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.     

ZnSe/SiO2半导体量子点玻璃的光谱特性

对采用溶胶凝胶法制备的ZnSe/SiO2半导体量子点玻璃的光谱性质进行了测试分析.UV-Vis透射光谱中观察到光吸收边相对于体相半导体有明显蓝移.稳态发射光谱(PL)中观察到ZnSe纳米晶体的位于蓝区的基本呈高斯分布的弱的最低激子发射峰、强而宽的表面态发光带以及对应杂质能级的三个锐峰发光.时间分辨荧光光谱(TRPL)中观察到发光效率高的最低激子发射峰,并测量其荧光衰减寿命,经尾部拟合为28.5 ps.同时,结合有效质量近似(EMA)模型,估计ZnSe纳米晶体的平均粒径介于2.45~3.60 nm之间,尺寸分布基本呈高斯型.     

Emission and energy relaxation of excitons in quantum dots with disordered interfaces grown in a low-permittivity matrix

Samples of borosilicate glasses doped by CdS with concentrations smaller than 1% are studied. It is shown that, due to a disorder at interfaces of quantum dots, the main channels of emission of excitons by quantum dots are the annihilation of excitons in quantum and localized surface states, while the efficiency of interaction between the channels largely depends on the radius of quantum dots. It is found for the first time that states that form the second emission channel are not discrete energy levels in the band gap, as is usually assumed in some experimental and theoretical works, but rather form a quasi-continuous tail of the density of localized states. These localized states appear as a result of dangling bonds of outer atoms of quantum dots. Energy relaxation of carriers via localized states is the reason for a long response time of these structures to an external action and can be enhanced due to a polarization effect caused by different dielectric constants of materials of quantum dots and matrix.     

Exciton in wurtzite GaN/AlxGa1−xN coupled quantum dots

Based on effective-mass approximation, we present a three-dimensional study of the exciton in GaN/Al_xGa_1−xN vertically coupled quantum dots (QDs) by a variational approach. The strong built-in electric field due to the piezoelectricity and spontaneous polarization is considered. The relationship between exciton states and structural parameters of wurtzite GaN/Al_xGa_1−xN coupled QDs is studied in detail. Our numerical results show that the strong built-in electric field in the GaN/Al_xGa_1−xN strained coupled QDs leads to a marked reduction of the effective band gap of GaN QDs. The exciton binding energy, the QD transition energy and the electron-hole recombination rate are reduced if barrier thickness L^AlGaN is increased. The sizes of QDs have a significant influence on the exciton state and interband optical transitions in coupled QDs.     

Charge and energy transfer in double asymmetric quantum wells with quantum dots

The luminescence and luminescence excitation spectra of CdSe/ZnSe quantum dots are studied in a set of double quantum wells with the ZnSe barrier of width 14 nm, the same amount of a deposited CdSe layer forming a deep well and shallow wells with different depths. It is found that for a certain relation between the depths of shallow and deep wells in this set, conditions are realized under which the exciton channel in the luminescence excitation spectrum of a shallow well dominates in the region of kinetic exciton energies exceeding 10 longitudinal optical phonons above the bottom of the exciton band of the ZnSe barrier. A model is developed for the transfer of electrons, holes, and excitons between the electronic states of shallow and deep quantum wells separated by wide enough barriers. It is shown that the most probable process of electronic energy transfer between the states of shallow and deep quantum wells is indirect tunneling with the simultaneous excitation of a longitudinal optical phonon in the lattice. Because the probability of this process for single charge carriers considerably exceeds the exciton tunneling probability, a system of double quantum wells can be prepared in which, in the case of weak enough excitation, the states of quantum dots in shallow quantum wells will be mainly populated by excitons, which explains experimental results obtained.     

