In-situ modification of laser-induced graphene with silver nanoparticles and its electronic conductivity modulation
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摘要: 随着高频通信技术的快速发展，由电磁波造成的电磁干扰问题日益严重，亟需开发针对5G频段的电磁屏蔽材料。以两次激光诱导法直接在固体材料上快速制备了银纳米颗粒/多孔石墨烯柔性复合薄膜：首次激光制备的亲水性激光诱导石墨烯(LIG)能够高效吸附AgNO3溶液，二次激光照射实现了银纳米粒子在多孔石墨烯上的原位生成和均匀负载。进一步研究了不同AgNO3浓度对所制得Ag/LIG材料的微观形貌、结构性质和导电特性的影响。结果表明：当AgNO3浓度为0.5 mol/L时，复合薄膜中银纳米颗粒保持小尺寸的同时分散性最好，其展现出2788 S/m的高电导率；同时，材料屏蔽效能从LIG的18~26 dB增加到复合材料的36~40 dB。在26 GHz频段处，Ag/LIG的屏蔽效能达到38 dB，经200次弯曲循环后效能保有率在90%以上。Abstract: With the rapid development of high-frequency communication technology, electromagnetic interference (EMI) issue has been increasing. Hence, EMI shielding materials for the 5G frequency band are in high demand. Here, a two-step laser-induced strategy was developed to rapidly prepare silver nanoparticles/porous graphene flexible composite in a solid-phase synthesis process. AgNO3 solution can be efficiently adsorbed by hydrophilic laser-induced graphene (LIG) obtained by the first laser irradiation with tuned parameters, which provides favorable conditions for the abundant and homogeneous loading of Ag nanoparticles on LIG after in-situ the second laser irradiation. Furthermore, the microstructures, structural properties and electronic conductivity of the prepared Ag/LIG composites with different AgNO3 additive concentrations are detailedly analyzed. As a result, with a 0.5 mol/L AgNO3 additive concentration, Ag nanoparticles in the composite film maintain small size while exhibiting the best dispersion, exhibiting a high conductivity of 2788 S/m. In the 18-27 GHz frequency band, the EMI shielding effectiveness increases from 18-26 dB of LIG to 36-40 dB of composite materials. The EMI shielding effectiveness of Ag/LIG-0.5 at the 26 GHz reaches 38 dB with an over 90% shielding effectiveness retention rate after 200 bending cycles.
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图 1 (a) Ag/激光诱导石墨烯(LIG)薄膜制备过程；(b) Ag/LIG复合材料的微观结构和电磁屏蔽(EMI)机制示意图
EMW—Electromagnetic wave
Figure 1. (a) Preparation process of Ag/laser-induced graphene (LIG) film; (b) Schematic diagram of microstructure and electromagnetic interference (EMI) shielding mechanism of Ag/LIG composite
图 2 不同激光聚焦条件下获得LIG的SEM图像：((a), (b))激光聚焦在样品表面；((c), (d))激光虚焦(插图为截面SEM图像)
PI—Polyimide
Figure 2. SEM images of LIG obtained at different laser focusing conditions: ((a), (b)) Laser focusing on the surface of the sample; ((c), (d)) Laser defocusing (The inset is a cross-sectional view)
图 3 不同激光聚焦条件下获得LIG的水接触角：(a)激光聚焦；(b)激光虚焦
Figure 3. Water contact angles of LIG obtained at different laser conditions: (a) Laser focusing; (b) Laser defocusing
图 4 不同浓度AgNO3溶液滴加后经激光还原的Ag/LIG 的SEM图像：((a), (d)) 0.2 mol/L；((b), (e)) 0.5 mol/L；((c), (f)) 0.8 mol/L
Figure 4. SEM images of Ag/LIG with different AgNO3 concentrations after laser reduction: ((a), (d)) 0.2 mol/L; ((b), (e)) 0.5 mol/L; ((c), (f)) 0.8 mol/L
图 5 ((a), (b))不同LIG、Ag/LIG样品的Raman图谱；(c)不同样品拉曼图谱的D峰与G峰强度比(ID/IG)、2D峰与G峰强度比(I2D/IG)
LIG-1, LIG-2—Hydrophobic LIG and hydrophilic LIG, respectively; Ag/LIG-0.2, Ag/LIG-0.5 and Ag/LIG-0.8 are samples prepared with Ag+ solutions of 0.2, 0.5 and 0.8 mol/L, respectively
Figure 5. ((a), (b)) Raman spectra of LIG and Ag/LIG samples; (c) Intensity ratio of D peak to G peak (ID/IG) and 2D peak to G peak (I2D/IG) in Raman spectra of different samples
图 6 Ag/LIG的TEM图像(a)和HRTEM图像(b)
D—Diameter of particle
Figure 6. TEM image (a) and HRTEM image (b) of Ag/LIG
图 8 Ag/LIG-0.5的XPS图谱：(a) 总谱；((b), (c)) C1s和Ag3d的高分辨XPS图谱
Figure 8. XPS spectrum of Ag/LIG-0.5: (a) Overview; ((b), (c)) High-resolution XPS spectra of C1s and Ag3d
图 9 LIG和Ag/LIG的面电阻、电导率及其载流子相关测试结果
Figure 9. Sheet resistance, electrical conductivity and carriers related characterization results of LIG and Ag/LIG
图 10 (a)不同AgNO3浓度制备的Ag/LIG复合材料及商用屏蔽膜的总屏蔽效能(EMI SET)；(b) LIG和Ag/LIG-0.5样品的吸收和反射屏蔽效能(SEA和SER)对比；不同AgNO3浓度制备的Ag/LIG复合材料在26 GHz频段的SET、SEA和SER (c)及反射、吸收和透射系数(R、A和T) (d)；(e) Ag/LIG-0.5复合薄膜在反复弯曲和超声处理后26 GHz处的屏蔽效能；(f)二次激光照射前后LIG和Ag/LIG-0.5的实物图及薄膜的柔性展示(插图为Ag/LIG的水接触角)
Figure 10. (a) Total EMI shielding efficicency (EMI SET) of Ag/LIG prepared with different AgNO3 concentrations and commercial film; (b) Comparison of shielding efficiency from absorption and reflection (SEA and SER) of LIG and Ag/LIG-0.5 samples; SET, SEA and SER (c), reflection, absorption and transmission coefficients (R, A, and T) coefficients (d) of Ag/LIG with different AgNO3 concentrations at the 26 GHz frequency band; (e) EMI SE of Ag/LIG-0.5 composite film at 26 GHz after bending or ultrasound; (f) Digital photograph of LIG and Ag/LIG-0.5 before and after secondary laser irradiation, as well as the flexibility of the film (The inset shows the water contact angle of Ag/LIG)
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