Revival of Degraded CsPbI3 Nanocrystals by Diselenide Ligand and Nanocrystal Self-Assembly on Nanofibrilar Ligand Template.

Among the lead halide perovskite (LHP) family, CsPbI3 is known to be significantly vulnerable to moisture, which hinders its use in real device applications. It is reported that chalcogen-based ligands can better stabilize CsPbI3 and revive nanocrystals (NCs). Here, diphenyl diselenide (DPhDSe) ligand is used to revive the degraded CsPbI3 NCs through a post-synthetic treatment of adding a small amount of DPhDSe in the degraded NC dispersion. DPhDSe in the dispersion formed nanofibrillar crystals at a low temperature through the π-π stacking of the phenyl ring. The nanofibrils played as a template on which the NCs self-assembled and they are attached side-by-side to form microfibers. The microfiber powder containing the NCs is optically stable at ambient conditions and morphologically self-healable by mild thermal annealing due to the dynamic Se─Se bond. The mechanism of the structural changes, optical transitions, and chemical changes has been systematically characterized through electron microscopy, diffraction, spectroscopy, and elemental analysis.

Interactive Deformable Colored Sound Display Achieved with Electrostrictive Fluoropolymer and Halide Perovskite.

The association of color and sound helps human cognition through a synergetic effect like intersensory facilitation. Although soft human-machine interfaces (HMIs) providing unisensory expression have been widely developed, achieving synchronized optic and acoustic expression in one device system has been relatively less explored. It is because their operating principles are different in terms of materials, and implementation has mainly been attempted through structural approaches. Here, a deformable sound display is developed that generates multiple colored lights with large sound at low input voltage. The device is based on alternating-current electroluminescence (ACEL) covered with perovskite composite films. A sound wave is created by a polymer matrix of the ACEL, while simultaneously, various colors are produced by the perovskite films and the blue electroluminescence (EL) emitted from the phosphors in the ACEL. By patterning different colored perovskite films onto the ACELs, associating the color and the sound is successfully demonstrated by a piano keyboard and a wearable interactive device.

Superior white electroluminescent devices using nitrogen-doped carbon dots/TiO2nanorods heterostructures.

Nitrogen-doped carbon dots (NCDs), exhibiting strong yellow emission in aqueous solution and solid matrices, have been utilized for fabricating heterostructure white electroluminescence devices. These devices consist of nitrogen-doped carbon dots as an emissive layer sandwiched between an organic hole transport layer (PEDOT:PSS) and an array of rutile TiO2nanorods, acting as an electron transport layer. Under an applied forward bias of 5 V, the device exhibits broadband electroluminescence covering the wavelength range of 390-900 nm, resulting in pure white light emission characteristics at room temperature. The result demonstrates the successful fabrication of all solution-processed, low-cost, eco-friendly NCDs-based LEDs with CIE (Commission Internationale d'Éclairage) coordinate of (0.31, 0.34) and color rendering index (CRI) > 90, which are close to ideal white light emission characteristics. The device functionalities are achieved based on defect-related NIR emission from TiO2nanorods array and visible emission from nitrogen-doped carbon dots. This result paves a new opportunity to develop low-cost, solution-processed nitrogen-doped carbon dots based on warm White light emitting diodes with high CRI for large-area display and lighting applications.

Ligand-Mediated Revival of Degraded α-CsPbI3 to Stable Highly Luminescent Perovskite.

Although α-CsPbI3 is regarded as an attractive optical luminophore, it is readily degraded to the optically inactive δ-phase under ambient conditions. Here, we present a simple approach to revive degraded ("optically sick") α-CsPbI3 through "medication" with thiol-containing ligands. The effect of different types of thiols is systematically studied through optical spectroscopy. The structural reconstruction of degraded α-CsPbI3 nanocrystals to cubic crystals in the presence of thiol-containing ligands is visualized through high-resolution transmission electron microscopy and supported by X-ray diffraction analysis. We found that 1-dodecanethiol (DSH) effectively revives degraded CsPbI3 and results in high immunity towards moisture and oxygen, hitherto unreported. DSH facilitates the passivation of surface defects and etching of degraded Cs4 PbI6 phase, thus reverting them back to the cubic CsPbI3 phase, leading to enhanced PL and environmental stability.

