铋化物发光玻璃中银表面等离激元对铒离子的发光增强作用

局域表面等离激元可以由自由空间的光直接激发,这也是局域表面等离激元的优点所在。研究铋化物发光玻璃中纳米银颗粒的表面等离激元对铒离子发光的增强效应、进一步的提高铋化物发光玻璃中铒离子的发光性能很有意义。首先,测量了(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃与(B)Er 3+(0.5%):铋化物发光玻璃样品的吸收谱,发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃在约600.0 nm处有一个较弱的宽的银表面等离激元共振吸收峰。同时发现两者都有典型的铒离子的吸收峰,它们的吸收几乎完全一样:在波峰形状、峰值强度和峰值波长等方面都很相近。测量了(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃和(B)Er 3+(0.5%):铋化物发光玻璃样品的激发谱,发现有位于379.0,406.0,451.0,488.0和520.5 nm的5个550.0 nm可见光的可见激发谱峰,和位于379.0,406.5,451.0,488.5,520.5,544.0,651.5和798.0 nm的8个1531.0 nm红外光的红外激发谱峰,容易指认出依次为Er 3+的4I 15/2→4G 11/2,4I 15/2→2H 9/2,4I 15/2→(4F 3/2,4F 5/2),4I 15/2→4F 7/2,4I 15/2→2H 11/2,4I 15/2→4S 3/2,4I 15/2→4F 9/2和4I 15/2→4I 9/2跃迁的吸收峰,通过测量发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃相对于(B)Er 3+(0.5%):铋化物发光玻璃样品的可见和红外激发谱的最大增强依次分别是238%和133%。最后,测量了它们的发光谱,发现有位于534.0,547.5和658.5 nm的三组可见发光峰,容易指认出依次为Er 3+的2H 11/2→4I 15/2,4S 3/2→4I 15/2,4F 9/2→4I 15/2荧光跃迁。还发现红外发光峰位于978.0和1531.0 nm,依次为Er 3+的4I 11/2→4I 15/2和4I 13/2→4I 15/2的荧光跃迁。通过测量发现(A)Er 3+(0.5%)Ag(0.5%):铋化物发光玻璃相对于(B)Er 3+(0.5%):铋化物发光玻璃样品的可见和红外发光谱的最大增强依次分别是215%和138%。对于银表面等离激元增强铒离子发光的机理,认为主要为纳米银颗粒的局域表面等离激元共振,造成金属纳米结构附近产生的局域电场的强度要远大于入射光的电场强度,从而导致了金属纳米结构对入射光产生强烈的吸收和散射,进而导致了荧光的增强;即局域表面等离子体共振局域场的场增强效应。     

ZnO:Er3+纳米晶的制备及发光性质研究

为了探讨稀土Er3 与纳米ZnO基质之间的能量传递,利用化学方法制备了ZnO:Er3 纳米晶,测量了样品的X射线衍射谱(XRD)、光致发光谱(PL)和激发谱(PLE).X射线衍射结果表明,ZnO:Er3 具有六角纤锌矿晶体结构.室温下,在365 nm激发下,在ZnO宽的可见发射背景上,观测到了Er3 的激发态4S3/2(550 nm),2H11/2(521 nm)和4F5/2(456 nn)的特征发射.分析了ZnO:Er3 纳米晶的带边发射和稀土Er3 的特征发射的峰值强度随掺Er3 浓度的变化关系,比较了ZnO:Er3 与未掺杂的ZnO的光致发射峰值强度的变化,给出了稀土Er3 的激发态4S3/2→4I15/2,2H11/2→4I15/2和4F5/2→4I15/2的发射机制,证实了纳米ZnO基质与稀土Er3 离子之间存在能量传递.     

