Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Efficient energy transfer from self-trapped excitons to Mn^(2+) dopants in CsCdCl_(3):Mn^(2+) perovskite nanocrystals

Mn^(2+)doping has been adopted as an efficient approach to regulating the luminescence properties of halide perovskite nano-crystals(NCs).However,it is still difficult to understand the interplay of Mn^(2+)luminescence and the matrix self-trapped exciton(STE)emission therein.In this study,Mn^(2+)-doped CsCdCl_(3) NCs are prepared by hot injection,in which CsCdCl_(3) is selected because of its unique crystal structure suitable for STE emission.The blue emission at 441 nm of undoped CsCdCl_(3) NCs originates from the defect states in the NCs.Mn^(2+)doping promotes lattice distortion of CsCdCl_(3) and generates bright orange-red light emission at 656 nm.The en-ergy transfer from the STEs of CsCdCl_(3) to the excited levels of the Mn^(2+)ion is confirmed to be a significant factor in achieving efficient luminescence in CsCdCl_(3):Mn^(2+)NCs.This work highlights the crucial role of energy transfer from STEs to Mn^(2+)dopants in Mn^(2+)-doped halide NCs and lays the groundwork for modifying the luminescence of other metal halide perovskite NCs.

Strengthening-softening transition and maximum strength in Schwarz nanocrystals

Recently,a Schwarz crystal structure with curved grain boundaries(GBs)constrained by twin-boundary(TB)networks was discovered in nanocrystalline Cu through experiments and atomistic simulations.Nanocrystalline Cu with nanosized Schwarz crystals exhibited high strength and excellent thermal stability.However,the grainsize effect and associated deformation mechanisms of Schwarz nanocrystals remain unknown.Here,we performed large-scale atomistic simulations to investigate the deformation behaviors and grain-size effect of nanocrystalline Cu with Schwarz crystals.Our simulations showed that similar to regular nanocrystals,Schwarz nanocrystals exhibit a strengthening-softening transition with decreasing grain size.The critical grain size in Schwarz nanocrystals is smaller than that in regular nanocrystals,leading to a maximum strength higher than that of regular nanocrystals.Our simulations revealed that the softening in Schwarz nanocrystals mainly originates from TB migration(or detwinning)and annihilation of GBs,rather than GB-mediated processes(including GB migration,sliding and diffusion)dominating the softening in regular nanocrystals.Quantitative analyses of simulation data further showed that compared with those in regular nanocrystals,the GB-mediated processes in Schwarz nanocrystals are suppressed,which is related to the low volume fraction of amorphous-like GBs and constraints of TB networks.The smaller critical grain size arises from the suppression of GB-mediated processes.

Nonlinear Absorption and Low-threshold Two-photon Pumped Amplified Stimulated Emission from FAPbBr_(3) Nanocrystals

Formamidinium lead bromide(FAPbBr_(3))nanocrystals(NCs)have been considered to be a good optoelectronic material due to their pure green emission,excellent stability and superior carrier transport characteristics.However,two-photon pumped amplified spontaneous emission(ASE)and the corresponding nonlinear optical properties of FAPbBr_(3) NCs are scarcely revealed.Herein,we synthesized colloidal FAPbBr_(3) NCs with different sizes by changing the molar ratio of FABr/PbBr_(2) in the precursor solution,using ligand assisted precipitation(LARP)technology at room temperature.Photoluminescence(PL)and time resolved photoluminescence(TRPL)spectroscopy were measured to characterize their ASE properties.And their nonlinear optical properties were studied through the Zscan technique and the two-photon excited fluorescence method.The stimulated emission properties including oneand two-photon pumped ASE have been realized from FAPbBr_(3) NCs.With large two-photon absorption coefficient(0.27 cm/GW)and high non-linear absorption cross-section(7.52×10^(5) GM),ASE with threshold as low as 9.8μJ/cm^(2) and 487μJ/cm^(2) have been obtained from colloidal FAPbBr_(3) NCs using one-and two-photon excitations.These results indicate that as a new possible green-emitting frequency-upconversion material with low thresholds,FAPbBr_(3) NCs hold great potential in the development of high-performance two-photon pump lasers.

