CdSe:Nd纳米晶及CdSe:Nd@SiO2核壳结构的合成及发光性能

利用有机相法合成Nd³⁺掺杂CdSe纳米晶（CdSe∶Nd）,通过X射线粉末衍射（XRD）、透射电镜（TEM）、紫外吸收光光谱及荧光光谱表征,证明Nd³⁺已经成功掺入到CdSe的晶格中。与纯CdSe纳米晶相比,CdSe∶Nd纳米晶的结构仍为立方晶型,且形貌近似球形,均匀分散,粒径约为2~4 nm。紫外吸收峰和荧光发射峰都发生红移,而且掺杂后的CdSe∶Nd纳米晶量子产率也提高,这可能是由于掺杂Nd³⁺引入了新的杂质能级,带隙减小。为了实现CdSe∶Nd纳米晶的可加工性和功能性,通过微乳法合成SiO₂壳包覆的CdSe∶Nd纳米球（CdSe∶Nd@SiO₂纳米球）,CdSe∶Nd@SiO₂纳米球呈均匀球形,直径约为100~115 nm,并且包壳后的CdSe∶Nd@SiO₂纳米球发射峰（581 nm）与CdSe∶Nd纳米晶（598 nm）相比,发光强度提高且发射峰蓝移,蓝移约为17 nm,可能是因为SiO₂壳可以减少纳米晶表面的非辐射跃迁以及改善表面缺陷导致的。     

基于CuInS2/ZnS核壳结构量子点的高光效暖白光LED

采用逐步热注射法合成了用于白光LED的CuInS₂/ZnS(CIS/ZnS)核壳结构量子点.通过调整Cu/In的比率, 在CuInS₂(CIS)量子点的基础上, 合成了发射波长在570~650 nm之间可调的CIS/ZnS量子点.与CIS量子点的低量子产率相比, 具有核壳结构的CIS/ZnS量子点的量子产率达到了78%.通过在黄光荧光粉YAG :Ce³⁺表面旋涂CIS/ZnS量子点的方式制备了暖白光LED器件.在工作电流为10 mA时, 暖白光LED的发光效率达到了244.58 lm/W.由于CIS/ZnS量子点的加入, 所制备的白光LED器件的显色指数达到86.7且发光颜色向暖色调发生了转移, 相应的色坐标为(0.340 6, 0.369 0).     

CdSe量子点的光物理性质研究与荧光杂化纤维的制备

半导体纳米晶体(NCs)具有良好的光稳定性,广泛的发射持久性和高消光系数,在过去几年被广泛研究报道,其中,硒化镉半导体纳米晶体(CdSe NCs)被广泛用于电子照明、太阳能发电、光电传感等领域.然而CdSe NCs的电学、热力学和光物理性质具有较强的尺寸依赖性,在传统的制备方法及应用中容易出现晶体表面缺陷和悬空键以及较...     

CdSe/CdS核/壳型纳米晶的光谱特性

以巯基乙酸为稳定剂制备了CdSe/CdS核／壳型纳米晶。用光吸收谱（Abs)、光致发光谱（PL）及光致发光激发谱（PLE）研究了CdS壳层对CdSe纳米晶电子结构，从而对其吸收和发光性能的影响。根据PL和PLE的结果以及带边激子精细结构的计算结果，我们用尺寸很小的纳米晶中所形成的基激缔合物解释了PL光谱与吸收边之间较大的Stokes位移。     

红、绿CdSe@ZnS量子点配比对三波段标准白光LED器件的影响

将一步法合成的具有梯度合金结构的红光、绿光CdSe@ZnS量子点与硅胶均匀混合后,作为光转换层涂覆到蓝色InGaN LED芯片上,制备了不含荧光材料的三波段白光LED器件。研究了峰值为650 nm和550 nm的高效率红、绿量子点在硅胶中的含量及配比对白光LED色坐标以及效率的影响。结果表明,当红、绿量子点配比为2：3时,可得到发射纯正白光的QDs-LED器件,色坐标为（0.322 8,0.335 9）、色温为5 725 K,功率效率为26.61 lm/W,显色指数为72.7。光谱中红、蓝、绿三色发光峰的半高宽分别为30,25,38 nm,表明器件具有很好的单色性和高色纯度。     

