Near‐Infrared Emission from Tin–Lead (Sn–Pb) Alloyed Perovskite Quantum Dots by Sodium Doping

Phase‐stable CsSn_xPb_1?xI₃ perovskite quantum dots (QDs) hold great promise for optoelectronic applications owing to their strong response in the near‐infrared region. Unfortunately, optimal utilization of their potential is limited by the severe photoluminescence (PL) quenching, leading to extremely low quantum yields (QYs) of approximately 0.3 %. The ultra‐low sodium (Na) doping presented herein is found to be effective in improving PL QYs of these alloyed QDs without alerting their favourable electronic structure. X‐ray photoelectron spectroscopy (XPS) studies suggest the formation of a stronger chemical interaction between I^? and Sn²⁺ ions upon Na doping, which potentially helps to stabilize Sn²⁺ and suppresses the formation of I vacancy defects. The optimized PL QY of the Na‐doped QDs reaches up to around 28 %, almost two orders of magnitude enhancement compared with the pristine one.     

CdSe Quantum Dots and N719‐Dye Decorated Hierarchical TiO2 Nanorods for the Construction of Efficient Co‐Sensitized Solar Cells

Three‐dimensional hierarchical TiO₂ nanorods (HTNs) decorated with the N719 dye and 3‐mercaptopropionic or oleic acid capped CdSe quantum dots (QDs) in photoanodes for the construction of TiO₂ nanorod‐based efficient co‐sensitized solar cells are reported. These HTN co‐sensitized solar cells showed a maximum power‐conversion efficiency of 3.93 %, and a higher open‐circuit voltage and fill factor for the photoanode with 3‐mercaptopropionic acid capped CdSe QDs due to the strong electronic interactions between CdSe QDs, N719 dye and HTNs, and the superior light‐harvesting features of the HTNs. An electrochemical impedance analysis indicated that the superior charge‐collection efficiency and electron diffusion length of the CdSe QD‐coated HTNs improved the photovoltaic performance of these HTN co‐sensitized solar cells.     

CdSe Spherical Quantum Dots Stabilised by Thiomalic Acid: Biphasic Wet Synthesis and Characterisation

CdSe quantum dots stabilised by thiomalic acid have been synthesised by an aqueous biphasic ligand exchange reaction in air. The materials are completely water‐soluble and were found to be stable over a long time. X‐ray diffraction and transmission electron microscopy reveal the formation of CdSe nanocrystals with cubic structure (a=0.6077 nm; spatial group: F‐43m). The average particle size is about 5 nm. Energy dispersive X‐ray analysis shows that the nanocrystals are nonstoichiometric, with a Cd/Se ratio varying between 60/40 and 70/30, and indicates the presence of Cd²⁺ ions at the nanocrystal surface. Diffuse reflectance infrared Fourier transform measurements suggest that thiomalic acid chelates CdSe through the thiol group and one carboxylic function, while the second COOH group is semi‐free. A complex‐like structure is proposed, in which thiomalic acid forms a five‐membered chelate ring with the Cd²⁺ ions present on the nanocrystal surface. Chelate effect accounts for the easiness of ligand exchange and is expected to additionally stabilise the nanosystem.     

有机体系中II–VI族量子点的制备及其合成机理

量子点由于其量子效应而具有既不同于体相材料又有别于一般分子的优异光学性能,因此在生物医学领域,特别是在生物标记中具有良好的应用前景。II–VI族量子点由于其荧光发射波长几乎覆盖了整个可见光区而引起人们的关注,其中在有机体系中合成油溶性II–VI族量子点具有反应产物稳定,量子产率高,并且可以制备性能更加优异的核–壳结构的量子点（CdSe/ZnS, CdSe/CdS等）等优点,因此在过去的十几年中被广泛而深入地研究。本文重点综述了在有机体系中,单分散、高荧光性能II–VI族量子点的制备方法——高温热解法及其合成机理的研究进展,并对今后的研究方向作了展望。     

Research Update of Emergent Sulfur Quantum Dots in Synthesis and Sensing/Bioimaging Applications

Due to their unique optical property, low toxicity, high hydrophilicity, and low cost, sulfur quantum dots (SQDs), an emerging luminescent nanomaterial, have shown great potential in various application fields, such as sensing, bioimaging, light emitting diode, catalysis, and anti-bacteria. This minireview updates the synthetic methods and sensing/bioimaging applications of SQDs in the last few years, followed by discussion of the potential challenges and prospects in their synthesis and sensing/bioimaging applications, with the purpose to provide some useful information for researchers in this field.     

