CuInS_2/ZnS/ZnS量子点的制备与光电性能研究
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摘要
首先以高温一锅煮法合成了CuInS_2核量子点,再通过连续和长时间的包覆ZnS外壳,制备出了量子产率高达76%的厚壳结构CuInS_2/ZnS/ZnS,将CuInS_2/ZnS/ZnS量子点作为发光层,利用简单的溶液处理法工艺成功制备出CuInS_2基量子点发光二极管(QLEDs)。同时对量子点的结构、形貌和光学性能及CuInS_2基QLEDs的光电性能进行表征和分析,研究结果表明,通过延长高温反应时间在CuInS_2核上包覆ZnS外壳,能够合成具有良好的光致发光性能的CuInS_2/ZnS/ZnS量子点,利用溶液法制备的CuInS_2基QLEDs开启电压值仅为2.5 V,并且其发光亮度能够达到5473 cd/m~2。CuInS_2/ZnS/ZnS的光致发光和电致发光性能都有了很大的提升。
CuInS_2-based quantum dots light-emitting diodes(QLEDs) were fabricated in three major steps.First,the CuInS_2 nuclear quantum-dots(QDs) were synthesized by one-pot reaction,next,the CuInS_2 QDs were uniformly covered with double thick ZnS shells grown one after another via chemical route under different growth conditions;and finally,QLEDs were fabricated with the CuInS_2/ZnS/ZnS QDs spin-coated on pre-patterned ITO substrate and used as the light-emission layer.The nanostructures/optical properties of CuInS_2/ZnS/ZnS QDs and photoelectric properties of QLEDs were characterized with X-ray diffraction photoluminescence spectroscopy and transmission electron microscopy.The results show that high quality QDs and QLEDs can be synthesized and fabricated bottom-up via chemical route.To be specific,the CuInS_2/ZnS/ZnS QDs had improved photoluminescence and electroluminescence properties and a quantum yield of～76%;the onset voltage and luminance of QLEDs were 2.5 V and 5473 cd/m~2,respectively.
CuInS_2-based quantum dots light-emitting diodes(QLEDs) were fabricated in three major steps.First,the CuInS_2 nuclear quantum-dots(QDs) were synthesized by one-pot reaction,next,the CuInS_2 QDs were uniformly covered with double thick ZnS shells grown one after another via chemical route under different growth conditions;and finally,QLEDs were fabricated with the CuInS_2/ZnS/ZnS QDs spin-coated on pre-patterned ITO substrate and used as the light-emission layer.The nanostructures/optical properties of CuInS_2/ZnS/ZnS QDs and photoelectric properties of QLEDs were characterized with X-ray diffraction photoluminescence spectroscopy and transmission electron microscopy.The results show that high quality QDs and QLEDs can be synthesized and fabricated bottom-up via chemical route.To be specific,the CuInS_2/ZnS/ZnS QDs had improved photoluminescence and electroluminescence properties and a quantum yield of～76%;the onset voltage and luminance of QLEDs were 2.5 V and 5473 cd/m~2,respectively.
引文
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[27] Tan Z N,Zhang Y,Xie C,et al.Near-Band-Edge Electroluminescence from Heavy-Metal-Free Colloidal Quantum Dots[J].Advanced Materials,2011,23(31):3553
[28] Kim J H,Lee K H,Jo D Y,et al.Cu-In-Ga-S Quantum Dot Composition-Dependent Device Performance of Electrically Driven Light-Emitting Diodes[J].Applied Physics Letters,2014,105(13)
[29] Liu Z Y,Zhao K,Tang A W,et al.Solution-Processed High-Efficiency Cadmium-free Cu-Zn-In-S-Based Quantum-Dot Light-Emitting Diodes with Low Turn-on Voltage[J].Organic Electronics,2016,36:97-102
[2] Lee K H,Lee J H,Kang H D,el at.Over 40 cd/A Efficient Green Quantum Dot Electroluminescent Device Comprising Uniquely Large-Sized Quantum Dots[J].ACS Nano,2014,8(5):4893-4901
[3] Lee K H,Lee J H,Song W S,et al.Highly Efficient,Color-Pure,Color-Stable Blue Quantum Dot Light-Emitting Devices[J].ACS Nano,2013,7(8):7295-7302
[4] Zhang H,Chen S M,Sun X W.Efficient Red/Green/Blue Tandem Quantum-Dot Light-Emitting Diodes with External Quantum Efficiency Exceeding 21%[J].ACS Nano,2018,12(1):697-704
[5] Dai X L,Zhang Z X,et al.Solution-Processed,High-Performance Light-Emitting Diodes Based on Quantum Dots[J].Nature,2014,515(7525):96-99
[6] Shen H B,Cao W R,Shewmon N T,et al.High-Efficiency,Low Turn-on Voltage Blue-Violet Quantum-Dot-Based Light-Emitting Diodes[J].Nano Letters,2015,15(2):1211-1216
[7] Zou Y T,Ban M Y,Cui W,et al.A General Solvent Selection Strategy for Solution Processed Quantum Dots Targeting High Performance Light-Emitting Diode[J].Advanced Functional Materials,2017,27(1)
[8] Li Xiyan,Zhao Yongbiao,Fan Fengjia,et al.Bright Colloidal Quantum Dot Light-Emitting Diodes Enabled by Efficient Chlorination[J].Nature Photonics,2018,12(3):159-164