Fluctuations of electroluminescence intensity of single CdSe nanocrystals excited by scanning tunneling microscope current

Electroluminescence from single CdSe nanocrystals (NCs) excited by tunneling current of scanning tunneling microscope (STM) has been measured. Two types of samples with low and high concentration of CdSe NCs deposited on the gold substrate have been prepared. Both types of samples had no plasmon emission. It enabled one to detect pure electroluminescence from single CdSe NCs. Samples with low concentration of NCs exhibit an intensive short-term luminescence of NCs for several seconds. Samples with high concentration of NCs exhibit a weak fluctuating long-term luminescence for thousand seconds. Fluctuations of NC electroluminescence differ considerably from those detected recently in photoluminescence of CdSe NCs embedded in polymer films. The difference in fluctuations results from the difference in physical conditions existing in electro- and photoluminescence. The distribution of photons w(N, T) emitted in time interval T has been found from statistical treating of fluctuating luminescence. Due to weakness of the pure signal, we paid a special attention to allowing for photomultiplier tube noise while treating these fluctuations. The photon distribution in pure signal is one of super-Poisson type, i.e. it is broader than Poisson distribution. A dynamical model for an absorber–emitter excited by tunneling current of STM has been offered. The model takes into account the thermal drift of STM tip.     

High Color-Rendering Index and Stable White Light-Emitting Diodes Based on Highly Luminescent Quantum Dots

Solid-phase color converter-based quantum dots (QDs) white light-emitting diodes (WLEDs) have become promising next-generation solid-state light sources. However, the development of these WLEDs’ production still suffers from constraints involving insufficient color-rendering index (CRI), low color stability, and short operation lifetimes. Here, thick-shell Cd_0.05Zn_0.95S/CdSe/Cd_xZn_1–xS spherical quantum wells are developed with good color tunability from green to red regions and high photoluminescence quantum yield (up to 88% for green wavelengths). QDs with five emission colors are used to fabricate a series of WLEDs, which possess a good correlated color temperature tunability from warm (3210 K) to cool (22 000K) white light, and a high CRI Ra (>90). Specifically, the neutral white light device with Commission Internationale de l´Eclairage (CIE, International Commission on illumination) of (0.36, 0.36) and the standard white light device with CIE of (0.33, 0.33) achieve a CRI Ra up to 95.8 and 95.11, respectively, they also exhibit long operating life and great color stability. These results indicate that the improvement of the performance and stability of the WLED based on thick-shell spherical quantum wells is remarkable progress in the commercialization of QD-based solid-state lighting.     

A novel two-phase thermal approach for synthesizing CdSe/CdS core/shell nanostructure

CdSe/CdS core/shell nanocrystals have been synthesized through a low cost and simple two-phase thermal route. The optical spectroscopy and structural characterization evidenced the core/shell structure of the CdSe/CdS nanoparticles. The X-ray diffraction patterns of CdSe and CdSe/CdS nanoparticles exhibited peak positions corresponding to those of their bulk cubic crystal structures. The X-ray photoelectron spectroscopy data confirmed the elemental composition of the CdSe/CdS nanoparticles. The absorption spectra of core/shell nanoparticles showed red shift with respect to the core CdSe nanoparticles. The photoluminescence study indicates that the intensity of the emission maximum is considerably increased in the core/shell structure as compared with the parent material, and the capping of CdS nanoparticles with CdSe material exhibit a near band-edge emission, indicating a successful passivation by removing surface defects. The high-resolution transmission microscope images of the bare and core/shell nanoparticles ascertained the monodispersed and well-defined spherical particles. The average particle sizes for CdSe and CdSe/CdS nanoparticles are 2.5 and 5 nm, respectively, thus confirming, the larger diameter of CdSe/CdS core/shell nanostructure than the core CdSe nanoparticles.     

