Probing single quantum dots by micro-photoluminescence

Using micro-photoluminescence, emissions from single CdSe quantum dots were observed from the cleaved (110) facets of ZnSe/CdSe/ZnSe heterostructures grown on GaAs (001) substrates. The emission intensity of a single quantum dot was linearly proportional to the excitation intensity, demonstrating excitonic features. Emissions from these single quantum dots were found to polarize within the (001) plane, providing information on the shapes of the quantum dots.     

CdSe/ZnSe量子点的制备及电化学发光性能

利用ZnSe半导体纳米材料晶体结构与CdSe相似、带隙更宽的特点,采用水热法合成了核-壳型CdSe/ZnSe量子点.结果表明:温度在70～160℃时,ZnSe壳逐渐包裹在CdSe核上,反应时间在0～4 h时,内壳在核上是均匀包裹的,当核壳摩尔比为1:3时,CdSe/ZnSe QDs的电化学发光性能最强,其电化学发光强度...     

Synthesis and size dependent optical studies in CdSe quantum dots via inverse micelle technique

Cadmium selenide quantum dots (CdSe QDs) were successfully synthesized without using trioctylphosphine (TOP). The XRD pattern showed zinc-blend phase of the CdSe QDs. The absorption and PL spectra exhibit a strong blue shift as the QDs size decreases due to the quantum confinement effect. In addition, the quantum efficiency of CdSe QDs with TOP capping is higher than CdSe QDs with oleic acid capping. TEM image shows a spherical shape, compact and dense structure of CdSe QDs. A good agreement between the Tauc's model and experimentally measured absorption spectra of CdSe QDs is achieved. The FTIR peak at ～1712 cm^?1 spectra confirms the influence of oleic acid as a capping agent.     

The Urbach–Martienssen absorption tails in the optical spectra of semiconducting variable-sized zinc selenide and cadmium selenide quantum dots in thin film form

The sub-bandgap exponential absorption tails of Urbach–Martienssen type in chemically deposited variable-sized ZnSe and CdSe quantum dots in thin film form were studied. The Urbach energy, characterizing the steepness of the exponential absorption tails, was found to decrease upon particle size enlargement due to thermal annealing of the as-deposited ZnSe and CdSe quantum dots in thin film form. Such decrease of the Urbach energy was attributed to the decrease of the degree of structural disorder upon annealing of the semiconducting quantum dot thin films, manifested through lattice strain relaxation, average crystal size and lattice constant increase and dislocation density decrease. This behavior is in line with the predictions of the Cody model, relating the Urbach energy to the degree of structural disorder for a given material. In this way, it is shown that semiconducting quantum dots deposited in thin film form have a certain non-thermal component to the exponential absorption tails of the Urbach–Martienssen type. This non-thermal component is due to the inherent nanocrystalline character of the semiconducting quantum dots, characterized with a rather pronounced structural disorder, manifested through a certain degree of lattice strain and the rather large values for the dislocation densities.     

Hybrid epitaxial-colloidal semiconductor nanostructures

We present a growth technique which combines wet-chemical growth and molecular beam epitaxy (MBE) to create complex semiconductor nanostructures with nanocrystals as active optical material. The obtained results show that wet-chemically prepared semiconductor nanocrystals can be incorporated in an epitaxally grown crystalline cap layer. As an exemplary system we chose CdSe nanorods and CdSe(ZnS) core-shell nanocrystals in ZnSe and discuss the two limits of thin (d approximately 2R) and thick (d>2R) ZnSe cap layers of thickness d for CdSe nanorods and nanodots of radii R between 2 and 4 nm. In contrast to the strain-induced CdSe/ZnSe Stranski-Krastanow growth of a quantum dot layer in a semiconductor heterostructure, the technique proposed here does not rely on strain and thus results in additional degrees of freedom for choosing composition, concentration, shape, and size of the nanocrystals. Transmission electron microscopy and X-ray diffractometry show that the ZnSe cap layer is of high crystalline quality and provides all parameters for a consecutive growth of Bragg structures, waveguides, or diode structures for electrical injection.     

Shake and break--shaking-induced changes of size quantization in aggregated quantum dots

We show how simple mechanical agitation of precipitated CdSe quantum dot aggregates causes partially reversible color changes (clearly visible to the eye) in the absorption spectrum of the CdSe (about 4 nm size). The color changes, which are due to changes in size quantization, are not accompanied by change in quantum dot size. This phenomenon is explained by partial deaggregation of the precipitates, leading to reduced charge overlap between neighboring dots. Shaking was shown to result in a looser aggregate structure. It is suggested that CdSO3 particles (an initial product of the CdSe formation reaction) act as weak bridges between CdSe quantum dots, mediating the interparticle interactions and allowing the deaggregation to occur on shaking.     

