Investigation of the radiative lifetime in core–shell CdSe/ZnS and CdSe/ZnSe quantum dots

Using the one band effective mass approximation model we computed the optical properties of the spherical shaped CdSe/ZnS and Cdse/ZnSe core–shell quantum dot (CSQD). For each structure we calculated the charge carrier energies and corresponding wave functions. We investigated the dependence of the carrier energies on various parameters of the CSQD, including its size. Then we calculated the radiative recombination lifetime for the two types of CSQDs nanocrystals. We found that as the size of the dot is increased the optical gap of CSQD is reduced, resulting in a reduction in electron energies and an increase in hole energies. We have shown that the radiative recombination lifetime in the CdSe/ZnS and CdSe/ZnSe CSQDs decreased by increasing the shell thickness around the core of the QD. We also showed that the radiative lifetime in the CdSe/ZnS is less than that in the CdSe/ZnSe CSQDs and is sensitive to the size and nature of shell of the semiconductor's material.     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。     

CdSe/CdS/ZnS 量子点体系中的超快载流子动力学

利用飞秒泵浦探测技术对CdSe/CdS/ZnS量子点体系中的超快载流子动力学过程进行了研究. 通过选择不同波长的泵浦光分别激发样品壳层和核层,研究了载流子在壳层和核层中的超快动力学过程. 实验结果表明,载流子在CdS壳层导带中弛豫过程非常迅速(约130 fs),时间明显短于载流子在CdSe核层导带中的弛豫时间(约400 fs). 实验中也发现在CdS壳层和CdSe核层的分界面存在一定量的缺陷态.     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

The electronic and optical properties of a triexciton in CdSe/ZnS core/shell quantum dot nanocrystals

In the study, we aim to investigate the electronic and optical properties of single excitons, biexcions and triexcitons in a CdSe/ZnS core/shell quantum dot nanocrystal. The electronic structure has been determined by solving of the Poisson–Schrödinger equations self-consistently. In calculations, the exchange-correlation effects between identical particles have been taken into account in the frame of the local density approximation. We have demonstrated that the optical properties of triexciton systems are remarkably different from the single and biexciton systems. Absorption peaks or transition energies of the triexciton system are well separated from those of single- and bi-exciton systems. We have observed that the core-radius dependent transition energy variations of triexcitons are higher when compared with single- and bi-excitonic systems. The transition energy shifts of double and triple excitons with respect to the single exciton have been calculated as a function of the core radius and we have shown that the energy shifts are inversely proportional with the radius. We have also investigated the radius-dependent changes in binding energies and lifetimes of the structures and the comparative results have been discussed in a detail manner.     

Superlinear photoluminescence in silicon nanocrystals: The role of excitation wavelength

We study the influence of the wavelength of picosecond excitation pulses on the properties of photoluminescence (PL) in a series of samples of silicon nanocrystals prepared by ion implantation into silica matrix. We observed a gradual change in the behaviour of the PL fast component (spectral shape, decay times, pump-intensity dependence) when tuning the excitation wavelength from 355 to 532 nm. We interpret the results in terms of an interplay between the PL originating from volume states of nanocrystals containing two photoexcited carrier pairs, and the PL due to the silicon oxide states. We discuss also the role of the implant fluence on the PL properties of samples.     

Hole mobility and trapping in PVK films doped with CdSe/CdS and CdSe quantum dots

Experimental study of the hole mobility in polyvinylcarbazole (PVK) films doped with two kinds of nanocrystals, on bare core CdSe and core-shell CdSe/CdS quantum dots, with concentrations ranging from 3 · 10¹⁰ to 3 · 10¹⁵ cm⁻³, is presented. The quantum dots investigated were made using colloidal chemistry. The hole mobility was measured using the time-of-flight technique as a function of the applied electrical field in the range 10⁵–10⁶ V/cm and for temperatures from 20°C to 50°C. The transient curves, being featureless on a linear plot, show on a double logarithmic scale a sharp inflection point indicating a dispersive carrier drift process. The recovered values of the mobility are in the range 3 · 10⁻⁸–10⁻⁶ cm²·V⁻¹·s⁻¹ and their field and temperature dependences can be analyzed formally within the framework of the Gaussian disorder model proposed by B?ssler. The energetic disorder is, within the experimental accuracy, independent of the concentration and type of quantum dots for the CdSe quantum dots at all concentrations and for the CdS/CdSe quantum dots up to 10¹⁴ cm⁻³. The spatial disorder factors are very large (from 5.3 to 8.7) and do not depend in a systematic way upon the type and concentration of quantum dots (QDs). The experiments show that the apparent mobility does not change considerably with concentration, but it was found that the samples with CdSe/CdS quantum dots at concentrations from 10¹⁵ to 3 · 10¹⁵ cm⁻³ show a decreased photocurrent response. The dependence of the time-integrated transients (corresponding to the full charge value) upon the quantum-dot concentration has been determined. Differences in total photogenerated charge for pure and doped polymer films imply that the quantum dots of that type are the hole traps with capture times much more smaller than the transit time and with emission times a few orders longer than the transit time. CdSe quantum dots without a shell do not seem to exhibit the same properties as core shells and do not produce considerable changes in the charge transfer, even at a density of 10¹⁵ cm⁻³.     

