Photoluminescence quantum and surface states of excitons in ZnSe and CdS nanoclusters

The optical spectra of quantum dots (QDs) of CdS and ZnSe grown in borosilicate glass by the sol-gel method are obtained and analyzed. It is found that at concentrations of the two semiconductors x<0.06% the emission spectra are due to annihilation of free (internal) excitons in quantum states. The mean size of the quantum dots for a given concentration of ZnSe and CdS is calculated and found to be in good agreement with the X-ray data, and the exciton binding energy is calculated with allowance for the dielectric mismatch between the semiconductor and matrix. It is proposed that this mismatch may be the cause giving rise to the exciton percolation level that is observed in QD arrays for both systems at x>0.06%. The emission from the surface level of CdS QDs in the region ~2.7 eV, formed by the outer atoms with dangling bonds, is observed for the first time, as is the emission band from surface localized states. The relation between the position of the maximum of this band and the energy of the 1S state of the free exciton is established. It is shown that the properties of surface localized states are largely similar to the analogous properties of localized states of 3D (amorphous semiconductors, substitutional solid solutions of substitution) and 2D (quantum wells and superlattices) structures.     

Three-dimensional confinement in the conduction band structure of InP

Strong quantum confinement in InP is observed to significantly reduce the separation between the direct and indirect conduction band states. The effects of three-dimensional confinement are investigated by tailoring the initial separation between conduction band states using quantum dots (QDs) of different sizes and hydrostatic pressure. Analyses of the QD emission spectra show that the X(1c) states are lowest in energy at pressures of approximately 6 GPa, much lower than in the bulk. The transition to the X(1c) states can be explained by either a sequence of gamma-L and L-X crossings, or by the crossover between strongly coupled gamma and X states.     

Selecting of modes in nano-laser of silicon quantum dots

In a nano-laser of Si quantum dots (QD), the smaller QD fabricated by nanosecond pulse laser can form the pumping level tuned by the quantum confinement (QC) effect. Coupling between the active centers formed by localized states of surface bonds and the two-dimensional (2D) photonic crystal used to select model can produce a sharp peak at 2.076 eV in the nano-laser. It is interesting to make a comparison between the localized electronic states in gap due to defect formed by surface bonds and the localized photonic states in gap of photonic band due to defect of 2D photonic crystal.     

Nonstationary effects in the system of coupled quantum dots influenced by Coulomb correlations

We investigate the time evolution of filling numbers of localized electrons in the system of two coupled single-level quantum dots (QDs) connected with the continuous-spectrum states in the presence of Coulomb interaction. We consider correlation functions of all orders for electrons in the QDs by decoupling higher-order correlations between localized and band electrons in the reservoir. We analyze different initial charge configurations and consider Coulomb correlations between localized electrons both within the dots and between the different dots. We reveal the presence of a dynamical charge trapping effect in the first QD in the situation where both dots are occupied at the initial instant. We also find an analytic solution for the time-dependent filling numbers of the localized electrons for a particular configuration of the dots.     

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     

Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO2 Interface in Quantum Dot‐Sensitized Solar Cells

Quantum dot‐sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next‐generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO₂ acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. To understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO₂ substrate are simulated using a rigorous ab initio density functional method. This method capitalizes on localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO₂ occurring via the strong bonding between the conduction bands of QDs and TiO₂ is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO₂ acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO₂ systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO₂ acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.     

Helical quantum states in HgTe quantum dots with inverted band structures

We investigate theoretically the electron states in HgTe quantum dots (QDs) with inverted band structures. In sharp contrast to conventional semiconductor quantum dots, the quantum states in the gap of the HgTe QD are fully spin-polarized and show ringlike density distributions near the boundary of the QD and spin-angular momentum locking. The persistent charge currents and magnetic moments, i.e., the Aharonov-Bohm effect, can be observed in such a QD structure. This feature offers us a practical way to detect these exotic ringlike edge states by using the SQUID technique.     

Photoluminescence of colloidal CdSe nano-tetrapods and quantum dots in oxygenic and oxygen-free environments

The effects of oxygenic versus oxygen-free environments on colloidal CdSe nano-tetrapods and quantum dots (QDs) were studied using both continuous and time-resolved photoluminescence (PL) measurements. The decays of PL intensities for tetrapods and QDs in oxygen-free solution (chloroform) and in air (on silicon) can be well fitted by a bi-exponential function. Based on the emission-energy dependence of carrier lifetimes and the amplitude ratio of the fast-decay component to the slow-decay component, the fast and slow PL decays of CdSe nanocrystals are attributed to the recombination of delocalized carriers in the core states and localized carriers in the surface states, respectively. The PL intensities of CdSe nano-tetrapods and QDs were found to be five times and an order of magnitude higher in air than in vacuum, respectively, which is explained by the passivation of surface defects by the polar gas (oxygen) absorption. The lower enhancement in PL intensities of CdSe nano-tetrapods is explained by the special morphology of the tetrapods.     

