一锅法制备三元ZnCdTe/ZnS量子点及其在照明中应用研究
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摘要
Cd系量子点由于其量子产率高,光谱调谐方便,成为世界各国科学家研究的热点;目前已经在生物荧光,传感,太阳能电池等领域有了很大的进展,但是Cd元素的毒性一直是限制其大规模应用的瓶颈。目前,降低含Cd量子点毒性的方法主要有两种:包覆保护层和采用合金化。二元CdTe量子点的制备技术以及包覆技术已较为成熟,但是三元量子点的研究相对比较少,目前的制备技术大多比较复杂,成本较高,不适合规模化生产。本文采用溶剂热法,以巯基乙酸(TGA)作为稳定剂,通过包覆与合金化相结合的手段,成功在高温下制备了量子产率高,性能稳定,发射波长能够覆盖可见光区域的水溶性ZnCdTe量子点。
Cd-based quantum dots(QDs) have attracted extensive attention for a long time due to high photoluminescence quantum yield(PLQY) and tunable spectrum. Currently, much progress has been made in the fields of bioluminescence, sensing and solar cells, but the toxicity of Cd has been the bottleneck restricting further large-scale application. There are two main methods to reduce the toxicity of Cd-based QDs including coating and alloying. The preparation and coating technology of binary CdTe QDs are relatively mature, but the research of ternary CdTe QDs still needs further investigation. The present synthetic process is complex and costly, which is not suitable for large-scale production. In this work, we successfully prepared water-soluble ZnCdTe QDs at high temperature by solvothermal method, using thioglycolic acid(TGA) as a stabilizer and combining coating with alloying. The as-prepared ZnCdTe QDs exhibit high PLQY, excellent stability and emission wavelength covering the visible region.
Cd-based quantum dots(QDs) have attracted extensive attention for a long time due to high photoluminescence quantum yield(PLQY) and tunable spectrum. Currently, much progress has been made in the fields of bioluminescence, sensing and solar cells, but the toxicity of Cd has been the bottleneck restricting further large-scale application. There are two main methods to reduce the toxicity of Cd-based QDs including coating and alloying. The preparation and coating technology of binary CdTe QDs are relatively mature, but the research of ternary CdTe QDs still needs further investigation. The present synthetic process is complex and costly, which is not suitable for large-scale production. In this work, we successfully prepared water-soluble ZnCdTe QDs at high temperature by solvothermal method, using thioglycolic acid(TGA) as a stabilizer and combining coating with alloying. The as-prepared ZnCdTe QDs exhibit high PLQY, excellent stability and emission wavelength covering the visible region.
引文
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[25] 单崇新.ZnCdSe量子点的制备及其表征[D].长春:中国科学院研究生院(长春光学精密机械与物理研究所),2004.
[2] PENG Z A,PENG X.Formation of high-quality CdTe,CdSe,and CdS nanocrystals using CdO as precursor[J].Journal of the American Chemical Society,2001,123(1):183-184.
[3] KIM S,FISHER B,EISLER H J,et al.Type-II quantum dots:CdTe/CdSe(core/shell) and CdSe/ZnTe(core/shell) heterostructures[J].Journal of the American Chemical Society,2003,125(38):11466-11467.
[4] TANG Z,KOTOV N A,GIERSIG M.Spontaneous organization of single CdTe nanoparticles into luminescent nanowires[J].Science,2002,297(5579):237-240.
[5] JANG E,JUN S,JANG H,et al.White-light-emitting diodes with quantum dot color converters for display backlights[J].Advanced Materials,2010,22(28):3076-80.
[6] QIAN L,ZHENG Y,XUE J,et al.Stable and efficient quantum-dot light-emitting diodes based on solution-processed multilayer structures[J].Nature Photonics,2011,5(9):543-548.
[7] DU J,XU S,WANG C,et al.Design and assembly of aqueous red CdTe QD-LED:major factors to fabricate aqueous QD-LEDs[J].Rsc Advances,2016,6(81):77963-77967.
