Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.     

Photoluminescence and time-resolved photoluminescence of star-shaped ZnO nanostructures

Optical properties of star-shaped ZnO nanostructures were studied. The temperature-dependent photoluminescence (PL) was examined up to fourth-order longitudinal optical (LO) phonon assisted emissions of free excitons and confirmed that the nature of the room temperature PL in ZnO is 1-LO phonon assisted emission of free excitons. Low threshold ultraviolet stimulated emissions (SE) were obtained for our powder samples at room temperature. Picosecond time-resolved PL measurements detected a bi-exponential decay behavior which is strongly dependent on the excitation intensity: the slow decay term decreased faster than the fast decay term as the excitation intensity increased and the emission decays were dominated by the fast one. We also found that the emission decays decreased super-linearly before the appearance of the SE. This behavior may be used to deduce the threshold of SE or lasing.     

Luminescence enhancement of ZnO nanoparticles on metal surface

We have studied luminescence enhancement of zinc oxide (ZnO) nanoparticles with the average size of 30 nm on several metal surfaces at low temperatures. Bandedge luminescence originated from bound exciton (BE) annihilation is observed at 3.360 eV, and strongly depends on the kind and surface roughness of metal. The luminescence intensity is about 10 times larger for Ag surface than that for quartz surface. Furthermore, the luminescence increases remarkably when the roughness of Ag surface is almost the same as the particle size. The intensity ratio of the fast decay component to the slow one decreases for Ag surface compared with quartz. These results suggest that the luminescence enhancement is partially attributed to suppressing of the nonradiative recombination process in ZnO nanoparticles on metal surface.     

Enhanced photoluminescence from three-dimensional ZnO photonic crystals

We have fabricated optically active ZnO inverse opals by infiltrating polystyrene (PS) opal templates using an electrodeposition process. Compared with bare ZnO films also prepared by electrodeposition, the three-dimensional (3D) ordered ZnO structure exhibits markedly enhanced photoluminescence. The effect of photonic band gap on PL spectra is also clearly observed from the ZnO inverse opal structure.     

Continuous-Wave Operation of GaN Based Multi-Quantum-Well Laser Diode at Room Temperature

Room-temperature operation of cw GaN based multi-quantum-well laser diodes （LDs） is demonstrated. The LD structure is grown on a sapphire （0001） substrate by metalorganic chemical vapour deposition. A 2.5μm × 800μm ridge waveguide structure is fabricated. The electrical and optical characteristics of the laser diode under direct current injection at room temperature are investigated. The threshold current and voltage of the LD under cw operation are 110mA and 10.5V, respectively. Thermal induced series resistance decrease and emission wavelength red-shift are observed as the injection current is increased. The full width at half maximum for the parallel and perpendicular far field pattern （FFP） are 12° and 32°, respectively.     

Exchange interaction and acoustical phonon modes in CdTe nanocrystals

Photoluminescence of CdTe nanocrystals (NC) is excited resonantly in the lowest energy absorption peak. The spectrum shows a luminescence line shifted to a lower energy and acoustical and optical phonon replica. The Stokes shift between the luminescence and excitation lines is attributed to the electron-hole exchange energy in the nanocrystal. By tuning the laser line inside the absorption peak, we are able to measure the Stokes shift as a function of the excitation energy. Calculation of the absorption gap and the Stokes shift is done in a tight-binding theory. It allows us to determine the radius R of NC excited at a given wavelength and to compare the experimental and theoretical values of the exchange energy as a function of R. A very good agreement is obtained. The observed size dependence of the acoustical phonon mode energy provides a further confirmation of our analysis.     

Photoluminescence properties of Co-doped ZnO nanocrystals

We performed photoluminescence experiments on colloidal, Co²⁺-doped ZnO nanocrystals in order to study the electronic properties of Co²⁺ in a ZnO host. Room temperature measurements showed, next to the ZnO exciton and trap emission, an additional emission related to the Co²⁺ dopant. The spectral position and width of this emission does not depend on particle size or Co²⁺ concentration. At 8 K, a series of ZnO bulk phonon replicas appear on the Co²⁺-emission band. We conclude that Co²⁺ ions are strongly localized in the ZnO host, making the formation of a Co²⁺d-band unlikely. Magnetic measurements revealed a paramagnetic behaviour.     

