Preparation and Broadband Optical Limiting Performance of Reduced Graphene Oxide Covalently Functionalized with Poly(N-vinylcarbazole)
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摘要: 用表面带负电荷的还原氧化石墨烯(RGO)作为阴离子聚合引发剂，在RGO表面使N-乙烯基咔唑(NVK)原位聚合，生成可溶性聚乙烯基咔唑(PVK)共价功能化的RGO非线性光学材料(RGO-PVK)。采用红外光谱、X光电子能谱和紫外-可见吸收光谱等对RGO-PVK进行了表征。将RGO-PVK嵌埋在非光学活性的聚甲基丙烯酸甲酯（PMMA）中制备了具有良好光学性能的RGO-PVK/PMMA薄膜，并利用开孔Z扫描技术研究了RGO、RGO-PVK、退火处理的RGO-PVK薄膜在532、1 064 nm激光辐照下的非线性光学(NLO)和光限幅(OL)性能。结果表明：与RGO相比，PVK在RGO表面的共价键合显著增强了材料的宽带NLO性能和OL效应。与没有经过退火处理的RGO-PVK/PMMA薄膜相比，退火后的RGO-PVK/PMMA薄膜展现出更加优良的NLO性能。在532、1 064 nm的激光激发时其非线性吸收系数(βeff)分别为306.17 cm/GW和350.32 cm/GW；相应的光限幅阈值分别为0.37和0.31 GW/cm2。Abstract: Graphene shows ultrafast carrier relaxation dynamics and ultra-broadband resonate nonlinear optical (NLO) response due to their extended p-conjugate system and the linear dispersion relation holding for their electronic band structure. In comparison with graphene, functionalized graphene derivatives would be expected to show more excellent NLO and optical limiting (OL) performance. By using as-synthesized graphene carbanions as initiator in the anionic polymerization, poly(N-vinylcarbazole)-covalently functionalized reduced graphene oxide (RGO) derivative (RGO-PVK) was in situ synthesized. The RGO-PVK was characterized by infrared spectroscopy, X-ray electron spectroscopy and UV-Vis absorption spectroscopy. This soluble material was embedded into an optically nonactive transparent poly(methylmeth-lacrylate) (PMMA) matrix to produce the PMMA-based RGO-PVK film for NOL and OL applications. The nonlinear optical and optical limiting properties of RGO, RGO-PVK, and annealed RGO-PVK films under 532 and 1 064 nm laser irradiation were also investigated using the open-aperture Z-scan technique.The results obtained by nonlinear fitting of the data show that in contrast to RGO, the covalent grafting of PVK chains to the RGO surface significantly improved NLO and broadband OL performance of the resultant material. Upon excitation with laser light, the achieved nonlinear coefficient (βeff) and OL threshold of the annealed RGO-PVK/PMMA film are 306.17 cm/GW and 0.37 GW/cm2 at 532 nm, and 350.32 cm/GW and 0.31 GW/cm2 at 1 064 nm. These findings would make it suitable for protecting the human eyes, optical sensors and optoelectronic devices from the laser beams in the visible and near-infrared spectral region.
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图 2 (a) RGO和RGO-PVK的全扫描XPS全谱；(b) RGO-PVK的C1 s 核能级XPS光谱
Figure 2. (a) Wide scan XPS spectra of RGO and RGO-PVK; (b) C1 s core-level XPS spectrum of RGO-PVK
图 5 （a）RGO-PVK和PVK的紫外-可见吸收光谱；（b）RGO-PVK的DMF溶液暴露在日光下不同天数时的紫外可见吸收光谱
Figure 5. (a)UV-Vis absorption spectra of RGO-PVK and PVK；(b) UV-Vis absorption spectrum of RGO-PVK before and after exposure to ambient light
图 6 样品的SEM照片
Figure 6. SEM images of the samples
(a)−GO; (b)−RGO; (c)−RGO-PVK before annealing; (d)−annealed RGO-PVK
图 7 （a~d）在532、1 064 nm，6 ns脉冲激光辐射下样品在DMF中的开孔Z扫描曲线(实线是理论拟合结果)；（e~f）样品在532、1 064 nm激光辐射下时，归一化透过率（空心点）和散射信号（实心点）随入射激光强度变化的关系曲线
Figure 7. (a—d) Typical open-aperture Z-scan data with normalized transmittance as a function of the sample position Z for samples in DMF under the excitation of 6 ns pulses at 532 and 1 064 nm. (The solid lines are the theoretical fitting results); (e—f) The normalized transmittance (open symbol) and scattering response (solid symbol) as a function of input laser intensity for samples at 532 and 1 064 nm
图 8 基于PMMA的薄膜样品在532、1 064 nm，6 ns脉冲激光辐射下的典型开孔Z扫描数据
Figure 8. Typical open-aperture Z-scan data for the PMMA-based films excited under 6 ns pulses at 532、1 064 nm
图 9 （a，b）532、1 064 nm下各PMMA薄膜样品归一化透过率作为入射激光强度的函数曲线；（c，d）PMMA样品的βeff作为激光脉冲能量的函数曲线
Figure 9. (a,b) Normalized transmittance as a function of input laser intensity for samples at 532、1 064 nm. (c,d) βeff as a function of the excitation pulse energy for these PMMA-based films
表 1 样品的线性和非线性参数
Table 1. Linear and NLO data for the samples
Laser Input pulse energy/μJ Sample T0/% α0/cm−1 Βeff/(cm·GW−1) Imχ(3) ×10−12/esu 532 nm
10 Hz
6 ns100 RGO in DMF 82.01 1.98 11.65 4.01 RGO-PVK in DMF 72.79 2.18 44.29 15.24 532 nm
2 Hz,
6 ns100 RGO/PMMA 65.96 34.97 88.61 30.54 Annealed RGO/PMMA 68.56 32.26 125.02 43.08 RGO-PVK/PMMA 51.73 51.49 235.80 81.27 Annealed
RGO-PVK/PMMA56.94 46.93 306.17 105.52 1 064 nm
10 Hz
6 ns150 RGO in DMF 82.27 1.95 9.80 6.75 RGO-PVK in DMF 77.19 2.59 50.88 35.04 1 064 nm
2 Hz
6 ns200 RGO/PMMA 75.97 23.17 196.62 135.45 Annealed
RGO/PMMA76.27 23.23 209.19 144.10 RGO-PVK/PMMA 62.57 36.63 336.11 231.53 Annealed
RGO-PVK/PMMA65.02 35.87 350.32 241.32 T0 : linear transmittance; α0 : linear absorption coefficient; βeff : nonlinear coefficient; Imχ(3) ：imaginary third-order susceptibility 
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