Nonlinear optical properties of nanometer-size silver coated polydiacetylene composite vesicles and resulting Langmuir–Blodgett films

Noble metal-coated PDA composite vesicles were expected to increase the effective third-order nonlinear optical susceptibility χ ⁽³⁾(ω), due to the enhancement of the optical electric field induced by localized surface plasmon resonance. Different size (20, 50 and 80 nm) Ag colloidal nanoparticles were coated on the outer surface of polydiacetylene (PDA) vesicles to form PDA/Ag nanocomposite vesicles and the size-dependent effect of Ag colloidal nanoparticles on NLO properties enhancement has been explored. The explanation based on the competition of a size-dependent light-confinement effect and a size-dependent dielectric constant of Ag particles had been presented. Furthermore, these PDA/Ag composite vesicles were successfully immobilized onto the solid substrate by the Langmuir–Blodgett (LB) method and their linear and nonlinear optical properties were characterized, respectively. Obviously, PDA/Ag composite vesicles Langmuir–Blodgett (LB) films promoted the enhancement of the third-order NLO properties.     

Effect of thermal treatment on the nonlinear optical response and stability of hybrid inorganic-organic films

Hybrid inorganic-organic second-order nonlinear optical (NLO) materials have been obtained through hydrolysis and co-condensation between tetraethyl silicate (TEOS), Vinyltriethoxysilane (VTES) and an alkoxysilane dye (ICTES-DR1). The hybrid materials showed a thermal stability up to 306 °C in thermogravimetric analysis (TGA) thermograms and no visible glass transition temperature (T_g) was observed in the range 50-200 °C in differential scanning calorimetry (DSC) thermograms. The poling profiles of the hybrid films were investigated by using the in situ second harmonic generation (SHG) measurement. The thermal stability of the second order NLO properties of the poled films were also investigated by the in situ SHG intensity probing. It has been shown that the NLO response and its thermal stability were strongly dependent on the thermal pretreatment of the films.     

Electronic properties of phenanthrimidazoles as hole transport materials in organic light emitting devices and in photoelectron transfer to ZnO nanoparticles

Phenanthrimidazoles as hole transport materials have been synthesized, characterized, and applied as nondoping emitters in organic light emitting devices. The synthesized molecules possess high fluorescent quantum yield and thermal properties and display film forming abilities. The highest occupied molecular orbital (HOMO) energies of these materials are shallower than the reported tris(8‐hydroxyquinoline)aluminum (Alq₃), which enables the hole transport ability of these phenanthrimidazoles. Taking advantage of the thermal stability and hole transporting ability, these compounds can be used as a functional layer between NPB [4,4‐bis(N‐(1‐naphthyl)‐N‐phenylamino)biphenyl] and Alq₃ layers and show that these phenanthrimidazoles can be alternatively used as novel hole transport materials and to improve the device performances. Geometrical, optical, electrical, and electroluminescent properties of these molecules have been probed. Further, natural bond orbital, nonlinear optical materials (NLO), molecular electrostatic potential, and HOMO–lowest unoccupied molecular orbital (LMO) energy analysis have been made by density functional theory (DFT) method to support the experimental results. Hyperpolarizability analysis reveals that the synthesized phenanthrimidazoles possess NLO behavior. The chemical potential, hardness, and electrophilicity index of phenanthrimidazoles have also been computed by DFT method. Photoinduced electron transfer explains the enhancement of fluorescence by nanoparticulate ZnO, and the apparent binding constant has been obtained. Adsorption of the fluorophore on ZnO nanoparticle lowers the HOMO and LUMO energy levels of the fluorophore. The strong adsorption of the phenanthrimidazoles on the surface of ZnO nanocrystals is likely due to the chemical affinity of the nitrogen atom of the organic molecule to Zn(II) on the surface of nanocrystal. Copyright © 2013 John Wiley & Sons, Ltd.     

