大气环境下合成白光发射的Tb3+/Eu3+共掺杂全无机卤化物钙钛矿量子点

为克服因混合不同卤化物钙钛矿量子点发生阴离子交换反应、不稳定的红光发射卤化物钙钛矿量子点等而导致在获取白光发射方面存在的不足,提出了一种可以在大气环境下合成Tb³⁺,Eu³⁺稀土离子共掺杂全无机卤化物钙钛矿量子点的方法。调节Tb³⁺,Eu³⁺稀土离子的掺杂比例,调控从钙钛矿量子点主晶格到Tb³⁺和Eu³⁺离子的能量转移,获得了单一组分、白光发射的钙钛矿量子点(Tb,Eu):CsPbCl3和(Tb,Eu):CsPb(Cl/Br)3,并对量子点的形貌、结构、发光性能及能量传递机理和稳定性进行了详细研究。研究结果表明:在365nm激光激发下,不同含量Tb³⁺/Eu³⁺离子共掺杂的钙钛矿量子点(Tb,Eu):CsPbCl3发射光谱对应的色坐标位于1931色度图中的白光区域。在进料比PbCl2∶TbCl3∶EuCl3为1∶1.5∶1时,量子产率为3.59%,比纯的CsPbCl3量子点的量子产率(0.57%)提高了6倍。进一步研究发现,该(Tb,Eu):CsPbCl3量子点在空气中储存2个月之后,量子产率几乎保持不变(3.63%),保持了良好的稳定性。此外,研究了采用不同溶剂(正辛烷、十八烯)合成Tb³⁺/Eu³⁺共掺杂钙钛矿量子点的发光特性。Tb³⁺/Eu³⁺离子共掺杂的钙钛矿量子点(Tb,Eu):CsPbCl3可实现单一组分的白光发射,有良好的稳定性,具备一定的应用前景。     

Electroluminescence of colloidal ZnSe quantum dots

The article reports a green chemical synthesis of colloidal ZnSe quantum dots at a moderate temperature. The prepared colloid sample is characterised by UV-vis absorption spectroscopy and transmission electron microscopy. UV-vis spectroscopy reveals as-expected blue-shift with strong absorption edge at 400 nm and micrographs show a non-uniform size distribution of ZnSe quantum dots in the range 1-4 nm. Further, photoluminescence and electroluminescence spectroscopies are carried out to study optical emission. Each of the spectroscopies reveals two emission peaks, indicating band-to-band transition and defect related transition. From the luminescence studies, it can be inferred that the recombination of electrons and holes resulting from interband transition causes violet emission and the recombination of a photon generated hole with a charged state of Zn-vacancy gives blue emission. Meanwhile electroluminescence study suggests the application of ZnSe quantum dots as an efficient light emitting device with the advantage of colour tuning (violet-blue-violet).     

低强度飞秒激光激发下CdTe和CdTe/CdS核壳量子点的荧光上转换研究

利用400 nm和800 nm不同波长的低强度飞秒激光,对CdTe和CdTe/CdS核壳量子点溶胶进行激发,研究其稳态和时间分辨荧光性质.800 nm飞秒激光激发下,CdTe和CdTe/CdS核壳量子点产生上转换发光现象,上转换荧光峰与400 nm激发下的荧光峰相比蓝移最多达15 nm,而且蓝移值与荧光量子产率有关.变功率激发确认激发光功率与上转换荧光强度间满足二次方关系,时间分辨荧光的研究表明荧光动力学曲线服从双e指数衰减.提出表面态辅助的双光子吸收模型是低激发强度上转换发光的主要机理.CdTe和CdT 关键词： CdTe量子点 CdTe/CdS核壳量子点 时间分辨荧光 上转换荧光     

