高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (10): 1865.doi: 10.7503/cjcu20150415

• 研究论文: 无机化学 • 上一篇    下一篇

低温合成广谱发光CuInS2/ZnS量子点

付敏1,2, 栾伟玲1,3, 涂善东1, MLECZKO Leslaw3   

  1. 1. 华东理工大学机械与动力工程学院, 承压系统与安全教育部重点实验室, 上海 200237;
    2. 拜耳技术工程(上海)有限公司技术开发部, 上海 201507;
    3. Bayer Technology Services GmbH, Technology Development, Leverkusen 51368, Germany
  • 收稿日期:2015-05-22 出版日期:2015-10-10 发布日期:2015-09-18
  • 通讯作者: 栾伟玲,女,博士,教授,博士生导师,主要从事荧光纳米材料的合成与工艺开发研究.E-mail:luan@ecust.edu.cn E-mail:luan@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 51172072, 51475166)、拜耳技术工程(上海)有限公司和Bayer Technology Services GmbH资金资助.

Synthesis of Broad Color-emitting CuInS2/ZnS Quantum Dots at Low Temperature

FU Min1,2, LUAN Weiling1,3, TU Shantung1, MLECZKO Leslaw3   

  1. 1. Key Laboratory of Pressure Systems and Safety, Ministry of Education, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai 200237, China;
    2. Division of Technology Development, Bayer Technology & Engineering(Shanghai) Co. Ltd., Shanghai 201507, China;
    3. Bayer Technology Services GmbH, Technology Development, Leverkusen 51368, Germany
  • Received:2015-05-22 Online:2015-10-10 Published:2015-09-18
  • Supported by:

    Supported by the National Natural Science Foundation of China(Nos.51172072, 51475166), Bayer Technology & Engineering(Shanghai) Co. Ltd. and Bayer Technology Services GmbH.

摘要:

以二乙基二硫代氨基甲酸锌(ZDC)为ZnS的前驱体材料、三辛基膦(TOP)为主要配体, 在温度不高于200 ℃的条件下合成了广谱发光的核壳结构CuInS2/ZnS(CIS/ZnS)量子点. 研究了ZDC用量、壳层包裹温度和配体对CIS/ZnS光学特性及荧光量子产率的影响. 结果表明, 使用ZDC可在相对较低的温度下实现ZnS的包裹过程, 并且随着包裹温度的提高, ZnS的包裹速度明显加快. 吸收光谱、荧光光谱及X射线衍射分析结果表明, 使用TOP为配体合成的CIS/ZnS量子点的明显吸收峰为其激发吸收峰. 使用荧光分光光度计、高分辨透射电子显微镜、X射线光电子能谱仪和傅里叶变换红外光谱仪对使用不同配体进行壳层包裹得到的样品进行了表征. 结果表明, 在ZnS的包裹过程中, 配体TOP和十二硫醇作为有机层包覆在颗粒表面也会影响量子点的光学性能和晶体生长速度. 使用TOP能够加速ZnS的包裹速度, 形成的颗粒尺寸均一, 其荧光波长可蓝移至550 nm.

关键词: 铜铟硫/硫化锌量子点, 核壳结构, 三辛基膦配体, 激发吸收

Abstract:

CuInS2/ZnS(CIS/ZnS) quantum dots(QDs) were synthesized below 200 ℃ with zinc diethyl dithiocarbamate(ZDC) as ZnS precursor materials and trioctylphosphine(TOP) as the main capping ligands. The influence of ZDC amount, shell growth temperature and ligands on the optical properties and quantum yield of CIS/ZnS quantum dots were investigated. The results showed that the growth of ZnS shell could happen above 150 ℃ and ZnS growth speed was accelerated by increasing temperature. The absorption peak of prepared CIS/ZnS using TOP as ligands was defined as exctionic absorption through photoluminescence(PL) spectromety and X-ray diffraction analysis. The samples were characterized by PL spectrometer, high resolution transmission electron microscope, energy dispersive X-ray spectrometer and Fourier transform infrared spectrometer. The results showed that ligands of TOP and dodecanethiol were overcoated on the surface of nanoparticles as organic layer, which would affect optical properties and crystal growth speed. TOP could increase the shell growth speed and the CIS/ZnS QDs with uniform size were obtained. The PL emission wavelength could be extended to 550 nm.

Key words: Copper indium sulfide/zinc sulfide(CIS/ZnS) quantum dots, Core-shell structure, Trioctylphosphine ligand, Excitonic absorption

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