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 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.     

Alkyl chain effects in thin films of substituted phthalocyanines studied using infrared spectroscopy

Thin films (2-50 nm) of unsubstituted and 1,4-octa-alkyl substituted zinc phthalocyanines were investigated using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, whereas the alkyl chains are C₄H₇, C₇H₁₃, C₁₀H₁₉. The absorption bands in the whole spectral range are discussed. We observe distinct differences in the spectra between the alkyl substituted Phthalocyanine (Pc) compounds. In contrast to PcZn and (but)₈PcZn, the spectra of (hep)₈PcZn and (dec)₈PcZn show two additional features in the spectral range between 3700 and 3000 cm⁻¹, which are discussed in detail.     

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.     

Formation of gold nanoparticles in heat-treated reactive co-sputtered Au-SiO2 thin films

In this work, formation of gold nanoparticles in radio frequency (RF) reactive magnetron co-sputtered Au-SiO₂ thin films post annealed at different temperatures in Ar + H₂ atmosphere has been investigated. Optical, surface topography, chemical state and crystalline properties of the prepared films were analyzed by using UV-visible spectrophotometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD) techniques, respectively. Optical absorption spectrum of the Au-SiO₂ thin films annealed at 800 °C showed one surface plasmon resonance (SPR) absorption peak located at 520 nm relating to gold nanoparticles. According to XPS analysis, it was found that the gold nanoparticles had a tendency to accumulate on surface of the heat-treated films in the metallic state. AFM images showed that the nanoparticles were uniformly distributed on the film surface with grain size of about 30 nm. Using XRD analysis average crystalline size of the Au particles was estimated to about 20 nm.     

An estimate of shape-distribution of small CdS particles with luminescence spectra

The luminescence spectra of CdS particles obtained by sedimentation method are studied. The comparison of measured and calculated photoluminescence spectra was used as the base of the method defining the shape distribution of the particles. For this purpose one can use the symmetry rule for absorption and luminescence spectra. Absorption spectra were calculated via dissipative function in terms of local field theory. The experimental spectra of the photoluminescence were measured during the process of sedimentation in the CdS nano-composite powder. The modification of luminescence spectra detected during sedimentation time is associated with changing the dimension and shape distributions of CdS suspension. As a result, the particles shape distribution was estimated for sizes less then 1 μm.     

Porous silicon as efficient surface enhanced Raman scattering (SERS) substrate

Silver nanocrystallites are obtained through immersion of porous silicon samples in AgNO₃ solutions and a successive thermal annealing. The efficiency of nanostructures as surface enhanced Raman scattering (SERS) substrates is checked on cyanine-based dyes and horseradish peroxidase, evidencing detectable concentrations as low as 10⁻⁷ to 10⁻⁸ M. The substrate efficiency is strictly related to the Ag particle morphology, which could yield to either local surface plasmons (LSP) coupled to individual particles or to inter-particle short-range interaction.     

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.     

Formation of periodic structures by the space-selective precipitation of Ge nanoparticles in channel waveguides

Thermally stabilized channel waveguides with Bragg gratings were fabricated by the space-selective precipitation technique of crystalline Ge nanoparticles using KrF excimer laser irradiation. The periodic structures consisting of Ge nanoparticles were formed in Ge-B-SiO₂ thin glass films after exposure to an interference pattern of the laser followed by annealing at 600 °C. The channel waveguides with the periodic structures were fabricated by the cladding of the patterned Cr layers on the films. The diffraction peak for the TE-like mode of 11.8 dB depth was observed clearly at a wavelength of 1526.4 nm, indicating that the periodic structure also served as the optical band-pass filter in optical communication wavelength. The spectral shape, diffraction efficiency, and diffraction wavelength remained unchanged even after annealing at 400 °C. Furthermore, a low temperature dependence of the diffraction wavelength - as low as 8.1 pm/°C - was achieved. The diffraction efficiency was further enhanced after subsequent annealing at 600 °C. The space-selective precipitation technique is expected to be useful for the fabrication of highly reliable optical filters or durable sensing devices operating at high temperature.     

Temperature dependent phonon confinement in silicon nanostructures

Temperature dependent variation in Raman line-shape from silicon (Si) nanostructures (NSs) is studied here. Asymmetry and red-shift in room temperature Raman spectrum is attributed to phonon confinement effect. Raman spectra recorded at higher temperatures show increase in FWHM and decrease in asymmetry ratio with respect to its room temperature counterpart. Theoretical Raman line-shape analyses of temperature dependence of phonon confinement is done by incorporating the temperature dependence of phonon dispersion relation. Experimental and theoretical temperature dependent Raman spectra are in good agreement.     

