Investigation of carrier relaxation dynamics in single CdSe/ZnSe self-organized quantum dot by time-resolved micro-photoluminescence

We have investigated carrier relaxation dynamics in single CdSe/ZnSe quantum dot (QD) by time-resolved micro-photoluminescence (PL). The discrete sharp lines, originated from individual QD states, exhibit various rise and decay time constants. The decay times of the sharp lines from ground states and excited states are estimated to be 700≈800 psec and 400≈500 psec, respectively, and the rise times of the ground states become longer compared with those of the excited states. There results are in contrast to successive change of the rise and decay times observed in time-resolved macro-PL with varying the detection wave-length. The quasi-continuum higher states with much shorter decay times are clearly observed over the discrete states of the QDs.     

Förster Resonance Energy Transfer and Harvesting in II–VI Fractional Monolayer Structures

We report on Förster resonance energy transfer in the dense arrays of epitaxial quantum dots (QDs), formed by fractional monolayer CdSe insertions within a ZnSe matrix. In such arrays comprising the QDs of different sizes, the energy transfer can take place between the ground levels of small QDs and the excited levels of large radiating QDs, when these states are in resonance. This mechanism provides directional excitation of a limited number of the large QDs possessing the excited levels. It reveals itself by the shrinkage of photoluminescence (PL) bands and the appearance of the narrow single excitonic lines in micro-PL spectra. The strong shortening of characteristic PL decay times in the energy-donating QDs is observed when the distance between them and the energy-accepting QDs decreases. Photoluminescence excitation spectroscopy demonstrates the switching of the dominant energy transfer mechanism at the energy predicted by theoretical modeling of the excitonic levels in the QD arrays. Our results pave the way for engineering of the architecture of excitonic levels in the QD arrays to realize efficient nano-emitters.     

Bright CdSe quantum dot inserted in single ZnSe nanowires

We report the evidence of CdSe quantum dot (QD) insertion in single defect-free ZnSe nanowire. These nanowires have been grown by molecular beam epitaxy in vapour-liquid-solid growth mode catalysed with gold particles. We developed a two-step process allowing us to grow very thin (from 15 to 5 nm) defect-free ZnSe nanowire on top of a nanoneedle, where all defects are localised. The CdSe QDs are incorporated to the defect-free nanowires part. Owing to the extraction efficiency of the nanowires and the reduced number of stacking fault defects in the two-step-process nanowires, a very efficient photoluminescence is observed even on isolated single nanowire. Time-resolved photoluminescence and correlation photon give evidences that the bright photon emission is related to the CdSe QD.     

CdSe/ZnSe quantum dot structures grown by molecular beam epitaxy with a CdTe submonolayer stressor

A procedure for formation of CdSe quantum dots (QDs) in a ZnSe matrix is suggested. The procedure is based on the introduction of a CdTe submonolayer stressor deposited on the matrix surface just before deposition of the material of the QDs. (For CdTe/ZnSe structure, the relative lattice mismatch is Δa/a ≈ 14%.) The stressor forms small strained islands at the ZnSe surface, thus producing local fields of high elastic stresses controlling the process of the self-assembling of the QDs. According to the data of transmission electron microscopy, this procedure allows a considerable increase in the surface density of QDs, with a certain decrease in their lateral dimensions (down to 4.5 ± 1.5 nm). In the photoluminescence spectra, a noticeable (～150 meV) shift of the peak to longer wavelengths from the position of the reference CdSe/ZnSe QD structure is observed. The shift is due to some transformation of the morphology of the QDs and an increase in the Cd content in the QDs. Comprehensive studies of the nanostructures by recording and analyzing the excitation spectra of photoluminescence, the time-resolved photoluminescence spectra, and the cathodoluminescence spectra show that the emission spectra involve two types of optical transitions, namely, the type-I transitions in the CdSeTe/ZnSe QDs and the type-II transitions caused mainly by the low cadmium content (Zn,Cd)(Se,Te)/ZnSe layer formed between the QDs.     

