室温离子液体中超声辐照制备氧化锌纳米棒的研究

离子液体与超声技术结合在纳米材料的制备中具有广阔的前景,但目前以离子液体为溶剂超声制备纳米材料的报道还不多见,相关的反应机理研究也亟待开展.本文首次在室温离子液体1-丁基-3-甲基咪唑四氟硼酸盐中超声制备了氧化锌纳米棒,该方法具有简便、快速和环境友好等特点.采用X射线衍射(XRD)、透射电子显微镜(TEM)对纳米氧化锌的结构和形貌进行表征.作为比较研究,采用传统的低蒸汽压有机溶剂二缩三乙二醇在同样的超声反应条件制备了纳米氧化锌材料.离子液体中超声合成样品为直径约20 nm,长度30-50 nm的纳米棒,而在二缩三乙二醇中超声制备的样品为直径6～8 nm的纳米颗粒.利用光声光谱(PAS)研究了纳米氧化锌样品的光学性能和量子尺寸效应.对离子液体中超声制备氧化锌纳米棒可能的反应机理进行了讨论并建立了的反应模型.结果表明在在超声辐照和离子液体溶剂的共同作用下氧化锌纳米棒得以生成.     

氧和氩等离子辅助电子束蒸发制备高质量ZnO薄膜

采用等离子辅助电子束蒸发技术制备高纯金属锌膜，然后在氧气气氛下经高温热处理得到氧化锌的多晶薄膜。X射线衍射谱的结果表明：未经热氧化样品由金属锌和氧化锌纳米晶组成，随着热氧化温度的升高氧化锌纳米晶粒长大，形成纳米氧化锌多晶薄膜且薄膜结晶性增强；光致发光谱表明：样品均具有较强的紫外自由激子发光。由于未经热氧化样品中氧化锌纳米晶粒较小，具有较强的量子限域效应，因而经高温氧化后样品发光峰有较大红移。随着热氧化温度的进一步升高，束缚激子发射随热氧化温度升高而减弱，且发光峰位随热氧化温度升高出现蓝移；变温光致发光谱表明：紫外发光主要来自自由激子发射。     

补偿离子掺杂与烧成温度对SrTiO3:0.002Pr3+ 材料的红色发光特性的影响

采用高温固相反应法合成SrTiO3：Pr^3＋系发光材料,利用荧光光谱、XRD等分析手段,研究了工艺参数,如不同价态K、Ca和Al离子掺杂,以及1050～1300℃不同烧成温度对SrTiO3：Pr^3＋体系发光性能的影响,以获得具有较好综合发光性能的SrTiO3：Pr^3＋系发光材料。选择不同价态补偿离子掺杂是为了研究电荷补偿作用机制对该类材料发光性能的作用。结果表明：随着烧成温度的升高,磷光体发光强度先增加后减弱,在1150℃烧成的材料其发光强度最大。无补偿掺杂与K、Ca或Al离子掺杂的所有样品均发出源于Pr^3＋的^1D2→^3H4跃迁的610nm红色光。在不同价态补偿离子掺杂样品中,以掺Al的SrTiO3：Pr^3＋体系发光强度最好;其发光强度比无补偿离子掺杂SrTiO3：Pr^3＋材料的发光强度提高10倍左右。另一方面,与Al离子具有类似的引入阴离子电荷缺陷的K离子掺杂材料的发光强度则基本没有变化,其发光强度与没有电荷补偿作用的无掺杂及Ca离子掺杂SrTiO3：Pr^3＋材料相似。上述实验结果可从电荷缺陷及微观固溶结构两方面的联合作用机制进行解释。在引入电荷缺陷的掺杂体系中,只有在发光离子PrSr^＋最近邻的Ti格位引入的电荷缺陷才能有效地起电荷补偿作用,达到增强发光强度的作用。研究结果给出了合理的制备工艺条件,并且提供了一种可有效提高发光强度的补偿离子掺杂的选择依据。     