Probing disorder and charged impurities in graphene by Raman spectroscopy

Disorder and doping can strongly affect the properties of graphene. Here we analyze these effects on several samples by Raman spectroscopy. In particular, we show that pristine and unprocessed graphene samples deposited on silicon, covered with a thin silicon oxide layer, show strong variations in their Raman spectra, even in absence of disorder. The variation in the Raman parameters is assigned to charged impurities. This shows that as‐deposited graphene is unintentionally doped, reaching charge concentrations up to 10¹³ cm^–2 under ambient conditions. The doping varies from sample to sample and the charges are inhomogeneously distributed on a submicron scale. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silver-Doping Induced Lattice Distortion in TiO2 Nanoparticles

The Ag-doping effects on Ti02 nanoparticles are investigated by means of x-ray diffraction （XRD） and Raman scattering spectroscopy. XRD and Raman results indicate that Ag-doping stabilizes the rutile phase in TiO2. We find an Ag-doping induced lattice expansion in both anatase and rutile phases. The Ag-doping has different influences on the lattice distortion for anatase and rutile phases, that is, the e/a-value for the anatase phase decreases with 0.5% Ag-doping and then increases with 1~ Ag-doping while that for the rutile phase shows a gradual increase with increasing Ag-doping. We have ascribed the different variations of lattice distortion due to Ag-doping to the change of interracial interaction between the anatase and rutile phases induced by different Ag concentrations.     

Synthesis and luminescence properties of nanocrystalline LiF:Mg,Cu,P phosphor

Nanocrystalline LiF:Mg,Cu,P phosphor material of different shapes and sizes (microcrystalline cubic shape, nanorod shape and nanocrystalline cubical shaped) have been prepared by the chemical co-precipitation method. Thermoluminescence (TL) and other dosimetric characteristics of the phosphor are studied and presented here. The formation of the materials was confirmed by the X-ray diffraction (XRD). Its shapes and sizes were also observed using scanning electron microscope (SEM). The TL glow curve of the microcrystalline powder shows a prominent single peak at 408 K along with another peak of lesser intensity at around 638 K. On the contrary, the nanocrystalline rod shaped particles show a peak of low intensity at 401 K and a prominent peak around 700 K while the nanocrystalline particles in cubical shapes again show two peaks, one at around 407 K and the other at around 617 K, of which the lower temperature (407 K) peak is more prominent. The glow curve structure changes at very high doses (100 kRad) and some new peaks appear at around 525 and 637 K also the first peak appearing at around 401 K becomes prominent. The observed changes in TL due to the change in the shape and sizes of the nanophosphor have been reported. The PL has also been studied and various excitation and emission peaks observed due to the presence of various impurities are explained. The observed results have been explained in the light of asymmetrical crystal field effects due to asymmetrical shapes of the nanocrystalline phosphor. The comparison of these properties with the microcrystalline material prepared by the same co-precipitation method is also done.     

Self-assembled and fluorescence enhancement of semiconductor nanoparticles induced by surfactant adsorption

When semiconductor colloidal CdS nanoparticles and nonylphenol are mixed together in dimethyl sulfoxide at room temperature, a self-assembling process is induced. In the course, the size tunable properties of CdS nanoparticles are amplified. A blue shift in the emission spectrum and a strong photoluminescence enhancement are observed without significant change in the absorption features of the colloidal nanoparticles. These results are attributed to the adsorption of nonylphenol onto the nanoparticles surface and to the association process of the surfactant molecules. The surfactant adsorption process provides a nanoparticle surface passivation and induces an associative phase that enlarges the photoluminescence stability. This strategy opens the possibility to improve simultaneously physicochemical and photoluminescence properties of nanocrystals in solution as well as to control their deposition on two-dimensional surfaces.     

Upconversion luminescence in Er-doped germanate-oxyfluoride and tellurium-germanate-oxyfluoride transparent glass-ceramics

Upconversion luminescence has been studied for Er³⁺ in a germanate-oxyfluoride and a tellurium-germanate-oxyfluoride transparent glass-ceramic using 800 nm excitation. Significantly increased upconversion luminescence was observed from transparent glass-ceramics compared with that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm from ⁴S_3/2 state and a weaker red emission centered at 662 nm from ⁴F_9/2 state generally seen from Er³⁺-doped glasses, a violet emission centered at 410 nm from ²H_9/2 state and a near-ultra-violet emission centered at 379 nm from ⁴G_11/2 state were also observed from transparent glass-ceramics. The upconversion luminescence of Er³⁺ ions in transparent glass-ceramics revealed sharp Stark-splitting peaks generally seen in a crystal host. The increased upconversion efficiency is attributed to the decreased effective phonon energy and the increased energy transfer between excited ions when Er³⁺ ions were incorporated into the precipitated β-PbF₂ nanocrystals.     

