Aqueous synthesis of Cu-doped ZnSe quantum dots

In this paper, we described a simple growth-doping approach for aqueous synthesis of Cu-doped ZnSe quantum dots (Cu:ZnSe d-dots) with mercaptopropionic acid as stabilizer. The influences of the ratios of precursors and the concentration of Cu dopant ions on Cu:ZnSe d-dots synthesis were studied in detail in this study. The Cu dopant ions had significant influence on the optical properties of ZnSe d-dots. The bandgap emission of ZnSe was effectively restrained through Cu doping. The prolonged reflux facilitates the doping of Cu, which led to the red-shift of the emission of Cu:ZnSe d-dots from 465 to 495 nm. The stable Cu:ZnSe d-dots with high quality can be obtained under optimal conditions. As compared with cadmium-based nanocrystals synthesized in aqueous solution, Cu:ZnSe d-dots have much lower toxicity, indicating that they can be applied as outstanding fluorescent labels for biological assays, imaging of cells and tissues, even in vivo investigations.     

Electroluminescence of colloidal ZnSe quantum dots

The article reports a green chemical synthesis of colloidal ZnSe quantum dots at a moderate temperature. The prepared colloid sample is characterised by UV-vis absorption spectroscopy and transmission electron microscopy. UV-vis spectroscopy reveals as-expected blue-shift with strong absorption edge at 400 nm and micrographs show a non-uniform size distribution of ZnSe quantum dots in the range 1-4 nm. Further, photoluminescence and electroluminescence spectroscopies are carried out to study optical emission. Each of the spectroscopies reveals two emission peaks, indicating band-to-band transition and defect related transition. From the luminescence studies, it can be inferred that the recombination of electrons and holes resulting from interband transition causes violet emission and the recombination of a photon generated hole with a charged state of Zn-vacancy gives blue emission. Meanwhile electroluminescence study suggests the application of ZnSe quantum dots as an efficient light emitting device with the advantage of colour tuning (violet-blue-violet).     

Mn掺杂ZnSe量子点变温发光性质研究

量子点(QD)照明器件中电流导致的焦耳热会使其工作温度高于室温,因此研究量子点的发光热稳定性十分重要。本文利用稳态光谱和时间分辨光谱研究了具有不同壳层厚度的Mn掺杂ZnSe(Mn: ZnSe)量子点的变温发光性质,温度范围是80～500 K。实验结果表明,厚壳层(6.5单层(MLs))Mn: ZnSe量子点的发光热稳定性要优于薄壳层(2.6 MLs)的量子点。从80 K升温到400 K的过程中,厚壳层Mn: ZnSe量子点的发光几乎没有发生热猝灭,发光量子效率在400 K高温下依然可以达到60%。通过对比Mn: ZnSe量子点的变温发光强度与荧光寿命,对Mn: ZnSe量子点发光热猝灭机制进行了讨论。最后,为了研究Mn: ZnSe量子点的发光热猝灭是否为本征猝灭,对具有不同壳层厚度的Mn: ZnSe量子点进行了加热-冷却循环(300-500-300 K)测试,发现厚壳层的Mn: ZnSe量子点的发光在循环中基本可逆。因此,Mn: ZnSe量子点可以适用于照明器件,即使器件中会出现不可避免的较强热效应。     

Distinguishability of stacks in ZnTe/ZnSe quantum dots via spectral analysis of Aharonov-Bohm oscillations

We have investigated the active-layer-thickness dependence of exciton-photon interactions in CuI microcavities. The active layer thickness was changed from λ/2 to 2λ, where λ corresponds to an effective resonant wavelength of the lowest-lying exciton. In the CuI active layer, thermal strain removes the degeneracy of the heavy-hole (HH) and light-hole (LH) excitons at the Γ point. Angle-resolved reflectance spectra measured at 10 K demonstrate the strong coupling between the HH and LH excitons and cavity photon, resulting in the formation of three cavity-polariton branches: the lower, middle, and upper polariton branches. The energies of the three cavity-polariton modes as a function of incidence angle are reasonably explained using a phenomenological Hamiltonian to describe the exciton-photon strong coupling. It is found that the interaction energies of the cavity-polariton modes, the so-called vacuum Rabi-splitting energies, are systematically controlled from 29 (50) to 48 (84) meV for the LH (HH) exciton by changing the active layer thickness from λ/2 to 2λ. The active-layer-thickness dependence of the Rabi-splitting energies is semi-quantitatively explained by a simple model.     

