Water-based route to colloidal Mn-doped ZnSe and core/shell ZnSe/ZnS quantum dots

Relatively monodisperse and highly luminescent Mn(2+)-doped zinc blende ZnSe nanocrystals were synthesized in aqueous solution at 100 °C using the nucleation-doping strategy. The effects of the experimental conditions and of the ligand on the synthesis of nanocrystals were investigated systematically. It was found that there were significant effects of molar ratio of precursors and heating time on the optical properties of ZnSe:Mn nanocrystals. Using 3-mercaptopropionic acid as capping ligand afforded 3.1 nm wide ZnSe:Mn quantum dots (QDs) with very low surface defect density and which exhibited the Mn(2+)-related orange luminescence. The post-preparative introduction of a ZnS shell at the surface of the Mn(2+)-doped ZnSe QDs improved their photoluminescence properties, resulting in stronger emission. A 2.5-fold increase in photoluminescence quantum yield (from 3.5 to 9%) and of Mn(2+) ion emission lifetime (from 0.62 to 1.39 ms) have been observed after surface passivation. The size and the structure of these QDs were also corroborated by using transmission electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction.     

Effect of the erbium dopant architecture on the femtosecond relaxation dynamics of silicon nanocrystals

Femtosecond pump-probe absorption spectroscopy is used to investigate the role of Er(3+) dopants in the early relaxation pathways of photoexcited Si nanocrystals. The fate of photoexcited electrons in three different Si nanostructures was studied and correlated with the effect of Er-doping and the nature of the dopant architecture. In Si nanocrystals without Er(3+) dopant, a trapping component was identified to be a major electron relaxation mechanism. Addition of Er(3+) ions into the core or surface shell of the nanocrystals was found to open up additional nonradiative relaxation pathways, which is attributed to Er-induced trap states in the Si host. Analysis of the photodynamics of the Si nanocrystal samples reveals an electron trapping mechanism involving trap-to-trap hopping in the doped nanocrystals, whereby the density of deep traps seem to increase with the presence of erbium. To gain additional insights on the relative depths of the trapping sites on the investigated nanostructures, benzoquinone was used as a surface adsorbed electron acceptor to facilitate photoinduced electron transfer across the nanocrystal surface and subsequently assist in back electron transfer. The established reduction potential (-0.45 V versus SCE) of the electron acceptor helped reveal that the erbium-doped nanocrystal samples have deeper trapping sites than the undoped Si. Furthermore, the measurements indicate that internally Er-doped Si have relatively deeper trapping sites than the erbium surface-enriched nanocrystals. The electron-shuttling experiment also reveals that the back electron transfer seems not to recover completely to the ground state in the doped Si nanocrystals, which is explained by a mechanism whereby the electrons are captured by deep trapping sites induced by erbium addition in the Si lattice.     

Magnetic and structural investigation of Mn(2+)-doped ZnSe semiconductor nanoparticles.

X-ray magnetic circular dichroism (XMCD) experiments on diluted magnetic semiconductor nanocrystals were carried out to study the local electronic structure and magnetic properties of Mn(2+) embedded in the lattice of ZnSe nanoparticles. It is shown that Mn(2+) is exclusively present in the bulk of ZnSe nanoparticles. Neither Mn-Mn coupling nor traces of oxidation to higher Mn oxidation states was observed. This result, which is consistent with EPR spectroscopic data, provides clear proof of the location of Mn(2+) in semiconductor nanoparticles. Further, it is shown that the magnetic ions are highly polarised inside the nanocrystals, where they reach about 50 % of the theoretical value of a pure d(5) state under identical conditions.     

