Showing papers on "Photoluminescence published in 2003"

Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals

Abstract: The extinction coefficient per mole of nanocrystals at the first exitonic absorption peak, e, for high-quality CdTe, CdSe, and CdS nanocrystals was found to be strongly dependent on the size of the nanocrystals, between a square and a cubic dependence. The measurements were carried out using either nanocrystals purified with monitored purification procedures or nanocrystals prepared through controlled etching methods. The nature of the surface ligands, the refractive index of the solvents, the PL quantum yield of the nanocrystals, the methods used for the synthesis of the nanocrystals, and the temperature for the measurements all did not show detectable influence on the extinction coefficient for a given sized nanocrystal within experimental error.

Type-II Quantum Dots: CdTe/CdSe(Core/Shell) and CdSe/ZnTe(Core/Shell) Heterostructures

Abstract: Type-II band engineered quantum dots (CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures) are described. The optical properties of these type-II quantum dots are studied in parallel with their type-I counterparts. We demonstrate that the spatial distribution of carriers can be controlled within the type-II quantum dots, which makes their properties strongly governed by the band offset of the comprising materials. This allows access to optical transition energies that are not restricted to band gap energies. The type-II quantum dots reported here can emit at lower energies than the band gaps of comprising materials. The type-II emission can be tailored by the shell thickness as well as the core size. The enhanced control over carrier distribution afforded by these type-II materials may prove useful for many applications, such as photovoltaics and photoconduction devices.

Dependence of Optical Transition Energies on Structure for Single-Walled Carbon Nanotubes in Aqueous Suspension: An Empirical Kataura Plot

Abstract: Spectrofluorimetric data for identified single-walled carbon nanotubes in aqueous SDS suspension have been accurately fit to empirical expressions. These are used to obtain the first model-independent prediction of first and second van Hove optical transitions as a function of structure for a wide range of semiconducting nanotubes. To allow for convenient use in support of spectral studies, the results are presented in equation, graphical, and tabular forms. These empirical findings differ significantly from Kataura plots computed using a simple tight-binding model. It is suggested that the empirically based results should be used in preference to conventional model-based predictions in spectroscopic nanotube research.

Optical Cavity Effects in ZnO Nanowire Lasers and Waveguides

Abstract: Wide band gap semiconductor nanostructures with near-cylindrical geometry and large dielectric constants exhibit two-dimensional ultraviolet and visible photonic confinement (i.e., waveguiding). Combined with optical gain and suitable resonant feedback, the waveguiding behavior facilitates highly directional lasing at room temperature in controlled-growth nanowires. We have characterized the nanowire emission in detail with high-resolution optical microscopy. The waveguiding behavior of individual zinc oxide (ZnO) nanowires depends on the wavelength of the emitted light and the directional coupling of the photoluminescence (PL) to the emission dipoles of the nanowire. Polarization studies reveal two distinct regimes of PL characterized by coupling to either guided (bound) or radiation modes of the waveguide, the extent of which depends on wire dimensions. Pumping with high pulse energy engenders the transition from spontaneous to stimulated emission, and analysis of the polarization, line width, and line spacing of the laser radiation facilitates identification of the transverse and longitudinal cavity modes and their gain properties. Interpretation of the lasing spectra as a function of pump fluence, with consideration of ZnO material properties and ultrafast excitation dynamics, demonstrates a transition from exciton (fluence 1 IJ/cm 2 ) and gain saturation behavior (fluence > 3 IJ/cm 2 ) modified by the constraints of the nanoscale cylindrical cavity.

Continuum generation from single gold nanostructures through near-field mediated intraband transitions

Abstract: A broad visible and infrared photoluminescence continuum is detected from surface-plasmon-enhanced transitions in gold nanostructures. We find that the ratio of generated infrared to visible emission is much stronger for gold nanostructures than for smooth gold films. While visible emission is well explained by interband transitions of d-band electrons into the conduction band and subsequent radiative recombination, the strong infrared emission cannot be accounted for by the same mechanism. We propose that the infrared emission is generated by intraband transitions mediated by the strongly confined fields near metal nanostructures (localized surface plasmons). These fields possess wave numbers that are comparable to the wave numbers of electrons in the metal, and the associated field gradients give rise to higher-order multipolar transitions. We compare photoluminescence spectra for single gold spheres, smooth and rough gold films, and sharp gold tips and demonstrate that the infrared signal is only present for surfaces with nanometer-scale roughness.