In vivo Quantum‐Dot Toxicity Assessment

Quantum dots have potential in biomedical applications, but concerns persist about their safety. Most toxicology data is derived from in vitro studies and may not reflect in vivo responses. Here, an initial systematic animal toxicity study of CdSe–ZnS core–shell quantum dots in healthy Sprague–Dawley rats is presented. Biodistribution, animal survival, animal mass, hematology, clinical biochemistry, and organ histology are characterized at different concentrations (2.5–15.0 nmol) over short‐term (<7 days) and long‐term (>80 days) periods. The results show that the quantum dot formulations do not cause appreciable toxicity even after their breakdown in vivo over time. To generalize the toxicity of quantum dots in vivo, further investigations are still required. Some of these investigations include the evaluation of quantum dot composition (e.g., PbS versus CdS), surface chemistry (e.g., functionalization with amines versus carboxylic acids), size (e.g., 2 versus 6 nm), and shape (e.g., spheres versus rods), as well as the effect of contaminants and their byproducts on biodistribution behavior and toxicity. Combining the results from all of these studies will eventually lead to a conclusion regarding the issue of quantum dot toxicity.     

Redistribution of localised excitons in CdSe/ZnSe quantum dot structures

Population processes and recombination mechanisms of excitons localised in CdSe/ZnSe quantum dot structures are investigated. The photoluminescence (PL) properties are governed by lateral energy transfer within a dense ensemble of quantum dots, which differ in size and Cd concentration, providing for a complex potential landscape with localisation sites of widely varying depth for excitons. At low temperatures, lateral transfer by tunnelling leads to a mobility edge at 2.561 eV. Thermally activated escape and recapture of excitons cause a strong redshift of the PL maximum and the mobility edge.     

Three-dimensional Si/Ge quantum dot crystals

Modern nanotechnology offers routes to create new artificial materials, widening the functionality of devices in physics, chemistry, and biology. Templated self-organization has been recognized as a possible route to achieve exact positioning of quantum dots to create quantum dot arrays, molecules, and crystals. Here we employ extreme ultraviolet interference lithography (EUV-IL) at a wavelength of lambda = 13.5 nm for fast, large-area exposure of templates with perfect periodicity. Si(001) substrates have been patterned with two-dimensional hole arrays using EUV-IL and reactive ion etching. On these substrates, three-dimensionally ordered SiGe quantum dot crystals with the so far smallest quantum dot sizes and periods both in lateral and vertical directions have been grown by molecular beam epitaxy. X-ray diffractometry from a sample volume corresponding to about 3.6 x 10(7) dots and atomic force microscopy (AFM) reveal an up to now unmatched structural perfection of the quantum dot crystal and a narrow quantum dot size distribution. Intense interband photoluminescence has been observed up to room temperature, indicating a low defect density in the three-dimensional (3D) SiGe quantum dot crystals. Using the Ge concentration and dot shapes determined by X-ray and AFM measurements as input parameters for 3D band structure calculations, an excellent quantitative agreement between measured and calculated PL energies is obtained. The calculations show that the band structure of the 3D ordered quantum dot crystal is significantly modified by the artificial periodicity. A calculation of the variation of the eigenenergies based on the statistical variation in the dot dimensions as determined experimentally (+/-10% in linear dimensions) shows that the calculated electronic coupling between neighboring dots is not destroyed due to the quantum dot size variations. Thus, not only from a structural point of view but also with respect to the band structure, the 3D ordered quantum dots can be regarded as artificial crystal.     

Charging and Spin Effects in Triple Dot Artificial Molecules

We have fabricated artificial molecules consisting of three coupled quantum dots defined in the two-dimensional electron gas of a GaAs/AlGaAs heterostructure using lithographically patterned gates and trenches. The three dots are arranged in a ring structure, where each dot is coupled to the other two dots. We find that, when tuned to the Coulomb blockade regime, the triple quantum dot device acts as a charge rectifier: an electron enters the third dot where it is trapped, producing a jamming effect where no other electron may enter the first dot. Triple quantum dots coupled in a ring will allow for the study of new molecular phases using artificial molecules and may also serve as building blocks of two-dimensional arrays for quantum computation.     

