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量子点是指空间三个维度上存在量子限域效应的半导体纳米晶材料。1962年,日本物理学家Kubo首次发现了量子尺寸效应,此外,量子点还具有表面效应、量子限域效应以及宏观量子隧道效应等,这些效应使量子点的性质与块体材料存在明显差别。当块体材料尺寸减小到纳米级别时,将会限制载流子的运动,导致动能增大,能隙随之增大,其发光波长范围及发光颜色也随着能隙变化而改变[12],从而导致光吸收带上的谱峰红移(向长波移动)或蓝移(向短波移动),这种可调控的荧光特性在红外探测器、光学遥感大气监测以及激光二极管等光学器件应用领域是非常有利的。
经过长期的发展,量子点的相关研究不断取得突破,各类量子点都实现了成功制备。笔者课题组[13]通过液相超声法成功制备了过渡金属碲化物中的CoTe2 QDs,发现该QDs光致发光强度较强,即使在近红外波段仍存在发光现象,而且荧光量子产率高达62.6%,有望成为新的红外探测器材料。表1列出了常见的量子点及其基本特性,其中应用较广泛的是以Cd为代表的Ⅱ-Ⅵ族半导体量子点、过渡金属硫族化合物量子点以及近年发展迅猛的钙钛矿量子点[14]。目前量子点的制备方法主要有:分子束外延法、电化学法、磁控溅射法、化学气相沉积法、热注入法、液相超声法、溶剂热法和范德瓦尔斯外延生长等[15-17],图1所示为其中几种具有代表性的制备方法示意图。
表 1 常见的量子点材料
Table 1. Common quantum dot materials
Materials Wavelength/nm Size/nm Peak/nm Photoluminescence quantum yield Ref. CdS / 3.5 505 50% [18] CsPbI3 / 11-16 673-692 100% [19] ZrS2 240-360 3 379-454 53.3% [20] MA3Bi2Br9 254 3.05 360-540 12% [21] MA3Bi2Cl9 254 2-4 360 15% [21] CoTe2 300-400 3.1 400-448 62.6% [13] Sb2Te3 300-600 2.3 400-450 / [2] ReS2 320-440 2.7 420-490 75.6% [22] N-Ti3C2 360 3.4 447 18.7% [23] ZnSeTe 422-500 5.3 460 75% [24] CdTe 480 2.3-2.7 / 80% [25] CsPbBr3 480 10 / 93% [26] WO3−WS2 600 0.8-2.1 630 11.6% [27] CdSe 600-650 4 / 97% [28] PbS 785 6-10 700-1 600 26% [29] Si 825 4 / 90% [30] PbTe 870 5-16 700-1 000 42% [31] InP/ZnS 1 200 2.1-4.1 480-590 68% [5] 图 1 量子点制备方法示意图:(a) 分子束外延法;(b) 电化学法[12];(c) 磁控溅射法[32];(d) 化学气相沉积法[33];(e) 热注入法[34];(f) 液相超声法[12]
Figure 1. Preparation methods of quantum dots: (a) Molecular beam epitaxy; (b) Electrochemical method[12]; (c) Magnetron sputtering[32]; (d) Chemical vapor deposition[33]; (e) Hot injection method[34]; (f) Liquid phase ultrasonic method[12]
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有机聚合物普遍具有透光率高、化学稳定性好、易于加工成型等特点。现阶段,实现量子点集成到器件的一种主要方法就是将量子点嵌入聚合物基质中得到杂化或复合的量子点材料,从而提升其性能。因此,聚合物材料的选择对于量子点集成而言尤为重要。
目前,在量子点-聚合物纳米复合材料制备中常用的聚合物有聚甲基丙烯酸甲酯(PMMA)[35]、聚乙烯醇(PVA)[36]、聚二甲基硅氧烷(PDMS)、聚乙烯亚胺(PEI)[37]、聚四氟乙烯(PTFE)[38]和聚苯乙烯(PS)[39]等,表2列出了部分常见的量子点-聚合物纳米复合材料的相关性能参数。基于聚合物所具有的优良加工性能以及价格低廉、无毒环保、水溶或油溶性等优势,聚合物在荧光太阳能聚光器、量子点电视及红外、紫外探测器等领域都有应用。
表 2 常用的量子点-聚合物纳米复合材料
Table 2. Commonly used quantum dot-polymer nanocomposites