New Approaches to Produce Large-Area Single Crystal Thin Films.

Wafer-scale growth of single crystal thin films of metals, semiconductors, and insulators is crucial for manufacturing high-performance electronic and optical devices, but still challenging from both scientific and industrial perspectives. Recently, unconventional advanced synthetic approaches have been attempted and have made remarkable progress in diversifying the species of producible single crystal thin films. This review introduces several new synthetic approaches to produce large-area single crystal thin films of various materials according to the concepts and principles.

CsPbI3/N-GQDs dual layer phosphor-converted white-LEDs with ultrahigh luminous efficiency and color rendering index.

Phosphor-converted LEDs or pc-LEDs, as a solid-state lighting source, are attractive for next-generation display technologies because of their energy savings, and green environmentally friendly nature. Recently, white LEDs are being produced commercially by coating blue LED (440-470 nm) chips with various yellow-emitting phosphors. However, the LEDs produced by this technique often exhibit high correlated color temperature (CCT) and low color rendering index (CRI) values, due to sufficient red spectral components not being present, and thus aren't suitable for commercial grade white illumination. To circumvent this drawback, our work reports for the first time the use of blue and green-emitting nitrogen-functionalized graphene quantum dots (GQDs) coupled with red-emitting CsPbI3NCs for phosphor-based LED applications. We deployed near-UV to visible excitable red-emitting perovskite CsPbI3nanocrystals which contribute toward the red spectral component, thus greatly improving the CRI of the LEDs. CsPbI3nanocrystals are optically excited by nitrogen-functionalized GQD with blue and green emissions in a remote double-layer phosphor stack technique. This double phosphor layer stacking greatly improves both the CRI and luminous efficiency of radiation (LER), which usually has a trade-off in previously reported phosphor stacks. A CCT of ∼5182 K providing daylight white tonality, with superior CRI (∼90%) and ultrahigh LER (∼250 lumens/watt) are reported, which are significantly higher than the established benchmarks.

Atomic-Scale Imaging and Nano-Scale Mapping of Cubic α-CsPbI3 Perovskite Nanocrystals for Inverted Perovskite Solar Cells.

Colloidal synthesized cubic α-CsPbI3 perovskite nanocrystals having a smaller lattice constant (a = 6.2315 Å) compared to the standard structure, and nanoscale mapping of their surfaces are reported to achieve superior photovoltaic performance under 45-55% humidity conditions. Atomic scale transmission electron microscopic images have been utilized to probe the precise arrangement of Cs, Pb, and I atoms in a unit cell of α-CsPbI3 NCs, which is well supported by the VESTA structure. Theoretical calculation using density functional theory of our experimental structure reveals the realization of direct band to band transition with a lower band gap, a higher absorption coefficient, and stronger covalent bonding between the Pb and I atoms in the [PbI6]4- octahedral, as compared to reported standard structure. Nanoscale surface mapping using Kelvin probe force microscopy yielding contact potential difference (CPD) and conductive atomic force microscopy for current mapping have been employed on α-CsPbI3 NCs films deposited on different DMSO doped PEDOT:PSS layers. The difference of CPD value under dark and light illumination suggests that the hole injection strongly depends on the interfaces with PEDOT:PSS layer. The carrier transport through grain interiors and grain boundaries in α-CsPbI3 probed by the single-point c-AFM measurements reveal the excellent photosensitivity under the light conditions. Finally, inverted perovskite solar cells, employing α-CsPbI3 NCs film as an absorber layer and PEDOT:PSS layer as a hole transport layer, have been optimized to achieve the highest power conversion efficiency of 10.6%, showing their potential for future earth abundant, low cost, and air stable inverted perovskite photovoltaic devices.