Essential Amino Acid–Enabled Lead Bromide Perovskite Nanocrystals with High Stability

This work reports the first synthesis of MAPbBr₃ perovskite nanocrystals (PNCs) using amino acids as the ligand with excellent optical properties. A variety of amino acids are used to optimize the luminescence properties. A mechanochemical approach has taken lead over conventional colloidal chemistry during synthesis. All morphological and optical studies are performed to characterize the synthesized perovskite nanoparticles. Later, stability studies are investigated through thermogravimetric analysis, temperature‐dependent photoluminescence, time‐dependent X‐ray diffraction, as well as X‐ray photoelectron spectroscopy. In an application, interestingly, these perovskites show high luminescence upon scratching on flexible conducting plates and on plain paper surface. These results suggest that the amino acid–ligated perovskite nanocrystals can be potential materials for optoelectronic application including light‐emitting diodes and imaging.     

Cr,Ag共掺杂ZnS纳米材料的制备及其对活性染料的吸附性能

通过水热法制备了纤锌矿ZnS∶Cr,Ag共掺杂纳米材料,考察了不同反应时间以及不同Cr和Ag掺杂比例对ZnS纳米材料光学性能的影响。分别采用荧光分光光度计、红外光谱仪、X射线衍射仪(XRD)、扫描电子显微镜(SEM)等对Cr和Ag共掺杂ZnS纳米材料的光学性能和结构等进行了表征,探讨了ZnS∶Cr, Ag共掺杂纳米材料分别对甲基紫(MV)、丁基罗丹明B(BRB),四氯四溴荧光素(TCTBF)以及曙红B(EB)四种活性染料的吸附性能。结果表明,Cr3+和Ag+取代和嵌入到了Zn2+的位置,掺入到了ZnS的晶格中。由光学表征和扫描电镜(SEM)发现,掺杂后ZnS纳米材料的光学性能和形貌发生了改变。掺入Cr和Ag后,使得Zn纳米材料的荧光强度降低,且其形貌较规则,表面蓬松,呈绒球形状。当反应时间为12 h,Cr和Ag掺杂比例分别为1%时,掺杂ZnS纳米材料的形貌和光学性能最佳。运用N₂等温吸脱附分析技术计算了Cr和Ag共掺杂ZnS材料的比表面积和孔径分布,将其用于对MV,BRB,TCTBF以及EB四种活性染料的吸附研究,并分别从吸附时间、温度、pH值等因素考察了掺杂ZnS对几种活性染料吸附性能的影响,得出了Cr和Ag共掺杂ZnS材料在pH 7,室温下,分别经9,11,9和9 h吸附时间后对四种活性染料的吸附效果达到最佳。     

Recent Advances of Light Propagation in Surface Plasmon Enhanced Quantum Dot Devices

Surface plasmons are of particular interest recently as their performance is approaching the enhancement of light emission efficiencies, after synthesized close to the vicinity of solid state materials, i.e., semiconductor structure. As other scientific works have been proposed to improve the light-emitting efficiency, such as the use of resonant cavities, photon recycling, and thin-light emitting layers with periodic surface texturing, surface plasmon possesses a promising way to the light enhancement, due to the energy coupling effect between the emitted photons from the semiconductor and the metallic nanoparticles fabricated by nanotechnology. The usual pathway of plasmon enhanced light emitting devices is the use of Ag/Au nanoparticles coating the surface of semiconductor quantum dot (QD) or quantum well (QW) structures. However, apart from efforts to extract as much light as possible from single-driven surface plasmon-QD/QW, it is possible to enhance the light emission rate with double optical-excitations. This approach is based on the quantum interference between the external lasers and the localized quantum light, and promised to stimulate the development of plasmon-enhanced optical sensors. In this review, we describe the quantum properties of light propagation in hybrid nanoparticle and semiconductor materials, i.e., quantum dot or nanomechanical resonator coupled to Ag/Au nanoparticles, driven by two optical fields. Distinct with single excitation, plasmon-assisted complex driven by two optical fields, exhibit specific quantum interference characteristics that can be used as sensitive all-optical devices, such as the slow light switch, nonlinear optical Kerr modulator, and ultra-sensitive mass sensing. We summarize the recent advances of light propagation in surface plasmon-enhanced quantum dot devices, driven by two optical fields, which would stimulate the development of novel optical materials, deeper theoretical insights, innovative new devices, and plasmonic applications with potential for significant technological and societal impact.     