水稳定的镁掺杂ZnO量子点:一锅法合成及细胞成像应用

一锅法合成了镁掺杂的ZnO量子点,利用APTES对其进行表面包覆,并采用XRD、TEM、UV-Vis、PL和FTIR等对材料进行了表征。结果表明镁掺杂能明显增强荧光发光强度,在合适的掺杂浓度(30%)下其量子产率由11%增加到33%。通过APTES的表面包覆使镁掺杂的ZnO量子点具有良好的水溶性和荧光稳定性,可用于MCF-7细胞成像研究。     

水稳定的镁掺杂ZnO量子点:一锅法合成及细胞成像应用

一锅法合成了镁掺杂的ZnO量子点, 利用APTES对其进行表面包覆, 并采用XRD、TEM、UV-Vis、PL和FTIR等对材料进行了表征。结果表明镁掺杂能明显增强荧光发光强度, 在合适的掺杂浓度(30%)下其量子产率由11%增加到33%。通过APTES的表面包覆使镁掺杂的ZnO量子点具有良好的水溶性和荧光稳定性, 可用于MCF-7细胞成像研究。     

异原子掺杂石墨烯量子点的制备、性能及应用

发光石墨烯量子点(graphene quantum dots,GQDs)的良好理化性能引起许多领域研究人员的关注,但其荧光量子产率不高、活性位点相对较少、选择性较差等缺陷限制了它在分析传感领域的应用。异原子掺杂GQDs可以在一定程度上解决这些问题。本文介绍了异原子掺杂GQDs的制备方法、理化性质和应用情况,并对异原子掺杂GQDs的发展和应用前景进行分析和展望。     

石墨相氮化碳量子点的制备及应用的研究进展

近年来,石墨相氮化碳(g-C3N4)因其稳定的物理化学性能和良好的生物相容性而受到研究者关注。与块体g-C3N4相比,石墨相氮化碳量子点(g-CNQDs)尺寸更小、荧光效率更高,且具有量子限域效应,因此拥有特殊的理化性质与更好的光催化性能。本文主要从g-CNQDs的制备策略和应用展开讨论,着重综述了微波辅助法、低温固相法、热化学腐蚀法和电化学刻蚀法制备g-CNQDs,以及g-CNQDs在催化剂、离子检测、生物传感与诊疗等领域的最新应用研究进展;指出了目前g-CNQDs在性质、制备和应用等研究方面的重点和难点;最后对g-CNQDs存在的问题和未来的发展方向作出了展望。     

Synthesis of Multifunctional Mn‐Doped CdTe/ZnS Core/Shell Quantum Dots

The synthesis of a novel water‐soluble Mn‐doped CdTe/ZnS core‐shell quantum dots using a proposed ultrasonic assistant method and 3‐mercaptopropionic acid (MPA) as stabilizer is descried. To obtain a high luminescent intensity, post‐preparative treatments, including the pH value, reaction temperature, reflux time and atmosphere, have been investigated. For an excellent fluorescence of Mn‐doped CdTe/ZnS, the optimal conditions were pH 11, reflux temperature 100°C and reflux time 3 h under N₂ atmosphere. While for phosphorescent Mn‐doped CdTe/ZnS QDs, the synthesis at pH 11, reflux temperature 100°C and reflux time 3 h under air atmosphere gave the best strong phosphorescence. The characterizations of Mn‐doped CdTe/ZnS QDs were also identified using AFM, IR, powder XRD and thermogravimetric analysis. The data indicated that the photochemical stability and the photoluminescence of CdTe QDs are greatly enhanced by the outer inorganic ZnS shell, and the doping Mn²⁺ ions in the as‐prepared quantum dots contribute to strong luminescence. The strong luminescence of Mn‐doped CdTe/ZnS QDs reflected that Mn ions act as recombination centers for the excited electron‐hole pairs, attributing to the transition from the triplet state (⁴T₁) to the ground state (⁶A₁) of the Mn²⁺ ions. All the experiments demonstrated that the surface states played important roles in the optical properties of Mn‐doped CdTe/ZnS core‐shell quantum dots.     

绿色、低成本球磨-水热法制备石墨烯量子点及其应用研究

以绿色、简单、成本低的球磨方法制备的石墨烯为碳源,采用一步水热法成功制备了分散性好、尺寸分布均一、平均直径为(4.80 ± 0.20) nm、厚度为1~3层石墨烯烯量子点.分别采用高分辨透射电镜、原子力显微镜、傅里叶变换红外光谱、X射线光电子能谱、紫外-可见吸收光谱、荧光光谱等对石墨烯量子点进行形貌、结构以及荧光性能的表征. 合成的石墨烯量子点可用于Fe.3+的非标记、特异性检测,检测线性范围为2.0×10.-6~7.0×10.-4 mol/L,检出限为1.8×10.-6 mol/L(S/N=3),同时对检测机理进行了推断,证明此石墨烯量子点用于自来水中Fe.3+的检测的可行性;基于其低毒性和优良的生物相容性,所制备的石墨烯量子点可应用于细胞成像研究.本研究为碳纳米材料的制备提供了一种新途径,也为石墨烯量子点在生化分析、成像等方面的研究奠定了基础.     

