Graphene plasmon enhanced infrared spectroscopy

Wu Chen-Chen; Guo Xiang-Dong; Hu Hai; Yang Xiao-Xia; Dai Qing

doi:10.7498/aps.68.20190903

Abstract

Infrared spectroscopy can accurately reflect the information of molecular vibration, and it is an important technology to characterize the composition and structure of materials. However, since the interaction between nanomaterials and infrared light is very weak due to the significant size mismatch, it is challenging to obtain the spectral information of nanomaterials in the field of infrared spectroscopy. The plasmon is a collective electron oscillation on the surface of the material inducing by the incident light, and it has excellent light field confinement, which can significantly enhance the interaction between light and nanomaterials. Graphene plasmon has prominent properties, such as high light field confinement, dynamic adjustment, and low intrinsic attenuation. Therefore it is an important solution to enhance the infrared absorption of nanomaterials. This article systematically introduces the infrared plasmon materials system. Then it summarizes the characteristics of graphene plasmon and their advantages on surface enhanced infrared spectroscopy, and it emphasizes the recent important researches and applications of graphene plasmon enhanced infrared spectroscopy in the world, including single molecular layer biochemical detection, gas identification, refractive index sensing, etc. Further prospects for the development and potential applications of graphene plasmon enhanced infrared spectroscopy are also demonstrated.

Keywords:

Authors and contacts

1.
Division of Nanophotonics, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Yang Xiao-Xia, yangxx@nanoctr.cn ; Dai Qing, daiq@nanoctr.cn

Funds: Project supported by the National Basic Key Research Program of China (Grant No. 2015CB932400), the National Key Research and Development Program of China (Grant No. 2016YFA0201600), the National Natural Science Foundation of China (Grant Nos. 11674073, 11504063, 11704085), the Key Program of the Bureau of Frontier Sciences and Education, Chinese Academy of Sciences (Grant No. QYZDB-SSW-SLH021), the Key Research Program of the Chinese Academy of Sciences (Grant No. ZDBS-SSW-JSC002), and the Youth Innovation Promotion Association Chinese Academy of Sciences and CAS Interdisciplinary Innovation Team (Grant No. JCTD-2018-03).

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Cited By

图 1 典型的表面等离激元材料及其相应的等离激元响应　等离激元损耗取决于等离子体响应频段和载流子迁移率; TI, 拓扑绝缘体; 图中描述了金属(Au, Ag, Al, K, Na, Al; Pt, Pb, Pd和Ti)、超导体(YBa₂Cu₃O_7－d)、石墨烯、拓扑绝缘体(HgTe和Bi₂Se₃), 以及各种半导体(In₂O₃/SnO, ZnO, Ge, Si, III-V族, 和SiC)的载流子迁移率、等离子体响应频段; 图上方给出了石墨烯、半导体和金属天线的典型尺寸, 并绘制了这些材料的等离激元天线尺寸与辐射损耗之间的关系^[3]

Figure 1. Typical plasmonic materials and their corresponding plasmonic responses^[3]. The plasmon damping largely depends on the plasma frequency and carrier mobility. TI, topological insulator. We present parameters for metals (Au, Ag, Al, K, Na; Au, Ag, Cu, Na, Al; Pt, Pb, Pd, and Ti), a superconductor (YBa₂Cu₃O_7－d), graphene, two TIs (HgTe and Bi₂Se₃), and various semiconductors (In₂O₃/SnO, ZnO, Ge, Si, III–V’s, and SiC). The relationship between the size of a dipole plasmon antenna made of these materials and radiative damping is schematically plotted in the upper part. Typical antenna sizes of graphene, semiconductor, and metals are indicated.

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图 2 (a)石墨烯能带三维结构^[81]; (b)石墨烯等离激元与金属等离激元色散关系对比^[83]

Figure 2. (a) Three-dimensional energy band structure of graphene^[81]; (b) comparison of dispersion relation between graphene plasmon and metal plasmon^[83].

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图 3 石墨烯等离激元性质　(a)石墨烯等离激元高光场束缚, 石墨烯与金的近场强度束缚的百分比随纳米结构空间距离d变化的关系^[25]; (b)石墨烯等离激元低本征损耗, 固定光子能量$ \hbar\omega_{\rm ph}$下, 石墨烯本征狄拉克等离激元的寿命τ_p与电子浓度n的关系^[74]; (c)石墨烯等离激元宽光谱响应, 不同石墨烯圆盘直径的等离激元响应^[84]; (d) SiO₂基底上不同条带宽度的石墨烯的消光光谱, 垂直虚线表示石墨烯光学声子频率^[19]; (e), (f) CaF₂基底栅压和条带宽度对石墨烯等离激元的调控^[24]; (g)直接堆叠的1层、2层和3层石墨烯纳米条带对应的等离激元消光谱线^[88]

Figure 3. Graphene plasmon: (a) High field confinement, percentage of space-integrated near-field intensity confined within a volume extending a distance d outside the nanoantenna^[25]; (b) low damping, the intrinsic Dirac plasmon lifetime τ_p is plotted as a function of electron density n and for a fixed photon energy $ \hbar\omega_{\rm ph}$^[74]; (c) broad spectral response, the graphene plasmon response by changing the diameter of graphene flakes^[84]; (d)−(g) tunability; (d) extinction spectra of graphene with different strip widths of SiO₂ substrate, vertical dashed lines indicate graphene optical phonon frequencies^[19]; (e), (f) CaF₂ substrates, gate voltage and strip width control of graphene plasmons^[24]; (g) extinction spectrum of directly stacked 1 layer, 2 layers and 3 layers of graphene corresponding to the plasmon^[88].

