生物质碳量子点的简便合成及对Hg~(2+)荧光传感研究

将厌氧条件处理的牛粪作为碳源通过水热法合成了蓝色荧光发射的碳量子点。该量子点在水中稳定性和分散性良好,具有激发波长依赖的荧光发射现象,从430nm红移至560nm。在中性水溶液中,汞离子(Hg~(2+))对碳量子点的荧光发射干扰明显。随着Hg~(2+)体积的增加,450nm处的荧光强度逐渐减弱,两者呈现出较好的线性关系。对定性定量检测环境中的Hg~(2+)具有重要的意义。     

Cu-In-S三元量子点的合成及其性能调控

采用前驱体分解法制备了Cu-In-S量子点,研究了制备工艺对Cu-In-S量子点的形貌以及光学性能的影响。实验结果表明,反应时间和反应温度可影响Cu-In-S纳米颗粒的尺寸和光学性能。随时间增加,Cu-In-S粒径变大,同时会伴随着棒状晶体的出现,荧光发射谱的峰位发生红移。随反应温度升高,纳米晶的形核速率和长大速率增加,并且粒径也有增大,纳米晶的形状可以由单一的球形变为球形与棒状的混合,荧光谱峰位亦会发生红移。X射线光电子能谱分析表明,所制备颗粒为CuInS2纳米晶。为进一步制备无毒量子点发光器件(QLEDs)奠定了基础。     

微波法一步制备新型荧光碳量子点及光学性能研究

首次以中药材贝母为碳源,采用微波法一步合成新型荧光碳量子点。通过原料用量、微波功率和反应时间优化,获得了制备荧光碳量子点的最佳实验条件。同时通过透射电镜和X射线光电子能谱仪对荧光碳量子点进行了形貌及结构表征,通过荧光光谱和紫外-可见吸收光谱对荧光碳量子点进行了光学性能研究。结果表明:原料用量2g,微波功率800W,反应时间8min为合成荧光碳量子点最佳反应条件,制备得到的荧光碳量子点平均粒径5nm,最大激发波长310nm,最大荧光发射波长位于400nm处,最大紫外吸收波长280nm。     

羧基CdSe荧光量子点的制备及其荧光特性研究

以氯化镉、硒粉为前驱体,巯基乙酸(TGA)为稳定剂,制备了羧基CdSe量子点,并研究了其荧光特性与影响因素。结果表明,反应温度、反应时间与反应体系的pH值是影响量子点生长和荧光性能的主要因素。制备羧基CdSe量子点的最优条件为反应温度90℃、pH=11、n(Cd)∶n(Se)=2∶1。制备的羧基CdSe量子点的粒径随反应时间的延长而逐渐增大,量子点荧光稳定性好,荧光强度高,光漂白时间延长。     

pH对离子液体辅助水热制备介孔二氧化钛结构的影响

以钛酸四丁酯为钛源, 离子液体1-丁基-3-甲基咪唑四氟化硼([C₄MIM]BF₄)为辅助剂, 采用水热法制备了锐钛矿相的介孔二氧化钛。用盐酸和氨水调节反应前驱体的pH, 考察了pH在1~11变化范围内对离子液体-水制备二氧化钛体系的影响。采用X射线衍射和N2吸附?脱附对样品的晶相和孔结构进行表征。结果表明: 离子液体抑制了板钛矿二氧化钛的形成, 随着pH的增大样品的晶化程度增强。pH在1~9较大范围变化时, 其孔径分布较窄, 平均孔径随pH增大由6.6 nm减小到5.0 nm, 此时离子液体能较好的将样品粒径控制在9 nm左右。这与透射电镜分析结果相一致。     

碳量子点的一步合成及其发光性质的研究

本文采用油浴加热柠檬酸一步法合成碳量子点,用HRTEM透射电镜和FTIR红外光谱对其形貌和结构进行表征。研究该碳量子点的荧光性质,初步探讨了其发光的可能机理。实验结果表明,该方法合成的碳量子点粒径大小为3~5 nm,在360 nm处有一个很强的紫外吸收峰,最大激发波长和发射波长分别为365 nm和460 nm,其光学稳定性良好,在pH5.0~7.0范围内,碳量子点的荧光强度随pH的变化比较敏感。     

水溶性ZnS量子点的共沉淀法制备、 表征及其光学性能

以硫化钠和乙酸锌为反应物,3-巯基丙酸为表面包覆剂,利用共沉淀法制备了水溶性ZnS量子点。并采用X射线衍射仪、透射电子显微镜和荧光分光光度计等对样品的结构、形貌、粒径和光学性能进行了表征。结果表明:所得样品为ZnS立方型闪锌矿结构,量子点的形状呈不规则球形,粒径主要集中在4.8nm左右;样品在585～590nm之间出现了黄色荧光发射波峰。同时,利用红外光谱对ZnS量子点的合成机理进行了初步分析。     