Bimodal bond-length distributions in cobalt-doped CdSe, ZnSe, and Cd1-xZnxSe quantum dots

Electronic absorption spectroscopy has been used to study changes in Co2+ ligand-field parameters as a function of alloy composition in Co2+-doped Cd(1-x)Zn(x)Se nanocrystals. A shift in the energy of the 4T1(P) excited-state with alloy composition is observed. Analysis reveals that Co2+-Se2- bond lengths change relatively little as the host is varied continuously from CdSe to ZnSe, generating a large difference between microscopic and average cation-anion bond lengths in Co2+-doped CdSe nanocrystals but not in Co2+-doped ZnSe nanocrystals. The bimodal bond-length distributions observed here are shown to cause a diameter-dependent enthalpic destabilization of doped semiconductor nanocrystals.     

Tuning the potentials of "extra" electrons in colloidal n-type ZnO nanocrystals via Mg2+ substitution

Colloidal reduced ZnO nanocrystals are potent reductants for one-electron or multielectron redox chemistry, with reduction potentials tunable via the quantum confinement effect. Other methods for tuning the redox potentials of these unusual reagents are desired. Here, we describe synthesis and characterization of a series of colloidal Zn(1-x)Mg(x)O and Zn(0.98-x)Mg(x)Mn(0.02)O nanocrystals in which Mg(2+) substitution is used to tune the nanocrystal reduction potential. The effect of Mg(2+) doping on the band-edge potentials of ZnO was investigated using electronic absorption, photoluminescence, and magnetic circular dichroism spectroscopies. Mg(2+) incorporation widens the ZnO gap by raising the conduction-band potential and lowering the valence-band potential at a ratio of 0.68:0.32. Mg(2+) substitution is far more effective than Zn(2+) removal in raising the conduction-band potential and allows better reductants to be prepared from Zn(1-x)Mg(x)O nanocrystals than can be achieved via quantum confinement of ZnO nanocrystals. The increased conduction-band potentials of Zn(1-x)Mg(x)O nanocrystals compared to ZnO nanocrystals are confirmed by demonstration of spontaneous electron transfer from n-type Zn(1-x)Mg(x)O nanocrystals to smaller (more strongly quantum confined) ZnO nanocrystals.     

Mn:ZnSe/ZnS核-壳结构纳米晶的无膦法制备和光学性质

以溶于十八烯的Se作为Se前驱体,在无膦条件下制备得到了具有较高量子产率的Mn:ZnSe纳米晶.为了进一步提高纳米晶的稳定性和发光强度,运用外延生长的方法进行ZnS壳层包覆并得到了具有核-壳结构的Mn:ZnSe/ZnS纳米晶.X射线衍射、透射电子显微镜及吸收和荧光光谱测试结果表明,该方法合成的Mn:ZnSe纳米晶以及核-壳结构Mn:ZnSe/ZnS纳米晶均为闪锌矿结构,具有良好的单分散性,包覆ZnS外壳层后量子产率可达到60%以上.此外,对ZnS壳层厚度和Mn2+的掺杂量对Mn:ZnSe/ZnS纳米晶发光强度的影响及发光机制也进行了初步讨论.     

Synthesis of colloidal Mn2+:ZnO quantum dots and high-TC ferromagnetic nanocrystalline thin films

We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.     

Electrochemical observation of the photoinduced formation of alloyed ZnSe(S) nanocrystals

Electrochemical studies of thiol-capped ZnSe nanocrystals in aqueous solution have demonstrated several distinct oxidation and reduction peaks in the voltammograms, with the peak positions being dependent on the size of the nanocrystals and their photoluminescence quantum efficiency. The evolution of the specific features in the cyclic voltammetric curves of ZnSe NCs as a function of their photochemical treatment is studied. The interpretation of the results based on the approaches previously developed for CdTe NCs is found to be in good correlation with the proposed mechanism of the ZnSe NCs phototreatment, i.e., the formation of a sulfur-enriched surface shell. By this, cyclic voltammetry has been demonstrated to be a powerful method for probing surface states of semiconductor NCs as well as for monitoring the evolution of these states during photochemical processing.     