Enhanced nonlinear optical responses of materials: Composite effects

We review recent theoretical progress in understanding physical processes of composite effects on enhanced third-order nonlinear optical responses of various kinds of the recently-proposed nonlinear optical materials, namely, colloidal nanocrystals with inhomogeneous metallodielectric particles or a graded-index host, metallic films with inhomogeneous microstructures adjusted by ion doping or temperature gradient, composites with compositional gradation or graded particles, and magneto-controlled ferrofluid-based nonlinear optical materials.     

CdSe量子点的光物理性质研究与荧光杂化纤维的制备

半导体纳米晶体(NCs)具有良好的光稳定性,广泛的发射持久性和高消光系数,在过去几年被广泛研究报道,其中,硒化镉半导体纳米晶体(CdSe NCs)被广泛用于电子照明、太阳能发电、光电传感等领域.然而CdSe NCs的电学、热力学和光物理性质具有较强的尺寸依赖性,在传统的制备方法及应用中容易出现晶体表面缺陷和悬空键以及较...     

Controllable synthesis of fullerene nano/microcrystals and their structural transformation induced by high pressure

Fullerene molecules are interesting materials because of their unique structures and properties in mechanical, electrical, magnetic, and optical aspects. Current research is focusing on the construction of well-defined fullerene nano/microcrystals that possess desirable structures and morphologies. Further tuning the intermolecular interaction of the fullerene nano/microcrystals by use of pressure is an efficient way to modify their structures and properties, such as creation of nanoscale polymer structures and new hybrid materials, which expands the potential of such nanoscale materials for di- rect device components. In this paper, we review our recent progress in the construction of fullerene nanostructures and their structural transformation induced by high pressure. Fullerene nano/microcrystals with controllable size, morphology and structure have been synthesized through the self-assembly of fullerene molecules by a solvent-assisted method. By virtue of high pressure, the structures, components, and intermolecular interactions of the assemblied fullerene nano/microcrystals can be finely tuned, thereby modifying the optical and electronic properties of the nanostructures. Several examples on high pressure induced novel structural phase transition in typical fullerene nanocrystals with C60 or C70 cage serving as build- ing blocks are presented, including high pressure induced amorphization of the nanocrystals and their bulk moduli, high pressure and high temperature （HPHT） induced polymerization in C60 nanocrystals, pressure tuned reversible polymeriza- tion in ferrocene-doped C60/C70 single crystal, as well as unique long-range ordered crystal with amorphous nanoclusters serving as building blocks in solvated C60 crystals, which brings new physical insight into the understanding of order and disorder concept and new approaches to the design of superhard carbon materials. The nanosize and morphology effects on the transformations of fullerene nanocrystals have also been discussed. These results provide the foundation for the fabrication of pre-designed and controllable geometries, which is critical in fullerenes and relevant materials for designing nanometer-scale electronic, optical, and other devices.     

Structural,electrical and optical properties of gamma irradiated methyl para-hydroxy benzoate single crystals

ABSTRACT

Nonlinear optical materials (NLO) have been garnering attention due to their role in optical data storage, optical communication and laser technology. Organic crystals have emerged as an extremely important class of NLO materials, since their NLO properties compare very well with traditional inorganic NLO materials like KCl, LiNbO₃, KDP (potassium dihydrogen phosphate), etc. They offer the additional advantage that they can be grown relatively inexpensively from solution close to room temperature, unlike the inorganic NLO materials which are grown from high temperature melts. In the present work, organic transparent single crystals of methyl para-hydroxy benzoate (MHB) were grown by slow evaporation solution growth technique (SEST) from aqueous solution at room temperature. The changes in structural, electrical and optical properties of gamma irradiated MHB single crystals were studied using X-ray diffraction (XRD), UV–Visible absorption spectroscopy, Photo-luminescence (PL), Fourier transform infrared (FTIR) spectroscopy and AC conductivity measurements at room temperature. The polished MHB single crystals were irradiated with gamma rays of doses 10 and 15 kilogray (kGy). From the XRD analysis, it was observed that gamma irradiation for these doses drastically decreases the crystallinity. The optical absorption constants were examined by UV-Visible absorption spectroscopy, measured over the wavelength range of 200–800?nm, at normal incidence. The optical band gap as estimated from the Tauc plot ((αhν)² vs hν) was found to be reduced with increasing gamma irradiation doses. PL spectra showed emission at wavelengths of 361?nm (3.43?eV) and 452?nm (2.74?eV), with enhanced intensities for the irradiated crystals. FTIR spectroscopy was utilised to identify the functional groups of MHB and indicated the rupture of specific types of bonds with gamma irradiation. Apart from that, the enhancement of AC conductivity with gamma irradiation was also observed for the gamma irradiated crystals.     

