Improved photoluminescence stability and defect passivation in SbBr3 post-treated CsPbBr3 quantum dots under ambient conditions.

Inorganic cesium lead halide perovskites have evoked wide popularity because of their excellent optoelectronic properties, high photoluminescence (PL) quantum yield (PLQY), and narrowband emission. Here, cesium lead bromide (CsPbBr3 ) quantum dots (QDs) were synthesized via the ligand-assisted re-precipitation method. Post-synthesis treatment of CsPbBr3 QDs using antimony tribromide improved the PL stability and optoelectronic properties of the QDs. In addition, the PLQY of the post-treated sample was enhanced to 91% via post-treatment, and the luminescence observed was maintained for 8 days. The post-synthesis treatment ensured defect passivation and improved the stability of CsPbBr3 perovskite QDs. High-resolution transmission electron microscopy revealed the presence of more ordered, uniform-sized CsPbBr3 QDs after post-synthesis treatment, and the uniformity of the sample improved as the day passed. The formation of a mixed crystal phase was observed from X-ray diffraction in both as-synthesized, as well as post-treated QDs samples with the possibility of a polycrystalline nature in the post-treated CsPbBr3 QDs as per the selected area electron diffraction pattern. The X-ray photoelectron spectroscopy spectra confirmed the presence of antimony and the possibility of defect passivation in the post-treated samples. These QDs can act as potential candidates in various optoelectronic applications such as photodetectors and light-emitting diodes due to their high PLQY and longer lifetime.

Annealing Induced Shape Transformation of CZTS Nanorods Based Thin Films.

Here we studied the annealing induced shape transformation of 1D Cu2ZnSnS4 (CZTS) nanorods from nanospheres and nanocubes by simple sol-gel method without using any toxic chemicals or complicated vacuum based technology. X-ray diffraction pattern and Raman spectra reveal the formation of kesterite structure CZTS thin films. The energy dispersive X-ray analysis results indicate the presence of Cu, Zn, Sn, and S. The elemental distribution of all the CZTS samples was studied using elemental mapping. The Hall effect studies of the CZTS thin film composed of nanorods exhibits the lowest resistivity values which indicates efficient charge transfer for unidirectional structure. The obtained optical band gap energy of CZTS thin film is in the range of 1.46-1.54 eV, which is quite close to the optimum theoretical value required for solar cell applications.

Wire-shaped perovskite solar cell based on TiO2 nanotubes.

In this work, a wire-shaped perovskite solar cell based on TiO2 nanotube (TNT) arrays is demonstrated for the first time by integrating a perovskite absorber on TNT-coated Ti wire. Anodization was adopted for the conformal growth of TNTs on Ti wire, together with the simultaneous formation of a compact TiO2 layer. A sequential step dipping process is employed to produce a uniform and compact perovskite layer on top of TNTs with conformal coverage as the efficient light absorber. Transparent carbon nanotube film is wrapped around Ti wire as the hole collector and counter electrode. The integrated perovskite solar cell wire by facile fabrication approaches shows a promising future in portable and wearable textile electronics.

Synthesis of Cu2SnSe3 nanocrystals for solution processable photovoltaic cells.

This paper describes the synthesis of ternary chalcogenide Cu(2)SnSe(3) nanocrystals as an alternative solar absorber material to conventional quaternary CuIn(x)Ga(1-x)Se(2). We used the hot coordination solvent method with hexadecylamine as the capping ligand for the first time for this material system. Using a variety of characterization techniques, such as X-ray diffraction, selected area electron diffraction, convergent beam electron diffraction, and Raman spectroscopy, the nanocrystals were found to be monoclinic Cu(2)SnSe(3) with an optical energy band gap of 1.3 eV and have a narrow size distribution. These nanocrystals are shown to be photosensitive in the range of wavelengths corresponding to the solar spectrum, which makes them highly promising as alternative photon absorber materials for photovoltaic applications.

Low temperature synthesis of wurtzite zinc sulfide (ZnS) thin films by chemical spray pyrolysis.