Energy-Transfer in CsPbBr_(3)Nanocrystals:Sensitization of Porphyrin Triplets

Sensitizing molecular triplets by colloidal nanocrystals via triplet energy transfer is important for applications such as upconversion or organic synthesis.Typically two step triplet energy transfer(TET)are included in these applications:firstly the triplet energy stored in nanocrystals are extracted into surface ligands,and then the ligands further transfer triplet energy into molecules in bulk solution.Here we report one-step TET application from CsPbBr_(3)perovskite nanocrystals(NCs)to surface-anchored metalloporphyrin derivative molecules(MP).Compared to conventional two-step TET,the one-step TET mechanism possess lower energy loss and higher TET efficiency which is more generally implementable.In this scheme,photoexcitation of CsPbBr_(3)NCs leads to the sensitization of MP ligands triplets which efficiently emit phosphorescence.The enhanced light absorption of MP ligands and down-shifted photon emission can be useful in devices such as luminescent solar concentrators.

Isolative Synthesis and Characterization of Cellulose and Cellulose Nanocrystals from Typha angustifolia

The application potential of cellulosic materials in natural composites and other fields needs to be explored to develop innovative, sustainable, lightweight, functional biomass materials that are also environmentally friendly. This study investigated Typha angustifolia (Typha sp.) as a potential new raw material for extracting cellulose nanocrystals (CNCs) for application in wastewater treatment composites. Alkaline treatments and bleaching were used to remove cellulose from the stem fibres. The CNCs were then isolated from the recovered cellulose using acid hydrolysis. The study showed a few distinct functional groups (O-H, -C-H, =C-H and C-O, and C-O-C) in the Fourier Transform Infrared (FTIR) spectra. A scanning electron microscope (SEM) revealed the smooth surface of CPC and CNCs, which resulted from removing lignin and hemicellulose from powdered Typha angustifolia. Based on the crystalline index, the powdered Typha angustifolia, CPC, and CNCs were 42.86%, 66.94% and 77.41%. The loss of the amorphous section of the Typha sp. fibre resulted in a decrease in particle size. It may be inferred from the features of a Typha sp. CNC that CNCs may be employed as reinforcement in composites for wastewater treatment.

Synthesis and upconversion luminescence of Lu_2O_3:Yb^(3+),Tm^(3+) nanocrystals

Lutetium oxide nanocrystals codoped with Tm3＋ and Yb3＋ were synthesized by the reverse-like co-precipitation method, using ammonium hydrogen carbonate as precipitant. Effects of the Tm3＋, Yb3＋ molar fractions and calcination temperature on the structural and upconversion luminescent properties of the Lu2O3 nanocrystals were investigated. The XRD results show that all the prepared nanocrystals can be readily indexed to pure cubic phase of Lu2O3 and indicate good crystallinity. The experimental results show that concentration quenching occurs when the mole fraction of Tm3＋ is above 0.2%. The optimal Tm3＋ and Yb3＋ doped molar fractions are 0.2% and 2%, respectively. The strong blue （490 nm） and the weak red （653 nm） emissions from the prepared nanocrystals were observed under 980 nm laser excitation, and attributed to the 1G4→3H6 and IG4→3F4 transitions of Tm3＋, respectively. Power-dependent study reveals that the 1G4 levels of Tm3＋ can be populated by three-step energy transfer process. The upconversion emission intensities of 490 nm and 653 nm increase gradually with the increase of calcination temperature. The enhancement of the upconversion luminescence is suggested to be the consequence of reducing number of OH- groups and the enlarged nanoerystal size.

Facile synthesis of tin oxide nanocrystals and their photocatalytic activity

Tin oxide nanociystals with diameters smaller than 10 nm were synthesized using Na2SnO3 and CO2 as reactants and cetyltrimethylammonium bromide（CTAB） as stabilizer under mild conditions.As a mild acidic gas,CO2 is favorable for the accurate adjustment of pH value of Na2SnO3 solution.Stannate salt is stable,cheap and easy in operation.The effects of Na2SnO3concentration,CTAB concentration,aging temperature,and aging time on the nanociystals were studied.It was found that,with the increasing Na2SnO3 concentration,aging temperature and aging time,SnO2 nanociystals size decreases.The formation of SnO2nanociystals can be interpreted by electrostatic-interaction mechanism.SnO2 nanociystals show high photocatalytic activities in the degradation of Rhodamine B solution.The catalytic activity of small nanocrystals is higher than that of large ones.

