Graphene-polymer multilayer heterostructure for terahertz metamaterials

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University of Wollongong Research Online Faculty of Engineering and Information Sciences - Papers: Part A Faculty of Engineering and Information Sciences 2013 Graphene-polymer multilayer heterostructure for terahertz metamaterials Zaiquan Xu Monash University Caiyun Chen Soochow University Steve Qing Yang Wu Agency For Science, Technology And Research Bing Wang Agency For Science, Technology And Research Jinghua Teng Agency For Science, Technology And Research See next page for additional authors Publication Details Xu, Z., Chen, C., Wu, S. Qing Yang., Wang, B., Teng, J., Zhang, C. & Bao, Q. (2013). Graphene-polymer multilayer heterostructure for terahertz metamaterials. In J. Friend & H. Hoe. Tan (Eds.), Proceedings of SPIE 8923, Micro/Nano Materials, Devices, and Systems (pp. 89230C-1-89230C-5). United States: S P I E - International Society for Optical Engineering. Research Online is the open access institutional repository for the University of Wollongong. For further information contact the UOW Library: research-pubs@uow.edu.au

Graphene-polymer multilayer heterostructure for terahertz metamaterials Abstract The optical response and plasmon coupling between graphene sheets for graphene/polymer multilayer heterostructures with controlled separation were systematically investigated. Anomalous transmission of light was experimentally observed in mid-infrared range. The position of the broad passband in the transmission spectra was observed to red-shift with the increase of the number of layers. Keywords terahertz, metamaterials, multilayer, polymer, heterostructure, graphene Disciplines Engineering Science and Technology Studies Publication Details Xu, Z., Chen, C., Wu, S. Qing Yang., Wang, B., Teng, J., Zhang, C. & Bao, Q. (2013). Graphene-polymer multilayer heterostructure for terahertz metamaterials. In J. Friend & H. Hoe. Tan (Eds.), Proceedings of SPIE 8923, Micro/Nano Materials, Devices, and Systems (pp. 89230C-1-89230C-5). United States: S P I E - International Society for Optical Engineering. Authors Zaiquan Xu, Caiyun Chen, Steve Qing Yang Wu, Bing Wang, Jinghua Teng, Chao Zhang, and Qiaoliang Bao This conference paper is available at Research Online: http://ro.uow.edu.au/eispapers/1762

Graphene-polymer Multilayer Heterostructure for Terahertz Metamaterials Zaiquan Xu, a Caiyun Chen, b Steve Qing Yang Wu, c Bing Wang, c, * Jinghua Teng, c Chao Zhang, d Qiaoliang Bao, a,* a Department of Materials Engineering, Monash University, Wellington Road, Clayton, Victoria, 3800, Australia b Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, Jiangsu 215123, China c Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), 3 Research Link, Singapore 117602 d School of Engineering Physics, University of Wollongong, New South Wales 2552, Australia *Correspondence: wangb@imre.a-star.edu.sg; qiaoliang.bao@monash.edu Abstract The optical response and plasmon coupling between graphene sheets for graphene/polymer multilayer heterostructures with controlled separation were systematically investigated. Anomalous transmission of light was experimentally observed in mid-infrared range. The position of the broad passband in the transmission spectra was observed to red-shift with the increase of the number of layers. Introduction The surface plasmon in graphene has attracted increasing research interests because of many desirable properties such as strong confinement and low loss. 1-3 The wavelength of graphene plasmons was experimentally observed at the order of 200 nanometres, more than 40 times smaller than the wavelength of illumination which is in the terahertz (THz) regime. 4, 5 Patterning graphene into micro-ribbons 6 or photonic-crystal-like structures 7 could induce plasmon resonance in THz range, which affords a new type of THz metamaterials. Graphene plasmonics is very promising to make transformation optics 8 due to its tunability via chemical modification or electrical gating. The activities of surface plasmons in graphene multilayers can be controlled more flexibly than graphene monolayers because of the vertical interlayer coupling or in-plane lateral coupling. It has been theoretically predicted that the plasmon resonance can be controlled by the coupling effect among adjacent layers, whereas less attention has been paid to the experimental demonstration. 9,10 Here we fabricate graphene/polymer multilayer heterostructure and systematically investigate the optical response as well as plasmon coupling between graphene sheets. Anomalous transmission of light was experimentally observed in THz range. The graphene/polymer multilayers could be a promising platform to filter infrared and terahertz waves and to tailor the propagation and diffraction of light along the graphene sheets deeply below the sub-diffraction-limit. Micro/Nano Materials, Devices, and Systems, edited by James Friend, H. Hoe Tan, Proc. of SPIE Vol. 8923, 89230C 2013 SPIE CCC code: 0277-786X/13/$18 doi: 10.1117/12.2049533 Proc. of SPIE Vol. 8923 89230C-1