Zinc sulfide (ZnS) thin films have been synthesized by spray pyrolysis at 310 °C using an aqueous solution of zinc chloride (ZnCl2) and thioacetamide (TAA). Highly crystalline films were obtained by applying TAA instead of thiourea (TU) as the sulfur source. X-ray diffraction (XRD) analyses show that the films prepared by TAA contained a wurtzite structure, which is usually a high temperature phase of ZnS. The crystallinity and morphology of the ZnS films appeared to have a strong dependence on the spray rate as well. The asymmetric polar structure of the TAA molecule is proposed to be the intrinsic reason of the formation of highly crystalline ZnS at comparatively low temperatures. The violet and green emissions from photoluminescence (PL) spectroscopy reflected the sulfur and zinc vacancies in the film. Accordingly, the photodetectors fabricated using these films exhibit excellent response to green and red photons of 525 nm and 650 nm respectively, though the band gaps of the materials, estimated from optical absorption spectroscopy, are in the range of 3.5-3.6 eV.

Solvent Evaporation Induced Large-Scale Synthesis of Cs4PbBr6 and CsPbBr3 Microcrystals: Optical Properties and Backlight Application for LEDs.

The contemporary work focuses on embossing the emissive nature of lead halide perovskite materials, specifically Cs4PbBr6 microcrystal powder prepared via single step bulk recrystallization method followed by the solvent evaporation route from gram to kilogram scale. The X-ray diffraction pattern confirms the formation of phase pure Cs4PbBr6 with a goodness of fit value of 1.51 calculated from Rietveld refinement and the fluorophore powder manifesting an intrinsic band gap of 3.76 eV. The experimental yield of 99.4% indicates the absence of any unreacted precursors. The fabricated flexible, free-standing Cs4PbBr6@PMMA film encompassed better moisture stability without undergoing phase transitions for 400 days. The temperature-dependent photoluminescence spectra denote that 51% of the intensity was retained when cooled back to room temperature after heating it till 180 °C. Moisture studies at two extreme humidity conditions also reveal the appreciable stability of the fluorophore film against moisture. The stability studies with respect to UV irradiation substantiate that the film retained its stability even after exposing it continuously to UV radiation for seven days. The outstanding optical properties of these microcrystals, owing to the higher exciton binding energy, make them a promising candidate as excellent fluorophores for color conversion, backlight, and light-emitting applications. The Cs4PbBr6@PMMA film was employed as the top cover of a commercial blue LED, producing a robust green emission which revealed its possible application as a phosphor material.

Novel assembly of an MoS2 electrocatalyst onto a silicon nanowire array electrode to construct a photocathode composed of elements abundant on the earth for hydrogen generation.

Mild-mannered catalyst: a novel procedure to load a MoS(2) co-catalyst onto the surface of silicon under mild-conditions (room temperature, atmospheric pressure, aqueous solution) by a photo-assisted electrodeposition process employing commercially available precursors is reported. The obtained Si-NW@MoS(2) photocathode showed similar catalytic activity for light-driven H(2) generation compared with a Si-NW@Pt photocathode.

A selective co-sensitization approach to increase photon conversion efficiency and electron lifetime in dye-sensitized solar cells.

Ruthenium-based C106 and organic D131 sensitizers have been judicially chosen for co-sensitization due to their complementary absorption properties and different molecular sizes. Co-sensitization yields a higher light-harvesting efficiency as well as better dye coverage to passivate the surface of TiO(2). The co-sensitized devices C106 + D131 showed significant enhancement in the performance (η = 11.1%), which is a marked improvement over baseline devices sensitized with either D131 (η = 5.6%) or C106 (η = 9.5%). The improved performance of the co-sensitized cell is attributed to the combined enhancement in the short circuit current, open circuit voltage, and the fill-factor of the solar cells. J(sc) is improved because of the complementary absorption spectra and favorable energy level alignments of both dyes; whereas, V(oc) is improved because of the better surface coverage helping to reduce the recombination and increase the electron life time. The origins of these enhancements have been systematically studied through dye desorption, absorption spectroscopy, and intensity modulated photovoltage spectroscopy investigations.

Enhancing the photocatalytic efficiency of TiO2 nanopowders for H2 production by using non-noble transition metal co-catalysts.

Co and Ni-nanoclusters are attractive alternatives to Pt catalysts for hydrogen generation. These earth abundant elements when loaded onto the TiO(2) nanopowders surface act as efficient co-catalysts. Co, Ni-decorated TiO(2) photocatalysts display only three (3) times lower catalytic activities for H(2) evolution under UV illumination compared with Pt-decorated TiO(2) photocatalysts.

Fluorescent coordination polymeric gel from tartaric acid-assisted self-assembly.