Optical properties of the ZnO nanotubes synthesized via vapor phase growth

Abstract: A large quantity of nanosized ZnO tubular structures was prepared using a very simple thermal evaporation of mixed Zn–ZnO powders under a wet oxidation condition. The ZnO nanotubes have a hollow core with crystalline wall of 8–20 nm in thickness. Optical properties of ZnO nanotubes were studied at room temperature. Raman peaks arising from the ZnO nanotubes were analyzed, which correspond well to that of the bulk ZnO sample. The photoluminescence measurements of ZnO nanotubes revealed an intensive UV peak at 377 nm corresponding to the free exciton emission, and a broad peak at about 500 nm arising from defect-related emission.

Composition-tunable ZnxCd1-xSe nanocrystals with high luminescence and stability

Abstract: High-quality ZnxCd1-xSe nanocrystals have been successfully prepared at high temperature by incorporating stoichiometric amounts of Zn and Se into pre-prepared CdSe nanocrystals. With increasing Zn content, a composition-tunable emission across most of the visible spectrum has been demonstrated by a systematic blue-shift in emission wavelength. The photoluminescence (PL) properties for the obtained ZnxCd1-xSe nanocrystals (PL efficiency of 70−85%, fwhm = 22−30 nm) are comparable to those for the best reported CdSe-based QDs. In particular, they also have good PL properties in the blue spectral range. Moreover, the alloy nanocrystals can retain their high luminescence (PL efficiency of over 40%) when dispersed in aqueous solutions and maintain a symmetric peak shape and spectral position under rigorous experimental conditions. A rapid alloying process was observed at a temperature higher than “alloying point”. The mechanism of the high luminescence efficiency and stability of ZnxCd1-xSe nanocrystals is exp...

Properties of arsenic-doped p-type ZnO grown by hybrid beam deposition

Abstract: As-doped ZnO (ZnO:As) films have been characterized. ZnO:As films show p-type characteristics determined by Hall-effect and photoluminescence (PL) measurements. The hole concentration can be increased up to the mid-1017-cm−3 range. The thermal binding energy of the As acceptor (EAth-b) is 120±10 meV, as derived from temperature-dependent Hall-effect measurements. The PL spectra reveal two different acceptor levels (EAopt-b), located at 115 and 164 meV, respectively, above the maximum of the ZnO valence band, and also show the binding energy of the exciton to the As-acceptor (EAXb) is about 12 meV. The values of the ratio EAXb/(EAth-b or EAopt-b) are located in the range from 0.07 to 0.11.

Surface-Related Emission in Highly Luminescent CdSe Quantum Dots

Abstract: We report our experimental studies of surface-related emission in highly luminescent CdSe quantum dots (QDs) with controlled quantum yield and photooxidation by time-resolved photoluminescence measurements. This kind of surface-related emission, with a radiative lifetime of tens of nanoseconds, implies the involvement of surface states in the carrier recombination process of such highly luminescent CdSe QDs.

Highly Luminescent Water-Soluble CdTe Quantum Dots

Abstract: Colloidal CdTe quantum dots prepared in TOP/DDA (trioctylphosphine/dodecylamine) are transferred into water by the use of amino−ethanethiol•HCl (AET) or mercaptopropionic acid (MPA). This results in an increase in the photoluminescence quantum efficiency and a longer exciton lifetime. For the first time, water-soluble semiconductor nanocrystals presenting simultaneously high band-edge photoluminescence quantum efficiencies (as high as 60% at room temperature), monoexponential exciton decays, and no observable defect-related emission are obtained.

Excitonic emissions observed in ZnO single crystal nanorods

Abstract: We report on the photoluminescent characteristics of ZnO single crystal nanorods grown by catalyst-free metalorganic vapor phase epitaxy. From photoluminescence (PL) spectra of the nanorods at 10 K, several PL peaks were observed at 3.376, 3.364, 3.360, and 3.359 eV. The PL peak at 3.376 eV is attributed to a free exciton peak while the other peaks are ascribed to neutral donor bound exciton peaks. The observation of the free exciton peak at 10 K indicates that ZnO nanorods prepared by the catalyst-free method are of high optical quality.

Photoluminescence dependence of ZnO films grown on Si(100) by radio-frequency magnetron sputtering on the growth ambient

Abstract: We report the effects of the growth ambient on photoluminescence (PL) emission properties of ZnO films grown on Si (100) by rf magnetron sputtering. Upon increasing the O2/Ar+O2 ratio in the growing ambient, the visible emission in the room-temperature PL spectra was drastically suppressed without sacrificing the band-edge emission intensity in the ultraviolet region. This tendency is estimated to be due to the reduction of the oxygen vacancies and zinc interstitials in the film induced by the improvement of the film stoichiometry with respect to high oxygen content, indicating that the visible emission in ZnO originates from oxygen vacancy or zinc interstitial related defects. The violet emission peaked at about 401 nm (3.09 eV) was observed in the low-temperature PL spectra of the ZnO films grown under oxygen-rich conditions. This emission band was assigned to the electron transition from the bottom of the conduction band to the Zn vacancy level, positioned approximately 3.06 eV below the conduction ban...