Nanocrystals precipitation and up-conversion luminescence in Yb^(3+)-Tm^(3+) co-doped oxyfluoride glasses

Rare earth ions doped oxyfluoride glass with composition of 28SiO2·22AlO1.5·40PbF2·10PbO·（4.8-x） GdFy0.1NdF3.xYbF3·0.1TmF3 （x=-0, 0.1, 0.2, 0.5, 1, 2, 3, 4 and 4.8） in molar ratio was developed. When the oxyfluoride glasses were heat-treated at the first crystallization temperature, the glasses gave transparent glass-ceramics in which rare earth containing fluorite-type nanocrystals of about 17.2 nm in diameter uniformly precipitated in the glass matrix. Compared with the glasses before heat treatment, the glass-ceramics exhibited very strong blue up-conversion luminescence under 800 nm light excitation. Rare earth containing nanocrystals were also space selectively precipitated upon laser irradiation in an oxyfluoride glass, the size of precipitated nanocrystals could be controlled by laser power and scan speed. The intensity of the blue up-conversion luminescence was strongly dependent on the precipitation of β-PbF2 nanocrystal and the YbF3 concentration. The reasons for the highly efficient Tm^3＋ up-conversion luminescence after laser irradiation were discussed.

Novel Strategy for Synthesis of High Quality CdTe Nanocrystals in Aqueous Solution

A novel aqueous route for the synthesis of high-quality CdTe nanocrystals（NCs） is presented in this article. With both glutathione（GSH） and cysteine[n（GSH）：n（cysteine）=1：3] as stabilizers, high-quality CdTe NCs with controllable photoluminescence（PL） wavelength from 500 to 630 nm can be prepared within 4 h. As-prepared CdTe NCs show higher photoluminescence quantum yields（PLQY） compared with CdTe NCs prepared via other aqueous methods. When the fluorescent emission peak appeared in orange-red window, the PLQY reaches 70% or above at room temperature without any post-preparative treatment.

Sol-gel preparation and characterization of Co_3O_4 nanocrystals

A new citrate acid-hydrazine sol-gel route for preparation of Co3O4 nanoparticles has been developed. Co3O4 nanoparticles with different particle-sizes and morphology were prepared at different heat-treatment temperatures and the pure cubic nanocrystals of Co3O4 were obtained at 600℃. The synthesis process was monitored by infrared spectroscopy (IR), thermal gravimetric and differential thermal analysis (TG-DTA). The structure and morphology of Co3O4 nanocrystals were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray-photoelectron spectroscopy (XPS). The infrared absorption bands blue-shifted with particle size decreasing, which could be attributed to increasing surface effect. XPS results showed that predominant species at surface layers of Co3O4 nanocrystals are octahedral Co (Ⅲ).

Synthesis and Characterization of CdSe Nanocrystals Capped by CdS

CdSe semiconductor nanocrystals capped by CdS were synthesized in the aqueous solution with 2 mercaptoethanol as the stabilizer. The CdS capping with a higher band gap than that of the core crystallite has successfully eliminated the surface traps. Optical absorption and fluorescence emission spectra were used to probe the effect of CdS passivation on the electronic structure of the nanocrystals. The composite CdSe/CdS nanocrystals exhibit strong, narrow(FWHM≤40 nm) and stable band edge photoluminescence. X ray powder diffraction, transmission electron microscopy and X ray photoelectron spectroscopy were used to analyze the composite nanocrystals and determine their average size, size distribution, shape, internal structure and elemental composition.

Recent Progress on Spectroscopy of Lanthanide Ions Incorporated in Semiconductor Nanocrystals

Doping luminescent lanthanide ions into semiconductor nanocrystals is an ideal approach for developing nanodevices for various applications. Quantum confinement effects are expected for lanthanide ions doped in small semiconductor nanocrystals. The most recent progress on the synthesis and spectroscopy of lanthanide ions in various semiconductor nanocrystals such as Ⅱ -Ⅵ, Ⅲ-Ⅴ and Ⅳ-Ⅵ families were systematically reviewed, focusing on our recent findings on the optical spectroscopy of Eu^3 ＋ doped in ZnO and TiO2 nanocrystals by wet chemical synthesis. The energy transfer from the band-gap excitation to lanthanides further confirmed that lanthanide ions could be successfully incorporated into the lattice sites in spite of the mismatch in ionic radii.

