Dynamics within the exciton fine structure of colloidal CdSe quantum dots

Evidence for an interaction between the quantum dot exciton fine structure states F = +/-1 is obtained by measuring the dynamics of transitions among those states, exciton spin relaxation or flipping. An ultrafast transient grating experiment based on a crossed-linear polarization grating is reported. By using the quantum dot selection rules for absorption of circularly polarized light, it is demonstrated that it is possible to detect transitions between nominally degenerate fine structure states, even in a rotationally isotropic system. The results for colloidal CdSe quantum dots reveal a strong size dependence for the exciton spin relaxation rate from one bright exciton state (F = +/-1) to the other in CdSe colloidal quantum dots at 293 K, on a time scale ranging from femtoseconds to picoseconds, depending on the quantum dot size. The results are consistent with an interaction between those states attributed to a long-range contribution to the electron-hole exchange interaction.     

The electrochemical behavior of core-shell CdSe/CdS magic-sized quantum dots linked to cyclodextrin for studies of the encapsulation of bioactive compounds

Semiconductor nanocrystal quantum dots have been the subject of extensive investigations in different areas of science and technology in the past years. In particular, there are few studies of magic-sized quantum dots (MSQDs), even though they exhibit features such as extremely small size, fluorescence quantum efficiency, molar absorptivity greater than traditional QDs, and highly stable luminescence in HeLa cell cultures, thereby enabling monitoring of biological or chemical processes. The present study investigated the electrochemical behavior of free CdSe/CdS MSQDs using glassy carbon electrode and CdSe/CdS MSQDs immobilized on a gold electrode modified with a self-assembled cyclodextrin monolayer. The MSQDs showed two peaks in aprotic medium. The functionalized film modifier was prepared and characterized by means of cyclic voltammetry and electrochemical impedance spectroscopy using ferricyanide ions as a redox probe. The prepared modified electrode exhibited a stable behavior. The proposed method was successfully applied to encapsulation studies of mangiferin, a natural antioxidant compound, and cyclodextrin associated with the quantum dot, and the response was compared with that of the modified electrode without QD. The fluorescence study revealed that CdSe/CdS quantum dots emit blue light when excited by an optical source of wavelength of 350 nm and a significant increase in fluorescence and absorbance intensity is observed from the core-shell CdSe/CdS MSQDs when quantities of mangiferin are added to the solution containing thiolated cyclodextrin. CdSe/CdS MSQDs are optically and electrochemically sensitive and can be used for the detection and interaction of compounds encapsulated in cyclodextrin.     

Electron transfer in quantum-dot-sensitized ZnO nanowires: ultrafast time-resolved absorption and terahertz study

Photoinduced electron injection dynamics from CdSe quantum dots to ZnO nanowires is studied by transient absorption and time-resolved terahertz spectroscopy measurements. Ultrafast electron transfer from the CdSe quantum dots to ZnO is proven to be efficient already on a picoseconds time scale (τ = 3-12 ps). The measured kinetics was found to have a two-component character, whose origin is discussed in detail. The obtained results suggest that electrons are injected into ZnO via an intermediate charge transfer state.     

Analysis of the atomic structure of colloidal quantum dots of the CdSe family: X-ray spectral diagnostics and computer modelling

Colloidal quantum dots of the CdSe family have been studied by X-ray absorption near edge structure (XANES) spectroscopy and computer modelling. CdK edge XANES spectra in colloidal quantum dots based on varisized CdSe nanoparticles have been recorded. Atomic structure of CdSe particles and also CdSe particles doped by transition metal atoms Mn and Co has been modelled based on the density functional theory. The embedding of the doping atoms is shown to result in considerable changes in the local atomic structure of CdSe particles. XANES spectra have been calculated above the CdK edge in CdSe particles, above the MnK edge in CdSe:Mn particles, above the CoK edge in CdSe:Co particles. The sensitivity of XANES spectroscopy to small changes in structural parameters of the nanoparticles of CdSe family has been demonstrated that furnishes an opportunity to apply it for the verification of atomic structure parameters around positions of cadmium and doping atoms of transition metals in quantum dots based on CdSe.     