水热法合成N-乙酰-L-半胱氨酸稳定的Cd_xZn_（1-x）Se合金量子点

采用了N-乙酰-L-半胱氨酸为稳定剂,通过水热法制备了荧光发射峰可调、粒径均匀且结晶性能良好的ZnxCd1-xSe合金量子点,并采用紫外-可见光吸收光谱（UV-Vis）、荧光光谱（PL）、X射线衍射（XRD）、高分辨透射电镜（HRTEM）等对其结构和性能进行了表征。重点研究了Cd2＋/Zn2＋比值、初始溶液pH值、水热反应温度和时间等实验条件对ZnxCd1-xSe量子点荧光性能的影响。研究表明所制备的量子点荧光量子产率高（35%）,荧光发射谱半峰宽窄（FWHM〈50nm）,有望作为生物荧光标记物。     

不同pH下3-吡啶取代类中氮茚化合物的荧光行为

合成了3个具不同取代基的3-吡啶取代类中氮茚化合物a、b和c,研究了它们在不同pH值缓冲溶液中荧光性能的变化。发现,3个化合物能发射强烈的蓝色荧光,且随着溶液pH值的增大,其荧光强度均有所增强,荧光发射波长也均有所红移,但增强、红移程度很不一样。其中,c、a的荧光强度可分别增强200、150倍;而b、a的荧光发射波长可分别红移49、30nm。     

ZnS/PVA纳米复合薄膜的制备与表征

采用提拉真空干燥的方法制备出以石英玻璃为基板的ZnS/PVA纳米复合薄膜.ZnS/PVA纳米复合溶胶是通过直接混合法将ZnS纳米粒子与聚乙烯醇(PVA)高分子材料水溶液直接混合制备得到.ZnS纳米粒子由微乳液法制备得到.利用透射电子显微镜(TEM)和X射线衍射(XRD)分析表征了ZnS纳米粒子的微观形貌和晶型,TEM结果表明C12H25SH与Zn2 的比例越大,ZnS粒子的粒径越小且在PVA中的分散越好,当C12H25SH/Zn2 的比例为8∶1时,ZnS纳米粒子的粒径为50 nm,呈球状;XRD分析表明,PVA中ZnS纳米粒子具有类似于立方β-ZnS晶相.用紫外-可见(UV-VIS)吸收光谱和荧光光谱(PL)对其光学性能进行了表征,结果表明随着C12H25SH/Zn2 的摩尔比从4:1增长到8:1,ZnS/PVA纳米复合薄膜的吸收峰的强度逐渐增强,峰位也逐渐向短波长方向偏移.在280 nm下激发,PL中出现了峰位位于365 nm处的荧光发射峰;并且发现随着C12H25SH/Zn2 摩尔比从2:1增大到8:1,在C12H25SH/Zn2 摩尔比为4:1时,荧光发射峰的强度相对较大, 其余的荧光发射峰蓝移并且强度增大,表现出较为明显的量子尺寸效应;当C12H25SH/Zn2 摩尔比较大时,出现了低能发光(450 nm～467 nm)的现象.     

Synthesis and luminescence characteristics of DHLA-capped PbSe quantum dots with biocompatibility

In this work, we report a facile aqueous route to prepare PbSe QDs with strong photoluminescent and near-infrared (NIR) emission using dihydrolipoic acid (DHLA) as the capping ligands. It was found that the synthesis parameters including the molar ratio of DHLA/Pb, the pH value and the reaction time have considerable influence on photoluminescent intensity (PL) of the PbSe QDs. The as-synthesized DHLA-capped PbSe QDs were characterized by high-resolution transmission electron microscopy (HRTEM), energy-dispersive analysis of X-ray (EDX) and X-ray diffraction (XRD), the results indicated that the QDs were about 8.0 ± 0.2 nm in size and had good monodisperse and a rock salt crystalline structure. Also, there was DHLA on the surface of QDs, which was confirmed by Fourier transform infrared (FT-IR) spectrometry. The PbSe QDs exhibited optimal PL intensity when Pb:Se:DHLA = 1:0.6:1 in weak alkaline aqueous. The as-synthesized QDs kept highly PL intensities when stored in the dark in normal air environment during the period of 60 days. In addition, the biocompatibility of these QDs was measured by hemolytic test, which indicated that DHLA-stabilized QDs are biocompatible. It is important for QDs as biomarkers in biological detection and diagnosis.     