Charging and Spin Effects in Triple Dot Artificial Molecules

We have fabricated artificial molecules consisting of three coupled quantum dots defined in the two-dimensional electron gas of a GaAs/AlGaAs heterostructure using lithographically patterned gates and trenches. The three dots are arranged in a ring structure, where each dot is coupled to the other two dots. We find that, when tuned to the Coulomb blockade regime, the triple quantum dot device acts as a charge rectifier: an electron enters the third dot where it is trapped, producing a jamming effect where no other electron may enter the first dot. Triple quantum dots coupled in a ring will allow for the study of new molecular phases using artificial molecules and may also serve as building blocks of two-dimensional arrays for quantum computation.     

Blinking suppression and intensity recurrences in single CdSe-oligo(phenylene vinylene) nanostructures: experiment and kinetic model

We report time-resolved single molecule fluorescence imaging of individual CdSe quantum dots that are functionalized with oligomeric conjugated organic ligands. The fluorescence intensity trajectories from these composite nanostructures display both a strong degree of blinking suppression and intensity fluctuations with characteristic recurrence times on the order of 10-60?s. In addition, fluorescence decay rate measurements of individual hybrid nanostructures indicate significantly modified non-radiative quantum dot decay rates relative to conventional ZnS-capped CdSe quantum dots. We show that a modified diffusive reaction coordinate model with slow fluctuations in quantum dot electron energies (1S(e), 1P(e)) can reproduce the experimentally observed behaviour.     

Temperature Effects on the Self-trapping Energy of a Polaron in a GaAs Parabolic Quantum Dot

The temperature and the size dependences of the self-trapping energy of a polaron in a GaAs parabolic quantum dot are investigated by the second order Rayleigh-Schrodinger perturbation method using the framework of the effective mass approximation. The numerical results show that the self-trapping energies of polaron in GaAs parabolic quantum dots shrink with the enhancement of temperature and the size of the quantum dot. The results also indicate that the temperature effect becomes obvious in small quantum dots     

Spin Dynamics in CdSe/ZnSe Quantum Dots: Resonant Versus Nonresonant Excitation

We have studied the exciton spin dynamics in CdSe/ZnSe quantum dots, comparing strictly resonant and nonresonant excitation. In case of strictly resonant excitation, excitons are generated in the quantum dot ground state, and because of the zero-dimensionality of the system no transient shift of the photoluminescence signal can be seen. No loss of the spin information is observed within the time window under investigation, if one excites the quantum dot eigenstates. Interestingly, even in case of nonresonant excitation, a high, time-independent polarization degree is obtained. We found maxima in the absolute value of the polarization degree if the laser excess energy amounts to a multiple of LO-phonon energies.     

A case study: Te in ZnSe and Mn-doped ZnSe quantum dots

Photoluminescence (PL) behavior of ZnSe(1-y)Te(y) quantum dots is investigated by varying Te concentration as well as size. The striking effect of quantum confinement is the observation of isoelectronic center-related emission at room temperature in lieu of near-band-edge emission that dominates the optical scenario. ZnSe(0.99)Te(0.01) quantum dots were also doped by Mn(2+) ions. The Mn(2+) ion-related d-d transition is drastically suppressed by Te isoelectronic centers. Incorporation of Mn(2+) at substitutional sites in ZnSe(0.99)Te(0.01) quantum dots is also confirmed by the electron paramagnetic resonance measurements. Effect of Te isoelectronic impurity on the emission behavior is more pronounced than that of Mn(2+) ions. A subtle blueshift in the orange d-d transition is a sign of a decrease in crystal field strength. PL and photoluminescence excitation measurements on Zn(1-x)Se(0.99)Te(0.01)Mn(x) quantum dots indicate that the transition probability from the lowest unoccupied molecular orbital to Te levels is substantially larger than that to Mn(2+) d-d levels.     

Bias-induced photoluminescence quenching of single colloidal quantum dots embedded in organic semiconductors

We demonstrate reversible quenching of the photoluminescence from single CdSe/ZnS colloidal quantum dots embedded in thin films of the molecular organic semiconductor N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD) in a layered device structure. Our analysis, based on current and charge carrier density, points toward field ionization as the dominant photoluminescence quenching mechanism. Blinking traces from individual quantum dots reveal that the photoluminescence amplitude decreases continuously as a function of increasing forward bias even at the single quantum dot level. In addition, we show that quantum dot photoluminescence is quenched by aluminum tris(8-hydroxyquinoline) (Alq3) in chloroform solutions as well as in thin solid films of Alq3 whereas TPD has little effect. This highlights the importance of chemical compatibility between semiconductor nanocrystals and surrounding organic semiconductors. Our study helps elucidate elementary interactions between quantum dots and organic semiconductors, knowledge needed for designing efficient quantum dot organic optoelectronic devices.     

