Thermally Activated Photoluminescence in Lead Selenide Colloidal Quantum Dots

The thermal activation processes in PbSe colloidal quantum dots and their influence on the ground‐state exciton emission are discussed. Activation of a dark exciton occurs at 1.4–7 K, assisted by an acoustic phonon coupling. Activation of a bright exciton occurs at 100–200 K, which appears as a sudden change in the photoluminescence band intensity, energy, and full width at half maximum. This activation overcomes the dark–bright‐state splitting, when the activation temperature increases with the decrease of the dots' size. The dark exciton lifetime is found to be ≈6–12 µs at 1.4 K, while the bright exciton lifetime at 300 K evaluated as 450 ns varies slightly with the change in the size of the dots. In addition, the emission quantum yield of these dots, measured at a variety of temperatures when dissolved in various solvents, reveals information about the influence of the environment on the recombination processes.     

Elucidation of Photoluminescence Blinking Mechanism and Multiexciton Dynamics in Hybrid Organic–Inorganic Perovskite Quantum Dots

Halide perovskites (ABX₃) have emerged as promising materials in the past decade owing to their superior photophysical properties, rendering them potential candidates as solar cells, light‐emitting diode displays, and lasing materials. To optimize their utilization into optoelectronic devices, fundamental understanding of the optical behaviors is necessary. To reveal the comprehensive structure–property relationship, CH₃NH₃PbBr₃ (MAPbBr₃) perovskite quantum dots (PQDs) of three different sizes are prepared by controlling the precipitation temperature. Photoluminescence (PL) blinking, a key process that governs the emission efficiency of the PQD materials, is investigated in detail by the time‐resolved spectroscopic measurements of individual dots. The nature of the generated species in the course of blinking events is identified, and the mechanism governing the PL blinking is studied as a function of PQD sizes. Further, the practical applicability of MAPbBr₃ PQDs is assessed by studying the multiexciton dynamics under high photoexcitation intensity under which most of the display devices work. Ultrafast transient absorption spectroscopy helped in uncovering the volume‐dependent Auger recombination rates, which are further explored by comparing the early‐time transitions related to surface trap states and higher band states.     

Improving the Stability of Metal Halide Perovskite Quantum Dots by Encapsulation

Metal halide perovskite quantum dots (PQDs), with excellent optical properties and spectacular characteristics of direct and tunable bandgaps, strong light‐absorption coefficients, high defect tolerance, and low nonradiative recombination rates, are highly attractive for modern optoelectronic devices. However, the stability issue of PQDs remains a critical challenge of this newly emerged material despite the recent rapid progress. Here, the encapsulation strategies to improve the stability of PQDs are comprehensively reviewed. A special emphasis is put on the effects of encapsulation, ranging from the improvement of chemical stability, to the inhibition of light‐induced decomposition, to the enhancement of thermal stability. Particular attention is devoted to summarizing the encapsulation approaches, including the sol–gel method, the template method, physical blending, and microencapsulation. The selection principles of encapsulation materials, including the rigid lattice or porous structure of inorganic compounds, the low penetration rate of oxygen or water, as well as the swelling–deswelling process of polymers, are addressed systematically. Special interest is put on the applications of the encapsulated PQDs with improved stability in white light‐emitting diodes, lasers, and biological applications. Finally, the main challenges in encapsulating PQDs and further investigation directions are discussed for future research to promote the development of stable metal halide perovskite materials.     

Mixed Lead Halide Passivation of Quantum Dots

Infrared‐absorbing colloidal quantum dots (IR CQDs) are materials of interest in tandem solar cells to augment perovskite and cSi photovoltaics (PV). Today's best IR CQD solar cells rely on the use of passivation strategies based on lead iodide; however, these fail to passivate the entire surface of IR CQDs. Lead chloride passivated CQDs show improved passivation, but worse charge transport. Lead bromide passivated CQDs have higher charge mobilities, but worse passivation. Here a mixed lead‐halide (MPbX) ligand exchange is introduced that enables thorough surface passivation without compromising transport. MPbX–PbS CQDs exhibit properties that exceed the best features of single lead‐halide PbS CQDs: they show improved passivation (43 ± 5 meV vs 44 ± 4 meV in Stokes shift) together with higher charge transport (4 × 10^‐2 ± 3 × 10^‐3 cm² V^‐1 s^‐1 vs 3 × 10^‐2 ± 3 × 10^‐3 cm² V^‐1 s^‐1 in mobility). This translates into PV devices having a record IR open‐circuit voltage (IR V_oc) of 0.46 ± 0.01 V while simultaneously having an external quantum efficiency of 81 ± 1%. They provide a 1.7× improvement in the power conversion efficiency of IR photons (>1.1 µm) relative to the single lead‐halide controls reported herein.     

