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摘要: 以石墨烯为代表的二维材料因其独特的结构和优异性能而受到广泛关注。随着二维材料在无限小的方向不断发展，二维（材料）量子片逐渐引起人们极大的兴趣。二维量子片不仅保留了二维材料的本征特性，而且表现出量子限域和突出的边缘效应，为二维材料的潜在应用带来全新机遇。本文详细介绍了二维量子片的基本概念，制备现状与光学性能的研究进展，特别强调了二维量子片本征、普适和规模制备的实现及其重大意义。此外，重点关注了二维量子片的光致发光特性以及在非线性光学、固态发光器件等领域的应用。最后，分析了二维量子片的发展趋势以及面临的主要挑战。Abstract: Two-dimensional (2D) materials like graphene have attracted much attention due to their unique structures and exotic properties. With significantly reduced lateral sizes, 2D quantum sheets (2D QSs) are attracting an increasing level of interest. 2D QSs have opportunities for new applications because of their intrinsic characteristics of being 2D materials and having emerging quantum confinement and prominent edge effects. This review focuses on the conceptual interpretation of 2D QSs and the recent progress on their preparation and optical properties. Particular focus is given to the realization and significance of the universal and scalable production of intrinsic 2D QSs. In addition, the photoluminescence of 2D QSs and their applications in nonlinear optics and solid-state light-emitting devices are reviewed. At the end, the perspectives and challenges towards the future development of 2D QSs are discussed.
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Key words:
- two-dimensional materials /
- quantum sheets /
- photoluminescence /
- nonlinear optics
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图 1 （a）量子片所处体系的示意图[31]；（b）二维量子片的文章发表数目（2007—2016）[4]；（c）二维量子片的应用领域：医药[24]，生物成像[25]，催化[26]，太阳能电池[27]，非线性光学[28]等。（b）转载自文献[4]，版权所有（2018）皇家化学学会。(c) 转载自文献[24]，版权所有（2018）施普林格；转载自文献[25]，版权所有（2018）施普林格；转载自文献[26]，版权所有（2016）自然出版集团；转载自文献[27]，版权所有（2018）施普林格；转载自文献[28]，版权所有（2020）美国化学学会
Figure 1. (a) Schematic diagram of the system in which the quantum sheet is located[31]；(b) number of journal publications on 2D QSs from 2007 to 2016[4]；(c) application fields of 2D QSs：medicine[24], biological imaging[25]，catalysis[26]，solar cell[27]，nonlinear optics[28]，etc. (b) Adapted with permission ref. [4]. Copyright 2018, Royal Society of Chemistry; (c) Reproduced with permission ref. [24]. Copyright 2018, Springer. Reproduced with permission ref. [25]. Copyright 2018, Springer; Reproduced with permission ref. [26]. Copyright 2016, Nature Publishing Group; Reproduced with permission ref. [27]. Copyright 2018, Springer; Reproduced with permission ref. [28]. Copyright 2020, American Chemical Society.
图 2 二维材料的原子结构。（a）石墨烯[3]；（b）氮化硼[3]；（c）二硫化钼[48]；（d）硒化铟[49]；（e）氮化碳[50]；（f）黑磷[41]。(a) 和（b）转载自文献[3]，版权所有（2017）美国化学学会；(c) 转载自文献[48]，版权所有（2011）自然出版集团；(d) 转载自文献[49]，版权所有（2017）自然出版集团；(e) 转载自文献[50]，版权所有（2017）皇家化学学会；(f) 转载自文献[41]，版权所有（2014）自然出版集团
Figure 2. Atomic structures of 2D materials. (a) Graphene[3]; (b) BN[3]; (c) MoS2[48]; (d) InSe[49]; (e) C3N4[50]; (f) BP[41]. (a) and (b) Adapted with permission ref. [3]. Copyright 2017, American Chemical Society. (c) Adapted with permission ref. [48]. Copyright 2011, Nature Publishing Group. (d) Adapted with permission ref. [49]. Copyright 2017, Nature Publishing Group. (e) Adapted with permission ref. [50]. Copyright 2017, Royal Society of Chemistry. (f) Adapted with permission ref. [41]. Copyright 2014, Nature Publishing Group.
