有机相微波合成AgInS2量子点及其白光发光二极管应用研究

doi:10.11949/0438-1157.20220758

化工学报 ›› 2022, Vol. 73 ›› Issue (11): 5167-5176.DOI: 10.11949/0438-1157.20220758

• 材料化学工程与纳米技术 • 上一篇下一篇

有机相微波合成AgInS₂量子点及其白光发光二极管应用研究

陈婷¹(), 胡泽浩², 秦喆¹, 陈园虹¹, 徐彦乔², 林坚¹, 谢志翔³()

^1.苏州科技大学材料科学与器件研究院，江苏苏州 215009
^2.景德镇陶瓷大学材料科学与工程学院，江西景德镇 333403
^3.苏州科技大学化学与生命科学学院，江苏苏州 215009

收稿日期:2022-05-30 修回日期:2022-09-26 出版日期:2022-11-05 发布日期:2022-12-06
通讯作者: 谢志翔
作者简介:陈婷(1984—)，女，博士，副教授，chenting@mail.usts.edu.cn
基金资助:
国家自然科学基金项目(52062019);江苏省高校青蓝工程资助项目

Microwave synthesis of AgInS₂ quantum dots in organic solvent and application for white light-emitting diodes

Ting CHEN¹(), Zehao HU², Zhe QIN¹, Yuanhong CHEN¹, Yanqiao XU², Jian LIN¹, Zhixiang XIE³()

^1.Institute of Materials Science & Devices, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China
^2.School of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, Jiangxi, China
^3.School of Chemistry and Life, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China

Received:2022-05-30 Revised:2022-09-26 Online:2022-11-05 Published:2022-12-06
Contact: Zhixiang XIE

摘要/Abstract

摘要：

AgInS₂量子点(AIS QDs)由于具有绿色环保、发射波长可调、荧光寿命长、斯托克斯位移大等优势，在光电和生物医药领域具有广阔的应用前景。采用微波辅助加热法在十八烯溶剂中制备了AIS QDs。通过X射线衍射、透射电子显微镜、光致发光光谱系统研究了反应时间对AIS QDs的物相、形貌及荧光性能的影响，采用傅里叶红外光谱和X射线光电子能谱表征了量子点表面结合的情况。实验结果表明：当微波功率为800 W、反应时间为5~25 min时均可以制备出AIS QDs。随着反应时间的延长，AIS QDs的粒径由3 nm增加至4 nm，发光峰位在592.0~619.6 nm范围内调谐；同时AIS QDs的荧光强度逐渐提高，并在15 min达到峰值，量子产率(PLQY)达到16.16%。进一步采用ZnS作为包覆壳层有效钝化量子点表面缺陷、提高荧光性能，制备出的AIS@ZnS QDs的PLQY增加至31.21%。将AIS@ZnS QDs和商用荧光粉共同作为发光层制备成白光发光二极管(WLED)器件，在20 mA电流驱动下发光效率(LE)为74.90 lm/W，显色指数(CRI)和色温(CCT)分别为83.31和3823 K，表明制备的量子点在固态照明领域具有潜在的应用前景。

关键词: 白光发光二极管, 量子点, 复合材料, 纳米结构, 有机相微波合成

Abstract:

AgInS₂ quantum dots (AIS QDs) have shown broad application prospects in the field of optoelectronics and biomedicine due to the advantages of environmental friendliness, tunable emission wavelength, long fluorescence lifetime and large Stokes shift. In this study, AIS quantum dots were prepared in octadecene solvent by microwave-assisted heating method. The effects of reaction time on the phase, morphology and fluorescence properties of AIS QDs were systematically investigated by X-ray diffraction, transmission electron microscope, and photoluminescence spectroscopy, respectively. The surface bonding of the AIS QDs was characterized by Fourier infrared spectroscopy and X-ray photoelectron spectroscopy. The results showed that AIS QDs could be synthesized within 5—25 min when the microwave power was 800 W. With the increase of reaction time, the particle size of AIS QDs increased gradually from 3 nm to 4 nm, and the PL peak position could be tuned in the range of 592.0—619.6 nm. The fluorescence intensity increased simultaneously and reached the maximum value at 15 min with photoluminescence quantum yield (PLQY) of 16.16%, In addition, the fluorescence properties of QDs were further improved by ZnS surface modification to passivate the defects, resulting in the enhanced PLQY of 31.21%. Furthermore, white light-emitting diode (WLED) devices were fabricated by using AIS@ZnS QDs and commercial phosphors as light conversion layer. The luminous efficiency (LE) of the fabricated WLED device was as high as 74.90 lm/W under the driving current of 20 mA, and the corresponding color rendering index (CRI) and correlated color temperature (CCT) were 83.31 and 3823 K respectively, indicating that the prepared QDs have great applications in solid-state lighting.