Enhanced transdermal delivery of meloxicam by nanocrystals: Preparation, in vitro and in vivo evaluation

Meloxicam(MLX) is efficient in relieving pain and inflammatory symptoms, which, however, is limited by the poor solubility and gastrointestinal side effects. The objective of this study is to develop a nanocrystal formulation to enhance transdermal delivery of MLX. MLX nanocrystals were successfully prepared by the nanoprecipitation technique based on acidbase neutralization. With poloxamer 407 and Tween 80(80/20, w/w) as mixed stabilizers,MLX nanocrystals with particle size of 175 nm were obtained. The crystalline structure of MLX nanocrystals was confirmed by both differential scanning calorimetry and X-ray powder diffractometry. However, the nanoprecipitation process reduced the crystallinity of MLX.Nanocrystals increased both in vitro and in vivo transdermal permeation of MLX compared with the solution and suspension counterparts. Due to the enhanced apparent solubility and dissolution as well as the facilitated hair follicular penetration, nanocrystals present a high and prolonged plasma MLX concentration. And 2.58-and 4.4-fold increase in AUC0 →2 4 h was achieved by nanocrystals comparing with solution and suspension, respectively. In conclusion, nanocrystal is advantageous for transdermal delivery of MLX.

Luminescence properties of ZnS:Cu, Eu semiconductor nanocrystals synthesized by a hydrothermal process

ZnS：Cu, Eu nanocrystals with an average diameter of 80 nm are synthesized using a hydrothermal approach at 200 ℃. The photoluminescence （PL） properties of the ZnS：Cu, Eu nanocrystals before and after annealing, as well as the doping form of Eu, are studied. The as-synthesized samples are characterized by X-ray diffraction, scanning electron microscopy, inductively coupled plasma-atomic emission spectrometry, and the excitation and emission spectra （PL）. The results show that both Cu and Eu are indeed incorporated into the ZnS matrix. Compared with the PL spectrum of the Cu mono-doped sample, the PL emission intensity of the Cu and Eu-codoped sample increases and a peak appears at 516 nm, indicating that Eu3＋ ions, which act as an impurity compensator and activator, are incorporated into the ZnS matrix, forming a donor level. Compared with the unannealed sample, the annealed one has an increased PL emission intensity and the peak position has a blue shift of 56 nm from 516 nm to 460 nm, which means that Eu3＋ ions reduce to Eu2＋ ions, thereby leading to the appearance of Eu2＋ characteristic emission and generating effective host-to-Eu2＋ energy transfer. The results indicate the potential applications of ZnS：Cu, Eu nanoparticles in optoelectronic devices.

Solution-Phase Synthesis and Characterization of Perovskite LaCoO_3 Nanocrystals via A Co-Precipitation Route

A facile co-precipitation route for the synthesis of well-dispersed LaCoO3 nanocrystals was developed. The asprepared products were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, energy dispersive X-ray spectrometer （EDX）, and laser Raman spectroscopy （LRS）. The resuks showed that modulating the growth parameters, such as the addition of surfactants as well as the adding manner of the precipitator had a significant effect on the overall shape and size of the obtained nanocrystals. The nanorods with the diameter of 20 nm and spherical LaCoO3 nanocrystals with the size of about 25 nm could be obtained at a relatively low calcining temperature of 600℃. Furthermore, the Raman properties of LaCoO3 products obtained at different calcining temperatures were investigated.