Experiments Large area monolayer graphene films used in the work were grown by chemical vapour deposition (CVD) on 25 μm thick Cu foil (Alfa Aesar AA13382RG). Poly(methyl methacrylate) (PMMA) was spin-coated on top of the graphene, the resulting thickness was characterized by variable angle spectrometric ellipsometer (VASE). The copper used to grow graphene was etched away and monolayer graphene-pmma (G-PMMA) heterostructure was wet-transferred onto intrinsic silicon substrates after doping with HNO 3. Multilayer heterostructure was formed by repeatedly transferring one layer of G-PMMA on top of the other, as shown in Fig. 1. THz transmittance measurements were carried out on Bruker Vertex 80V Fourier Transform Infrared (FTIR) with a mercury lamp as THz source and DTGS as THz detector. Graphene grown on copper foil Spin -coating 100 nm PRIMA Etching of copper foil Stacking of graphene /PMMA Figure 1. Schematic diagram of fabrication procedure for graphene/pmma heterostructures. Experimental and simulation results The Raman spectra and images were measured on WITEC Alpha 300 confocal micro-raman system equipped with a 532 nm laser source and 100 objective lens. The representative Raman spectrum from monolayer graphene transferred onto intrinsic silicon is shown in Fig. 2. It is found that the Raman 2D band is much stronger than G band with a 2D/G ratio of 1.5, indicating the nature of one atomic layer. The G and 2D band can be fitted well by single Lorentzian peak with full-width at half-maximum (FWHM) of 26 and 38 cm-1 respectively, which suggested that the graphene used was of high crystalline quality. These are key Raman characteristics for monolayer graphene. Proc. of SPIE Vol. 8923 89230C-2

1500-2D I 1 000 - I ci) c c D - "A,...-' `---- "...,...,. 1200 1600 2000 2400 2800 Raman shift (cm -1) Figure 2. Raman spectrum of monolayer graphene. The extinction spectra measured on as-prepared PMMA/Graphene (PMMA/G) heterostructures with one, two and three graphene layers are shown in Fig. 3a and Fig. 3b. It is found that the number of graphene layers plays an important role to determine the extinction ratio. The introduction of monolayer graphene between the polymer and intrinsic silicon (i-si) leads to an increase of the extinction ratio up to 22.5% at 2.55 THz due to free carrier absorption. 7 The extinction ratio increases with the number of graphene sheets, i.e., an extinction ratio of 55.6% is achieved for a graphene/polymer heterostructure with three graphene layers. The transmission properties of multilayer graphene sheets and in particular, the influence of the number of graphene sheets are studied as well, as shown in Fig. 3c. A passband can be observed for the samples with two, three, four, five graphene sheets. It is very interesting to find that the peaks of the passband evolve with the number of graphene sheets, i.e., the lager the number of graphene sheets, the sharper the edges of the passband and the lower the transmission peak intensity. The transmission peak tends to shift towards longer wavelength for larger number of graphene sheets, due to the lateral boundary surface plasmon polarition (SPP) coupling between graphene sheets. 10 a) 500-20- ó C O 10- : UC : Ẋ W 0 100 200 300 400 500 Wave Number (cm-1) 600 60- (b) -1 PMMA/G/i-Si -2 PMMA/G/i-Si 50- -3 PMMA/G/i-Si c 40- C O 30- U 20- X W 10-0- 100 200 300 400 500 600 Wave Number (cm-') Proc. of SPIE Vol. 8923 89230C-3