A fluorescent organogel is obtained from the reaction of Zn(OAc)(2) x 2 H(2)O, 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (bpd), and tartaric acid (H(4)tar) in methanol. The gel is proposed to have formed by the cross-linking of linear 1D coordination polymers [Zn(bpd)](n) with tartarate coligand in a highly random fashion which entrapped the solvent molecules through hydrogen-bonding interactions between the tar coligand and solvent molecules. Higher dimensional coordination polymeric structure is proposed for this gel based on the corresponding complexes formed by oxalic and succinic acids. The presence of three components is essential for the gelation. Interestingly, organogelation of the coordination polymer has induced remarkable fluorescence properties in the weakly emissive bpd. Such fluorescence enhancement is attributed to the reduction in nonradiative decay in the aggregated state. The organogel exhibits viscoelastic behavior as evidenced from the rheological studies.

Reversible Light-Responsive Solventless-Liquid Switch: Polarization-Induced Dynamic Surface Ordering-Disordering in Liquid-Like Carbon Quantum Dots.

Naturally stimulated dynamic ordering-disordering of biomolecules via noncovalent interactions is a commonly occurring phenomenon in biological systems. Herein, we report the effect of induced polarization on the charge carrier dynamics of carbon-quantum-dot-based nano ionic materials (CQD-NIMs) under simulated solar radiation. The solventless liquid-like CQD-NIMs is composed of polystyrenesulfonate (PSS)-passivated CQD as the core-corona system with a polyetheramine (Jeffamine) forming the canopy. The material was observed to behave as a dielectric when placed between two electrodes. Dynamic ordering-disordering of the corona around the CQD surface under induced polarization allowed excess current flow through the solventless material when exposed to simulated solar radiation. Such reversible molecular-assembly-induced photoconducting behavior of the CQDs was characterized with impedance spectroscopy and steady state fluorescence spectroscopy. The concept depicted in the present manuscript may be further developed to design smart light-sensitive molecular switching devices.

Coordination-Polymeric Nanofibers and their Field-Emission Properties.

The large-scale fabrication of nanofibers of coordination polymers (CPs) is reported for the first time from CP gel precursors by the electrospinning method. In the absence of organic polymeric additives, viscous solutions suitable for drawing fibers have been made by diluting the gel precursors, which are obtained by mixing Ni(OAc)(2) and 4-trifluoromethylbenzoic acid with 4,4'-bis(pyridyl)ethylene (bpe) or 4,4'-bipyridine (bpy) linear spacer ligands in organic solvents. One-dimensional polymeric structures have been proposed for these gels and nanofibers based on the crystal structures of the compounds isolated. These fibers show some interesting field-emission properties. The results described here may well be extended to other one-dimensional polymers, thus opening the door for processing of the coordination polymers.

Hierarchical assembly of carbon nanotubes-liquid crystal nanocomposite.

Fabrication of liquid crystalline (LC) nanomaterials in an aligned pattern along the multiwalled carbon nanotubes (CNT) has been reported here. The nanocomposite was prepared by sonicating esterified CNTs and the ferroelectric liquid crystal (FLC) in chloroform. The nanohybrid shish kebab (NHSK) like pattern was observed in SEM analysis. The nanocomposite materials were characterized by Fourier transform infrared spectroscopy (FTIR), polarizing optical microscopy and electron microscopy. The DC and AC electrical properties of the composite materials were investigated. The DC conductivity of the nanocomposite increased by 2 order from the FLC materials and AC relaxation has been observed, in the nanocomposite, which was totally absent in the FLC materials.

Nanostructures of bismuth sulphide: synthesis and electrical properties.

Bismuth ammonium citrate complex (C24H20Bi4O28 x 6NH3 x 10H2O) interacted with sodium sulphide (Na2S) in presence of beta-cyclodextrin (beta-CD) yielding Bi2S3 nanospheres. Solvothermal treatment of the bismuth complex and dimethyl sulphoxide (DMSO) produced Bi2S3 nanorods. Reaction conditions were optimized to investigate the morphology evolution of the product. Electrical properties of the nanorods were monitored in details.

Electrical bistability in zinc oxide nanoparticle-polymer composites.

The article reports observed electrical bistability in thin films of ZnO nanoparticles embedded in an insulating polymer matrix. From the current-voltage and impedance characteristics, they studied transport mechanisms involved in the two conducting-states. The electrical bistability in such films has been associated with a memory phenomenon. The bistability, which is reversible in nature, led to read-only and random-access memory applications in the devices based on such nanoparticles.

Preparation and characterization of silver-poly(vinylidene fluoride) nanocomposites: formation of piezoelectric polymorph of poly(vinylidene fluoride).

