Potassium Bromide Surface Passivation on CsPbI3-xBrx Nanocrystals for Efficient and Stable Pure Red Perovskite Light-Emitting Diodes.

All-inorganic lead halide perovskite nanocrystals (NCs) are potential candidates for fabricating high-performance light-emitting diodes (LEDs) owing to their precisely tunable bandgaps, high photoluminescence (PL) efficiency, and excellent color purities. However, the performance of pure red (630-640 nm) all-inorganic perovskite LEDs is still limited by the halide segregation-induced instability of the electroluminescence (EL) of mixed halide CsPbI3-xBrx NCs. Herein, we report an effective approach to improving the EL stability of pure red all-inorganic CsPbI3-xBrx NC-based LEDs via the passivation of potassium bromide on NCs. By adding potassium oleate to the reaction system, we obtained potassium bromide surface-passivated (KBr-passivated) CsPbI3-xBrx NCs with pure red PL emission and a photoluminescence quantum yield (PLQY) exceeding 90%. We determine that most potassium ions present on the surface of NCs bind with bromide ions and thus demonstrate that potassium bromide surface passivation of NCs can both improve the PL stability and inhibit the halide segregation of NCs. Using KBr-passivated CsPbI3-xBrx NCs as an emitting layer, we fabricated stable and pure red perovskite LEDs with emission at 637 nm, showing a maximum brightness of 2671 cd m-2, maximum external quantum efficiency of 3.55%, and good EL stability. The proposed KBr-passivated NC strategy will open a new avenue for fabricating efficient, stable, and tunable pure color perovskite NC LEDs.

Highly Luminescent Copper Iodide Cluster Based Inks with Photoluminescence Quantum Efficiency Exceeding 98.

Highly luminescent inks are desirable for various applications such as decorative coating, art painting, and anticounterfeiting, to name a few. However, present inks display low photoluminescent efficiency requiring a strong excitation light to make them glow. Here, we report a highly luminescent ink based on the copper-iodide/1-Propyl-1,4-diazabicyclo[2.2.2]octan-1-ium (Cu4I6(pr-ted)2) hybrid cluster with a quantum efficiency exceeding 98%. Under the interaction between the Cu4I6(pr-ted)2 hybrid cluster and polyvinylpyrrolidone (PVP), the highly luminescent Cu4I6(pr-ted)2/PVP ink can be facilely prepared via the one-pot solution synthesis. The obtained ink exhibits strong green light emission that originates from the efficient phosphorescence of Cu4I6(pr-ted)2 nanocrystals. Attractively, the ink displays high conversion efficiency for the ultraviolet light to bright green light emission due to its wide Stokes shift, implying great potential for anticounterfeiting and luminescent solar concentrator coating.

Polytypic Nanocrystals of Cu-Based Ternary Chalcogenides: Colloidal Synthesis and Photoelectrochemical Properties.

Heterocrystalline polytype nanostructured semiconductors have been attracting more and more attention in recent years due to their novel structures and special interfaces. Up to now, controlled polytypic nanostructures are mostly realized in II-VI and III-V semiconductors. Herein, we report the synthesis and photoelectrochemical properties of Cu-based ternary I-III-VI2 chalcogenide polytypic nanocrystals, with a focus on polytypic CuInS2 (CIS), CuInSe2 (CISe), and CuIn(S0.5Se0.5)2 alloy nanocrystals. Each obtained polytypic nanocrystal is constructed with a wurtzite hexagonal column and a zinc blende/chalcopyrite cusp, regardless of the S/Se ratio. The growth mechanisms of polytypic CIS and CISe nanocrystals have been studied by time-dependent experiments. The polytypic nanocrystals are solution-deposited on indium-tin oxide glass substrate and used as a photoelectrode, thus showing stable photoelectrochemical activity in aqueous solution. Density functional theory calculation was used to study the electronic structure and the band gap alignment. This versatile synthetic method provides a new route for synthesis of novel polytypic nanostructured semiconductors with unique properties.

