Dominant ultraviolet-blue photoluminescence of ZnO embedded into synthetic opal

The temperature-dependent photoluminescence (PL) characteristics of zinc oxide (ZnO) embedded into the voids of synthetic opal were studied. ZnO was infiltrated into opal from aqueous solution with zinc nitrate precursor followed by thermal annealing. The PL spectra of the ZnO powder exhibit very high and broad emission peaks in the green region due to crystal defects, such as oxygen vacancies and zinc ion interstitials. In contrast to the PL spectra of ZnO powder, nanocrystals of ZnO embedded into the voids of FCC packed opal matrix exhibit dominant ultraviolet (UV)-blue and rapidly decreasing green PL emissions with decreasing temperature. The temperature-dependent PL characteristics show that the green band suppression in the ZnO nanocrystals is due to the influence of photonic crystal. The infiltration of nanoparticles into synthetic opal may be used for the fabrication of polycrystalline ZnO with dominant UV-blue PL. These results indicate that the luminescent materials embedded into photonic crystal may be promising for the fabrication of the RGB pixels in full-color displays.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

Characterisation of porous doped ZnO thin films deposited by spray pyrolysis technique

Al or Sn doped ZnO films were deposited by spray pyrolysis using aqueous solutions. The films were deposited on either indium tin oxide coated or bare glass substrates. ZnCl₂, AlCl₃ and SnCl₂ were used as precursors. The effect of ZnCl₂ molar concentration (0.1-0.3 M) and doping percentage (2-4% AlCl₃ or SnCl₂) have been investigated. The main goal of this work being to grow porous ZnO thin films, small temperature substrates (200-300 °C) have been used during the spray pyrolysis deposition. It is shown that, if the X-ray diffraction patterns correspond to ZnO, the films deposited onto bare glass substrate are only partly crystallized while those deposited onto ITO coated glass substrate exhibit better crystallization. The homogeneity of the films decreases when the molar concentration of the precursor increases, while the grain size and the porosity decrease when the Al doping increases. The optical study shows that band tails are present in the absorption spectrum of the films deposited onto bare glass substrate, which is typical of disordered materials. Even after annealing 4 h at 400 °C, the longitudinal resistivity of the films is quite high. This result is attributed to the grain boundary effect and the porosity of the films. Effectively, the presence of an important reflection in the IR region in samples annealed testifies of a high free-carriers density in the ZnO crystallites. Finally it is shown that when deposited in the same electrochemical conditions, the transmission of a polymer film onto the rough sprayed ZnO is smaller than that onto smooth sputtered ZnO.     

Study of the microstructural and photoluminescence properties of Li-doped ZnO thin films prepared by spray pyrolysis

Lithium-doped zinc oxide films were synthesized by spray pyrolysis technique, and their structural and optical properties were characterized by X-ray diffraction, transmission electron microscope, atomic force microscope, and photoluminescence spectroscopy. The effect of doping on the photoluminescence properties was investigated at room temperature (300 K). Polycrystalline nature of the films was confirmed from X-ray diffraction and electron microscopic studies. A two-dimensional fringe moiré pattern with spacing of 1.2 nm was observed for the doped thin film. Lithium doping has been found to increase the roughness of the surface, thus making the film more passivated. Lithium was found to play a key role in the excitonic as well as visible luminescence of ZnO.     

Structural, optical and magnetic properties of Cr doped ZnO microrods prepared by spray pyrolysis method

A series of Cr-doped ZnO micro-rod arrays were fabricated by a spray pyrolysis method. X-ray diffraction patterns of the samples showed that the undoped and Cr-doped ZnO microrods exhibit hexagonal crystal structure. Surface morphology analysis of the samples has revealed that pure ZnO sample has a hexagonal microrod morphology. From X-ray photoelectron spectroscopy studies, the Cr 2p3/2 binding energy is found to be 577.3 eV indicating that the electron binding energy of the Cr in ZnO is almost the same as the binding energy of Cr³⁺ states in Cr₂O₃. The optical band gap E_g decreases slightly from 3.26 to 3.15 eV with the increase of actual Cr molar fraction from x = 0.00 to 0.046 in ZnO. Photoluminescence studies at 10 K show that the incorporation of chromium leads to a relative increase of deep level band intensity. It was also observed that Cr doped samples clearly showed ferromagnetic behavior; however, 2.5 at.% Cr doped ZnO showed remnant magnetization higher than that of 1.1 at.% and 4.6 at.% Cr doped samples, while 4.6 at.% Cr doped ZnO samples had a coercive field higher than the other dopings.     