Nano-laser on silicon quantum dots

A new conception of nano-laser is proposed in which depending on the size of nano-clusters (silicon quantum dots (QD)), the pumping level of laser can be tuned by the quantum confinement (QC) effect, and the population inversion can be formed between the valence band and the localized states in gap produced from the surface bonds of nano-clusters. Here we report the experimental demonstration of nano-laser on silicon quantum dots fabricated by nanosecond pulse laser. The peaks of stimulated emission are observed at 605 nm and 693 nm. Through the micro-cavity of nano-laser, a full width at half maximum of the peak at 693 nm can reach to 0.5 nm. The theoretical model and the experimental results indicate that it is a necessary condition for setting up nano-laser that the smaller size of QD (d < 3 nm) can make the localized states into band gap. The emission energy of nano-laser will be limited in the range of 1.7-2.3 eV generally due to the position of the localized states in gap, which is in good agreement between the experiments and the theory.     

Mn掺杂Zn-In-S量子点的制备及发光性质研究

制备了Mn掺杂Zn-In-S量子点并研究了Zn/In的量比和反应温度对其发光性质的影响。在Mn掺杂的Zn-In-S量子点的发光谱中观测到一个600 nm发光带。通过改变Zn/In的量比,掺杂量子点的吸收带隙可从3.76 e V(330 nm)调谐到2.82 e V(440 nm),但600 nm发光峰的波长只有略微移动。这些掺杂量子点的最长荧光寿命为2.14 ms。当反应温度从200℃增加到230℃时,掺杂量子点的发光强度增加并达到最大值;而继续升高温度至260℃时,发光强度迅速减弱。此外,测量了Mn掺杂Zn-In-S量子点的变温发光光谱。发现随着温度的升高,发光峰位发生蓝移,发光强度明显下降。分析认为,Mn掺杂Zn-In-S量子点的600 nm发光来自于Mn2+离子的4T1和6A1之间的辐射复合。     

Contactless electroreflectance spectroscopy of optical transitions in low dimensional semiconductor structures

The authors present the application of contactless electroreflectance (CER) spectroscopy to study optical transitions in low dimensional semiconductor structures including quantum wells (QWs), step-like QWs, quantum dots (QDs), quantum dashes (QDashes), QDs and QDashes embedded in a QW, and QDashes coupled with a QW. For QWs optical transitions between the ground and excited states as well as optical transitions in QW barriers and step-like barriers have been clearly observed in CER spectra. Energies of these transitions have been compared with theoretical calculations and in this way the band structure has been determined for the investigated QWs. For QD and QDash structures optical transitions in QDs and QDashes as well as optical transitions in the wetting layer have been identified. For QDs and QDashes surrounded by a QW, in addition to energies of QD and QDash transitions, energies of optical transitions in the surrounded QW have been measured and the band structure has been determined for the surrounded QW. Finally some differences, which can be observed in CER and photo-reflectance spectra, have been presented and discussed for selected QW and QD structures.     

Redox-mediated reversible modulation of the photoluminescence of single quantum dots

Precise control over the photoluminescence(PL) of single quantum dots(QDs) is important for their practical applications. We show that the PL of individual Cd Se/Zn S core/shell QDs can be effectively enhanced and continuously modulated by electrochemically manipulating the electron transfer(ET) between the QDs and the attached redox-active ligands such as 2-mercaptoethanol(BME). We found that i) the ET from BME to the QDs' surface trap states suppresses the blinking of the QDs, ii) the ET from the QDs' conduction band to the oxidization product results in dimmed PL when BME is oxidized,and iii) further oxidization of BME results in a significant PL brightening. The single particle measurements help us unveil the important features hidden in ensemble measurements and understand the underlying mechanism of the PL modulation.The results also suggest a simple yet efficient method to produce bright and non-blinking QDs and offer opportunities for further development of high resolution fluorescent bioimaging and nanodevices.     

Experimental observation of quantum confinement in the conduction band of CdSe quantum dots

X-ray absorption spectroscopy has been used to characterize the evolution in the conduction band (CB) density of states of CdSe quantum dots (QDs) as a function of particle size. We have unambiguously witnessed the CdSe QD CB minimum (CBM) shift to higher energy with decreasing particle size, consistent with quantum confinement effects, and have directly compared our results with recent theoretical calculations. At the smallest particle size, evidence for a pinning of the CBM is presented. Our observations can be explained by considering a size-dependent change in the angular-momentum-resolved states at the CBM.     