Temperature-dependent photoluminescence of dimethylzinc-treated ZnSe/ZnS quantum dots

Temperature-dependent photoluminescence (PL) measurements were carried out ZnSe/ZnS quantum dots (QDs) grown with post-growth interruption under a dimethylzinc (DMZn) flow. The PL spectra showed sigmoidal peak shifts and V-shaped full width at half maximum (FWHM) variations with increasing temperature, which strongly suggest that the QD structure of ZnSe/ZnS is quite similar to that of other material systems grown in the Stranski–Krastanov mode. Apparent differences are revealed as a consequence of DMZn treatment: (i) the PL spectra of ZnSe/ZnS QDs showed peaks at higher energies and persisted up to 300 K, and(ii) the minimum points of the V-shaped FWHM appear at a higher temperature compared to H₂-purged ZnSe/ZnS QDs. Experimental results demonstrate the enhancement of localization energy.     

热分解含硫金属有机配合物制备近红外PbS量子点

以Pb(NO₃)₂, Na(S₂CNEt₂)·3H₂O为反应物, 在去离子水中合成含硫金属有机配合物Pb(S₂CNEt₂)₂. 氩气保护下, 在油酸和十八烯混合溶液中热分解前躯体Pb(S₂CNEt₂)₂, 反应时间分别为30, 60, 90, 120 min, 获得PbS量子点样品a, b, c, d. 通过红外光谱分析和热重-差热等手段对前躯体进行表征, 证明配体Na(S₂CNEt₂)·3H₂O中的两个硫原子与Pb²⁺配位成功. PbS量子点样品X射线衍射和透射电子显微镜分析表明, 合成的PbS为类球形纯立方晶系PbS纳米晶; 对PbS量子点样品紫外-可见吸收光谱和光致发光谱进行研究发现, 吸收光谱和光致发光谱随着反应时间的增加顺序红移, 表明优化热分解反应时间可以调控PbS量子点的吸收光谱和光致发光谱. PbS量子点样品a发射峰在1080 nm, 与硅基太阳能电池相匹配, 可作为硅基荧光太阳能聚集器的荧光材料. 关键词： 热分解法 含硫金属有机配合物 PbS量子点 反应时间     

Relaxation of hot excitons in CdZnSe/ZnSe quantum wells and quantum dots

The relaxation dynamics of hot excitons was studied in (Zn,Cd)Se/ZnSe quantum wells and quantum dots. A fast population of the radiative excitonic ground state occurs for an excitation excess energy corresponding to an integer number of optical phonon energies. This is indicated by a spectrally narrow photoluminescence peak observed immediately after the exciting laser pulse. Spatial diffusion of excitons, controlled by the interaction between excitons and acoustic phonons, causes a distinct linewidth broadening with increasing delay time in quantum wells. In contrast, this process is found to be strongly suppressed in quantum dots.     

分子束外延生长ZnSe自组织量子点光、电行为研究

分别应用光致发光、电容电压和深能级瞬态傅里叶谱技术详细研究ZnSe自组织量子点样品的光学和电学行为.光致发光温度关系表明ZnSe量子点的光致发光热猝火过程机理.两步猝火过程的理论较好模拟和解释了相关的实验数据.电容电压测量表明样品表观载流子积累峰出现的深度(样品表面下约100nm处)大约是ZnSe量子点层的位置.深能级瞬态傅里叶谱获得的ZnSe量子点电子基态能级位置为ZnSe导带下的011eV,这与ZnSe量子点光致发光热猝火模型得到的结果一致.     

