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.

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.

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.

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.

Carbon nanotubes as an efficient hole collector for high voltage methylammonium lead bromide perovskite solar cells.

A high open circuit voltage (V(OC)) close to 1.4 V under AM 1.5, 100 mW cm(-2) conditions is achieved when carbon nanotubes (CNTs) are used as a hole conductor in methyl ammonium lead bromide (MAPbBr3) perovskite solar cells. Time-resolved photoluminescence and impedance spectroscopy investigations suggest that the observed high V(OC) is a result of the better charge extraction and lower recombination of the CNT hole conductor. Tandem solar cells with all perovskite absorbers are demonstrated with a MAPbBr3/CNT top cell and a MAPbI3 bottom cell, achieving a V(OC) of 2.24 V in series connection. The semitransparent and high voltage MAPbBr3/CNT solar cells show great potential for applications in solar cell windows, tandem solar cells and solar driven water splitting.

Facile water-based spray pyrolysis of earth-abundant Cu2FeSnS4 thin films as an efficient counter electrode in dye-sensitized solar cells.

A novel approach to produce earth-abundant Cu2FeSnS4 (CFTS) thin film using spray pyrolysis of nontoxic aqueous precursors followed by sulfurization is reported. The CFTS phase formation was confirmed by both Raman spectroscopy and X-ray diffraction techniques. Hall measurements of these films reveal p-type conductivity with good charge carrier density and mobilities appropriate for solar harvesting devices. To the best of our knowledge, this is the first report on the electrical properties of solution-processed Cu2FeSnS4 thin films estimated using Hall measurements. Dye-sensitized solar cells (DSSC) fabricated with CFTS thin film as a photocathode in iodine/iodide electrolyte exhibit good power conversion efficiency, 8.03%, indicating that CFTS would be a promising cheaper alternative to replace Pt as a counter electrode in DSSCs.

Photoactive nanocrystals by low-temperature welding of copper sulfide nanoparticles and indium sulfide nanosheets.

We successfully utilize the concept of coalescence and room-temperature sintering to prepare morphologically different nanoparticles. n-Type chalcogenide (CuIn5 S8 ) nanocrystals are synthesized at room temperature by simple mixing of oppositely charged precursor nanoparticles. The coalescence of polycation-coated CuS nanoparticles and negatively charged In2 S3 nanoplates is driven by close contact of the particles due to electrostatic interactions. Analysis by X-ray diffraction, transmission electron microscopy (TEM) imaging, and Raman spectroscopy confirms the formation of single-phase CuIn5 S8 without traceable secondary phase. In a photovoltaic device, the use of the coalesced particles yields a power conversion efficiency of 1.8%.

Laminated carbon nanotube networks for metal electrode-free efficient perovskite solar cells.

Organic-inorganic metal halide perovskite solar cells were fabricated by laminating films of a carbon nanotube (CNT) network onto a CH3NH3PbI3 substrate as a hole collector, bypassing the energy-consuming vacuum process of metal deposition. In the absence of an organic hole-transporting material and metal contact, CH3NH3PbI3 and CNTs formed a solar cell with an efficiency of up to 6.87%. The CH3NH3PbI3/CNTs solar cells were semitransparent and showed photovoltaic output with dual side illuminations due to the transparency of the CNT electrode. Adding spiro-OMeTAD to the CNT network forms a composite electrode that improved the efficiency to 9.90% due to the enhanced hole extraction and reduced recombination in solar cells. The interfacial charge transfer and transport in solar cells were investigated through photoluminescence and impedance measurements. The flexible and transparent CNT network film shows great potential for realizing flexible and semitransparent perovskite solar cells.

Spray pyrolysis of CuIn(S,Se)2 solar cells with 5.9% efficiency: a method to prevent Mo oxidation in ambient atmosphere.

Direct spray pyrolysis to form CuInS2 (CIS) on molybdenum substrate in ambient environment has been a challenge because of the ease of Mo oxidation at low temperatures. MoO2 formation affects the wettability of precursor solution during spray pyrolysis, which degrades the uniformity of CIS film and acts as a resistive layer for carrier transport. In this paper, Mo oxidation was prevented by using excess sulfur in the precursor solution under a gradual heating and spray process. A thin precursor layer was initially deposited as a barrier layer to prevent oxygen adsorption on Mo surface before the temperature was increased further to form polycrystalline CuInS2. The CuIn(S,Se)2 (CISSe) device fabricated from selenization of the spray-pyrolyzed CIS film exhibited a power conversion efficiency (PCE) of 5.9%. The simple spray method proposed here can be used to deposit a variety of Cu-based chalcopyrite precursor to produce high-quality thin film solar cells.

Bulk antimony sulfide with excellent cycle stability as next-generation anode for lithium-ion batteries.

Nanomaterials as anode for lithium-ion batteries (LIB) have gained widespread interest in the research community. However, scaling up and processibility are bottlenecks to further commercialization of these materials. Here, we report that bulk antimony sulfide with a size of 10-20 µm exhibits a high capacity and stable cycling of 800 mAh g(-1). Mechanical and chemical stabilities of the electrodes are ensured by an optimal electrode-electrolyte system design, with a polyimide-based binder together with fluoroethylene carbonate in the electrolyte. The polyimide binder accommodates the volume expansion during alloying process and fluoroethylene carbonate suppresses the increase in charge transfer resistance of the electrodes. We observed that particle size is not a major factor affecting the charge-discharge capacities, rate capability and stability of the material. Despite the large particle size, bulk antimony sulfide shows excellent rate performance with a capacity of 580 mAh g(-1) at a rate of 2000 mA g(-1).

High-capacity antimony sulphide nanoparticle-decorated graphene composite as anode for sodium-ion batteries.