Dynamic Passivation in Perovskite Quantum Dots for Specific Ammonia Detection at Room Temperature

Perovskite structured CsPbX₃ (X = Cl, Br, or I) quantum dots (QDs) have attracted considerable interest in the past few years due to their excellent optoelectronic properties. Surface passivation is one of the main pathways to optimize the optoelectrical performance of perovskite QDs, in which the amino group plays an important role for the corresponding interaction between lead and halide. In this work, it is found that ammonia gas could dramatically increase photoluminescence of purified QDs and effectively passivate surface defects of perovskite QDs introduced during purification, which is a reversible process. This phenomenon makes perovskite QDs a kind of ideal candidate for detection of ammonia gas at room temperature. This QD film sensor displays specific recognition behavior toward ammonia gas due to its significant fluorescence enhancement, while depressed luminescence in case of other gases. The sensor, in turn‐on mode, shows a wide detection range from 25 to 350 ppm with a limit of detection as low as 8.85 ppm. Meanwhile, a fast response time of ≈10 s is achieved, and the recovery time is ≈30 s. The fully reversible, high sensitivity and selectivity characteristics make CsPbBr₃ QDs ideal active materials for room‐temperature ammonia sensing.     

Spin–Lattice Relaxation of Mn Ions in Nanostructures with Semiconductor Quantum Dots

We use the combination of nonequilibrium phonon and exciton luminescence techniques to study the spin dynamics in diluted magnetic semiconductor structures with (Cd,Mn)Te and (Cd,Mn)Se quantum dots (QDs). We show that the spin–lattice relaxation (SLR) of Mn ions in these structures differs strongly from the SLR in quantum wells. We explain the results by a model where SLR process in structures with QDs is modified by the spin diffusion on Mn ions from the QD to a wetting layer.     

Recent Progress and Development in Inorganic Halide Perovskite Quantum Dots for Photoelectrochemical Applications

Inorganic halide perovskite quantum dots (IHPQDs) have recently emerged as a new class of optoelectronic nanomaterials that can outperform the existing hybrid organometallic halide perovskite (OHP), II–VI and III–V groups semiconductor nanocrystals, mainly due to their relatively high stability, excellent photophysical properties, and promising applications in wide‐ranging and diverse fields. In particular, IHPQDs have attracted much recent attention in the field of photoelectrochemistry, with the potential to harness their superb optical and charge transport properties as well as spectacular characteristics of quantum confinement effect for opening up new opportunities in next‐generation photoelectrochemical (PEC) systems. Over the past few years, numerous efforts have been made to design and prepare IHPQD‐based materials for a wide range of applications in photoelectrochemistry, ranging from photocatalytic degradation, photocatalytic CO₂ reduction and PEC sensing, to photovoltaic devices. In this review, the recent advances in the development of IHPQD‐based materials are summarized from the standpoint of photoelectrochemistry. The prospects and further developments of IHPQDs in this exciting field are also discussed.     

Co2+掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,以3-巯基丙酸为表面修饰剂,成功制备出Co2+掺杂水溶性ZnS量子点。采用X射线衍射仪、透射电子显微镜、原子发射光谱仪、紫外-可见吸收光谱仪和荧光分光光度计等,研究了Co2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明:所得产物均为ZnS立方型闪锌矿结构,量子点呈不规则球形,粒径主要集中在5.2 nm左右;掺杂样品发红色荧光,发光性能明显增强,属于Co2+形成的杂质能级(4A1—4T1)与缺陷的复合发光。同时,利用红外吸收光谱对Co2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

圆偏振光诱导CdTe量子点再生长及其对光致发光的影响

实验研究了以3-巯基丙酸为配体合成的水溶性CdTe量子点经过非偏振光与圆偏振光照射处理后, 量子点的再生长变化规律。采用光致发光谱、紫外-可见吸收光谱、透射电子显微镜与X射线衍射等表征手段分析表明: 非偏振光会促进CdTe量子点的光氧化, 导致量子点尺寸缩小, 荧光发光峰位蓝移, 且发光效率降低; 而圆偏振光增强了配体的光氧化, 在量子点表面形成CdS层, 导致量子点尺寸进一步增大, 荧光发光峰红移, 且发光效率提升。进一步讨论了CdTe量子点与配体之间的键合作用, 相关光化学反应机制及其对量子点光致发光性质的影响。     