分子束外延生长ZnSe自组织量子点光、电行为研究

分别应用光致发光、电容-电压和深能级瞬态傅里叶谱技术详细研究ZnSe自组织量子点样品的光学和电学行为.光致发光温度关系表明ZnSe量子点的光致发光热猝火过程机理.两步猝火过程的理论较好模拟和解释了相关的实验数据.电容-电压测量表明样品表观载流子积累峰出现的深度(样品表面下约100nm处)大约是ZnSe量子点层的位置.深能级瞬态傅里叶谱获得的ZnSe量子点电子基态能级位置为ZnSe导带下的0.11eV,这与ZnSe量子点光致发光热猝火模型得到的结果一致.     

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.     

Time-gated biological imaging by use of colloidal quantum dots

The long (but not too long) fluorescence lifetime of CdSe semiconductor quantum dots was exploited to enhance fluorescence biological imaging contrast and sensitivity by time-gated detection. Significant and selective reduction of the autofluorescence contribution to the overall image was achieved, and enhancement of the signal-to-background ratio by more than an order of magnitude was demonstrated.     

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.     

Growth and characterization of ZnSe/CdSe/ZnSe quantum dots fabricated by using an alternate molecular beam supplying method

ZnSe/CdSe/ZnSe structures inserted CdSe thin layer are fabricated using an alternate molecular beam supply (ALS). Examining the PL peak energy dependence on beam irradiation time in ALS cycle, we studied the initial stage of CdSe growth. When CdSe below the critical thickness is supplied on ZnSe grown on GaAs (1 0 0), two kinds of 2D islands (platelets) appear. We confirmed the alloying of 2D-CdSe islands and 3D-CdSe islands (dots) is prominent under Cd beam irradiation in ALS growth.     

Growth and time-resolved photoluminescence study of self-organized CdSe quantum dots in ZnSe

Employing two different growth methods: standard molecular beam epitaxy (MBE) and low-temperature atomic layer epitaxy (ALE) with subsequent annealing, we have obtained high-quality quantum dot structures consisting of CdSe embedded in ZnSe. Single dot emission lines are observed in micro-luminescence. The samples have been investigated by further optical methods including time-resolved photoluminescence under resonant excitation at 4.2 K. Distinct properties of systems with three-dimensional confinement are observed such as the suppression of the interaction between isolated quantum dots (QDs). In standard quantum wells tunneling/hopping processes generally lead to a pronounced red shift of the luminescence over time due to a lateral localization of excitons in potential fluctuations. A much less pronounced red shift is observed for the QDs reflecting only the different lifetimes of single dots and higher excited states. The red shift completely vanishes under resonant excitation that selectively excites only a few QDs of the ensemble in the layer. Typical behaviour is also observed from the halfwidth of the quantum dot emission.     

Highly luminescent (ZnSe)ZnS core-shell quantum dots for blue to UV emission: synthesis and characterization

We synthesized nearly monodisperse bare ZnSe nanocrystallites having luminescence which ranges in wavelength from 340 to 430 nm via nucleation due to supersaturation and growth followed by size selective precipitation. Bare ZnSe dots' outermost surface is passivated with organic HDA/TOP. In order to enhance the radiative emission from the semiconductor nanocrystals, we capped the bare ZnSe quantum dots with ZnS semiconductor materials of a wider band gap and 5% of lattice mismatch and produced highly luminescent core-shell (ZnSe)ZnS quantum dots. The core-shell (ZnSe)ZnS nanocrystals show 20 times or more as greatly enhanced luminescence quantum yields as those of bare ZnSe nanocrystals. The ZnSe bare dots and the (ZnSe)ZnS core-shell dots have cubic zinc blende structures as expected from the bulk structure. The observed shapes of bare ZnSe and core-shell (ZnSe)ZnS dots are nearly spherical or ellipsoidal with the aspect ratios of 1.2 and 1.4, respectively. They are not faceted.     

