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     

The excitation spectrum of quantum antidots

Source-drain bias measurements of transport across quantum antidots reveal a ladder of excited states analogous to the excitation spectrum of quantum dots. The antidot excitation spectrum provides an unambiguous method of determining the Coulomb-blockade charging energy and the energy difference between antidot single-particle states. The energy-level spacings and the presence of strong Kondo resonances in this regime cannot be explained within a non-interacting model.     

Quantum dots in quantum well structures

Recent progress toward fabricating and characterizing quantum dots in III–V quantum well structures is reviewed. Quantum dots made by use of lithography and etching, including deep-etched, barrier-modulated, strain-induced and interdiffused quantum dots, are described. Quantum dots fabricated by growth, including natural quantum dots, dots on patterned substrates, and self-assembled dots, are discussed. Dot sizes and uniformity, energy-level splittings, and luminescence efficiencies that are now being achieved are discussed. The status of key issues, such as the energy relaxation in quantum dots, is mentioned.     

铯铅溴量子点的合成与发光性质

通过改进的热注射法制备了铯铅溴量子点材料。制得的量子点属于立方相结构,形貌是纳米立方体形状,尺寸均匀,边长约为10 nm,分散良好,在空气中可稳定2个月以上。铯铅溴量子点有较宽的激发光谱和强烈的绿光发射峰,荧光呈双指数过程衰减,平均寿命为纳秒量级。所得的量子点胶体可以通过滴制或旋涂的方法制成均匀的薄膜,在太阳能电池、光电探测器、LED和激光等半导体光电领域都有潜在的应用。     

Aqueous Synthesis of Water-Soluble Citrate-Modified Cadmium Selenide/Cadmium Sulfide/Zinc Sulfide Quantum Dots

Water-soluble cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots were synthesized in aqueous solution using trisodium citrate as modifier. The crystal structure, morphology, component, and spectral properties of cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots were characterized by X-ray power diffraction, transmission electron microscope, energy dispersive X-ray analysis, infrared spectrum, ultraviolet–visible absorption spectrum, and fluorescence spectrum. The results show that the spherical citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots with diameter around 3.6 nm belong to the cubic zinc blende structure. The citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots show a narrow, symmetric, and strong fluorescence emission spectrum band with narrow full width at half maximum of 53 nm, and the fluorescence quantum yield can reach up to 37.3%. The high-quality citrate-modified cadmium selenide/cadmium sulfide/zinc sulfide core/shell/shell quantum dots with good fluorescence properties have potential for application in biological fluorescence analysis.     

利用B-splines特性计算PbS量子点中的激子基态能量的量子尺寸效应

利用B-splines特性构建量子点中激子的波函数,计算PbS量子点中激子的基态能量E_g的量子尺寸效应,并将计算结果与实验结果及其他理论计算结果进行比较;利用B-splines技术计算的激子的基态能量在整个区域与实验完全符合,同时计算了有效质量和势垒高度对基态能量E_g的量子尺寸效应的影响.     

Tunable Infrared Luminescence and Optical Amplification in PbS Doped Glasses

PbS-doped glasses are prepared. Absorption and luminescence spectra show that both the absorption and infrared emission can be tuned widely by thermal treatment conditions. Optical amplification at 1300 nm is observed, and amplified spontaneous emission （ASE） spectrum is also measured to confirm the optical gain from PbS quantum dots.     

Size-dependent radiative emission of PbS quantum dots embedded in Nafion membrane

PbS quantum dots (QDs) have been incorporated in a Nafion membrane, where the QD sizes were adjusted by changing the reaction time due to the steady growing process. The radiative emissions of the samples were investigated by optical absorption, photoluminescence (PL), and time-resolved PL spectroscopy. Size-tunable emissions are shown by the PL spectrum in a range of 1.84–1.65 eV, and the emission mechanism was investigated based on a four-band envelope-function model. Possible energy transitions for the radiative emission are listed. The PL lifetime depending on the particle size is about one microsecond, and PL decay curves exhibit a trend of decreasing decay time with an increase of the PbS QD size.     

Ultrasound-assisted synthesis of PbS quantum dots stabilized by 1,2-benzenedimethanethiol and attachment to single-walled carbon nanotubes

Lead sulfide (PbS) quantum dots stabilized by 1,2-benzenedimethanethiol can be synthesized by mixing Pb(NO₃)₂ and Na₂S solutions in ethanol under ultrasound irradiation. The PbS quantum dots (2.7 and 3.6 nm in diameter) are characterized by their absorption and fluorescence spectra in the near infrared region and by other surface analytical techniques. With addition of single-walled carbon nanotubes (SWNT) to the system, this ultrasound-assisted procedure allows attachment of PbS nanoparticles to SWNT surface via π–π stacking, thus providing a simple one-pot method for preparation of SWNT–PbS nanoparticle composite materials. Using the ultrasound-assisted method for synthesizing silica composites containing PbS nanoparticles by a sol–gel process is also described.     

