单相硫化锌量子点制作白光发光二极管(WQLEDs)

doi:10.6023/A23050231

摘要/Abstract

制备不含稀土元素、价格低廉且对环境友好的单相量子点发光材料, 对于实现白光量子点二极管(WQLEDs)的大规模商业化应用至关重要. 用一步水热法合成了硫化锌量子点(ZnS-QDs), 其热分解温度高达680 ℃, 荧光量子产率为16.3%. 通过紫外吸收光谱和理论计算探讨了ZnS-QDs的锌空位发光机理, 并制备出发标准白光的WQLEDs, 工作电流在300 mA时的国际照明委员会(CIE)坐标为(0.3725, 0.4006), 显色指数(CRI)为76.6, 相关色温(CCT)为4500 K, 三色比(R, G, B)为R=14.6%, G=83.5%, B=1.8%, 红绿蓝三种颜色中绿光占比最多, 蓝光含量最少, 有利于眼睛的保护. 该研究实现了使用无稀土掺杂的单相量子点制备WQLEDs的目标.

关键词: 单相量子点, 硫化锌, 发光二极管(LED), 白光量子点二极管

Preparation of undoped rare earth element, inexpensive and environmentally friendly single-phase quantum dots luminescent materials is crucial for realizing large-scale commercial application of white-light quantum dots diodes (WQLEDs). In this work, zinc sulfide quantum dots (ZnS-QDs) were prepared by a one-step hydrothermal method. The experimental method was to add zinc acetate into the mixed solution of water and ethanol, adjust the pH to 5~6, and then add thiourea. All raw materials were evenly mixed and put into a high-temperature hydrothermal reactor, and then ZnS-QDs was synthesized under the high-temperature condition of 240 ℃. By changing the ratio of water and ethanol in the solution and adjusting the pH, ZnS-QDs was obtained. The fluorescence emission peak of ZnS-QDs was about 535~566 nm. The thermogravimetric analysis of the obtained ZnS-QDs showed that the thermal decomposition temperature was up to 680 ℃. The measured fluorescence quantum yield was 16.3%. The luminescence mechanism of zinc vacancy in ZnS-QDs and the influence of changing synthesis conditions on the band gap width were discussed by UV absorption spectrum and theoretical calculation. After the mixture of ZnS-QDs phosphors and organic silica gel was dropped on the ultraviolet LED chip with the excitation light source of 365 nm, the input voltage was 3.4 V and the current was 100~500 mA, the light was lit. Standard white quantum dot LEDs were obtained. The international commission on illumination (CIE) coordinates of WQLEDs at 300 mA are (0.3725, 0.4006), the color rendering index (CRI) is 76.6 and the correlation color temperature (CCT) was 4500 K. The tricolor ratio (R, G, B) was R=14.6%, G=83.5%, B=1.8%. It could be seen that green was the majority of the three colors, and the blue content was relatively small, which was conducive to the protection of eyes. This study provides a promising method for realizing WQLEDs using single-phase quantum dots.

Key words: single phase quantum dot, zinc sulfide, light-emitting diodes (LED), white-light quantum dots diodes

引用此文

李奎琛, 郑开元, 何静嘉, 金泽浩, 何秋, 王丽丽. 单相硫化锌量子点制作白光发光二极管(WQLEDs)[J]. 化学学报, 2023, 81(10): 1327-1333.

Kuichen Li, Kaiyuan Zheng, Jingjia He, Zehao Jin, Qiu He, Lili Wang. Single Phase Zinc Sulfide Quantum Dots for Fabrication of White Light Emitting Diodes (WQLEDs)[J]. Acta Chimica Sinica, 2023, 81(10): 1327-1333.

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图/表 7

图1. (a)不同反应时间、(b)不同溶剂组成、(c)不同温度及(d)不同pH下ZnS-QDs的XRD图

Figure 1. XRD patterns of ZnS-QDs at different (a) reaction time, (b) solvent composition, (c) temperatures, and (d) pH

图2. (a) 50 nm和(b) 5 nm标尺下ZnS-QDs的TEM图、(c) ZnS-QDs的晶格条纹及(d)粒径统计图

Figure 2. TEM image of ZnS-QDs at (a) 50 nm scale and (b) 5 nm scale, (c) lattice fringes of ZnS-QDs, and (d) particle size statistics

图3. (a)不同反应时间、(b)不同溶剂组成、(c)不同温度及(d)不同pH下ZnS-QDs的发射光谱

Figure 3. Emission spectra of ZnS-QDs at different (a) reaction time, (b) solvent composition, (c) temperatures, and (d) pH

图4. (a) ZnS-QDs的紫外-可见漫反射光谱及(b) Kubelka-Munk (K-M)公式处理得到的禁带宽度图

Figure 4. (a) UV-visible diffuse reflectance of ZnS-QDs and (b) the band gap spectra processed by Kubelka-Munk (K-M) formula

图5. (a) ZnS-QDs及(b)含有VZn的ZnS-QDs能带结构图

Figure 5. Band structure diagram of (a) ZnS-QDs and (b) ZnS-QDs containing VZn

图6. ZnS-QDs的DTG曲线

Figure 6. DTG curve of ZnS-QDs

图7. (a) WQLEDs在300 mA下工作的照片、(b) WQLEDs在100~500 mA下的发射光谱、(c) WQLEDs在300 mA时的PL光谱及(d) WQLEDs的色坐标图

Figure 7. (a) Photograph of WQLEDs working at 300 mA, (b) emission spectra of WQLEDs at 100~500 mA, (c) PL spectrum of the WQLEDs at 300 mA, and (d) color coordinates of WQLEDs

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