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为了实现同步防护脉冲激光和连续波或准连续波激光的攻击, 人们在过去几十年间已经投入了大量的人力和物力来研发高性能光限幅材料. 石墨烯、过渡金属硫化物、黑磷等二维纳米材料拥有许多优异独特的性质, 激发了全世界的广泛研究兴趣. 本文简要回顾了基于石墨烯、黑磷、过渡金属硫化物和钙钛矿等最具代表性的二维材料及其有机/高分子衍生物在激光防护领域中的研究进展、存在的亟待解决的关键科学问题和未来的发展趋势. 为了充分利用这些二维纳米材料的优点, 人们可以使用功能小分子或聚合物与它们进行共混掺杂, 制备复杂的多相材料体系, 也可以将可溶性的有机/高分子共价功能化的二维纳米材料掺杂于高分子基质中形成主客体复合材料, 这些制备方法有助于促进或提高整个体系的光限幅能力. 总而言之, 一个优化的复杂的多组份纳米材料体系能极大地增强光限幅器件的性能和适应性. 此外, 开展二维纳米材料和它们的衍生物在不同固体基质中展现出来的光物理和光子性质研究, 将有助于在分子水平上实现对这些纳米材料的改性.To achieve simultaneous protection against both pulsed and continuous wave (CW) or quasi-CW lasers, significant research effort has been devoted to the state-of-the-art optical limiting (OL) materials and processes in an attempt to achieve some measures of protection against such laser beams in the past decades. Two-dimensional (2D) nanomaterials with a lot of unique properties, including graphene, transition metal dichalcogenides, black phosphorus and others, have aroused the extensive research interest of many researchers. In this review paper, we describe systematically the OL mechanisms and the recent achievements in the 2D nanomaterials and their organic/polymeric derivatives for laser protection. In an effort to sustain the advantage of 2D nanomaterials, one can not only introduce the functional molecules or polymers to blend with them to form a complex multi-phase material system, but also embed the soluble 2D nanosheets covalently functionalized with organic/polymeric materials in a polymer host to form host-guest composite materials that are expected to improve the OL performance of the whole system. All in all, an optimized complex multi-component nanomaterial system enormously enhances the performance and applicability of OL devices. In addition, the fundamental studies of the photophysical and photonic properties of 2D nanomaterials and their derivatives in various solid hosts are of significance for modifying the nanomaterials at a molecular level.
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Keywords:
- two-dimensional nanomaterials /
- covalent chemical modification /
- nonlinear optics /
- optical limiting
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图 4 (a) GO-Pt-1和GO-Pt-2的合成路线; (b), (c) 532 nm脉冲激光下开孔Z-扫描性能图[27]; (d) PF-GO和ZnP-GO结构示意图(插图为DMF分散液照片 (I) ZnTNP-PAES; (II) GO; (III) ZnP-GO; (IV) PF-GO; (V) PF-RGO; (VI) ZnP–RGO); (e) 532 nm和(f) 1064 nm脉冲激光下开孔Z-扫描曲线[36]
Fig. 4. (a) Synthesis of GO-Pt-1 and GO-Pt-2; (b) typical open-aperture Z-scan data and (c) optical limiting performance of the samples at 532 nm[27]; (d) schematic illustration of the structure of PF-GO and ZnP-GO (insert shows the photographs of dispersions in DMF: (I) ZnTNP-PAES; (II) GO; (III) ZnP-GO; (IV) PF-GO; (V) PF-RGO; (VI) ZnP-RGO.); open-aperture Z-scan curves with normalized transmittance (open symbols) and scattering signal (solid symbols) for the samples at (e) 532 and (f) 1064 nm[36].
图 5 (a) PFTP-GRO的合成路线; (b)光限幅性能曲线, 其中(b1), (b3) 在532和1064 nm处薄膜归一化透射率随入射激光强度的变化; (b2), (b4) 相应的βeff系数随激发脉冲能量的变化[37]
Fig. 5. (a) Synthesis of PFTP-RGO. (b) Variation of the normalized transmittance as a function of input laser intensity for the films: (b1) at 532 nm; (b3) at 1064 nm; the corresponding βeff coefficients as a function of the excitation pulse energy (b2), (b4)[37].
图 6 (a) BP晶格结构俯视图; (b) BP椅式结构侧视图; 插图: 红色突出显示BP椅式六元环结构; BP晶体的扫描隧道电子显微镜图[42]
Fig. 6. (a) Top view of the puckered honeycomb lattice of black phosphorus; (b) lateral view on the lattice in armchair direction. Insets: BP lattice with a six-membered ring in chair configuration highlighted in red; scanning tunneling electron microscopyimage of the BP lattice [42].