Synthesis and size control of luminescent ZnSe nanocrystals by a microemulsion-gas contacting technique

A scalable method for controlled synthesis of luminescent compound semiconductor nanocrystals (quantum dots) using microemulsion-gas contacting at room temperature is reported. The technique exploits the dispersed phase of a microemulsion to form numerous identical nanoreactors. ZnSe quantum dots were synthesized by reacting hydrogen selenide gas with diethylzinc dissolved in the heptane nanodroplets of a microemulsion formed by self-assembly of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) amphiphilic block copolymer in formamide. A single nanocrystal is grown in each nanodroplet, thus allowing good control of particle size by manipulation of the initial diethylzinc concentration in the heptane. The ZnSe nanocrystals exhibit size-dependent luminescence and excellent photostability.     

Luminescence in colloidal Mn-doped semiconductor nanocrystals

Recent advances in nanocrystal doping chemistries have substantially broadened the variety of photophysical properties that can be observed in colloidal Mn²⁺-doped semiconductor nanocrystals. A brief overview is provided, focusing on Mn²⁺-doped II–VI semiconductor nanocrystals prepared by direct chemical synthesis and capped with coordinating surface ligands. These Mn²⁺-doped semiconductor nanocrystals are organized into three major groups according to the location of various Mn²⁺-related excited states relative to the energy gap of the host semiconductor nanocrystals. The positioning of these excited states gives rise to three distinct relaxation scenarios following photoexcitation. A brief outlook on future research directions is provided.     

Giant excitonic Zeeman splittings in colloidal Co2+ -doped ZnSe quantum dots

Colloidal Co(2+):ZnSe diluted magnetic semiconductor quantum dots (DMS-QDs) were prepared by the hot injection method and studied spectroscopically. Ligand-field electronic absorption and magnetic circular dichroism (MCD) spectra confirm homogeneous substitutional speciation of Co(2+) in the ZnSe QDs. Absorption spectra collected at various times throughout the syntheses reveal that dopants are absent from the central cores of the QDs but are incorporated at a constant concentration during nanocrystal growth. The undoped cores are associated with dopant exclusion from the ZnSe critical nuclei. Analysis of low-temperature electronic absorption and MCD spectra revealed excitonic Zeeman splitting energies (DeltaE(Zeeman)) of these Co(2+):ZnSe QDs that were substantially smaller than anticipated from bulk Co(2+):ZnSe data. This reduction in DeltaE(Zeeman) is explained quantitatively by the absence of dopants from the QD cores, where dopant-exciton overlap would be greatest. Since dopant exclusion from nucleation appears to be a general phenomenon for DMS-QDs grown by direct chemical methods, we propose that DeltaE(Zeeman) will always be smaller in colloidal DMS-QDs grown by such methods than in the corresponding bulk materials.     

Size- and shape-controlled synthesis of ZnSe nanocrystals using SeO2 as selenium precursor

Here we report a low-cost and "green" phosphine-free route for the size- and shape-controlled synthesis of high-quality zinc blende (cubic) ZnSe nanocrystals. To avoid the use of expensive and toxic solvents such as trioctylphosphine (TOP) or tributylphosphine (TBP), SeO(2) was dispersed in 1-octadecene (ODE) as a chalcogen precursor. It has been found that the temperature and the surface ligand influenced the nucleation, the reaction speed and the formation of different shapes. Absorption spectroscopy, fluorescence spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used for the characterization of the as-synthesized ZnSe nanocrystals. The size-dependent photoluminescence (PL) range of the as-prepared ZnSe nanocrystals was between 390 and 450 nm, with the PL full width at half-maximum (FWHM) well controlled between 14 and 18 nm and PL quantum yields reached up to 40% at room temperature. Moreover, this new selenium precursor can be used to form tetrapod-shaped ZnSe nanocrystals when zinc acetylacetonate was introduced as the zinc precursor with a one-pot method.     

