Bandgap Modulation of Cs2AgInX6 (X = Cl and Br) Double Perovskite Nano- and Microcrystals via Cu2+ Doping

Recently, the double perovskite Cs2AgInCl6, which has high stability and low toxicity, has been proposed as a potential alternative to Pb-based perovskites. However, the calculated parity-allowed transition bandgap of Cs2AgInCl6 is 4.25 eV; this wide bandgap makes it difficult to use as an efficient solar absorber. In this study, we explored the effect of Cu doping on the optical properties of Cs2AgInCl6 double perovskite nano- and microcrystals (MCs), particularly in its changes of absorption profile from the ultraviolet (UV) to near-infrared (NIR) region. Undoped Cs2AgInCl6 showed the expected wide bandgap absorbance, but the Cu-doped sample showed a new sharp absorption peak at 419 nm and broad absorption bands near 930 nm, indicating bandgap reduction. Electron paramagnetic resonance (EPR) spectroscopy demonstrated that this bandgap reduction effect was due to the Cu doping in the double perovskite and confirmed that the Cu2+ paramagnetic centers were located on the surface of the nanocrystals (NCs) and at the center of the perovskite octahedrons (g(parallel to) > g(perpendicular to) > g(e)). Finally, we synthesized Cu-doped Cs2AgInCl6 MCs and observed results similar to those of the NCs, showing that the application range could be expanded to multidimensions

Facile Method to Prepare for the Ni2P Nanostructures with Controlled Crystallinity and Morphology as Anode Materials of Lithium-Ion Batteries

Conversion reaction materials (transition metal oxides, sulfides, phosphides, etc.) are attractive in the field of lithium-ion batteries because of their high theoretical capacity and low cost. However, the realization of these materials in lithium-ion batteries is impeded by large voltage hysteresis, high polarization, inferior cycle stability, rate capability, irreversible capacity loss in first cycling, and dramatic volume change during redox reactions. One method to overcome these problems is the introduction of amorphous materials. This work introduces a facile method to synthesize amorphous and crystalline dinickel phosphide (Ni2P) nanoparticle clusters with identical morphology and presents a direct comparison of the two materials as anode materials for rechargeable lithium-ion batteries. To assess the effect of crystallinity and hierarchical structure of nanomaterials, it is crucial to conserve other factors including size, morphology, and ligand of nanoparticles. Although it is rarely studied about synthetic methods of well-controlled Ni2P nanomaterials to meet the above criteria, we synthesized amorphous, crystalline Ni2P, and self-assembled Ni2P nanoparticle clusters via thermal decomposition of nickel-surfactant complex. Interestingly, simple modulation of the quantity of nickel acetylacetonate produced amorphous, crystalline, and self-assembled Ni2P nanoparticles. A 0.357 M nickel-trioctylphosphine (TOP) solution leads to a reaction temperature limitation (similar to 315 degrees C) by the nickel precursor, and crystalline Ni2P (c-Ni2P) nanoparticles clusters are generated. On the contrary, a lower concentration (0.1 M) does not accompany a temperature limitation and hence high reaction temperature (330 degrees C) can be exploited for the self-assembly of Ni2P (s-Ni2P) nanoparticle clusters. Amorphous Ni2P (a-Ni2P) nanoparticle clusters are generated with a high concentration (0.714 M) of nickel-TOP solution and a temperature limitation (similar to 290 degrees C). The a-Ni2P nanoparticle cluster electrode exhibits higher capacities and Coulombic efficiency than the electrode based on c-Ni2P nanoparticle clusters. In addition, the amorphous structure of Ni2P can reduce irreversible capacity and voltage hysteresis upon cycling. The amorphous morphology of Ni2P also improves the rate capability, resulting in superior performance to those of c-Ni2P nanoparticle clusters in terms of electrode performance

Solution-processed CdS transistors with high electron mobility

Solution-processed CdS field effect transistors (FETs) and solar cells are demonstrated via spin-coating and thermal annealing of soluble cadmium thiolate compounds. The synthesis is carried out in one simple step using cadmium oxide and tertiary alkane thiols. The cadmium thiolates are soluble in organic solvents such as chloroform and may be spin-coated, like organic semiconductors, to form thin films. The cadmium thiolate films decompose rapidly at 300 ??C to yield semiconducting cadmium sulfide films. FETs are easily fabricated using these films and exhibit electron mobilities of up to 61 cm2 V -1 s-1, which compare favourably to FETs prepared from other solution-processed materials such as organic semiconductors, inorganic nanoparticles or chalcogenide films. Initial attempts to prepare hybrid bilayer solar cells were successfully realized by spin-coating a p-type semiconducting polymer layer on top of the n-type CdS film. These devices show significant photocurrent response from both the CdS and polymer layers, indicating that the CdS films are able to participate in photo-induced electron transfer from the polymer to the CdS layer as well as photo-induced hole transfer from CdS to the polymer layer.close2

Eco-Friendly Synthesis of Water-Glass-Based Silica Aerogels via Catechol-Based Modifier