Quantum cutting effect and photoluminescence emission at about 1,000 nm from Er–Yb co-doped ZnO nanoplates prepared by wet chemical precipitation method

ZnO nanoplates with Er-doping concentrations varying in the range from 3 to 7 wt% and co-doped with (Er–Yb) (7 + 7 wt%) were successfully prepared by wet chemical precipitation method. The effects of doping on the structural and optical properties of ZnO nanostructures have been systematically investigated. The structural morphology of the prepared nanostructures was found to change with increasing Er-doping concentrations. The visible photoluminescence and infrared photoluminescence of the prepared nanostructures were measured at room temperature. The intensity of visible emission spectra was found to increase with increasing Er-doping concentrations and was further enhanced for (Er–Yb) co-doped ZnO nanoplate samples. Additionally, Er-doped (7 wt%) and Yb-doped (7 wt%) ZnO nanoplates showed an enhanced emission peak at 950 nm, whereas two enhanced emission peaks at 950 and 980 nm have been found for (Er–Yb)-co-doped (7 + 7 wt%) ZnO nanoplates samples when excited at 310, 365 and 371 nm excitation wavelengths.     

微量Mg掺杂ZnO薄膜的光致发光光谱和带隙变化机理研究

利用射频磁控溅射(RF-MS)法在450℃玻璃基底上制备了Mg掺杂量分别为0.81at%,2.43at%和4.05at%的ZnO薄膜,对其微观结构、室温光致发光光谱(PL)、光学和电学性质进行了研究.结果发现,微量Mg掺杂ZnO薄膜晶体具有六方纤锌矿结构并保持高结晶质量;掺杂0.81at%和2.43at%Mg的ZnO薄膜室温PL谱中近带边发射(NBE)峰的短波方向出现了高能发射带与NBE峰同时存在;随着Mg掺杂量增加至4.05at%,这个高能发射带逐步将NBE峰掩盖.推测在Mg掺杂ZnO薄膜中,Mg2+替代Zn2+附近核外电子的能量增大并产生了一个高能级.而未被Mg2+替代的Zn2+周围的核外电子能量状态不变,带间能级依然存在,随着Mg掺杂量的增加处于高能级的电子数目逐步增加并占绝对优势.因此,ZnO薄膜随着Mg掺杂量增加薄膜禁带宽度增大,这是由于Mg掺杂后周围电子能量增大与Burstein-Moss效应共同作用的结果.另外,薄膜在可见光区域的平均透射率均大于85%,随着Mg掺杂量的增加,薄膜禁带宽度增大并在3.36—3.52eV内变化;Mg掺杂量为0.81at%,2.43at%和4.05at%时,薄膜电阻率分别为2.2×10-3,3.4×10-3和8.1×10-3Ω.cm.     

Er~(3+)/Tm~(3+)/Yb~(3+)共掺杂BaGa2ZnO5粉末的上转换发光

对Er~(3+)/Tm~(3+)/Yb~(3+)共掺杂BaGa_2ZnO5粉末的上转换发光特性进行了研究。首先,通过不同的制备工艺研究了BaGa2ZnO5粉末的生成条件。XRD分析表明,由于ZnO的高温分解,必须密封烧结并增加ZnO用量才能制备出BaGa2ZnO5。其次,测量了Er~(3+)/Tm~(3+)/Yb~(3+)共掺杂BaGa2ZnO5粉末在980nmLD激发下的上转换发射光谱,发现存在8个较强上转换发射峰,其中480nm和798nm对应于Tm~(3+)离子能级跃迁,其他上转换峰对应于Er~(3+)离子能级跃迁。另外,测量了980nmLD不同激发功率对应的上转换发射峰强度,并根据激发功率-上转换强度曲线拟合得到了各发射峰对应的多光子吸收过程。最后,根据上转换发射光谱和CIE1931标准数据计算了样品粉末的色坐标为(x=0.4151,y=0.4794) ,比较接近白光色坐标,说明所制备的粉末样品具有产生上转换白光的前景。     

La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

ZnO对EU:LiNbO3晶体的性能及光谱性质影响

应用坩埚下降法技术，以同成份化学摩尔分数[x（Li2O）=48．6％,x（Nb2O3）=51．4％]为原料，生长出了以不同Zn，Eu双掺杂的LiNbO3晶体。测定了晶体下部与上部的X射线衍射图（XRD）、激发光谱、荧光光谱以及声子边带谱。Zn的掺杂量对Eu^3＋离子在晶体中的分布产生很大的影响。Zn掺杂摩尔分数为3％时．Eu^3＋离子在进入品格时受到有效的压制。随着Zn掺杂摩尔分数提高，达到6％时，压制作用减弱。从Zn^2＋离子在LiNbO3中随浓度变化的分凝情况以及对Eu^3＋离子的排斥作用解释了Eu^3＋离子分布的原因。同时测定了Zn掺杂样品的声子边带谱。     