利用离子型Cd源制备ZnSe/CdSe核-壳结构纳米晶

在有机相体系中利用ZnSe前驱体纳米晶制备过程中的富Se环境,以引入Cd2+的方式在相对温和的环境下通过控制Cd2+离子的加入量及调节反应时间,成功制备了ZnSe/CdSe核-壳复合结构纳米晶.利用X射线衍射(XRD)、透射电镜(TEM)、紫外-可见吸收光谱(UV-vis)和荧光光谱(FL)对其结构形貌以及光学性质进行表征和分析的结果表明,CdSe以外延生长的方式包覆在ZnSe纳米晶表面从而形成具有良好结晶性的核-壳复合结构,其荧光发射始终保持良好单色性,同时实现了在500～620nm可见光范围内的连续可调.     

An alternative of CdSe nanocrystal emitters: pure and tunable impurity emissions in ZnSe nanocrystals

The concept, decoupling doping from nucleation and/or growth, allows us to dope nearly all nanocrystals in a given sample which is indicated by complete quenching of the host emission and bright emission from the dopants at characteristic wavelengths tunable in most parts of the visible window using a ZnSe host. In an extreme case, ZnSe coated MnSe nanocrystals (MnSe:ZnSe) emit similarly as commonly known doped nanocrystals. In comparison with CdSe nanocrystals, these alternative emitters not only are intrinsically less toxic but also show some unexpected and expected advantages: stable against thermal and environmental changes, zero reabsorption, and no Forster energy transfer. In addition to their applications to replace CdSe based nanocrystal emitters, the unique structure and properties of the doped nanocrystals are of interest for studying fundamental issues in the field.     

线性升温条件下纳米ZnSe的生成动力学

用非等温TG-DTG技术,在5.0、10.0、15.0和20.0 K•min－1 4个不同线性升温条件下,研究了从配合物ZnSe(C2H8N2)制备纳米ZnSe的过程动力学.结果表明: 该过程为三维扩散机理；机理函数为反Jander方程, f(α)＝ ，G(α)＝ ；表观活化能E=209.61 kJ•mol－1,指前因子A=1015.7 s－1,动力学方程为 ,并用结果解释了实验现象.初次报导了纳米ZnSe在420 ℃左右氧化为粒度低于40 nm的纳米ZnO.     

pH-sensitive Photoluminescence of CdSe/ZnSe/ZnS Quantum Dots in Human Ovarian Cancer Cells

The photoluminescence of mercaptoacetic acid (MAA)-capped CdSe/ZnSe/ZnS semiconductor nanocrystal quantum dots (QDs) in SKOV-3 human ovarian cancer cells is pH-dependent, suggesting applications in which QDs serve as intracellular pH sensors. In both fixed and living cells the fluorescence intensity of intracellular MAA-capped QDs (MAA QDs) increases monotonically with increasing pH. The electrophoretic mobility of MAA QDs also increases with pH, indicating an association between surface charging and fluorescence emission. MAA dissociates from the ZnS outer shell at low pH, resulting in aggregation and loss of solubility, and this may also contribute to the MAA QD fluorescence changes observed in the intracellular environment.     

PbSe/CdSe and PbSe/CdSe/ZnSe hierarchical nanocrystals and their photoluminescence

Multiple CdSe and ZnSe semiconductor shells were grown on PbSe semiconductor spherical cores with monolayer control. For CdSe shell coating, we found that there was little room to further increase the quantum yields of freshly-made high-quality PbSe nanocrystals that already owned very high initial values because of their good surface status; but there was great improvement for the PbSe nanocrystals with low initial quantum yields because of the poor surface status. Nonetheless, the quantum yield for the latter case could not reach the former's value. Additional ZnSe shells on PbSe/CdSe could further increase the quantum yield and protect the nanocrystals from air oxidation. The observed phenomena in the synthesis of the PbSe/CdSe and PbSe/CdSe/ZnSe core/shell structures were explained through the carrier wave function expansion and the surface polarization.     