Materials Preparation method Wavelength/nm Size/nm Peak/nm Quantum dot content/wt% Photoluminescence quantum yield Ref. CdTe/PMMA Thermal evaporation / 2.21-3.42 538-584 6.1 13.5% [40] Si/PMMA Doctor blading / 100 750 0-3.3 35% [41] PbSe/PVA Solution casting 200-800 2.1 1110 5 / [42] SnO2/
PCz(Polycarbazole)In-situ chemical polymerization 320-550 15-20 410-422 5-20 / [43] N-CQD/MIPs(Molecularly Imprinted Polymer) Sol-gel 330 3.2-4.9 431 / / [44] MAPbBr3/PMMA In-situ polymerization 350 4 543 / 88% [45] GQD/PVA Solution casting 350-650 500 / 10 / [46] CdSe/PS Colloidal synthesis 360-370 400-500 510-570 / / [47] CDs/b-PEI(Branched Polyethylenimine) one-step hydrothermal 365 30-50 508-528 / 90.49% [48] CdTe/WPU(Waterborne Polyurethane) Casting and Evaporating 373 2.5-4.1 528-665 0.3 18% [49] TiO2/Acrylate UV polymerization 393 150 530 0.1 / [50] InP@GaP/ZnS/PDMS SAM Encapsulating 400-700 / 527 10 / [51] PbSe/PDTPBT(Poly(2,6-(N-(1-octylnonyl)dithieno[3,2-b:20,30-d]pyrrole)-alt-4,7-(2,1,3-benzothiadiazole))) Ligand exchange 400-900 150 700-800 0.9 / [52] Sb2S3/PMMA One-pot synthesis 450 / 645 9 20% [35] CsPbBr3/PS In-situ photoactivated polymerization 450-650 / 530 0.2 44% [39] MAPbBr3 /PDMS Template 488 5.6-9.8 528 30 10% [53] ZnS/MQ(5-(2-methacryloylethyloxymethyl)-
8-quinolinol)In-situ polymerization 495 3 500 / 40% [54] WS2/PVA Liquid phase exfoliation 532 60-120 617 / / [55] C/PS Solvatothermal 800 12-35 410-580 0.4 22% [56] CeF3/PS Solution casting 975 27-57 1530 10 / [57] -
聚甲基丙烯酸甲酯(Poly(methyl methacrylate), PMMA),一种热塑性塑料,不溶于水,透光率高达92%,介电和电绝缘性能良好,韧性和化学稳定性高,紫外线屏蔽能力强,广泛用于量子点复合材料制备。Huang[40]等人采用热蒸发工艺以PMMA和水溶性CdTe QDs作为原料,制备出具有高光致发光强度的柔性CdTe/PMMA复合薄膜,通过配体交换得到油溶性CdTe QDs,当分别具有539 nm、555 nm、566 nm和588 nm发射波长的油溶性CdTe QDs掺入PMMA中后,在波长为365 nm的紫外灯照射下,所得的柔性透明复合薄膜分别发出绿色、黄绿色、黄色和橙色荧光。该项研究表明:CdTe QDs与PMMA相容性良好,成膜后的量子点仍保持着良好的荧光性能,且光致发光增强。近年来随着钙钛矿材料研究的快速发展,其优异的光电性能受到人们的广泛关注,但提升稳定性是其亟待解决的问题[58]。Zhang 等人[35]以PMMA和CsPbBr3为原料,利用紫外光聚合法制备出钙钛矿-聚合物复合材料,研究结果表明PMMA有效提升了钙钛矿在空气和水中的稳定性。
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聚乙烯醇(Poly(vinyl alcohol),PVA) 是一种水溶性聚合物,透明度高、热稳定性好、绿色无毒、成膜能力强、化学性能优异。Meng等人[59]采用石墨烯与PVA复配并将其拉伸成为纳米纤维,研究结果显示石墨烯自身的结构和机械性能不仅没有受到PVA的影响,而且光学非线性得到显著增强,其脉冲能量最低阈值可达0.25 pJ/pulse。Cosgun等人[60]将掺杂合成得到的ZnSe:Mn/ZnS QDs与PVA结合,并将复合后的材料用于制作白色荧光LED,获得具有高发光特性及显色指数值(CRI) 高达 93.5的LED,其在20 mA电流下连续工作25 h也能保持高稳定性。