高浓度Er/Yb共掺ZnO薄膜的结构及室温光致发光特性

采用射频磁控溅射方法制备了Er/Yb共掺ZnO薄膜,研究了退火处理对高浓度Er/Yb共掺ZnO薄膜的结构演化和光致发光(PL)特性的影响。X射线衍射分析结果表明:Er/Yb掺杂导致ZnO薄膜的晶粒细化及择优取向性消失,ZnO晶粒随退火温度的增加而逐渐长大。900℃退火时,出现Er3 、Yb3 偏析,退火温度高于1000℃时,薄膜与基体间发生了界面反应,1200℃时,ZnO完全转变为Zn2SiO4相。光致发光测量结果表明:高于900℃退火处理后,Er/Yb共掺ZnO薄膜在1540 nm附近具有明显的光致发光,发光强度在退火温度为1050℃时达到最大值;光致发光光谱呈现典型的晶体基质中Er3 离子发光光谱所具有的明锐多峰结构特征。此外,探讨了薄膜结构演化及其对光致发光光谱的影响。     

Er^3＋／Yb^3＋共掺杂ZnO粉末的上转换发光特性

采用高温氧化法制备了Er3 /Yb3 共掺杂ZnO粉。通过X射线衍射和扫描电镜对其进行了成分和组织结构分析,发现样品主要由ZnO和YbF3组成。在ZnO中测量到少量Er3 和Yb3 ,而YbF3中无Er3 ,故发光主要是由ZnO产生的。在980nm半导体激光器的激发下,观察到由处于激发态能级4F9/2,4S3/2,2H11/2和2H9/2的Er3 离子向基态4I15/2跃迁时发出的波长依次为658,538,522和409nm的上转换发光。在488nmAr 激光器的激发下,观察到了较强的409nm的紫光,466和450nm的弱蓝光以及379nm的紫外光,分别对应于Er3 离子的2H9/2→4I15/2,2P3/2→4I11/2,4F3/2/4F5/2→4I15/2,4G11/2→4I15/2等跃迁。上转换发光强度随激发功率的变化关系表明,488nm激发下紫色上转换荧光为双光子过程,主要是通过Er3 /Yb3 离子间正向和反向的能量传递来实现的。     

Co与Cu掺杂ZnO薄膜的制备与光致发光研究

采用溶胶-凝胶旋涂法在玻璃衬底上制备了Co, Cu单掺杂及Co,Cu共掺杂ZnO薄膜.用金相显微镜观察了Co与Cu掺杂对ZnO薄膜形貌的影响.X射线衍射（XRD）研究揭示所有ZnO薄膜样品都存在（002）择优取向,在Cu单掺的ZnO薄膜中晶粒尺寸最大.对所有样品的室温光致发光测量都观察到较强的蓝光双峰发射和较弱的绿光发射,其中长波长的蓝光峰和绿光峰都能够通过掺杂进行控制.对不同掺杂源的ZnO薄膜发光性能进行了分析,认为蓝光峰来源于电子由导带底到锌空位能级的跃迁及锌填隙到价带顶的跃迁,绿光峰是由于掺杂造成的 关键词： ZnO薄膜 溶胶-凝胶 Co Cu掺杂 光致发光     

Superparamagnetic behaviour of cement clinker and its ferrite phase doped with different impurities

Two oxide mixtures of clinker and its ferrite phase of compositions (66.5 wt.% CaO+24.5 wt.% SiO₂+6.0 wt.% Al₂O₃+3.0 wt.% Fe₂O₃) and (60.4 wt.% CaO+15.4 wt.% Al₂O₃+24.2 wt.% Fe₂O₃) respectively were divided into protions and were mixed individually with 0.5, 1, 1.5 or 3 wt.% of LiF, MgF₂, CaF₂, CaCl₂ or ZnO. Each portion of clinker was fired at 1450°C and each portion of ferrite was fired at 1350°C for 30 min. then quenched in air. Mössbauer effect and X-ray diffraction measurements were performed on each sample. The impurities doping produced small particle size. The LiF doping gave the smallest particle size and the highest blocking temperature. The ferrite with LiF exhibited two Fe³⁺ sites while the other used impurities gave one site only. The superparamagnetic relaxation appeared only in the spectra of ferrite with impurities, which means that the impurities in clinker have a tendency to combine with the calcium silicate phases not with C₄AF.     