硫化铜量子点的研究进展

硫化铜量子点作为一种p型半导体纳米晶,具有很强的表面等离子体共振效应、低的毒性以及独特的光学和电学性能,在光催化、生物技术、光电转换材料领域受到了极大关注。由于单分散的硫化铜量子点的制备过程复杂,效率较低,并且纯的硫化铜量子点电导率较低,这极大地限制了其在能量存储器件方面的应用。此外,由于硫化铜量子点复杂的能带结构和独特的p型半导体特性,针对硫化铜量子点的光学性能调控尚不成熟。基于此,本文综述了硫化铜量子点在制备方面的研究现状与取得的进展,介绍了硫化铜量子点的能带结构、晶体结构,及其在量子点敏化太阳能电池、光催化降解污染物、肿瘤细胞诊断与治疗等方面的研究进展,并对硫化铜量子点或Cu系量子点更进一步的研究、开发应用提出了几点建议。     

From Lead Halide Perovskites to Lead‐Free Metal Halide Perovskites and Perovskite Derivatives

Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb‐free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb‐free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature. The theoretical understanding explains well why Pb halide perovskites exhibit superior photovoltaic properties, but Pb‐free perovskites and perovskite derivatives do not.     

Enhanced Stability and Tunable Photoluminescence in Perovskite CsPbX3/ZnS Quantum Dot Heterostructure

All‐inorganic perovskite CsPbX₃ (X = Cl, Br, I) and related materials are promising candidates for potential solar cells, light emitting diodes, and photodetectors. Here, a novel architecture made of CsPbX₃/ZnS quantum dot heterodimers synthesized via a facile solution‐phase process is reported. Microscopic measurements show that CsPbX₃/ZnS heterodimer has high crystalline quality with enhanced chemical stability, as also evidenced by systematic density functional theory based first‐principles calculations. Remarkably, depending on the interface structure, ZnS induces either n‐type or p‐type doping in CsPbX₃ and both type‐I and type‐II heterojunctions can be achieved, leading to rich electronic properties. Photoluminescence measurement results show a strong blue‐shift and decrease of recombination lifetime with increasing sulfurization, which is beneficial for charge diffusion in solar cells and photovoltaic applications. These findings are expected to shed light on further understanding and design of novel perovskite heterostructures for stable, tunable optoelectronic devices.     

CdSe胶质量子点的电致发光特性研究

采用胶体化学法合成硒化镉(CdSe)胶质量子点, 在此基础上制成了以CdSe胶质量子点为有源层, 结构为ITO/ZnS/CdSe/ZnS/Al的电致发光(EL)器件. 透射电镜测量表明量子点的尺寸为4.3 nm, 扫描电子显微镜测量ZnS薄膜和Al薄膜结果显示表面均较为平整, 由器件结构的X射线衍射分析观察到了CdSe(111)、ZnS(111)等晶面的衍射, 表明器件中包含了CdSe量子点和ZnS绝缘层材料. 光致发光谱表征胶质量子点的室温发光峰位于614 nm, 电致发光测量得到器件在室温下的发光波长位于450 ~ 850 nm, 峰值在800 nm附近. 本文对电致发光机制及其与光致发光谱的区别进行了讨论.     

Cerium and Ytterbium Codoped Halide Perovskite Quantum Dots: A Novel and Efficient Downconverter for Improving the Performance of Silicon Solar Cells

Quantum cutting can realize the emission of multiple near‐infrared photons for each ultraviolet/visible photon absorbed, and has potential to significantly improve the photoelectric conversion efficiency (PCE) of solar cells. However, due to the lack of an ideal downconversion material, it has merely served as a principle in the laboratory until now. Here, the fabrication of a novel type of quantum cutting material, CsPbCl_1.5Br_1.5:Yb³⁺, Ce³⁺ nanocrystals is presented. Benefiting from the larger absorption cross‐section, weaker electron–phonon coupling, and higher inner luminescent quantum yield (146%), the doped perovskite nanocrystals are successfully explored as a downconverter of commercial silicon solar cells (SSCs). Noticeably, the PCE of the SSCs is improved from 18.1% to 21.5%, with a relative enhancement of 18.8%. This work exhibits a cheap, convenient, and effective way to enhance the PCE of SSCs, which may be commercially popularized in the future.