Correlation between photon-emission intervals in blinking luminescence of single CdSe/CdS nanocrystals

The statistics of luminescence from single CdSe/CdS core/shell semiconductor nanocrystals under CW laser excitation at room temperature is experimentally investigated by recording sequences of absolute arrival times of the emitted photons. It is shown that the correlation coefficient for consecutive intervals between the photon-arrival times differs from zero. The correlation persists for photon-arrival intervals separated by two or more photon-detection events, until the time between the two intervals becomes, on average, as long as 180 ms, which corresponds to about 10³ detected photons. A simulation of the luminescence process supports the conclusion that this correlation is linked to the blinking character of the quantum-dot luminescence.     

A direct measurement of g-factors in II–VI and III–V core–shell nanocrystals

This study describes a direct measurement of spectroscopic g-factors of photo-generated carriers in InP/ZnS and HgTe/Hg_xCd_1−xTe(S) core–shell nanocrystals. The g-factor of trapped electrons and their spin-lattice versus radiative relaxation ratio (T₁/τ) were measured by the use of continuous-wave and time-resolved optically detected magnetic resonance (ODMR) spectroscopy. The g-factors of excitons and donor–hole pairs were derived by the use of field-induced circular-polarized photoluminescence (CP-PL) spectroscopy. The combined information enabled to determine the g-factors of the individual band-edge electrons and holes. The results suggested an increase of the g-factor of the exciton and conduction electron with a decrease of the nanocrystal size.     

Modification of carrier dynamics in CdSe nanocrystals by excess Cd in deposition bath

Photoexcited carrier dynamics in thin CdSe nanocrystalline films prepared by chemical bath deposition are strongly dependent on the deposition parameters. In this paper, we show how an increase in concentration of CdSO₄ in deposition bath affects the photoexcited carrier dynamics in nanocrystals. We used ultrafast absorption and photoluminescence laser spectroscopy to compare the carrier dynamics in samples prepared with and without increased CdSO₄ concentration. We have found that in the Cd-rich samples the spectral dependences of both photoluminescence and absorption dynamics are considerably less pronounced and the dynamics are slower. The observed effects were explained by the suppression of surface mediated carrier relaxation due to the passivation of individual nanocrystals by cadmium hydroxide and/or by sulphatocomplexes of Cd²⁺.     

Study of higher-energy core states in CdSe/CdS octapod nanocrystals by ultrafast spectroscopy

We present a study of the intermediate energy transitions in octapod CdSe/CdS nanocrystals accomplished by ultrafast pump probe spectroscopy (150 fs resolution) combined with effective mass calculations. The bleaching features revealed in the differential transmission spectrum indicate that intermediate transitions occur from higher-energy hole states confined in the core, to the few electron states mildly localized in the core by the weak geometrical confinement. The detection of bleaching features of the intermediate states at long time implies that electron-hole recombination is inhibited in these structures, meanwhile electrons are available for further transport along the nanostructures. This information indicates that such nanostructures could be promising for photovoltaic applications.     

Luminescent CdSe and CdSe/CdS core-shell nanocrystals synthesized via a combination of solvothermal and two-phase thermal routes

A new solvothermal route has been developed for synthesizing the size-controlled CdSe nanocrystals with relatively narrow size distribution, and the photoluminescence (PL) quantum yields (QYs) of the nanocrystals can reach 5-10%. Then the obtained CdSe nanocrystals served as cores to prepare the core/shell CdSe/CdS nanocrystals via a two-phase thermal approach, which exhibited much higher PL QYs (up to 18-40%) than the CdSe core nanocrystals. The nanocrystal samples were characterized by ultraviolet-visible (UV-vis) absorption spectra, PL spectra, wide-angle X-ray diffraction (WAXD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

Charge storage and electron/light emission properties of silicon nanocrystals

Monodispersed silicon nanocrystals show novel electrical and optical characteristics of silicon quantum dots, such as single-electron tunneling, ballistic electron transport, visible photoluminescence and high-efficiency electron emission.Single-electron memory effects have been studied using a short-channel MOSFET incorporating Si quantum dots as a floating gate. Surface nitridation of Si nanocrystal memory nodes extends the charge-retention time significantly. Single-electron storage in individual Si dots has been evaluated by Kelvin probe force microscopy.Photoluminescence and electron emission are observed for surface-oxidized silicon nanocrystals. Efficiency of the no-phonon-assisted transition increases with decreasing core Si size. Electron emission efficiency as high as 5% has been achieved for the Si-nanocrystal-based cold electron emitter devices. The non-Maxwellian energy distribution of emitted electrons suggests that the mechanism of electron emission is due to ballistic transport through arrays of surface-oxidized Si nanocrystals. Combined with the ballistic electron emission, the quasi-direct light emission properties can be used for developing Si-based lasers.     