铕掺杂纳米氧化锌晶体结构和荧光光谱的研究

以醋酸锌、氧化铕、氢氧化钠为主要原材料,利用共沉淀法制备ZnO∶Eu3+纳米晶体.在X射线衍射谱中,只观察到氧化锌的峰,没有观察到氧化铕的特征峰.比较了ZnO和ZnO∶Eu3+拉曼光谱,在ZnO∶Eu3+样品拉曼光谱中观察到新的局部振动模.这些现象表明铕离子已经进入氧化锌晶格中.SEM形貌显示Eu3+离子掺入使ZnO晶...     

掺铟氧化锌纳米阵列的制备、结构及性质研究

通过碳热辅助化学气相沉积法,用Au做催化剂在850℃下制备了铟掺杂的氧化锌（In/ZnO）纳米阵列.纳米棒的尺寸均匀,表面光滑,直径约为400 nm,长为2—3 μm.能量色散谱和X射线光电子能谱分析表明, 六棱柱状的纳米阵列中成功地进行了In 的掺杂,含量约为08%.室温光致发光谱显示掺杂后的紫外发射峰位有红移,峰的半高宽变大, 没有观察到绿光发射峰位.拉曼光谱显示出ZnO的峰位有不同程度的偏移,并且有新的峰位出现,这表明In的掺杂有效地取代了部分Zn的晶格. 关键词： In掺杂 ZnO 纳米阵列 光致发光     

Fe掺杂对溶胶凝胶法制备的ZnO: Ni薄膜结构及发光特性的影响

采用溶胶凝胶法在玻璃基片上制备了ZnO及Ni, Fe共掺杂的Zn_0.95-xNi_0.05Fe_xO (x=0, 0.005, 0.01, 0.03, 0.05) 薄膜. 通过扫描电镜(SEM) 和X射线衍射(XRD) 研究了薄膜样品的表面形貌和晶体结构. 结果表明所有样品都具有(002) 择优取向, Fe掺杂导致ZnO: Ni薄膜的晶体质量变差, 晶粒尺寸减小, 但适当的Fe掺杂有利于获得致密、 均匀的薄膜. XPS测试结果表明样品中Ni离子的价态为+2价, Fe离子的价态为+2价和+3价.室温光致发光(PL) 测量表明, 所有样品均观察到较强的紫外发光峰, 蓝光双峰和绿光发光峰. ZnO: Ni薄膜的发光强度可以通过Fe掺杂进行有效调节. 进而我们讨论了Ni, Fe共掺杂ZnO样品的发光机理.     

Er~(3+)、Pr~(3+)共掺杂AlN薄膜的发光特性和能量传递机理

采用离子注入的方法在氮化铝(AlN)薄膜中实现Er~(3+)和Pr~(3+)的共掺杂,以阴极荧光光谱仪为主要表征手段,对其发光特性进行研究.对于Er~(3+)单掺杂的AlN薄膜,在410nm和480nm可以观察到Er~(3+)较强的发光峰,在537nm、560nm、771nm和819nm可观察到Er~(3+)的较弱的发光峰;对于Pr~(3+)单掺杂的AlN薄膜,Pr~(3+)的最强发光峰位于528nm,在657nm和675nm可以观察到Pr~(3+)的较弱的发光峰;而对于Er~(3+)和Pr~(3+)共掺杂的AlN薄膜,在494nm观察到与Pr~(3+)相关的新跃迁峰.根据实验现象,对AlN薄膜中Er~(3+)和Pr~(3+)之间的能量传递机制进行了深入分析,结果表明Er~(3+)的4F7/2→4I15/2能级跃迁与Pr~(3+)的3P0→3H4能级跃迁之间发生了共振能量传递,从而使Pr~(3+)产生了494nm新的发光峰.     

