离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用

doi:10.15541/jim20190260

无机材料学报 ›› 2020, Vol. 35 ›› Issue (4): 439-446.DOI: 10.15541/jim20190260

所属专题：功能陶瓷论文精选(一)：发光材料；【虚拟专辑】LED发光材料

离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用

陈婷^1,²,徐彦乔¹,江伟辉^1,²,谢志翔¹,王连军^2,³,江莞^2,³

1. 景德镇陶瓷大学材料科学与工程学院, 景德镇 333001
2. 国家日用及建筑陶瓷工程中心, 景德镇 333001
3. 东华大学材料科学与工程学院, 功能材料研究所, 上海 201620

收稿日期:2019-05-30 修回日期:2019-06-28 出版日期:2020-04-20 网络出版日期:2019-09-04
作者简介:陈婷(1984-), 女, 博士, 副教授. E-mail: chenting@jci.edu.cn
基金资助:
国家自然科学基金(51432004);国家自然科学基金(51774096);江西省杰出青年人才资助计划(20171BCB23071);江西省自然科学基金(20181BAB216009);江西省自然科学基金(20171BAB216008);江西省教育厅基金项目(GJJ190705);江西省教育厅基金项目(GJJ190736);景德镇市科技局基金(20192GYZD008-15);景德镇市科技局基金(20192GYZD008-18)

Ionic Liquid Assisted Microwave Synthesis of Cu-In-Zn-S/ZnS Quantum Dots and Their Application in White LED

CHEN Ting^1,²,XU Yanqiao¹,JIANG Weihui^1,²,XIE Zhixiang¹,WANG Lianjun^2,³,JIANG Wan^2,³

1. School of Material Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China
2. National Engineering Research Center for Domestic & Building Ceramics, Jingdezhen 333001, China
3. Institute of Functional Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Received:2019-05-30 Revised:2019-06-28 Published:2020-04-20 Online:2019-09-04
Supported by:
National Natural Science Foundation of China(51432004);National Natural Science Foundation of China(51774096);Fund for Distinguished Young Scholars of Jiangxi Province(20171BCB23071);Natural Science Foundation of Jiangxi Province(20181BAB216009);Natural Science Foundation of Jiangxi Province(20171BAB216008);Science Foundation of Jiangxi Provincial Department of Education(GJJ190705);Science Foundation of Jiangxi Provincial Department of Education(GJJ190736);Projects of Jingdezhen Science and Technology Bureau(20192GYZD008-15);Projects of Jingdezhen Science and Technology Bureau(20192GYZD008-18)

摘要/Abstract

摘要：

Cu-In-Zn-S(CIZS)量子点具有毒性低、发射谱覆盖范围广、Stokes位移大等特点, 在照明领域具有广阔的应用前景。通过离子液体辅助微波法水相合成CIZS量子点, 系统研究了反应时间、配体添加量和前驱体溶液pH对样品的物相组成、显微形貌以及荧光性能的影响。结果表明, 与未添加离子液体制备的样品相比, 离子液体的引入提高了反应速率, 可有效地将反应时间由180 min缩短至30 min; 随着反应时间的延长, 量子点的粒径增大, 其发射峰位由609.2 nm红移至634.6 nm。随着n_{GSH(谷胱甘肽)}/n_(CuInZn)的增大, 量子点的粒径逐渐增大, 导致其发射峰位由622.6 nm红移至631.6 nm, 同时量子点的发光强度逐渐增强; 当该比值为15时, 量子点的荧光强度最高。此外, 随着pH的增大, 去质子化的-SH和-NH₂与量子点的作用逐渐增强, 有效地钝化了量子点的表面态, 使其荧光强度逐渐上升, 当pH为8.5时, 样品的荧光性能最佳, 同时量子点的平均水合粒径由99 nm增大至241 nm; 量子点溶液的Zeta电位为-27.7~-41.1 mV, 说明量子点溶液具有优异的稳定性。通过ZnS表面修饰可有效提高量子点的荧光强度。将CIZS/ZnS量子点与蓝光芯片结合, 获得了显色指数为85.6、发光效率为34.8 lm/W的白光LED器件, 为水相制备的多元量子点在白光LED中的应用提供了参考。

关键词: 离子液体, 微波, 水相合成, Cu-In-Zn-S, 量子点

Abstract:

Cu-In-Zn-S (CIZS) quantum dots (QDs) are considered as promising fluorescent materials owing to their low toxicity, wide emission range and large Stokes shifts, which have a wide prospect in lighting field. CIZS QDs were prepared via ionic liquid assisted microwave method in aqueous solution. The effects of reaction time, addition amount of ligand and pH of precursor solution on phase composition, microscopic morphology and photoluminescence (PL) property were investigated. Results showed that the reaction rate could be accelerated with the assistance of ionic liquid, i.e. the reaction time reducing from 180 min to 30 min. The size of QDs gradually increased with the increase of reaction time, resulting in red shift of emission peak from 609.2 to 634.6 nm. Moreover, the particle size of CIZS QDs increased with the increase of n_GSH/n_(CuInZn)ratios, resulting in the red shift of emission peak from 622.6 nm to 631.6 nm. Meanwhile, the PL intensity of QDs increased and reached the maximum at n_GSH/n_(CuInZn)=15. Furthermore, the surface defect state was effectively passivated with the increase of pH of precursor solution due to enhanced bonding force between deprotonized groups (-SH, -NH₂) and QDs, resulting in enhancement of PL intensity. And the optimal pH was 8.5. The average hydrodynamic size of CIZS QDs increased from 99 nm to 241 nm with the increase of pH, and the relative Zeta potential ranged from -27.7 mV to -41.1 mV, indicating the excellent stability of CIZS QDs solution. Emission intensity of QDs could be enhanced significantly after coating with ZnS shells. White LED device was fabricated by combining CIZS QDs and a blue chip, the color rendering index and luminous efficiency of device were 85.6 and 34.8 lm/W, respectively, which provided a reference for the application of water soluble multiple QDs in white LEDs.

