CdS量子点的酿酒酵母仿生合成及光谱表征

以酿酒酵母为载体,常温下利用仿生法成功合成了CdS量子点。荧光发射光谱、紫外吸收光谱以及荧光显微镜照片证明,该方法合成的CdS量子点的荧光发射峰位置在443nm,在紫外灯下能发蓝绿色荧光。透射电子显微镜(TEM)表征结果表明,该仿生法合成的CdS量子点为六方纤锌矿结构。以荧光发射和紫外吸收光谱为性能指标,考察了酿酒酵母生长时期、Cd2+的反应浓度以及反应时间等条件对合成CdS量子点的影响。当酿酒酵母处于生长稳定期初期时,与浓度为0.5mmol.L-1的Cd2+共培养24h后所合成的CdS量子点荧光最强。实验中观察到,换液培养可有效提高酿酒酵母合成CdS量子点的产量。     

Pressure-dependent photoluminescence of CdSe/ZnS quantum dots: Critical point of different pressure regimes

High pressure condition can alter and control the electronic structure of semiconductor quantum dots, and therefore provides novel insight for designing optoelectronic devices. Here we report the pressure-dependent photoluminescence (PL) of CdSe/ZnS core/shell quantum dots (QD) in different pressure regimes. The center of the PL spectrum has blue-shift when hydrostatic pressure increases, due to the increasing bulk modulus. However, the shifting rate becomes lower in the higher pressure regime, i.e. above the critical pressure point, mainly due to the interaction between QDs. Accordingly, the lifetimes of PL drop in the low pressure regime, due to the increased pressure-induced trapping states, then increase above the critical pressure point, indicating the interaction between dots likewise. The observed critical pressures for both cases are consistent with each other, and strongly depend on the QD concentration, which forcefully support the aforementioned interaction model.     

核壳结构硒化镉/硫化镉/巯基乙酸量子点载流子输运特性

采用水溶液法合成了巯基乙酸(TGA) 包覆的CdSe 量子点. 通过X 射线粉末衍射和高分辨透射显微镜检测结果证实, 合成得到闪锌矿结构CdSe 量子点. 能谱图和傅里叶变换红外光谱图结果说明, 在核CdSe 纳米粒子表面与配体TGA 之间有CdS 壳层结构形成. 利用样品表面光电压(SPV) 谱, 指认CdSe 量子点精细能带结构以及各自对应的激发态特征: 475 nm (2.61 eV) 和400 nm (3.1 eV) 两个波长处的SPV 响应峰分别与CdSe 核和CdS 壳层带-带隙跃迁相对应; 370 nm (3.35 eV) 附近SPV 响应峰可能与TGA 中羰基与巯基或羧基之间发生的n →π^* 跃迁有关. 场诱导表面光电压谱结果证实, 合成的CdSe 量子点具有明显的N 型表面光伏特性, 而上述n→π^* 跃迁则具有P 型表面光伏特性. 荧光光谱谱线均匀增宽以及SPV 响应峰位蓝移, 说明样品具有明显的量子尺寸效应. 结合不同pH 值下合成的CdSe 量子点的SPV 谱和表面光声谱发现, SPV 响应强度与表面光声光谱信号强度变化趋势恰好相反. 上述样品表面光伏效应表明, CdSe 量子点表面和相界面处的精细电子结构以及光生载流子的输运特性均与量子点的尺寸大小存在某种内在联系. 关键词： 硒化镉量子点 光生载流子 表面光电压谱 表面光声光谱     

Optical transitions in CdSe quantum dots: From discrete levels to broad gain spectra

The optical transition energies have been determined for the lowest electron-hole pair states of CdSe quantum dots embedded in glass. The data obtained by photoluminescence, differential absorption and photoluminescence excitation spectroscopy have been compared and a general size dependence could be established. Based on theoretical calculations, the dominant features in the spectra have been assigned to the different transitions from the ground state to the one-pair states. Within the lowest one pair transition, a fine structure due to exchange interaction has been observed. The change in the optical properties with increasing intensity has been studied and the two-pair states identified in luminescence. Spectrally broad optical gain has been found due to stimulated transitions involving both one- and two-pair states.     

Photostability comparison of CdTe and CdSe/CdS/ZnS quantum dots in living cells under single and two-photon excitations

The photostability is an outstanding feature of quantum dots (QDs) used as fluorescence probes in biological staining and cell imaging. To find out the related factors in the QD photostability, the photobleaching of naked CdTe QDs and BSA coated CdSe/CdS/ZnS QDs in human hepatocellular carcinoma (QGY) cells and human nasopharynx carcinoma (KB) cells were studied under single photon excitation (SPE) and two-photon excitation (TPE). In these two cell lines the cellular QDs were irradiated by a 405 nm continuous wave laser for SPE or an 800 nm femto-second (fs) laser for TPE. The QD photobleaching with the irradiation time was found to fit a biexponential decay. The fast decay plays a dominant role in the bleaching course and thus can be used as the parameter to quantitatively evaluate the QD photostability. The TPE decreased the QD photobleaching as compared to SPE. The BSA coated core/shell QDs had improved the photostability up to 4-5 times than the naked QDs due to the shielding effect of the QD shell. Therefore, it is better to use core/shell structured QDs as the fluorescence probe combining with a TPE manner for those long-term monitoring studies.     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