Metal-semiconductor transition in undoped ZnO films deposited by spray pyrolysis

ZnO films were deposited on glass substrate by using spray pyrolysis method. Films were deposited at different solution molarities 0.02 and 0.1 M. The films are highly transparent in the visible range of the electromagnetic spectrum with a transmission reaching up values to 90%. Band gaps were calculated as 3.24 and 3.28 eV with the help of transmission spectrums. When the solution molarity of the sprayed solution is increased from 0.02 to 0.1 M, carrier concentrations of the films increase from 1.6×10¹⁹ cm⁻³ to 5.1×10¹⁹ cm⁻³. Temperature-dependent conductivity measurements of these conducting and transparent films also showed, for the first time, a metal-semiconductor transition (MST). The deposited ZnO films show metallic conductivity above ∼420 K and semiconducting behavior at temperatures below it.     

控制纳米结构以调控氧化锌的发光、磁性和细胞毒性

氧化锌(ZnO) 纳米材料因其在UV 激光器、发光二极管、太阳能电池、稀磁半导体、生物荧光标示、靶向药物等领域中的广泛应用而成为最热门的研究课题之一. 调节和优化ZnO 纳米结构的性质是ZnO 的实际应用迫切所需. 在此, 通过发展聚乙烯吡咯烷酮导向结晶法、微波加热强制水解法、表面活性剂后处理法, 成功地制备出了尺寸、表面电荷或成分可调的球、半球、棒、管、T 型管、三脚架、片、齿轮、两层、多层、带盖罐子、碗等一系列ZnO 纳米结构. 通过简单地改变ZnO 纳米粒子的尺寸、形貌和表面电荷或成分, 有效地调控ZnO 本身的发光强度和位置, 并近90 倍地增强了荧光素染料的荧光强度; 诱使了强度可调的室温铁磁性; 实现了对ZnO纳米颗粒的细胞毒性的系统性调控.     

火焰喷雾法合成ZnO和MgxZn1-xO纳米颗粒的光学性能研究

利用火焰喷雾法成功制备了纳米级的ZnO和Mgxzn1-xO颗粒.通过对样品的X射线衍射谱和场发射扫描电子显微镜照片分析,发现制备的颗粒大小较为均匀,直径在20 nm左右;镁元素的掺入引起晶格常数变小.通过透射光谱和光致发光谱的测量,发现MgxZn1-xO颗粒的禁带宽度远大于ZnO颗粒的禁带宽度,同时对两组样品的紫外发光和可见发光的强度变化和发光机理进行了探讨.     

Preparation of ZnO-doped Al films by spray pyrolysis technique

Al-doped zinc oxide (AZO) thin films have been prepared by spray pyrolysis (SP) technique of zinc acetate and aluminium nitrate, and the effect of thickness on structural and optical properties has been investigated. The structural and optical characteristics of the AZO films were examined by X-ray diffraction (XRD) and double-beam spectrophotometry. These films, deposited on glass substrates at an optimal substrate temperature (T_S = 450 °C), have a polycrystalline texture with a hexagonal structure. Transmission measurements showed that for visible wavelengths, the AZO films have an average transmission of over 90%. The optical parameters have been calculated. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for the sprayed films is also reported. Optical band gap of AZO is 3.30 and 3.55 eV, respectively, depending on the film thicknesses.     

Structural, Raman, and photoluminescence characteristics of ZnO nanowires coated with Al-doped ZnO shell layers

Al-doped ZnO (AZO) shell layers were coated on core ZnO nanowires to fabricate ZnO/AZO core–shell nanowires. The energy-dispersive X-ray spectra confirmed the presence of Al element in the shell layers, and the lattice resolved transmission electron microscopy image revealed that these layers corresponded to the hexagonal ZnO structure. The X-ray diffraction pattern exhibited a shift of the ZnO peaks, suggesting the substitutive incorporation of Al into the ZnO lattice. The A₁(LO) mode line in the Raman spectra was enhanced by the AZO coating. In the photoluminescence measurements, the AZO coating enhanced the intensity ratio of the UV to green emission.     