Controlled synthesis of kinked ultrathin ZnS nanorods/nanowires triggered by chloride ions: a case study.

Colloidal synthesis of kinked ultrathin ZnS nanorods/nanowires with mixed phases using tiny Ag2S nanocrystals as catalysts is reported. It is found that chloride ions can induce the controlled morphology transition from straight to kinking. The synthetic parameters modulating the growth of kinked ZnS nanorods/nanowires are systematically investigated. Chloride ions introduced in the reaction can generate more proportion of wurtzite phase by slowing the nucleation and growth rates during the growth of one-dimensional (1D) ZnS nanorods/nanowires. The formation of kinked morphology is responsible for the increased domains of mixed stacking and twinning in single 1D nanostructures. The present recipe on controlled synthesis of 1D kinked nanorods/nanowires provides a model of crystal growth control, and these unique 1D nanostructures may also offer new opportunities to fabricate nanodevices with special functions.

A library of polytypic copper-based quaternary sulfide nanocrystals enables efficient solar-to-hydrogen conversion.

Designing polytypic homojunction is an efficient way to regulate photogenerated electrons and holes, thereafter bringing desired physical and chemical properties and being attractive photocatalysts for solar-to-hydrogen conversion. However, the high-yield and controllable synthesis of well-defined polytypes especially for multinary chalcogenide - the fundamental factor favoring highly efficient solar-to-hydrogen conversion - has yet to be achieved. Here, we report a general colloidal method to construct a library of polytypic copper-based quaternary sulfide nanocrystals, including Cu2ZnSnS4, Cu2CdSnS4, Cu2CoSnS4, Cu2MnSnS4, Cu2FeSnS4, Cu3InSnS5 and Cu3GaSnS5, which can be synthesized by selective epitaxial growth of kesterite phase on wurtzite structure. Besides, this colloidal method allows the precise controlling of the homojunction number corresponding to the photocatalytic performance. The single-homojunction and double-homojunction polytypic Cu2ZnSnS4 nanocrystal photocatalysts show 2.8-fold and 3.9-fold improvement in photocatalytic hydrogen evolution rates relative to the kesterite nanocrystals, respectively. This homojunction existed in the polytypic structure opens another way to engineer photocatalysts.

Biomimetic non-classical crystallization drives hierarchical structuring of efficient circularly polarized phosphors.

Hierarchically structured chiral luminescent materials hold promise for achieving efficient circularly polarized luminescence. However, a feasible chemical route to fabricate hierarchically structured chiral luminescent polycrystals is still elusive because of their complex structures and complicated formation process. We here report a biomimetic non-classical crystallization (BNCC) strategy for preparing efficient hierarchically structured chiral luminescent polycrystals using well-designed highly luminescent homochiral copper(I)-iodide hybrid clusters as basic units for non-classical crystallization. By monitoring the crystallization process, we unravel the BNCC mechanism, which involves crystal nucleation, nanoparticles aggregation, oriented attachment, and mesoscopic transformation processes. We finally obtain the circularly polarized phosphors with both high luminescent efficiency of 32% and high luminescent dissymmetry factor of 1.5 × 10-2, achieving the demonstration of a circularly polarized phosphor converted light emitting diode with a polarization degree of 1.84% at room temperature. Our designed BNCC strategy provides a simple, reliable, and large-scale synthetic route for preparing bright circularly polarized phosphors.

Colloidal synthesis of Cu2CdSnSe4 nanocrystals and hot-pressing to enhance the thermoelectric figure-of-merit.

We report a solution-based synthesis of monodispersed Cu(2)CdSnSe(4) nanocrystals and a study on the thermoelectric properties of these wide-band-gap dense materials compacted from nanocrystals for the first time. With the help of copper dopants and selenium vacancies generated during wet-chemistry synthesis, a large increment in the power factor is observed, and the dimensionless figure-of-merit ZT reaches a peak value of 0.65 at 450 °C.

