Tunable emission of cadmium-free transition metal(Cu, Mn, Ag) co-doped ZnInS/ZnS core-shell quantum dots

Color tunable quantum dots（QDs） based on the Cu, Mn, Ag co-doped Zn In S core and Zn S outer-shell were synthesized by using an eco-friendly method. Core-shell doped QDs with the average size of 3.85 nm were obtained by using a one-pot synthesis followed by a hot injection with n-dodecanethiol（DDT） and oleylamine（OLA） as stabilizers in oil phase. Cu, Mn and Ag ions were introduced as single-dopant or co-dopants during the synthesis, providing an effective means to control the emission color of the QDs. The as-synthesized QDs showed photoluminescence emission ranging from green（530 nm） to near-red（613 nm）, adjusted by doping components, dopant concentration, and Zn/In ratio. Importantly, quasi-white emission has been achieved by controlling the concentration of co-doped metal ions（Mn, Cu and Ag）. The primary results demonstrated the promising potential of co-doped QDs as alternative materials for future high quality white LED applications.

Large-scale control of enhancement and quenching of photoluminescence for ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution

We investigated the optical properties of hybrid exciton–plasmon coupling ensembles composed of ZnSe/ZnS quantum dots and Ag nanoparticles in aqueous solution. We modulated their average interval by changing the ratio of quantum dots and Ag nanoparticles. The transition from dramatic PL enhancement to PL quenching state was experimentally observed, according to the continuous decrease of the PL lifetime. The PL enhancement rate exceeded 10, with the Purcell factor of 3.5. Meanwhile, the proportion of fast decay increased from 0.3 to 0.6, corresponding to the proportion of slow decay decreased from 0.7 to 0.4. Our experiment is important for the hybrid exciton–plasmon coupling system to be practicable in optoelectronic application.

Improved carrier transport in Mn:ZnSe quantum dots sensitized La-doped nano-TiO2 thin film

Mn:ZnSe/ZnS/L-Cys core-shell quantum dots(QDs)sensitized La-doped nano-TiO2 thin film(QDSTF)was prepared.X-ray photoelectron spectroscopy(XPS),nanosecond transient photovoltaic(TPV),and steady state surface photovoltaic(SPV)technologies were used for probing the photoelectron behaviors in the Mn-doped QDSTF.The results revealed that the Mn-doped QDSTF had a p-type TPV characteristic.The bottom of the conduction band of the QDs as a sensitizer was just 0.86 eV above that of the La-doped nano-TiO2 thin film,while the acceptor level of the doped Mn2+ions was located at about 0.39 eV below and near the bottom of the conduction band of the QDs.The intensity of the SPV response of the Mn-doped QDSTF at a specific wavelength was ~2.1 times higher than that of the undoped QDSTF.The region of the SPV response of the Mn-doped QDSTF was extended by 191 nm to almost the whole visible region as compared with the undoped QDSTF one.And the region of the TPV response of the Mn-doped QDSTF was also obviously wider than that of the undoped QDSTF.These PV characteristics of the Mn-doped QDSTF may be due to the prolonged lifetime and extended diffusion length of photogenerated free charge carriers injected into the sensitized La-doped nano-TiO2 thin film.

Zebrafish imaging and two-photon fluorescence imaging using ZnSe quantum dots

This study is to report a ZnSe quantum dot with a large two-photon absorption cross section and good biocompatibility,which can be used in bioimaging.Fluorescence emission at 410 nm is observed in the quantum dot under 760-nm laser excitation.These biocompatible quantum dots exhibit a two-photon cross-section of 9.1×105 GM(1 GM=10-50 cm4·s/photon).Two-photon excited laser scanning microscopic images show that cells co-cultured with ZnSe quantum dots are found in the blue channel at a fluorescence intensity that is 14.5 times that of control cells not cocultured with quantum dots.After incubating zebrafish larvae with ZnSe quantum dots for 24 h,the fluorescence intensity of the yolk sac stimulated by ultraviolet light is 2.9 times that of the control group.The proposed material shows a great potential application in biological imaging.

ZnSe quantum dots downshifting layer for perovskite solar cells

To date, the instability of organometal halide perovskite solar cells（PSCs） has become the focus issue that limits the development and long-term application of PSCs. Both the ultraviolet（UV） rays in sunlight and moisture in air can significantly accelerate the disintegration of the perovskite. Here, we introduced a Zn Se quantum dots layer as downshifting materials, which was spin-coated onto the backside of PSCs.This layer converted the UV rays into visible light to prevent the destruction of PSCs as well as increase the light harvesting of the perovskite layer. Under the UV irradiation in the moisture ambient（40%）, the destruction speed of the unencapsulated perovskite films were also delayed evidently. In addition, the power conversion efficiency（PCE） of the PSCs was increased from 16.6% to 17.3% due to the increase of the visible light absorbance of the perovskite.