利用声致发光成像技术的液体中超声场动态分布的实时测量方法

根据超声空化原理,运用声致发光成像技术测量超声在液体中的动态分布。利用高灵敏度的ICCD成像系统记录水在超声作用下的声致发光图像,并且分析了声致发光的分布和强度与作用超声的关系。结果表明,超声作用下的发光图像能够反映该作用超声在水中的分布情况,从而提出利用声致发光成像技术测量液体中超声场的分布是一种动态测量声场强度的新方法。     

稀土配合物掺杂凝胶的原位光声光谱研究及其共发光效应

采用溶胶-凝胶方法,制备了Ln(Sal)₃·H₂O(Ln3+∶La3+, Nd3+, Tb3+; Sal: 水杨酸) 稀土配合物掺杂的二氧化硅凝胶样品。首次采用光声光谱对稀土配合物在凝胶中的形成进行研究。结果表明,经110 ℃热处理后,Tb3+, La3+和Nd3+配合物掺杂的凝胶样品在配体吸收处的光声强度依次明显增强;而对仅在室温陈化、干燥的湿凝胶样品,其配体吸收处的光声强度几乎完全相同。研究发现,未经适当的热处理过程凝胶样品中稀土配合物尚不能形成。结合荧光光谱,分析了凝胶中稀土离子配位环境的变化和稀土配合物的形成。首次发现了稀土芳香羧酸配合物掺杂凝胶的共发光效应,考察Tb_0.8Gd_0.2(Sal)₃·H₂O和Tb_0.8Nd_0.2(Sal)₃·H₂O配合物掺杂的凝胶样品,发现Gd3+离子的引入了增强了凝胶样品中Tb3+的发光效率,而Nd3+离子的引入明显减弱了凝胶中Tb3+的发光,并对共发光效应可能的机理进行了讨论。     

Er3+,Yb3+共掺杂NaGd（MoO4）2荧光粉的发光特性

采用高温固相法制备了Er3+,Yb3+共掺杂的NaGd(MoO4)2荧光粉,通过X射线衍射对样品的物相结构进行了分析,采用荧光光谱手段对样品的下转换发光特性和上转换发光特性进行了研究。通过对激发、发射光谱的分析,发现基质到Er3+存在有效的能量传递。通过对样品上转换发光光谱的分析,发现在不同Yb3+掺杂浓度样品中,红光和绿光上转换发光均为双光子过程,并对样品上转换发光强度与LD泵浦电流和掺杂离子浓度的关系进行了讨论。     

补偿离子掺杂与烧成温度对SrTiO_3∶0.002Pr~(3+)材料的红色发光特性的影响

采用高温固相反应法合成SrTiO3∶Pr3+系发光材料,利用荧光光谱、XRD等分析手段,研究了工艺参数,如不同价态K、Ca和A l离子掺杂,以及1 050~1 300℃不同烧成温度对SrTiO3∶Pr3+体系发光性能的影响,以获得具有较好综合发光性能的SrTiO3∶Pr3+系发光材料。选择不同价态补偿离子掺杂是为了研究电荷补偿作用机制对该类材料发光性能的作用。结果表明:随着烧成温度的升高,磷光体发光强度先增加后减弱,在1 150℃烧成的材料其发光强度最大。无补偿掺杂与K、Ca或A l离子掺杂的所有样品均发出源于Pr3+的1D2→3H4跃迁的610 nm红色光。在不同价态补偿离子掺杂样品中,以掺A l的SrTiO3∶Pr3+体系发光强度最好;其发光强度比无补偿离子掺杂SrTiO3∶Pr3+材料的发光强度提高10倍左右。另一方面,与A l离子具有类似的引入阴离子电荷缺陷的K离子掺杂材料的发光强度则基本没有变化,其发光强度与没有电荷补偿作用的无掺杂及Ca离子掺杂SrTiO3∶Pr3+材料相似。上述实验结果可从电荷缺陷及微观固溶结构两方面的联合作用机制进行解释。在引入电荷缺陷的掺杂体系中,只有在发光离子PrS+r最近邻的Ti格位引入的电荷缺陷才能有效地起电荷补偿作用,达到增强发光强度的作用。研究结果给出了合理的制备工艺条件,并且提供了一种可有效提高发光强度的补偿离子掺杂的选择依据。     