Exfoliated Molybdenum Disulfide-Wrapped CdS Nanoparticles as a Nano-Heterojunction for Photo-Electrochemical Water Splitting.

We developed a heterojunction photocathode, MoS2@CdS, based on the wrapping of CdS nanoparticles by the MoS2 nanocrystals. The liquid-phase exfoliation method was adopted for preparing few-layer MoS2 nanocrystals of a layer thickness of ∼7.9 nm, whereas CdS nanoparticles of an average diameter of ∼17 nm were synthesized by the one-step hydrothermal process. The synthesized nanocrystals and nanoparticles were characterized by AFM, FESEM, HRTEM, STEM, XRD, GIXRD, UV-vis absorption, fluorescence emission, and Raman spectroscopy. The difference between two modes in the Raman spectrum of MoS2 indicates the formation of few-layer MoS2. The photoelectrochemical performance of the heterojunction photocathode was excellent. The MoS2@CdS heterostructure photocathode increased the photocurrent density (JPh) under 100 mW/cm2 illumination. We obtained the maximum applied biased photoconversion efficiency (ABPE) of ∼1.2% of the MoS2@CdS heterojunction photocathode in optimum device configuration. The production of H2 was measured as ∼72 µmol/h for the MoS2@CdS heterostructure with a cyclic stability of up to 7500 s.

A Multifunctional Smart Textile Derived from Merino Wool/Nylon Polymer Nanocomposites as Next Generation Microwave Absorber and Soft Touch Sensor.

In recent times e-textiles have emerged as wonder safeguards due to the great potential background in space, military, healthcare, or portable electronics. As a result, widespread research and development have been done to make significant advancement in this field, but it still remains a key challenge to use one single product with multifunctional attributes with the past performance of key characteristics. In this work, phase-separated PEDOT:PSS ornamented with reduced graphene oxide (rGO) nanosheets, deposited on the newly fabricated ultralightweight, superhydrophobic, and mechanically enriched merino wool/nylon (W-N) composite textile followed by the dipping and drying strategy. The open edges-layered structure of rGO helping uniform deposition of PEDOTs clusters, which allows the formation of a stacked layer of PEDOTs/rGO-PEDOTs/PEDOTs for robust three-dimensional electrical transforming channel network within the W-N textile surface. These dip-coated multifunctional textiles show high electrical conductivities up to 90.5 S cm-1 conjugated with a flexible electromagnetic interference shielding efficiency of 73.8 dB (in X-band) and in-plane thermal conductivity of 0.81 W/mK with a minimum thickness of 0.84 mm. This thin coating maintained the hydrophobicity (water contact angle of ∼150°) leading to an excellent EM protective cloth combined with real-life antenna performance under high mechanical or chemical tolerance. Interestingly, this multiuse textile can also act as an exceptional TASER Proof Textile (TPT) due to a short out of the electrical shock coming from the TASER by its unique conducting network architecture. Remarkably, this coated textile can get a response by the soft touch to lighten up the household bulb and could establish wireless communication via an HC-05 Bluetooth module as a textile-based touch switch. This developed fabric could perform as a new potentially scalable single product in intelligent smart garments, portable next-generation electronics, and the growing threat of EM pollution.

Surfactant-Induced Anion Exchange and Morphological Evolution for Composition-Controlled Caesium Lead Halide Perovskites with Tunable Optical Properties.

