基于MEH-PPV/ZnSe纳米复合器件的电致发光特性的研究

以巯基乙酸作为稳定剂在水相中制备了ZnSe纳米晶,用X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对其进行了表征。用表面活性剂将ZnSe纳米晶从水相中转移到有机相中,使其与聚合物MEH-PPV复合作为发光层,制备了多层电致发光器件Glass/ITO/MEH-PPV∶ZnSe/BCP/Alq₃。对ZnSe纳米晶和MEH-PPV薄膜的光致发光谱及其吸收光谱的比较表明ZnSe纳米晶和MEH-PPV之间存在着能量传递,这是导致纳米复合薄膜的光致发光光谱和电致发光光谱存在差异的原因之一。文章对其在光激发和载流子注入条件下的不同发光机制进行了讨论。通过对器件的光电特性进行研究,发现ZnSe纳米晶发光的比例随着外加电压的增加而增加,而且器件的I-V特性基本上符合二极管的特性。     

氧化石墨烯/硒化锌纳米光电材料的制备及其蓝光发射特性

采用一种简单有效的原位水热合成方法,使用石墨烯氧化物（GO）作为反应物和晶体生长基底成功制备出了还原氧化石墨烯/硒化锌（r-GO/ZnSe）纳米复合材料。采用X射线粉末衍射（XRD）、透射电子显微镜（TEM）、高分辨透射电镜（HRTEM）以及红外-可见光谱（FT-IR）等方法对r-GO/ZnSe纳米复合材料进行了检测。结果表明,平均粒径在30 nm的立方闪锌矿晶体结构的ZnSe粒子均匀分散在氧化石墨烯片层上,构成纳米复合结构。 UV-Vis光谱显示,纳米复合材料的光学吸收的起始波长在445 nm附近。PL光谱显示,纳米复合材料在470 nm附近存在一个很强的发射峰。这种石墨烯基纳米复合材料在白光二极管领域中有重要的应用价值。     

Highly luminescent (ZnSe)ZnS core-shell quantum dots for blue to UV emission: synthesis and characterization

We synthesized nearly monodisperse bare ZnSe nanocrystallites having luminescence which ranges in wavelength from 340 to 430 nm via nucleation due to supersaturation and growth followed by size selective precipitation. Bare ZnSe dots' outermost surface is passivated with organic HDA/TOP. In order to enhance the radiative emission from the semiconductor nanocrystals, we capped the bare ZnSe quantum dots with ZnS semiconductor materials of a wider band gap and 5% of lattice mismatch and produced highly luminescent core-shell (ZnSe)ZnS quantum dots. The core-shell (ZnSe)ZnS nanocrystals show 20 times or more as greatly enhanced luminescence quantum yields as those of bare ZnSe nanocrystals. The ZnSe bare dots and the (ZnSe)ZnS core-shell dots have cubic zinc blende structures as expected from the bulk structure. The observed shapes of bare ZnSe and core-shell (ZnSe)ZnS dots are nearly spherical or ellipsoidal with the aspect ratios of 1.2 and 1.4, respectively. They are not faceted.     

CdSe/ZnSe核-壳结构纳米粒子合成新方法

报道用“一步”合成新方法制备了CdSe/ZnSe核-壳结构的发光纳米粒子.该方法是将锌的前驱体注入表面Se富集的CdSe发光纳米粒子溶液中,通过Zn²⁺与Se共价键结合,从而在CdSe发光纳米粒子的表面形成ZnSe壳.分别通过X射线粉末衍射、光电子能谱、透射电镜、紫外-可见吸收光谱和光致发光光谱,对核-壳结构的发光纳米粒子的结构及光学性质进行了表征.结果表明,以较宽带隙的ZnSe在较窄带隙的CdSe纳米粒子表面形成的壳层有效地钝化了CdSe纳米粒子的表面缺陷,明显地提高了室温下CdSe纳米粒子的光致发光效率.X射线粉末衍射表明随着Zn²⁺的不断注入,CdSe/ZnSe的衍射峰逐渐移向ZnSe衍射峰.光电子能谱数据显示,Zn2p的双峰分别位于1020,1040eV附近,通过与体材料ZnO相比,确定为Zn²⁺的光电子发射,说明Zn是以共价键形式存在于CdSe纳米粒子的表面.透射电镜照片显示纳米粒子具有良好的单分散性,核-壳结构的发光纳米粒子直径较CdSe核的直径明显增加.     