The influence of silver ion exchange on the formation and luminescent properties of lead sulfide molecular clusters and quantum dots

PbS molecular clusters and quantum dots are formed by heat treatment in fluorophosphate glasses of the Na₂O₃–Р₂O₅–Ga₂O₃–AlF₃–ZnO(S)–PbF₂ system with different lead concentrations. PbS molecular clusters are characterized by optical absorption in the range of 300–800 nm and low quantum yields, which decrease from 8.9 to 2.7% with a semiconductor component concentration. It is shown that the parameters of formation of quantum dots luminescing in the wavelength range of 1000–1500 nm are considerably different at different semiconductor component concentrations. The influence of silver ion exchange on the formation of PbS nanoparticles is studied. Introduction of silver stimulates the growth of molecular clusters, which is seen in the absorption spectra. A possible mechanism of interaction of silver nanoparticles with PbS quantum dots is presented.     

Growth and characteristics of lead sulfide nanocrystals produced by the porous alumina membrane

Lead sulfide (PbS) nanocrystals were formed by using Pb nanowires reacted with hydrogen sulfide (H₂S) gas. The structure and composition of the as-prepared nanocrystals were confirmed by scanning electron microscopy, X-ray diffraction, transmission electron microscope and energy dispersive X-ray spectroscopy. According to the differential scanning calorimeter analysis, the PbS nanocrystals in a cubic structure owned excellent thermal stability. Furthermore, the optical properties including photoluminescence (PL) and Raman scatting spectrum were also measured. The PL emission measurement of the PbS nanocrystal showed that there was an orange-red emission peak located around 655 nm. A significant quantum confinement effect made the energy gap of PbS produce a blue shift from 0.41 eV to 1.9 eV.     

Spectral response of the intrinsic region of a GaAs–InAs quantum dot solar cell considering the absorption spectra of ideal cubic dots

Recently, attempts have been made by some researchers to improve the efficiency of quantum dot solar cells by incorporating different types of quantum dots. In this paper, the photocurrent density has been obtained considering the absorption spectra of ideal cubic dots. The effects of quantum dot size dispersion on the spectral response of the intrinsic region of a GaAs–InAs quantum dot solar cell have been studied. The dependence of the spectral response of this region on the size of quantum dots of such solar cell has also been investigated. The investigation shows that for smaller quantum dot size dispersion, the spectral response of the intrinsic region of the cell increases significantly. It is further observed that by enlarging the quantum dot size it is possible to enhance the spectral response of such solar cells as it causes better match between absorption spectra of the quantum dots and the solar spectrum. These facts indicate the significant role of quantum dot size and size dispersion on the performance of such devices. Also, the power conversion efficiency of such solar cell has been studied under 1 sun, AM 1.5 condition.     

Calibration of the spectral sensitivity of instruments for the near infrared region

We present an analysis of methods for calibration of the spectral sensitivity of instruments in the near IR region of the spectrum (0.90–2.05 μm), using as an example recording of the luminescence spectra of PbS semiconductor quantum dots using a diffraction monochromator and an InGaAs photodiode as the detector. We show that when high-sensitivity detectors are employed for calibration using the emission spectrum of an ideal black body, the problem of attenuation of the radiation flux is still important. Instead of neutral density glass and mesh light filters for attenuation of the radiation, we propose using UFS ultraviolet optical glasses (together with PS purple glasses), the maximum optical density of which is within the region of maximum spectral sensitivity of InGaAs photodiodes. We give examples of spectral calibration, taking into account instrumental characteristics and the effect of absorption by water vapor in the air, and also corrections of the luminescence spectra of quantum dots.     

溶胶-凝胶法制备PbS量子点玻璃的研究

采用溶胶-凝胶法合成了半导体PbS量子点掺杂的Na₂O-B₂O₃-SiO₂玻璃,研究了不同热处理工艺对玻璃结构的影响,利用多种表征手段研究了量子点掺杂玻璃中的微晶结构及其光学性能.孔径分析结果表明随着热处理温度的升高玻璃内部孔径不断减小,最终孔结构几乎完全消失;红外光谱分析表明玻璃网络结构在较低温度下己经形成,随温度的升高不断密实化; X射线光电子能谱证明了玻璃中存在PbS,高分辨透射电镜表征了玻璃基质中掺杂的微晶结构是PbS,统计计算表明,玻璃中微晶的平均粒径尺寸为3.5nm;吸收光谱分析发现,微晶掺杂玻璃的吸收边界较PbS的块体材料发生了明显的蓝移,产生了量子尺寸效应;通过Z扫描技术测得其非线性折射率γ为-2.03×10^-14cm²/GW. 关键词： PbS量子点 半导体 非线性光学效应 溶胶-凝胶法     

Facile and low cost chemosynthesis of nanostructured PbS with tunable optical properties