Preparation and luminescence of water soluble poly (N-vinyl-2-pyrrolidone)/LaF3:Eu nanocrystals

Lanthanide-doped luminescent nanocrystals have great potential as biological luminescent labels, but their use has been limited because of most of these nanocrystals are hydrophobic. In this work, water soluble LaF₃:Eu³⁺ down-conversion nanocrystals were prepared by encapsulated individual nanocrystals with polyvinylpyrrolidone (PVP). Their morphology, surface structure and luminescence properties were explored in detail. The results indicate that these nanocrystals can be readily dispersed in water, forming a stable and transparent colloidal solution. The colloidal solution displayed unique red luminescence with high emission intensity under ultraviolet excitation. These results suggest that these nanocrystals have great potential as luminescent labeling materials for biological applications.     

Recent advances on single photon sources based on single colloidal nanocrystals

Single colloidal quantum dots (QDs) are increasingly exploited as triggered sources of single photons. This review reports on recent results on single photon sources (SPS) based on colloidal quantum dots, whose size, shape and optical properties can be finely tuned by wet chemistry approach. First, we address the optical properties of different colloidal nanocrystals, such as dots, rods and dot in rods and their use as single photon sources will be discussed. Then, we describe different techniques for isolation and positioning single QDs, a major issue for fabrication of single photon sources, and various approaches for the embedding single nanocrystals inside microcavities. The insertion of single colloidal QDs in quantum confined optical systems allows one to improve their overall optical properties and performances in terms of efficiency, directionality, life time, and polarization control. Finally, electrical pumping of colloidal nanocrystals light emitting devices and of NC-based single photon sources is reviewed.     

Controlled synthesis of luminescent CuInS2 nanocrystals and their optical properties

Luminescent CuInS₂ nanocrystals have been synthesized in dodecanethiol using air-stable precursors. The nanocrystals were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The optical properties of the CuInS₂ nanocrystals can be controlled by changing the reaction conditions, such as reaction time, temperature, and addition of ligands. It was found that the steady-state photoluminescence spectrum of the close-packed CuInS₂ nanocrystals on glass substrate peaked at longer wavelength than that of the colloidal ones and the close-packed nanocrystals possessed a shorter luminescence decay time. This behavior was explained on the basis of Förster resonant energy transfer due to the shorter distance between nanocrystals on substrate.     