Single crystalline quaternary sulfide nanobelts for efficient solar-to-hydrogen conversion.

Although solar-driven water splitting on semiconductor photocatalysts is an attractive route for hydrogen generation, there is a lack of excellent photocatalysts with high visible light activity. Due to their tunable bandgaps suitable for superior visible-light absorption, copper-based quaternary sulfides have been the important candidates. Here, we first assessed the preferred facet of wurtzite Cu-Zn-In-S for photocatalytic hydrogen evolution reaction using the relevant Gibbs free energies determined by first principle calculation. We then developed a colloidal method to synthesize single crystalline wurtzite Cu-Zn-In-S nanobelts (NBs) exposing (0001) facet with the lowest reaction Gibbs energy, as well as Cu-Zn-Ga-S NBs exposing (0001) facet. The obtained single crystalline Cu-Zn-In-S and Cu-Zn-Ga-S NBs exhibit superior hydrogen production activities under visible-light irradiation, which is composition-dependent. Our protocol represents an alternative surface engineering approach to realize efficient solar-to-chemical conversion of single crystalline copper-based multinary chalcogenides.

Selective epitaxial growth of zinc blende-derivative on wurtzite-derivative: the case of polytypic Cu2CdSn(S(1-x)Se(x))4 nanocrystals.

Polytypic nanocrystals with zinc blende (ZB) cores and wurtzite (WZ) arms, such as tetrapod and octopod nanocrystals, have been widely reported. However, polytypic nanocrystals with WZ cores and ZB arms or ends have been rarely reported. Here, we report a facile, solution-based approach to the synthesis of polytypic Cu2CdSn(S1-xSex)4 (CCTSSe) nanocrystals with ZB-derivative selectively engineered on (000±2)WZ facets of WZ-derived cores. Accordingly, two typical morphologies, i.e., bullet-like nanocrystals with a WZ-derivative core and one ZB-derivative end, and rugby ball-like nanocrystals with a WZ-derivative core and two ZB-derivative ends, can be selectively prepared. The epitaxial growth mechanism is confirmed by the time-dependent experiments. The ratio of rugby ball-like and bullet-like polytypic CCTSSe nanocrystals can be tuned through changing the amount of Cd precursor to adjust the reactivity difference between (0002)WZ and (000-2)WZ facets. These unique polytypic CCTSSe nanocrystals may find applications in energetic semiconducting materials for energy conversion in the future.

Selective hydrogenation of nitroaromatics by ceria nanorods.

Ceria (CeO2) nanorods with well-defined surface planes can be synthesized and utilized for the hydrogenation of nitroaromatics. The CeO2 nanorods containing a {110} plane can efficiently and selectively catalyse the hydrogenation of nitroaromatics with N2H4 as a reducing agent, while nano-ceria with a {100} or {111} plane shows poor performance for the reaction.

Composition- and band-gap-tunable synthesis of wurtzite-derived Cu2ZnSn(S(1-x)Se(x))4 nanocrystals: theoretical and experimental insights.

The wurtzite-derived Cu2ZnSn(S(1-x)Se(x))4 alloys are studied for the first time through combining theoretical calculations and experimental characterizations. Ab initio calculations predict that wurtzite-derived Cu2ZnSnS4 and Cu2ZnSnSe4 are highly miscible, and the band gaps of the mixed-anion alloys can be linearly tuned from 1.0 to 1.5 eV through changing the composition parameter x from 0 to 1. A synthetic procedure for the wurtzite-derived Cu2ZnSn(S(1-x)Se(x))4 alloy nanocrystals with tunable compositions has been developed. A linear tunable band-gap range of 0.5 eV is observed in the synthesized alloy nanocrystals, which shows good agreement with the ab initio calculations.

Pt-Ni alloyed nanocrystals with controlled architectures for enhanced methanol oxidation.