N掺杂ZnO薄膜的荧光特性研究

以N2为掺杂源,通过改变O2∶N2比,利用射频磁控溅射法在玻璃衬底上制备了具有[002]择优取向的N掺杂ZnO薄膜,研究了ZnO薄膜的光致发光谱随着N掺入量的不同而变化的规律.结果表明,薄膜主衍射峰为402 nm处的发光峰;由于N掺杂量的不同,有的薄膜在445 nm和524 nm处也有发光发存在,但随着薄膜N含量的不同,其发光峰强度明显不同,其峰位也发生了相应的红移或者蓝移.当O2∶N2为10∶ 15时,制备的薄膜N掺杂量最大,光学性能最好,此工艺为研究ZnO薄膜的缺陷类型及导电类型提供了重要的研究参考.     

Nanomaterial electronic structure investigation by valence electron energy loss spectroscopy - an example of doped ZnO nanowires

The effects of doping (by ion implantation) on the electronic structure of ZnO nanowires, particularly on the defect states generation in the band gap of ZnO, are investigated using valence electron energy loss spectroscopy (VEELS) performed in a transmission electron microscope (TEM). The improved spectrum energy resolution via the introduction of a gun monochromator, together with the reduced intensity in the zero loss peak tail as realized by spectrum acquisition at non-zero momentum transfer, enable us to extract such electronic structure information from the very low loss region of the EEL spectra. We have compared the doping effects of several dopant elements, i.e., Er, Yb, and Co, and found that generation of the band tail states ( approximately 2-3.3eV) is a common consequence of the ion implantation process. On the other hand, specific mid-gap state(s) in the lower energy range are created only in the rare earth element doped ZnO nanowires, suggesting the dopant-sensitive nature of such state.     

Sol-gel preparation and enhanced photocatalytic performance of Cu-doped ZnO nanoparticles

Cu-doped ZnO nanoparticles were prepared by a sol-gel method for the first time. XRD, XPS, UV-vis and FS techniques were used to characterize the Cu-doped ZnO samples. The photocatalytic activity was tested for methyl orange degradation under UV irradiation. The results show that the crystal sizes of ZnO and 0.5% Cu/ZnO nanoparticles with wurtzite phase are 32.0 and 28.5 nm, indicating that Cu-doping hinder the growth of crystal grains. The doped Cu element existed as Cu²⁺. The optimal Cu doping concentration in ZnO is 0.5%. The optimal calcination condition is at 350 °C for 3 h. The MO degradation rate of 0.5% Cu/ZnO reaches 88.0% when initial concentration of MO is 20 mg/L, exceeding that of undoped ZnO. The enhanced charge carrier separation and increased surface hydroxyl groups due to Cu-doping contributed to the enhanced photocatalytic activity of 0.5% Cu/ZnO.     

Ni掺杂ZnO薄膜的荧光特性

采用脉冲激光沉积技术(PLD)在单晶Si 衬底上制备了Ni掺杂的ZnO薄膜,通过VARAIN Cary-Eclips 500型荧光光谱仪研究了样品的荧光特性。观察到360和380 nm左右2个荧光峰。通过Ni掺杂,研究了360 nm左右荧光峰的起源。结果表明,随着靶材中Ni掺杂量的不同,荧光峰峰位不变,而相应的发光强度发生了明显的变化。当靶材中Ni∶ZnO的摩尔比X_s为5％时,样品中360 nm紫外荧光峰的发光强度最佳,表明360 nm左右荧光峰并不是重掺杂后杂质能级深入到导带的结果,有可能是起源于分裂的价带与导带间的复合跃迁。     

Green electroluminescence from an n-ZnO: Er/p-Si heterostructured light-emitting diode

Erbium-doped ZnO (ZnO:Er) thin films with various doping concentrations were deposited on p-Si substrates by ultrasonic spray pyrolysis (USP). The n-ZnO:Er/p-Si heterojunctions were further employed to fabricate light-emitting diodes (LEDs). The devices showed diode-like rectifying current–voltage characteristics with a low reverse breakdown voltage, attributed to the avalanche breakdown. A distinct green electroluminescence peaking at 537 nm and 558 nm were observed at room temperature under reverse bias. The green electroluminescence originated from the electron impact excitation of Er³⁺ ions doped in ZnO films.