Sodium-ion batteries are an alternative to lithium-ion batteries for large-scale applications. However, low capacity and poor rate capability of existing anodes are the main bottlenecks to future developments. Here we report a uniform coating of antimony sulphide (stibnite) on graphene, fabricated by a solution-based synthesis technique, as the anode material for sodium-ion batteries. It gives a high capacity of 730 mAh g(-1) at 50 mA g(-1), an excellent rate capability up to 6C and a good cycle performance. The promising performance is attributed to fast sodium ion diffusion from the small nanoparticles, and good electrical transport from the intimate contact between the active material and graphene, which also provides a template for anchoring the nanoparticles. We also demonstrate a battery with the stibnite-graphene composite that is free from sodium metal, having energy density up to 80 Wh kg(-1). The energy density could exceed that of some lithium-ion batteries with further optimization.

Chemical welding of binary nanoparticles: room temperature sintering of CuSe and In2S3 nanoparticles for solution-processed CuInS(x)Se(1-x) solar cells.

Chemical welding of oppositely charged dissimilar metal chalcogenide nanomaterials is reported to produce a quaternary metal chalcogenide. CuSe and In2S3 nanoparticles were synthesized with opposite surface charges by stabilizing with polyacrylic acid and polydiallyldimethylammonium chloride. Upon mixing these nanoparticles at room temperature, the electrostatic attraction induced coalescence of these nanoparticles and led to the formation of CuInSxSe1-x nanoparticles.

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.

Nanoparticle-induced grain growth of carbon-free solution-processed CuIn(S,Se)2 solar cell with 6% efficiency.

Chalcopyrite-based solar cell deposited by solution processes is of great research interest because of the ease of fabrication and cost effectiveness. Despite the initial promising results, most of the reported methods encounter challenges such as limited grain growth, carbon-rich interlayer, high thermal budget, and the presence of secondary Cu-rich phases, which limit the power conversion efficiency (PCE). In this paper, we develop a new technique to deposit large grain, carbon-free CISSe absorber layers from aqueous nanoparticle/precursor mixture which resulted in a solar cell with PCE of 6.2%. CuCl2, InCl3, and thiourea were mixed with CuS and In2S3 nanoparticles in water to form the unique nanoparticle/precursor solution. The Carbon layer formation was prevented because organic solvents were not used in the precursor. The copper-rich (CuS) nanoparticles were intentionally introduced as nucleation sites which accelerate grain growth. In the presence of nanoparticles, the grain size of CISSe film increased by a factor of 7 and the power conversion efficiency of the solar cell is 85% higher than the device without nanoparticle. This idea of using nanoparticles as a means to promote grain growth can be further exploited for other types of chalcopyrite thin film deposited by solution methods.

In situ photo-assisted deposition of MoS2 electrocatalyst onto zinc cadmium sulphide nanoparticle surfaces to construct an efficient photocatalyst for hydrogen generation.

We reported herein a facile and scalable preparation process for MoS(2)-decorated Zn(x)Cd(1-x)S hybrid photocatalysts for hydrogen generation. Zn(x)Cd(1-x)S nanopowder was first prepared from commercially available precursors employing a solution based process. MoS(2) hydrogen evolution reaction catalyst was then loaded onto the Zn(x)Cd(1-x)S nanopowder via a photo-assisted deposition process which employed mild conditions (room temperature, atmospheric pressure and visible light illumination). Thus, this process represents an important advantage in the large scale production of semiconductor/MoS(2) hybrid photocatalysts in comparison to the conventional method relying on thermal decomposition of (NH(4))(2)[MoS(4)] precursor at high temperature and under H(2)S pressure. The best Zn(0.2)Cd(0.8)S/MoS(2) 3% showed two hundred-and-ten times (210 times) faster hydrogen generation rate on visible light illumination compared with that obtained for un-treated Zn(0.2)Cd(0.8)S. That was the most impressive catalytic enhancement ever recorded for a semiconductor photocatalyst decorated with a noble metal free electrocatalyst.

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.

Nanoclay gelation approach toward improved dye-sensitized solar cell efficiencies: an investigation of charge transport and shift in the TiO2 conduction band.

Nanoclay minerals play a promising role as additives in the liquid electrolyte to form a gel electrolyte for quasi-solid-state dye-sensitized solar cells, because of the high chemical stability, unique swelling capability, ion exchange capacity, and rheological properties of nanoclays. Here, we report the improved performance of a quasi-solid-state gel electrolyte that is made from a liquid electrolyte and synthetic nitrate-hydrotalcite nanoclay. Charge transport mechanisms in the gel electrolyte and nanoclay interactions with TiO(2)/electrolyte interface are discussed in detail. The electrochemical analysis reveals that the charge transport is solely based on physical diffusion at the ratio of [PMII]:[I(2)] = 10:1 (where PMII is 1-propyl-3-methylimidazolium iodide). The calculated physical diffusion coefficient shows that the diffusion of redox ions is not affected much by the viscosity of nanoclay gel. The addition of nitrate-hydrotalcite clay in the electrolyte has the effect of buffering the protonation process at the TiO(2)/electrolyte interface, resulting in an upward shift in the conduction band and a boost in open-circuit voltage (V(OC)). Higher V(OC) values with undiminished photocurrent is achieved with nitrate-hydrotalcite nanoclay gel electrolyte for organic as well as for inorganic dye (D35 and N719) systems. The efficiency for hydrotalcite clay gel electrolyte solar cells is increased by 10%, compared to that of the liquid electrolyte. The power conversion efficiency can reach 10.1% under 0.25 sun and 9.6% under full sun. This study demonstrates that nitrate-hydrotalcite nanoclay in the electrolyte not only solidifies the liquid electrolyte to prevent solvent leakage, but also facilitates the improvement in cell efficiency.

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.

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.