Key words: white light-emitting diodes, quantum dot, composites, nanostructure, organic phase microwave synthesis

中图分类号:

TB 383.1

陈婷, 胡泽浩, 秦喆, 陈园虹, 徐彦乔, 林坚, 谢志翔. 有机相微波合成AgInS₂量子点及其白光发光二极管应用研究[J]. 化工学报, 2022, 73(11): 5167-5176.

Ting CHEN, Zehao HU, Zhe QIN, Yuanhong CHEN, Yanqiao XU, Jian LIN, Zhixiang XIE. Microwave synthesis of AgInS₂ quantum dots in organic solvent and application for white light-emitting diodes[J]. CIESC Journal, 2022, 73(11): 5167-5176.

图/表 9

图1 微波辅助加热法制备AIS@ZnS QDs的流程

Fig.1 Schematic diagram of the preparation of AIS@ZnS QDs via microwave-assisted heating method

图2 不同反应时间制备的AIS量子点的XRD谱图

Fig.2 XRD patterns of AIS QDs prepared with different reaction time

图3 不同反应时间合成 AIS QDs的TEM照片[(a)~(c)(插图为HRTEM照片)]及粒度分布[(d)~(f)]

Fig. 3 TEM images [(a)—(c) (inset is the HRTEM image)] and size distributions [(d)—(f)] of AIS QDs prepared with different reaction time

图4 不同反应时间制备的AIS QDs的荧光性能

Fig.4 Optical properties of AIS QDs prepared with different reaction time

图5 核壳结构AIS@ZnS QDs的结构和光学性能

Fig.5 Structure and optical properties of core-shell structure AIS@ZnS QDs

图6 AIS@ZnS核壳结构量子点的XPS能谱

Fig.6 XPS spectra of AIS@ZnS core-shell QDs

图7 AIS@ZnS QDs、AIS QDs、DDT、丙三醇、正己烷和十八烯的红外谱图

Fig.7 FT-IR spectra of AIS@ZnS QDs, AIS QDs, DDT, glycerol, n-hexane, and ODE

图8 AIS QDs基WLED和AIS@ZnS QDs基WLED的荧光性能

Fig.8 Fluorescence of WLEDs based on AIS QDs and AIS@ZnS QDs

表1 量子点基WLED器件的CRI、CCT、LE和CIE坐标

Table 1 Comparison of CRI， CCT， LE and CIE coordinate of WLEDs based on QDs

QDs	CIE	CRI	LE/(lm/W)	CCT/K	Ref.
CdSe	—	90.1	14	8864	[35]
CdS	—	87.9	0.233	5000	[36]
CdSe@ZnS	(0.34, 0.34)	—	66	—	[36]
ZnCdSe	—	81	57	4000	[37]
ZnSe	(0.38, 0.41)	—	—	—	[38]
InP@ZnS	—	86	53	3200~6500	[39]
InP@ZnSe@ZnS	(0.34, 0.33)	90	—	5313	[40]
AIS@ZnS	(0.39, 0.36)	87.5	—	3669	[5]
AIS@ZnS	(0.38, 0.38)	83.31	74.90	3823	this work

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有机相微波合成AgInS₂量子点及其白光发光二极管应用研究

Microwave synthesis of AgInS₂ quantum dots in organic solvent and application for white light-emitting diodes

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