Fabrication of water-resistant fluorescent ink using the near-unity photoluminescence quantum yield of CsPbBr3 doped with NiBr2.

Doping with transition and alkaline earth metal ions into all-inorganic perovskite nanocrystals (NCs) has attracted attention recently for tuning the photoluminescence quantum yield (PLQY). We report on the hot injection synthesis of nickel ion-doped CsPbBr3 NCs with near-unity PLQYs. Nickel ions were successfully incorporated into the octahedral environment of CsPbBr3 NCs, replacing the lead ions. The introduction of nickel ions into CsPbBr3 NCs substantially eliminates intrinsic defects and halide vacancies for improved structural order and near-unity PLQYs. Benefiting from these unique properties, nickel ion-doped CsPbBr3 NCs were dispersed in a polymer to prepare an efficient fluorescent ink. The fluorescent ink shows excellent thermal and water stability under harsh environmental conditions. Moreover, the usefulness of the fluorescent ink for security purposes was demonstrated by designing and recognizing a fluorescent QR code. This study reveals that doped CsPbBr3 NCs can be used to prepare efficient water-resistant fluorescent ink for anti-counterfeiting applications, widening the usefulness of doped all-inorganic perovskite NCs.

Stereochemically Active Lone Pair Leads to Birefringence in the Vacancy Ordered Cs3Sb2Cl9 Perovskite Single Crystals.

Stereochemically active lone pair (SCALP) cations are attractive units for realizing optical anisotropy. Antimony(III) chloride perovskites with the SCALP have remained largely unknown to date. We synthesized a new vacancy ordered Cs3Sb2Cl9 perovskite single crystals with SbCl6 octahedral linkage containing the SCALP. Remarkably, all-inorganic halide perovskite Cs3Sb2Cl9 single crystals exhibit an exceptional birefringence of 0.12 ± 0.01 at 550 nm. The SCALP brings a large local structural distortion of the SbCl6 octahedra promoting birefringence optical responses in Cs3Sb2Cl9 single crystals. Theoretical calculations reveal that the considerable hybridization of Sb 5s and 5p with Cl 3p states largely contribute to the SCALP. Furthermore, the change in the Sb-Cl-Sb bond angle creates distortion in the SbCl6 octahedral arrangement in the apical and equatorial directions within the crystal structure incorporating the required anisotropy for the birefringence. This work explores pristine inorganic halide perovskite single crystals as a potential birefringent material with prospects in integrated optical devices.

Colloidal semiconductor nanocrystals: from bottom-up nanoarchitectonics to energy harvesting applications.

Colloidal semiconductor nanocrystals (NCs) have been extensively investigated owing to their unique properties induced by the quantum confinement effect. The advent of colloidal synthesis routes led to the design of stable colloidal NCs with uniform size, shape, and composition. Metal oxides, phosphides, and chalcogenides (ZnE, CdE, PbE, where E = S, Se, or Te) are few of the most important monocomponent semiconductor NCs, which show excellent optoelectronic properties. The ability to build quantum confined heterostructures comprising two or more semiconductor NCs offer greater customization and tunability of properties compared to their monocomponent counterparts. More recently, the halide perovskite NCs showed exceptional optoelectronic properties for energy generation and harvesting applications. Numerous applications including photovoltaic, photodetectors, light emitting devices, catalysis, photochemical devices, and solar driven fuel cells have demonstrated using these NCs in the recent past. Overall, semiconductor NCs prepared via the colloidal synthesis route offer immense potential to become an alternative to the presently available device applications. This feature article will explore the progress of NCs syntheses with outstanding potential to control the shape and spatial dimensionality required for photovoltaic, light emitting diode, and photocatalytic applications. We also attempt to address the challenges associated with achieving high efficiency devices with the NCs and possible solutions including interface engineering, packing control, encapsulation chemistry, and device architecture engineering.

Origin of Intense Luminescence from Supramolecular 2D Molecular Crystals.