[9] Bai Z L,Ji W Y,Han D B,et al.Hydroxyl-Terminated CuInS2 Based Quantum Dots:Toward Efficient and Bright Light Emitting Diodes[J].Chemistry of Materials,2016,28(4):1085-1091
[10] Wang H C,Zhang H,Chen H Y,et al.Cadmium-Free InP/ZnSeS/ZnS Heterostructure-Based Quantum Dot Light-Emitting Diodes with a ZnMgO Electron Transport Layer and a Brightness of Over 10 000 cd/m2[J].Small,2017,13(13)
[11] Chen B,Pradhan N,Zhong H.From Large-Scale Synthesis to Lighting Device Applications of Ternary I-III-VI Semiconductor Nanocrystals:Inspiring Greener Material Emitters[J].J Phys Chem Lett,2018:435-445
[12] Kim H Y,Park Y J,Kim J,et al.Transparent InP Quantum Dot Light-Emitting Diodes with ZrO2 Electron Transport Layer and Indium Zinc Oxide Top Electrode[J].Advanced Functional Materials,2016,26(20):3454-3461
[13] Chen B K,Zhong H Z,Zhang W Q,et al.Highly Emissive and Color-Tunable CuInS2-Based Colloidal Semiconductor Nanocrystals:Off-Stoichiometry Effects and Improved Electroluminescence Performance[J].Advanced Functional Materials,2012,22(10):2081-2088
[14] Kolny-Olesiak J,Weller H.Synthesis and Application of Colloidal CuInS2 Semiconductor Nanocrystals[J].ACS Applied Materials & Interfaces,2013,5(23):12221-12237
[15] Chuang P H,Lin C C,Liu R S.Emission-Tunable CuInS2/ZnS Quantum Dots:Structure,Optical Properties,and Application in White Light-Emitting Diodes with High Color Rendering Index[J].ACS Applied Materials & Interfaces,2014,6(17):15379-15387
[16] Choi D B,Kim S,Yoon H C,et al.Color-Tunable Ag-In-Zn-S Quantum-Dot Light-Emitting Devices Realizing Green,Yellow and Amber Emissions[J].Journal of Materials Chemistry C,2017,5(4):953-959
[17] Jong-Hoon Kim,Dae-Yeon Jo,Ki-Heon Lee,et al.White Electroluminescent Lighting Device Based on a Single Quantum Dot Emitter[J].Advanced Materials,2016,28(25):5093-5098
[18] Kim J H,Yang H.High-Efficiency Cu-In-S Quantum-Dot-Light-Emitting Device Exceeding 7%[J].Chemistry of Materials,2016,28(17):6329-6335
[19] Jong-Hoon Kim,Bu-Yong Kim,Eun-Pyo Jang,et al.A Near-Ideal Color Rendering White Solid-State Lighting Device Copackaged with Two Color-Separated Cu-X-S(X=Ga,In) Quantum Dot Emitters[J].J Mater Chem C,2017,5(27):6755-6761
[20] Park S H,Hong A,Kim J H,et al.Highly Bright Yellow-Green-Emitting CuInS2 Colloidal Quantum Dots with Core/Shell/Shell Architecture for White Light-Emitting Diodes[J].ACS Applied Materials & Interfaces,2015,7(12):6764-6771
[21] Li J L,Jin H,Wang K L,et al.High luminance of CuInS2-Based Yellow Quantum Dot Light Emitting Diodes Fabricated by All-Solution Processing[J].Rsc Advances,2016,6(76):72462-72470
[22] Zhang Y D,Wang S J,Chen L,et al.Solution-Processed Quantum Dot Light-Emitting Diodes Based on NiO Nanocrystals Hole Injection Layer[J].Organic Electronics,2017,44:189-197
[23] Ji C Y,Lu M,Wu H,et al.1,2-Ethanedithiol Treatment for AgIn5S8/ZnS Quantum Dot Light Emitting Diodes with High Brightness[J].ACS Applied Materials & Interfaces,2017,9(9):8187-8193
[24] Kim J H,Han C Y,Lee K H,et al.Performance Improvement of Quantum Dot-Light-Emitting Diodes Enabled by an Alloyed ZnMgO Nanoparticle Electron Transport Layer[J].Chemistry of Materials,2015,27(1):197-204
[25] Zhong H Z,Wang Z B,Bovero E,et al.Colloidal CuInSe2 Nanocrystals in the Quantum Confinement Regime:Synthesis,Optical Properties,and Electroluminescence[J].Journal of Physical Chemistry C,2011,115(25):12396-12402
[26] Zhang Y,Xie C A,Su H P,et al.Employing Heavy Metal-Free Colloidal Quantum Dots in Solution-Processed White Light-Emitting Diodes[J].Nano Letters,2011,11(2):329-332
[27] Tan Z N,Zhang Y,Xie C,et al.Near-Band-Edge Electroluminescence from Heavy-Metal-Free Colloidal Quantum Dots[J].Advanced Materials,2011,23(31):3553
[28] Kim J H,Lee K H,Jo D Y,et al.Cu-In-Ga-S Quantum Dot Composition-Dependent Device Performance of Electrically Driven Light-Emitting Diodes[J].Applied Physics Letters,2014,105(13)
[29] Liu Z Y,Zhao K,Tang A W,et al.Solution-Processed High-Efficiency Cadmium-free Cu-Zn-In-S-Based Quantum-Dot Light-Emitting Diodes with Low Turn-on Voltage[J].Organic Electronics,2016,36:97-102