Fabrication of ZnO and its enhancement of charge injection and transport in hybrid organic/inorganic light emitting devices

ZnO nanocrystals were synthesized by hydrolysis in methanol. X-ray diffraction and photoluminescence spectra confirm that good crystallized ZnO nanoparticles were formed. Utilizing those ZnO nanoparticles and poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), light emitting devices with indium tin oxide (ITO)/poly(3,4-oxyethyleneoxy-thiophene):poly(styrene sulfonate) (PEDOT:PSS)/ZnO:MDMO-PPV/Al and ITO/PEDOT:PSS/MDMO-PPV/Al structures were fabricated. Electroluminescence (EL) spectra reveal that EL yield of hybrid MDMO-PPV and ZnO nanocrystals devices increased greatly as compared with pristine MDMO-PPV devices. The current-voltage characteristics indicate that addition of ZnO nanocrystals can facilitate electrical injection and charge transport. The decreased energy barrier to electron injection is responsible for the increased efficiency of electron injection.     

In situ preparation and fluorescence quenching properties of polythiophene/ZnO nanocrystals hybrids through atom-transfer radical polymerization and hydrolysis

In this paper, a new approach for in situ preparing nanocomposites of conjugated polymers (CPs) and semiconductor nanocrystals was developed. Polythiophene grafted poly(zinc methacrylate) (PTh-g-PZMA) copolymer was synthesized by atom-transfer radical polymerization (ATRP) of zinc methacrylate (ZMA) initiated from the macroinitiator poly(2,5-(3-(bromoisopropyl-carbonyl-oxymethylene) thiophene)) (PTh-Br) with pendant initiator groups. Subsequently, the polythiophene grafted poly(methacrylate)/ZnO (PTh-g-PMA/ZnO) hybrid heterojunction nanocomposites were successfully prepared by in situ hydrolysis of PTh-g-PZMA casting films in alkaline aqueous solution. The structures of PTh-Br, PTh-g-PZMA and PTh-g-PMA/ZnO were confirmed by the proton nuclear magnetic resonance (¹H NMR) spectra, Fourier transform infrared (FTIR) spectra and X-ray photoelectron spectroscopy (XPS). The morphologies of PTh-g-PMA/ZnO films prepared for different hydrolysis time were observed in the cross-sections by scanning electron microscope (SEM). The SEM images revealed that ZnO nanocrystals were uniformly dispersed in polymers without any aggregation and the appearances of ZnO nanocrystals changed from nanoparticles to nanorods with the hydrolysis treatment time increasing. The optical properties of these nanocomposites were studied by ultraviolet-visible (UV-vis) absorption and fluorescence spectroscopy. UV-vis absorption spectroscopy showed that the adsorption band of PTh-g-PMA/ZnO hybrids was broader than that of PTh-Br, implying that the existence of ZnO nanocrystals increased the optical absorption region of hybrids. The photoluminescence (PL) spectra of the hybrids showed that fluorescence quenching occurred in PTh-g-PMA/ZnO blends and a maximum of 85% of the fluorescence intensity quenched in the PTh-g-PMA/ZnO obtained from treatment in NaOH aqueous solution for 2 h, which revealed the existence of photo-induced charge transfer between the polythiophene chains and ZnO. These results indicated that the hybrid heterojunction nanocomposites could be promising candidates for photovoltaic applications.     