Luminescence enhancement in 2D molecular crystals (2D crystals) is promising for a variety of optical applications, yet the availability is limited because of unclear mechanism and inefficient design strategy of luminescence control. Herein, the room temperature phosphorescence from micron long molecular thin free-standing 2D crystals of a mono-cyclometalated Ir(III) complex designed at the water surface is reported. A large luminescence enhancement is observed from the 2D crystals at 300 K, which is comparable with the rigidified solution at 77 K suggesting room temperature phosphorescence origin of the luminescence. In situ synchrotron grazing incidence X-ray diffraction measurements determine the constituent centered rectangular unit cells with precise molecular conformation that promotes the formation of 2D crystals. The molecular crystal design leads to a reduced singlet-triplet energy gap (ΔEST ) and mixing of singlet-triplet states by spin-orbit coupling (SOC) for efficient intersystem crossing, which explains the phosphorescence origin at room temperature and luminescence enhancement. The supramolecular assembly process provides an elegant design strategy to realize room temperature phosphorescence from 2D crystals by rigid intermolecular interactions.

Virstatin-Conjugated Gold Nanoparticle with Enhanced Antimicrobial Activity against the Vibrio cholerae El Tor Biotype.

Because of the emergence of multidrug-resistant pathogenic bacteria, there is a growing interest for the development of an efficient alternative to antibiotics. Gold nanoparticles (AuNPs) are promising candidates due to their inherent non-toxicity and can be used as effective carriers of drugs. Cholera caused by Gram-negative Vibrio cholerae is still a potential threat in many developing countries. Virstatin, a small molecule, has been reported to inhibit virulence regulation in V. cholerae. Herein, we report an efficient synthesis of virstatin-conjugated gold nanoparticles (VL-AuNPs) and their antibacterial efficacy against the El Tor biotype of V. cholerae (VcN16961). The spherical-shaped NPs have an average diameter of ∼17 nm. The uniqueness of VL-AuNPs relies in the enhanced antibacterial efficacy compared to virstatin, as evidenced from the inhibitory concentration obtained from growth kinetics, and attributed to the inhibition of ATPase activity and DNA damage. More importantly, the expression of cholera toxin, the most important virulence factor of V. cholera, is reduced to a far greater extent than by any of the component molecules. The effect of VL-AuNPs on VcN16961 was monitored using various assays such as confocal microscopy, FACS, fluorescence spectroscopy, and so on. Overall, VL-AuNPs could be a potential candidate for the use as an effective agent for combating diarrheal diseases caused by V. cholera.

The range of antiferromagnetic coupling governs the conductivity: semiconducting behavior and ammonia gas sensing property of diamagnetic hexaradical-containing tetranuclear CoIII4 cluster and its nonradical congener.

Long-range antiferromagnetic coupling impeded electron flow through the hexaradical-containing tetranuclear CoIII4 complex (1), while the nonradical-containing tetranuclear CoIII4 complex (2), with no paramagnetic centres, was a semiconductor and sensed NH3 efficiently at room temperature (25 °C).

Transparent, flexible MAPbI3 perovskite microwire arrays passivated with ultra-hydrophobic supramolecular self-assembly for stable and high-performance photodetectors.

The emergence of organic-inorganic hybrid perovskites (OHPs) has revolutionised the potential performance of optoelectronic devices; most perovskites are opaque and hence incompatible with transparent optoelectronics and sensitive to environmental degradation. Here, we have reported a single-step fabrication of ultra-long MAPbI3 perovskite microwire arrays over a large area using stencil lithography based on sequential vacuum sublimation. The environmental stability of MAPbI3 is empowered with a newly designed and synthesized transparent supramolecular self-assembly based on a mixture of two tripodal l-Phe-C11H23/C7F15 molecules, which showed a contact angle of 105° and served as ultra-hydrophobic passivation layers for more than 45 days in an ambient atmosphere. The MAPbI3 microwire arrays passivated with the supramolecular self-assembly demonstrated for the first time both excellent transparency of ∼89% at 550 nm and a remarkable photoresponse with a photo-switching ratio of ∼104, responsivity of 789 A W-1, detectivity of 1014 Jones, linear dynamic range of ∼122 dB, and rise time of 432 µs. Furthermore, the photodetector fabricated on a flexible PET substrate demonstrated robust mechanical flexibility even beyond 1200 bending cycles. Therefore, the scalable stencil lithography and supramolecular passivation approaches have the potential to deliver next-generation transparent, flexible, and stable optoelectronic devices.

Large-area transparent flexible guanidinium incorporated MAPbI3 microstructures for high-performance photodetectors with enhanced stability.