Enhanced transient photovoltaic characteristics of core–shell ZnSe/ZnS/L-Cys quantum-dot-sensitized TiO_2 thin-film

Photoanodic properties greatly determine the overall performance of quantum-dot-sensitized solar cells（QDSCs）. In the present report, the microdynamic behaviors of carriers in the nanocomposite thin-film, a Zn Se QD-sensitized mesoporous La-doped nano-TiO2 thin-film, as a potential candidate for photoanode, are probed via nanosecond transient photovoltaic（TPV） spectroscopy. The results confirm that the L-Cys ligand has a dual function serving as a stabilizer and molecular linker. Large quantities of interface states are located at the energy level with a photoelectric threshold of1.58 eV and a quantum well（QW） depth of 0.67 eV. This QW depth is approximately 0.14 eV deeper than the depth of QW buried in the Zn Se QDs, and a deeper QW results in a higher quantum confinement energy. A strong quantum confinement effect of the interface state may be responsible for the excellent TPV characteristics of the photoanode. For example, the peak intensity of the TPV response of the QD-sensitized thin-film lasts a long time, from 9.40 × 10^（-7） s to 2.96 × 10^（-4） s,and the end time of the PTV response of the QD-sensitized thin-film is extended by approximately an order of magnitude compared with those of the TiO2 substrate and the QDs. The TPV characteristics of the QD-sensitized thin-film change from p-type to n-type for the QDs before and after sensitizing. These properties strongly depend on the extended diffusion length of the photogenerated carries and the reduced recombination rate of photogenerated electron-hole pairs, resulting in prolonged carrier lifetime and an increased level of electron injection into the TiO2 thin-film substrate.

ZnSe基蓝光量子点的中间壳层结构调控及其发光性能研究

ZnSe作为一种不含重金属的宽带隙量子点(QDs),近年来在蓝光量子点及其发光二极管器件领域受到广泛关注。然而,ZnSe基核壳结构蓝光量子点的核壳界面处通常存在较大的晶格失配,易于形成缺陷态捕获载流子,从而影响其光学性能。本文通过将均质的单层ZnSeS合金层替换为具有组分渐变结构的ZnSeS合金层,合成了具有径向方向Se/S浓度渐变梯度的ZnSeS合金中间壳层的ZnSeTe/ZnSe/ZnSeS/ZnS量子点,并利用X射线衍射谱、稳态光致发光光谱、时间分辨发光光谱、透射电镜和电致发光测试等表征手段研究了不同合金中间壳层对量子点结构、形貌和光学性能的影响。结果表明,所合成的具有组分梯度ZnSeS壳层的量子点的发射波长均为深蓝色(444.5 nm),发射线宽窄(<18 nm),尺寸均一,具有闪锌矿结构,结晶度高;随着ZnSeS合金中间壳层沿量子点径向方向组分渐变平滑度的不断提高,量子点的荧光量子效率(PLQY)和色纯度等光学性质依次改善,其中通过S原子扩散形成的具有线性缓变ZnSeS壳层的量子点具有最窄的发射线宽(15.8 nm)和最高的PLQY(20.7%)。利用这种具有最优荧光性能的量子点作为发光材料制备的发光二极管器件的最大外量子效率为1.8%,最高亮度为750 cd/m^(2)。本研究提出的量子点合成方案和结构优化策略有助于促进高质量无毒蓝光ZnSe基核/壳量子点的发展。

Overcoming side reaction effects in the colloidal synthesis of ZnSe/ZnS core/shell quantum dots with an etching strategy

The potential use of large-size ZnSe quantum dots as blue emitters for display applications has greatly inspired the colloidal synthesis.Herein,we report the negative effects of side reactions of large-size ZnSe quantum dots.The side reactions between oleic acid and oleylamine generated amidation products and H_(2)O,which led to the hydrolysis of Zn(OA)2 to Zn(OH)2 and the subsequent formation of zinc oxide(ZnO)and zinc bis[diphenylphosphinate](Zn(DPPA)2)precipitates.These side reactions resulted in the formation of a defective surface including a Se-rich surface and oxygen-related defects.Such negative effects can be overcome by adopting an etching strategy using potassium fluoride and myristic acid in combination.By overcoating a ZnS shell,blue emissive ZnSe/ZnS quantum dots with a maximum photoluminescence quantum yield of up to 91%were obtained.We further fabricated ZnSe quantum dots-based blue light-emitting diodes with an emission peak at 456 nm.The device showed a turn-on voltage of 2.7 V with a maximum external quantum efficiency of 4.2%and a maximum luminance of 1223 cd·m^(−2).

Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H_(2)O_(2) production by using femtosecond transient absorption spectroscopy

Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.

Influence of coating on the photoluminescence of Tb^3＋ doped ZnSe/ZnS core-shell quantum dots

Tb3＋-doped ZnSe and ZnSe/ZnS nanocrystals were synthesized using modified hot-injection method. The observation of the characteristic quantum dots absorption features in a time-gated excitation spectrum was recorded while monitoring Tb3＋ emission at 545 nm provided direct evidence for successful incorporation of dopant ions into semiconductor host. Relatively long decay time （-1.5 ms） of Tb3＋ emission indicated that dopant ions were well protected from interaction with surface ligands. Emission properties of core ZnSe：Tb3＋ nanocrystals were only slightly modified upon growth of ZnS shell.

面向量子点电致发光二极管的蓝光InP和ZnSe量子点研究现状

作为传统显示器强有力的竞争者之一,量子点发光二极管(QLED)在显示领域备受关注。然而,高性能蓝光QLED器件的发光材料中通常含有镉或铅,这两类重金属有毒元素对人体健康和生态环境不利,也阻碍了QLED器件的规模化商用进程。因此,高质量无镉无铅型蓝光量子点材料的研发成为推动新型显示产业发展的动力和业界迫切追求的目标。历经数十年发展,InP和ZnSe等无镉无铅量子点材料的蓝光发射性能已取得较大进步,随着合成策略及蓝光材料的进一步优化改进,环境友好型蓝光量子点发光二极管器件性能有望追上传统红、绿光量子点器件的步伐。本文分别从合成优化手段、表面包覆策略、核壳结构类型、发光性能参数等方面进行汇总,系统综述了当前无镉无铅型蓝光InP和ZnSe量子点材料的研究进展,指出了QLED蓝光材料未来的发展方向。

纯蓝光ZnSe基核/壳结构量子点的合成与发光性能

探索了纯蓝光ZnSe基核/壳结构量子点的合成方法,研究了各种反应参数对量子点发光性能的影响,通过Te元素掺杂和尺寸调控相结合的方法使量子点发光波长红移至蓝光波段,并通过引入氟化锌对表界面缺陷进行腐蚀/钝化,从而提高了所制备量子点的发光强度。结果表明,当初始反应温度为200℃、初始反应时间为120 min时,得到的ZnSe核可以实现380 nm波长的发光,且更加适合后续的Te元素掺杂;当Te和Se的摩尔比为0.01时,所合成的ZnSe基核/壳量子点在实现442 nm波长的蓝色发光的同时,保持了15 nm的窄发光半峰全宽;当ZnF_(2)的添加量为1.5 mmol时,量子点的发光强度比不添加ZnF_(2)时提升了约3倍;量子点尺寸均一且在正辛烷中保持了高分散性,具有良好的成膜性,所制备出的量子点薄膜表面致密平滑无明显裂纹。本研究结果有助于促进高质量无毒蓝光ZnSe基核/壳量子点合成技术的发展及其在下一代显示技术中的应用。

CdZnSe/ZnSe/ZnSeS量子点材料的制备及其量子点电致发光器件性能研究

量子点(QDs)材料由于其出色单色性,发光可调等优点,在电致器件方面得到了快速的发展。文章研究通过物理方法在QDs核生长的过程中用溶剂稀释单体的浓度,减少QDs核的生长时间,从而可在不改变化学成分比例的基础上改变QDs的发光波长。进一步通过包覆ZnSe与ZnSeS壳层对发光波长进行调制,最终得到光致波长在540 nm的绿色QDs。通过对比实验以及LaMer模型解释了发生变色的原理。仅在核的生长阶段进行干涉才能控制QDs的发光峰位。同时发现提高QDs外壳的包覆温度对QDs的缺陷的减少有积极作用。随后将得到的QDs用于制备量子点电致发光器件,在8 V电压下得到了348993 Cd/m^(2)的亮度,以及32 Cd/A的电流效率。另外,该方法可以为其它类型的由热注入法制备的纳米材料制备提供新的思路。

Cu掺杂ZnSe高效量子点的合成及其光学特性研究

采用生长掺杂方式制备了Cu掺杂ZnSe高效量子点,探索了不同Zn、Se前驱体配比对ZnSe晶核以及ZnSe:Cu量子点质量的影响,并研究了Cu离子掺杂过程中的光谱特征。研究表明,进一步通过在表面掺杂的ZnSe:Cu量子点上同质包覆ZnSe壳层,能够实现其发光效率和稳定性的有效提高;采用配体交换能够实现ZnSe:Cu量子点由油溶性到水溶性的转变。这种新型的掺杂量子点有望替代传统含Cd量子点应用于环境友好型固体发光器件和生物标记。

