Nucleotide-directed growth of semiconductor nanocrystals

We engineer colloidal quantum dot nanocrystals through the choice of biomolecular ligands responsible for nanoparticle nucleation, growth, stabilization, and passivation. We systematically vary the presence of, and thereby elucidate the role of, phosphate groups and a multiplicity of functionalities on the mononucleotides used as ligands. The results provide the basis for synthesis of nanoparticles using precisely controlled synthetic oligonucleotide sequences.     

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.     

Optical properties of single semiconductor nanocrystals

We present an overview of the current progress in the understanding of the (steady state) optical properties of individual II-VI semiconductor nanocrystals. We begin with a presentation of the conceptual development of the theory required to model the electronic structure of these systems. This is followed by an overview of the current experimental results obtained from the spectroscopy of individual semiconductor nanocrystals, and in particular, we focus on the study of photoluminescence intermittency (blinking) and spectral diffusion. Where possible, we link the experimental observations to the predictions of current theories. We conclude that the surface of small semiconductor crystals plays an important role in determining their optical properties.     

Quantum confinement in silver selenide semiconductor nanocrystals

We prepare Ag(2)Se nanocrystals with average diameters between 2.7 and 10.4 nm that exhibit narrow optical absorption features in the near to mid infrared. We demonstrate that these features are broadly tunable due to quantum confinement. They provide the longest wavelength absorption peaks (6.5 μm) yet reported for colloidal nanocrystals.     

Stable photogenerated carriers in magnetic semiconductor nanocrystals

We report the preparation and investigation of charged colloidal Co2+:ZnO and Mn2+:ZnO nanocrystals. Although both charged and magnetically doped colloidal semiconductor nanocrystals have been reported previously, colloidal charged and magnetically doped semiconductor nanocrystals as described herein have not. Conduction band electrons were introduced into colloidal ZnO diluted magnetic semiconductor (DMS) nanocrystals photochemically, and the resulting TM2+-e-CB interactions were observed by electron paramagnetic resonance spectroscopy (TM2+ = Co2+ or Mn2+). This new motif of colloidal charged magnetic semiconductor nanocrystals reveals attractive new opportunities for studying spin effects in DMS nanostructures relevant to proposed spintronics technologies.     

Surface-functionalization-dependent optical properties of II-VI semiconductor nanocrystals

We report a study of the surface-functionalization-dependent optical properties of II-VI zinc-blende semiconductor nanocrystals on the basis of ligand-exchange chemistry, isomaterial core/shell growth, optical spectroscopy, transmission electron microscopy, and X-ray powder diffraction. Our results show that the transition energy and extinction coefficient of the 2S(h3/2)1S(e) excitonic band of these nanocrystals can be strongly modified by their surface ligands as well as ligand associated surface atomic arrangement. The oleylamine exchange of oleate-capped zinc-blende II-VI nanocrystals narrows the energy gap between their first and second excitonic absorption bands, and this narrowing effect is size-dependent. The oleylamine exchange results in the quenching, subsequent recovery, and even enhancing of the photoluminescence emission of these II-VI semiconductor nanocrystals. In addition, the results from our X-ray powder diffraction measurements and simulations completely rule out the possibility that oleate-capped zinc-blende CdSe nanocrystals can undergo zinc-blende-to-wurtzite crystal transformation upon ligand exchange with oleylamine. Moreover, our theoretical modeling results suggest that the surface-functionalization-dependent optical properties of these semiconductor nanocrystals can be caused by a thin type II isomaterial shell that is created by the negatively charged ligands (e.g., oleate and octadecyl phosphonate). Taking all these results together, we provide the unambiguous identification that II-VI semiconductor nanocrystals exhibit surface-functionalization-dependent excitonic absorption features.     

Architectural control of magnetic semiconductor nanocrystals.

Shape- and dopant-controlled magnetic semiconductor nanocrystals have been achieved by the thermolysis of nonpyrophoric and less reactive single molecular precursors under a monosurfactant system. Reaction parameters governing both the intrinsic crystalline phase and the growth regime (kinetic vs thermodynamic) are found to be important for the synthesis of various shapes of MnS nanocrystals that include cubes, spheres, 1-dimensional (1-D) monowires, and branched wires (bipods, tripods, and tetrapods). Obtained nanowires exhibit enhanced optical and magnetic properties compared to those of 0-D nanospheres. Proper choice of molecular precursors and kinetically driven low-temperature growth afford dopant controlled 1-D Cd1-xMn(x)S nanorods at high levels (up to approximately 12%) of Mn, which is supported by repeated surface exchange experiments and X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) analyses.     