Unveiling the transparency and flexibility in perovskite-based photodetectors with superior photoresponse and environmental stability remains an open challenge. Here we report on guanidinium incorporated metal halide perovskite (MA1-xGuaxPbI3, x = 0 to 0.65) random percolative microstructure (RPM) fabrication using an ultra-fast spray coating technique. Remarkably, RPMs over a large area of 5 × 5 cm2 on flexible substrates with a transparency of ∼50% can be achieved with enriched environmental stability. Transparent photodetectors based on MA1-xGuaxPbI3 (x = 0.12) RPMs manifest excellent performance with a responsivity of 187 A W-1, a detectivity of 2.23 × 1012 Jones and an external quantum efficiency of 44 115%. Additionally, the photodetectors exhibited superior mechanical flexibility under a wide range of bending angles and large number of binding cycles. Integrating features including transparency, high performance, stability, flexibility and scalability within a photodetector is unmatched and holds potential for novel applications in transparent and wearable optoelectronic devices.

Light-Induced Defect Healing and Strong Many-Body Interactions in Formamidinium Lead Bromide Perovskite Nanocrystals.

Organic lead halide perovskite (OLHP) nanocrystals (NCs) have paved the way to advanced optoelectronic devices through their extraordinary electrical and optical properties. However, understanding of the light-induced complex dynamic phenomena in OLHP NCs remains a subject of debate. Here we used wide field microscopy and time-resolved spectroscopy to correlate the local changes in photophysics and the dynamical behavior of photocarriers. We demonstrate that light-induced brightening of the photoluminescence from the formamidinium lead bromide NC films is related to the film preparation condition and reduction of trap density. The density of trap states is reduced via halide ion migration from interstitial position. Our femtosecond transient absorption study identifies transient Stark effect due to the generation of hot carriers. Because of slow carrier trapping, Auger recombination through many-body carrier-carrier interactions dominates over trion recombination. This work presents unprecedented insights into the light-driven processes enabling better device design in the future.

Vortex-Aligned Ordered Film of Crystalline Fullerene C70 Microtubes with Enhanced Photoluminescence and Photovoltaics Properties.

Crystalline fullerene C70 microtubes (FMTs) were produced employing ultrasound-assisted liquid- liquid interfacial precipitation (ULLIP) technique at the interface between fullerene C70 solution in 1,2 dichlorobenzene (DCB) and isopropanol (IPA) at 15 °C. Using the vortex-flow motion of the subphase water (also called Vortex-Langmuir-Blodgett technique), the FMTs were aligned and homogeneous films were prepared at the air-water interface. The aligned FMTs film exhibited enhanced photoluminescence (PL) with PL intensity ~5 times higher than that of the pristine C70. Moreover, the aligned FMT film showed better photovoltaics properties compared with randomly oriented FMTs and pristine C70 film obtained from the spin coating. The compact, directional orientation and proper surface coverage of the FMT film enhanced the charge transport properties in the photovoltaic device.

Unveiling Peritoneum Membrane for a Robust Triboelectric Nanogenerator.

Triboelectric nanogenerators (TENGs) are smart alternative energy harvesters to convert mechanical energy into electrical energy to power small and portable electronic devices. A key challenge in fabricating an efficient TENG lies in the choice of an active material in addition to the mechanical stability and robust output performance of the device. This report suggests, for the first time, the use of a peritoneum membrane as a triboelectrically positive material for designing TENGs. The peritoneum covers the abdominal wall and diaphragm of mammals except for the kidneys and the adrenal glands and consists of a structure of a well-defined network of elastic fibers. Our peritoneum-based TENG (p-TENG) can generate an open-circuit output voltage of ∼550 V, output current density of ∼100 mA m-2, and instantaneous output power density of 9.4 Wm-2. This work demonstrates the p-TENG as a portable power source, a self-powered pedometer, and a speedometer, which conveys its futuristic applications for health care purposes. Our p-TENG is highly stable, delivering a constant output voltage of ∼550 V over a period of 90 days. The introduction of a biowaste peritoneum membrane as a triboelectrically positive component in the TENG has great potential as a portable alternative energy source owing to its abundance, stability, low cost, and ease of fabrication.

Postsynthesis Spontaneous Coalescence of Mixed-Halide Perovskite Nanocubes into Phase-Stable Single-Crystalline Uniform Luminescent Nanowires.