稀土钇、镧掺杂TiO2薄膜的拉曼谱分析

采用溶胶-凝胶法在石英玻璃衬底上用旋涂法制备了未掺杂、掺杂钇和掺杂镧的TiO₂薄膜样品,对样品在700—1100 ℃范围内进行退火处理,并对样品的拉曼光谱进行了分析.分析表明:随着退火温度的升高,未掺杂TiO₂薄膜发生了从锐钛矿相经混相最终向金红石相的转换,掺杂钇和掺杂镧对TiO₂薄膜的晶相转换起阻碍作用,掺杂镧的阻碍作用更强;稀土掺杂能使TiO₂薄膜晶粒细化,并使晶粒内部应力增大从而阻碍晶格振动,掺杂镧比掺杂钇的效果 关键词： 2薄膜')" href="#">TiO₂薄膜 稀土掺杂 拉曼光谱 溶胶-凝胶     

镉掺杂氧化锌纳米晶禁带宽度的尺寸效应和掺杂效应研究（英文）

本文采用超声化学法快速简便地制备了在量子限制区域的镉掺杂氧化锌纳米晶.X-射线衍射、透射电镜和红外光谱的分析结果证实纳米晶样品具有合金结构.当镉对锌摩尔比从0增加到2.0,纳米晶的尺寸从5.1 nm减少到2.6 nm,其禁带宽度先出现红移,然后蓝移,最后又发生红移.研究表明量子尺寸效应和掺杂效应可以很好地解释上述禁带宽度的变化.通过对比实验研究发现,超声空化产生非热力学平衡的化学反应条件以及三甘醇溶剂的配位性质对镉掺杂氧化锌纳米晶的形成起重要作用.     

光子晶体增强中红外发光研究EI北大核心CSCD

稀土掺杂硫系玻璃是实现中红外发光的重要手段,通过在稀土掺杂硫系玻璃样品上构造光子晶体结构可以大大增强其发光效率。制备了Tm3+离子掺杂硫系玻璃样品并测试了其光谱特性,通过设计光子晶体结构来增强Tm3+离子跃迁产生的3.73 mm处的荧光强度。利用有限时域差分法(FDTD)进行运算,模拟结果表明,通过优化设计的光子晶体结构参数,掺杂样品在3.73 mm处的光子态密度相比于未采用光子晶体结构所产生的光子态密度有极大提高,计算其Purcell放大因子可达到未进行结构设计的50倍以上。光子态密度的极大提高以及Purcell放大因子为增强发光强度提供了理论依据,该研究结果对实现高效率中红外光源器件具有重要的指导意义。     

Ultrasound and ionic liquid: an efficient combination to tune the mechanism of alkenes epoxidation

In this proof of concept study, the advantageous properties of both H₂O₂/NaHCO₃/imidazole/Mn(TPP)OAc oxidation system and MOPyrroNTf₂ ionic liquid have been combined under ultrasonic irradiation to give an exceptionally favorable environment for Mn(TPP)OAc catalyzed olefin oxidations. The results reveal the crucial role played by the ultrasonic irradiations that influence drastically the oxidation process. In MOPyrroNTf₂ and under ultrasonic irradiation, the mechanism probably involves an oxo-manganyl intermediate at the expense of the classical bicarbonate-activated peroxide route.     

Structural and optical properties of germanium-doped zinc oxide nanorods as a function of annealing temperature

Zinc oxide nanorods with germanium doping were prepared by ion implantation and annealing treatment method, the microstructural and optical properties of which were studied by means of the X-ray diffraction, photoluminescence, and transmission electron microscopy measurements. The pristine sample exhibited a remarkable ultraviolet emission owing to the band edge emission from the zinc oxide matrix, indicated a good crystalline quality. Three emission peaks appeared after germanium ions were doped into zinc oxide nanorods. The 513?nm photoluminescence peak was ascribed to the transition between the vacancy defect in zinc oxide matrix. Photoluminescence peaks located at 548 and 778?nm were ascribed to germanium ions luminescence center in zinc germanate grain and germanium monoxide luminescence center. The light emission tuning was obtained by germanium doping and annealing treatment, which may help the development of the practical optoelectronic devices based on zinc oxide nanomaterials.     