Effect of branching of tetrapod-shaped CdTe/CdSe nanocrystal heterostructures on their luminescence

We have studied the CdTe/CdSe tetrapod-shaped nanocrystal heterostructures with the use of photoluminescence spectra measurements and time-correlated single photon counting technique. The tetrapods were grown to have CdTe arms with different thickness of the CdSe shell. We have observed non-exponential photoluminescence decay of excited tetrapod-nanocrystals and proposed kinetic theory based on the branched crystal morphology and on the assumption about a potential barrier in the junction point of tetrapod. Analysis of studied nanocrystal behavior gives an evidence for tetrapods to behave as four weakly connected quantum wells. This interesting effect might find applications in nanoelectronics.     

Energy shift of photoemission spectra for organics-passivated CdSe nanoparticles: The final-state effect

Size-dependent energy shift of photoemission spectra with respect to bulk sample has been examined for colloidally prepared CdSe nanoparticles with a series of particle sizes. The core-level shifts are well described by a theoretical calculation based on a final-state effect model, whereas an additional initial-state effect due to quantum confinement is required to elucidate the valence-band edge shifts. The results indicate that the interaction between the photohole and the dielectric background in the final state has to be considered in photoemission measurements for organics-passivated nanoparticles. The calculated results in the literature appear to overestimate the initial-state effect compared to our experimental observation.     

Size-dependent photo-induced shift of the first exciton band in CdTe quantum dots in glass prepared by a two-stage heat-treatment process

CdTe nanocrystals were grown from commercially available RG850 Schott filter glass by two-step heat-treatment process which almost doubles the particle to matrix volume fraction. A calculation shows that a quantized-state effective mass model in the strong confinement regime might be used to deduce the average radius for the nanocrystals larger than 2 nm in radius from the energetic position of the first exciton peak in optical absorption spectrum. Size-induced shift of ∼360 meV in the first exciton peak position was observed. The steady state photoluminescence spectra exhibit a broad band red shifted relative to the first exciton band, which indicates the existence of shallow trap states. The non-linear optical properties of CdTe nanocrystals were studied by room temperature resonant photoabsorption spectroscopy. The differential absorption spectra had three-lobed structure whose size-dependent evolution was explained by bleaching of the absorption, red shift and broadening in the Gaussian absorption band used to fit the first exciton peak. A maximum red shift of 2.32 meV for the average nanocrystal radius of 4.65 nm was estimated by fitting the photomodulation spectra with a combination of first and second derivative Gaussian absorption bands. We presume that the red shift is induced by the electric field of trapped charges in surface states. Internal electric field strengths of 23 and 65 kV/cm were predicted for the average nanocrystal radii of 3.95 and 4.65 nm, respectively, with the help of second-order perturbation theory in the strong confinement limit.     

Third-order nonlinear optical response of Au-core CdS-shell composite nanoparticles embedded in BaTiO<Subscript>3</Subscript> thin films

Au-core CdS-shell composite nanoparticles were synthesized by a direct self-assembly process and integrated into BaTiO₃ thin films. Characterization by transmission electron microscopy showed that the average diameter of these composite nanoparticles was about 8 nm. Using the femtosecond time-resolved optical Kerr effect method, we investigated the third-order nonlinear optical response of the Au@CdS nanoparticles embedded in the BaTiO₃ thin films at a wavelength of 800 nm. An ultrafast nonlinear response and a large effective third-order nonlinear susceptibility of χ⁽³⁾=7.7×10^-11 esu were observed. We attributed the enhancement of the third-order optical nonlinearity to a localized electric field effect originating from the core-shell structure under off-surface-plasmon resonance conditions. Received: 13 May 2002 / Revised version: 23 October 2002 / Published online: 3 April 2003 RID="*" ID="*"Corresponding author. Fax: +86-21/6510-4949, E-mail: sxqian@fudan.ac.cn     

Effects of citric acid additive on photoluminescence properties of YAG:Ce nanoparticles synthesized by glycothermal reaction

We synthesize Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) nanoparticles in the presence of citric acid by glycothermal method. Fourier transform infrared absorption spectroscopy measurement indicates that the intensity of the peak corresponding to carboxyl groups coordinating to the nanoparticles increases with increasing amount of citric acid. At the same time, the primary particle diameter decreases from 10.2 to 4.0 nm. In addition, the internal quantum efficiency of the photoluminescence (PL) due to the 4f-5d transition of Ce³⁺ increases from 22.0% to 40.1% with increasing amount of citric acid. Two kinds of PL decay lifetimes, 16-26 and 72-112 ns, are detected for YAG:Ce³⁺ nanoparticles, whereas the micron sized YAG:Ce³⁺ bulk shows the lifetime of 57 ns. We discuss these phenomena from the aspects of the coordination of citric acid and the incorporation of Ce³⁺ ions into the nanoparticles.