Quantum confinement in layer-by-layer deposited colloidal HgTe nanocrystals determined by spectroscopic ellipsometry

We report spectroscopic ellipsometry studies in the energy range of 0.5-5 eV on samples of 1-10 bilayers of polymer and HgTe nanocrystals, which exhibit strong transitions at higher critical points in the dispersion relation. We show that the dispersion relation for nanocrystals can be modelled with the same concepts for critical points as used in semiconductor bulk optics. We find an energy shift of up to 0.4 eV of the critical points to higher energies compared to the HgTe bulk properties, caused by quantum confinement in the nanocrystals, which increases with decreasing nanocrystal size.     

Surface effects on photoluminescence of single ZnO nanowires

The influence of surface effects on the temperature dependent photoluminescence (PL) spectra from individual ZnO nanowires has been studied. It is found that the surface effects of the nanowire are very important in both ultraviolet (UV) and visible emission. We propose a new luminescence mechanism based on the recombination related to oxygen vacancies to explain the temperature dependent visible emission, which is significantly influenced by the carrier depletion and band bending caused by surface effects. In addition, the observed attenuation of UV emission with increasing temperature is ascribed to the decreasing depletion region and the increasing surface states related nonradiative recombination.     

Decay dynamics of ultraviolet photoluminescence in ZnO nanocrystals

Time resolved photoluminescence (PL) measurements at low temperature are performed on colloidal ZnO nanocrystals dispersed in t-butanol. Considering the particle size dependence of the decay times we conclude that the luminescence is composed of two trap related emissions one of which undergoes lifetime shortening due to a non-radiative process. Initial fast shift of the spectrum within 30 ps is observed and it is interpreted as a fast hole cooling just after the excitation.     

Gain mechanisms in field‐free InGaN layers grown on sapphire and bulk GaN substrate

The gain mechanisms and recombination dynamics of InGaN layers strongly depend on the structural properties of the substrate material. The 4.5 nm and 9.5 nm thick layers were grown by metal organic chemical vapor deposition on two different substrates (sapphire and GaN) with different dislocation densities. Time‐resolved photoluminescence spectroscopy at high excitation densities identifies the saturation of nonradiative recombination centers through excited carriers as a major gain mechanism. The prime argument is an unusual nonexponential luminescence decay. This was confirmed by a lower threshold of the optical gain for the structures grown on GaN with lower dislocation densities. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural, optical, and electronic properties of colloidal CuO nanoparticles formed by using a colloid-thermal synthesis process

Colloidal cupric oxide (CuO) nanoparticles were formed by using a colloid-thermal synthesis process. X-ray diffraction patterns, transmission electron microscopy (TEM) images, high-resolution TEM images, and X-ray energy dispersive spectrometry profiles showed that the colloidal CuO nanoparticles were formed. The optical band-gap energy of CuO nanoparticles at 300 K, as determined from the absorbance spectrum, was 3.63 eV. A photoluminescence spectrum at 300 K showed that a dominant emission peak appeared at the blue region. X-ray photoelectron spectroscopy profiles showed that the O 1s and the Cu 2p peaks corresponding to the CuO nanoparticles were observed.     

Optimization of (002)-Oriented ZnO Film Synthesis in Sol-Gel Process and Film Photoluminescence Property

By orthogonal design theory, technological parameters of the (002)-oriented ZnO film prepared in sol-gel process are optimized. A set of technological parameters for growing highly (002)-oriented ZnO film is obtained. As a result, it is proven that the Zn²⁺ concentration is the most important factor to grow a highly (002)-oriented ZnO film. We take an appropriate Zn²⁺ concentration 0.35mol/L for the aimed film, of which photoluminescence property is better than those of the films derived from other Zn²⁺ concentrations precursor solution. The Zn²⁺ concentration either larger or smaller than 0.35mol/L leads to the (002)-oriented degree decrease of films. By employing an atom force microscope, a hexagonal atom arrangement, which indicates that the film site detected is a ZnO single crystal, is observed in the surface of the highly (002)-oriented film.     

