presence of strong acidic anchors (such as -PO3H2) in state-of-the-art SAM is detrimental to device stability. Herein, we report for the first time that acidity-weakened boric acid can function as an alternative anchor to construct efficient SAM-based hole-selective contact (HSC) for PSCs. Theoretical calculations reveal that boric acid spontaneously chemisorbs onto indium tin oxide (ITO) surface with oxygen vacancies facilitating the adsorption progress. Spectroscopy and electrical measurements indicate that boric acid anchor significantly mitigates ITO corrosion. The excess boric acid containing molecules improves perovskite deposition and results in a coherent and well-passivated bottom interface, which boosts the fill factor (FF) performance for a variety of perovskite compositions. The optimal boric acid-anchoring HSC (MTPA-BA) can achieve power conversion efficiency close to 23% with a high FF of 85.2%. More importantly, the devices show improved stability: 90% of their initial efficiency is retained after 2400 h of storage (ISOS-D-1) or 400 h of operation (ISOS-L-1), which are 5-fold higher than those of phosphonic acid SAM-based devices. Acidity-weakened boric acid SAMs, which are friendly to ITO, exhibits well the great potential to improve the stability of the interface as well as the device.

A Quadri-Dimensional Manipulable Laser with an Intrinsic Chiral Photoswitch.

Dynamic and multi-dimensional manipulation of laser emission with light allows for optical coding, computing, and imaging photonic chips. However, the coupling balance between photonic resonance and transmission is a formidable challenge due to the uncontrollable chiral microcavity with photo-reversibility, which is limited to the multi-freedom of the laser with sustainable and repeatable output beams. Herein, a helical superstructure system with a unique intrinsic chiral photoswitch is developed for resolving the always pendent problems on organized defects in the microcavity. The unique intrinsic chirality based on the photoswitchable system allows laser emission with a sharp and narrow band-width, with both remarkable thermodynamic stability and robust fatigue-resistance. A quadri-dimensional manipulable laser, featuring wavelength-tunability, wavefront-shaping, spin angular momentum (SAM), and orbital angular momentum (OAM), is successfully established with the assistance of the photoresponsive intrinsic chiral superstructure with photoreversibility. This technology marks an important milestone, and sketches a future framework for the realms of nanophotonic information encoding, security imprinting, and integrated photonics.

Dynamically actuated soft heliconical architecture via frequency of electric fields.

Dynamic electric field frequency actuated helical and spiral structures enable a plethora of attributes for advanced photonics and engineering in the contemporary era. Nevertheless, leveraging the frequency responsiveness of adaptive devices and systems within a broad dynamic range and maintaining restrained high-frequency induced heating remain challenging. Herein, we establish a frequency-actuated heliconical soft architecture that is quite distinct from that of common frequency-responsive soft materials. We achieve reversible modulation of the photonic bandgap in a wide spectral range by delicately coupling the frequency-dependent thermal effect, field-induced dielectric torque and elastic equilibrium. Furthermore, an information encoder prototype without the aid of complicated algorithm design is established to analogize an information encoding and decoding process with a more convenient and less costly way. A technique for taming and tailoring the distribution of the pitch length is exploited and embodied in a prototype of a spatially controlled soft photonic cavity and laser emission. This work demonstrates a distinct frequency responsiveness in a heliconical soft system, which may not merely inspire the interest in field-assisted bottom-up molecular engineering of soft matter but also facilitate the practicality of adaptive photonics.