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.     

A comparative study of conventional type II and inverted core–shell nanostructures based on CdSe and ZnS

The objective of this work is to investigate structural, morphological and optical properties of conventional CdSe/ZnS core–shell and inverted ZnS/CdSe core–shell nanostructures for opto-electronic device applications. For this purpose both nanostructures were synthesized using chemical bath deposition technique in thin film form. The structural properties were studied using X-ray diffraction technique with Rietveld refinement and transmission electron microscopy (TEM). The surface morphology of synthesized thin film was illustrated in the form 2D and 3D images using atomic force microscopy (AFM). The optical properties were explained using UV–Vis absorption spectroscopy and photo luminescence (PL) spectroscopy in in situ monitoring process. A comparison of estimated particle size from XRD, high resolution AFM and TEM images was resulted in good agreement as 2.1, 2.4 and 2.1 nm respectively for conventional CdSe/ZnS core–shell and as 2.5, 2.5 and 2.2 nm respectively for inverted ZnS/CdSe core–shell nanostructures.     

CdSe/ZnSe/ZnS多壳层结构量子点的制备与表征

展示了一种简捷的多壳层量子点合成路线。在含有过量Se源的CdSe体系中直接注入Zn源,"一步法"合成了CdSe/ZnSe量子点;进一步以CdSe/ZnSe为"核",表面外延生长ZnS壳层制备了核/壳/壳结构CdSe/ZnSe/ZnS量子点。相对于以往报道的多壳层结构量子点的制备方法,该方法通过减少壳层的生长步骤有效地简化了实验操作,缩短了实验周期,同时减少对原料的损耗。对量子点进行高温退火处理,能够大幅提高CdSe/ZnSe/ZnS量子点的发光量子产率。透射电镜、XRD以及光谱研究表明:所制备的量子点接近球形,核与壳层纳米晶均为闪锌矿结构,最终获得的CdSe/ZnSe/ZnS量子点的光致发光量子产率达到53％。为了实现量子点的表面生物功能化,通过巯基酸进行了表面配体交换修饰,使量子点表面具有水溶性的羧基功能团,并且能够维持较高的光致发光量子产率。     

Synthesis of quantum dots via microreaction: structure optimization for microreactor system

Microreactor systems existed as a powerful tool for the continuous synthesis of quantum dots. However, the lack of structure optimization for the discrete units led to empirical determination of the length scale, and the properties of the formed products varied in different cases. In this article, the optimizations for the micromixer volume and capillary diameter were presented based on the synthesis of CdSe nanocrystals (NCs). Spectra investigation revealed that the application of a small convective mixer of 36 μL led to 1/3 increase of CdSe concentration in the crude solution. The enhanced mixing of the precursors in this case was also demonstrated favorable to achieve CdSe NCs with narrow PL width. Fast heating and uniform reaction condition achieved in a narrow channel favored the preparation of high quality CdSe NCs under short residence time. However, the application of wide channel did not necessarily result in CdSe NCs with poor quality. Here, we demonstrated that high-quality CdSe NCs with narrow full width at half maximum (FWHM) as 32 nm and high quantum yield (QY) 34.7% could be prepared using an 844 μm inner diameter capillary. Based on the obtained results, the scaled-up synthesis of CdSe NCs was demonstrated, and a high quantity of 0.8 g dry CdSe NCs powder (3.5 nm, σ ~ 8.2%) was obtained within 1 h.     