Optimization, characterization and in vitro/vivo evaluation of azilsartan nanocrystals

Azilsartan(AZL), a poorly soluble drug, was considered to be fit for nanocrystals to improve its solubility. Our study intended to prepare AZL nanocrystals by means of bead milling method. Eight stabilizers or their binary combination and the milling time were set to be variable factors to optimize AZL nanosuspension formulation, and six types of freezedrying supports were investigated to reduce the aggregation of particles during the solidification. AZL nanocrystals with or without sodium deoxycholate(NaDC) as combined stabilizer with Poloxamer 188(F68) were prepared owning mean particle sizes of about 300 nm and 460 nm. During the screening processes, the formulation containing NaDC showed a smaller particle size and better stability during lyophilization. The irregular shape and crystal form changing in AZL nanocrystals were discovered by various characterizations. And with physical mixture as reference, nanocrystals showed its improvement about in-vitro dissolution and in-vivo bioavailability. In conclusion, the nanocrystals of AZL could be prepared well in our study. Additionally, our results suggested that NaDC was an appreciated excipient on the nanocrystals platform, which can exhibit the abilities of size-reduction and stabilitymaintaining on freeze-drying.

Preparation, characterization and nonlinear optical properties of colloidal gallium arsenide nanocrystals

GaAs nanocrystals were prepared via a simple mechanical ball milling technique. The prepared GaAs nanocrystals have high purity and could form colloidal ethanol suspension without any surfactant additives. The colloidal GaAs nanocrystal suspension displayed excellent two-photon absorption property over the visible and near-infrared region from 490 nm to 1064 nm, which enables it to become a promising broadband optical limiting material.

Development of Biomimetic Needle-like Apatite Nanocrystals by a Simple New Method

A new method of calcium nitrate and sodium phosphate as reactants was employed to prepare biomimetic apatite nanocrystals by a simple heating treatment in water. The structure and properties of the apatite crystals were investigated by TEM, XRD, IR, ICP and TG. It is found that the apatite nanocrystals contain OH-, CO32-, Na+ and HPO42- ions in their crystal structure. The crystal water is removed during heating from 200℃ to 400℃. CO32-and HPO42- are decomposed at 600℃ to 800℃, also there is lattice vvater lost at this temperature stage. The morphology of the apatite nanocrystals is needle-like with a length less than 80 nm. The size and crystallinity of the apatite nanocrystals increase with vvater treatment temperature and time. Compared to the apatite crystals sintered at 800℃, water treated apatite nanocrystals are poorly crystallized apatite. The results indicate that the apatite nanocrystals have similarity in composition, structure, morphology and crystallinity to that of bone apatite crystals. It can be used to make apatite crystals/polymer biomimetic bone repair materials or for other biomedicai applications.

Growth Kinetics of Nanocrystals and Nanorods by Employing Small-angle X-ray Scattering (SAXS) and Other Techniques

In this article, we report the results of our detailed investigations of the growth kinetics of zero-dimensional nanocrystals as well as one-dimensional nanorods by the combined use of small angel X-ray scattering （SAXS）, transmission electron microscopy （TEM） along with other physical techniques. The study includes growth kinetics of gold nanocrystals formed by the reduction of HAuCl4 by tetrakis（hydroxymethyl） phosphonium chloride in aqueous solution, of CdSe nanocrystals formed by the reaction of cadmium stearate and selenium under solvothermal conditions, and of ZnO nanorods formed by the reaction of zinc acetate with sodium hydroxide under solvothermal conditions in the absence and presence of capping agents. The growth of gold nanocrystals does not follow the diffusion-limited Ostwald ripening, and instead follows a Sigmoidal rate curve. The heat change associated with the growth determined by isothermal titration calorimetry is about 10 kcal·mol^-1 per I nm increase in the diameter of the nanocrystals. In the case of CdSe nanocrystals also, the growth mechanism deviates from diffusion-limited growth and follows a combined model containing both diffusion and surface reaction terms. Our study of the growth kinetics of uncapped and poly（vinyl pyrollidone） （PVP）-capped ZnO nanorods has yielded interesting insights. We observe small nanocrystals next to the ZnO nanorods after a lapse of time in addition to periodic focusing and defocusing of the width of the length distribution. These observations lend support to the diffusion-limited growth model for the growth of uncapped ZnO nanorods. Accordingly, the time dependence on the length of uncapped nanorods follows the L3 law as required for diffusion-limited Ostwald ripening. The PVP-capped nanorods, however, show a time dependence, which is best described by a combination of diffusion （L^3） and surface reaction （L^2） terms.