( c ) C -5 PMMA/G/i-Si -4 PMMA/G/i-Si -3 PMMA/G/i-Si -2 PMMA/G/i-Si - 1 PMMA/G/i-Si 1000 2000 3000 4000 5000 6000 7000 Wave number (cm-1) Figure 3. (a) The extinction spectra of monolayer PMMA/G stack and reference sample (PMMA only on intrinsic silicon substrate). Inset shows the schematic of PMMA/G stack. (b) The extinction spectra of the PMMA/G stacks with different number of layers; (c) The transmission spectra as a function of the number of the doped graphene sheets. Conclusion and outlook In summary, we have studied light transmitting properties of the graphene multilayers composed of arbitrary layers of graphene sheets. The extinction co-efficiency resulting from monolayer graphene/polymer stack due to the free carrier absorption is ~22.5% and it increases with the number of layers. A broad passband was observed in the transmission spectrum and it can be tuned by the number of layers. Future efforts will be put on tuning the broadband transmission by electrically gating the heterostructures. Reference 1. Bao, Q. L.; Loh, K. P. Graphene Photonics, Plasmonics, and Broadband Optoelectronic Devices. ACS Nano 2012, 6, 3677-3694. 2. Grigorenko, A.; Polini, M.; Novoselov, K. Graphene Plasmonics. Nature Photonics 2012, 6, 749-758. 3. Koppens, F. H.; Chang, D. E.; García de Abajo, F. J. Graphene Plasmonics: A Platform for Strong Light Matter Interactions. Nano letters 2011, 11, 3370-3377. 4. Chen, J.; Badioli, M.; Alonso-González, P.; Thongrattanasiri, S.; Huth, F.; Osmond, J.; Spasenović, M.; Centeno, A.; Pesquera, A.; Godignon, P. Optical Nano-Imaging of Gate-Tunable Graphene Plasmons. Nature 487, 77 81 2012. 5. Fei, Z.; Rodin, A.; Andreev, G.; Bao, W.; McLeod, A.; Wagner, M.; Zhang, L.; Zhao, Z.; Thiemens, M.; Dominguez, G. Gate-Tuning of Graphene Plasmons Revealed by Infrared Nano-Imaging. Nature 487, 82 852012. 6. Ju, L.; Geng, B.; Horng, J.; Girit, C.; Martin, M.; Hao, Z.; Bechtel, H. A.; Liang, X.; Zettl, A.; Shen, Y. R. Proc. of SPIE Vol. 8923 89230C-4

Graphene Plasmonics for Tunable Terahertz Metamaterials. Nature Nanotechnology 2011, 6, 630-634. 7. Yan, H.; Li, X.; Chandra, B.; Tulevski, G.; Wu, Y.; Freitag, M.; Zhu, W.; Avouris, P.; Xia, F. Tunable Infrared Plasmonic Devices Using Graphene/Insulator Stacks. Nature Nanotechnology 2012, 7, 330-334. 8. Vakil, A.; Engheta, N. Transformation Optics Using Graphene. Science 2011, 332, 1291-1294. 9. Wang, B.; Zhang, X.; García-Vidal, F. J.; Yuan, X.; Teng, J. Strong Coupling of Surface Plasmon Polaritons in Monolayer Graphene Sheet Arrays. Physical Review Letters 2012, 109, 073901. 10. Wang, B.; Zhang, X.; Yuan, X.; Teng, J. Optical Coupling of Surface Plasmons between Graphene Sheets. Applied Physics Letters 2012, 100, 131111-4. Proc. of SPIE Vol. 8923 89230C-5