Preparation of Highly Biocompatible ZnSe Quantum Dots Using a New Source of Acetyl Cysteine as Capping Agent

In this paper, we describe a facile method for preparation of ZnSe quantum dots (QDs) using an inexpensive and biocompatible source of acetyl cysteine in aqueous media. The structural properties of the ZnSe QDs have been characterized using XRD, FT-IR, and TEM techniques. The optical properties of the as-prepared QDs were found to be size-dependent, due to the strong confinement regime at relatively low refluxing time. Effect of solution pH and refluxing temperature on absorption and emission characteristics of the ZnSe QDs was studied. The empirical effective mass approximation also reveals that, both solution pH and refluxing temperature parameters would effect on ZnSe QDs growth, and increase their size. However, the influence of the solution pH was found to be more prominent. Water-solubility, high emission intensity and sub-10 nm nanocrystals size are the most essential features that suggest our synthesized aqueous-based ZnSe QDs (with a very cost-effective and biocompatible capping agent) can be utilized for biological intentions.     

A Simple Strategy to Prepare Colloidal Cu‐Doped ZnSe(S) Green Emitter Nanocrystals in Aqueous Media

A novel and simple method is described for preparing colloidal Cu‐doped ZnSe(S) quantum dots (QDs) in aqueous media by introducing copper ions using the same method as to prepare colloidal ZnSe(S). More specifically, the Cu‐doped ZnSe(S) are prepared through the nucleation‐doping method in the presence of 3‐mercaptopropionic acid as stabilizers using zinc perchlorate, copper sulphate, and NaHSe as precursors. Confirmation of the preparation of Cu‐doped ZnSe(S) nanocrystals (NCs) is done with absorption and emission spectroscopies (UV–vis and PL) as the QDs show intensive green emissions. The reduction of ions Cu²⁺ to Cu⁺ is confirmed by using electron paramagnetic resonance (EPR), in which Cu⁺ ions are silent. The size determination is performed by using transmission electron microscopy (TEM) and dynamic light scattering (DLS), resulting in Cu‐doped ZnSe(S) particles with a mean diameter of 4.6 ± 3.5 nm. The excellent stability observed for the nanoparticles overcomes the intrinsic instability of traditional aqueous Cu‐doped ZnSe(S) NCs.     

ZnSe/ZnS/L-Cys核壳结构量子点光声与表面光伏特性

ZnSe量子点光电子特性的研究对于其微观电子结构探测和应用领域的扩展具有重要的意义.本文结合表面光伏与光声技术以及激光Raman研究了不同回流温度下制备L-半胱氨酸(L-Cys)为配体核壳结构ZnSe量子点的微结构和光声与表面光伏特性.结果发现,具有n-型光伏特性的ZnSe量子点在近紫外到可见光范围内展示出优良的表面光伏性质.尤其在波长为350-550 nm范围内光子能量绝大部分用于产生表面光伏效应,而不是用于无辐射跃迁导致的晶格热振动,同时证实了光声与表面光伏效应之间的能量互补关系.实验指认ZnSe量子点在300-350 nm短波区域出现的光声信号和在1120,1340和1455 cm~(-1)高频区域出现的Raman峰与配体L-Cys的多声子振动模式密切相关.实验结果表明,随着回流温度的降低,ZnSe量子点的平均粒径有减小趋势,这在改善样品的表面效应和小尺寸效应的同时,有利于提高核壳结构ZnSe量子点的光伏转换效率.     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

ZnO/ZnS核-壳量子点的双光子吸收效应

利用飞秒激光Z-扫描与泵浦-探测技术,研究了室温下ZnO/ZnS与ZnO/ZnS/Ag核-壳胶体量子点的双光子吸收效应.研究发现:ZnO基核-壳量子点的本征双光子吸收系数比ZnO体材料增大了3个数量级;测量得到的660 nm处的ZnO/ZnS核-壳量子点双光子吸收截面约为4.3×10^-44 cm⁴·s·photon^-1,比相应的ZnS、ZnSe及 CdS量子点大2个数量级;当ZnO/ZnS核-壳量子点镶嵌了银纳米点时,非线性吸收有所增强.ZnO基复合纳米结构的双光子吸收增强可归因于量子限域与局域场效应.     