Influence of Mg content on optical properties of exciton confinement in wurtzite ZnO/MgxZn1−xO coupled quantum dots

Based on the framework of effective-mass approximation and variational approach, optical properties of exciton are investigated theoretically in ZnO/Mg_xZn_1−xO vertically coupled quantum dots (QDs), with considering the three-dimensional confinement of electron and hole pair and the strong built-in electric field effects. The exciton binding energy, the emission wavelength and the oscillator strength as functions of the structural parameters (the dot height, the barrier thickness between the coupled wurtzite ZnO QDs and Mg content x in the barrier layers) is calculated in detail. The results elucidate that Mg content have a significant influence on the exciton state and optical properties of ZnO coupled QDs. When Mg content x increases, the strong built-in electric field increases and leads to the redshift of the effective band gap of the Mg_xZn_1−xO layer. These theoretical results are useful for design and application of some important photoelectronic devices constructed by using ZnO strained QDs.     

Activation of silicon quantum dots and coupling between the active centre and the defect state of the photonic crystal in a nanolaser

A new nanolaser concept using silicon quantum dots (QDs) is proposed. The conduction band opened by the quantum confinement effect gives the pumping levels. Localized states in the gap due to some surface bonds on Si QDs can be formed for the activation of emission. An inversion of population can be generated between the localized states and the valence band in a QD fabricated by using a nanosecond pulse laser. Coupling between the active centres formed by localized states and the defect states of the two-dimensional (2D) photonic crystal can be used to select the model in the nanolaser.     

Exciton states and interband optical transitions in wurtzite InGaN/GaN quantum dot nanowire heterostructures

Within the framework of the effective-mass approximation, the exciton states and interband optical transitions in In_xGa_1−xN/GaN strained quantum dot (QD) nanowire heterostructures are investigated using a variational method, in which the important built-in electric field (BEF) effects, dielectric-constant mismatch and three-dimensional confinement of the electron and hole in In_xGa_1−xN QDs are considered. We find that the strong BEF gives rise to an obvious reduction of the effective band gap of QDs and leads to a remarkable electron-hole spatial separation. The BEF, QD height and radius, and dielectric mismatch effects have a significant influence on exciton binding energy, electron interband optical transitions, and the exciton oscillator strength.     

Optical properties of exciton confinement in wurtzite ZnO/MgxZn1−xO coupled quantum dots

Based on the framework of effective-mass approximation and variational approach, optical properties of exciton are investigated theoretically in ZnO/Mg_xZn_1−xO vertically coupled quantum dots (QDs), with considering the three-dimensional confinement of electron and hole pair and the strong built-in electric field effects due to the piezoelectricity and spontaneous polarization. The exciton binding energy, the emission wavelength and the oscillator strength as functions of the different structural parameters (the dot height and the barrier thickness between the coupled wurtzite ZnO QDs) are calculated with the built-in electric field in detail. The results elucidate that structural parameters have a significant influence on the exciton state and optical properties of ZnO coupled QDs. These results show the optical and electronic properties of the quantum dot that can be controlled and also tuned through the nanoparticle size variation.     

神经网络法研究多溴代二苯胺热力学性质

通过时间分辨光谱技术详细地研究了ZnCuInS/ZnSe/ZnS量子点的激子弛豫动力学. 基于速率分布模型,波长依赖的发射动力学表明本征激子、界面缺陷态中的激子、给-受体对态中的激子都会参与量子点的发光过程,整个发光过程主要依赖于给-受体对态发射. 瞬态吸收数据表明激发后本征激子和界面缺陷物种可能会同时出现,在高激发光强下,光强依赖的俄歇复合过程也存在于量子点中     

Optical absorption and refraction index change of a confined exciton in a spherical quantum dot nanostructure

Electronic energies of an exciton confined in a strained Zn_1−x Cd _x Se/ZnSe quantum dot have been computed as a function of dot radius with various Cd content. Calculations have been performed using Bessel function as an orthonormal basis for different confinement potentials of barrier height considering the internal electric field induced by the spontaneous and piezoelectric polarizations. The optical absorption coefficients and the refractive index changes between the ground state (L = 0) and the first excited state (L = 1) are investigated. It is found that the optical properties in the strained ZnCdSe/ZnSe quantum dot are strongly affected by the confinement potentials and the dot radii. The intensity of the total absorption spectra increases for the transition between higher levels. The obtained optical nonlinearity brings out the fact that it should be considered in calculating the optical properties in low dimensional semiconductors especially in quantum dots.     

