Blue shift in the luminescence spectra of MEH-PPV films containing ZnO nanoparticles

Luminescence properties of nanocomposites consisting of ZnO nanoparticles in a conjugated polymer, poly [2-methoxy-5-(2′-ethyl hexyloxy)-phenylene vinylene] (MEH-PPV), were investigated. Photoluminescence measurements reveal a blue shift in the emission spectrum of MEH-PPV upon incorporation of ZnO nanoparticles into the polymer film while the emission is increasingly quenched with increasing ZnO concentration. In contrast, the structure of the polymer and its conjugation length are not affected by the presence of ZnO nanoparticles (up to 16 wt% ZnO) as revealed by Raman spectroscopy. The blue shift and photoluminescence quenching are explained by the separation of photogenerated electron-hole pairs at the MEH-PPV/ZnO interface and the charging of the nanoparticles.     

Influence of Tb doping on the luminescence characteristics of ZnO nanoparticles

Structural and optical properties of the Tb-doped ZnO nanoparticles with average diameter ≈4 nm have been systematically investigated. Our X-ray diffraction studies show a contraction of the ZnO lattice with the increase of the Tb mole-fraction x for x ≤ 0.02 and an expansion beyond x ≈ 0.02. The photoluminescence spectra are found to be comprised of a near band edge ultra violet luminescence (UVL) and a broad green luminescence (GL) band. Under the atmospheric condition, the intensity of the GL band is found to increase with the Tb mole-fraction over the entire doping range. On the other hand, under the vacuum condition, it has been observed that the GL intensity decreases with the increase of x up to x ≈ 0.02 but further increase of x leads to a gradual revival of the GL emission. Our study suggests that for x ≤ 0.02, GL results due to the physisorption of certain groups on the surface of the nanoparticles (GL-groups). It is also found that in this Tb mole-fraction regime, Tb incorporates mostly on the surface of the nanoparticles and affects the UVL to GL intensity ratio by influencing the attachment of the GL-groups. However, for x > 0.02, GL originates not only from the GL-groups but also from certain point defects, which are likely to be generated due to the incorporation of Tb in the core of the nanoparticles. A simple rate equation model is introduced to get a quantitative understanding about the variation of the density of the centers responsible for the GL emission as a function of x under the atmospheric and the vacuum conditions.     

Red luminescence of Eu3+ doped ZnO nanoparticles fabricated by laser ablation in aqueous solution

Fabrication of Eu³⁺-doped ZnO nanoparticles by laser ablation in liquid medium is reported. Sintered disks made of mixed powders of ZnO and Eu₂O₃ are used for targets, and surfactant of sodium dodecyl sulfate or LiOH is included in solution. Round-shaped nanoparticles with the diameter of 5??30?nm are synthesized. When the ZnO host is photoexcited, broad green photoluminescence (PL) of oxygen vacancies in the ZnO host as well as red PL of Eu³⁺ is observed at room temperature. The red PL peak of Eu³⁺ included in the ZnO host lattice is different from that of the source material of Eu₂O₃. Energy transfer from the ZnO host to Eu³⁺ is demonstrated in site-selectively excited PL spectra and its excitation spectra. This result shows that the liquid-phase laser ablation is useful for doping active centers into nanoparticles.     

The luminescence of ZnO ceramics

The luminescence properties of ZnO ceramics with grains 100–5000 nm sintered by different techniques from nanopowders were studied. The luminescence decay times were compared with that obtained for ZnO single crystal. The temperature dependence of non-exponential decay of defect luminescence (2.0–2.6 eV) was measured in wide time, intensity and temperature range. The luminescence decay kinetic at T ≤ 20 K shows the decay close to I(t) ～ t^?1 dependence. At temperature region 50–250 K the decay kinetics is more complicate since the TSL was observed in this temperature region. It is shown that the luminescence properties of NP and ceramics strongly depend on defect distribution on grains surface and the volume/surface ratio determine the luminescence decay in ZnO nanostructures and ceramics.     

Localized luminescence in ZnO: Mn ceramics

Experimental conditions leading to the appearance of a Mn-related green emission band in ZnO ceramics are investigated. The emission has been found to be associated with the presence of small luminescent particles in the matrix.     