退火温度对聚对苯乙炔MOPPV-ZnSe量子点复合材料太阳电池性能影响

利用原位缩合法制备了聚(2-甲氧基-5辛氧基)对苯乙炔(MOPPV)-ZnSe量子点复合材料,通过对复合材料的X射线衍射、透射电子显微镜、扫描电子显微镜、紫外可见吸收光谱等研究,发现聚合物MOPPV与ZnSe量子点以包覆形式有效地复合在一起,复合材料中ZnSe量子点结晶性良好,尺寸约为4 nm;且两者之间发生光诱导电荷转移,复合材料随着退火温度的升高,其吸收光谱范围发生红移。通过对MOPPV-ZnSe复合材料光电性能的研究发现,复合材料光电性能随着退火温度的升高逐渐表现出明显的二极管特性,转换效率出现先增大后减小的趋势,且在160℃时转换效率达到最大为0.3726%。     

Synthesis and properties of CdSe Quantum Dot sensitized ZnO nanocomposites

In this work, zinc oxide nanocrystals with an average particle size of 13–22 nm are readily synthesized in aqueous medium by the wet synthesis method. Different sized nanocrystals obtained with change in calcination temperature are characterized by PL photoluminescence (PL) and UV–vis absorption spectroscopies, X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The average crystal size of the as prepared ZnO nanopowder is determined by XRD and was found to be in good agreement with the UV–vis absorption analysis. The quality of different ZnO nanopowders is confirmed by XRD spectra. On the basis of different characterizations, ZnO calcined for 1 h (due to its large size and less agglomeration) is chosen for synthesis of ZnO–CdSe nanocomposites with variable sized CdSe QD's (Quantum Dots). Nano-composites are synthesized using bifunctional linker molecule Mercaptopropionic Acid (MPA), and by directly adsorbing CdSe QD's over the surface of ZnO nanocrystals. The difference in charge transfer mechanism in ZnO–CdSe nanocomposites due to different crystallite size of CdSe QD's is studied. Higher crystallinity of ZnO–CdSe nanocomposites can be determined from XRD characterization. Size and mode of attachment in various ZnO–CdSe nanocomposites are determined by SEM studies.     

Preparation and nonlinear characterization of zinc selenide nanoparticles embedded in polymer matrix

Nanocomposites of ZnSe nanoparticles embedded in polyvinyl alcohol (PVA) matrix have been prepared by in-situ synthesis. ZnSe/PVA nanocomposites are characterized by X-ray diffraction (XRD), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and UV/Vis spectra. The nanocomposite structure is confirmed by the blue-shift of the absorption edge. The nonlinear refractive index and two-photon absorption (TPA) coefficient are measured by the Z-scan technique using low power CW He–Ne laser light. The results show that the ZnSe nanocomposite films show large optical nonlinearity and the magnitude of the third-order nonlinear susceptibility χ⁽³⁾ is calculated to be 2.62×13^?11 m²/V².     

ZnSe/SiO2半导体量子点玻璃的光谱特性

对采用溶胶凝胶法制备的ZnSe/SiO2半导体量子点玻璃的光谱性质进行了测试分析.UV-Vis透射光谱中观察到光吸收边相对于体相半导体有明显蓝移.稳态发射光谱(PL)中观察到ZnSe纳米晶体的位于蓝区的基本呈高斯分布的弱的最低激子发射峰、强而宽的表面态发光带以及对应杂质能级的三个锐峰发光.时间分辨荧光光谱(TRPL)中观察到发光效率高的最低激子发射峰,并测量其荧光衰减寿命,经尾部拟合为28.5 ps.同时,结合有效质量近似(EMA)模型,估计ZnSe纳米晶体的平均粒径介于2.45~3.60 nm之间,尺寸分布基本呈高斯型.     

GaAs(100)衬底上ZnSe薄膜的热壁束外延生长

介绍热壁束外延法生长ZnSe/GaAs异质结工作。低能电子衍射和俄歇电子能谱对样品的原位检测表明,用此方法可以在GaAs(100)衬底上外延得到单晶的ZnSe(100)薄膜。当外延生长速率大时,Znse薄膜质量下降,样品的Raman谱中出现TO模。X射线衍射实验结果表明,这种外延膜质量的退化主要是由于在ZnSe(100)薄膜体内存在〈111〉方向的晶核。 关键词：     

掺杂ZnSe/BeTe Ⅱ型量子阱结构中带电激子的磁场效应

报道了n型掺杂ZnSe/BeTe/ZnSe Ⅱ型量子阱(type-Ⅱ QW)在极低温 (5—10 K)条件下的各种光学性质. 磁场中(Farada配置)ZnSe层的反射光谱展示了一个典型的负的带电激子(X^-)的跃迁特征. 对于空间间接光致发光(spacially indirect PL)光谱,它的主发光峰显示了一个反玻尔兹曼分布的非对称性,并且在磁场中(Voigt配置)它的峰值能量随磁场的增加而降低. 这些实验结果显示了该掺杂样品的空间间接PL是来自Ⅱ型QW结构所特有的带电激子的跃迁. 关键词： 光致发光 二维电子气 带电激子 Ⅱ型量子阱     