All inorganic mixed-halide perovskite, CsPb(Br xI1- x)3 (0 ≤ x ≤ 1), nanocrystals possess tunable photoluminescence with high quantum yield in the visible window. However, the photoluminescence degrades rapidly with postsynthetic aging due to the spontaneous ion separation and phase instability. Here we show that the postsynthetic aging of CsPb(Br xI1- x)3 nanocubes spontaneously forms highly uniform single-crystalline nanowires with a diameter of 9 ± 0.5 nm and length of up to several micrometers. The nanowires show bright photoluminescence with an absolute photoluminescence quantum yield of 41%. Rietveld refinement identifies the stable orthorhombic phase of the nanowires, implying a phase transition from the cubic crystallographic phase of the nanocubes during the morphology evolution. Transient absorption spectroscopy reveals a faster excited-state decay dynamic with a large exciton delocalization length in 1D nanowires. Our findings elucidate the insights into the postsynthesis morphology evolution of mixed-halide perovskite nanocrystals leading to luminescent nanowires with excellent crystal phase stability for potential optoelectronic applications.

Realization of Diverse Waveform Converters from a Single Nanoscale Lateral p-n Junction Cu2S-CdS Heterostructure.

A differentiator is an electronic component used to accomplish mathematical operations of calculus functions of differentiation for shaping different waveforms. Differentiators are used in numerous areas of electronics, including electronic analog computers, wave-shaping circuits, and frequency modulators. Conventional differentiators are fabricated using active operational amplifiers or using passive resistor-capacitor combinations. Here, we report that a single Cu2S-CdS heterostructure acts as a differentiator for performing numerical functions of input waveform conversion into different shapes. When a rectangular wave signal is applied through the tip of a conductive atomic force microscope, a spikelike wave signal is obtained from the Cu2S-CdS heterostructure. The Cu2S-CdS differentiator is able to convert a sine wave signal into a cosine wave signal and a triangular wave signal into a square wave signal similar to the classical differentiators. The finding of a nanoscale differentiator at extremely small length scales may have profound applications in different domains of electronics.

Unidirectional Branching Growth of Dipeptide Single Crystals for Remote Light Multiplication and Collection.

Herein, we report on the unidirectional branched assembly of diphenylalanine dipeptide through a one-step rapid evaporation process. Large numbers of crystalline tubular branches with smooth surfaces are developed from a hexagonal solid microrod mimicking a "Christmas tree". Density functional theory suggests the formation of tubular diphenylalanine aggregates with cis isomers. The diphenylalanine branched assembly shows good optical waveguide properties that can transmit light homogeneously along the crystal fibers as well as harvest light from the tips of branches to the microrod terminals. These findings hold importance in the development of bioinspired optical fibers for information transmission in a microscale.

Hierarchical heterostructure of Ag-nanoparticle decorated fullerene nanorods (Ag-FNRs) as an effective single particle freestanding SERS substrate.

A hierarchical heterostructure composed of silver nanoparticles (Ag-NPs: average diameter ∼10 nm) on fullerene nanorods (FNRs: average length ∼11 µm and average diameter ∼200 nm) was fabricated using a simple solution route. It was used as an effective single particle freestanding surface enhanced Raman scattering (SERS) substrate for the detection of target molecules (Rhodamine 6G: R6G). FNRs were formed ultra-rapidly (formation process completed in a few seconds) at a liquid-liquid interface of methanol and C60/mesitylene solution then Ag-NPs were grown directly on the surfaces of the FNRs by treatment with a solution of silver nitrate in ethanol. This unique hierarchical heterostructure allows efficient adsorption of target molecules also acting as an effective SERS substrate capable of detecting the adsorbed R6G molecules in the nanomolar concentration range. In this study, SERS spectra are acquired on an isolated single Ag-FNR for the detection of the absorbed molecule rather than from a bulk, large area film composed of silver/gold nanoparticles as used in conventional methods. Thus, this work provides a new approach for the design and fabrication of freestanding SERS substrates for molecular detection applications.

Phonon Coupling with Excitons and Free Carriers in Formamidinium Lead Bromide Perovskite Nanocrystals.

Organometal halide perovskites in the form of nanocrystals (NCs) have attracted enormous attention due to their unique optoelectronic and photoluminescence (PL) properties. Here, we examine the phase composition and the temperature dependence of emission line width broadening in formamidinium lead bromide (FAPbBr3) perovskite nanocrystals (NCs) for light-emitting applications and identify different charge-carrier scattering mechanisms. Our results show most of the emission is from the orthorhombic phase. The PL line width broadening at high temperature is dominated by the Fröhlich interaction between the free charge carriers and the optical phonons. At low temperatures, the peak of the PL spectrum exhibits a continuous red shift indicating an increase of excitons contribution at lower temperatures, and concurrently the line width also narrows down due to the inhibition of the optical phonons. From the temperature-dependent measurements, the coupling strength of both the charge phonon interaction and the exciton phonon interaction have been determined. The obtained results indicate that the charge phonon coupling strengths are higher compared to the exciton phonon coupling.