图 7 (a)—(e) 532 nm, 6 ns脉冲激光照射下基于PMMA的样品薄膜的开孔Z-扫描曲线; (f) BP:C60共混物示意图[53]
Fig. 7. (a)−(e) Typical open-aperture Z-scan data with normalized transmittance as a function of the sample position Z for the samples embedded in PMMA matrix under the excitation of 6 ns pulses at λ = 532 with different energies. The solid lines are the theoretical fitting results. (f) Structure of BP:C60 blends[53].
图 8 (a) BP-Big和(b) BP-Small的开孔Z-扫描曲线; (c) BP-Big和BP-Small的非线性光学响应对比图[54]; (d), (e), (g), (h) BP分散液在不同波长和脉冲时间激光激发下的开孔Z-扫描曲线; 532 nm脉冲激光条件下, (f) BP分散液在不同激发能量下的开孔Z-扫描曲线和(i)散射信号曲线[55]
Fig. 8. Open-aperture Z-scan fitted data of (a) BP-Big and (b) BP-Small; (c) NLO response of BP nanosheets with variable sizes BP-Big and BP-Small as a function of pulse fluence[54]; open-aperture Z-scan results of the BP dispersion for nanosecond pulse excitation at (d) 532 nm and (e) 1064 nm and femtosecond pulse excitation at (g) 515 nm and (h) 1030 nm; (f) open-aperture Z-scan result and (i) corresponding scattering signal of BP dispersions at a 532 nm ns laser[55].
图 9 (a) F12PcZn-BP的合成路线; (b) 532 nm, 6 ns脉冲激光照射下基于PMMA的样品薄膜的(I)−(III)开孔Z-扫描曲线和(IV)归一化透过率与激光能量关系图[56]
Fig. 9. (a) Schematic illustration of the fabrication F12PcZn-BP; (b) (I)−(III) typical open-aperture Z-scan data of the samples and (IV) variation in the normalized transmittance as a function of input laser intensity for the PMMA-based films at 532 nm[56].
图 10 1 T'相构型的h-LiMoS2 和2 H相构型的MoS2材料在不同入射激光能量下的(a)开孔Z-扫描曲线和(b)闭孔Z-扫描曲线[58]
Fig. 10. Open (a) and closed (b) aperture Z-scan measurements of h-LiMoS2 and MoS2 at different input laser power, indicated at the top left of each curve, showing saturable absorption and self-focusing behavior of h-LiMoS2 at a lower pumping power[58].
图 12 (a) MoS2-PAN 和 pyro-MoS2-PAN的合成; (b) PAN 的裂解过程; (c) 退火前MoS2-PAN 的Mo 3d XPS 谱; (d) 退火后pyro-MoS2-PAN的Mo 3 d XPS 谱; 2H相和1T相分别用红色线和绿色线表示[65,66]
Fig. 12. (a) Synthesis of MoS2-PAN and pyro-MoS2-PAN; (b) pyrolytic process of PAN; the Mo 3 d core level XPS spectra of (c) the non-annealed MoS2-PAN and (d) the pyro-MoS2-PAN. The 2 H and 1 T contributions are represented by red and green plots, respectively[65,66].
图 13 (a) 能影响钙钛矿性能的重要结构特征[74]; (b)不同尺寸维度的钙钛矿(I)结构示意图, (II)形态示意图和(III)晶体构型示意图[75]
Fig. 13. (a) Key structural factors that influence the properties of halide perovskites[74]; (b) (I) representative crystal structures of halide perovskites in different dimensions; (II) nanoscale morphologies of halide perovskites; (III) schematic representation of the 2D organic-inorganic perovskites from different cuts of the 3D halide perovskite structure[75].
图 14 (a) 钙钛矿非线性光学材料示意图; (b) 1064 nm激光照射下CH3NH3PbI3和CH3NH3PbI3–xClx的开孔Z-扫描曲线; (c) 532 nm波长激光照射下CH3NH3PbI3和CH3NH3PbI3–xClx的开孔Z-扫描曲线[83]
Fig. 14. (a) Illustration of halide perovskites based NLO materials; (b) typical open-aperture Z-scan curves of CH3NH3PbI3 and CH3NH3PbI3–xClx at 1064 nm; (c) typical open-aperture Z-scan curves of CH3NH3PbI3 and CH3NH3PbI3–xClx at 532 nm[83].
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