Environmentally stable lead halide perovskite nanostructures with engineered composition and morphology are attractive because of their exotic optical properties. Here, we report the synthesis of monodispersed (∼20 nm) CsPbI3 cubic perovskite nanocrystals (NCs) using edible olive oil as a solvent as well as a chelating reagent. Thereafter, bromide anion exchange reaction using the cetyl trimethyl ammonium bromide surfactant in hexane is carried out at relatively lower temperatures to synthesize caesium lead halide perovskites with variable halide compositions and tunable band gaps. Interestingly, because of the formation of micelles, continuous morphology evolution varying from NCs of different sizes to nanowires (NWs) and nanosheets is observed. The anion exchange temperature has a distinct effect on the morphology of the CsPbBr3 nanostructure and the anion exchange reaction rate. Finally, an easy solution-processed photoconductive device is demonstrated using as-grown CsPbBr3 NWs, indicating its potential for optoelectronic applications.

Application of tungsten disulfide quantum dot-conjugated antimicrobial peptides in bio-imaging and antimicrobial therapy.

Two-dimensional (2D) tungsten disulfide (WS2) quantum dots offer numerous promising applications in materials and optoelectronic sciences. Additionally, the catalytic and photoluminescence properties of ultra-small WS2 nanoparticles are of potential interest in biomedical sciences. Addressing the use of WS2 in the context of infection, the present study describes the conjugation of two potent antimicrobial peptides with WS2 quantum dots, as well as the application of the resulting conjugates in antimicrobial therapy and bioimaging. In doing so, we determined the three-dimensional solution structure of the quantum dot-conjugated antimicrobial peptide by a series of high-resolution nuclear magnetic resonance (NMR) techniques, correlating this to the disruption of both model lipid and bacterial membranes, and to several key biological performances, including antimicrobial and anti-biofilm effects, as well as cell toxicity. The results demonstrate that particle conjugation enhances the antimicrobial and anti-biofilm potency of these peptides, effects inferred to be due to multi-dendate interactions for the conjugated peptides. As such, our study provides information on the mode-of-action of such conjugates, laying the foundation for their potential use in treatment and monitoring of infections.

Multivalent gold nanoparticle-peptide conjugates for targeting intracellular bacterial infections.

Although nanoparticle-tagged antimicrobal peptides have gained considerable importance in recent years, their structure-function correlation has not yet been explored. Here, we have studied the mechanism of action of a designed antimicrobial peptide, VG16KRKP (VARGWKRKCPLFGKGG), delivered via gold nanoparticle tagging against Salmonella infection by combining biological experiments with high- and low-resolution spectroscopic techniques. In comparison with the free VG16KRKP peptide or gold nanoparticle alone, the conjugated variant, Au-VG16KRKP, is non-cytotoxic to eukaryotic cells, but exhibits strong bacteriolytic activity in culture. Au-VG16KRKP can penetrate host epithelial and macrophage cells as well as interact with intracellular S. Typhi LPS under both in vitro and in vivo conditions. Treatment of mice with Au-VG16KRKP post-infection with S. Typhi resulted in reduced intracellular bacterial recovery and highly enhanced protection against S. Typhi challenge. The three-dimensional high resolution structure of nanoparticle conjugated VG16KRKP depicted the generation of a well-separated amphipathic structure with slight aggregation, responsible for the increase of the local concentration of the peptide, thus leading to potent activity. This is the first report on the structural and functional characterization of a nanoparticle conjugated synthetic antimicrobial peptide that can kill intracellular pathogens and eventually protect against S. Typhi challenge in vivo.

Superior heterojunction properties of solution processed copper-zinc-tin-sulphide quantum dots on Si.

CZTS nanocrystals have been synthesized via a new facile and environmentally friendly route using olive oil at a relatively low temperature. Nanocrystals synthesized using olive oil have a smaller average size in comparison to those synthesized with a conventional solvent-like ethylenediamine. Nanocrystals with an average diameter of 40, 20 and 6 nm have been extracted from the olive oil at different centrifugation speeds of 500, 1000 and 2000 rpm, respectively. The photovoltaic characteristics of p-CZTS/n-Si heterojunctions fabricated using the synthesized colloidal quaternary nanocrystals are demonstrated. The device fabricated with smallest sized CZTS nanocrystals, having an average diameter of ∼6 nm, exhibits an enhancement in power conversion efficiency of 61% in comparison to that of the device fabricated with the nanocrystals of 40 nm in diameter. A lower reflectance and higher minority carrier life time along with a larger surface-to-volume ratio resulted in an enhanced power conversion efficiency for smaller sized CZTS nanocrystals.

