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.     

Non-radiative exciton recombination through excitation energy transfer in quantum dot clusters

Excitation energy transfer (EET) processes in CdSe/CdZnS quantum dot (QD) clusters have been investigated in this study by measuring their time-resolved and spectrally resolved fluorescence intensities. The contributions of radiative and non-radiative exciton recombination through EET are evaluated, where the latter is expected to occur in a large class of QD ensembles because of the presence of nonluminescent QDs. It appears that the fluorescence decay in larger QDs serving as acceptor does not show an initial rise, in addition the lifetime of the acceptor QD is independent of the excitation wavelength, suggesting that an EET is followed mostly by non-radiative recombination.     

CdSSe quantum dots: effect of the hydrogen RF plasma treatment on exciton luminescence

This work deals with effective passivation of CdS_XSe_1−X quantum dot surface after treating it by low-temperature hydrogen RF plasma. An enhancement of the exciton luminescence was observed, which can be interpreted as consequence of a decreasing number of surface non-radiative traps.     

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.     

Encapsulation of highly confined CdSe quantum dots for defect free luminescence and improved stability

This is the first report on the generation of trap states and their effective elimination in highly confined CdSe quantum dots in order to obtain enhanced and stable optical properties prepared by aqueous route. Surface plays an important role in optical properties of quantum dots (QDs) and surface modification of quantum dots can improve optical properties. In present work luminescent CdSe QDs were prepared using 2-Mercaptoethanol (2-ME) as stabilizing agent and encapsulated by polymer. Different concentrations of 2-ME were used to tune the emission spectra with respect to their reduced size. Addition of 2-ME to CdSe QDs enhances the trap emission and quenching band edge emission due to (i) increased surface to volume ratio and; (ii) presence of high concentration of sulfide ions as confirmed from EDX analysis as sulfide ions possesses the hole scavenging characteristics. Polymer encapsulation of QDs was carried out to make them stable and to improve their optical properties. Even though there are previous reports addressing the improved optical properties by polymer encapsulation and silica encapsulation but experimentally it has not been reported yet experimentally. In this work we have synthesized and characterized water soluble polymer encapsulated QDs and proved the facts experimentally. Photoluminescence spectroscopy clearly reveals the role of polymer encapsulation in boosting the optical properties of CdSe QDs. FTIR spectra validate the presence of biocompatible functional groups on CdSe4/PEG (Polymer encapsulated QDs).     

Measuring the energy level repulsion in quantum dots

Energy level repulsion is one of the remnants of classical chaos in quantum mechanics. Measurements of the distribution of nearest neighbor spacings in quantum dots reveal, in contrast to other classically chaotic systems, deviations from the predictions made by random matrix theory. Here, we survey possible contributions to these deviations from experimental peculiarities present in measurements on quantum dots, and discuss the methods to eliminate or reduce such distortions.     

Synthesis and photoluminescence of water-soluble Mn-doped ZnS quantum dots

The water-soluble Mn²⁺-doped ZnS quantum dots (Mn:ZnS d-dots) were synthesized by using thioglycolic acid (TGA) as stabilizer in aqueous solutions in air, and characterized by X-ray powder diffraction (XRD), UV-vis absorption spectra and photoluminescence (PL) emission spectroscopy. The sizes of Mn:ZnS d-dots were determined to be about 2 nm using XRD measurements and the UV-vis absorption spectra. It was found that the Mn²⁺⁴T₁ → ⁶A₁ emission intensity of Mn:ZnS d-dots significantly increased with the increase of Mn²⁺ concentration, and showed a maximum when Mn²⁺ doping content was 1.5%. If Mn²⁺ concentration continued to increase, namely more than 1.5%, the Mn²⁺⁴T₁ → ⁶A₁ emission intensity would decrease. In addition, the effects of TGA/(Zn + Mn) molar ratio on PL were investigated. It was found that the peak intensity ratio of Mn²⁺⁴T₁ → ⁶A₁ emission to defect-states emission showed a maximum when the TGA/(Zn + Mn) molar ratio was equal to 1.8.     