Key words: ionic liquid, microwave, aqueous phase synthesis, Cu-In-Zn-S, quantum dots

中图分类号:

O611

陈婷, 徐彦乔, 江伟辉, 谢志翔, 王连军, 江莞. 离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用[J]. 无机材料学报, 2020, 35(4): 439-446.

CHEN Ting, XU Yanqiao, JIANG Weihui, XIE Zhixiang, WANG Lianjun, JIANG Wan. Ionic Liquid Assisted Microwave Synthesis of Cu-In-Zn-S/ZnS Quantum Dots and Their Application in White LED[J]. Journal of Inorganic Materials, 2020, 35(4): 439-446.

图/表 11

图1 添加离子液体, 在不同反应时间制备的CIZS量子点的XRD图谱(nGSH/n(CuInZn)=15, pH=8.5)

Fig. 1 XRD patterns of CIZS QDs prepared with different reaction time (with adding ionic liquid, nGSH/n(CuInZn)=15, pH=8.5)

图2 未添加离子液体, 在不同反应时间制备的CIZS量子点的(a)荧光光谱和(b)发射强度-峰位的变化关系(nGSH/n(CuInZn)=15, pH=8.5)

Fig. 2 (a) PL spectra and (b) evolution of the emission intensity and peak position of CIZS QDs prepared with different reaction time (without ionic liquid, nGSH/n(CuInZn)=15, pH=8.5)

图3 添加离子液体, 在不同反应时间制备CIZS量子点(a)荧光光谱和(b)发射强度-峰位的变化关系(nGSH/n(CuInZn)=15, pH=8.5)

Fig. 3 (a) PL spectra and (b) evolution of the emission intensity and peak position of CIZS QDs prepared with different reaction time (with ionic liquid, nGSH/n(CuInZn)=15, pH=8.5)

图4 添加离子液体, 在不同反应时间制备CIZS量子点的TEM照片(nGSH/n(CuInZn)=15, pH=8.5)

Fig. 4 TEM images of CIZS QDs prepared with ionic liquid for different reaction time (nGSH/n(CuInZn)=15, pH=8.5) (a) 10 min; (b) 20 min; (c) 30 min

图5 添加离子液体, 不同nGSH/n(CuInZn)制备的CIZS量子点的XRD图谱(反应时间为30 min, pH=8.5)

Fig. 5 XRD patterns of CIZS QDs prepared with different nGSH/n(CuInZn) ratios (with ionic liquid for 30 min, pH=8.5)

图6 添加离子液体, 不同nGSH/n(CuInZn)制备的CIZS量子点的(a)PL谱和(b)发射强度与峰位的变化关系(反应时间为30 min, pH=8.5)

Fig. 6 (a) PL spectra and (b) evolution of the emission intensity and peak position of CIZS QDs with different nGSH/n(CuInZn) ratios (with ionic liquid for 30 min, pH=8.5)

图7 添加离子液体, 不同nGSH/n(CuInZn)配比制备的CIZS量子点的TEM照片(反应时间为30 min, pH=8.5)

Fig. 7 TEM images of CIZS QDs prepared with nGSH/n(CuInZn) ratios (with ionic liquid for 30 min, pH=8.5) at (a) 5, (b) 15, and (c) 25

图8 添加离子液体, 不同pH条件下制备的CIZS量子点的(a)PL谱和(b)发射强度-峰位的变化关系(反应时间为30 min, nGSH/n(CuInZn)=15)

Fig. 8 (a) PL spectra and (b) evolution of the emission intensity and peak position of CIZS QDs prepared with different pH (with ionic liquid for 30 min, nGSH/n(CuInZn)=15)

图9 添加离子液体, 不同pH制备的CIZS量子点的Zeta电位与平均水合粒径的关系(反应时间为30 min, nGSH/n(CuInZn)=15)

Fig. 9 Zeta potential and average hydrodynamic size of CIZS QDs with different pH (with ionic liquid for 30 min, nGSH/n(CuInZn)=15)

图10 CIZS与CIZS/ZnS量子点的PL谱

Fig. 10 PL spectra of CIZS and CIZS/ZnS QDs

图11 白光LED器件的(a) EL光谱、(b) CIE坐标

Fig. 11 (a) EL spectra and (b) CIE coordinate of white LED

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离子液体辅助微波法水相合成Cu-In-Zn-S/ZnS量子点及其在白光LED中的应用

Ionic Liquid Assisted Microwave Synthesis of Cu-In-Zn-S/ZnS Quantum Dots and Their Application in White LED

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