In situ Ag nanoparticles are produced on reduction of Ag+ with N,N-dimethylformamide in the presence of poly(vinylidene fluoride) (PVF2). The plasmon band transition is monitored with time in the reaction mixture for three sets of experiments by UV-vis spectroscopy. The plasmon band absorbance increases sigmoidally with log(time). Analysis of the data with the Avrami equation yields an exponent n value between 1.5 and 2.0, indicating two-dimensional nucleation with linear or diffusion controlled growth. The TEM study of the polymer nanocomposites (PNC) indicates both spherical and rodlike morphology for PNC0.5 and PNC2.5 samples, whereas the PNC11 sample has spherical and agglomerated structures (the numerical number associated with PNC indicates percentage (w/w) of Ag in the nanocomposite). The WAXS and FTIR studies indicate the formation of piezoelectric beta-polymorphic PVF2 in the nanocomposites. The DSC study indicates some increase of the melting point and enthalpy of fusion of PVF2 in the nanocomposite, although with increase in Ag nanoparticle concentration the increase is smaller. The crystallization temperatures of PNCs also increased, indicating nucleating effect of Ag nanoparticles in the composite. In the TGA curves, the PNCs exhibit a three-step degradation process. The degradation temperatures of PNCs are lower than that of PVF2. The storage modulus data indicate a significant reinforcement of the mechanical property in the PNCs where also the reinforcement effect decreases with increasing nanoparticle concentration. Both the loss modulus and tan delta plots indicate two peaks; the lower temperature peak has been attributed for glass transition temperature, whereas the higher one has been attributed to a similar type relaxation process for the crystalline-amorphous interface. The increase in the glass transition is marginal for the PNCs, but the increase of later transition temperature is somewhat higher. The FTIR study shows that the dipolar interaction of the >CF2 dipole with the surface charges of Ag nanoparticle stabilizes the nanoparticle in the nanocomposite.

Electrical bistability and memory phenomenon in carbon nanotube-conjugated polymer matrixes.

We have observed electrical bistability and large conductance switching in functionalized carbon nanotube (CNT)-conjugated polymer composites at room temperature. The concentration of the CNTs in the polymer matrix controlled the degree of bistability. Conduction mechanism applicable in each of the conducting states has been identified. The switching had an associated memory phenomenon and was reversible in nature. In the bistable devices, the active layer retained its high-conducting state until a reverse voltage erased it. We could "write" or "erase" a state and "read" it for many cycles for random-access memory applications.

Electrical bistability in electrostatic assemblies of CdSe nanoparticles.

We report electrical bistability in electrostatic assembly of CdSe nanoparticles. We obtained thin films of the nanoparticles via layer-by-layer electrostatic assembly technique, which provided a nanoscale control to tune the thickness. Devices based on such thin films exhibit electrical bistability along with memory phenomenon. The bistability is due to charge confinement in the nanoparticles. Conduction mechanism changes from an injection-dominated to a bulk one during switching from a low- to a high-conducting state. Additionally, results from impedance spectroscopy show that the dielectric constant of the material increases during the transition. Both random-access and read-only memory applications are observed in these systems.

Morphological modifications of selenium by recrystallization of its aqueous complex solutions.

Recrystallization of elemental selenium (Se) from aqueous solution in presence of sodium sulphite (Na2SO3) and sodium sulphide (Na2S) acting as complexing agents has resulted in the formation of nano and microstructures of Se having five different morphological modifications. (1) An aqueous solution of sodium selenosulphate (Na2SO3Se) obtained by dissolving Se in Na2SO3 under refluxing condition yields hemispherical microcrystals. (2) The filtrate of the above reaction mixture on aging produces hexagonal prismatic microrods of Se. Addition of Na2SO3Se solution to formalin (HCHO) at room temperature and refluxing conditions generates (3) Se nanorods, and (4) spherical microcrystals, respectively. (5) Recrystallization of Se from aqueous solution of Na2S develops flower shaped microcrystals.

Nanorods of tellurium: synthesis and self-assembly.

A simple solution phase approach is described to prepare tellurium nanorods which undergo morphological modifications to yield different microstructures under varied experimental conditions. The morphology of the prepared products is drastically altered in presence of a few oxidizing agents such as sodium oxychloride (NaOCl), hydrogen peroxide (H2O2) etc. The effects of poly (sodium 4-styrene sulphonate) (PSS) and Isooctyl phenoxy poly oxyethanol (TritonX-100) on the size and shape of the products in presence of air/NaOCl have also been monitored.