反应磁控溅射ZnO/MgO多量子阱的光致荧光光谱分析

采用反应射频磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO/MgO多量子阱.利用X射线反射、X射线衍射、电子探针，光致荧光光谱等表征技术，研究了ZnO/MgO多量子阱的结构、成份和光致荧光特性.研究结果表明，多量子阱的调制周期在1.85—22.3 nm之间，所制备的多量子阱具有量子限域效应，导致了室温光致荧光峰的蓝移，并观测到了量子隧穿效应引起的荧光效率下降.建立了基于多声子辅助激子复合跃迁理论的室温光致荧光光谱优化拟合方法，通过室温光致荧光光谱拟合发现，ZnO/MgO比ZnO/ZnMgO多量子阱具有更大的峰位蓝移，探讨了导致光致荧光光谱展宽的可能因素. 关键词： ZnO/MgO 多量子阱 磁控溅射 光致荧光 量子限域效应     

Optical properties of ZnO and ZnO:Ce layers grown by spray pyrolysis

In this paper, zinc oxide (ZnO) and cerium-doped zinc oxide (ZnO:Ce) films were deposited by reactive chemical pulverization spray pyrolysis technique using zinc and cerium chlorides as precursors. The effects of Ce concentration on the structural and optical properties of ZnO thin films were investigated in detail. These films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence (PL) measurements. All deposited ZnO layers at the temperature 450 °C are polycrystalline and indicate highly c-axis oriented structure. The dimension of crystallites depends on incorporation of Ce atoms into the ZnO films. The photoluminescence spectra of the films have been studied as a function of the deposition parameters such as doping concentrations and post grows annealing. Photoluminescence spectra were measured at the temperature range from 13 K to 320 K.     

超声处理对ZnO薄膜光致发光特性的影响

对于结晶状态好的ZnO薄膜，测量了其光致发光(PL)光谱，发射光谱中只发现了峰值波长约389 nm的近紫外光.样品进行超声处理后，发射谱中不仅观察到近紫外峰，又观察到波长约508 nm的绿光峰.绿光峰的强度比近紫外光的强度强得多，且近紫外峰红移.进一步的热处理使绿光峰大大增强.超声处理改变了ZnO薄膜的质量和结晶状态，使晶格中产生氧空位.处理过程中的热效应使得薄膜晶格振动加剧.当晶格振动加剧到一定程度，晶格中的氧脱离格点形成氧空位.510 nm左右的绿色发光峰是ZnO晶体中的氧空位产生的.薄膜的温度越高， 关键词： ZnO薄膜 超声 光致发光     

Morphology and photoluminescence study of electrodeposited ZnO films

ZnO films on ITO substrates and Au coated ITO substrates were fabricated by using electrodeposition technique. We carried out the experiments by adjusting the concentration of solution, potential, substrate, and temperature. The effect of temperature on the growth of the film has been examined. SEM images have shown that there are several kinds of grown competitions for the deposition of ZnO films, but three kinds of them are dominant. One is the discrete hexagonal column structure, the other is the pentagonal structure, and the third one is of well-oriented hexagonal columns with well-aligned structure. The explanation on the grown competition is discussed. ZnO hexagonal column structures with well-aligned and well-perpendicular to the surface were successfully obtained on Au/ITO substrate in aqueous solvent of electrolyte. Clearly the main columns in the film were obtained by increasing the temperature. Its photoluminescence (PL) study at low temperature exhibited the optical properties as wurtzite ZnO and indicated the existence of macrocrystalline ZnO. A better quality of ZnO columnar structures after annealing was demonstrated from PL analysis and discussion on the existence of 370 nm, 384 nm and 639 nm in the emission bands before and after annealing.     

Ga掺杂对ZnO纳米结构可见光发射的抑制效应

采用碳热还原反应和原位掺杂的方法制备了不同Ga掺杂浓度的ZnO纳米结构. X射线衍射 显示掺杂纳米结构中为单一的氧化锌纤锌矿结构. 扫描电子显微镜 观测发现随掺杂浓度的增大, 纳米结构的形貌逐渐从纳米六棱柱变为纳米锥.光致发光 和X射线光电子能谱 测量分别发现随着掺杂浓度升高, 纳米结构的可见发光强度和其中空位 氧峰相对强度逐渐减小直至消失, 两者存在很强的相关性. 上述结果为ZnO可见光发射的氧空位机理提供了新的实验证据. 对Ga掺杂抑制纳米结构中氧空位的原因进行了分析.     

