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Carbon

Volume 159, 15 April 2020, Pages 1-8
Carbon

Enhanced optical limiting properties of graphene oxide-ZnS nanoparticles composites

https://doi.org/10.1016/j.carbon.2019.12.013Get rights and content

Abstract

Graphene oxide-ZnS (GOZS) nanocomposites were successfully prepared by solvothermal method. The microstructure, morphology and nonlinear optical properties of the obtained GOZS nanocomposites were characterized by XRD, Raman, SEM, TEM, Mapping, UV–vis and open aperture Z-scan test. The results show that ZnS particles with a diameter of about 20 nm are evenly distributed on the GO surface. And GOZS exhibited enhanced nonlinear absorption and optical limiting (OL) action under ultrafast (1030 nm, 340 fs) excitation. The theoretical nonlinear coefficients of GO, ZnS, GOZS(4:5), GOZS(2:5) and GOZS(1:5) at 20.8 GW/cm2 are calculated as 27.6 cm/GW, 25.4 cm/GW, 554.9 cm/GW, 193.3 cm/GW and 117.1 cm/GW, respectively. The nonlinear performance of GOZS is 5–22 times higher than that of pure GO and ZnS, making it a potential optical limiting material. These results may be useful to design GOZS composites with better OL properties.

Introduction

In recent years, Graphene has attracted more and more attention in the field of nonlinear optics. Graphene has excellent third-order nonlinear optical (NLO) properties including third harmonic generation(THG), second harmonic generation(SHG), broadband absorption and so on, due to its unique electronic band structure and wideband gap tunability (Linear dispersion) [[1], [2], [3], [4], [5]]. Graphene as a nonlinear optical material has many remarkable advantages, such as short response time and wide frequency band [6,7]. All of these indicate that Graphene has great potential as a optical material. Graphene is recognized as a potential material for many photonic devices, including satuable absorbers, optical switches, optical modulators and wavelength converters [[8], [9], [10], [11]]. Graphene obtained by different preparation methods or doping methods also has many nonlinear optical properties, such as reverse saturated absorption(RSA), saturated absorption(SA), two-photon absorption(TPA), optical limiting(OL) and so on [12,13]. In particular, GO can be easily modified by surface modification to improve its NLO properties due to the presence of a large number of oxygen-containing groups on its surface, such as epoxy (–COO–) and hydroxyl (-OH) groups [[14], [15], [16]]. In recent years, Graphene oxide composites have gradually become a research highlight of researchers [17,18]. Recently, Solati E and Ouyang Q et al. reported the nonlinear optical and optical limiting properties of graphene-ZnO composite [19,20]. Zinc ferrite decorated reduced graphene oxide exhibited enhanced nonlinear absorption, refraction and optical limiting (OL) action under ultrafast (800 nm, 150 fs) excitation in Ref. [21]. Nonlinear optical and optical limiting properties of graphene oxide-Fe3O4 hybrid material is also investigated in Ref. [22]. Sakho E H M et al. Studied the NLO and OL properties of non-covalent functionalized reduced graphene oxide/silver nanoparticle [23].

Zinc sulphide(ZnS) is a di- and six-group compound semiconductor with a band gap of 3.6 eV. ZnS has excellent fluorescence and electroluminescence functions. ZnS has attracted great attention not only because of its excellent physical properties, such as wide band gap, high refractive index, and high transmittance in the visible range. And its enormous potential to apply optical, electronic and optoelectronic devices [24,25].Nano-ZnS has a unique photoelectric effect and exhibits many excellent properties in the fields of electricity, magnetism, optics, mechanics and catalysis. Therefore, the research of nano-ZnS has attracted more people’s attention [[26], [27], [28]]. Because of its band gap structure, ZnS has excellent NLO properties that make it an ideal candidate for NLObased devices [29]. However, the current nonlinear optical properties of graphene oxide-zinc sulfide composites are rare. In this paper, GOZS nanocomposites were successfully prepared by solvothermal method. The microstructure and morphology of GOZS nanocomposites were characterized. Then, the results of the Z-scan show that GOZS nanocomposites exhibit more significant optical limiting (OL) performance than pure ZnS and GO.

Section snippets

Synthetic procedures

In this paper, Graphene-ZnS nanocomposites were synthesized by solvothermal method [30]. The synthesis process is shown in Fig. 1.

100 mg of Graphene oxide (GO, brown powder) was dissolved in 300 ml of ethanol (CH3CH2OH, analytical grade). Ultrasonic stirring was carried out in an ultrasonic cleaner for 1 h. Then 500 mg of zinc acetate dihydrate ((CH3COO) 2Zn·2H2O, white crystal) was slowly added thereto and stirred uniformly, and ultrasonic dispersion was continued for 1 h. After the solution

X-ray diffraction

The diffraction peaks at 24° and 42° in Fig. 2 correspond to the diffraction peak corresponding to the (002) and (100) crystal plane of Graphene, and the characteristic peak of GO is very noticeable around 10° [34]. Then, at 28.6°, 47.5°, and 56.4°, the diffraction peaks of (111), (220), and (311) of ZnS are respectively shown. This is the same as the JPPC 01–0792 unit cell parameter on the PDF card: a = 5.413 Å, b = 5.413 Å, c = 5.413 Å cubic zinc sulfide phase. This indicates that ZnS having

Conclusions

In this paper, GOZS nanoparticle composites were prepared by hydrothermal method, and three samples with different concentration concentrations were synthesized: GOZS(4:5), GOZS(2:5) and GOZS(1:5). The three samples were separately characterized and tested for nonlinear optical properties. The main conclusions were as follows: (1) The results of XRD, Raman, UV–vis and morphological studies (SEM, TEM, Mapping), confirm the successful compound of GOZS nanoparticle composite. This shows that the

Author contribution

Pei-ling Li,Yu-hua Wang and Xiang-Xiang Yu conceived and designed the study.

Pei-ling Li, Meng Shang and Lan-fu Wu performed the experiments.

Pei-ling Li analyzed and organized the data.

Pei-ling Li and Lan-fu Wu wrote the papter.

Pei-ling Li, Yu-hua Wang, Meng Shang, Lan-fu Wu, Xiang-Xiang Yu reviewed and edited the manuscript.

All authors read and approved the manuscript.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No.11375136).

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