Influence of capping layer thickness on the polarization of photoluminescence of CdSe/ZnSe quantum dots grown by metalorganic chemical vapor phase deposition

The polarization of the photoluminescence (PL) of self-assembled CdSe quantum dots (QDs), grown by metalorganic chemical vapor phase deposition, was measured. From the (001) surface, the PL was found preferentially polarized in the direction, while from the cleaved surface in the [001] direction. The polarization of PL depends strongly on the ZnSe capping layer thickness and the PL energy. With an increase in ZnSe coverage, the intensity ratio was found to increase first, then decrease after the coverage is thicker than a critical value. Moreover, such a critical thickness is smaller for larger QDs (lower PL energies). Possible origins of the PL polarization are discussed. We suggest that besides the quantum confinement effects, the strain field in the QDs also plays an essential role in the observed polarization of PL.     

Progress in Epitaxial Growth and Performance of Quantum Dot and Quantum Wire Lasers

We report on interplay of epitaxial growth phenomena and device performance in quantum dot (QD) and quantum wire (QWW) lasers based on self-organized nanostructures. InAs QDs are the most explored model system for basic understanding of "near-ideal" QD devices. Vertically-coupled growth of QDs and activated phase separation allow ultimate QD wavefunction engineering enabling GaAs lasers beyond 1400 nm and polarization-insensitive optical amplification. A feasibility of QD semiconductor optical amplifiers at terabit frequencies using InAs QDs is manifested at 1300 and 1500 nm. 1250-1300 nm QD GaAs edge emitters and VCSELs operate beyond 10 Gb/s with ultimate temperature robustness. Furthermore, temperature-insensitive operation without current or modulation voltage adjustment at >20 Gb/s is demonstrated up to ~90 degC. Light-emitting devices based on InGaN-QDs cover ultraviolet (UV) and visible blue-green spectral ranges. In these applications, InN-rich nanodomains prevent diffusion of nonequilibrium carries towards crystal defects and result in advanced degradation robustness of the devices. All the features characteristic to QDs are unambiguously confirmed for InGaN structures. For the red spectral range InGaAlP lasers are used. Growth on misoriented surfaces, characteristic to these devices, leads to nano-periodi- cally-step-bunched epitaxial surfaces resulting in two principal effects: 1) step-bunch-assisted alloy phase separation, leading to a spontaneous formation of ordered natural super lattices; 2) formation of quantum wire-like structures in the active region of the device. A high degree of polarization is revealed in the luminescence recorded from the top surface of the structures, in agreement with the QWW nature of the gain medium. QD and QWW lasers are remaining at the frontier of the modern optoelectronics penetrating into the mainstream applications in key industries.     

Origin of size distributions in ZnSe self-organized quantum dots grown on ZnS layers

Main factors which determine the size, the standard deviations which show the degree of the size fluctuations for the average dot height and diameter, and density in ZnSe self-organized quantum dots (QDs) grown on ZnS layers were studied. By lowering the growth temperature the QDs average size and its standard deviation decreased and the density increased due to the slower surface migration. With the application of the scaling theory, it was revealed that the normalized size distributions were uniquely determined by the nucleation process although the apparent standard deviations of the QD sizes were dependent on the growth temperature. The influence of surface roughness of the underneath layer on the formation of the relations of the dot height and diameter was also examined. It was shown that the fluctuation of the surface potential contributes significantly to the apparent standard deviations of ZnSe self-organized QDs sizes.     

Shape stabilization and size equalization of InGaAs self-organized quantum dots

We report a simultaneous shape stabilization and size equalization after shape transformation of InGaAs self-organized quantum dots (QDs) formed via a fractional monolayer (ML) deposition technique. The density of QD increases rapidly from an initial value of 110±10/μm² (at a total deposition of 4 ML) to 270±30/μm² (at 5 ML) and saturates at a level of 240±20/μm² (at 10 ML). At an intermediate stage of 7 ML deposition, bimodal QD height (peaked at 8.5 nm and 14.5 nm) and aspect ratio (peaked at 0.18 and 0.26) distributions occur, confirming the QD shape transformation from a shallower to a steeper shape. The eventual convergence in lateral size, height and aspect ratio is the direct result of the simultaneous QD size equalization and shape stabilization. The QD size and shape evolution is also substantiated by the low temperature (4 K) photoluminescence (PL) data taken from samples with QDs capped by GaAs.     