Carbon Nanosheets by Morphology-Retained Carbonization of Two-Dimensional Assembled Anisotropic Carbon Nanorings.

Two-dimensional (2D) carbon nanomaterials possessing promising physical and chemical properties find applications in high-performance energy storage devices and catalysts. However, large-scale fabrication of 2D carbon nanostructures is based on a few specific carbon templates or precursors and poses a formidable challenge. Now a new bottom-up method for carbon nanosheet fabrication using a newly designed anisotropic carbon nanoring molecule, CPPhen, is presented. CPPhen was self-assembled at a dynamic air-water interface with a vortex motion to afford molecular nanosheets, which were then carbonized under inert gas flow. Their nanosheet morphologies were retained after carbonization, which has never been seen for low-molecular weight compounds. Furthermore, adding pyridine as a nitrogen dopant in the self-assembly step successfully afforded nitrogen-doped carbon nanosheets containing mainly pyridinic nitrogen species.

Transparent, Flexible Silicon Nanostructured Wire Networks with Seamless Junctions for High-Performance Photodetector Applications.

Optically transparent photodetectors are crucial in next-generation optoelectronic applications including smart windows and transparent image sensors. Designing photodetectors with high transparency, photoresponsivity, and robust mechanical flexibility remains a significant challenge, as is managing the inevitable trade-off between high transparency and strong photoresponse. Here we report a scalable method to produce flexible crystalline Si nanostructured wire (NW) networks fabricated from silicon-on-insulator (SOI) with seamless junctions and highly responsive porous Si segments that combine to deliver exceptional performance. These networks show high transparency (∼92% at 550 nm), broadband photodetection (350 to 950 nm) with excellent responsivity (25 A/W), optical response time (0.58 ms), and mechanical flexibility (1000 cycles). Temperature-dependent photocurrent measurements indicate the presence of localized electronic states in the porous Si segments, which play a crucial role in light harvesting and photocarrier generation. The scalable low-cost approach based on SOI has the potential to deliver new classes of flexible optoelectronic devices, including next-generation photodetectors and solar cells.

Supramolecular Aggregates of Tetraphenylethene-Cored AIEgen toward Mechanoluminescent and Electroluminescent Devices.

Luminescent materials possessing both the mechanoluminescence (MCL) and electroluminescence (EL) properties are the quest for sensing and optoelectronic applications. We report on the synthesis of a new tailor-made luminogen, 1,2-bis(4-(1-([1,1'-biphenyl]-4-yl)-2,2-diphenylvinyl)phenyl)-1,2-diphenylethene (TPE 5), using Suzuki coupling reaction with high yield. An aggregation-induced emission (AIE) active complex TPE 5 forms supramolecular spherical aggregates at the air-water interface of a Langmuir trough. As a consequence, a large enhancement of luminescence is obtained from the mono- and multilayer Langmuir-Blodgett films of TPE 5 owing to the AIE effect. The luminogen TPE 5 exhibits a reversible MCL response, displaying photoluminescence switching due to change in the crystalline states under external stimuli. The unique feature of luminescence enhancement upon aggregate formation is utilized for the fabrication of light-emitting diodes with low threshold voltage using supramolecular aggregates as the active layer. This work demonstrates an efficient strategy for obtaining controlled supramolecular aggregates of AIEgen with a potential in the dual applications of MCL and EL.

Self-Powered Sensors and Flexible Triboelectric Nanogenerator for Powering Portable Electronics.

We report on a flexible triboelectric nanogenerator (FTENG) designed using polydimethylsiloxane (PDMS) and aluminium (Al) combinations to convert ambient mechanical energy into electrical outputs. An open-circuit output voltage of ~40 V and short-circuit current density of ~63.6 mA m-2 with power density 0.62 W m-2 was easily obtained from the FTENG. The harvested mechanical energy is used for lighting ~100 light emitting diodes and to operate seven segment display enabling prospects for carbon-emission free environment friendly source for powering portable electronic devices. We have shown the capability of using the FTENG as self-powered weight and pressure sensors. Additionally, flexible design of the FTENG extends its application scope for self-powered tactile sensing in electronic skin for robotic application. The FTENG is simply designed, cost-effective, scalable and high-throughput for possible uses in flexible electronics, self-powered systems and body sensor networks.