[8] 易觉民.CdTe纳米晶/GaN基白光LED研究[D].北京:北京大学,2008.
[9] SHEN C Y,CHU J L,QIAN F,et al.High color rendering index white LED based on nano-YAG∶Ce3+ phosphor hybrid with CdSe/CdS/ZnS core/shell/shell quantum dots[J].Journal of Modern Optics,2012,59(14):1199-1203.
[10] 唐永安,胡军,杨祥良,等.镉系量子点的生物毒性及相应机制[J].化学进展,2014,26(10):1731-1740.
[11] SUN H,ZHANG H,ZHANG J H,et al.Effect of electrostatic interactions on the photophysical properties of the composites of CdTe nanocrystals and carbazole-containing polymers[J].Journal of Physical Chemistry C,2008,112(7):2317-2324.
[12] VOLLATH D,SZABóD V.Coated Nanoparticles:A new way to improved nanocomposites[J].Journal of Nanoparticle Research,1999,1(2):235-242.
[13] DERFUS A M,CHAN W C W,BHATIA S N.Probing the cytotoxicity of semiconductor quantum dots[J].Nano Letters,2004,4(1):11-18.
[14] GAO M,STEFAN K A,M?HWALD H,et al.Strongly photoluminescent CdTe nanocrystals by proper surface modification[J].Journal of Physical Chemistry B,1999,30(2).8360-8363.
[15] SADAF A,ZESHAN B,WANG Z,et al.A comparative study of CdTe quantum dots and CdTe@SiO2 nanoparticles:fabrication and cytotoxicity in HEK293 cells[J].Journal of Nanoscience & Nanotechnology,2012,12(9):6900.
[16] WANG M P,LIN J H,SHAN C S.Synthesis of CdTe/SiO2 composites and their fluorescence properties[J].Chemical Research in Chinese Universities,2011,27(4):540-542.
[17] WANG M P,LIN J H,HAO X L.Preparation and characterization of CdTe/SiO2 composite[J].Advanced Materials Research,2011,233-235(3):1946-1949.
[18] LADHA J K,TIROL-PADRE A,DAROY M L G,et al.A simple route to the synthesis of core/shell nanoparticles of chalcogenides[J].Chemistry of Materials,2002,14(5):2004-2010.
[19] YANG Y,CHEN O,ANGERHOFER A,et al.Radial-position-controlled doping in CdS/ZnS core/shell nanocrystals[J].Journal of the American Chemical Society,2017,128(38):12428-12429.
[20] PENG H,ZHANG L,SOELLER C,et al.Preparation of water-soluble CdTe/CdS core/shell quantum dots with enhanced photostability[J].Journal of Luminescence,2007,127(2):721-726.
[21] WUISTER S F,DONEGá C D M,MEIJERINK A.Influence of thiol capping on the exciton luminescence and decay kinetics of CdTe and CdSe quantum dots[J].Journal of Physical Chemistry B,2004,108(45):17393-17397.
[22] TOROPOV A A,LEBEDEV A V,SOROKIN S V,et al.Magneto-photoluminescence studies of diluted magnetic semiconductor type-II quantum wells ZnMnSe/ZnSSe[J].Physica E:Low-dimensional Systems and Nanostructures,2003,17(1):352-354.
[23] LEE S,DARUKA I,KIM C S,et al.Dynamics of ripening of self-assembled II-VI semiconductor quantum dots[J].Physical Review Letters,1998,81(16):3479-3482.
[24] LUO Y,GUO S P,MAKSIMOV O,et al.Patterned three-color ZnCdSe/ZnCdMgSe quantum-well structures for integrated full-color and white light emitters[J].Applied Physics Letters,2000,77(26):4259-4261.
[25] 单崇新.ZnCdSe量子点的制备及其表征[D].长春:中国科学院研究生院(长春光学精密机械与物理研究所),2004.