基于CdSe/ZnS量子点光转化层的高稳定性白光LED器件

采用一步法合成了510,550和630 nm三种峰值的高稳定性、高量子效率核壳结构CdSe/ZnS量子点材料,其量子产率分别达到82%,98%,97%。将该量子点材料取代传统的荧光粉材料,与硅胶均匀混合后作为光转换层涂覆到蓝色InGaN LED芯片上,制备了白光LED器件。通过依次添加不同颜色量子点制备的量子点光转换层,考察了510,550和630 nm三色CdSe/ZnS量子点在硅胶中的不同配比对白光LED器件性能的影响,研究了不同颜色量子点之间的能量转换机制,利用量子点对白光光谱及其色坐标的影响机制,得到优化的白光器件结果及其三色量子点的配比,结果表明,当绿色、黄绿色、红色三种量子点之间的配比为24∶7∶10时,得到高稳定性、高效率的正白光器件特性,在电流20～200 mA范围内,色温变化为4 607～5 920 K,色坐标变化为（0.355 1,0.348 3）～（0.323 4,0.336 1）,显色指数变化为77.6～84.2,器件最高功率效率达到31.69 lm W-1@20 mA。另外,为了进一步考察器件性能稳定的原因,研究了时间、温度以及UV处理对CdSe/ZnS QDs/硅胶混合光转换材料稳定性的影响,结果表明,器件的高稳定性可归因于所采用的一步法合成的核壳结构量子点材料本身的稳定性,研究的优化器件结果是一种低能耗的优质白光光源,可使人们真实地感知物体的原貌,在正白光光源领域具有很好的应用前景。     

Macroscale alignment of CdSe/CdS nanorods by porous anodic alumina templates

Centimeter‐scale assemblies of highly ordered CdSe/CdS core‐shell nanorods have been successfully fabricated by infiltration of the nanorods into the pores of a transparent porous anodic alumina membrane. The high degree of the nanorod ordering is proved by the demonstration of both highly polarized PL and absorption of the aligned nanorods. The measured PL linear polarization degree is 53%. We have found that both the elongated CdS shell and the nearly spherical CdSe core exhibit a strong dependence of absorption on polarization angle with respect to the nanorod axis. We conclude that both CdS shell and CdSe core absorb more efficiently light with polarization along the axis of the nanorod. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

近红外量子点的发光机理研究

近红外量子点具有独特的光学性质,如荧光量子产率高,荧光寿命长,荧光发射波长可调,半峰宽窄且斯托克斯位移较大,耐光漂白能力强等, 及“近红外生物窗口”的优势,使它们在生物荧光标记、太阳能电池、量子化计算、光催化、化学分析、食品检测及活体成像等领域具有巨大的潜在应用价值。目前对近红外量子点的发光机理研究还不够完善,针对国内外的研究现状,重点对核/壳结构的量子点(CdTe/CdSe,CdSe/CdTe/ZnSe等)、三元量子点(Cu-In-Se,CuInS₂等)和掺杂型量子点(Cu∶InP等)三种不同类型近红外量子点的发光机理进行了综述。其中,Type-Ⅱ型核/壳结构量子点的发光机理多为带间复合发光,三元量子点以本征缺陷型发光为主,掺杂型量子点多为杂质缺陷型发光。探讨了近红外量子点发光原理存在的问题及发展的方向。对近红外量子点的发光机理进行系统地研究不仅有助于我们理解近红外量子点的发光性质,而且对完善相似高品质量子点的合成方法具有重要意义。     

Room-temperature ordered photon emission from multiexciton states in single CdSe core-shell nanocrystals

We report room-temperature ordered multiphoton emission from multiexciton states of single CdSe(CdZnS) core(-shell) colloidal nanocrystals (NCs) that are synthesized by wet chemical methods. Spectrally and temporally resolved measurements of biexciton and triexciton emission from single NCs are also presented. A simple four level system models the results accurately and provides estimates for biexciton and triexciton radiative lifetimes and quantum yields.     

