Two-dimensional nanomaterials and their derivatives for laser protection

Liu Zhi-Wei; Zhang Bin; Chen Yu

doi:10.7498/aps.69.20200313

Abstract

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.

Keywords:

Authors and contacts

Key Laboratory for Advanced Materials, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Chen Yu, chentangyu@yahoo.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 61378072)

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References

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Cited By

图 1 几种典型的二维材料及其应用示意图^[29]

Figure 1. Schematic illustration of different kinds of typical ultrathin 2D nanomaterials^[29].

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图 2 光限幅机理　(a) 非线性散射; (b) 多光子吸收; (c) 反饱和吸收; (d) 自由载流子吸收^[11]

Figure 2. Optical limiting mechanisms: (a) Nonlinear scattering; (b) multi-photon absorption; (c) reverse saturable absorption; (d) free-carrier absorption^[11].

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图 3 (a) Au-Fe₂O₃-RGO的合成路线; (b) 700, (c) 800和(d) 900 nm脉冲激光辐照时获得的开孔Z-扫描曲线^[35]

Figure 3. (a) Synthesis of Au-Fe₂O₃-RGO composites; open aperture patterns of the samples at (b) 700, (c) 800, and (d) 900 nm^[35].

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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]

Figure 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].

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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β_eff系数随激发脉冲能量的变化^[37]

Figure 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 β_eff coefficients as a function of the excitation pulse energy (b2), (b4)^[37].

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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]

Figure 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].

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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]

Figure 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].

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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]

Figure 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].

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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]

Figure 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].

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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]

Figure 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].

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图 11 MoS2-PVK的(a)合成路线和(b), (c)非线性光学(光限幅)性能^[18,64]

Figure 11. (a) Synthesis and (b), (c) NLO (OL) performance of MoS₂-PVK^[18,64]

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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]

Figure 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].

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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]

Figure 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].

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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CH₃NH₃PbI_3–xCl_x的开孔Z-扫描曲线; (c) 532 nm波长激光照射下CH₃NH₃PbI₃和CH₃NH₃PbI_3–xCl_x的开孔Z-扫描曲线^[83]

Figure 14. (a) Illustration of halide perovskites based NLO materials; (b) typical open-aperture Z-scan curves of CH₃NH₃PbI₃ and CH₃NH₃PbI_3–xCl_x at 1064 nm; (c) typical open-aperture Z-scan curves of CH₃NH₃PbI₃ and CH₃NH₃PbI_3–xCl_x at 532 nm^[83].

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图 15 具有不同的CH₃NH₃PbI₃:PVK浓度比的CH₃NH₃PbI₃:PVK/PMMA薄膜在退火前后的开孔Z-扫描曲线(退火条件: 在氮气中200 ℃, 30 min)^[84]

Figure 15. Typical open-aperture Z-scan data of the CH₃NH₃PbI₃:PVK/PMMA films with different CH₃NH₃PbI₃:PVK concentrations. The annealing condition: 200 ℃ for 30 min in N₂^[84].

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[3]	Ashkin A 1970 Phys. Rev. Lett. 24 156 Google Scholar
[4]	Ashkin A 1997 Proc. Natl. Acad. Sci. USA 94 4853 Google Scholar
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[6]	Block S M, Blair D F, Berg H C 1989 Nature 338 514 Google Scholar
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