柠檬酸盐稳定的水溶性CdSe量子点的合成及表征

以柠檬酸三钠为稳定剂在水溶液中合成了水溶性CdSe量子点,用X射线粉末衍射、透射电镜、紫外-可见吸收光谱和荧光发射光谱对CdSe量子点的结构、形貌及其荧光性质进行了表征.结果表明合成的CdSe量子点为立方闪锌矿结构,呈球形,分散性良好,平均尺寸约为2.6nm,具有窄且对称的荧光发射光谱,半峰宽为45nm.     

Spectroscopic investigation of defect-state emission in CdSe quantum dots

CdSe quantum dots are the most studied Cd-based quantum dots with their high quantum yield, high photostability, narrow emission band, and easy synthesis procedure. They are frequently used to develop light emitting diode (LED) due to their unique photophysical properties; however, their narrow emission band causes a challenge to design white LEDs because white light emission requires emission in multiple wavelengths with broad emission bands. Here in this study, we developed CdSe quantum dots with a narrow band-edge emission band and broad defect-state emission band through a modified two-phase synthesis method. Our results revealed that defect-state emission is directly linked to the surface of quantum dots and can be excited through exciting surfactant around the quantum dot. The effect of surfactant on emission properties of CdSe quantum dots diminished upon growing a shell around CdSe quantum dots; as a result, surface-dependent defect-state emission cannot be observed in gradient heterogeneous alloyed CdS_xSe_1-x quantum dots.     

水溶性CdSe/CdS量子点的合成及其与牛血清蛋白的共轭作用

用巯基乙酸(TGA)作为稳定剂，合成了水溶性的CdSe和核壳结构的CdSe/CdS半导体量子点。吸收光谱和荧光光谱研究表明，核壳结构的CdSe/CdS半导体量子点比单一的CdSe量子点具有更优异的发光特性。用TEM、电子衍射(ED)和XPS分别表征了CdSe和CdSe/CdS纳米微粒的结构、形貌及分散性。红外光谱和核磁共振谱证实了巯基乙酸分子中的硫原子和氧原子与纳米微粒表面的金属离子发生了配位作用。在pH值为7.4的条件下，将合成的CdSe和CdSe/CdS量子点直接与牛血清白蛋白(BSA)相互作用。实验发现，两种量子点均对BSA的荧光产生较强的静态猝灭作用；而BSA对两种量子点的荧光则具有显著的荧光增敏作用，存在BSA时CdSe/CdS量子点的荧光增强是不存在BSA时体系荧光强度的3倍。     

Synthesis CdSe(x)S(1-x) core/shell type quantum dots via one injection method

The photoluminescence quantum yield (PL-QY) of ternary colloidal CdSe(x)S(1-x) quantum dots (QDs), which were prepared by a one-injection method, enhances with increasing S content. The possible enhancement mechanism was explored by structural analysis via X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Both found that the enhancement of PL-QY of ternary CdSe(x)S(1-x) QDs strongly correlated with self-formed core/shell conformation in the non-coordination solution.     

Investigation of the crystallization process in 2 nm CdSe quantum dots

Investigation of the growth of CdSe nanocrystals ( approximately 160 atoms) to the uniquely stable size of 2 nm allows the monitoring of the crystallization process in semiconductor quantum dots. By using a combination of optical techniques, high-resolution transmission electron microscopy (HRTEM), and powder X-ray diffractometry (XRD), new phenomena were explored during the CdSe nanocrystal growth process, which involved significant morphological reconstruction and crystallization of the initially formed amorphous nanoparticles. During the crystallization, the absorption onset of the CdSe quantum dots blue shifted toward higher energies at 3 eV (414 nm), while the photoluminescence red shifted to lower energies. Furthermore, an apparent increasing Stokes shift was observed during the formation of small CdSe nanoparticles. On the other hand, the photoluminescence excitation spectra showed constant features over the reaction time. Additionally, results from HRTEM and XRD studies show that the CdSe nanoparticles were amorphous at early reaction stages and became better crystallized after longer reaction times, while the particle size remained the same during the crystallization process. These observations demonstrate the important role of the surface on the optical properties of small CdSe quantum dots and facilitated the spectroscopic monitoring of the crystallization process in quantum dots.     