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聚二甲基硅氧烷(Poly dimethylsiloxane, PDMS) 是由硅、氧连接形成主链组成的热固性材料,属于有机硅化合物,具有光学透明性高、应力低、绿色无毒、耐高低温、吸附性强、与硅衬底相容性好等特性。Song等人[61]设计了一种基于PDMS负载的ZnS层电致发光器件,此器件通过调制电流频率能够获得可拉伸的特性,而且色彩调节能力得到明显增强。Kim等人[62]基于已有光学触觉传感器的不足设计了一种新型的石墨烯光波导触觉传感器:利用PDMS与石墨烯嵌合调整界面面积,增加石墨烯的吸光量,使上层的折射率大于光波导芯的折射率,实现了实时响应。
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聚乙烯亚胺(Polyethyleneimine, PEI) 是一种水溶性聚合物,稳定性极佳,耐热性良好,价格低廉,附着能力强,其丰富的胺基官能团可与量子点产生相互作用进而结合。Li等人[63] 利用PEI的亲水性处理钙钛矿太阳电池的界面接触,经处理后的电池转换效率(Power Conversion Efficiency, PCE)达14.4%,此外,该电池在自然环境下的稳定性也得到有效改善,10天内电池效率下降小于10%。
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聚苯乙烯(polystyrene, PS) 是一种强度大、刚性好、化学稳定性高的无毒热塑性聚合物材料。PS对于量子点在薄膜形成过程中出现的成分流失和相分离现象能起到有效的抑制作用,且具有疏水性的PS可以有效隔绝空气中的水分,从而增强量子点的稳定性。Ghimire等人[64]选用壳聚糖-聚苯乙烯共聚物(Chitosan-Polystryrene, CS-g-PS)将CdSe/ZnS QDs均匀分布在PS中,在相转移反应下量子点与聚合物紧密结合,形成QDs/聚合物共轭膜。研究结果显示:该复合膜能够保护量子点不受外界干扰并保持其强光致发光的特性,且与纯量子点薄膜相比,复合膜的荧光寿命更长,光稳定性更好。
Research advances in optoelectronic devices of quantum dot-polymer nanocomposites
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摘要: 量子点因具有优异的光电特性,近年来备受关注。但量子点的规模化应用因受到其加工工艺及稳定性等因素限制而尚待开发。量子点-聚合物纳米复合材料的出现有效弥补了这一问题,将量子点分散到有机聚合物中形成纳米复合材料,集合量子点与聚合物的各自优势于一体,是解决量子点当前应用问题的一种有效方法,具有显著的发展潜力。文中介绍了量子点的主要制备技术,并在此基础上对量子点-聚合物复合材料的制备方法及其在激光器、发光二极管、光电探测器、量子点电视等光电子器件中的应用进展进行了概述,最后对其在光电器件领域的应用进行了展望。Abstract: Quantum dots have attracted much attention in recent years because of their excellent photoelectric properties. However, the large-scale application of quantum dots has yet to be developed due to its processing technology and stability. The emergence of quantum dot-polymer nanocomposites effectively makes up for this problem. It is an effective method to solve the current application problems of quantum dots by disperses quantum dots into organic polymers to form nanocomposites and integrates the respective advantages of quantum dots and polymers. It has significant development potential. The main preparation technology of quantum dots was introduced, on this basis, the preparation methods of QD-polymer composites and their applications in lasers, light emitting diodes, photodetectors, QD-TVs and other optoelectronic devices were summarized, and finally its application in the field of optoelectronic device was prospected.