Electronic absorption spectroscopy of cobalt ions in diluted magnetic semiconductor quantum dots: demonstration of an isocrystalline core/shell synthetic method.

This paper reports the application of ligand-field electronic absorption spectroscopy to probe Co(2+) dopant ions in diluted magnetic semiconductor quantum dots. It is found that standard inverted micelle coprecipitation methods for preparing Co(2+)-doped CdS (Co(2+):CdS) quantum dots yield dopant ions predominantly bound to the nanocrystal surfaces. These Co(2+):CdS nanocrystals are unstable with respect to solvation of surface-bound Co(2+), and time-dependent absorption measurements allow identification of two transient surface-bound intermediates involving solvent-cobalt coordination. Comparison with Co(2+):ZnS quantum dots prepared by the same methods, which show nearly isotropic dopant distribution, indicates that the large mismatch between the ionic radii of Co(2+) (0.74 A) and Cd(2+) (0.97 A) is responsible for exclusion of Co(2+) ions during CdS nanocrystal growth. An isocrystalline core/shell preparative method is developed that allows synthesis of internally doped Co(2+):CdS quantum dots through encapsulation of surface-bound ions beneath additional layers of CdS.     

On doping CdS/ZnS core/shell nanocrystals with Mn

This paper presents a mechanistic study on the doping of CdS/ZnS core/shell semiconductor nanocrystals with Mn based on a three-step synthesis, which includes host-particle synthesis, Mn-dopant growth, and ZnS-shell growth. We used a combination of electron paramagnetic resonance spectroscopy (EPR) and inductively coupled plasma atomic emission spectroscopy (ICP) to monitor Mn-doping level and growth yield during doping synthesis at both the dopant-growth and ZnS-shell-growth steps. First, our kinetic study shows that Mn adsorption onto the nanocrystal surface includes the formation of weakly and strongly bound Mn. The formation of weakly bound Mn is associated with a chemical equilibrium between adsorbed Mn species on the nanocrystal surface and free Mn species in growth solution, while the formation of strongly bound Mn exhibits first-order kinetics with an activation-energy barrier of 211 +/- 13 kJ/mol. Second, our results demonstrate that both weakly and strongly bound Mn can be removed from the surface of nanocrystals during ZnS-shell growth. The replacement of strongly bound Mn requires a higher temperature than that of weakly bound Mn. The yield of the replacement of strongly bound Mn is strongly dependent on the temperature of ZnS-shell growth. Third, our results show that the Mn-growth yield is not dependent on the size and crystal structure of nanocrystals. All together, these results suggest a mechanism in which nanocrystal doping is determined by the chemical kinetics of three activation-controlled processes: dopant adsorption, replacement, and ZnS-shell growth.     

Growth kinetic on the optical properties of the Pb(1-x)Mn(x)Se nanocrystals embedded in a glass matrix: thermal annealing and Mn2+ concentration

Semimagnetic Pb(1-x)Mn(x)Se nanocrystals were synthesized by a fusion method in a glass matrix and characterized by optical absorption (OA), atomic/magnetic force microscopy (AFM/MFM), and photoluminescence techniques. MFM images strongly indicated the formation of Pb(1-x)Mn(x)Se magnetic phases in the glass system. Quantum dot size was manipulated by tuning annealing time. It was shown that Mn(2+) impurity affects nucleation, where Mn(2+)-doped samples present a redshift of the OA peak after a short annealing time and a blueshift after long annealing time compared to undoped PbSe NCs. This behavior was linked to the dependence of band-gap energy and the absorption selection rule on Mn(2+) concentration. Photoluminescence in the Pb(1-x)Mn(x)Se nanocrystals increases as the temperature rises up to a point and then decreases at higher temperatures. Anomalous increases in emission efficiency were analyzed by considering temperature induced carrier-transfer in semimagnetic Pb(1-x)Mn(x)Se quantum dots nanocrystals of different sizes.