CdSe/CdS核壳纳米晶微波水热法一步合成与发光光谱分析

采用微波水热法一步合成了核壳结构的CdSe/CdS纳米晶,讨论了巯基丙酸中S^2-的释放过程对纳米晶生长的影响。XRD和Raman光谱结果表明,140℃合成温度下获得了CdSe/CdS核壳结构的纳米晶。FTIR光谱结果表明,巯基丙酸随时间的分解有助于CdS壳层的形成。PL光谱呈现出CdSe纳米晶的带间发射和缺陷发射,随着核壳结构的形成,CdSe纳米晶的表面缺陷被抑制,相关的荧光发射减弱。     

Photoluminescence quenching of CdTe/CdS core-shell quantum dots in aqueous solution by ZnO nanocrystals

Photoluminescence (PL) properties of 3-mercaptopropionic acid (MPA) coated CdTe/CdS core-shell quantum dots (QDs) in aqueous solution in the presence of ZnO colloidal nanocrystals were studied by steady-state and time-resolved PL spectroscopy. The PL quenching of CdTe/CdS core-shell QDs with addition of purified ZnO nanocrystals resulted in a decrease in PL lifetime and a small red shift of the PL band. It was found that CdTe(1.5 nm)/CdS type II core-shell QDs exhibited higher efficiency of PL quenching than the CdTe(3.0 nm)/CdS type I core-shell QDs, indicating an electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals. The experimental results indicated that the efficient electron transfer process from CdTe/CdS core-shell QDs to ZnO nanocrystals could be controlled by changing the CdTe core size on the basis of the quantum confinement effect.     

Strong enhancement of band-edge photoluminescence in CdS nanocrystals prepared by one-step aqueous synthesis method

CdS nanocrystals were prepared by a simple one-step aqueous synthesis method using thioglycolic acid (TGA) as the capping molecule. The effects of Cd precursor concentration and the TGA/Cd molar ratio on the photoluminescence properties of the CdS nanocrystals were investigated. It was found that both the remained free cadmium monomers and Cd-(SR)_x complexes played an important role in the nanocrystal nucleation growth and surface reconstruction. CdS nanocrystals with desired surface state could be obtained at high Cd precursor concentration and low TGA/Cd molar ratio.     

Size-dependence of the anharmonicities in the vibrational potential of colloidal CdSe nanocrystals

We investigated multi-phonon processes in two types of CdSe nanocrystals, spherical quantum dots and nanorods by temperature-dependent Raman spectroscopy. We find the anharmonic constants relating to the two- and three-phonon decay channels to systematically change with changing nanocrystal size. The contributions from two-phonon processes decrease with decreasing diameter, while the contributions from higher-order processes increase. The anharmonicities in the vibrational potential increase due to the phonon confinement, and we did not find a shape dependence.     

AgInS2–ZnS nanocrystals: Evidence of bistable states using light‐induced electron paramagnetic resonance and photoluminescence

The precursor (AgIn)_x Zn_2(1–x)(S₂CN(C₂H₅)₂)₄ was used to prepared AgInS₂–ZnS nanocrystals with different compositions (x = 0.4 and x = 0.7) and with different time of reaction (10 min and 75 min). The photoluminescence features of the nanocrystals were addressed by combining steady‐state spectroscopy and light‐induced electron paramagnetic resonance. Both techniques showed the contribution of at least two components for the emission, previously assigned to surface and intrinsic states. Light‐induced electron paramagnetic resonance allowed detection of the photocreation both of irreversible paramagnetic species that are likely responsible for the nano‐crystals degradation assigned to surface states and of reversible paramagnetic species assigned to intrinsic states. Moreover, reversible bistable paramagnetic states were observed. This Letter provides a scheme that might be useful in addressing the well‐known problem of aging of the nanocrystals. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface control of CdSe nanocrystals by UV-exposure in air and successive thermal treatment under ultra high vacuum

Colloidal CdSe nanocrystals were synthesized through a solution process. The CdSe nanocrystals coated on Si(1 0 0) wafers were UV-exposed in either an air or argon atmosphere to distinguish the effect of generated ozone from UV-radiation at 365 nm on the removal of surface capping pyridine molecules. The pyridine on the CdSe nanocrystal's surface could be effectively removed by the ozone generated during UV-exposure with an accompanying highly oxidized surface state of the CdSe nanocrystals. For the removal of surface oxides of CdSe nanocrystals, a successive thermal treatment under ultra high vacuum (UHV) was adopted. The optical energy bandgap measured by using UV-vis absorption spectroscopy showed a red shift with treatment with an increase of annealing temperature. The electronic energy structure of UHV-annealed CdSe nanocrystals film was analyzed in situ using X-ray absorption and photoelectron spectroscopy. A great resemblance was found between the values of the optical and electron energy bandgaps of effectively surface-treated CdSe nanocrystals film after UHV-annealing at 400 °C.