Emission properties of colloidal quantum dots on polyelectrolyte multilayers

We present steady state and time-resolved photoluminescence (PL) characteristics of differently charged CdTe quantum dots (QDs) adsorbed onto a polyelectrolyte (PE) multilayer. The PE multilayer is built up using a layer-by-layer assembly technique. We find that the diffusion of the QDs into the PE multilayer is an important factor in the case of 3-mercapto-1, 2-propanediol stabilized QDs (neutral surface charge), resulting in a ～31-fold enhancement in PL intensity accompanied by a blue shift in the PL spectra and an increase in decay lifetime from 3.74?ns to a maximum of 11.65?ns. These modified emission properties are attributed to the enhanced surface related emission resulting from the interaction of the QD's surface with the PE. We find that diffusion does not occur for thioglycolic acid (TGA) stabilized QDs (negative surface charge) or 2-mercaptoethylamine stabilized QDs (positive surface charge), indicating localization of the QDs on top of the PE multilayer. However, the PL lifetime of the TGA stabilized QDs decreases from 9.58 to 5.78?ns with increasing PE multilayer thickness. This provides evidence for increased intrinsic exciton recombination relative to surface related emission, which results in an overall reduction in the average lifetime. Our studies indicate the importance of the QD surface charge in determining the interaction with the PE multilayers and the subsequent modification of the QD emission properties.     

一种简单的水热法制备油溶性PbSe量子点

本研究采用简单的水热法得到了单一形态学和小尺寸分布的油溶性PbSe量子点。所得到的立方相PbSe量子点颗粒呈现近球形, 且平均颗粒尺寸为4.0 ± 0.5 nm。PbSe量子点在435 nm近紫外区域呈现出较强的和相对较窄的光致发光光谱, 光谱的半高宽值约为80 nm。随着反应时间的延长和反应温度的升高, 发光光谱向低能量区域移动, 谱峰的半高宽也随之变大。在改变前驱体Pb/S摩尔比的条件下, 发光光谱相对强度降低, 光谱也发生向长波长区域移动。另外, 随着反应温度和前驱体Pb/S摩尔比的改变, PbSe量子点颗粒表面的缺陷也增多。在反应过程中, 小颗粒长大成大尺寸颗粒促使PbSe量子点的发光光谱向长波长移动, 这个现象符合奥斯瓦尔德熟化定律。热力学不稳定和颗粒表面低浓度油酸包覆也造成PbSe量子点颗粒表面产生缺陷。     

Self-surface passivation of CdX (X = Se, Te) quantum dots

A small portion of a reaction mixture including unpurified CdX (X = Se or Te) quantum dots (QDs), in which unreacted Cd and Se ions were left together with coordinating solvents, was dropped into an organic solvent. The CdX QDs in this organic solution showed enhancement of photoluminescence (PL) efficiency, growth of particles, and focusing of size distribution for more than 10 h at room temperature (RT, -23 degrees C). These effects were attributed to passivation of QDs' surface by Cd and X ions present in the solution. No external energy source was used for these achievements; therefore, the process is termed as self-surface passivation. The self-surface passivation was reproduced using purified CdX QDs with additional Cd and X ions in an organic solvent. The self-surface passivation method was applied to RT-synthesized CdSe QDs, which is characterized by a broad PL spectrum (fwhm - 150 nm) for monodispersed QDs, to modify their emission characteristics. On self-surface passivation, the broad PL spectrum was narrowed (fwhm - 35 nm) and the QDs were grown. The X-ray diffraction measurements of RT-synthesized CdSe QDs and that subsequently aged in 1-butanol showed that crystallinity of the samples was improved on aging.     

Dark-red-emitting CdTe0.5Se0.5/Cd0.5Zn0.5S quantum dots: Effect of chemicals on properties

CdTe_0.5Se_0.5/Cd_0.5Zn_0.5S core/shell quantum dots (QDs) with a tunable photoluminescence (PL) range from yellow to dark red (up to a PL peak wavelength of 683 nm) were fabricated using various reaction systems. The core/shell QDs created in the reaction solution of trioctylamine (TOA) and oleic acid (OA) at 300 °C exhibited narrow PL spectra and a related low PL efficiency (38%). In contrast, the core/shell QDs prepared in the solution of 1-octadecene (ODE) and hexadecylamine (HDA) at 200 °C revealed a high PL efficiency (70%) and broad PL spectra. This phenomenon is ascribed that the precursor of Cd, reaction temperature, solvents, and ligands affected the formation process of the shell. The slow growth rate of the shell in the solution of ODE and HDA made QDs with a high PL efficiency. Metal acetate salts without reaction with HDA led to the core/shell QDs with a broad size distribution.     

