稀土掺杂氧化物纳米发光材料研究

综述了稀土掺杂纳米发光材料方面的研究进展;主要介绍稀土掺杂氧化物纳米晶与体相材料相比所具有的一些特有的光谱学性质,包括光谱的移动与谱线的展宽、4fN电子的跃迁与弛豫过程、表面局域环境和格位对称性、电子-声子耦合、能量传递、浓度猝灭、温度猝灭以及光诱导发光强度变化等光谱现象,同时也探寻了其中的物理实质。主要对上转换纳米发光材料和一维纳米线/管的发光性质进行了介绍。     

Ni掺杂提高紫光CsPbCl3钙钛矿纳米晶的发光热稳定性

为了提高紫光CsPbCl_3纳米晶的发光热稳定性,研究了不同掺杂浓度的Ni离子对CsPbCl_3纳米晶的结构和发光性质的影响。通过改变Ni/Pb进料量比,在190℃温度下制备出不同浓度Ni掺杂的CsPbCl_3(Ni∶CsPbCl_3)纳米晶。发现随着Ni/Pb进料量比的增加,Ni∶CsPbCl_3纳米晶的405 nm发光量子效率得到了较大的提高,高达54%,但当Ni/Pb进料比超过4∶1之后,Ni∶CsPbCl_3纳米晶的发光量子效率开始下降,这是由于氯化镍的浓度过高,影响了CsPbCl_3纳米晶的成核和生长过程。还观察到,随着Ni/Pb进料比的增加,Ni∶CsPbCl_3纳米晶的平均尺寸逐渐减小,晶格变得更加有序。通过对不同浓度的Ni∶CsPbCl_3纳米晶的变温光谱测量,发现Ni离子明显地减少CsPbCl_3纳米晶的发光热猝灭,有效地改善了其发光热稳定性。实验结果表明,Ni离子掺杂有效地提高了紫光CsPbCl_3纳米晶的发光效率,可能归因于Ni离子掺杂减少了CsPbCl_3纳米晶中的缺陷。     

Eu3+:Y态效应2O3纳米微粒的尺寸效应和表面的研究

通过相同掺杂浓度但不同颗粒尺寸的Eu:Y2O3纳米晶,和相同颗粒尺寸但掺杂浓度不同的纳米晶的发光衰减曲线研究了表面态和限域作用对能量传递的影响.纳米晶与体材料相比,有更高的猝灭浓度,分析了纳米材料中发光中心的猝灭浓度提高的原因.由于纳米材料与体材料相比,纳米晶中的缺陷密度很小,纳米晶中有较少的体猝灭中心.选择合适的颗粒尺寸并对其进行表面修饰,将获得较高发光效率和较高的猝灭浓度.     

基于单个金纳米棒的表面等离子体共振增强单个纳米晶上转换发光

稀土离子掺杂上转换纳米晶在生物成像和光伏领域具有广泛的应用前景,但其较低的上转换效率限制了其应用。利用原子力显微镜探针在纳米尺度下操控单个金纳米棒与单个上转换纳米晶耦合,通过单颗粒光谱学研究了金纳米棒局域表面等离子体共振对纳米晶上转换发光的影响。结果表明纳米晶上转换发光强度对激发光的偏振方向具有强烈的依赖性。当激发光偏振方向平行于金纳米棒长轴时,纳米晶的绿色和红色上转换发光可以分别获得最大增强倍数为18和40的发光增强。     

核壳结构纳米颗粒Gd2O3:Tb3+/SiOx的制备及发光性能研究

以二甘醇为溶剂合成Gd2O3:Tb3+纳米颗粒,并在其表面包覆聚硅氧烷层,得到核壳结构纳米颗粒Gd2O3∶Tb3+/SiOx。为了研究Tb3+离子掺杂浓度对纳米颗粒发光性能的影响,采用几种不同Tb3+掺杂浓度进行纳米颗粒的合成,并对其发光性能进行了检测。结果表明:包裹聚硅氧烷层后的Gd2O3∶Tb3+纳米颗粒分散较好,聚硅氧烷层不会减弱Gd2O3∶Tb3+纳米颗粒的发光性能。Tb3+掺杂浓度对核壳结构纳米颗粒Gd2O3∶Tb3+/SiOx的发光存在浓度猝灭现象,猝灭摩尔分数为5%。这种具有发光特性的核壳结构纳米颗粒可作为生物传感器的探针用于生物分子的检测。     