Thermally stimulated luminescence of Mg-doped ZnO Nanophosphors

Nanosized ZnO:Mg phosphors were synthesized through a controlled chemical reaction. X-ray diffraction patterns confirmed that Mg entered in a substitutive way in Zn sites. To investigate their thermoluminescence (TL) properties, some samples were exposed to beta-particle irradiation. The results reported here show that Mg doping improves ZnO TL features that are important for TL dosimetry applications, such as the shape of the glow curve, the temperature at which the maximum TL intensity is observed, and the TL fading and reproducibility. No saturation clues of the TL response as a function of the dose is observed for doses below 1600 Gy.     

Temperature-dependent luminescence dynamics for ZnO thin films

The paper presents the photoluminescence investigation of zinc oxide thin films. A high quality ZnO films fabricated by dip-coating (sol–gel) method were grown on quartz wafers. The films with different thickness (number of layers) were annealed at different temperatures after the preparation process. It was found that high quality, transparent ZnO thin films could be produced on quartz substrates at relatively low annealing temperature (450–550  $^{\circ }\mathrm{C}$ ). The dependence of the ZnO thin film quality was studied by X-ray diffraction and atomic force microscopy techniques. Optical properties were investigated by classic and time-resolved photoluminescence (TRPL) measurements. Photoluminescence spectra allowed us to estimate energy of the free excitons, bond excitons and their longitudinal optical (LO) phonon replicas as a function of the annealing temperature. An innovative TRPL technique let us precisely measure the decay time of the free- and bond excitons’ in the real time. TRPL measurements as a function of temperature reveal a biexponential decay behavior with typical free/bound exciton decay constants of 970/5310 ps for the as-grown sample and 1380/5980 ps after annealing process. Presented spectra confirm high structural and optical quality of investigated films. We proved that the thermal treatment improve both optical and structural quality and extend the photoluminescence’s lifetimes. The obtained experimental results are important for identification of exciton’s peaks and their LO phonon replicas for the investigated ZnO films.     

Positron annihilation studies in ZnO nanoparticles

We report results on positron annihilation spectroscopic (PAS) studies using lifetime and coincidence Doppler broadening techniques in zinc oxide (ZnO) nanoparticles (4 to 40 nm) synthesized by solid state pyrolytic reaction followed by annealing in the temperature range of 200 ^°C to 800 ^°C. Positron lifetime in the nanoparticles are observed to be higher than bulk lifetime in all the cases. Theoretical calculation of lifetime indicates the presence of either Zn or (Zn, O) vacancy clusters which migrate and anneal out at high temperature. Comparison of ratio spectra from coincidence Doppler broadening measurement and calculated electron momentum distribution indicates the presence of either Zn or (Zn, O) vacancies. In addition, photoluminescence (PL) measurements have been carried out to examine the role of defects on the intensity of emission in the visible region.     

Fe离子注入ZnO生成超顺磁纳米颗粒

过渡族元素掺杂ZnO生成稀磁半导体, 成为近期国际材料科学研究的热点. 在本文中, 研究Fe离子注入ZnO单晶的结构和磁性变化, 目标是建立磁性和结构的对应关系, 澄清铁磁性的来源. 采用卢瑟福背散射/沟道技术 (RBS/Channelling)、同步辐射X射线衍射 (SR-XRD)和超导量子干涉仪 (SQUID), 研究注入温度和退火对样品的晶格损伤、结构及磁性的影响. 研究表明: 样品注入区损伤随注入温度升高而降低; 低温253 K注入样品中, SR-XRD未检测到新相, Fe离子分布于Zn位, ZnO (0002) 峰右侧肩峰可能属于Zn_1-xFe_xO, 5 K下测试样品不具有铁磁性; 623 K注入和823 K真空退火 (253 K注入) 样品中形成α和γ相金属Fe, 5 K下样品具有明显的剩磁和矫顽力, 零场冷却和场冷却 (ZFC/FC) 曲线和300 K下的磁滞回线显示纳米Fe颗粒具有超顺磁性. Fe离子注入ZnO的磁性源于第二相α-Fe和γ-Fe. 关键词： 离子注入 ZnO 同步辐射X射线衍射 超顺磁性     