基于InP/ZnS核壳结构量子点的色转换层设计及制作

提出了采用环境友好型InP/ZnS核壳结构量子点材料制备匹配蓝光Micro-LED阵列的量子点色转换层以实现Micro-LED阵列器件全彩化的技术方案。通过采用倒置式量子点色转换层方案,实现了InP/ZnS量子点材料和Micro-LED阵列的非直接接触,从而可以缓解LED中热量聚集导致的量子点材料发光主波长偏移、半峰宽展宽以及发光效率衰减等问题。量子点色转换层中内嵌PDMS聚合物柔性膜层,可以消除咖啡环效应,同时,色转换层中内嵌飞秒激光图案化处理的500 nm长波通滤光膜层,可以抑制蓝光从非蓝色像素单元出射。最后,实验制备了像素单元中心间距90μm的16×16 InP/ZnS量子点色转换层。该设计可以实现基于蓝光Micro-LED阵列的全彩色Micro-LED显示器件的制备,并且该制备方法可以降低全彩色Micro-LED阵列显示器件的制备成本。     

Photoluminescence from surface-oxidized Ge nanoclusters

Photoluminescence from gas-evaporated Ge nanoclusters consisting of a crystalline core encased in an oxide shell are presented. An as-grown sample shows room temperature luminescence with separate peaks around 357 and 580 nm. Prolonged air exposure of the clusters reduces the Ge core dimensions, and the emission initially at 580 nm shifts to 420 nm; however, the violet luminescence at 357 nm displays no difference. These results indicate that there are two mechanisms involved with light emission from Ge nanoclusters, visible light emission associated with the quantum confinement effect, and violet light emission correlated to luminescent centers.     

Influence of pH on luminescence from water-soluble colloidal Mn-doped ZnSe quantum dots capped with different mercaptoacids

Water-soluble ZnSe/ZnS core–shell quantum dots with ZnSe core doped by manganese ions show different luminescence response to pH changes in aqueous solutions depending on the type of solubilizing agents (thioglycolic acid, mercaptoundecanoic acid, sodium mercaptopropylsulfonate). In the case of long-chain mercaptoundecanoic acid only excitonic emission is affected by pH changes. Short-chain thioglycolic acid brings about equal excitonic/Mn emission variations with pH, while mercaptopropylsulfonate-stabilized quantum dots are insensitive to pH. The mechanism discussed here is based on the competition between different relaxation channels for excited excitons in ZnSe: excitonic radiative recombination, energy transfer to Mn ion and the photogenerated electron trapping due to the presence of protonated carboxyl group. ZnSe:Mn/ZnS quantum dots stabilized with long-chain mercaptoacids may be used as a new type of fluorescence ratiometric pH-sensor or indicator.     

超声法制备碳量子点发光性能的影响因素分析

超声法制备碳量子点过程简单,成本低廉,不易产生二次污染,应用前景广泛。为优化超声法制备碳量子点的各工艺参数,制备了关键工艺参数不同的碳量子点样品,测试其发射与激发光谱,分析了量子点浓度,溶剂种类,辅助剂种类、浓度,超声功率、时间等参数对碳量子点发光性能影响。结果表明超声法制备的碳量子点具有激发光波长依赖性,发射峰位置随激发波长的变化而发生明显改变;碳量子点浓度增加,发光强度由于非辐射能量传递和团聚作用,先增大后减小;由于溶剂效应,碳量子点在乙醇中比在水中发光强度更强,波长更短,且浓度越大时波峰移动越明显;相比盐酸,以NaOH为辅助剂制备的碳量子点表面钝化程度高,发光强度强;增加辅助剂NaOH浓度可提高量子点表面钝化程度,增大发光强度;同等时间下增加超声功率或同等功率下适量增加超声时间,可制备更多的碳量子点样品,但超声时间过长,碳量子点容易发生团聚猝灭现象。以上影响因素分析为超声法制备碳量子点的工艺参数优化提供了理论基础,有利于碳量子点大规模低成本的生产应用。     

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。     

Role of nitrogen and oxygen in emission of Si quantum dots formed by pulse laser

Silicon quantum dots fabricated by nanosecond pulsed laser in nitrogen, oxygen or air atmosphere have enhanced photoluminescence (PL) emission with the stimulated emission observed at about 700 nm. It is difficult to distinguish between the photoluminescence peaks emitted from samples prepared in different atmospheres. The reason for the appearance of similar peaks may be the similar distribution of the localised states in the gap for different samples when silicon dangling bonds of quantum dots are passivated by nitrogen or oxygen. It is revealed that both the kind and the density of passivated bonds on quantum dot surface prepared in oxygen or nitrogen have a strong influence on the enhancement of PL emission.     