掺杂Mn2+的浓度对CdS纳米颗粒光致发光的影响

采用反胶束法,合成了硅土包裹的掺有不同浓度的Mn2 的CdS纳米颗粒.高分辨电镜表明这些颗粒的直径小于5 nm.仅仅改变Mn2 的掺杂浓度,研究了这些颗粒的光致发光谱和光致发光激发谱,结果表明:Mn2 浓度的大小对掺杂CdS纳米颗粒的发光产生了重要的影响.通过电子顺磁共振谱的测量和分析揭露了Mn2 浓度影响这些掺杂颗粒发光效率的原因.     

微波法制备Mn2+掺杂ZnSe纳米材料及谱学性能研究

过渡金属掺杂的Ⅱ-Ⅳ族纳米材料有望替代CdSe类量子点作为新型的荧光标记物而受到广泛关注.利用微波加热法的体加热特点,以不同有机胺为配体溶剂,控制反应条件,制备了Mn2+掺杂的ZnSe纳米材料,并分别利用TEM、EDS、荧光光谱等手段对其形貌、结构和性能的关系进行了探索.Mn2+掺杂的纳米ZnSe粒子为200～500 nm的球形粒子,表面平整,为单晶的纤锌矿结构.掺杂后纳米粒子的发射峰显示Mn2+的跃迁发射,但不同的配体溶剂和掺杂量对产物的发光性能有明显影响.     

A Simple Strategy to Prepare Colloidal Cu‐Doped ZnSe(S) Green Emitter Nanocrystals in Aqueous Media

A novel and simple method is described for preparing colloidal Cu‐doped ZnSe(S) quantum dots (QDs) in aqueous media by introducing copper ions using the same method as to prepare colloidal ZnSe(S). More specifically, the Cu‐doped ZnSe(S) are prepared through the nucleation‐doping method in the presence of 3‐mercaptopropionic acid as stabilizers using zinc perchlorate, copper sulphate, and NaHSe as precursors. Confirmation of the preparation of Cu‐doped ZnSe(S) nanocrystals (NCs) is done with absorption and emission spectroscopies (UV–vis and PL) as the QDs show intensive green emissions. The reduction of ions Cu²⁺ to Cu⁺ is confirmed by using electron paramagnetic resonance (EPR), in which Cu⁺ ions are silent. The size determination is performed by using transmission electron microscopy (TEM) and dynamic light scattering (DLS), resulting in Cu‐doped ZnSe(S) particles with a mean diameter of 4.6 ± 3.5 nm. The excellent stability observed for the nanoparticles overcomes the intrinsic instability of traditional aqueous Cu‐doped ZnSe(S) NCs.     

Fabrication of rare-earth/quantum-dot nanocomposites for color-tunable sensing applications

We developed a new fluorescent nanocomposite by using a layer-by-layer approach to link NaYF₄:Ce,Tb rare-earth (RE) nanocrystals and CdSe/ZnSe semiconductor quantum dots (QDs) with opposite charges. Under ultraviolet light excitation, the nanocomposites exhibited both the green Tb emission centered at 550 nm, and the red QD emission at 650 nm. Sensing applications showed that the red QD emission was quenched by trace amount of Cu²⁺ (or Ag⁺) ions due to the ion displacement mechanism, while the green RE emission kept constant. Thus, the nanocomposites with the decreased QD/RE emission intensity ratio and changed fluorescence output color provided a visible “indicator” to detect metal ions quantificationally. In comparison with single emission materials, the dual emission nanocomposites can be a more reliable probe for various sensing applications.     