Eu^3＋：Y2O3纳米微粒的尺寸效应和表面态效应的研究

通过相同掺杂浓度但不同颗粒尺寸的Ｅｕ：Ｙ２Ｏ３纳米晶，和相同颗粒尺寸但掺杂浓度没的纳米晶的发光衰减曲线研究了表面态和限域作用对能量传递的影响。纳米晶与体材料相比，有更高的猝灭浓度，分析了纳米材料中发光中心的猝灭浓度提高的原因。由于纳米材料与体材料相比，纳米晶中的缺陷密度很小，纳米晶中有较少的体猝灭中心。选择合适的颗粒尺寸并对其进行表面修饰，将获得较高发光效率和较高的猝灭浓度。     

瞬态荧光方法研究溶剂诱导的三苯胺衍生物的对称性破缺电荷转移动力学

在缺乏特征红外振动的情况下追踪具有四极或八极对称性分子的激发态对称性破缺电荷转移通常是很困难的.本文以一种具有八极对称性的三苯胺衍生物为研究对象,利用飞秒时间分辨瞬态荧光光谱方法获得发光跃迁偶极矩的演化动力学,进而实时表征了其溶剂诱导对称性破缺电荷转移的动力学过程.当该分子处于弱极性甲苯溶液中时,在激发态弛豫过程中其发射偶极矩变化较小;当处于较强极性的四氢呋喃溶液中时,其发射偶极矩在数皮秒内快速减小.在对比单体偶极分子的荧光动力学后,推断八极分子的发光态在强极性溶剂中经历溶剂诱导的结构变化,由激子耦合的八极对称性降低至激发定域的偶极对称性;而在较弱极性的溶剂中,其八极对称性在溶剂化稳定中得以较大程度的保持.     

ZnO:Tb纳米晶的协同发光现象

用光致发光的方法研究了掺铽的ZnO纳米晶这种新型掺杂纳米晶体系,观察到了其中的协同发光现象,指出ZnO纳米基质与掺入其中的铽中心之间存在有效的能量传递.该能量传递对稀土铽离子的特征发光起决定性的作用. 关键词： 光致发光 掺杂 纳米晶     

非稀土掺杂协同核壳包裹对氟化物纳米晶上转换发光性能的增强

为提高上转换纳米晶的发光效率,提出协同增强的策略,将核壳包裹和非稀土离子掺杂两种方式进行有效的结合,使上转换纳米晶的发光效率实现"1+12"的增强效果。以Na Gd F_4作为基质材料,Yb~(3+)和Er~(3+)分别作为敏化离子和发光离子,以Li~+离子和Na Gd F_4作为非稀土掺杂离子和包裹壳层来构建核/壳纳米结构,研究两种增强方式的协同作用对Na Gd F4∶Yb~(3+)/Er~(3+)纳米晶的上转换发光性能的影响。结果表明,Li+离子掺杂与包裹Na Gd F4壳层共同作用使得β-Na Gd F4∶Yb~(3+)/Er~(3+)纳米晶的上转换发光增强了39倍,明显优于单一方式的增强效果。通过一系列的优化实验结果发现,Li+离子的最佳掺杂摩尔分数为4%。基于以上实验结果,给出了非稀土离子掺杂核壳纳米晶协同增强上转换发光效率的机理。     

Eu~(3+):Y_2O_3纳米微粒的尺寸效应和表面态效应的研究

通过相同掺杂浓度但不同颗粒尺寸的Ｅｕ：Ｙ２Ｏ３纳米晶，和相同颗粒尺寸但掺杂浓度不同的纳米晶的发 光衰减曲线研究了表面态和限域作用对能量传递的影响。纳米晶与体材料相比，有更高的猝灭浓度，分析了纳 米材料中发光中心的猝灭浓度提高的原因。由于纳米材料与体材料相比，纳米晶中的缺陷密度很小，纳米晶中 有较少的体猝灭中心。选择合适的颗粒尺寸并对其进行表面修饰，将获得较高发光效率和较高的猝灭浓度。     

阴极修饰层CuPc、ZnPc、C60对OLED光电性能的影响

采用真空蒸镀法分别制备了以CuPc、ZnPc、C₆₀为阴极修饰层的OLED,对比研究了它们对OLED光电性能的影响。从能级结构、表面形貌、折射率及纳米界面等方面对载流子注入和输运进行了探讨。结果表明:修饰层使器件性能显著提高,它不仅降低OLED开启电压（最低至4.2 V）、提高OLED电流密度及发光效率（最高至13.49 lm/W）,同时增强了器件的发光稳定性（180 s后光强保持在90%以上）,其中以CuPc为阴极修饰层的器件表现的性能最好。发光光谱方面,以CuPc和ZnPc作为修饰层的器件对550~650 nm的红光部分略有吸收,而C₆₀作为修饰层的器件光谱则无太大变化,这是由修饰层材料的吸收系数随不同波长而变化所致。实验结果说明,若想较大程度地提高器件电性能,酞菁材料是不错的选择;若对光谱有要求,可用C₆₀做阴极修饰层。     