Surface-induced structural modification in ZnO nanoparticles

Cobalt?Ccobalt carbide [Co _x C (x?=?2 or 3)] and cobalt (FCC-Co) microwires have been synthesized using a polyol method in the presence of a high external magnetic field of 4.3?kOe. It was reported before that the synthesis of these particles in the absence of magnetic field leads to the formation of spherical particles. Analysis of the X-ray diffraction (XRD) scans indicates that the synthesized Co _x C wires consist of four phases?? ??-Co, ??-Co, Co₃C, and Co₂C. The percent composition of these phases was 53.3?% Co₃C, 26.8?% Co₂C, 12.5?% ??-Co, and 7.4?% ??-Co. XRD analysis of the as-synthesized cobalt wires shows that it consists of single-phase FCC-Co. Based on Scherrer analysis of the XRD data, the average crystallite sizes of the cobalt carbide and the cobalt particles are 18.5 and 16.3?nm, respectively. Scanning electron microscopy (SEM) studies show that the diameter of Co _x C wires is in the range of 1.6(±0.2)???m with their length varying between 18 and 30???m while the diameter of the cobalt wires is 1.65(±0.1). The SEM results infer that the morphology of the growing particles was controlled by the magnetic field with the applied field directs the growth of the particles into wires. The magnetic measurements indicate a superparamagnetic character of the cobalt wires and a soft ferromagnetic nature of the synthesized Co _x C chains. The degree and field range of the interactions between magnetic domains have been investigated using a Henkel plot.     

Efficient multiphoton-absorption-induced luminescence in single-crystalline ZnO at room temperature

At room temperature, multiphoton absorption- (MPA-) induced photoluminescence in ZnO strongly driven by a femtosecond (fs) near-infrared laser is studied. Two-photon absorption and three-photon absorption are proved to be responsible for the intense luminescence, when the wavelength of the fs excitation laser is above and below the half-bandgap of ZnO, respectively. Strong MPA absorption in ZnO is unambiguously evidenced by the interferometric autocorrelation measurements of the luminescence signal.     

Picosecond excitonic luminescence in ZnO and other wide-gap semiconductors

Radiative lifetimes of free-atom transitions, scaled by ω³ for comparison at 368 nm, are not faster than about 6.9 ns. BaF₂ core-valence luminescence, scaled in the same way from 220 to 368 nm, corresponds to 4.1 ns. In contrast, excitonic transitions in wide-gap semiconductors display subnanosecond radiative lifetimes, and in particular ZnO has radiative lifetimes measured at 50–300 ps for D^o,X and 400–900 ps for free excitons. The “giant oscillator strength” corresponding to these lifetimes can be explained by theories developed initially for defect-bound excitons, then quantum wells, and nanoparticles. An exciton is a coherent array of N dipoles, where N is the number of sites covered by coherent translational motion of the exciton. This is not essentially a phenomenon of multiple excitons, but applies as well to single-exciton decay. It differs in that regard from the more familiar Dicke giant dipole of N coherently excited atoms lacking translational periodicity. The phenomenon suggests possibilities for achieving ultrafast scintillators and high light yield.     

Decay kinetics of the defect-based visible luminescence in ZnO

Photoluminescence spectra and decays under pulsed N₂ (337 nm) laser excitation were measured for hydrothermally grown bulk and liquid-phase epitaxy (LPE)-grown film ZnO samples within 9-300 K. Temperature dependence of integrated spectra over the exciton and visible spectral regions was evaluated using a model involving standard energy barrier processes. Decay curves measured within a broad time window (10 ns-1 ms) and with extreme signal/background ratio (five orders of magnitude) point to complex decay mechanism in which the exponential and inverse power-law processes can coexist. There is no straightforward interconnection between the observed temperature dependence of integrated visible photoluminescence intensity and its decay shape over the 9-300 K temperature interval.     