One-step synthesis of water-soluble ZnSe quantum dots via microwave irradiation

A facile strategy has been developed for the synthesis of glutathione-capped ZnSe quantum dots (QDs) in aqueous media. The reaction was carried out in air atmosphere with a single step by using Na₂SeO₃, a stable and commercial Se source, to replace the commonly adopted NaHSe or H₂Se. Moreover, microwave irradiation improved the photoluminescence quantum yield (PLQY) as well as lowered the trap emission of as-prepared ZnSe QDs. The obtained QDs performed strong band-edge luminescence (PLQY reached 18%), narrow size distribution (full width at half maximum was 26-30 nm) and weak trap emission without post-treatments. The results of transmission electron microscopy and X-ray diffraction demonstrated the small particle size (2-3 nm), good monodispersity and ZnSe(S) alloyed structure of as-prepared QDs. The experimental variables including precursors and stabilizer amounts as well as pH value had significant influence on the PL properties of the ZnSe QDs.     

Preparation of lanthanide doped CdS, ZnS quantum dots in natural polysaccharide template and their optical properties

Employing a biomimic method using polysaccharide as template, luminescent lanthanide ions doped CdS and ZnS quantum dots (QDs) were prepared. According to the results of TEM and absorbance, nanocrystals with an average size of 6 nm were formed under mild condition without any toxic and expensive agent applied. Differentiating from the un-doped CdS and ZnS QDs prepared in polysaccharide template, the lanthanide doped QDs exhibited obvious dopant emission in their photoluminescence spectrum. It was also found that the dopant PL became more prominent with increasing lanthanide doping concentration, while the highest PL intensity was obtained at a doping level of 1% for both of CdS and ZnS QDs. When different lanthanide ions were introduced into the CdS QDs in polysaccharide template, varied emission wavelength were able to be obtained. This study provides an easy, mild and environmental friendly alternative method to prepare doped quantum dots. In addition, the bioactivity and processabilities endowed by the polysaccharide template may expand the applications potential of this type of optical materials.     

树形分子包覆硫化镉量子点的抗老化性能研究

以聚酰胺-胺树形分子为模板制备了平均粒径为2.5nm的CdS量子点, 采用HRTEM、EDS、UV-vis、PL等手段对样品进行表征, 研究了其在室温避光条件下的老化过程. 结果表明, CdS量子点在刚制备的前5d里UV-vis、PL谱峰半峰宽变窄, 发光效率迅速上升, 表明量子点以尺寸窄化生长为主; 5d后UV-vis、PL谱峰半峰宽逐渐宽化, 发光效率缓慢下降, 表明量子点以尺寸宽化(Ostwald 熟化)过程为主. 树形分子的配位作用和模板作用赋予CdS量子点良好的抗老化性能, 6个月后量子点粒径增量<0.3nm, PL强度约降低22%.     

Facile synthesis and luminescence characteristics of high-quality CdS: Eu/ZnS core/shell nanocrystals with biocompatibility

In this paper, we report a facile method to synthesize high quality CdS: Eu nanocrystals (NCs) and CdS: Eu/ZnS NCs with strong photoluminescence (PL). The influence of various experimental variables including the concentration of Eu3+ ions, the reaction time and the reaction temperature were investigated systematically. In addition, the PL properties of CdS: Eu NCs exhibited pH sensitive. Under the acid condition, pH value of the CdS: Eu NCs solution played an important role in determining PL emission intensity. However, under the alkaline condition, the obtained CdS: Eu NCs exhibited a tunable PL emission wavelength (from 490 nm to 610 nm) when pH value was adjusted from pH 7 to 10. After coating with ZnS shell, the CdS: Eu/ZnS NCs showed enhanced PL intensity compare with one of the CdS: Eu NCs. The CdS: Eu NCs and CdS: Eu/ZnS NCs were characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). In addition, the biocompatibility of these NCs was measured by hemolytic test, which indicated that CdS: Eu/ZnS NCs were more biocompatible than CdS: Eu NCs at the same conditions. It can be expected that CdS: Eu/ZnS NCs are promising biolabeling materials.     

Tunable emission properties of core-shell ZnCuInS-ZnS quantum dots with enhanced fluorescence intensity

Cadmium-free I-III-VI quantum dots (QDs), represented by Cu-In-S (CIS), are widely investigated for their non-toxicity and tunable emission properties. In this work, Zn-Cu-In-S (ZCIS) alloyed QDs were synthesized via a solvothermal approach by heating up a mixture of the corresponding metal precursors and sulphur powder with dodecanethiol in oleylamine media, and the fluorescent intensity was greatly enhanced by coating ZnS (ZS) shell. By changing the ratio of Cu, the as prepared ZCIS-ZS QDs showed composition-tunable photoluminescent (PL) emission over the visible spectral window from about 500 nm to 620 nm, which is much wider than that of CIS QDs. Moreover, the influence of excitation wavelength, reaction temperature and time on the optical properties of the ZCIS-ZS QDs was also studied. This research provides a feasible and simple approach to prepare ZCIS-ZS QDs with large tunable spectral range on visible region, which could greatly contribute to the development of potential applications due to their non-toxicity and excellent optical properties.