Structural design and controllable preparation of metal-graphene multilayer composite films based on electromagnetic field simulation
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摘要: 石墨烯薄膜因其独特的层状结构、高电导率以及良好的柔韧性，在电磁屏蔽领域被广泛研究。然而，石墨烯薄膜存在趋肤深度大的问题，导致其难以兼顾超薄厚度和高屏蔽效能。针对以上问题，基于传输线理论对石墨烯薄膜进行表面修饰和多层阻抗失配界面设计，建立金属-石墨烯多层异质结构模型并开展电磁仿真模拟研究，探索了金属类型、厚度、周期数等结构参数对电磁屏蔽性能的影响规律；依据仿真模型，采用磁控溅射方式构筑了Ag-石墨烯-Ag三明治结构复合薄膜(A-G-A CF)并研究了其电磁屏蔽性能及屏蔽机制。结果表明：石墨烯薄膜表面镀Ag后，电导率提高了近两个数量级，使趋肤深度大幅度减小，4~18 GHz频率范围的屏蔽效能由24 dB提高至44 dB。同时，三明治结构的构筑也增强了电磁波的损耗，使屏蔽效能进一步提高至51 dB。随着金属镀层厚度增加，A-G-A CF的屏蔽效能逐渐提高，金属镀层厚度约580 nm的A-G-A CF的屏蔽效能高达65 dB，可以屏蔽超99.9999%的电磁波能量。Abstract: Graphene film has been widely studied in the field of electromagnetic interference (EMI) shielding due to its unique layered structure, high conductivity, and good flexibility. However, graphene film has a large skin depth, which makes it difficult to balance high shielding effectiveness (SE) and thin thickness. To solve the above problems, the surface modification of graphene film and the design of multi-layer impedance mismatch interface were carried out based on the transmission line theory. The model of metal-graphene multilayer heterostructure was established for electromagnetic simulation. The influence of structural parameters on the EMI shielding performance was studied. According to the simulation model, Ag-graphene-Ag sandwich composite films (A-G-A CF) were fabricated by magnetron sputtering, and their EMI shielding performance and mechanism were investigated. After depositing Ag on graphene film, the conductivity increases by nearly two orders of magnitude, making the skin depth significantly decrease and the SE in 4~18 GHz increase from 24 dB to 44 dB. Moreover, the sandwich structure enhances the electromagnetic loss of the film and further improves the SE to 51 dB. With the increase of metal coating thickness, the SE of A-G-A CF gradually increases. The SE of A-G-A CF with a metal coating thickness of about 580 nm is as high as 65 dB, which can shield more than 99.9999% of electromagnetic wave energy.
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Key words:
- Electromagnetic interference shielding /
- Graphene /
- Simulation /
- Skin depth /
- Magnetron sputtering
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图 1 金属-石墨烯多层异质结构的电磁仿真模型
Figure 1. Electromagnetic simulation model of metal-graphene multilayer heterostructure
图 2 Ag-石墨烯-Ag三明治结构复合薄膜(A-G-A CF)的制备流程示意图
Figure 2. Schematic representation of the preparation process of Ag-graphene-Ag sandwich composite films (A-G-A CF)
图 3 金属-石墨烯多层复合薄膜的屏蔽效能仿真结果：(a) 金属类型，(b) 石墨烯层厚度，(c) 金属层厚度，(d) 周期数对屏蔽效能的影响
Figure 3. Simulation results of shielding effectiveness for metal-graphene multilayer composite films: the influence of (a) metal type, (b) thickness of graphene layer, (c) thickness of metal layer, and (d) period number on shielding effectiveness
图 4 不同周期数的金属-石墨烯多层复合薄膜的电磁波传射特性示意图：(a) 1个周期；(b) 1.5个周期
Figure 4. Schematic representation of electromagnetic wave transmission characteristics of metal-graphene multilayer composite films with different periods: (a) 1 period; (b) 1.5 periods
图 5 (a) A-G-A CF的实物图；(b) A-G-A CF的横截面SEM图；(c) A-G-A CF的横截面EDS mapping图；不同溅射时间制备的A-G-A CF的表面形貌：(d) 10 min；(e) 20 min；(f) 30 min
Figure 5. (a) Photograph of A-G-A CF; (b) cross-section SEM image of A-G-A CF; cross-section EDS mapping of A-G-A CF; surface morphologies of A-G-A CF at different sputtering times: (d) 10 min; (e) 20 min; (f) 30 min
图 6 A-G-A CF的结构信息：(a) XRD图谱；(b) Ag(111)晶面的高分辨率XRD图谱；(c) XPS图谱；(d) Ag 3d峰的高分辨率XPS图谱
Figure 6. Structural information of A-G-A CF: (a) XRD pattern; (b) high-resolution XRD patterns of Ag (111) crystal plane; (b) XPS spectra; (d) high-resolution XPS spectrum of Ag 3d peak
图 7 石墨烯薄膜、A-G CF和A-G-A CF的屏蔽性能： (a) 趋肤深度，(b) 屏蔽效能，(d) SER、SEA和SEtotal值，(e) 透射系数T、反射系数R和吸收系数A；不同溅射时间制备的A-G-A CF的屏蔽性能：(c) 屏蔽效能，(f) SER、SEA和SEtotal值
Figure 7. (a) Skin depth, (b) shielding effectiveness, (d) SER, SEA, and SEtotal values, and (e) transmittance, reflectance, and absorbance of graphene film, A-G CF, and A-G-A CF; (c) shielding effectiveness, and (f) SER, SEA, and SEtotal values of A-G-A CF with different magnetron sputtering time
表 1 石墨烯薄膜、不同溅射时间制备的Ag-石墨烯复合薄膜(A-G CF)和A-G-A CF的镀层厚度和导电性能
Table 1. Coating thickness, and conductivity of graphene film, Ag-graphene composite films (A-G CF) and A-G-A CF prepared with different sputtering time
Samples Sputtering time /min Coating thickness /μm Conductivity/(S·m−1) 1#graphene film — 0 1.9×104 2# A-G CF 20 0.20 7.8×105 3# A-G CF 30 0.29 9.0×105 4# A-G CF 40 0.38 1.0×106 5# A-G CF 50 0.49 1.3×106 6# A-G CF 60 0.58 1.6×106 7#A-G-A CF 2×10 0.20 7.1×105 8# A-G-A CF 2×15 0.28 8.1×105 9# A-G-A CF 2×20 0.36 9.3×105 10# A-G-A CF 2×25 0.48 1.1×106 11# A-G-A CF 2×30 0.58 1.4×106 
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表 2 A-G-A CF与先前报道的石墨烯基复合薄膜的电磁屏蔽性能对比
Table 2. EMI shielding performance of graphene-based composite film reported in previous references and A-G-A CF
Samples Thickness /μm Shielding effectiveness /dB Frequency range /GHz References Graphene film 8.4 20 8~12 14 Fe3O4/graphene film 50 52.76 8~12 17 CNF/RGO@Ni film 15~20 32.2 8~12 22 Iodine-doped graphene film 12.5 52.2 8~18 30 Cu/graphene film 7.8 52 1~18 31 Graphene/polyimide composite films 151 31.37 8~12 32 Graphene/MXene composite films 100 96.3 8~12 33 A-G-A CF 26 65 4~18 This work Note: CNF—cellulose nanofibers; RGO—Reduced graphene oxide.
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