Cathodoluminescence study of visible luminescence in hydrothermal ZnO crystals

We present a study of the visible luminescence in ZnO hydrothermal crystals. The study is carried out on oxygen polarity basal plane (000-1) plates that are sliced through several distinct growth sectors of the crystal. The plates reveal three distinct regions that display differences in the luminescence emission, especially in the visible range. These differences should be related to the variation in the distribution of impurities and native defects in the various growth sectors of hydrothermal ZnO. CL images also expose the presence of nonradiative recombination centers that are associated with point defects or complexes of point defects. CL measurements varying the acceleration voltage of the e-beam reveal that the deep levels responsible for the green luminescence, and in a minor extension those responsible for the yellow-orange luminescence are depleted near the surface. A discussion about the main hypothesis accounting for such behavior is presented. PACS 71.55.Gs; 71.55.-i; 78.55.Et; 78.60.Hk     

Photochemical preparation of ZnO nanoparticles

Preparation of zinc oxide nanoparticles from aqueous solutions containing zinc nitrate or formate using UV irradiation was investigated. Analysis of solid phase formed during irradiation confirmed the presence of zinc oxide or zinc peroxide nanoparticles ranging in size from 1 to 70 nm, depending on initial precursors. Annealing at temperatures 650–1000 °C results in forming of rice-like zinc oxide particles, up to hundreds of nm in size. Photochemical method yields material with high chemical purity and uniform particle size distribution. In addition, photo-induced doping of zinc oxide with lanthanum was studied. Presence of lanthanum in zinc oxide crystal lattice and post-preparation treatment in reduction atmosphere significantly increase the UV excitonic luminescence at 395 nm in radioluminescence spectra.     

氧化锌纳米颗粒薄膜的近紫外电致发光特性研究

利用溶胶-凝胶法(sol-gel method)制备了ZnO纳米颗粒薄膜(ZnO nanoparticle film),并以此为发光层制备了结构为ITO/ZnO nanoparticle/MEH-PPV/LiF/Al的电致发光器件.通过调整器件发光层厚度,对器件的发光光谱和电学特性进行测试研究,发现该器件在一定的直流电压下可以得到以ZnO近紫外(中心波长390 nm)发光为主的电致发光光谱,显示出较好的ZnO近紫外电致发光特性.对该器件的发光机理进行了一定的研究,认为该器件的发光是基于载流子隧穿.     

Bound exciton luminescence of Ar- and Al-implanted ZnO

Argon- and aluminum-implanted ZnO single crystals (N_impl=10¹⁶?10¹⁹cm^?3) were investigated at liquid helium temperature by photoluminescence. We obtained highly resolved emission spectra of implanted and thermally annealed samples. Maximum luminescence yield was achieved after annealing with an oxygen ambient at 800°C and an anneal time of 30 min. In Al-implanted ZnO crystals, we observed a strong emission line $\text{I}{}_{\mathrm{<mtext>5</mtext><mtext>6</mtext>}}\text{at λ = 3688}\text{A}\text{?}$. The intensity of this line is correlated with the implanted Al concentration. The I_{$\text{5}\text{6}$} line is interpreted as the recombination of a bound exciton at a polycentric Al complex.     

Morphology-dependent upconversion luminescence of ZnO:Er nanocrystals

Morphology impact on the upconverted luminescence of ZnO:Er³⁺ nanocrystals was studied with controllable morphology of nanorod, prickly sphere-like, column-like, branch rod, prism-like, and grain-like, prepared via the cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process. The upconversion emission of Er³⁺ with 980 nm excitation demonstrated morphology sensitivity which was related with the local environments of Er³⁺ ions in ZnO and doping efficiency. Under ultraviolet (UV) direct excitation, where exciton and defect emissions of ZnO appeared, morphology sensitivity was discussed in terms of surface-to-volume ratios.     

Catalyst-free synthesis and luminescence of aligned ZnO nanorods

Quasi-aligned undoped ZnO nanorods with diameter in the range 100–300 nm and length of several micrometers have been grown catalyst-free on Si(1 0 0) wafer in a one-step process by direct heating of Zn powders. All nanowires are single crystals and are aligned vertically to the substrate surface with c-axis preferred orientation. XRD, HRTEM and Raman studies revealed that the ZnO nanorods have wurtzite phase, are highly crystalline and well aligned with the lattice parameters a=0.32 nm and c=0.52 nm. The PL spectra measured at different temperatures are dominated by excitonic emission at 380 nm and less intense below band gap emission band centered at 520 nm.