衬底钝化处理对CsPbBr3 量子点薄膜发光稳定性影响

钙钛矿量子点因具有发光谱线窄、发光效率高、发光波长可调谐等优异的光学性能,在照明、显示、激光和太阳能电池等领域得到了广泛研究。然而,钙钛矿材料的稳定性问题,一直制约着其在光电器件中的应用。其中,钙钛矿材料在空气中受潮易分解的不稳定性尤为突出,这将严重影响其发光性质。为此,研究人员采用多种手段来改善钙钛矿材料的稳定性。目前,常见的方法是将一些具有疏水性的聚合物材料（例如POSS,PMMA等）引入到钙钛矿纳米晶中,或将钙钛矿纳米晶嵌入到介孔二氧化硅材料中,避免钙钛矿纳米晶暴露于空气中破坏其结构,以此来增强钙钛矿材料的发光稳定性。此外,钝化处理钙钛矿纳米晶表面,也是改善钙钛矿发光稳定性的一种常用方法。这些方法虽然在一定程度上可以改善钙钛矿的发光稳定性,但是在与有机物合成的过程中不免会引入其他有机官能团,介孔二氧化硅的引入,其处理方式相对复杂,而对钙钛矿纳米晶表面的钝化处理会破坏材料的原有结构。以上问题,都会影响钙钛矿的发光性质,不利于其在光电器件中的应用。硅（Si）具有低成本、大尺寸、高质量、导电好等优点,常被选作钙钛矿量子点光电器件的衬底材料。但是,由于Si衬底长时间暴露于空气,其表面易形成一层具有硅烷醇基团（Si-OH）的亲水性薄膜,这将对硅基钙钛矿器件的稳定性产生影响。因此,对Si表面进行钝化处理,破坏其表面Si-OH键,可以降低衬底表面的亲水性,增强疏水性,从而提高钙钛矿材料在器件中的稳定性。本研究使用氢氟酸（HF）对Si衬底表面进行钝化处理,发现钝化处理后的Si衬底表面与水的接触角由50.4°逐渐增大至87.7°,表明Si衬底表面由亲水性逐渐转变为疏水性。利用场致发射扫描电子显微镜(FE-SEM)测试发现,钝化处理后的Si衬底表面变粗糙,并且其表面上的CsPbBr₃量子点(CsPbBr₃ QDs)相对于未处理表面的分散性较好。利用光致发光(PL)光谱研究不同钝化处理时间的Si衬底表面上的CsPbBr₃ QDs薄膜的发光性质。其中,处理与未处理的Si衬底表面上CsPbBr₃QDs薄膜的PL积分强度随功率变化拟合值分别为1.12和1.203,表明其发光机制为激子发光。温度依赖性的PL光谱分析显示,随着温度的升高（10～300 K）,由于晶格热膨胀使CsPbBr₃ QDs带隙增大,发光峰位逐渐蓝移。并且,随着衬底钝化处理时间的增加,CsPbBr₃ QDs薄膜的发光热稳定性逐渐增强,最佳热稳定性可达220 K。而时间依赖性的PL光谱则进一步说明,钝化处理后的Si衬底表面CsPbBr₃QDs薄膜发光的时间稳定性逐渐增强,最高发光时间稳定性可达15 d。因此,通过简单而有效的对Si衬底表面进行钝化处理,可以有效减少了Si表面亲水基团,提高CsPbBr₃QDs薄膜的发光稳定性,为增强钙钛矿量子点在光电器件中的稳定性应用提供了新的研究思路。     

可用于电光材料的新型非线性光学活性的玻璃分子

通过在枝化苯胺-吡咯啉发色团接入具有π-π作用的葸官能团,设计并合成了一种可用于二阶非线性光学材料的新型树枝状玻璃分子发色团ETO和ETF.所得到的分子玻璃发色团具有良好的自成膜性能,其玻璃化温度测得分别为41℃(ETO)和39℃(ETF),用SHG法测得薄膜的非线性电光系数(d33)分别为38,32 pm/V.结果表...     

Supra- and nanocrystallinities: a new scientific adventure

Nanomaterials exist in the interstellar medium, in biology, in art and also metallurgy. Assemblies of nanomaterials were observed in the early solar system as well as silicate particle opals. The latter exhibits unusual optical properties directly dependent on particle ordering in 3D superlattices.The optical properties of noble metal nanoparticles (Ag, Au and Cu) change with the ordering of atoms in the nanocrystals, called nanocrystallinity. The vibrational properties related to nanocrystallinity markedly differ with the vibrational modes studied. Hence, a drastic effect on nanocrystallinity is observed on the confined acoustic vibrational property of the fundamental quadrupolar modes whereas the breathing acoustic modes remain quasi-unchanged. The mechanical properties characterized by the Young's modulus of multiply twinned particle (MTP) films are markedly lower than those of single nanocrystals.Two fcc supracrystal growth mechanisms, supported by simulation, of Au nanocrystals are proposed: heterogeneous and homogeneous growth processes. The final morphology of nanocrystal assemblies, with either films by layer-by-layer growth characterized by their plastic deformation or well-defined shapes grown in solution, depends on the solvent used to disperse the nanocrystals before the evaporation process.At thermodynamic equilibrium, two simultaneous supracrystal growth processes of Au nanocrystals take place in solution and at the air-liquid interface. These growth processes are rationalized by simulation. They involve, on the one hand, van der Waals interactions and, on the other hand, the attractive interaction between nanocrystals and the interface.Ag nanocrystals (5 nm) self-order in colloidal crystals with various arrangements called supracrystallinities. As in bulk materials, phase diagrams of supracrystals with structural transitions from face-centered-cubic (fcc) to hexagonal-close-packed (hcp) and body-centered-cubic (bcc) structures are observed. They depend on the chain length of the coating agent and on the solvent used to disperse the nanocrystals before evaporation. The transition from fcc to hcp is attributed to specific stacking processes depending on evaporation kinetics whereas the formation of bcc supracrystals is attributed to van der Waals attractions.These results open up a new research area, which currently suffers from an extensive lack of knowledge.     