Highly Efficient Quantum‐Dot‐Sensitized Solar Cell Based on Co‐Sensitization of CdS/CdSe

Cadmium sulfide (CdS) and cadmium selenide (CdSe) quantum dots (QDs) are sequentially assembled onto a nanocrystalline TiO₂ film to prepare a CdS/CdSe co‐sensitized photoelectrode for QD‐sensitized solar cell application. The results show that CdS and CdSe QDs have a complementary effect in the light harvest and the performance of a QDs co‐sensitized solar cell is strongly dependent on the order of CdS and CdSe respected to the TiO₂. In the cascade structure of TiO₂/CdS/CdSe electrode, the re‐organization of energy levels between CdS and CdSe forms a stepwise structure of band‐edge levels which is advantageous to the electron injection and hole‐recovery of CdS and CdSe QDs. An energy conversion efficiency of 4.22% is achieved using a TiO₂/CdS/CdSe/ZnS electrode, under the illumination of one sun (AM1.5,100 mW cm^?2). This efficiency is relatively higher than other QD‐sensitized solar cells previously reported in the literature.     

Band Gap Engineering Improves the Efficiency of Double Quantum Dot Upconversion Nanocrystals

Solution‐processed core/multishell semiconductor quantum dots (QDs) could be tailored to facilitate the carrier separation, promotion, and recombination mechanisms necessary to implement photon upconversion. In contrast to other upconversion schemes, upconverting QDs combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Nevertheless, their upconversion quantum yield (UCQY) is fairly low. Here, design rules are uncovered that enable to significantly enhance the performance of double QD upconversion systems, and these findings are leveraged to fabricate upconverting QDs with increased photon upconversion efficiency and reduced saturation intensities under pulsed excitation. The role of the intra‐QD band alignment is exemplified by comparing the upconversion process in PbS/CdS/ZnSe QDs with that of PbS/CdS/CdSe ones with variable CdSe shell thicknesses. It is shown that electron delocalization into the shell leads to a longer‐lived intermediate state in the QDs, facilitating further absorption of photons, and enhancing the upconversion process. The performance of these upconversion QDs under pulsed excitation versus continuous pumping is also compared; the reasons for the significant differences between these two regimes are discussed. The results show how one can overcome some of the limitations of previous upconverting QDs, with potential applications in biophotonics and infrared detection.     

Optical properties of CdSe quantum dots grown on ZnSe and ZnBeSe by molecular beam epitaxy

We report detailed studies of the optical properties of CdSe quantum dots (QDs) grown on ZnSe and ZnBeSe by molecular-beam epitaxy (MBE). We performed steady-state and time-resolved photoluminescence (PL) measurements and observe that nonradiative processes dominate at room temperature (RT) in the CdSe/ZnBeSe QDs structures, though these nonradiative processes do not dominate in the CdSe/ZnSe QDs structures up to RT. We performed secondary ion-mass spectrometry (SIMS) measurement and propose that the oxygen incorporation in the ZnBeSe layers (possibly caused by the reactivity of Be) may contribute to the dominant nonradiative processes at high temperatures in the QDs grown on ZnBeSe.     

Wigner Localization and Whispering Gallery Modes of Electrons in Quantum Dots

We used a low temperature near-field scanning optical microscopy (NSOM) to study a formation of Wigner molecules (WMs) in the emission spectra of self-organized InP/GaInP QDs having up to seven electrons. We used a Schottky diode structure for the electrostatic control of the number of the electrons (N) in QD, and we observed the emission of the charged excitons (for N < 3) and of the WMs (for N > 2) in the regime of weak Wigner localization. We show, that a contribution of whispering gallery modes (WGMs) of the electrons and rearrangement of the electrons between the WM and WGM states in the QDs, can explain the anomalous dependence of NSOM image size on the quantum confinement observed for some dots.     