1.5 μm emission from InAs quantum dots with InGaAsSb strain-reducing layer grown on GaAs substrates

InGaAsSb strain-reducing layers (SRLs) are applied to cover InAs quantum dots (QDs) grown on GaAs substrates. The compressive strain induced in InAs QDs from the GaAs is reduced due to the tensile strain induced by the InGaAsSb SRL, because the lattice constant of InGaAsSb is closer to InAs lattice constant than that of GaAs, resulting in a significant red shift of photoluminescence peaks of the InAs QDs. The emission wavelength from InAs QDs can be controlled by changing the Sb composition of the InGaAsSb SRL. The 1.5 μm band emissions were achieved in the sample with an InGaAsSb SRL whose Sb compositions were above 0.3. The calculation of the electron and the hole wave functions using the transfer matrix method indicates that the electron and the hole were localized around InAs QDs and InGaAsSb SRL.     

Electronic structure of rectangular HgTe quantum dots

We theoretically investigate the single- and few-electron ground-states properties of HgTe topological insulator quantum dots with rectangular hard-wall confining potential using configuration interaction method. For the case of single electron, the edge states is robust against the deformation from a square quantum dot to a rectangular ones, in contrast to the bulk states, the energy gap of the QDs increased due to the coupling of the opposite edge states; for the case of few electrons, the electrons first fill the edge states in the bulk band gap and the addition energy exhibit universal even-odd oscillation due to the shape-independent two-fold degeneracy of the edge states. The size of this edge shell can be controlled by tuning the dot size, shape or the bulk band gap via lateral or vertical electric gating respectively of the HgTe quantum dot.     

Effect on photophysical properties of colloidal ZnS quantum dots by doping with cobalt, copper, and cobalt�Ccopper mixtures

Colloidal ZnS quantum dots (QDs) are prepared by passing H₂S gas through a solution of Zn(CH₃COO)₂ in acetonitrile. Photophysical properties are investigated using UV?CVisible and photoluminescence (PL) spectroscopy. The spectrum shows an absorption shoulder at 271 nm representing a band gap of 4.6 eV. The doping of ZnS QDs with Co, Cu, and a mixture of Co and Cu not only increased the band gap to 0.2 eV but also turns these otherwise colorless QDs to blue in color due to cobalt, and green due to Cu. The observed emission in the visible region suggests that the dopants may have induced additional excited states to the ZnS QDs. This absorbance in the visible region can be utilized in the optoelectronic applications.     

不同厚度CdSe阱层的表面上自组织CdSe量子点的发光性质

利用变温和变激发功率分别研究了不同厚度CdSe阱层的自组织CdSe量子点的发光。稳态变温光谱表明:低温下CdSe量子阱有很强的发光,高温猝灭,而其表面上的量子点发光可持续到室温,原因归结于量子点的三维量子尺寸限制效应;变激发功率光谱表明:量子点激子发光是典型的自由激子发光,且在功率增加时。宽阱层表面上的CdSe量子点有明显的带填充效应。通过比较不同CdSe阱层厚度的样品的发光,发现其表面上量子点的发光差异较大,这可以归结为阱层厚度不同导致应变弛豫的程度不同,直接决定了所形成量子点的大小与空间分布^[1]。     

Force control between quantum dots by light in polaritonic molecule states

Photomediated force between quantum dots (QDs) is theoretically studied. An attractive (repulsive) interparticle radiation force (IRF) arises by selectively exciting the lower (higher) split state of coupled polaritons in QDs. Since these states are analogous to bonding and antibonding states of a diatomic molecule, we term this system the "polaritonic molecule (PM)". IRF in PM states is controlled by the photon energy, polarization, and phase at each QD. This mechanism can be used to probe internal quantum properties of nano-objects and to manipulate collective dynamics of QDs.     

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.     

Encapsulation of highly confined CdSe quantum dots for defect free luminescence and improved stability

This is the first report on the generation of trap states and their effective elimination in highly confined CdSe quantum dots in order to obtain enhanced and stable optical properties prepared by aqueous route. Surface plays an important role in optical properties of quantum dots (QDs) and surface modification of quantum dots can improve optical properties. In present work luminescent CdSe QDs were prepared using 2-Mercaptoethanol (2-ME) as stabilizing agent and encapsulated by polymer. Different concentrations of 2-ME were used to tune the emission spectra with respect to their reduced size. Addition of 2-ME to CdSe QDs enhances the trap emission and quenching band edge emission due to (i) increased surface to volume ratio and; (ii) presence of high concentration of sulfide ions as confirmed from EDX analysis as sulfide ions possesses the hole scavenging characteristics. Polymer encapsulation of QDs was carried out to make them stable and to improve their optical properties. Even though there are previous reports addressing the improved optical properties by polymer encapsulation and silica encapsulation but experimentally it has not been reported yet experimentally. In this work we have synthesized and characterized water soluble polymer encapsulated QDs and proved the facts experimentally. Photoluminescence spectroscopy clearly reveals the role of polymer encapsulation in boosting the optical properties of CdSe QDs. FTIR spectra validate the presence of biocompatible functional groups on CdSe4/PEG (Polymer encapsulated QDs).