图 3 二维量子片的制备方法。自下而上：（a）化学气相沉积[66]；（b）湿化学法[35]。自上而下：（c）电化学剥离[54]；（d）研磨结合超声剥离[62]；（e）液氮预处理和超声剥离[57]；（f）回流预处理和超声剥离[63]；（g）超薄切片结合液相剥离[59]。(a) 转载自文献[66]，版权所有（2016）美国化学学会；(b)转载自文献[35]，版权所有（2019）自然出版集团；(c) 转载自文献[54]，版权所有（2015）皇家化学学会。(d) 转载自文献[62]，版权所有（2015）威立出版集团；（e）转载自文献[57]，版权所有（2017）美国科学促进会；（f）转载自文献[63]，版权所有（2019）爱思唯尔；（g）转载自文献[59]，版权所有（2020）施普林格
Figure 3. The preparation methods of 2D QSs. Bottom-up: (a) CVD [66]; (b) wet chemical method[35]. Top-down: (c) electrochemical exfoliation[54]; (d) grinding combined with sonication exfoliation[62]; (e) liquid nitrogen pretreatment combined with sonication exfoliation[57]; (f) reflux pretreatment combined with sonication exfoliation[63]; (g) ultrathin section combined with liquid phase dissection[59]. (a) Reproduced with permission ref. [66]. Copyright 2016, American Chemical Society; (b) adapted with permission ref. [35]. Copyright 2019, Nature Publishing Group; (c) reproduced with permission ref. [54]. Copyright 2015, Royal Society of Chemistry; (d) reproduced with permission ref. [62]. Copyright 2015, Wiley-VCH; (e) reproduced with permission ref. [57]. Copyright 2017, AAAS; (f) adapted with permission ref. [63]. Copyright 2019, Elsevier; (g) reproduced with permission ref. [59]. Copyright 2020, Springer.
图 4 二维量子片的本征、普适和规模制备。（a）盐辅助球磨和超声辅助溶剂剥离[60]；（b）量子片的制备机理示意图[60]；（c）硅球辅助球磨和超声辅助溶剂剥离[23]；（d）量子片分散液和粉体照片及对应的高分辨透射电镜照片[23]；（e）从多壁碳纳米管制备石墨烯量子片[64]。（a-b）转载自文献[60]，版权所有（2017）美国化学学会；（c-d）转载自文献[23]，版权所有（2019）皇家化学学会；（e）转载自文献[64]，版权所有（2020）美国化学学会
Figure 4. Universal and scalable production of intrinsic 2D QSs. (a) Salt-assisted ball-milling and sonication-assisted solvent exfoliation[60]; (b) schematic diagram of the fabrication mechanism of 2D QSs[60]; (c) silica-assisted ball-milling and sonication-assisted solvent exfoliation[23]; (d) photographs of the QS dispersions and powders and their HRTEM images; (e) robust strategy for tailoring multi-walled carbon nanotubes into GQSs[64]. (a-b) Reproduced with permission ref. [60]. Copyright 2017, American Chemical Society; (c-d) Reproduced with permission ref. [23]. Copyright 2019, Royal Society of Chemistry; (e) Reproduced with permission ref. [64]. Copyright 2020, American Chemical Society.