Thiolate‐Mediated Photoinduced Synthesis of Ultrafine Ag2S Quantum Dots from Silver Nanoparticles

Photoinduced syntheses offer significant advantages over conventional thermal strategies, including improved control over reaction kinetics and low synthesis temperatures, affording nanoparticles with nontrivial and thermodynamically unstable structures. However, the photoinduced syntheses of non‐metallic nanocrystalline products (such as metal sulfides) have not yet been reported. Herein, we demonstrate the first photoinduced synthesis of ultrafine (sub‐2 nm) Ag₂S quantum dots (QDs) from Ag nanoparticles at 10 °C. By thorough investigation of the mechanism for the transformation, a fundamental link was established between the intrinsic structures of the molecular intermediates and the final Ag₂S products. Our results confirm the viability of low‐temperature photochemical approaches in metal sulfide synthesis, and demonstrate a new rule which could be followed in it.     

Incorporating Zn2SnO4 Quantum Dots and Aggregates for Enhanced Performance in Dye‐Sensitized ZnO Solar Cells

The performance of dye‐sensitized ZnO solar cells was improved by a facile surface‐treatment approach through chemical‐bath deposition. After the surface treatment, the quantum dots of Zn₂SnO₄ were deposited onto ZnO nanoparticles accompanied by the aggregations of Zn₂SnO₄ nanoparticles. The ZnO film displayed a better resistance to acidic dye solution on account of the deposited Zn₂SnO₄ nanoparticles. Meanwhile, the open‐circuit photovoltage was greatly enhanced, which can be ascribed to the increased conduction‐band edge of ZnO and inhibited interfacial charge recombination. Although the deposition of Zn₂SnO₄ decreased the adsorption amounts of N719 dye, the aggregates of Zn₂SnO₄ with a size of 350–450 nm acted as the effective light‐scattering layer, thereby resulting in an improved short‐circuit photocurrent. By co‐sensitizing 10 μm‐thick ZnO film with N719 and D131 dyes, a top efficiency of 4.38 % was achieved under the illumination of one sun (AM 1.5, 100 mW cm^?2).     

双靶向CdTe量子点的制备及其在细胞标记中的应用

以巯基乙酸和巯基乙酰肼为稳定剂,制备了酸度敏感型CdTe量子点。经与抗体链接,该量子点具备酸度敏感、免疫识别双重靶向功能。经荧光光谱分析、透射电镜图像及细胞免疫成像证明,抗体已成功链接于量子点表面,且该量子点具有酸度敏感及抗体识别的双重靶向功能,可以实现对肿瘤细胞的特异性标记。     

Bottom-Up Synthesis,Dispersion and Properties of Rectangular-Shaped Graphene Quantum Dots

Carbon nanomaterials have attracted the attention of the scientific community for more than 30 years now; first with fullerene, then with nanotubes and now with graphene and graphene related materials. Graphene quantum dots (GQDs) are nanoparticles of graphene that can be synthesized following two approaches, namely top-down and bottom-up methods. The top-down synthesis used harsh chemical and/or physical treatments of macroscopic graphitic materials to obtain nanoparticles, while the second is based on organic chemistry through the synthesis of polycyclic aromatic hydrocarbons exhibiting various sizes and shapes that are perfectly controlled. The main drawback of this approach is related to the low solubility of carbon materials that prevents the synthesis of nanoparticles containing more than few hundreds of sp² carbon atoms. Here we report on the synthesis of a family of rectangular-shaped graphene quantum dots containing up to 162 sp² carbon atoms. These graphene quantum dots are not functionalized on their periphery in order to keep the maximum similarity with nanoparticles of pure graphene. We chose water with sodium deoxycholate surfactant to study their dispersion and their optical properties (absorption, photoluminescence and photoluminescence excitation). The electronic structure of the particles and of their aggregates are studied using Tight-Binding (TB). We observe that the larger particles ( GQD 3 and GQD 4 ) present a slightly better dispensability than the smaller ones, probably because the larger GQDs can accommodate more surfactant molecules on each side, which helps to stabilize their dispersion in water.     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.