Spectral Optical Properties of Polymer Composite Nanomaterials Based on Carbon Nanotubes in a High-Density Polyethylene Matrix

Spectral, kinetic, and nonlinear optical regularities that demonstrate the exchange of electronic excitations between the components of hybrid associates of Ag₂S colloid quantum dots (1.7–1.8 nm) in gelatin with molecules of thiazine dyes (Ds) are found. When the IR luminescence of Ag₂S quantum dots (QDs) is excited by radiation from the thionine absorption region, its enhancement due to nonradiative resonant energy transfer is observed. The association with methylene-blue molecules blocked the IR luminescence of Ag₂S QDs upon its excitation by radiation from the absorption region of the dye due to the transfer of charge carriers. It is demonstrated that the hybrid association of thionine molecules and Ag₂S QDs adversely affects the nonlinear optical properties of the latter, which manifests itself in inverse saturated absorption by the action of 10-ns second-harmonic pulses (532 nm) of a Nd³⁺:YAG laser. For the associates of Ag₂S QDs with methylene-blue molecules, the radiation focusing caused by the transfer of charge carriers from the dye and the change in the population of small traps in nanocrystals is found. It is concluded that the direction of the transfer of electronic excitations and the photophysical processes in these objects are determined by the mutual arrangement of the HOMO–LUMO levels of the dye with respect to the levels of dimensional quantization of the Ag₂S QDs.     

Successful growth of two different quantum dots on one substrate

We report the successful growth of ZnSe and ZnTe quantum dots (QDs) embedded in ZnS on GaAs substrate. These QDs have good optical properties and show quantum confinement effect. High-resolution electron scanning microscope studies show that these QDs are grown in Volmer–Weber mode. It is found that the size of the QDs is controlled by the growth duration. When the growth time is short, high density of QDs could be fabricated, but with a long growth time the small QDs get together to form a large cluster. We also show that with this growth method it is possible to grow both ZnSe quantum and ZnTe QDs on one substrate at the same time. For this dual QDs system, two peaks corresponding to the emission from the ZnSe dots (3.0 eV, blue–violet) and ZnTe dots (2.6 eV, green–blue) could be observed at the same time in the photoluminescence measurement.     

Preparation and nonlinear characterization of zinc selenide nanoparticles embedded in polymer matrix

Nanocomposites of ZnSe nanoparticles embedded in polyvinyl alcohol (PVA) matrix have been prepared by in-situ synthesis. ZnSe/PVA nanocomposites are characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and UV/Vis spectra. The nanocomposite structure is confirmed by the blue-shift of the absorption edge. The nonlinear refractive index and two-photon absorption (TPA) coefficient are measured by the Z-scan technique using low power CW He–Ne laser light. The results show that the ZnSe nanocomposite films show large optical nonlinearity and the magnitude of the third-order nonlinear susceptibility χ⁽³⁾ is calculated to be 2.62×13^?11 m²/V².     

Structural,morphological and optical properties of PEDOT:PSS/QDs nano-composite films prepared by spin-casting

This paper describes the structural, morphological and optical properties of the nano-composite of poly (3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and quantum dots (QDs). The ZnSe and CdSe QDs have been synthesized, with the aid of Mercaptoacetic acid (MAA), by a colloidal method with an average size of ~5 to 7 nm. QDs have been embedded in PEDOT:PSS using a simple solution processing approach and has been deposited as thin films by spin coating technique. The QDs embedded PEDOT:PSS enhances the light absorption spectra of samples, prominently in terms of absorption intensity which may consequently improve sensitivity of the optoelectronic devices.     

Demonstration of Spatial Asymmetric Light Propagation Performance Using Violet Phosphorus Quantum Dots with Tunable Bandgap

The spatial self-phase modulation (SSPM) of phosphorus-based nanomaterials is widely studied and developed as passive nonlinear photonic devices for applications in all-optical switches, logic gates, information converters, etc. In this work, violet phosphorus quantum dots (VP QDs) are prepared and characterized in three different solvents, their SSPM is investigated, and their spatial asymmetric light propagation performances are demonstrated. It is shown that VP QDs prepared in three different solvents exhibit different bandgaps, mainly due to the interaction between the dangling bonds of VP QDs and functional groups in different solvents. The SSPM experiment characterizes the nonlinear optical response of solvent-dependent VP QDs. It is found that VP QDs exhibit strong nonlinear optical effect and their nonlinear refractive indexes are comparable to other phosphorus-based 2D materials. Unlike the previously reported principle of spatial asymmetric light propagation (i.e., a cascaded sample based on SSPM composed of nanomaterials with excellent nonlinear refraction and SnS₂ with reverse saturation absorption), the spatial asymmetric light propagation performance based on SSPM is demonstrated using a cascaded sample of VP QDs with significantly different nonlinear optical response prepared in two different solvents.     