Exciton states and optical transitions in InGaN/GaN quantum dot nanowire heterostructures: Strong built-in electric field and dielectric mismatch effects

Considering the strong built-in electric field (BEF), dielectric-constant mismatch and 3D confinement of the electron and hole, the exciton states and interband optical transitions in [0 0 0 1]-oriented Ga-rich wurtzite In_xGa_1−xN/GaN strained quantum dot (QD) nanowire heterostructures are investigated theoretically using a variational approach under the effective mass approximation. We find that the strong BEF gives rise to an obvious reduction of the effective band gap of QDs and leads to a remarkable electron-hole spatial separation. The BEF, QD height and radius, and dielectric mismatch effects have a significant influence on exciton binding energy, electron interband optical transitions, and the radiative decay time. Our calculations show that the radiative decay time of the redshifted transitions is large and increases almost exponentially when the QD height increases, which is in good agreement with the previous experimental and theoretical results.     

Magneto-optical properties and exciton dynamics in diluted magnetic semiconductor nanostructures

Nanostructures of diluted magnetic semiconductors were fabricated to study novel magneto-optical properties that are derived from quantum confined band electrons interacting with magnetic ions. Quantum dots (QDs) of Cd_0.97Mn_0.03Se were grown by the self-organization on a ZnSe substrate layer. QDs of Zn_0.69Cd_0.23Mn_0.08Se and quantum wires (QWRs) of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se were fabricated by the electron beam lithography. A single quantum well (QW) of ZnTe/Zn_0.97Mn_0.03Te and double QWs of Cd_0.95Mn_0.05Te–CdTe were grown by molecular beam epitaxy. Magneto-optical properties and the formation and relaxation dynamics of excitons were investigated by ultrafast time-resolved photoluminescence (PL) spectroscopy. Excitons in these nanostructures were affected by the low-dimensional confinement effects and the interaction with magnetic ion spins. The exciton luminescence of the Cd_0.97Mn_0.03Se QDs shows the confined exciton energy due to the dot size of 4–6 nm and also shows marked increase of the exciton lifetime with increasing the magnetic field. The QDs of Zn_0.69Cd_0.23Mn_0.08Se fabricated by the electron beam lithography display narrow exciton PL spectrum due to the uniform shape of the dots. The exciton luminescence from the QWRs of Cd_0.92Mn_0.08Se and Zn_0.69Cd_0.23Mn_0.08Se shows the influence of the one-dimensional confinement effect for the exciton energy and the luminescence is linearly polarized parallel to the wire direction. The transient PL from the ZnTe/Zn_0.97Mn_0.03Te QWs displays, by the magnetic field, the level crossing of the exciton spin states of the nonmagnetic and magnetic layers and the spatial spin separation for the excitons. Cd_0.95Mn_0.05Te–CdTe double QWs show the injection of the spin polarized excitons from the magnetic well to the nonmagnetic QW.     

Mechanism of fluorescence energy transfer in aqueous solution cadmium sulfide quantum dots

Cadmium sulfide (CdS) quantum dots (QDs) prepared by a convenient chemical method have been characterized using absorption, fluorescence, and photoluminescence excitation techniques. The photoluminescence excitation studies show that there is an electron transfer from the surface adsorbate (thiourea) to CdS QDs in aqueous solution. The excitation band with peak maximum at 5.8 eV is assigned to the electronic transitions in the chemisorbed thiourea, whereas the excitation band between 3.45 and 3.7 eV corresponds to the band-to-band transition within the nanocrystalline CdS host. The absorption spectroscopy of the CdS QD solutions shows a strong absorption peak which is generated from thiourea. The band-edge fluorescence of the CdS QDs has also been investigated. It is shown that the fluorescence property of the CdS QDs can be enhanced by adding cadmium chloride (CdCl₂) solution.     