ZnS薄膜参数对有机/无机复合发光器件特性的影响

半导体量子点(QDs)具有发光效率高和发光波长可调等特点。采用胶体CdSe QDs作电致发光器件的有源材料,TPD(N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine)作空穴传输层,ZnS作电子传输层,研究了有机/无机复合发光器件ITO/TPD/CdSe QDs/ZnS/Ag的电致发光特性。TPD和CdSe QDs薄膜采用旋涂方法、ZnS薄膜采用磁控溅射方法沉积,器件表面平整。CdSe QDs的光致发光和电致发光谱峰位波长均位于～580 nm,属于量子点的带边激子发光。我们与以前的ITO/ZnS/CdSe QDs/ZnS/Ag发光器件结构进行了对比,发现新的器件结构的电致发光谱没有观察到QDs表面态的发光,而且新器件的发光强度是ITO/ZnS/CdSe QDs/ZnS/Ag结构的～10倍。发光效率的提高归因于碰撞激发与载流子注入两种发光机制并存的结果：一方面电子经过ZnS 层加速后,碰撞激发CdSe QDs发光;另一方面,空穴从TPD层注入CdSe QDs 与QDs中激发的电子复合发光。我们进一步研究了ZnS电子加速层厚度对发光特性的影响,选择ZnS薄膜的厚度分别是80,120 和160 nm,发现随着ZnS层厚度增大,器件启亮电压升高,EL强度增大,但是击穿电压降低。EL峰位随着ZnS厚度的减小发生明显蓝移,对上述实验现象进行了机理解释。     

CdSe/CdS核壳量子点复合材料合成及其在白光发光二极管中的应用

采用有机化学合成法,利用正三辛基膦(TOP)辅助的快速注入生长方法,改进传统的制备工艺,实现了CdSe/CdS厚壳层核壳(8.6 ML)量子点复合材料的合成制备,并对所合成的核、核壳量子点及其复合材料的晶格结构、形貌特点与发光性质进行了XRD、TEM、SEM、UV-Vis、PL表征和红光补偿效果测试。测试结果表明,CdSe核具有立方纤锌矿晶格结构;CdSe/CdS量子点复合材料直径为45~75μm,呈菱形规则形貌,且颗粒分散性良好。采用该方法,可以提高量子产率,产率由4%(CdSe核)升至48%(CdSe/CdS核壳量子点);可以增强激子态发光能力,CdSe/CdS核壳量子点复合材料的荧光强度约为CdSe核的13倍。将该材料与YAG∶Ce~(3+)黄色荧光粉组合应用,获得了高光效(148.29 lm/W)、高显色指数(Ra为90.1,R9为97.0)的白光发光二级管,表明按照上述方法获得的CdSe/CdS核壳量子点复合材料在白光发光二极管中深红光波段具有较好的补偿效果。     

Mg掺杂ZnO纳米晶的低温共沉淀法制备及光学性质

采用共沉淀(co-precipitation)法制备了Mg掺杂ZnO纳米晶,分别用X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、紫外可见吸收(UV-Vis)光谱、光致发光(PL)光谱、透射电镜(TEM)、电子顺磁共振(EPR)等分析手段对样品进行了表征。探究了Mg离子在ZnO纳米晶中的存在状态,ZnO纳米晶颗粒尺寸和发射光谱随Mg掺杂浓度的变化,并对其发光机理进行了分析。结果表明:Mg离子在ZnO晶格中以部分晶格位,部分间隙位的方式存在,没有形成MgO表面壳层结构;随Mg掺杂浓度的增大,ZnO纳米晶的颗粒尺寸变小,发射光的光强增大。发射光的最佳激发波长为342nm,中心波长为500nm,荧光量子产率为22.8%。实验分析表明:Mg离子的掺杂在ZnO纳米晶中引入了锌空位(VZn),间隙位的镁离子(IMg),提供了新的复合中心,从而增强了ZnO纳米晶的光致发光。     

单核/双壳结构CdSe/CdS/ZnS纳米晶的合成与发光性质

以巯基乙酸为稳定剂,在水溶液中合成了单核/双壳结构的CdSe/CdS/ZnS纳米晶。在内核CdSe和外壳ZnS之间的内壳CdS作为晶格匹配调节层,能够很好的改善核/壳界面处的性能,而且,最外层ZnS能够最大程度地使激子受限。用TEM和XPS对纳米晶进行了表征,并且用光致发光光谱和吸收光谱对不同核壳结构的纳米晶的发光性能进行了比较,结果表明单核/双壳结构的纳米晶具有更加优异的发光特性。