Superheating of silicon nanocrystals observed by Raman spectroscopy

In the Raman spectra of silicon nanocrystals a new anomalous component was detected. Close to the usual first order Raman peak situated for a bulk crystal at 521 cm⁻¹ at room temperature, two peaks arise shifting towards lower energy and demonstrating a huge temperature increase, as measured by the ratio of the Stokes/anti-Stokes peak intensities. This behavior is dependent on the laser power and on the morphology of the nanocrystals. We can exclude, however, confinement effects, although surface enhanced phonon modes could be responsible of such superheating. Alternative explanations are also suggested and discussed.     

Photoluminescence from doped ZnS nanostructures

Photoluminescence (PL) properties of differently doped nanocrystalline ZnS encapsulated by ZnO (ZnS/ZnO) are reported. It is found that in all cases aluminium as an extra/additional dopant leads to PL enhancement. In comparison to reported blue emitting bulk ZnS:Ag, or green emitting bulk ZnS:Cu, our nanocrystalline samples show a different PL emission profile. This observation is attributed to nanogranule formation, different dopant levels and ZnO capping related energy level modifications.     

Evidence for fast decay dynamics of the photoluminescence from Ge nanocrystals embedded in SiO2

We have investigated the origin of room temperature photoluminescence from ion-beam synthesized Ge nanocrystals (NCs) embedded in SiO₂ using steady state and time-resolved photoluminescence (PL) measurements. Ge NCs of diameter 4-13 nm were grown embedded in a thermally grown SiO₂ layer by Ge⁺ ion implantation and subsequent annealing. Steady state PL spectra show a peak at ∼2.1 eV originating from Ge NCs and another peak at ∼2.3 eV arising from ion-beam induced defects in the SiO₂ matrix. Time-resolved PL studies reveal double exponential decay dynamics on the nanoseconds time scale. The faster component of the decay with a time constant τ₁∼3.1 ns is attributed to the nonradiative lifetime, since the time constant reduces with increasing defect density. The slower component with time constant τ₂∼10 ns is attributed to radiative recombination at the Ge NCs. Our results are in close agreement with the theoretically predicted radiative lifetime for small Ge NCs.     

Photoluminescence spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532-nm laser radiation and gamma-rays

We have investigated temporal behavior of the photoluminescence (PL) spectra of thin films containing CdSe/ZnS quantum dots irradiated by 532 nm laser radiation and gamma-rays. Under ∼100 W/cm² laser radiation, the PL intensity (I_PL) increases with irradiation time upto about 500 s and thereafter declines linearly. The wavelength of the PL emission (λ_peak) exhibits a blue-shift with exposure time. Upon simultaneous irradiation by 100 W/cm² 532-nm laser, as well as 0.57 and 1.06 MeV gamma-rays, the temporal behaviors of both I_PL and λ_peak are significantly different; I_PL increases to a saturation level, and the magnitude of the blue-shift in λ_peak is reduced. We discuss possible mechanisms underlying these results.     

Micro-photoluminescence study of electron-spin injection in self-assembled semiconductor quantum dots

We present a micro-photoluminescence (m-PL) study of electron-spin injection under magnetic fields in self-assembled semiconductor quantum dots (QDs) of CdSe. A characteristic band line-up of the CdSe QDs coupled with a diluted magnetic semiconductor quantum well (DMS-QW) of ZnCdMnSe through a ZnSe barrier layer enabled us to inject the electron spins from the DMS-QW into QDs. An experimental evidence of the electron-spin injection was provided by observations of circularly polarized m-PL spectra from individual QDs in this coupled QD structure. We find anti-correlation of PL intensity in between the DMS-QW (spin injector) and the individual QDs (spin receiver).     

Random laser action in ZnO

We report a direct evidence of random laser in optically pumped ZnO powder. Discrete lasing modes are observed above threshold. The laser emission spectra depend on the angle of observation and are random. The lasing action is attributed to the coherent feedback due to recurrent light scattering in the powder. The lasing threshold intensity depends on the excitation volume. Received: 15 September 1999 / Revised version: 2 February 2000 / Published online: 5 July 2000