Optical properties of individual manganese-doped quantum dots

The magnetic state of a single magnetic ion (Mn²⁺) embedded in an individual quantum dot is optically probed using micro-spectroscopy. The fine structure of a confined exciton in the exchange field of a single Mn²⁺ ion (S=) is analyzed in detail. The exciton–Mn²⁺ exchange interaction shifts the energy of the exciton depending on the Mn²⁺ spin component and six emission lines are observed at zero magnetic field. The emission spectra of individual quantum dots containing a single magnetic Mn atom differ strongly from dot to dot. The differences are explained by the influence of the system geometry, specifically the in-plane asymmetry of the quantum dot and the position of the Mn atom. Depending on both these parameters, one has different characteristic emission features which either reveal or hide the spin state of the magnetic atom. The observed behavior in both zero field and under magnetic field can be explained quantitatively by the interplay between the exciton–Mn²⁺ exchange interaction (dependent on the Mn position) and the anisotropic part of the electron–hole exchange interaction (related to the asymmetry of the quantum dot).     

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.     

Size-dependent optical properties and carriers dynamics in CdSe/ZnS quantum dots

Size-dependence of optical properties and energy relaxation in CdSe/ZnS quantum dots （QDs） were investigated by two-colour femtosecond （fs） pump-probe （400/800 nm） and picosecond time-resolved photoluminescence （ps TRPL） experiments. Pump-probe measurement results show that there are two components for the excited carriers relaxation, the fast one with a time constant of several ps arises from the Auger-type recombination, which shows almost particle sizeindependence. The slow relaxation component with a time constant of several decades of ns can be clearly determined with ps TRPL spectroscopy in which the slow relaxation process shows strong particle size-dependence. The decay time constants increase from 21 to 34 ns with the decrease of particle size from 3.2 to 2.1 nm. The room-temperature decay lifetime is due to the thermal mixing of bright and dark excitons, and the size-dependence of slow relaxation process can be explained very well in terms of simple three-level model.     

Temperature-dependent photoluminescence of vertically stacked self-assembled CdSe quantum dots in ZnSe

We studied the optical properties of multiple layers of self-assembled CdSe quantum dots (QDs) embedded in ZnSe, grown by molecular beam epitaxy. The ZnSe barrier thicknesses separating the QD layers ranged from 30 to 60 monolayers (ML). For stacks with thinnest ZnSe barriers photoluminescence (PL) measurements reveal blue shifts as large as 180 meV relative to PL observed for single QD layers. The amount of blue shift decreases with increasing barrier thickness, and for the 60 ML spacer the PL energy returns to that emitted by a single layer of QDs. Temperature dependence of the integrated intensity of the emission spectra reveals that the activation energy for PL quenching is largest for barrier thicknesses of 30 and 45 ML. We tentatively attribute these effects to a decrease in the size of the vertically stacked QDs when the thickness of the barrier layers is small.     

Magneto-bound polaron in CdSe spherical quantum dots: strong coupling approach

The effect of a magnetic field on the ground-state energy of a donor impurity confined in a polar CdSe spherical quantum dot embedded in a nonpolar matrix is studied theoretically. The interaction between the all charge carriers (electron and ion) and the confined longitudinal optical phonons (LO-phonons) is taken into account by considering the strong coupling method (Landau–Pekar approach). A variational calculation is performed in the framework of the effective mass approximation using a trial wave function deduced from the second-order perturbation and assuming that the quantum dot has a finite depth potential.     

Studies on light emitting CdSe quantum dots in commercial polymethylmethacrylate

CdSe quantum dots (QDs) prepared using an aqueous sodium selenosulphite and N,N′-dimethylformamide (DMF) in commercial polymethylmethacrylate (PMMA) showed excellent optical properties. Tuning of the absorption and emission wavelengths by varying the selenium concentration with respect to cadmium is studied. As-prepared CdSe quantum dots showed absorption band at 405 nm (3.06 eV) associated with the formation of ‘early-stage’ CdSe nano-particles along with weak absorption at 480–90 nm due to continuous growth of the particles. The blue-green and yellow-green light emissions were observed from as-prepared solutions. Photoluminescence (PL) measurement showed band-edge emissions at around 430 nm for small clusters but a more stable emission at 544 nm for the 1:1 CdSe sample. X-ray diffraction (XRD) pattern of the CdSe/PMMA powder with Cd/Se ratio of 1:1 showed broad pattern for cubic CdSe. Transmission electron microscopy (TEM) showed cube like de-shaped spherical dots in the region of about 5 nm.     

Differential capacitance between circular stacked quantum dots

We have investigated the differential capacitance between two stacked, circular quantum dots. An expression defining such differential capacitance has been derived on the basis of that for the self-capacitance of a single quantum dot. By means of a self-consistent simulation we have obtained numerical results showing that the differential capacitance between the two dots is strongly influenced by shell-filling effects, and that the classical limit of the parallel-plate capacitor is retrieved when the two dots are in close proximity. Our results represent a contribution to the effort for the definition of a capacitance matrix for a complex system of quantum dots.     