Photoluminescence study of ZnO films prepared by thermal oxidation of Zn metallic films in air.

Abstract: Zinc oxide (ZnO) films were synthesized by thermal oxidation of metallic zinc films in air. The influence of annealing temperatures ranging from 320 to 1000 °C on the structural and optical properties of ZnO films is investigated systematically using x-ray diffraction and room temperature photoluminescence (PL). The films show a polycrystalline hexagonal wurtzite structure without preferred orientation. Room temperature PL spectra of the ZnO films display two emission bands, predominant excitonic ultraviolet (UV) emission and weak deep level visible emission. It is observed that the ZnO film annealed at 410 °C exhibits the strongest UV emission intensity and narrowest full width at half maximum (81 meV) among the temperature ranges studied. The excellent UV emission from the film annealed at 410 °C is attributed to the good crystalline quality of the ZnO film and the low rate of formation of intrinsic defects at such low temperature. The visible emission consists of two components in the green and yellow ...

Oligomeric Ligands for Luminescent and Stable Nanocrystal Quantum Dots

Abstract: We report a new family of oligomeric alkyl phosphine ligands for nanocrystal quantum dots. These oligomeric phosphines show effective binding affinity to quantum dot surfaces. They form thin and secure organic shells that stabilize quantum dots in diverse environments including serum and polymer matrices. They maintain the initial as-grown photoluminescence quantum yield of the quantum dots and enable homogeneous incorporation into various matrices. They present a chemically flexible structure that can be used for further chemistry, such as cross-linking, copolymerization, and conjugation to biomolecules.

Characterization and Field‐Emission Properties of Needle‐like Zinc Oxide Nanowires Grown Vertically on Conductive Zinc Oxide Films

Abstract: Needle-like ZnO nanowires with high density are grown uniformly and vertically over an entire Ga-doped conductive ZnO film at 550 °C. The nanowires are grown preferentially in the c-axis direction. The X-ray diffraction (XRD) θ-scan curve shows a full width at half maximum (FWHM) value of 2°. This indicates that the c-axes of the nanorods are along the normal direction of the substrate surface. The investigation using high-resolution transmission electron microscopy (HRTEM) confirmed that each nanowire is a single crystal. A room-temperature photoluminescence (PL) spectrum of the wires consists of a strong and sharp UV emission band at 380 nm and a weak and broad green–yellow band. It reveals a low concentration of oxygen vacancies in the ZnO nanowires and their high optical quality. Field electron emission from the wires was also investigated. The turn-on field for the ZnO nanowires was found to be about 18 V μm–1 at a current density of 0.01 μA cm–2. The emission current density from the ZnO nanowires reached 0.1 mA cm–2 at a bias field of 24 V μm–1.

Quantum-dot optical temperature probes

Abstract: The steady-state photoluminescence (PL) properties of cadmium selenide quantum dots (QDs) with a zinc sulfide overlayer [(CdSe)ZnS] can be strongly dependent on temperature in the range from 100 to 315 K. The PL intensity from 50 to 55 A (CdSe)ZnS QDs in poly(lauryl methacrylate) matrices increases by a factor of ∼5 when the temperature is decreased from 315 to 100 K, and the peak of the emission band is blueshifted by 20 nm over the same range. The change in PL intensity is appreciable, linear, and reversible (−1.3% per °C) for temperatures close to ambient conditions. These properties of (CdSe)ZnS dots are retained in a variety of matrices including polymer and sol–gel films, and they are independent of excitation wavelength above the band gap. The significant temperature dependence of the luminescence combined with its insensitivity to oxygen quenching establishes (CdSe)ZnS dots as optical temperature indicators for temperature-sensitive coatings.

Temperature dependence of the fundamental band gap of InN

Abstract: The fundamental band gap of InN films grown by molecular beam epitaxy have been measured by transmission and photoluminescence spectroscopy as a function of temperature The band edge absorption energy and its temperature dependence depend on the doping level The band gap variation and Varshni parameters of InN are compared with other group III nitrides The energy of the photoluminescence peak is affected by the emission from localized states and cannot be used to determine the band gap energy Based on the results obtained on two samples with distinctly different electron concentrations, the effect of degenerate doping on the optical properties of InN is discussed

Size-tunable infrared (1000–1600 nm) electroluminescence from PbS quantum-dot nanocrystals in a semiconducting polymer

Abstract: Nanocomposites consisting of PbS nanocrystals in a conjugated polymer matrix were fabricated. We report results of photo- and electroluminescence across the range of 1000 to 1600 nm with tunability obtained via the quantum-size effect. The intensity of electroluminescence reached values corresponding to an internal quantum efficiency up to 1.2%. We discuss the impact of using different-length capping ligands on the transfer of excitations from polymer matrix to nanocrystals.