Silica aerogels have attracted much attention owing to their excellent thermal insulation properties. However, the conventional synthesis of silica aerogels involves the use of expensive and toxic alkoxide precursors and surface modifiers such as trimethylchlorosilane. In this study, cost-effective water-glass silica aerogels were synthesized using an eco-friendly catechol derivative surface modifier instead of trimethylchlorosilane. Polydopamine was introduced to increase adhesion to the SiO2 surface. The addition of 4-tert-butyl catechol and hexylamine imparted hydrophobicity to the surface and suppressed the polymerization of the polydopamine. After an ambient pressure drying process, catechol-modified aerogel exhibited a specific surface area of 377 m(2)/g and an average pore diameter of approximately 21 nm. To investigate their thermal conductivities, glass wool sheets were impregnated with catechol-modified aerogel. The thermal conductivity was 40.4 mWm(-1)K(-1), which is lower than that of xerogel at 48.7 mWm(-1)K(-1). Thus, by precisely controlling the catechol coating in the mesoporous framework, an eco-friendly synthetic method for aerogel preparation is proposed

High colloidal stability ZnO nanoparticles independent on solvent polarity and their application in polymer solar cells

Significant aggregation between ZnO nanoparticles (ZnO NPs) dispersed in polar and nonpolar solvents hinders the formation of high quality thin film for the device application and impedes their excellent electron transporting ability. Herein a bifunctional coordination complex, titanium diisopropoxide bis(acetylacetonate) (Ti(acac)2) is employed as efficient stabilizer to improve colloidal stability of ZnO NPs. Acetylacetonate functionalized ZnO exhibited long-term stability and maintained its superior optical and electrical properties for months aging under ambient atmospheric condition. The functionalized ZnO NPs were then incorporated into polymer solar cells with conventional structure as n-type buffer layer. The devices exhibited nearly identical power conversion efficiency regardless of the use of fresh and old (2 months aged) NPs. Our approach provides a simple and efficient route to boost colloidal stability of ZnO NPs in both polar and nonpolar solvents, which could enable structure-independent intense studies for efficient organic and hybrid optoelectronic devices

Large-Scale Synthesis of Highly Luminescent InP@ZnS Quantum Dots Using Elemental Phosphorus Precursor

Department of Chemical EngineeringColloidal quantum dots can control the bandgap by controlling the particle size, and are capable of solution processing, which is cost competitive, and has a narrow half width of the emission wavelength. Using these characteristics, it is possible to utilize various kinds of LED, solar cell, and bio imaging. Among them, indium phosphide (InP) quantum dots have a bandgap capable of emitting light in the near-infrared region from the visible light region, and are less toxic to humans and the environment than cadmium-based quantum dots, and are attracting attention as next generation light emitting materials. However, the limited choice and high cost of P precursors have a negative impact on their practical applicability. In this work, I report the large-scale synthesis of highly luminescent InP@ZnS QDs from an elemental P precursor (P4), which was simply synthesized via the sublimation of red P powder. The size of the InP QDs was controlled by varying the reaction parameters such as the reaction time and temperature, and the type of In precursors. This way, the photoluminescence properties of the synthesized InP@ZnS QDs could be easily tuned across the entire visible range, while their quantum yield could be increased up to 60% via the optimization of reaction conditions. Furthermore, possible reaction pathways for the formation of InP QDs using the P4 precursor have been investigated with nuclear magnetic resonance spectroscopy and it was demonstrated that the direct reaction of P4 precursor with In precursor produces InP structures without the formation of intermediate species. The large-scale production of InP@ZnS QDs was demonstrated by yielding more than 6 g of QDs per one-batch reaction. In the case of InP using different precursor P except the Tris(Trimethylsilyl) phosphine ((TMS)3P) there has been a problem that the size distribution is poor. Two kinds of P precursors with different reactivities were used to separate the nucleation and growth processes and to induce growth along the Lamer mechanism to produce uniform particles. For this, (TMS)3P and DEAP were used as fast reacting P precursors, and P4 was used as a slow reacting P precursor. Through this, the possibility of uniform particle formation was observed. I strongly believe that the newly developed approach bears the potential to be widely used for manufacturing inexpensive high-quality QD emitters.ope

Compact Biocompatible Quantum Dots via RAFT-Mediated Synthesis of Imidazole-Based Random Copolymer Ligand

We present a new class of polymeric ligands for quantum dot (QD) water solubilization to yield biocompatible and derivatizable QDs with compact size (~10-12 nm diameter), high quantum yields (>50%), excellent stability across a large pH range (pH 5-10.5), and low nonspecific binding. To address the fundamental problem of thiol instability in traditional ligand exchange systems, the polymers here employ a stable multidentate imidazole binding motif to the QD surface. The polymers are synthesized via reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization to produce molecular weight controlled monodisperse random copolymers from three types of monomers that feature imidazole groups for QD binding, polyethylene glycol (PEG) groups for water solubilization, and either primary amines or biotin groups for derivatization. The polymer architecture can be tuned by the monomer ratios to yield aqueous QDs with targeted surface functionalities. By incorporating amino-PEG monomers, we demonstrate covalent conjugation of a dye to form a highly efficient QD-dye energy transfer pair as well as covalent conjugation to streptavidin for high-affinity single molecule imaging of biotinylated receptors on live cells with minimal non-specific binding. The small size and low serum binding of these polymer-coated QDs also allow us to demonstrate their utility for in-vivo imaging of the tumor microenvironment in live mice.Chemistry and Chemical Biolog