EXTENDED SSH MODEL FOR C58B2 AND C58N2

The extended Su-Schrieffer-Heeger model is used to study the electronic energy levels and molecular structures for two kinds of isomers of C₅₈X₂(X=B, or N). In each case we obtain two sets of stable solutions. For C₅₈X₂ (1, 2), both sets of solutions are found to be reasonable, indicating two different phases. For C₅₈X₂(1, 60 ), only one set of solutions which satisfy the central inversion symmetry is physically reasonable.     

Studies of fullerenes by the excitation, emission, and scattering of electrons

This paper presents an overview of how electron spectroscopies have contributed to advances in fullerene research. In particular, we illustrate the vital role these techniques have played in improving our understanding of the importance of strong electronic correlation and of electron-phonon coupling in these materials, in the derivation of electron hopping rates, in providing a direct determination of charge transfer and hybridisation in both fullerene salts and adsorbed fullerenes and in determining the optical gap of these systems. We discuss systems of increasing complexity, starting with C₆₀ in the gas phase and in the solid state, and moving on to C₆₀ salts and to C₆₀ adsorbed on surfaces. Finally we look at both higher fullerenes and fullerenes with a heteroatom either on or inside the cage.     

Enhanced optical limiting performance of a novel molybdenum complex of fullerene

Reverse saturable absorption of a novel molybdenum complex of fullerene (η²-C₆₀) Mo(CO)₂(o-phen)(DBM)·2C₆H₆·C₅H₁₂ has been investigated under irradiation of 10 ns laser pulses at 532 nm. An enhancement of the optical limiting behavior was observed in comparison with C₆₀. An explanation based on the enhanced triplet-state absorption caused by the intra-molecular charge transfer was predicted. The relationship between the clamped laser fluence and low-intensity transmissivity, or the concentration of the solution, was also investigated and a linear dependence was revealed.     

X@C20F20(X=He,Ne,Ar,Kr)几何结构和 电子结构的理论研究

采用密度泛函理论中的广义梯度近似, 对X@C₂₀F₂₀(X=He, Ne, Ar, Kr)几何结构和电子结构进行了计算研究. 几何结构优化发现: 惰性气体原子X内掺到C₂₀F₂₀笼后, 均稳定于碳笼中心, 随着内掺X原子序数的增大, X原子对C₂₀F₂₀笼的影响越来越大. 能隙、内掺能和振动频率计算表明: 内掺X原子使得C₂₀F₂₀的稳定性得到了显著提升, X@C₂₀F₂₀(X=He, Ne, Ar, Kr)都具有良好的稳定性, 并且随着X原子序数的增大, 其稳定性也基本呈现逐渐增强的趋势. 电子结构研究发现: X原子对X@C₂₀F₂₀费米能级附近的占据轨道基本没有贡献, 而对其未占据轨道贡献较大. 计算还发现: 在X@C₂₀F₂₀中, He 和Kr分别从C₂₀F₂₀的C 笼上获得了0.126和0.271个电子, 而Ne和Ar却分别向C笼转移了0.060和0.012个电子. 由此可见: X原子与C原子之间都发生了电荷转移, C笼上的C原子与惰性气体原子X间形成了一定的离子键.     

BOND STRUCTURE AND ELECTRON STATES OF CHARGED C60

In the alkali-metal doped C₆₀, the charge transfer induces the distortion of the bond structure and forms the self-trapping electronic bound states. Our theory manifests: 1, the charge transfer reduces the symmetry of C₆₀ from I_h to D_5d. 2, Both the bond distortion and the self-trapping states possess layer structures and are localized in the equatorial area. 3, The carbon atoms in charged C₆₀ are divided into eight layers with an inversion center, then there exist four nonequivalent groups of carbon atoms. It makes the NMR line split into a fine structure with strength ratio 1:1:2:2. 4, The charged C₆₀ has two self-trapping bound states, one is 0.06eV above HOMO with odd parity and the other is 0.05 eV below LUMO with even parity.     