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Key words:
- quantum dots /
- polymers /
- nanocomposites /
- preparation methods /
- photoelectronic devices
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图 1 量子点制备方法示意图:(a) 分子束外延法;(b) 电化学法[12];(c) 磁控溅射法[32];(d) 化学气相沉积法[33];(e) 热注入法[34];(f) 液相超声法[12]
Figure 1. Preparation methods of quantum dots: (a) Molecular beam epitaxy; (b) Electrochemical method[12]; (c) Magnetron sputtering[32]; (d) Chemical vapor deposition[33]; (e) Hot injection method[34]; (f) Liquid phase ultrasonic method[12]
图 4 (a) 基于喷墨打印技术制作CQDs微激光器的方案[84];(b) QD-WLED结构示意图[85];(c) ZnO发光二极管器件结构示意图[86];(d) 使用蓝色LED芯片组合的背光单元装置结构[87];(e) QD/PTPA-b-CAA制备的QLED器件结构示意图[88];(f) CPB@SHFW复合材料结构示意图,右上角插图为LED[89];(g) CsPbBr3-P QDs 与介孔聚苯乙烯(MPMs)在SiO2包覆下制备的杂化微球制备的白光LED结构图,插图是LED在10 mA时拍摄的照片[26];(h) QD/PTPA-b-CAA制备的QLED混合发射层能带结构图[88];(i) 浸泡在水中的CPB@SHFW复合粉末其PLQY随时间的变化图(插图:材料在水中浸泡31天)[89]
Figure 4. (a) Schematic of fabricating CQDs microlaser based on the inkjet printing technique[84]; (b) QD-WLED structure diagram[85]; (c) ZnO light-emitting diode device structure diagram[86]; (d) Device structure with a combined backlight unit using a blue LED chip[87]; (e) Structure diagram of QLED device prepared by QD/ PTPA-B-CAA[88]; (f) CPB@SHFW composites structural diagram, upper right illustration is LED[89]; (g) Structure diagram of white LED prepared by hybrid microspheres of CSPbBr3-P QDs and mesoporous polystyrene (MPMs) coated with SiO2, the inset is a digital photo of the device taken at 10 mA[26]; (h) Energy band structure diagram of QLED hybrid emitting layer prepared by QD/ PTPA-B-CAA[88]; (i) Variation of PLQY of CPB@SHFW composite powder with time in water (illustration: material soaked in water for 31 days)[89]
图 5 光电探测器:(a) Au/CNDs/n-Si紫外光电探测器的装置[93];(b) N-GQDs光电探测器原理图[93];(c) 典型的Si-QD/石墨烯/Si光电探测器[93];(d) Si NWs阵列/CuO异质结构光电探测器[93];(e) PMDTC配体的器件结构[94];(f) ZnO/P3 HT:PVK光电探测器结构示意图,BCP层为量子点和聚合物复合层[95];(g) CdTe和P3 HT光电探测器结构[96];(h) 器件在光照射下的J-V曲线。在反向偏压下观察到更高的光电流密度[94];(i) 量子点-聚合物复合材料中电子-空穴对的1产生、2分裂、3空穴传输和电子捕获过程的说明[95]
Figure 5. Photoelectric detector: (a) Device of Au/CNDS/n-Si ultraviolet photoelectric detector[93]; (b) N-GQDs photodetector schematic diagram[93]; (c) Typical Si-QD/Graphene /Si photodetector[93]; (d) Si NWs array /CuO heterostructure photodetector[93]; (e) Device structure of the PMDTC ligand[94]; (f) Schematic diagram of ZnO/P3 HT:PVK photodetector structure, the BCP layer is a composite layer of Quantum dots and polymer[95]; (g) CdTe and P3 HT photodetector structure[96]; (h) J-V curve of the device under light irradiation. Higher photocurrent density was observed under reverse bias[94]; (i) Description of 1 the generation, 2 splitting, 3 hole transport, and electron capture processes of electron-hole pairs in quantum dot polymer composites[95]