Photoluminescence and magneto-optical properties of multilayered type-II ZnTe/ZnSe quantum dots

Multilayered Zn–Se–Te structures grown by migration enhanced epitaxy are studied by temperature- and excitation-dependent photoluminescence (PL) as well as magneto-PL. The PL consists of two bands: a blue band, overlaid with band edge sharp lines, dominant at low temperatures and high excitation, and a green band, which appears at elevated temperature and low excitation. Upon varying excitation intensity by four orders of magnitude, the green band peak energy shifts by ∼60 meV, indicating recombination of excitons in type-II quantum dots (QDs); no significant shift is observed for the blue band. Therefore, the green emission is attributed to ZnTe/ZnSe type-II QDs, which co-exist with isoelectronic centers, responsible for the blue and band edge emissions. The existence of type-II ZnTe/ZnSe QDs is further confirmed by magneto-PL, for which the observed oscillations in the PL intensity as a function of magnetic field is explained in terms of the optical Aharonov–Bohm effect.     

Polymer-assisted synthesis of water-soluble PbSe quantum dots

Stable PbSe quantum dots were synthesised in water-based media using poly(amidehydroxyurethane) water-soluble polymer. The polymer acts like a precursor carrier, blocks the particles aggregation and assures their solubility. Atomic force microscopy data show that the particle radius is smaller than the Bohr radius of PbSe. Interactions studies, performed by Fourier transform IR spectroscopy, show that the quantum dots are capped with poly(amidehydroxyurethane). The proposed synthesis was realised in the absence of any organic solvent. As a result, the produced particles have good water solubility, stability and good arguments to be biologically compatible.     

Sonoelectrochemical synthesis of water-soluble CdTe quantum dots

A facile and fast one-pot method has been developed for the synthesis of CdTe quantum dots (QDs) in aqueous phase by a sonoelectrochemical route without the protection of N₂. The morphology, structure and composition of the as-prepared products were investigated by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and energy dispersive X-ray spectrometer (EDS). The influences of current intensity, current pulse width, and reaction temperature on the photoluminescence (PL) and quantum yield (QY) of the products were studied. The experimental results showed that the water-soluble CdTe QDs with high PL qualities can be conveniently synthesized without precursor preparation and N₂ protection, and the PL emission wavelength and QY can be effectively controlled by adjusting some parameters. This method can be expected to prepare other QDs as promising building blocks in solar cell, photocatalysis and sensors.     

Exciton photoluminescence of ZnSe and CdS quantum dots in borosilicate glasses prepared by the sol-gel method

The spectra of exciton photoluminescence (PL) of ZnSe and CdS quantum dots (QDs) synthesized in borosilicate glasses by the sol-gel method are measured and analyzed. It is shown that the positions of the PL bands in the spectra of both systems are related to the spatial quantization of the energy of excitons in QDs. Significant differences in the conditions of this process in ZnSe and CdS QDs are revealed. It is ascertained that, at some critical concentration of the semiconductors (x _cr), exciton percolation levels are formed in both systems, which manifest themselves in an abrupt change in the shape and spectral position of the emission bands of both systems and the constancy of the noted band parameters with a further increase in the concentration. The values of the critical and mean radii of QDs in the stage of their Ostwald ripening are obtained for several concentrations of the doping semiconductors.     

Electrical transport properties of consolidated ZnSe quantum dots at and above room temperature

Here we report a comprehensive study on the prevailing conduction mechanism and dielectric relaxation behavior of consolidated Zinc Selenide quantum dots in the frequency range of 1 kHz ≤ f ≤ 1.5 MHz and in the temperature range of 298K ≤ T ≤ 573 K. The ac conductivity increases either with increase in temperature or with increase in frequency, which is explained by the Jonscher Power law. At higher temperatures, correlated barrier hopping is found to be the prevalent charge transport mechanism with a maximum barrier height of 0.88 eV. The dielectric constant of the sample is found to exhibit weak temperature dependence. DC conductivity study reveals the semiconducting nature of the sample and it is discussed in the light of polaron hopping conduction. From the impedance spectroscopic study, role of the grains and grain boundaries in the overall electrical transport properties have been elucidated by considering an electrical equivalent circuit (composed of resistances and constant phase elements). Electric modulus study reveals non-Debye responses of the sample in the experimental range.