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图 4 分子红外指纹区增强探测　(a)石墨烯等离激元增强红外生物探测蛋白质^[25]; (b)红外指纹区增强探测PEO分子振动模式^[24]; (c)柔性云母基底石墨烯红外传感器^[90]; (d), (e)声学石墨烯等离激元增强红外探测^[91,82]; (f)悬空石墨烯红外窗片^[89]

Figure 4. (a) Graphene plasmon-enhanced infrared bio-sensing of protein^[25]; (b) infrared fingerprint region enhanced detection of PEO vibration modes^[24]; (c) flexible mica based graphene infrared sensor^[90]; (d), (e) acoustic graphene plasmon enhanced infrared detection^[91,82]; (f) suspended graphene to be infrared window^[89].

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图 5 气体识别　(a)金属等离激元检测氢气^[97]; (b)石墨烯等离激元红外传感器探测丙酮和己烷气体^[98]; (c)基于石墨烯等离激元的红外传感器对气体的无标记识别^[27]

Figure 5. (a) Metal plasmon detection of hydrogen^[97]; (b) graphene plasmon infrared sensor for the detection of acetone and hexane vapor^[98]; (c) label-free identification of gas by infrared sensors based on graphene plasmon^[27].

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图 6 分子振动全方向识别　(a)石墨烯等离激元全方向传感能力^[99]; (b)石墨烯等离激元灵敏识别hBN面内及面外振动模式^[24]

Figure 6. (a) Graphene plasmon omnidirectional sensing capability^[99]; (b) graphene plasmons sensitively identify the in-plane and out-of-plane vibration modes of hBN^[24].

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图 7 折射率传感　(a)石墨烯等离激元对不同折射率覆盖物的反射率^[28]; (b) Ag-石墨烯杂化结构折射率传感^[102]; (c)具有H, T和HC高阶模式的石墨烯Fano超材料结构的透射光谱和Fano高阶模式对不同分析物(由折射率标记)的折射率传感^[29]

Figure 7. Refractive index sensing: (a) Reflectance from the structure for different values of the refractive index on top of the graphene^[28]; (b) Ag-graphene hybrid structure for refractive index sensing^[102]; (c) the transmission spectra of the Fano metamaterials with H, T, and HC order modes and simulated transmission spectra of the HC Fano resonance mode with different analyte (marked by refractive indices)^[29].

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表 1 比较红外等离激元材料金属、半导体、超导体、拓扑绝缘体、石墨烯及碳纳米管的载流子迁移率、可调性、局域能力以及传输距离; 等离激元波矢可以表示为q = q'+ iq'', q'为等离激元波矢实部, q''为等离激元波矢虚部; λ_p为等离激元波长, $ {\lambda _{\rm{p}}} = 2{\text{π}} /q' $; 局域能力λ_IR/λ_p, λ_IR为自由空间光波长; 品质因子Q = q'/q''^[30]

Table 1. Comparing carrier mobility, adjustability, confinement ratio, and propagation length of SEIRA materials (metal, semiconductor, superconductor, topological insulator, graphene, and carbon nanotube). Plasmon wave vector q = q'+ iq'', the real part q' is used to define plasmon wavelength $ {\lambda _{\rm{p}}} = 2{\text{π}} /q' $, and the imagine part q'' is used to define propagation length L_p=1/(2q''). Confinement ratio = λ_IR/λ_p, λ_IR free space wavelength, and quality factorQ = q'/q''^[30]

红外表面等离激元材料	载流子迁移率cm²/(V·s)	可调性	局域能力λ_IR/λ_p	品质因子
金属(如Au, Ag)^[31,32]	～10⁰—10^{2 [33]}	电学不可调	< 5^[34]	< 36^[30]
半导体(如Ge, ITO)^[35,36]	～10⁰—10^3[36]	电学可调	< 10^[30]	< 37^[30]
超导体(如FeSe)^[37,38]	～10^4[39]*	电学可调	—	—
拓扑绝缘体(如Bi₂Se₃)^[40,41]	～10^4[42]	电学可调	< 900^[41,43]	3^[43]
石墨烯^[30,31]	～10³—10^5[30]	电学可调	～40—220^{[7,18,30,34,43]}	< 130*^[30]
碳纳米管^[44,45]	～10³—10^{4 [46]}	电学可调	～100—1000^[47]	< 26^[47,48]
注: *表示低温.

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表 2 不同波段的石墨烯等离激元性质比较

Table 2. Properties of graphene plasmon in different plasmon wavelength.

石墨烯等离激元
等离激元响应波段	近红外(0.7—2.5 μm)	中红外(2.5—25 μm)	远红外及太赫兹(> 25 μm)
能否激发	否	能	能
尺寸	—	～100 nm	～1 μm
本征寿命	—	～20—120 ps^a	～0—40 ns^a
局域能力	—	～40—220^b	< 50^c
注: a摘自文献[74]; b摘自文献[7,17,43]; c摘自文献[76,77].

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