Pt-Ni alloy nanocrystals with controlled architectures (multi-arms and flowers) have been synthesized via a simple colloid chemistry method. The crystal surfaces possess abundant low-coordination defect sites, where the reaction kinetics of methanol oxidation can be improved, resulting in the catalysts exhibiting better stability and higher resistance to poisoning.

Cu(1.94)S nanocrystal seed mediated solution-phase growth of unique Cu2S-PbS heteronanostructures.

Unique Cu(2)S-PbS heteronanostructures with good photothermal conversion effect have been synthesized for the first time by a Cu(1.94)S nanocrystal seed mediated colloidal solution-phase growth method. The present nanocrystal seed mediated growth method may be extended for the growth of other unique semiconductor heteronanostructures.

Large-scale colloidal synthesis of non-stoichiometric Cu(2) ZnSnSe(4) nanocrystals for thermoelectric applications.

Over 10 g of non-stoichiometric Cu(2) ZnSnSe(4) colloidal nanocrystals for thermoelectric applications are prepared after one single reaction. The obtained pellet made from the colloidal nanocrystals shows a peak ZT value of 0.44 at 450 °C, which is similar to those of state-of-the-art Cu(2) ZnSnSe(4) -based bulk materials at the same temperature.

A family of carbon-based nanocomposite tubular structures created by in situ electron beam irradiation.

We report a unique approach for the fabrication of a family of curling tubular nanostructures rapidly created by a rolling up of carbon membranes under in situ TEM electron beam irradiation. Multiwall tubes can also be created if irradiation by electron beam is performed long enough. This general approach can be extended to curve the conductive carbon film loaded with various functional nanomaterials, such as nanocrystals, nanorods, nanowires, and nanosheets, providing a unique strategy to make composite tubular structures and composite materials by a combination of desired optical, electronic, and magnetic properties, which could find potential applications, including fluid transportation, encapsulation, and capillarity on the nanometer scale.

Linearly arranged polytypic CZTSSe nanocrystals.

Even colloidal polytypic nanostructures show promising future in band-gap tuning and alignment, researches on them have been much less reported than the standard nano-heterostructures because of the difficulties involved in synthesis. Up to now, controlled synthesis of colloidal polytypic nanocrsytals has been only realized in II-VI tetrapod and octopod nanocrystals with branched configurations. Herein, we report a colloidal approach for synthesizing non-branched but linearly arranged polytypic I(2)-II-IV-VI(4) nanocrystals, with a focus on polytypic non-stoichiometric Cu(2)ZnSnS(x)Se(4-x) nanocrystals. Each synthesized polytypic non-stoichiometric Cu(2)ZnSnS(x)Se(4-x) nanocrystal is consisted of two zinc blende-derived ends and one wurtzite-derived center part. The formation mechanism has been studied and the phase composition can be tuned through adjusting the reaction temperature, which brings a new band-gap tuning approach to Cu(2)ZnSnS(x)Se(4-x) nanocrystals.

Superlong beta-AgVO3 nanoribbons: high-yield synthesis by a pyridine-assisted solution approach, their stability, electrical and electrochemical properties.

Monoclinic beta-silver vanadate (beta-AgVO(3)) nanoribbons with widths of 300-600 nm, thicknesses of ca. 40 nm, and lengths of 200-300 microm can be easily synthesized in high yield directly from a hydrothermal reaction between V(2)O(5) and AgNO(3) in a solution containing a small amount of pyridine. The results demonstrated that the formation of single-crystal AgVO(3) nanoribbons is strongly dependent on the reaction temperature, especially, the presence of pyridine and its dosage. A possible growth mechanism of single-crystal AgVO(3) nanoribbons has been proposed. Exposure of the nanoribbons to electron beam will easily result in the formation of Ag nanoparticles embedded in situ on the backbone of the nanoribbons, making the nanoribbons potentially useful as efficient catalyst support. The electrical conductivity of an individual single-crystal beta-AgVO(3) nanoribbon exhibits nonlinear and symmetric current/voltage (I-V) characteristics for bias voltages in the range of -6 to 6 V.