Aqueous synthesis and bio-imaging application of highly luminescent and low cytotoxicity Mn-doped ZnSe nanocrystals

In this paper, Mn²⁺-doped ZnSe quantum dots (Mn:ZnSe d-dots) are synthesized successfully by a nucleation-doping method in aqueous solution with 3-Mercaptopropionic acid as the stabilizer and sodium selenite as the Se source for the first time in contrast to the use of oxygen-sensitive NaHSe or H₂Se as Se source. The obtained quantum dots performed strong band-edge luminescence, narrow size distribution and weak trap emission without post-treatments. The results of transmission electron microscopy and X-ray diffraction demonstrated the small particle size (3-4 nm), good monodispersity and ZnSe(S) alloyed structure of as-prepared quantum dots. Finally, the biological application of luminescent Mn²⁺-doped ZnSe nanocrystals to PK 15 cell imaging was also illustrated, which showed excellent biocompatibility and low cytotoxicity, implying their potential as a new generation of fluorescent labels for biological assays, tissues, and even in vivo investigations.     

Self-assembling InAs and InP quantum dots for optoelectronic devices

Stranski–Krastanov growth in molecular beam epitaxy allows the preparation of self assembling InAs and InP quantum dots on GaAs and Ga_0.52In_0.48P buffer layers, respectively. InAs dots in GaAs prepared by slow growth rates and low temperature overgrowth provide intense photoluminescence at the technologically important wavelength of 1.3 μm at room temperature. Strain induced vertical alignment, size modification and material interdiffusion for stacked dot layers are studied. A blue shift of the ground state transition energy is observed for the slowly deposited stacked InAs dots. This is ascribed to enhanced strain driven intermixing in vertically aligned islands. For very small densely stacked InP and InAs dots the reduced confinement shift causes a red shift of the ground state emission. The InP quantum dots show intense and narrow photoluminescence at room temperature in the visible red spectral range. First InP/Ga_0.52In_0.48P quantum dot injection lasers are prepared using threefold stacked InP dots. We observe lasing at room temperature in the wavelength range between 690–705 nm depending on the size of the stacked InP dots.     

On the absence of detectable carrier multiplication in a transient absorption study of InAs/CdSe/ZnSe core/Shell1/Shell2 quantum dots

Tunable femtosecond pump-near IR probe measurements on InAs/CdSe/ZnSe core/shell1/shell2 nanocrystal quantum dots were conducted to quantify spontaneous carrier multiplication previously reported in this system. Experimental conditions were chosen to eliminate the need for determining absolute wavelength dependent cross sections of the nanocrystals and allow direct comparison of band edge absorption bleach kinetics for different excitation energies up to 3.7 times the band gap. Results for two sample sizes show no signs of carrier multiplication within that range. This result is discussed in light of reports describing occurrence of this novel phenomenon in quantum dots based on this as well as numerous other semiconductor materials.     

Multicolor quantum dot encoding for polymeric particle-based optical ion sensors

Multicolor quantum dot-encoded polymeric microspheres are prepared with controllable and uniform doping levels that function as chemical sensors on the basis of bulk optode theory. TOP/TOPO-capped CdSe quantum dots and CdTe quantum dots capped with CdS (lambdaem = 610 and 700 nm, lambdaex = 510 nm) are blended with a THF solution of poly(methyl methacrylate-co-decyl methacrylate), poly(n-butylacrylate), or poly(vinyl chloride) plasticized with bis(2-ethylhexyl) sebacate without a need for ligand exchange. Polymeric microspheres are generated under mild, nonreactive conditions with a particle caster that breaks down a polymer stream containing the quantum dots into fine droplets by the vibration of a piezocrystal. The resulting microspheres exhibit uniform size and fluorescence emission intensities. Fluorescent bar codes are obtained by subsequent doping of two quantum dots with different colors and mass ratios into the microspheres. A linear relationship is found between the readout fluorescence ratio of the two types of nanocrystals and the mixing ratio. Quantum dot-encoded ion sensing optode microspheres are prepared by simultaneous doping of sodium ionophore X, chromoionophore II, a lipophilic tetraphenylborate cation exchanger, and TOPO-capped CdSe/CdS quantum dot as the fluorescent label. A net positive charge of the quantum dots is found to induce an anion-exchange effect on the sensor function, and therefore, an increased concentration of the lipophilic cation exchanger is required to achieve proper ion sensing properties. The modified quantum dot-labeled sodium sensing microspheres show satisfactory sodium response between 10(-4) and 0.1 M at pH 4.8, with excellent selectivity toward common interferences. The amount of the carried positive charges of the CdSe quantum dots is estimated as 2.8 mumol/g of quantum dots used in this study.