Size-dependent Raman red shifts of semiconductor nanocrystals

The size effects on Raman red shifts in low-dimensional semiconductor nanocrystals are investigated by considering the size-dependent root-mean-square average amplitude associated with the thermal vibration of atoms. The lower limit of vibrational frequency was obtained by matching the calculation results of Raman red shifts with the experimental data of Si, InP, CdSe, CdS0.65Se0.35, ZnO, CeO2, as well as SnO2 nanocrystals. The results indicate the following: (1) the Raman frequency decreases as the nanocrystal size decreases in both narrow and wide bandgap semiconductors; (2) the influence of crystal size on the Raman frequency of nanoparticles is more pronounced than that of nanowires and thin films; and (3) the Raman red shift is ascribed to the size-induced phonon confinement effect and surface relaxation. This model may provide new insights into the fundamental understanding of the underlying mechanism behind the Raman red shifts.     

New strategy for band-gap tuning in semiconductor nanocrystals

In the last decade, the main efforts have focused on the preparation of different sized binary II–VI group semiconductor nanocrystals to obtain different color-emitting luminescence. However, the tuning of physical and chemical properties by changing the particle size could cause problems in many applications, in particular if unstable small particles are used. Recent advances have led to the exploration of tunable optical properties by changing their constituent stoichiometries in ternary alloy nanocrystals. High-quality Zn _x Cd_1?x Se alloy nanocrystals have been successfully prepared at high temperature by incorporating stoichiometric amounts of Zn and Se into pre-prepared CdSe nanocrystals or embryonic CdSe nuclei. With increasing Zn content, a composition-tunable emission across the whole visible spectrum has been demonstrated by a systematic blue-shift in emission wavelength. High-quality alloy Zn _x Cd_1?x S nanocrystals have been obtained by the conucleation and co-growth of the constituents through the reaction of a mixture of CdO- and ZnO-oleic acid complexes with sulfur at elevated temperatures. The obtained Zn _x Cd_1?x S alloy nanocrystals possess superior optical properties with photoluminescence quantum yields of 25–50%, especially the extremely narrow emission spectral width (fwhm=14 nm).     

Growth kinetics of ZnO nanocrystals: a few surprises

Using extensive state-of-the-art experiments over a wide range of synthesis parameters, such as the temperature and concentrations of different reactants, we establish qualitatively different growth kinetics for ZnO nanocrystals compared to all growth kinetics of semiconductor nanocrystals, including ZnO, discussed so far in the literature. The growth rate is shown to be strongly dependent on the concentration of (OH)- in an intriguing nonmonotonic manner as well as on temperature and is almost invariably much slower than well-known and generally accepted growth mechanisms based on a diffusion-controlled Ostwald ripening process or that expected in the surface reaction controlled regime. We show that these qualitatively different results arise from the unexpected role played by a part of the reactants by inhibiting rather than facilitating the reaction; we explain this extraordinary result in terms of an effective passivating layer around the growing nanocrystals formed by a virtual capping shell of Na+ ions.     

Colloidal CdSe nanocrystals synthesized in noncoordinating solvents with the addition of a secondary ligand: exceptional growth kinetics

The addition of a secondary ligand, trioctylphosphine oxide, in the synthesis of cadmium selenide nanocrystals performed in a system with oleic acid as the primary ligand and octadecene as the noncoordinating solvent gives rise to the improvement of nanocrystal size distribution. This phenomenon, which is more significant in the nucleation process than in the growth process, demonstrates that the existence of trioctylphosphine oxide allows for superior nucleation control and permits the facile and reproducible production of extremely small CdSe nanocrystals with narrow size distribution. A systematic study of the nanocrystal formation processes shows that the well-established colloidal nanocrystal growth mechanism, in which nucleation is followed by focusing of size distribution and ended with defocusing of size distribution, cannot be applied to our reactions. Instead, we observed an exceptional type of growth mechanism in which, after nucleation, clear defocusing instead of focusing follows; then slight focusing occurs.     

Functionalized semiconductor nanocrystals for ultrasensitive detection of peptides

Semiconductor CdS nanoparticle have been prepared and modified with thiovanic acid. The functionalized nanoparticles are water-soluble. They were used as the fluorescence probes in the ultrasensitive detection of peptides. This method is based on the fluorescence enhancement of functionalized nano-CdS in the presence of peptide with mercapto groups (GN-9) and the fluorescence quenching of functionalized nano-CdS in the presence of peptide (GA-8 and MT-25). Excitation and emission wavelengths were 360 and 530 nm, respectively. Under optimum conditions, the calibration graphs are linear over the range of 0.15-3.5, 0.2-4.0, and 0.2-3.8 μg ml⁻¹ for GN-9, GA-8 and MT-25, respectively. The corresponding detection limits were 0.010 μg ml⁻¹ for GN-9, 0.018 μg ml⁻¹ for GA-8 and 0.022 μg ml⁻¹ for MT-25, respectively. This method has been proved to be a simple, rapid and sensitive method.     