Pressure-induced modulation of the confinement in self-organized quantum dots produced and detected by a near-field optical probe

Near-field optical probing, or nanoprobing, achieves spatial resolution that surpasses the diffraction limit of light and makes possible the luminescence imaging and spectroscopy of single quantum dots in dense arrays of dots. We use optical nanoprobing to study self-organized InGaAs quantum dots grown on (3 1 1)B oriented GaAs substrates. Here, we emphasize a new feature of nanoprobing: pressure-induced strain modulation near the surface. Operating in near-field optical excitation–collection mode, the probe makes contact with the surface and exerts direct pressure whose main effect is a compressive uniaxial strain under the probe. By adjusting the applied pressure, we modulate the local strain environment in and around a quantum dot, but still preserve the capability to capture its near-field luminescence. Nanoprobe pressure effects modify the confinement potential and radiative emission of single quantum dots, and the coupling strength between dots. This opens new possibilities for the study and control of the optical and electronic properties of single- and coupled-quantum dots.     

Narrow luminescence linewidth of a silicon quantum dot

Single-dot luminescence spectroscopy was used to study the emission linewidth of individual silicon nanocrystals from low temperatures up to room temperature. The results show a continuous line narrowing towards lower temperatures with a linewidth as sharp as 2 meV at 35 K. This value, clearly below the thermal broadening at this temperature, proves the atomiclike emission from silicon quantum dots subject to quantum confinement. The low temperature measurements further reveal a approximately 6 meV replica, whose origin is discussed. In addition, an approximately 60 meV TO-phonon replica was detected, which is only present in a fraction of the dots.     

水溶胶CdSe/CdS核/壳结构纳米晶制备及光学性质的研究

以巯基乙酸为稳定剂在水溶液中合成了水溶胶CdSe/CdS核/壳结构的量子点,利用X射线粉末衍射(XRD)和X射线光电子能谱(XPS)对量子点结构进行了表征;并对化学组成和尺寸分布进行了研究。通过紫外-可见吸收光谱、激发光谱与发射光谱研究了它们的发光特性。     

Chemiluminescence resonance energy transfer in the luminol-CdTe quantum dots conjugates

The luminol-CdTe quantum dots (QDs) conjugates were prepared through the reaction between -NH₂ and -COOH. The resonance energy transfer between chemiluminescence donor (luminol-H₂O₂ system) and quantum dots (QDs, with different emission peaks) acceptors (CRET) was investigated. The luminescence of QDs in luminol-QDs conjugates in the process of CRET was influenced by the molar ratio of luminol/QDs. It could reach higher luminescence intensity while the luminol/QDs value was 1/1. Quantum yield of QDs and overlapping areas between the emission spectrum of luminol and adsorption spectrum of QDs played important roles in the CRET efficiency of luminol-QDs conjugates. The higher CRET efficiency (21.2%) was observed when the 540 nm QDs were used as acceptors. This work will offer helpful knowledge for the CRET studies based on QDs.     

Luminescence of a semiconductor quantum dot system

A microscopic theory is used to study photoluminescence of semiconductor quantum dots under the influence of Coulomb and carrier-photon correlation effects beyond the Hartree-Fock level. We investigate the emission spectrum and the decay properties of the time-resolved luminescence from initially excited quantum dots. The influence of the correlations is included within a cluster expansion scheme up to the singlet-doublet level.     