Metalorganic Chemical Vapor Deposition Route to GaN Nanowires with Triangular Cross Sections

Abstract: High-quality gallium nitride nanowires have been synthesized via metal-initiated metalorganic chemical vapor deposition for the first time. Excellent substrate coverage was observed for wires prepared on silicon, c-plane, and a-plane sapphire substrates. The wires were formed via the vapor−liquid−solid mechanism with gold, iron, or nickel as growth initiators and were found to have widths of 15-200 nm. Transmission electron microscopy confirmed that the wires were single-crystalline and were oriented predominantly along the [210] or [110] direction. Wires growing along the [210] orientation were found to have triangular cross-sections. Transport measurements confirmed that the wires were n-type and had electron mobilities of ∼65 cm2/V·s. Photoluminescence measurements showed band edge emission at 3.35 eV (at 5 K), with a marked absence of low-energy emission from impurity defects.

Temperature dependence of the free-exciton transition energy in zinc oxide by photoluminescence excitation spectroscopy

Abstract: Photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies are used to track the temperature dependence of the A exciton energy (EXA) in undoped bulk ZnO crystals grown by the seeded-chemical-vapor-transport method. For T>150 K, the edge emission becomes broad as the A exciton recombination and its longitudinal-optical (LO) phonon replica become superimposed. We use PLE to determine the temperature dependence of EXA by monitoring the broad green emission commonly observed in as-grown ZnO crystals, and thus have established the energy difference between the EXA and PL emission peak energies. The PL emission at 3.26 eV at room temperature is shown to be offset by about 50 meV to lower energy than the actual EXA transition. The temperature dependence of the energy difference between the EXA and PL peaks is compared with predictions based on the lineshape function for the EXA– LO recombination. At 300 K, the PL is predominantly composed of EXA– LO recombination. Further, the temperature depe...

Multiple temperature regimes of radiative decay in CdSe nanocrystal quantum dots: Intrinsic limits to the dark-exciton lifetime

Abstract: We investigate the strongly temperature-dependent radiative lifetime of electron–hole excitations in colloidal CdSe nanocrystal quantum dots over nearly three orders of magnitude in temperature (300 K to 380 mK). These studies reveal an intrinsic, radiative upper limit of ∼1 μs for the storage of excitons below 2 K. At higher temperatures, exciton lifetimes are consistent with thermal activation from the dark-exciton ground state, but with two different activation thresholds.

Photoenhancement of Luminescence in Colloidal CdSe Quantum Dot Solutions

Abstract: Enhancement of the photoluminescence (PL) of colloidal CdSe and (core)shell (CdSe)ZnS quantum dots has been observed when the dots are illuminated above the band-gap energy. The effect occurs in dots suspended in a variety of organic or aqueous environments. During periods of constant illumination, the exciton PL quantum yield was found to reach a value of up to 60 times that of the solution of as-prepared quantum dots and, if illumination continued, subsequently declined slowly because of photooxidation. When returned to the dark, the PL reverted to near its original value. The rate and magnitude of photoenhancement are found to depend on the illumination wavelength, the presence of a ZnS shell, the solvent environment, and the concentration of surfactant molecules. Time-resolved measurements of the fluorescence decay reveal multiexponential kinetics and an average lifetime that lengthens during the illumination period and shortens when quantum dots are returned to darkness. It is postulated that the stabilization of surface trap states, lengthening their average lifetime, could occur by a light-activated rearrangement of surfactant molecules, thus increasing the probability of thermalization back to the lowest emitting exciton state and enhancing the quantum dot PL.

Single-step synthesis to control the photoluminescence quantum yield and size dispersion of CdSe nanocrystals

Abstract: A comprehensive investigation is presented on the factors governing the photoluminescence (PL) quantum yields (QYs) and size dispersion of colloidal CdSe nanocrystals. The temporal evolution of the ensemble PL properties (absorption and luminescence spectra, QYs and lifetimes) during growth at different temperatures (170−310 °C) and different Cd:Se ratios was followed for several hours (2−6 h). The QY values increase during the growth to a maximum and, after a variable time interval (from minutes to hours, depending on the growth temperature), decrease gradually. Low QYs are due to poor passivation, surface disorder, and surface degradation, which arise at different stages of the growth. High QYs can be achieved and maintained only under an ideal combination of growth temperature, solvent composition, and Cd:Se ratio, which leads to an optimum surface. The overgrowth of a fresh surface layer restores high QYs to CdSe nanocrystals with decreased efficiencies because of surface degradation. The insight gain...