Destabilization of ultrafine bubbles in water using indirect ultrasonic irradiation

Ultrafine bubble (UFB) is a bubble with a diameter of less than 1 μm. Little attention has been paid to the defoaming and removal of UFBs. This study proposes a method to destabilize UFBs by using indirect ultrasonic irradiation. Besides, the destabilization mechanism of UFB was investigated. The ultrasonic frequency was 1.6 MHz and the dissipated power was 30 W. UFB dispersions were prepared using two different types of bubble generators: pressurized dissolution method and swirling liquid flow method. The effects of ultrasonic irradiation on the stability of UFBs were evaluated by particle tracking analysis (PTA) and electrophoretic zeta potential measurement. Results showed that the indirect ultrasonic irradiation for 30 min reduced the number concentration of UFBs by 90% regardless of the generation method. This destabilization was attributed to a decrease in the magnitude of zeta potential of UFBs due to the changes in pH and electrical conductivity. These changes in the electrochemical properties were caused by the formation of nitric acid. To study the destabilization mechanism, the pH of the UFB dispersions were modified by titration; the chemical and mechanical effects of ultrasound were separately examined. It was found that not only the chemical effect caused by the formation of nitric acid but also the mechanical effect contributed to the destabilization of UFB. Feasibility studies were also performed for UFBs in an aqueous surfactant solution and UFBs in a solid particle dispersion. The proposed method selectively destabilized UFBs in the solutions.     

Study on the spatial distribution of the liquid temperature near a cavitation bubble wall

A simple new model of the spatial distribution of the liquid temperature near a cavitation bubble wall (T_li) is employed to numerically calculate T_li. The result shows that T_li is almost same with the ambient liquid temperature (T₀) during the bubble oscillations except at strong collapse. At strong collapse, T_li can increase to about 1510 K, the same order of magnitude with that of the maximum temperature inside the bubble, which means that the chemical reactions occur not only in gas-phase inside the collapsing bubble but also in liquid-phase just outside the collapsing bubble. Four factors (ultrasonic vibration amplitude, ultrasonic frequency, the surface tension and the viscosity) are considered to study their effects for the thin liquid layer. The results show that for the thin layer, the thickness and the temperature increase as the ultrasonic vibration amplitude rise; conversely, the thickness and the temperature decrease with the increase of the ultrasonic frequency, the surface tension or the viscosity.     

Effect of laser annealing using high repetition rate pulsed laser on optical properties of phosphorus-ion-implanted ZnO nanorods

The effect of high repetition rate pulsed laser annealing with a KrF excimer laser on the optical properties of phosphorus-ion-implanted zinc oxide nanorods has been investigated. The recovery levels of phosphorus-ion-implanted zinc oxide nanorods have been measured by photoluminescence spectra and cathode luminescence images. Cathode luminescence disappeared over 300 nm below the surface due to the damage caused by ion implantation with an acceleration voltage of 25 kV. When the annealing was performed at a low repetition rate of the KrF excimer laser, cathode luminescence was recovered only in a shallow area below the surface. The depth of the annealed area was increased along with the repetition rate of the annealing laser. By optimizing the annealing conditions such as the repetition rate, the irradiation fluence and so on, we have succeeded in annealing the whole damaged area of over 300 nm in depth and in observing cathode luminescence. Thus, the effectiveness of high repetition rate pulsed laser annealing on phosphorus-ion-implanted zinc oxide nanorods was demonstrated.     