Facile synthesis of highly luminescent ZnSe(S) alloyed quantum dot for biomedical imaging

An alloyed complex of zinc, sulphur and selenium was synthesized in a controlled fashion using 3-mercaptopropionic acid (MPA) surfactant to obtain a new class of biocompatible, highly luminescent imaging probes. These ZnSe(S) alloyed quantum dots (QDs) exhibited a five fold enhancement in photoluminescence over the native ZnSe nanocrystals. The enhancement in photoluminescence was brought about without any post-preparative surface treatments, under ambient conditions. 3-mercaptopropionic acid (MPA) was found to optimally stabilize the ZnSe(S) alloyed system. The incorporation of S^2? from MPA after prolonged refluxing time enabled the formation of ZnSe(S) alloyed QDs with low cytotoxicity. The in vitro assays revealed the synergistic enhancement of photoluminescence with enhancement in dispersibility and high biocompatibility for the ZnSe(S) system. The experimental findings give us a novel range of blue-emitting, Zn-based high luminescence QDs for development of nano-probes for bioimaging applications.     

Simulation of nonlinear optical absorption in ZnSe:Co crystals

The paper presents theoretical approach to simulation of nonlinear optical absorption in zinc selenide crystals doped with cobalt (II) ions (ZnSe:Co²⁺), which was reported by us earlier (Opt. Laser Technology, V. 35, (2003), 169). We used ZnSe:Co²⁺ crystals as saturable absorbers for generation of giant-pulse eye-safe laser radiation. It was found that minimal optical losses (maximal final transmission) occurred for ZnSe samples containing 1.6×10¹⁹ cm⁻³ of Co²⁺ ions. Band structure and photoinduced molecular dynamics simulations were performed to explain the parabolic dependence of optical losses versus Co²⁺ concentration. The minimum was shown to be the result of photoinduced anharmonic electron–phonon interaction.     

Two and four photon absorption and nonlinear refraction in undoped,chromium doped and copper doped ZnS quantum dots

The ZnS quantum dots (QDs) with Cr and Cu doping were synthesized by chemical co-precipitation method. The nanostructures of the prepared undoped and doped ZnS QDs were characterized by UV–vis spectroscopy, Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The sizes of QDs were found to be within 3–5 nm range. The nonlinear parameters viz. Two photon absorption coefficient (β₂), nonlinear refractive index (n₂), third order nonlinear susceptibility (χ³) at wavelength 532 nm and Four photon absorption coefficient (β₄) at wavelength 1064 nm have been calculated by Z-scan technique using nanosecond Nd:YAG laser in undoped, Cr doped and Cu doped ZnS QDs. Higher values of nonlinear parameters for doped ZnS infer that they are potential material for the development of photonics devices and sensor protection applications.     

Nonlinear change in refractive index of Co2+:ZnSe at short-pulse single-beam 1.54-μm Z-scan probing

An experimental study and theoretical modeling of the nonlinear change in refractive index of a Co^{2 +}: ZnSe crystal at the short-pulse single-beam probing at the wavelength 1.54 μm is reported. In the experimental conditions of negligible contributions in the index non-linearity stemming from the Kerr-effect and inhomogeneous heating, the nonlinear change in refractive index in Co^{2 +}:ZnSe is shown to be caused by the resonant Co^{2 +} population-perturbation effect (i.e., by the Co^{2 +} ground-state absorption saturation). The Z-scan single-beam technique and novel theoretical approach addressing the resonant nonlinear refraction in a saturable doped medium are used, respectively, for an experimental and theoretical inspection of the phenomenon. For a set of Co^{2 +}:ZnSe samples with different concentrations of Co^{2 +} ions at the short-pulse (200 ns) mJ-range probing, we show that the maximal nonlinear change in refractive index is about of units of 10^{− 4} at the chosen wavelength.     

ZnSe、ZnS量子点的可控合成与表征

采用改进后的合成方法,以Se和ZnO粉末为原料,在十六胺(HDA)、月桂酸(LA)和三辛基膦(TOP)有机溶剂体系中合成了胶体ZnSe和ZnS量子点。主要研究了溶剂配比、反应温度及生长时间对ZnSe量子点粒径和光学性质的影响。结果表明:制得的ZnSe和ZnS量子点均是纤锌矿型结构,且具有较好的尺寸均匀性、分散性及荧光特性。粒子直径可控制在4.5~8 nm范围内。采用参数n(ZnO) : n(HDA) : n(LA)=1 : 2.1 : 5.2,c(TOPSe)=1 mol/L,在280 ℃成核,240 ℃生长条件下合成的ZnSe量子点具有最佳的尺寸范围,并且随着生长时间的延长,粒径变大,荧光发射峰明显红移。     