Carrier transport and memory mechanisms of multilevel resistive memory devices with an intermediate state based on double-stacked organic/inorganic nanocomposites

Multilevel resistive memory devices with an intermediate state were fabricated utilizing a poly(methylmethacrylate) (PMMA) layer sandwiched between double-stacked PMMA layers containing CdSe/ZnS core–shell quantum dots (QDs). The current–voltage (I–V) curves on a Al/[PMMA:CdSe/ZnS QD]/PMMA/[PMMA:CdSe/ZnS QD]/indium-tin-oxide/glass device at low applied voltages showed current bistabilities with three states, indicative of multilevel characteristics. A reliable intermediate state was realized under positive and negative applied voltages. The carrier transport and the memory mechanisms of the devices were described on the basis of the I–V curves and energy band diagrams, respectively. The write-read-erase-read-erase-read sequence of the devices showed rewritable, nonvolatile, multilevel, and memory behaviors. The currents as functions of the retention time showed that three current states were maintained for retention times larger than 1 × 10⁴ s, indicative of the good stability of the devices.     

A novel nonvolatile memory based on self-organized quantum dots

A novel type of memory based on self-organized quantum dots (QDs) is presented, which merges the advantages of the most important semiconductor memories, the dynamic random access memory (DRAM) and the Flash. A nonvolatile memory with fast access times and good endurance (>10¹⁵ write/erase cycles) as an ultimate solution seems possible. A storage time of 1.6 s at 300 K in InAs/GaAs QDs with an additional Al_0.9Ga_0.1As barrier is demonstrated and a retention time of 10⁶ years is predicted for GaSb QDs in an AlAs matrix. A minimum write time of 6 ns is obtained for InAs/GaAs QDs. This value is already in the order of the access time of a DRAM cell and at the moment limited by the RC low pass of the device. An erase time of milliseconds is shown in first measurements on GaSb/GaAs QDs at . Faster write/erase times below even at room temperature are expected for improved device structures.     

Tuning the spectrometric properties of white light by surface plasmon effect using Ag nanoparticles in a colour converting light-emitting diode

We report on the spectral tunability of white light by localized surface plasmon (LSP) effect in a colour converting hybrid device made of CdSe/ZnS quantum dots (QDs) integrated on InGaN/GaN blue light-emitting diodes (LEDs). Silver (Ag) nanoparticles (NPs) are mixed with QDs for generating LSP effect. When the plasmon absorption of Ag NPs is synchronized to the QW emission at 448 nm, the NPs selectively absorb the blue light and subsequently enhance the QD emission. Using this energy transfer scheme, the (x, y) chromaticity coordinates of the hybrid white LED was tuned from (0.32, 0.17) to (0.43, 0.26), and thereby generated warm white light emission with correlated colour temperature (CCT) around 1800 K. Moreover, a 47% enhancement in the external quantum efficiency (EQE) was realized.     

MO-PPV/ZnSe量子点复合材料的制备及光致发光特性研究

采用水相法制备了颗粒尺寸为3.75nm的硒化锌(ZnSe)量子点,采用表面活性剂将ZnSe量子点转移到有机相聚(2-甲氧基-5-辛氧基)对苯乙炔(MO-PPV)中,获得了MO-PPV/ZnSe复合材料。通过对MO-PPV和ZnSe量子点的吸收光谱(ABS)和光致发光(PL)光谱的研究发现,随着ZnSe量子点掺杂浓度的提高,复合材料的发光强度明显增强,发光峰位置出现了蓝移。当ZnSe∶MO-PPV的质量比为1∶0.181时,发光峰位置蓝移10nm。结果表明,MO-PPV与ZnSe量子点之间存在着能量传递,这是导致MO-PPV/ZnSe量子点复合材料具有PL增强的重要原因。     

Construction of White‐Light‐Emitting Silk Protein Hybrid Films by Molecular Recognized Assembly among Hierarchical Structures