Far-infrared spectroscopy of quantum wires and dots, breaking Kohn’s theorem

We review far-infrared experiments on quantum wires and dots. In particular, we show that with tailored deviations from a parabolic external lateral confinement potential one can break Kohn’s theorem. This allows a detailed investigation of the internal relative motion in quantum dots and wires and the study of electron–electron interaction effects, for example, the formation of compressible and incompressible states in quantum dots and antidots.     

CdSe quantum dots decorated by mercaptosuccinic acid as fluorescence probe for Cu

Water-soluble CdSe quantum dots (QDs) were synthesized using mercaptosuccinic acid (MSA) as a stabilizer. The growth process and characterization of CdSe quantum dots were determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, Ultraviolet-visible (UV-vis) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. Results demonstrated the MSA-capped CdSe QDs were highly crystalline and possessed good optical properties. Further, the resulting products could be used as fluorescent probes to detect Cu²⁺ ions in physiological buffer solution. The response was linearly proportional to the concentration of Cu²⁺ ion in the range 2×10⁻⁸- 3.5×10⁻⁷ mol L⁻¹ with a detection limit of 3.4 nmol L⁻¹.     

Light emitting CdS quantum dots in PMMA: Synthesis and optical studies

Freshly prepared CdS-quantum dots (QDs) in DMF (clear pale solution) when loaded in polymethylmethacrylate (PMMA) lead to excellent optical properties. The tuning of the absorption and emission wavelengths via experimentally control parameters is considered novel and significant. The absorption band for CdS was observed at about 370 nm in polymeric matrix. The blue, green and orange light emissions from such composite solution were tuned and stabilized by simply varying the concentration of CdS, cadmium and sulphur in the final product. Photoluminescence (PL) measurement with 2% CdS loading showed band-edge emissions from the composite with only about 20-25 nm Stokes shift in emission wavelength. Observation of such optical properties indicated that the composite has narrow particle size distribution and particle diameter may well be below 10 nm. X-ray diffraction (XRD) patterns of the film with higher loading of CdS showed broad pattern for hexagonal CdS. Thermo-gravimetric analysis (TGA) of CdS/PMMA composite film revealed that it has better thermal stability than PMMA alone. Transmission electron microscopy (TEM) showed agglomerated tiny dots in nano-meter regime.     

Photoconductivity of composites based on CdSe quantum dots and low-band-gap polymers

Photoconductivity of thin layers prepared by spin coating of blends of CdSe quantum dots (QDs) and a low-band-gap polymer PCDTBT or PTB7 has been studied. It has been found that photocurrent in the composites containing QDs of 10-nm in size is significantly higher than in those of containing 5-nm QDs. Analysis of the results showed that the photoresponse of the thin layers is mainly determined by the relative positions of the frontier energy levels of the materials used, organic semiconductors and QDs. Therefore, the ability to tune the relative positions of these levels by varying the QD size is of special importance, thus allowing the optimization of photodetectors and photovoltaic cells.     

室温下CdSe胶体量子点超快自旋动力学

利用时间分辨法拉第旋转光谱技术研究了室温下CdSe胶体量子点的自旋相干特性.获得了不同磁场下的自旋退相干时间,并分析了自旋退相干的物理机理.零磁场时量子点激子自旋退相干时间为102 ps,主要受电子与核自旋之间的超精细相互作用所影响.当外加横向磁场强度为250 mT时,激子自旋退相干时间为294 ps;增大磁场强度,自旋退相干时间逐渐减小.在较强磁场环境中(≥250mT),量子点激子自旋动力学由非均匀退相干机制所主导.     

Energy-selective charging of type-II GaSb/GaAs quantum dots

The hole confinement in type-II self-organized GaSb/GaAs quantum dots (QDs) was investigated by combining optical excitation and time-resolved capacitance spectroscopy. The experimental results indicate energy-selective charging even for type-II QDs. With increasing excitation energy the apparent hole activation energy decreases, which is attributed to light absorption in sub-ensembles of QDs with decreasing hole localization. The large localization energy of about 450 meV and the possibility of optical-multiplexing makes type-II GaSb/GaAs QDs a potential material system for QD memory concepts.     

Enhancement of spin polarization in asymmetrically coupled CdSe and CdZnMnSe quantum dots in ZnSe matrix

An asymmetrically coupled double quantum dot (QD) system consisting of adjacent CdSe and CdZnMnSe QD layers in a ZnSe matrix was investigated using polarization-selective magneto-photoluminescence (PL). Two well-resolved PL peaks are observed corresponding, respectively, to the CdSe and the CdZnMnSe QDs. The peaks exhibit significant change in the intensity and energy position when a magnetic field is applied. The enhancement of the degree of σ⁻ circular polarization emitted by the non-magnetic CdSe QDs is observed in the double layer system, as compared to that observed in CdSe QDs without the influence of neighboring CdZnMnSe QDs. This behavior was discussed in terms of antiferromagnetic interaction between carrier spins localized in pairs of CdSe and CdZnMnSe QDs that are electronically coupled.