Exciton-phonon coupling and disorder in the excited states of CdSe colloidal quantum dots

We study the origin of the spectral line shape in colloidal CdSe nanocrystal quantum dots. The three-pulse photon echo peak shift (3PEPS) data reveal a temperature-independent fast decay, obscuring the quantification of the homogeneous linewidth. The optical gap and Stokes shift are found to have an anomalous behavior with temperature, which is size, capping group, and surrounding polymer matrix independent. Using these results and combining them with simulations, we discuss the role of exciton-phonon coupling, static inhomogeneity, exciton fine structure, and exciton state disorder in the linewidth of the nanocrystal. In particular, our analysis shows that the disorder due to surface imperfections and finite temperature effects, as well as the relaxation within the fine structure, can have significant impact on the steady-state absorption spectrum, 3PEPS data, and dephasing processes.     

Designed Long‐Lived Emission from CdSe Quantum Dots through Reversible Electronic Energy Transfer with a Surface‐Bound Chromophore

The size‐tunable emission of luminescent quantum dots (QDs) makes them highly interesting for applications that range from bioimaging to optoelectronics. For the same applications, engineering their luminescence lifetime, in particular, making it longer, would be as important; however, no rational approach to reach this goal is available to date. We describe a strategy to prolong the emission lifetime of QDs through electronic energy shuttling to the triplet excited state of a surface‐bound molecular chromophore. To implement this idea, we made CdSe QDs of different sizes and carried out self‐assembly with a pyrene derivative. We observed that the conjugates exhibit delayed luminescence, with emission decays that are prolonged by more than 3 orders of magnitude (lifetimes up to 330 μs) compared to the parent CdSe QDs. The mechanism invokes unprecedented reversible quantum dot to organic chromophore electronic energy transfer.     

Layer-by-layer quantum dot constructs using self-assembly methods

We describe the creation of CdSe/ZnS quantum dot assemblies using layer-by-layer construction strategies, using self-assembly. In the first approach, a dithiol linker was used to make multilayers of CdSe/ZnS quantum dots, while in the second biotin- and streptavidin-conjugated CdSe/ZnS quantum dots were used to make multilayer constructs. Both the chemical bonding nature and fluorescence spectroscopic properties of quantum dot films were characterized using X-ray photoelectron spectroscopy (XPS) and fluorescence spectroscopy.     

The VUV electronic spectroscopy of acetone studied by synchrotron radiation

The electronic state spectroscopy of acetone (CH3)2CO has been investigated using high-resolution VUV photoabsorption spectroscopy in the energy range 3.7-10.8 eV. New vibronic structure has been observed, notably in the low energy absorption band assigned to the 1(1)A(1) --> 1(1)A2 (ny --> pi*) transition. The local absorption maximum at 7.85 eV has been tentatively attributed to the 4(1)A1 (pi --> pi*) transition. Six Rydberg series converging to the lowest ionisation energy (9.708 eV) have been assigned as well as a newly-resolved ns Rydberg series converging to the first ionic excited state (12.590 eV). Rydberg orbitals of each series have been classified according to the magnitude of the quantum defect (delta) and are extended to higher quantum numbers than in the previous analyses.     

Interaction between excitons determines the non-linear response of nanocrystals

The non-linear response of semiconductor quantum dots is investigated using three-pulse photon echo peak shift (3PEPS) experiments and simulations. The third-order non-linear response is modeled by a three-level system, utilizing Brownian oscillators to model the line-broadening functions. Our results show that biexciton formation and exciton–exciton scattering significantly influence the non-linear response of quantum dots. The exciton to biexciton excited state absorption pathways are also investigated for quantum dots with different crystal structures. Our calculations suggest that the probability of excited state absorption to the biexcitonic state is higher for zinc-blende structured nanocrystals.     

High-resolution analytical transmission electron microscopy of semiconductor quantum structures

Analytical transmission electron microscopy was applied to characterize the size, shape, real structure, and, in particular, the composition of different semiconductor quantum structures. Its potential applicability is demonstrated for heterostructures of III-V semiconducting materials and II-VI ones, viz. (In,Ga)As quantum wires on InP and (In,Ga)As quantum dots on GaAs both grown by metal organic chemical vapor deposition, and CdSe quantum dots on ZnSe grown by molecular beam epitaxy. The investigations carried out show that the element distribution even of some atomic layers can be detected by energy-dispersive X-ray spectroscopy, however, exhibiting a smeared profile. Contrary to that, sub-nanometre resolution has been achieved by using energy-filtered transmission electron microscopy to image quantum dot structures.     