Localized surface plasmon resonances of anisotropic semiconductor nanocrystals

We demonstrate that anisotropic semiconductor nanocrystals display localized surface plasmon resonances that are dependent on the nanocrystal shape and cover a broad spectral region in the near-IR wavelengths. In-plane and out-of-plane dipolar resonances were observed for colloidal dispersions of Cu(2-x)S nanodisks, and the wavelengths of these resonances are in good agreement with calculations carried out in the electrostatic limit. The wavelength, line shape, and relative intensities of these plasmon bands can be tuned during the synthetic process by controlling the geometric aspect ratio of the disk or using a postsynthetic thermal-processing step to increase the free carrier densities.     

The detailed balance principle in matrix kinetics

The method to derive the rate matrix K of a chemical reaction in a direct and straightforward way is here completed with the introduction of a new rule due to the application of the detailed balance principle. This principle let us discover a further characteristic of the rate matrices for cyclic reactions, a characteristic that can be used both to check the validity of the rate matrix and to improve the mechanical method used to derive the structure of these matrices in a straightforward way.     

General synthesis of I-III-VI2 ternary semiconductor nanocrystals

Metastable orthorhombic phase of AgInS2 nanocrystals with various shapes, including particles, rods, and worms, have been obtained to demonstrate a facile and effective one-pot chemical route for the synthesis of high quality I-III-VI2 ternary semiconductor nanocrystals (AgInS2, CuInS2, AgInSe2) with controllable shape and size.     

Wurtzite Cu2ZnSnS4 nanocrystals: a novel quaternary semiconductor

A new wurtzite phase Cu(2)ZnSnS(4) was discovered and the corresponding nanocrystals have been successfully synthesized. They have been characterized in detail and showed the photoelectric response, which demonstrated their potential in the application of photovoltaic devices.     

Fast scintillation processes in CsCl crystals comprising semiconductor nanocrystals

We analyzed the scintillation mechanism in CsCl single crystals comprising CsPbCl₃-like semiconductor nanocrystals. A decay component with a subnanosecond lifetime was observed and ascribed to the exciton luminescence in the nanocrystals. This is the first observation of scintillation from semiconductor nanocrystals. In addition, slower components were observed and ascribed to the intraionic transition at isolated Pb²⁺ ions and the Auger-free luminescence in the CsCl matrix. Furthermore, it was shown that the nanocrystals absorbed and re-emitted the scintillation photons from the isolated Pb²⁺ ions. The results in this report clearly indicates that the semiconductor nanocrystals function as ultrafast “luminescent centers,” and complicated scintillation dynamics are observed due to the luminescence from different components in the crystal and the radiative energy transfer between them.     

Determination of defect states in semiconductor nanocrystals by cyclic voltammetry

Colloidal, monodisperse CdSe nanocrystals were homogeneously dispersed in an ionic liquid and investigated by means of cyclic voltammetry. Almost all known defect states in semiconductor nanocrystal were quantitatively measured with this nonoptical method (including nonradiative defect states). Variation of the illumination and temperature resulted in excitation of defect-trapped electrons into the conducting band. Thus, we succeeded for the first time to correlate defect states in nanocrystals with those in the corresponding bulk crystals.     

Controllable growth of semiconductor heterostructures mediated by bifunctional Ag2S nanocrystals as catalyst or source-host

We demonstrate that Ag(2)S nanocrystals are the bifunctional mediator for controllable growth of semiconductor heterostructures including more complicated multisegments heterostructures in solution-phase, which is a new type of nanomediator and quite different from the metal nanoparticle catalyst. The intrinsic high Ag(+) ion mobility makes Ag(2)S nanocrystals not only exhibit excellent catalytic function for growth of metal sulfide heterostructures but also act as a source-host for growth of ternary semiconductor heterostructures, for example, Ag(2)S-AgInS(2). The semiconductors grow epitaxially from or inward in Ag(2)S nanocrystals forming single-crystalline heterostructures. Moreover, the method developed here also can construct multisegments heterostructures, for example, Ag(2)S-CdS-ZnS, AgInS(2)-Ag(2)S-AgInS(2). The interfacial structure is still stable even if the lattice mismatch is quite large, which is a unique feature of this method.