Modifications in track registration response of PADC detector by energetic protons

It has been well established that different ionising radiations modify the track registration properties of dielectric solids. In an effort to study the response of Polyallyl diglycol carbonate (PADC Homalite) detector towards fission fragment, PADC detectors were exposed to 10⁴ Gy dose of 62 MeV protons and then one set of samples were exposed to fission fragments from a ²⁵²Cf source. Two of these detectors were containing a thin layer of Buckminsterfullerene (C₆₀). The study of the etched tracks by Leitz Optical Microscope reveals that the track diameters are enhanced by more than 70% in the proton irradiated zone as compared to that in the unirradiated zone. Scanning Electron Microscopy was performed after etching the sample in 6 N NaOH at 55°C for different etching times, to study the details of the surface modifications due to proton irradiation of PADC detectors with and without C₆₀ layer. Our observations revealed that the diameters and density of proton tracks have increased with etching time on the surface facing the fullerene layer as well as the other surface. However, a relatively more open structure of the etched surface containing C₆₀ as compared to the bare one may be an indication of the extra damage caused by the energy released upon the destruction of C₆₀ molecules by energetic protons.     

Au-Si_(60)-Au分子结电子输运性质的理论计算

运用密度泛函理论对Si60团簇的结构进行几何优化,得到基态结构是一个直径为1.131 nm,平均键长为0.239 nm,分子最低未占据轨道与最高占据轨道能量差即能隙值为0.72 eV,具有C1点群的空心笼状结构.然后把它与两半无限的Au(100)-4×4电极相连构成Au-Si60-Au三明治结构分子结点,运用密度泛函理论结合非平衡格林函数的方法对其电子输运性质进行了第一性原理计算.当两电极的距离为1.74 nm时,分子结点的平衡电导为1.93G0(G0=2e2/h),然后在-2.0—2.0 V的电压范围内,计算了不同电压下的电导与电流,得到其I-V曲线成近线性关系,从分子前线轨道与透射谱分析了Si60分子的电子输运特性,讨论了电荷转移量与电导之间的关系.     

碳分子线C5在激光场中的含时密度泛函理论研究

运用含时密度泛函理论和分子动力学相结合的方法, 研究了C₅分子线在强激光场中的电离激发.研究发现, 当考虑激光强度对C₅分子线激发的影响时, 激光强度越强, 分子吸收的能量越多, 电离也越早, 最终电离的电子也越多, 而且沿激光极化方向的偶极矩的变化及峰值也越大. 关于激光极化方向对C₅分子线激发的影响的研究表明, 当激光极化方向沿着C₅分子线轴向时, 分子的电离大大增强, x方向的激光脉冲仅能激发起x方向的偶极振荡, 而y方向的激光脉冲仅能激发起y方向的偶极振荡, 而且x方向的激光脉冲激发的偶极振荡强. 研究还表明, 当激光极化方向沿着C₅分子线轴向时, 尽管由于电离增强而导致C₅分子线C–C键振动的同步性变差, 但在两种激光极化方向情况下, C₅分子线的振动模式与中性C₅分子线的振动模式相同. 关键词： 含时密度泛函理论 分子动力学 分子电离 碳分子线     

ELECTRONIC STRUCTURE STUDIES OF THE C60 FILM CONDENSED ON 2H-MoS2(0001) SURFACE

The electronic structure and vibrational spectrum of the C₆₀ film condensed on a 2H- MoS₂(0001) surface have been investigated by X-ray photoelectron spectroscopy (XPS), ul-traviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES) and infrared high-resolution electron-energy-loss spectroscopy (HREELS). AES analysis showed that at low energy side of the main transition, C₆₀ contains a total of three peaks just like that of graphite. However, the energy position of the KLL main Auger transition of C₆₀ looks like that of diamond, indicating that the hybridization of the carbon atoms in C₆₀ is not strictly in sp²- bonded state but that the curvature of the molecular surface introduces some sp²pz- bonded character into the molecular orbitals. XPS showed that the C 1s binding energy in C₆₀ was 285.0eV, and its main line was very symmetric and offered no indication of more than a single carbon species. In UPS measurement the valence band spectrum of C₆₀ within 10eV below the Fermi level (E_F) shows a very distinct five-band structure that character-izes the electronic structure of the C₆₀ molecule. HREEL results showed that the spectrum obtained from the C₆₀ film has very rich vibrational structure. At least, four distinct main loss peaks can be identified below 200 meV. The most intense loss was recorded at 66 meV, and relatively less intense losses were recorded at 95, 164 and 197meV at a primary energy of electron beam E_P = 2.0eV. The other energy-loss peaks at 46, 136, 157 and 186meV in HREEL spectrum are rather weak. These results have been compared to infrared spectrum data of the crystalline solid C₆₀ taken from recent literatures.