表 1 常见的量子点材料
Table 1. Common quantum dot materials
Materials Wavelength/nm Size/nm Peak/nm Photoluminescence quantum yield Ref. CdS / 3.5 505 50% [18] CsPbI3 / 11-16 673-692 100% [19] ZrS2 240-360 3 379-454 53.3% [20] MA3Bi2Br9 254 3.05 360-540 12% [21] MA3Bi2Cl9 254 2-4 360 15% [21] CoTe2 300-400 3.1 400-448 62.6% [13] Sb2Te3 300-600 2.3 400-450 / [2] ReS2 320-440 2.7 420-490 75.6% [22] N-Ti3C2 360 3.4 447 18.7% [23] ZnSeTe 422-500 5.3 460 75% [24] CdTe 480 2.3-2.7 / 80% [25] CsPbBr3 480 10 / 93% [26] WO3−WS2 600 0.8-2.1 630 11.6% [27] CdSe 600-650 4 / 97% [28] PbS 785 6-10 700-1 600 26% [29] Si 825 4 / 90% [30] PbTe 870 5-16 700-1 000 42% [31] InP/ZnS 1 200 2.1-4.1 480-590 68% [5] 表 2 常用的量子点-聚合物纳米复合材料
Table 2. Commonly used quantum dot-polymer nanocomposites
Materials Preparation method Wavelength/nm Size/nm Peak/nm Quantum dot content/wt% Photoluminescence quantum yield Ref. CdTe/PMMA Thermal evaporation / 2.21-3.42 538-584 6.1 13.5% [40] Si/PMMA Doctor blading / 100 750 0-3.3 35% [41] PbSe/PVA Solution casting 200-800 2.1 1110 5 / [42] SnO2/
PCz(Polycarbazole)In-situ chemical polymerization 320-550 15-20 410-422 5-20 / [43] N-CQD/MIPs(Molecularly Imprinted Polymer) Sol-gel 330 3.2-4.9 431 / / [44] MAPbBr3/PMMA In-situ polymerization 350 4 543 / 88% [45] GQD/PVA Solution casting 350-650 500 / 10 / [46] CdSe/PS Colloidal synthesis 360-370 400-500 510-570 / / [47] CDs/b-PEI(Branched Polyethylenimine) one-step hydrothermal 365 30-50 508-528 / 90.49% [48] CdTe/WPU(Waterborne Polyurethane) Casting and Evaporating 373 2.5-4.1 528-665 0.3 18% [49] TiO2/Acrylate UV polymerization 393 150 530 0.1 / [50] InP@GaP/ZnS/PDMS SAM Encapsulating 400-700 / 527 10 / [51] PbSe/PDTPBT(Poly(2,6-(N-(1-octylnonyl)dithieno[3,2-b:20,30-d]pyrrole)-alt-4,7-(2,1,3-benzothiadiazole))) Ligand exchange 400-900 150 700-800 0.9 / [52] Sb2S3/PMMA One-pot synthesis 450 / 645 9 20% [35] CsPbBr3/PS In-situ photoactivated polymerization 450-650 / 530 0.2 44% [39] MAPbBr3 /PDMS Template 488 5.6-9.8 528 30 10% [53] ZnS/MQ(5-(2-methacryloylethyloxymethyl)-
8-quinolinol)In-situ polymerization 495 3 500 / 40% [54] WS2/PVA Liquid phase exfoliation 532 60-120 617 / / [55] C/PS Solvatothermal 800 12-35 410-580 0.4 22% [56] CeF3/PS Solution casting 975 27-57 1530 10 / [57] -
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