Recombination processes in structures with GaN/ALN quantum dots

Mechanisms of the generation and the radiative and nonradiative recombination of carriers in structures with GaN quantum dots in the AlN matrix are studied experimentally and theoretically. Absorption, stationary and nonstationary photoluminescence of quantum dots at different temperatures are investigated. It is found that the photoluminescence intensity considerably decreases with the temperature while the photoluminescence kinetics weakly depends on the temperature. The photoluminescence kinetics is shown to be determined by radiative recombination inside quantum dots. A mechanism of nonradiative recombination is proposed, according to which the main reason for the thermal quenching of photoluminescence is nonradiative recombination of charge carriers, generated by optical transitions between quantum dots and wetting layer states.     

Interactions between CdSe/CdS quantum dots and DNA through spectroscopic and electrochemical methods

The interaction of CdSe/CdS quantum dots (QDs) with Herring sperm-DNA (hs-DNA) has been studied by UV-vis spectroscopy and electrochemical method. Cu(phen)₂^2+/1+ (phen = 1, 10-phenanthroline) was used as an indicator for electroactive dsDNA or ssDNA. The apparent association constant has been deduced (4.94 × 10³ M⁻¹ and 2.39 × 10² M⁻¹) from the absorption spectral changes of the dsDNA-QDs and ssDNA-QDs. The results of dissociation method suggest that Cu(phen)₂^2+/1+ is more easily dissociated from dsDNA or ssDNA modified gold electrode (dsDNA/Au or dsDNA/Au) in presence of QDs. The dissociation rate constant (k) of Cu(phen)₂^2+/1+ on dsDNA/Au is 4.48 times higher than that in absence of QDs, while k is 2.34 times higher than that in absence of QDs on ssDNA/Au in Tris buffer with low ionic strength (pH 7.0, 0.5 mM NaCl). The results illuminate that hs-DNA has high affinity for QDs due to electrostatic force, hydrogen bonds, and van der Waals interactions, and the binding force of QDs with dsDNA is stronger than ssDNA.     

A new strategy to assemble CdSe/ZnS quantum dots with multi-walled carbon nanotubes for potential application in imaging and photosensitization

With objective to enhance luminescence intensities of carbon nanotubes (CNTs), we hereby report the attachment of CdSe/ZnS quantum dots (QDs) on to the surface of shortened Multi Walled Carbon Nanotubes (sMWCNTs). The resultant QDs-sMWCNTs nanohybrid complex have been characterized by Fourier transform infrared (FT-IR) spectroscopy, optical microscopy (OM), ultraviolet (UV) light, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) diffraction spectroscopy and thermogravimetric analysis (TGA). Based on IR peaks characteristics of organic functional groups, optical brightness of sMWCNTs under polarized and UV light, the roughness of the sMWCNTs surface as observed in SEM images and black spots observed on the surface of sMWCNTs in TEM images, it is reasonable to conclude that CdSe/ZnS quantum dots (QDs) were attached on to the surface of sMWCNTs. Additionally, signals of Zn, S, Cd and Se along with carbon on the surface of sMWCNTs in EDX data and onset of thermal degradation of QDs-sMWCNTs nanohybrid complex at much lower temperature than that of sMWCNTs under TGA analysis further confirms the formation of QDs-sMWCNTs nanohybrid complex.     

Carrier dynamics in strain-induced InGaAsP/InP quantum dots

Carrier dynamics of strain-induced InGaAsP/InP quantum dots (QDs) is investigated. In this structure, self-assembled InAs islands on the surface act as stressors and create a lateral confinement potential in the near surface InGaAsP/InP quantum well. Photoluminescence (PL) measurements reveal that decreasing the distance from the QD to the surface significantly diminishes the QD–PL intensity, presumably due to surface states of the InAs islands. Moreover, time-resolved measurements show a faster decay of the QD–PL with decreasing distance. To analyze the carrier dynamics, rate equation model is applied and surface state-related transitions are taken into account. The model is found to agree with measurements, and thus provides a possible explanation for the observed temporal behavior of the carriers.     