Morphology and optical properties of zinc oxide nanostructures synthesized by the methods of thermal and discharge sputtering

Zinc oxide nanostructures are obtained by the methods of electrothermal and discharge sputtering in gaseous and liquid media. Structure and phase peculiarities of synthesized samples, as well as morphology and luminescence properties of synthesized structures with and without doping are examined. The luminescence spectra of the deposited zinc oxide nanostructures have characteristic luminescence maxima (at λ = 380 and 520 nm) associated with exciton emission and defects in nanocrystals, respectively.     

Numerical investigation on acoustic cavitation characteristics of an air-vapor bubble: Effect of equation of state for interior gases

The cavitation dynamics of an air-vapor mixture bubble with ultrasonic excitation can be greatly affected by the equation of state (EOS) for the interior gases. To simulate the cavitation dynamics, the Gilmore-Akulichev equation was coupled with the Peng–Robinson (PR) EOS or the Van der Waals (vdW) EOS. In this study, the thermodynamic properties of air and water vapor predicted by the PR and vdW EOS were first compared, and the results showed that the PR EOS gives a more accurate estimation of the gases within the bubble due to the less deviation from the experimental values. Moreover, the acoustic cavitation characteristics predicted by the Gilmore-PR model were compared to the Gilmore-vdW model, including the bubble collapse strength, the temperature, pressure and number of water molecules within the bubble. The results indicated that a stronger bubble collapse was predicted by the Gilmore-PR model rather than the Gilmore-vdW model, with higher temperature and pressure, as well as more water molecules within the collapsing bubble. More importantly, it was found that the differences between both models increase at higher ultrasound amplitudes or lower ultrasound frequencies while decreasing as the initial bubble radius and the liquid parameters (e.g., surface tension, viscosity and temperature of the surrounding liquid) increase. This study might offer important insights into the effects of the EOS for interior gases on the cavitation bubble dynamics and the resultant acoustic cavitation-associated effects, contributing to further optimization of its applications in sonochemistry and biomedicine.     

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.     

Spectrometric Studies on the Sonodynamic Damage of Protein in the Presence of Levofloxacin

Taking bovine serum albumin (BSA) as typical molecules, the sonodynamic damage of protein in the presence of Levofloxacin (LVFX) and its mechanism were studied by fluorescence and UV-vis spectra. Various influencing factors such as ultrasonic irradiation time, pH value, ionic strength and solution temperature on the damage of BSA were also discussed. The results showed that ultrasound can enhance the damage of LVFX on BSA. The damage degree of BSA was aggravated with the increase of ultrasonic irradiation time, solution temperature and ionic strength, whereas decreased with the increase of solution pH value. Furthermore, the reactive oxygen species (ROS) in reaction system were studied by oxidation and extraction photometry. Experimental results showed that the amounts of superoxide anion radical (·O₂ ^ˉ) and hydroxyl radical (·OH) were significantly more than that of singlet oxygen (¹O₂) in the presence of LVFX under ultrasonic irradiation.     

稀土Tb3+掺杂纳米ZnO的发光性质

ZnO是一种优良的直接宽带隙半导体发光材料(Eg=3.4 eV),具有优异的晶格、光学和电学性质,稀土离子掺杂浓度和热处理温度对ZnO∶Re3 纳米晶发光强度、峰位变化等光学性质具有重要影响.利用溶胶-凝胶法(Sol-Gel),在不同退火温度下,制备了不同浓度的ZnO∶Tb3 纳米晶.室温下,测量了样品的X射线衍射谱(XRD)、光致发光谱(PL)和激发谱(PLE).观察到纳米ZnO基质在520 nm附近宽的绿光可见发射和稀土Tb3 在485,544,584和620 nm附近的特征发射.通过ZnO基质可见发射强度和稀土Tb3 特征发射强度随Tb3 掺杂浓度、退火温度的变化关系,获得了5D4→7F5跃迁的绿色主发射峰最强的样品制备工艺参数,其退火温度为600℃、掺杂浓度为4 at%;给出了稀土Tb3 的激发态5D4→7F6(485 nm),5D4→7F5(544 nm)和5D4→7F4(584 nm)的发射机制;证实了稀土Tb3 与纳米ZnO基质之间存在双向能量传递.