图 5 二维量子片的光致发光性能。（a）发射波长(nm)对GQSs尺寸的依赖关系[74]；（b）不同尺寸石墨烯量子片的颜色变化[75]；（c）元素掺杂的影响[80]；（d-f）激发波长依赖性[23]；（g）浓度依赖性[23]；（h）溶剂依赖性[23]；（i）固态荧光性能[23]。 (a) 转载自文献[74]，版权所有（2015）皇家化学学会；(b) 转载自文献[75]，版权所有（2014）美国化学学会；(c) 转载自文献[80]，版权所有（2014）威立出版集团；（d-i）转载自文献[23]，版权所有（2019）皇家化学学会
Figure 5. Photoluminescence of 2D QSs. (a) Dependence of emission wavelength (nm) on the size of GQSs[74]; (b) color changes of GQSs with different sizes[75]; (c) effects of elemental doping[80]; (d-f) excitation wavelength dependence[23]; (g) concentration dependence[23]; (h) solvent dependence[23]; (i) solid-state fluorescence[23]. (a) Reproduced with permission ref. [74]. Copyright 2015, Royal Society of Chemistry. (b) Adapted with permission ref. [75]. Copyright 2014, American Chemical Society. (c) Reproduced with permission ref. [80]. Copyright 2014, Wiley-VCH. (d-i) Reproduced with permission ref. [23]. Copyright 2019, Royal Society of Chemistry.
图 6 二维量子片在非线性光学中的应用。（a）等离激元增强石墨烯量子片二阶非线性效应[89]；（b）黑磷量子片的三阶非线性效应[94]；（c）锑烯量子片的光学克尔效应[96]；（d）N掺杂的石墨烯量子片的非线性生物成像[87]；（e）量子片-PMMA复合薄膜的非线性饱和吸收性能[23]。(a) 转载自文献[89]，版权所有（2015）美国化学学会；(b)转载自文献[94]，版权所有（2016）威立出版集团；(c) 转载自文献[96]，版权所有（2017）威立出版集团；（d）转载自文献[87]，版权所有（2013）美国化学学会；(e)转载自文献[23]，版权所有（2019）皇家化学学会
Figure 6. Application of 2D QSs in nonlinear optics.（a）Plasmon-enhanced GQSs second-order nonlinearity[89]；（b）third-order nonlinearity of BPQSs[94]；（c）Kerr effect of AQSs[96];（d）nonlinear biological imaging of N-GQSs[87]；（e）nonlinear saturation absorption of QSs-PMMA hybrid films[23]. (a) Reproduced with permission ref. [89]. Copyright 2015, American Chemical Society. (b) Reproduced with permission ref. [94]. Copyright 2016, Wiley-VCH. (c) Reproduced with permission ref. [96]. Copyright 2017, Wiley-VCH.（d）Reproduced with permission ref. [87]. Copyright 2013, American Chemical Society.（e）Reproduced with permission ref. [23]. Copyright 2019, Royal Society of Chemistry.
图 7 二维量子片在固态发光器件中的应用情况。（a）基于GQSs的垂直腔面发射激光器[104]；（b）基于V2C MXene量子片的白色激光器[110]；（c）基于MoS2 QSs的可拉伸和宽带无腔激光器[106]；（d）基于MoS2 QSs（组氨酸掺杂）的白色发光二极管[112]。(a) 转载自文献[104]，版权所有（2019）美国化学学会；(b) 转载自文献[110]，版权所有（2019）威立出版集团；(c) 转载自文献[106]，版权所有（2020）威立出版集团； (d) 转载自文献[112]，版权所有（2019）威立出版集团
Figure 7. Applications of 2D QSs in solid-state light emitting device. (a) Vertical cavity surface-emitting lasers based on GQSs[104];（b）white lasers with V2C MXene quantum sheets (MQSs)[110]; (c) stretchable and broadband cavity-free laser devices based on MoS2 QSs[106]; (d) white-light-emitting diodes based on histidine-doped MoS2 QSs[112]. (a) Reproduced with permission ref. [104]. Copyright 2019, American Chemical Society. (b) Reproduced with permission ref. [110]. Copyright 2019, Wiley-VCH. (c) Reproduced with permission ref. [106]. Copyright 2020, Wiley-VCH. (d) Reproduced with permission ref. [112]. Copyright 2019, Wiley-VCH.
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