Colour tunability in a bimodal fluorescent hybrid nanostructure UCNPs@AuNPs@QDs

In the present work, lysine modified NaY_0.78Er_0.02Yb_0.2F₄ upconversion nanoparticles (UCNPs, positively charged) and lysine modified ZnSe:Mn²⁺ quantum dots (QDs, positively charged) are attached onto the surface of citrate reduced gold nanoparticles (AuNPs, negatively charged). The gold nanoparticles not only entangle the QDs and the UCNPs, through electrostatic interaction, but also tune the optical properties of UCNPs through the effect of surface plasmon resonance. The hybrid nanostructure gives green emission both through photoluminescence (under UV excitation) and through photon upconversion (under IR light excitation) process. The colour tuning is observed through variation in the size of QDs and through plasmonic effect of gold nanoparticles. In both the cases, the colour of emission gradually changes from green to red. The colour tunability and bi-modal photon conversion property of this material could be useful for its application in the field of bio-imaging and solar energy harvesting.     

Large two-photon absorbance of chitosan–ZnS quantum dots nanocomposite film

ZnS semiconductor nanoparticles with average size of 3.4 nm were prepared in situ in chitosan film. TEM, UV–vis spectra and PL spectra show the ZnS nanoparticles in chitosan template were monodispersed and well passivated. The two-photon absorption coefficient (β) of the chitosan–ZnS quantum dots (QDs) nanocomposite film was obtained to be 2.29×10² cm/Gw from a standard Z-scan setup with femtosecond laser pusles at 790 nm wavelength. Results show the novel biomacromolecule/QDs nanocomposite film has large third-order optical nonlinear absorption, the mechanism responsible for which was discussed.     

胶体水相法制备高量子产率及高稳定性的水溶性ZnSe量子点

采用简便的胶体水相法制备了高荧光强度且稳定性良好的ZnSe量子点(ZnSe QDs),克服了以往水相合成法稳定性差、量子产率低等缺陷。优化后的最佳合成条件为：以还原型L-谷胱甘肽作为稳定剂,L-谷胱甘肽∶Se2-∶Zn2+摩尔比为5∶1∶5,介质pH 10.5,反应温度在90～100 ℃之间。且合成后不需要采取任何光照后处理,ZnSe QDs的量子产率(QYs) 即可高达50.1%,放置3个月后荧光强度基本不变,水溶性优良。用紫外-可见分光光度法(UV-Vis)、荧光分光光度法(FL)、透射电子显微镜(TEM)等分析检测手段,对得到的ZnSe QDs的性能进行表征。合成的量子点在300 nm激发下发蓝紫色荧光(370 nm),其优良的光化学特性将有利于其在光热器件的制造及化学生物领域的应用。     

Electric and photoelectric properties of GaAs/ZnSe-Ge/ZnSe/Al structures with Ge quantum dots

Current-voltage characteristics and spectral dependences of photovoltage are investigated at T=4.2 and 300 K in stress-free structures with germanium quantum dots (QDs) in the GaAs/ZnSe/QD-Ge/ZnSe/Al system. The “Coulomb staircase” type features in the current-voltage characteristic observed at room temperature without illumination are due to the Coulomb interaction of electrons in resonant tunneling through intrinsic levels in QDs. The features in the photovoltage spectra are related to the absorption of radiation in the system of discrete levels of QDs. An energy band diagram of the structure is constructed based on the experimental data.     

Temperature-dependent photoluminescence of vertically stacked self-assembled CdSe quantum dots in ZnSe

We studied the optical properties of multiple layers of self-assembled CdSe quantum dots (QDs) embedded in ZnSe, grown by molecular beam epitaxy. The ZnSe barrier thicknesses separating the QD layers ranged from 30 to 60 monolayers (ML). For stacks with thinnest ZnSe barriers photoluminescence (PL) measurements reveal blue shifts as large as 180 meV relative to PL observed for single QD layers. The amount of blue shift decreases with increasing barrier thickness, and for the 60 ML spacer the PL energy returns to that emitted by a single layer of QDs. Temperature dependence of the integrated intensity of the emission spectra reveals that the activation energy for PL quenching is largest for barrier thicknesses of 30 and 45 ML. We tentatively attribute these effects to a decrease in the size of the vertically stacked QDs when the thickness of the barrier layers is small.