Growth and time-resolved photoluminescence study of self-organized CdSe quantum dots in ZnSe

Employing two different growth methods: standard molecular beam epitaxy (MBE) and low-temperature atomic layer epitaxy (ALE) with subsequent annealing, we have obtained high-quality quantum dot structures consisting of CdSe embedded in ZnSe. Single dot emission lines are observed in micro-luminescence. The samples have been investigated by further optical methods including time-resolved photoluminescence under resonant excitation at 4.2 K. Distinct properties of systems with three-dimensional confinement are observed such as the suppression of the interaction between isolated quantum dots (QDs). In standard quantum wells tunneling/hopping processes generally lead to a pronounced red shift of the luminescence over time due to a lateral localization of excitons in potential fluctuations. A much less pronounced red shift is observed for the QDs reflecting only the different lifetimes of single dots and higher excited states. The red shift completely vanishes under resonant excitation that selectively excites only a few QDs of the ensemble in the layer. Typical behaviour is also observed from the halfwidth of the quantum dot emission.     

Spontaneous emission of two quantum dots in a single-mode cavity

The spontaneous emission spectrum from two quantum dots （QDs） that are strongly coupled with a single-mode nanocavity is investigated using rigorous numerical calculations and simple analytical solutions of quantum dynamics. The emission spectra both from the side and along the axis of the cavity are considered. Modification of two parameters, the coupling strength and the detuning between the transition frequencies of the two quantum dots, allows us to efficiently control the shape of the spontaneous emission spectrum. Different profiles and their physical origins can be well understood in the dressed-state picture for the light-QD interaction in the on-resonance and off-resonance situations. In the on-resonance situation, the emission spectra exhibit symmetric features, and they are not altered by the asymmetry in the coupling pa- rameters. The axis spectra show two emission peaks while the side spectra have three emission peaks. In the off-resonance situation, the emission spectra always show an asymmetrical three-peak feature. When the two QDs have different decay parameters, singular features （a peak or a dip） can take place at the frequency of the cavity mode, and this is attributed to the unbalanced process of the emission and absorption of a single photon.     

Activation of silicon quantum dots for emission

The emission of silicon quantum dots is weak when their surface is passivated well. Oxygen or nitrogen on the surface of silicon quantum dots can break the passivation to form localized electronic states in the band gap to generate active centers where stronger emission occurs. From this point of view, we can build up radiative matter for emission. Emissions of various wavelengths can be obtained by controlling the surface bonds of silicon quantum dots. Our experimental results demonstrate that annealing is important in the treatment of the activation, and stimulated emissions at about 600 and 700 nm take place on active silicon quantum dots.     

不同气体氛围下硅量子点的结构及其发光机理

纳秒脉冲激光在氮气、氧气和空气等不同氛围中加工出的硅量子点都有光致荧光(PL)的发光增强效应,并且在700 nm波长附近观察到了受激辐射.在不同氛围下生成的样品有几乎相同的PL光谱分布,其原因是不同氛围下加工出的样品带隙中有相同的电子态分布.计算结果显示:当硅量子点表面被氮或氧钝化后,在带隙中能够形成几乎相同的局域电子态,这种局域电子态可以俘获来自导带的电子,从而形成亚稳态,这是PL发光增强乃至产生受激辐射的关键因素. 关键词： 硅量子点 PL光谱 发光增强 电子局域态     

高压下低维材料的光学特性调控

压力作为独立于物质温度和组分的热力学参量,为物质科学的研究和创新提供了新的维度,已成为发展新概念、创造新理论及探索新材料的重要源泉。本文主要概述了作者近年来在高压下低维材料的光学特性调控方面所取得的一些进展。通过压力改变激子结合能和卤素八面体的扭曲行为,实现了低维卤化物钙钛矿纳米材料发光从“0”到“1”的突破,提出了压力诱导发光的概念;通过引入压力效应,利用压力对纳米材料表面配体的调控,改变了表面配体与CdSe量子点的相互作用和能级耦合,促进了Hirshfeld电荷转移,从而实现了CdSe量子点的荧光大幅度增强近一个数量级;借助高压手段调控能带结构,成功实现了CdSe/CdS半导体纳米晶由准Ⅱ型核壳结构向Ⅰ型核壳结构的构型转变。上述工作加深了对发光材料在极端压缩条件下构效关系的深入理解和认识,研究成果为设计和制备具有特定功能的低维材料提供了新方法。     

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.