水溶性的CdSe/CdS/ZnS量子点的合成及表征

用L-半胱氨酸盐(Cys)作为稳定剂,合成了水溶性的双壳结构的CdSe/CdS/ZnS半导体量子点。吸收光谱和荧光光谱结果表明,双壳结构的CdSe/CdS/ZnS纳米微粒比单一的CdSe核纳米粒子和单核壳结构的CdSe/CdS纳米粒子具有更优异的发光特性。用透射电子显微镜(TEM)、ED、XRD、XPS和FTIR等方法对CdSe核和双壳层的CdSe/CdS/ZnS纳米微粒的结构、分散性及形貌分别进行了表征。     

Synthesis and characterization of mondispersed CdSe nanocrystals at lower temperature

Nearly monodispersed CdSe quantum dots have been prepared by a soft solution approach using air-stable reagents at lower temperature. The temporal evolution of the absorption and room temperature photoluminescence spectra were used to follow the reaction process and to characterize the optical properties of as-prepared CdSe quantum dots. The results exhibited clear exciton peaks in absorption and bright band-edge luminescence. The structures of the CdSe nanocrystals were determined by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The influence of the temperature on the properties of the resultant CdSe nanocrystals was investigated. The distribution of properties within ensembles of CdSe nanocrystals was also studied. A drastic difference in the photoluminescence efficiencies of size-selected fractions was observed.     

Photoinduced ultrafast electron transfer from CdSe quantum dots to Re-bipyridyl complexes

Ultrafast dissociation of excitons in CdSe quantum dots via electron transfer to adsorbed Re-bipyridyl complexes was demonstrated. The dissociation pathway was determined by the observation of reduced adsorbate using femtosecond IR spectroscopy. The rate of electron transfer was shown to increase at smaller QD sizes. Electron transfer time as fast as 2.3 ps was observed, faster than the exciton annihilation time in CdSe. The ultrafast charge separation in this quantum dot-adsorbate donor-acceptor complex provides a potential approach for separating multiple excitons in quantum dots.     

表面活性剂对CdSe量子点荧光性能的影响

通过添加不同类型的表面活性剂在水相中制备了CdSe量子点。用透射电子显微镜(TEM)、X射线衍射(XRD)、X-射线光电子能谱(XPS)对其进行了表征,并用紫外-可见(UV-Vis)和荧光(PL)分光光度法研究了不同类型的表面活性剂对CdSe量子点吸收光谱和荧光光谱的影响。结果表明,加入长链的非离子型和阴离子型表面活性剂制备的CdSe量子点颗粒只有几个纳米,分散性好,量子点的荧光强度也有明显的增强,而加入阳离子表面活性剂制备的量子点颗粒团聚明显,其荧光出现淬灭。     

Quantum dot solar cells. harvesting light energy with CdSe nanocrystals molecularly linked to mesoscopic TiO2 films

By using bifunctional surface modifiers (SH-R-COOH), CdSe quantum dots (QDs) have been assembled onto mesoscopic TiO(2) films. Upon visible light excitation, CdSe QDs inject electrons into TiO(2) nanocrystallites. Femtosecond transient absorption as well as emission quenching experiments confirm the injection from the excited state of CdSe QDs into TiO(2) nanoparticles. Electron transfer from the thermally relaxed s-state occurs over a wide range of rate constant values between 7.3 x 10(9) and 1.95 x 10(11) s(-1). The injected charge carriers in a CdSe-modified TiO(2) film can be collected at a conducting electrode to generate a photocurrent. The TiO(2)-CdSe composite, when employed as a photoanode in a photoelectrochemical cell, exhibits a photon-to-charge carrier generation efficiency of 12%. Significant loss of electrons occurs due to scattering as well as charge recombination at TiO(2)/CdSe interfaces and internal TiO(2) grain boundaries.