Highly Luminescent WS2 Quantum Dots/ZnO Heterojunctions for Light Emitting Devices.

Sonication induced vertical fragmentation of two-dimensional (2D) WS2 nanosheets into highly luminescent, monodispered, zero-dimensional (0D) quantum dots (QDs) is reported. The formation of 0D structures from 2D sheets and their surface/microstructure characterization are revealed from their microscopic and spectroscopic investigations. Size dependent optical properties of WS2 nanostructures have been explored by UV-vis absorption and photoluminescence spectroscopy. Interestingly, it is observed that, below a critical dimension (∼2 nm), comparable to the Bohr exciton radius, the tiny nanocrystals exhibit strong emission. Finally, the electroluminescence characteristics are demonstrated for the first time, by forming a heterojunction of stabilizer free WS2 QDs and ZnO thin films. The signature of white light emission in the light emitting device is attributed to the adequate intermixing of emission characteristics of WS2 QDs and ZnO. The observation of white electroluminescence may pave the way to fabricate prototype futuristic efficient light emitting devices.

Exfoliation of WS2 in the semiconducting phase using a group of lithium halides: a new method of Li intercalation.

Lithium halide assisted high yield synthesis of few layers of 2H phase semiconducting WS2 in organic solvents is reported. A group of lithium halides (LiCl, LiBr and LiI) has been employed for the first time to intercalate WS2 by using Li, followed by mild sonication to exfoliate in dispersive polar solvents. In contrast to the n-butyllithium (n-BuLi) assisted exfoliation method, which yields only the metallic 1T phase on prolonged reaction (3-7 days) at higher temperatures, the proposed exfoliation method produces only semiconducting 2H WS2 in a much shorter time (5 minute sonication). A very high yield of 19 mg ml(-1) has been obtained using LiI as an exfoliating agent due to its lower lattice energy compared to other alkali halides and the smaller size of the cation. Detailed microscopy and spectroscopic characterization reveals exfoliation of few layered WS2 with stoichiometric composition. Absorption and emission characteristics of the 2D WS2 layer exhibit a characteristic band edge and quantum confined transitions. As a proof-of-concept, we have successfully demonstrated photodetector devices comprising solution proccessed p-WS2/n-Si heterojunctions, which behave as diodes with a high rectification ratio (>10(2)) exhibiting a broad band photoresponse over the entire visible region.

Novel silicon compatible p-WS2 2D/3D heterojunction devices exhibiting broadband photoresponse and superior detectivity.

We report for the first time, the fabrication of novel two-dimensional (2D) p-WS2/n-Si vertical heterostructures with superior junction and photoresponse characteristics. Few layer WS2 has been synthesized by a lithium-ion intercalation technique in hexane and coated on Si substrates for realization of CMOS compatible devices. Atomic force microscopy and Raman spectroscopy have been used to confirm the 2D nature of WS2 layers. Sharp band-edge absorption and emission peaks have indicated the formation of mono-to-few-layers thick direct band gap WS2 films. The electrical and optical responses of the heterostructures have exhibited superior properties revealing the formation of an abrupt heterojunction. The fabricated photodetector device depicts a peak responsivity of 1.11 A W(-1) at -2 V with a broadband spectral response of 400-1100 nm and a moderate photo-to-dark current ratio of ∼10(3). The optical switching characteristics have been studied as a function of applied bias and illuminated power density. A comparative study of the reported results on 2D transition metal chalcogenides indicates the superior characteristics of WS2/n-Si heterostructures for future photonic devices.