Silver nanoparticles and silver ions stabilized in NaCl nanocrystals

This study presents a two-step synthesis of nanoparticles and the stabilization process of Ag ions in the matrix of NaCl nanocrystals. Ag⁺ ions are incorporated to NaCl with a new and attractive method that can be easily used for the different types of alkaline halides. The nanoparticles with predominant size found between 10 and 15 nm were stabilized on the surface and/or interior of NaCl nanocrystals using, in the first stages, the ionic-exchange property of zeolite A4. The optical properties of the materials were characterized through optical absorption, leading to well defined absorption bands located in the wave length values between 217–275 nm and 350–770 nm approximately, for Ag⁺ and AgNp, respectively. The antibacterial property of Ag ions and nanoparticles stabilized in NaCl was analyzed against gram-negative Escherichia Coli and Klebsiella bacteria. In order to quantify the antibacterial effect of Ag ions and nanoparticles the inhibition ratio was used as a parameter on the bacteria colonies grown in culture medium by conventional methods. Ag⁺ ions that were stabilized in NaCl nanocrystals show a mayor inhibition ratio in contact with Klebsiella bacteria, conversely Ag nanoparticles showed better results in contact with E. coli.     

表面修饰基团对金纳米颗粒非线性光学效应的影响研究

采用两相法分别制备一级硫醇修饰和二级十六烷基三甲基溴化铵(CTAB) 修饰的金纳米颗粒,通过透射电子显微镜和紫外-可见吸收光谱表征了其结构和线性光学性质. 采用开孔Z扫描技术,研究表面修饰对金纳米颗粒在532 nm波长激光作用下的非线性光学效应及光限幅性能的影响行为.结果表明,二级CTAB的修饰增强了颗粒在激光照射下的局域场作用, 并提高了热电子对非线性光学效应的贡献程度,从而有效地提高了金纳米颗粒的光限幅性能.     

Lateral quantization of two-dimensional electron states by embedded Ag nanocrystals

We show that quantization of image-potential state (IS) electrons above the surface of nanostructures can be experimentally achieved by Ag nanocrystals that appear as stacking-fault tetrahedrons (SFTs) at Ag(111) surfaces. By means of cryogenic scanning tunneling spectroscopy, the n=1 IS of the Ag(111) surface is revealed to split up in discrete energy levels, which is accompanied by the formation of pronounced standing wave patterns that directly reflect the eigenstates of the SFT surface. The IS confinement behavior is compared to that of the surface state electrons in the SFT surface and can be directly linked to the particle-in-a-box model. ISs provide a novel playground for investigating quantum size effects and defect-induced scattering above nanostructured surfaces.     

Cohesive energy and physical properties of nanocrystals

Recently, a lattice-type-sensitive model, free of any adjustable parameter, for the size dependence of the cohesive energy of nanocrystals (nanodisks, -films, -wires and -particles) has been developed, taking into account the effects of the averaged structural and energetic properties of their surface and volume. These effects are related to the first- and second-nearest-neighbor atomic interactions. Now, considering the intimate relation between cohesive energy and other physical properties of materials, the recently obtained formula for the cohesive energy of nanocrystals has been applied to the cases of melting point (In, Bi, Si and Ag), evaporation temperature (Ag and Au), vacancy formation energy (Au), diffusion activation energy (Au), surface energy (Au, Al and Na), liquid–vapor interfacial energy (Al and Na), Curie temperature (Pb), Debye temperature (Au and Fe) and band gap energy (Si) of nanocrystals. In general, good agreement between the present model and the data has been obtained. Moreover, the surface-area-difference (SAD) model has been derived as a first-order approximation of the present model.