Mg掺杂ZnO所致的禁带宽度增大现象研究

采用第一性原理的超软赝势方法，研究了纤锌矿ZnO及不同量Mg掺杂ZnO合金的电子结构.理论计算表明，Mg的掺杂导致ZnO晶体的禁带宽度增大.研究发现，Zn 4s态决定导带底的位置，Mg的掺入导致Zn 4s态向高能端的偏移是导致禁带宽度增大的根本原因. 关键词： 密度泛函理论 赝势 Mg掺杂ZnO     

Fabrication and photoluminescence of P doped ZnO nanobelts by thermal evaporation method

Uniform and flat single crystal ZnO:P nanobelts (NBs) were fabricated on Si (1 0 0) substrates by the thermal evaporation method. The growth process, free-catalyst self-assembly vapor-solid (V-S) mechanism, was described and investigated deeply in terms of thermodynamics and kinetics. Then, the photoluminescence (PL) properties of ZnO NBs were studied in a temperature range from 10 to 270 K. At 10 K the recombination of acceptor-bound exciton (A⁰X) was predominant in the PL spectrum, and was attributed to the transition of P_Zn−2V_Zn complex bound exciton. The active energy of A⁰X and acceptor binding energy were calculated to be 17.2 and 172 meV, respectively. The calculated acceptor binding energy of P doped ZnO nanostructure is in good agreement with that of P doped ZnO film.     

Microstructure and photoluminescence of MoOx decorated ZnO nanorods

Various MoO_x decorated ZnO nanorods (ZnO-MoO_x) samples were fabricated by physical vapor deposition of MoO_x on the surface of ZnO nanorods with varying deposition time and temperature. The microstructure and photoluminescence (PL) of the ZnO-MoO_x samples were investigated. It was found that the morphology of the ZnO nanorods is changed from hexagonal prisms to lotus-roots-like shapes by the decoration of MoO_x. The lotus-roots-like shapes may be formed by partial melting and evaporating of ZnO-MoO_x during the MoO_x decoration. This result shows that one can use the thermal instability of a nano-material to obtain an interesting structure, although a thermal instability should often be avoided. The intensity of the ultraviolet and visible light emission the of ZnO nanorods have different dependencies on the MoO_x decoration. Although the position of the ultraviolet light emission is not obviously changed by the MoO_x decoration, the ultraviolet light emission intensity is greatly weakened. In contrast, the intensity and position of visible light emission is largely changed. The blue shift of the visible light emission might be related to defects introduced by melting of the ZnO nanorods.     

Improved photoluminescence of BaMgAl10O17 blue phosphor prepared by spray pyrolysis

BaMgAl₁₀O₁₇:Eu²⁺ (BAM) blue phosphor particles with improved photoluminescence (PL) intensity under vacuum ultraviolet (VUV) excitation were prepared by a spray pyrolysis process. In order to improve the PL intensity, Er³⁺ and Nd³⁺ ions were used as co-doping elements. The VUV characteristics of BAM:Eu²⁺, M⁺ (M=Er, Nd) were monitored with varying the Er³⁺ and Nd³⁺ content in order to find the optimal co-doping concentration when they were prepared by spray pyrolysis. It was found that doping Er³⁺ or Nd³⁺ enhances the PL intensity of BAM:Eu²⁺ blue phosphor particles. In particular, the M³⁺ doping effect on the PL intensity was pronounced when the prepared BAM:Eu²⁺, M³⁺ particles were excited by 172 nm VUV. The maximum intensity was obtained when the M³⁺ content was 1.0 at% with respect to Ba element. The PL intensity of BAM:Eu²⁺, M⁺ (M=Er³⁺, Nd³⁺) particles was also further improved by producing them in a spherical shape, which was successfully achieved by controlling the spray solution. The optimized BAM:Eu²⁺, M⁺ particles had about 10% higher PL intensity than that of the commercial particles, which are made by a conventional solid-state reaction.     

Electrochromic and photoluminescence properties of cobalt oxide thin films prepared by spray pyrolysis

Cobalt oxide thin films were prepared by a facile spray pyrolysis technique, using a perfume atomizer with an aqueous solution of hydrated cobalt chloride salt with a molar concentration of 0.025?M as a source of cobalt. The films were deposited onto glass substrates at temperature of 350?°C. The structural, morphological, and electrochromic properties of the obtained films were studied. It was found from X-ray diffraction analysis that the films were polycrystalline in nature with spinel-type cubic structure and preferred orientation along [111] direction. The Scanning Electron Microscopy images revealed a porous structure with the average grain size around 200?nm. The cyclic voltammetry measurements revealed that Cobalt oxide thin film is an anodically coloring electrochromic material with a transmittance variation in the visible range of 31%, and a fast response time (about 2?seconds) and a good cycling stability. These electrochromic performances make cobalt oxide thin film an attractive material for using as an anodic electrochromic material in smart windows devices. The photoluminescence spectra exhibited a strong emission in the visible region confirming the good crystallinity properties of Co₃O₄ thin films.