The fabrication of bio‐hybrid functional films is demonstrated by applying a materials assembly technique. Based on the hierarchical structures of silk fibroin materials, functional molecular/materials, i.e., quantum dots (QDs), can be fixed to amino acid groups in silk fibroin films. It follows that white‐light‐emitting QD silk hybrid films are obtained by hydrogen bond molecular recognition to the –COO^– groups functionalized to blue luminescent ZnSe (5.2 nm) and yellow luminescent CdTe (4.1 nm) QDs in a molar ratio of 30:1 of ZnSe to CdTe QDs. Simultaneously, a systematic blue shift in the emission peak is observed from the QD solution to QDs silk fibroin films. The significant blue shift hints the appearance of the strong interaction between QDs and silk fibroins, which causes strong white‐light‐emitting uniform silk films. The molecular recognized interactions are confirmed by high resolution transmission electron microscopy, field scanning electron microscope, and attenuated total internal reflectance Fourier transform infrared spectroscopy. The QD silk films show unique advantages, including simple preparation, tunable white‐light emission, easy manipulation, and low fabrication costs, which make it a promising candidate for multicomponent optodevices.     

CdSe/ZnS和PbSe量子点光纤及光纤放大器研究进展

近年来,纳米晶体(量子点)以及量子点光纤、量子点光纤放大器成为一个研究热点。介绍了CdSe/ZnS和PbSe量子点的光谱特性以及量子点的吸收-辐射截面,表明量子点具有强的吸收和发射。总结了低浓度和较高浓度CdSe/ZnS量子点掺杂光纤、熔融法及溶胶凝胶法制备PbSe量子点光纤材料的最新研究进展,分析了两种方法制备量子点光纤材料的优缺点,概述了PbSe量子点光纤放大器的研究近况,展望了量子点光纤的应用前景。     

Pharmacokinetics of Nanoscale Quantum Dots: In Vivo Distribution,Sequestration, and Clearance in the Rat

Advances in nanotechnology research on quantum dots (QDs)—water soluble ZnS‐capped, CdSe fluorescent semiconductor nanocrystals—for in vivo biomedical applications have prompted a close scrutiny of the behavior of nanostructures in vivo. Data pertaining to pharmacokinetics and toxicity will undoubtedly assist in designing better in vivo nanostructure contrast agents or therapies. In vivo kinetics, clearance, and metabolism of semiconductor QDs are characterized following their intravenous dosing in Sprague–Dawley rats. The QDs coated with the organic molecule mercaptoundecanoic acid and crosslinked with lysine (denoted as QD‐LM) are cleared from plasma with a clearance of 0.59 ± 0.16 mL min^–1 kg^–1. A higher clearance (1.23 ± 0.22 mL min^–1 kg^–1) exists when the QDs are conjugated to bovine serum albumin (denoted as QD‐BSA, P < .05 (P = statistical significance). The biodistribution between these two QDs is also different. The liver takes up 40 % of the QD‐LM dose and 99 % of QD‐BSA dose after 90 min. Small amounts of both QDs appear in the spleen, kidney, and bone marrow. However, QDs are not detected in feces or urine for up to ten days after intravenous dosing.     

InGaAs-GaAs quantum dots for application in long wavelength (1.3 µm) resonant vertical cavity enhanced devices

Microcavity structures containing InGaAs-GaAs quantum dots (QDs) emitting at 1.3μm at 300 K have been studied. The energy distribution of excitons remains an nonequilibrium one up to room temperature due to high localization energies in these QDs. Carrier relaxation is found to proceed mainly via multiphonon processes. The luminescence emission from QDs in a microcavity exhibits a large spectral splitting of TE and TM components as observed in angle-resolved measurements amounting up to 10 nm for an angle of incidence of 30°. A 1.3 μm vertical cavity enhanced QD photodetector based on a single sheet of QDs is shown to have a quantum efficiency >10%. The ground state electroluminescence of a quantum dot resonant cavity light emitting diode shows no saturation up to 2 kAcm⁻².