The present work reports on the chemosynthesis of nanocrystalline lead sulphide (PbS) thin films by a facile and cost-effective chemical bath deposition (CBD) method onto soda-lime glass substrates. The X-ray diffraction (XRD) pattern shows the formation phase pure PbS with cubic crystal structure. Electronic structures and chemical states of PbS film have been performed by X-ray photoelectron spectroscopy (XPS). Field emission-scanning electron microscopy (FESEM) images show the transition from granular-to-cubic-to-cubo-octahedra like surface morphology with the increase in the deposition time from 20 to 90 min. The UV–vis–NIR absorption spectra of PbS thin films are measured, and a classical Tauc approach was employed to estimate their band gap energies. The increase in band gap energy from 0.99 to 2.06 eV with the reduction in crystallite size evinces quantum size effect. This work demonstrates a simple and effective solution approach to deposit PbS nanostructured thin films having predominant quantum confinement. This approach would be helpful in nano-PbS sensitized oxide based solar cells, which are recently under intensive investigations.     

Optical vibration modes in (Cd,Pb, Zn)S quantum dots in the Langmuir-Blodgett matrix

The structures with CdS, PbS, and ZnS quantum dots produced using the Langmuir-Blodgett method are investigated by infrared (IR) spectroscopy, Raman scattering, and ultraviolet (UV) spectroscopy. The quantum dot size estimated from the UV spectra and high-resolution transmission electron microscopy (HRTEM) falls in the range 2–6 nm. The longitudinal optical (LO) phonons localized in quantum dots and the surface optical vibration modes are revealed in the IR reflection and Raman scattering spectra of the structures under investigation. The frequencies of the surface optical modes are adequately described with allowance made for the effect of localizing optical phonons in the quantum dots.     

Preparation of Group IIB Selenide Nanoparticles Using Soft-Hard Dual Template Method

Using a celloidin membrane as template, the uniform Group IIB selenide nanoparticles were inductively synthesized at room temperature and ambient pressure. The nanoparticles are cubic ZnSe quantum dots, hexagonal CdSe quantum dots and cubic HgSe nanoparticles with average diameters of 3.1, 2.0 and 44nm, respectively. In the ultraviolet-visible spectra, their absorption peaks are at about 360, 480 and 440nm individually, and have large blue shifts due to quantum size effect. The corresponding photoluminescence peaks individually showed at 367, 438 and 440nm. In addition, the preparation conditions and formation mechanism have been explored.     

Achievement of Narrow-Band CARS Signal by Manipulating Broad-band Laser Spectrum

We theoretically demonstrate the achievement of narrow-band coherent anti-Stokes Raman scattering （CARS） signal by manipulating broad-band probe spectrum. The narrowing of the CARS signal depends on the spectrum bandwidth of the probe beam, and thus high-resolution CARS signal for a complicated quantum system can be obtained by the simple spectrum manipulation. Furthermore, the energy-level diagram for the complicated quantum system can also be labelled by measuring the CARS signal at a given frequency.     

核壳型ZnS∶Cu/ZnS量子点的制备及发光性质

本文采用水相合成方法制备了ZnS∶Cu量子点并进行了ZnS壳层修饰,研究了壳层厚度对ZnS∶Cu量子点光学性质的影响,采用TEM、XRD、PL、PLE和UV-Vis等测试方法对其进行了表征。实验结果表明,合成的ZnS∶Cu/ZnS量子点为立方闪锌矿,尺寸分布均匀呈球形,分散性良好,经过壳层修饰平均粒径由2 nm增加到3.2 nm。随着ZnS壳与ZnS核量的比的增加,量子点的PLE激发峰位置和UV-Vis吸收谱线出现红移,也说明了量子点的尺寸增大,证明ZnS在ZnS∶Cu量子点的表面生长,形成了核壳结构的ZnS∶Cu/ZnS量子点。随着壳层增厚,量子点与铜离子发光中心相关的发射峰强度先增大后减小,当壳核比n_s/n_c=2.5时,发光强度达到最大。     

ZnO对硫硒化镉量子点玻璃发光性能的影响

以CdS、Se、Zn粉和玻璃基质为原料,采用高温熔融法制备了CdS_xSe_(1-x)量子点硅酸盐玻璃,研究了ZnO含量对CdS_xSe_(1-x)量子点发光玻璃微观结构及发光性能的影响。结果表明:ZnO对CdS_xSe_(1-x)量子点玻璃的发光性能有显著的影响,紫外-可见吸收光谱和荧光光谱分析结果说明在470 nm蓝光激发下,掺Zn O的CdS_xSe_(1-x)量子点玻璃中CdS_xSe_(1-x)量子点处于强限域区,出现了强烈的带边激子发射现象,证明量子点具有明显的量子尺寸效应。当样品中ZnO的质量分数为13%时,荧光光谱峰强最大,半峰宽最窄。