Tailoring of the Wave Function Overlaps and the Carrier Lifetimes in InAs/GaAs1−xSbx Type-II Quantum Dots

Effects of thermal annealing on the emission properties of type-II InAs quantum dots (QDs) covered by a thin GaAs_1−xSb_x layer are investigated by photoluminescence (PL) and time-resolved PL measurements. Apart from large blueshifts and a pronounced narrowing of the QD emission peak, the annealing induced alloy intermixing also leads to enhanced radiative recombination rates and reduced localized states in the GaAs_1−xSb_x layer. We find that the type-II QD structure can sustain thermal annealing up to 850 °C. In particular, we find that it is possible to manipulate between type-I and type-II recombinations in annealed QDs by using different excitation powers. We demonstrate that postgrowth thermal annealing can be used to tailor the band alignment, the wave function overlaps, and hence the recombination dynamics in the InAs/GaAs_1−xSb_x type-II QDs.     

Interband optical absorption in a strained CdxZn1−xO/ZnO quantum dot

Numerical calculations of the excitonic absorption spectra in a strained Cd_xZn_1−xO/ZnO quantum dot are investigated for various Cd contents. We calculate the quantized energies of the exciton as a function of dot radius for various confinement potentials and thereby the interband emission energy is computed considering the internal electric field induced by the spontaneous and piezoelectric polarizations. The optical absorption as a function of photon energy for different dot radii is discussed. Decrease of exciton binding energy and the corresponding optical band gap with the Cd concentration imply that the confinement of carriers decreases with composition x. The main results show that the confined energies and the transition energies between the excited levels are significant for smaller dots. Non-linearity band gap with the increase in Cd content is observed for smaller dots in the strong confinement region and the magnitude of the absorption spectra increases for the transitions between the higher excited levels.     

水溶胶CdSe/CdS核/壳结构纳米晶制备及光学性质的研究

以巯基乙酸为稳定剂在水溶液中合成了水溶胶CdSe/CdS核/壳结构的量子点,利用X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对量子点结构进行了表征;并对化学组成和尺寸分布进行了研究。通过紫外-可见吸收光谱、激发光谱与发射光谱研究了它们的发光特性。     

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.     

Exciton tunnelling in ZnCdSe quantum well/CdSe quantum dots

Exciton tunnelling through a ZnSe barrier layer of various thicknesses is investigated in a Zn_0.72Cd_0.28Se/CdSe coupled quantum well/quantum dots (QW/QDs) structure using photoluminescence (PL) spectra and near resonant pump-probe technique. Fast exciton tunnelling from quantum well to quantum dots is observed by transient differential transmission. The tunnelling time is 1.8, 4.4 and 39 ps for barrier thickness of 10, 15 and 20 nm, respectively.     

硅量子点的形状及其弯曲表面效应

硅量子点的弯曲表面引起系统的对称性破缺, 致使某些表面键合在能带的带隙中形成局域电子态.计算结果表明:硅量子点的表面曲率不同形成的表面键合结合能和电子态分布明显不同. 例如, Si–O–Si桥键在曲率较大的表面键合能够在带隙中形成局域能级, 而在硅量子点曲率较小的近平台表面上键合不会形成任何局域态, 但此时的键合结合能较低. 用弯曲表面效应(CS)可以解释较小硅量子点的光致荧光光谱的红移现象. CS效应揭示了纳米物理中又一奇妙的特性. 实验证实, CS效应在带隙中形成的局域能级可以激活硅量子点发光. 关键词： 硅量子点 弯曲表面效应 表面键合 局域能级