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。

ZnSe量子点增敏鲁米诺-铁氰化钾化学发光测定牛奶中的己烯雌酚

碱性介质中,ZnSe量子点能够增强鲁米诺-铁氰化钾体系的化学发光,己烯雌酚对该体系的化学发光有很强的抑制作用,据此建立了测定己烯雌酚的新方法,并对可能的反应机理进行了探讨。结果表明,在优化实验条件下,己烯雌酚在6.0×10-9～4.0×10-5mol/L的浓度范围内与发光强度呈良好的线性关系,检出限为2.0×10-9mol/L(信噪比S/N=3)。对于浓度为4.0×10-6mol/L的己烯雌酚,测定11次的相对标准偏差为1.4%。将该体系用于牛奶中己烯雌酚的测定,回收率为94.47%～107.61%。

胶体水相法制备高量子产率及高稳定性的水溶性ZnSe量子点

采用简便的胶体水相法制备了高荧光强度且稳定性良好的ZnSe量子点（ZnSe QDs）,克服了以往水相合成法稳定性差、量子产率低等缺陷。优化后的最佳合成条件为：以还原型L-谷胱甘肽作为稳定剂,L-谷胱甘肽∶Se2-∶Zn2＋摩尔比为5∶1∶5,介质pH 10.5,反应温度在90~100℃之间。且合成后不需要采取任何光照后处理,ZnSe QDs的量子产率（QYs）即可高达50.1%,放置3个月后荧光强度基本不变,水溶性优良。用紫外-可见分光光度法（UV-Vis）、荧光分光光度法（FL）、透射电子显微镜（TEM）等分析检测手段,对得到的ZnSe QDs的性能进行表征。合成的量子点在300 nm激发下发蓝紫色荧光（370 nm）,其优良的光化学特性将有利于其在光热器件的制造及化学生物领域的应用。

金黄色葡萄球菌活细胞合成ZnSe量子点

利用"时-空耦合策略"在金黄色葡萄球菌内制得ZnSe量子点,从而将金黄色葡萄球菌转变成为荧光细胞.采用透射电子显微镜(TEM)、原子力显微镜(AFM)、动态光散射(DLS)、紫外-可见吸收光谱和荧光发射光谱等对从细胞内提取出的ZnSe量子点进行了表征.结果表明,提取出的ZnSe量子点粒径均一、分散性好,平均粒径为(2.96±0.76)nm,具有良好的荧光性质,最大荧光发射波长为537 nm.

ZnSe:Cu/CdS核壳量子点的合成及光学性能研究

以CdS为壳层材料对核水溶性ZnSe:Cu量子点进行包覆,得到ZnSe:Cu/CdS核壳结构的量子点。研究了壳层厚度对ZnSe:Cu量子点光学性能的影响,采用TEM、XRD、PL和UV-Vis手段对所得样品进行表征。实验结果表明:量子点为立方闪锌矿结构,分散性好,形状为球形,经壳层修饰后量子点的粒径由2.7 nm增大到4.0 nm。随着包覆CdS壳层数的增加,量子点的发射和紫外吸收谱红移,说明量子点在长大,证明CdS壳层生长在ZnSe:Cu量子点的表面,形成了核壳结构的ZnSe:Cu/CdS量子点。包覆CdS壳层后ZnSe:Cu量子点的发光强度减弱,但稳定性得到了提高。

ZnCuInS/ZnSe/ZnS量子点发光光谱特性的研究

ZnCuInS/ZnSe/ZnS量子点是一种无毒,无重金属的'绿色'半导体纳米材料。在研究中,制备了三种尺寸的ZnCuInS/ZnSe/ZnS核壳量子点,其直径分别为3.3,2.7,2.3nm。通过测量不同尺寸的ZnCuInS/ZnSe/ZnS量子点的光致发光光谱,其发射峰值波长随尺寸的减小而蓝移。其吸收峰值波长和发射峰值波长分别是510,611(3.3nm),483,583(2.7nm)以及447,545nm(2.3nm)。ZnCuInS/ZnSe/ZnS量子点具有显著的尺寸依赖效应。ZnCuInS/ZnSe/ZnS量子点的斯托克斯位移分别为398meV(3.3nm),436meV(2.7nm)以及498meV(2.3nm),这样大的斯托克斯位移证明,ZnCuInS/ZnSe/ZnS量子点的发光机制与缺陷能级有关。同时,对直径为3.3nm的ZnCuInS/ZnSe/ZnS量子点进行了温度依赖的光致发光光谱的测量,当温度为15～90℃时,该量子点发射峰值波长随温度的升高而红移,发光强度随温度的升高而降低,说明ZnCuInS/ZnSe/ZnS量子点是以导带能级与缺陷能级之间跃迁为主的复合发光。