Effect of deposition parameters on structural, optical and electrical properties of nanocrystalline ZnSe thin films

This paper presents the chemical bath deposition of zinc selenide (n-ZnSe) nanocrystalline thin films on non-conducting glass substrates, in an aqueous alkaline medium using sodium selenosulphate as Se²⁻ ion source. The X-ray diffraction studies show that the deposited ZnSe material is nanocrystalline with a mixture of hexagonal and cubic phase. The direct optical band gap ‘E_g’ for the as-deposited n-ZnSe films is found to be 3.5 eV. TEM studies show that the ZnSe nanocrystals (NCs) are spherical in shape. Formation of ZnSe has been confirmed with the help of infrared (IR) spectroscopy by observing bands corresponding to the multiphonon absorption. We demonstrate the effect of the deposition temperature and reactant concentration on the structural, optical and electrical properties of ZnSe films.     

ZnSe and copper-doped ZnSe nanocrystals (NCs): Optical absorbance and precise determination of energy band gap beside their exact optical transition type and Urbach energy

The using of a reliable and accurate new method (called in literature as derivation of absorption spectrum fitting (DASF)) for evaluation of the optical band gap (E_g) and also the exact nature of charge carriers optical transitions, is investigated in ZnSe and ZnSe:Cu nanocrystals (NCs) synthesized by rapid microwave irradiation. This method can be performed by using the output of UV–Visible spectroscopy. The obtained E_g values are within the range of 2.985–3.261 eV, depending to the microwave irradiation time and Cu dopant percentage (decreasing trend with increasing of irradiation time and Cu content). The DASF-based obtained results for ZnSe and ZnSe:Cu nanoparticles, showed the more precise values of band gap, with the same trend of previously qualitative reported data on the same samples. Also, the direct gap nature of their optical transitions was justified. To perform the method, there is no any need to the concentration of solutions and merely one need the direct absorption or transmission spectra. In other word, DASF technique was employed on ZnSe NCs to confirm its validity and to avoid non-precise reports on optical band gap which can affect on the device optimizations based on these samples. Moreover, using the values of E_g, refractive index and dielectric constant of each sample were obtained at the absorption edge. Also, the width of the tailing states in the gap (Urbach energy: E_Tail) was estimated and were within the range of 0.049–0.122 eV, which their very small values in compare with E_g imply to the sharp valence and conduction band edges; it means the good crystallinity nature of the produced samples.     

[Au(PH_3)]~+芳香基发光材料的光谱性质研究

用二阶微扰(MP2)法和单激发组态相互作用(CIS)法分别优化了发光材料H3PAuPh和(H3PAu)2(1,4-C6H4)2的基态和激发态的几何结构,并用含时密度泛函(TD-DFT)法计算了各发光材料的吸收光谱与磷光发射光谱。计算结果表明,H3PAuPh和(H3PAu)2(1,4-C6H4)2的磷光发射光谱均具有在Au(6p)→C(2p)的金属向配体的电荷转移(MLCT)参与下的pπ*(Ph)→pπ(Ph)跃迁的本质,并伴有Au(6p)→Au(5d)的金属中心电荷转移(MCCT)的性质。(H3PAu)2(1,4-C6H4)2是由两个H3PAuPh连接而成的。因此(H3PAu)2(1,4-C6H4)2的分子轨道也是由H3PAuPh的分子轨道组合而成的。在磷光发射中,由于轨道组合中存在pπ*或pπ的相互作用,所以(H3PAu)2(1,4-C6H4)2的最低能量磷光发射光谱谱线的波长大于H3PAuPh的相应值。     

MEH-PPV/CdSe纳米复合器件的光电导特性的研究

以CdO和Se粉作为前驱物,在TOPO/TOP有机体系中制备了CdSe纳米晶,将其与聚合物MEH-PPV复合制备了复合光电导器件,研究了它的光电导特性,并将其与单层MEH-PPV光电导器件的特性进行了比较。结果发现纳米复合光电导器件的光电流响应光谱的2个峰的位置基本上与MEH-PPV和CdSe纳米晶的吸收峰的位置相对应,这说明CdSe纳米晶和聚合物MEH-PPV的吸收对光电流都有贡献,主要是由于CdSe纳米晶和MEH-PPV界面处的激子离化和电荷转移造成的。而且复合器件的光电流较单层有所增强,且MEH-PPV器件光谱的响应范围更宽。