Optical characterization of individual quantum dots

Optical characterization of single quantum dots (QDs) by means of micro-photoluminescence (μPL) will be reviewed. Both QDs formed in the Stranski–Krastanov mode as well as dots in the apex of pyramidal structures will be presented. For InGaAs/GaAs dots, several excitonic features with different charge states will be demonstrated. By varying the magnitude of an external electric or magnetic field and/or the temperature, it has been demonstrated that the transportation of carriers is affected and accordingly the charge state of a single QD can be tuned. In addition, we have shown that the charge state of the QD can be controlled also by pure optical means, i.e. by altering the photo excitation conditions. Based on the experience of the developed InAs/GaAs QD system, similar methods have been applied on the InGaN/GaN QD system.     

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.     

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.     

Quantum confined Stark effect in single self-assembled GaN/AlN quantum dots

We have experimentally and theoretically investigated quantum confined Stark effect in hexagonal self-assembled GaN/AlN quantum dots. We have observed a blueshift of up to 100 meV for vertical electric field applied against the built-in electric field while we have observed a redshift for the electric field along the built-in field. The experimental result is compared with a charge self-consistent effective mass calculation, taking into account strain, piezoelectric charge, and pyroelectric charge. The tunability of the emission energy and the exciton binding energy is discussed.     

Investigation of populated InAs/GaAs quantum dots by photoluminescence and photoreflectance

We studied self-assembled InAs/GaAs quantum dots by contrasting photoluminescence and photoreflectance spectra from 10 K to room temperature. The photoluminescence spectral profiles comprise contributions from four equally separated energy levels of InAs quantum dots. The emission profiles involving ground state and excited states have different temperature evolution. Abnormal spectral narrowing occurred above 200 K. In the photoreflectance spectra, major features corresponding to the InAs wetting layer and GaAs layers were observed. Temperature dependences of spectral intensities of these spectral features indicate that they originate from different photon-induced modulation mechanisms. Considering interband transitions of quantum dots were observed in photoluminescence spectra and those of wetting layer were observed in photoreflectance profiles, we propose that quantum dot states of the system are occupied up to the fourth energy level which is below the wetting layer quantum state.     

Luminescence study of Si/Ge quantum dots

We present a photoluminescence (PL) study of Ge quantum dots embedded in Si. Two different types of recombination processes related to the Ge quantum dots are observed in temperature-dependent PL measurements. The Ge dot-related luminescence peak near 0.80 eV is ascribed to the spatially indirect recombination in the type-II band lineup, while a high-energy peak near 0.85 eV has its origin in the spatially direct recombination. A transition from the spatially indirect to the spatially direct recombination is observed as the temperature is increased. The PL dependence of the excitation power shows an upshift of the Ge quantum dot emission energy with increasing excitation power density. The blueshift is ascribed to band bending at the type-II Si/Ge interface at high carrier densities. Comparison is made with results derived from measurements on uncapped samples. For these uncapped samples, no energy shifts due to excitation power or temperatures are observed in contrast to the capped samples.     

Electroluminescence of colloidal ZnSe quantum dots

The article reports a green chemical synthesis of colloidal ZnSe quantum dots at a moderate temperature. The prepared colloid sample is characterised by UV-vis absorption spectroscopy and transmission electron microscopy. UV-vis spectroscopy reveals as-expected blue-shift with strong absorption edge at 400 nm and micrographs show a non-uniform size distribution of ZnSe quantum dots in the range 1-4 nm. Further, photoluminescence and electroluminescence spectroscopies are carried out to study optical emission. Each of the spectroscopies reveals two emission peaks, indicating band-to-band transition and defect related transition. From the luminescence studies, it can be inferred that the recombination of electrons and holes resulting from interband transition causes violet emission and the recombination of a photon generated hole with a charged state of Zn-vacancy gives blue emission. Meanwhile electroluminescence study suggests the application of ZnSe quantum dots as an efficient light emitting device with the advantage of colour tuning (violet-blue-violet).