Nano‐scale analysis of graphene layers by tip‐enhanced near‐field Raman spectroscopy
Abstract
We demonstrate nano‐scale optical analysis of graphene layers by tip‐enhanced near‐field Raman spectroscopy (TERS). In this technique, the spatial resolution ∼30 nm is realized by the near‐field probe which acts as a nano‐light source. From the intensity change of the Raman band of silicon generated from the near‐field probe, we can conveniently estimate the edge boundaries and the number of stacking layers. TERS measurement across the layer edges reveals the nano‐scale properties of the material as well as the existence of local defects and edge boundaries. The intensity change of the G‐band shows the step‐like behavior that follows the layer boundary, whereas the two components in 2D peak show more complex behaviors even inside layers. The peak fluctuation in the 2D band also suggests the local stress distribution due to interlayer interactions. An excess charge effect is observed through the correlation between the peak position and the width of the G‐band and their nano‐scale distribution within a layer is revealed. Besides the vibrational analysis, we successfully performed the estimation of the number of layers in two‐dimensional imaging by the same experimental platform, which allows us high‐throughput nondestructive identification of graphene layers critical for the evaluation of this material especially in future device applications. Copyright © 2009 John Wiley & Sons, Ltd.
Number of times cited: 70
- Matthieu Paillet, Romain Parret, Jean‐Louis Sauvajol and Philippe Colomban, Graphene and related 2D materials: An overview of the Raman studies, Journal of Raman Spectroscopy, 49, 1, (8-12), (2017).
- Ryan Beams, Tip‐enhanced Raman scattering of graphene, Journal of Raman Spectroscopy, 49, 1, (157-167), (2017).
- G. Kolhatkar, J. Plathier and A. Ruediger, Nanoscale investigation of materials, chemical reactions, and biological systems by tip enhanced Raman spectroscopy – a review, Journal of Materials Chemistry C, 6, 6, (1307), (2018).
- Afua A. Antwi‐Boasiako, Derrick Dunn, Samuel S. R. Dasary, Yolanda K. Jones, Sandra L. Barnes and Anant K. Singh, Bioconjugated graphene oxide‐based Raman probe for selective identification of SKBR3 breast cancer cells, Journal of Raman Spectroscopy, 48, 8, (1056-1064), (2017).
- Takuya Iwasaki, Taharh Zelai, Sheng Ye, Yoshishige Tsuchiya, Harold M.H. Chong and Hiroshi Mizuta, Local hole doping concentration modulation on graphene probed by tip-enhanced Raman spectroscopy, Carbon, 111, (67), (2017).
- Jan Rogalski, Kai Braun, Anke Horneber, Marius van den Berg, Johannes Uihlein, Heiko Peisert, Thomas Chassé, Alfred J. Meixner and Dai Zhang, STM tip-enhanced Raman spectroscopy and the investigation of doped graphene, Vibrational Spectroscopy, 91, (128), (2017).
- Dmitri V. Voronine, Gaotian Lu, Daoquan Zhu and Andrey Krayev, Tip-Enhanced Raman Scattering of MoS2, IEEE Journal of Selected Topics in Quantum Electronics, 23, 1, (138), (2017).
- Satoshi Kawata, Taro Ichimura, Atsushi Taguchi and Yasuaki Kumamoto, Nano-Raman Scattering Microscopy: Resolution and Enhancement, Chemical Reviews, 10.1021/acs.chemrev.6b00560, 117, 7, (4983-5001), (2017).
- Tanja Deckert-Gaudig, Atsushi Taguchi, Satoshi Kawata and Volker Deckert, Tip-enhanced Raman spectroscopy – from early developments to recent advances, Chemical Society Reviews, 10.1039/C7CS00209B, 46, 13, (4077-4110), (2017).
- Taka-aki Yano, Yuta Tsuchimoto, Masahito Mochizuki, Tomohiro Hayashi and Masahiko Hara, Laser Scanning-Assisted Tip-Enhanced Optical Microscopy for Robust Optical Nanospectroscopy, Applied Spectroscopy, 70, 7, (1239), (2016).
- Sanpon Vantasin, Shohei Uemura, Yoshito Tanaka, Daichi Doujima, Tadaaki Kaneko and Yukihiro Ozaki, Tip-Enhanced Raman Scattering of Local Nanostructure on Large Sheet and Microisland Epitaxial Graphene Grown on 4H–SiC (000 ) , Frontiers of Plasmon Enhanced Spectroscopy Volume 2, 10.1021/bk-2016-1246.ch010, (227-245), (2016).
- P. James Schuck, Wei Bao and Nicholas J. Borys, A polarizing situation: Taking an in-plane perspective for next-generation near-field studies, Frontiers of Physics, 10.1007/s11467-015-0526-5, 11, 2, (2016).
- Ado Jorio and Antonio G. Souza Filho, Raman Studies of Carbon Nanostructures, Annual Review of Materials Research, 10.1146/annurev-matsci-070115-032140, 46, 1, (357-382), (2016).
- Yingchao Zhang, Dmitri V. Voronine, Shangran Qiu, Alexander M. Sinyukov, Mary Hamilton, Zachary Liege, Alexei V. Sokolov, Zhenrong Zhang and Marlan O. Scully, Improving resolution in quantum subnanometre-gap tip-enhanced Raman nanoimaging, Scientific Reports, 10.1038/srep25788, 6, 1, (2016).
- Sara J. Fraser-Miller, Jukka Saarinen and Clare J. Strachan, Vibrational Spectroscopic Imaging, Analytical Techniques in the Pharmaceutical Sciences, 10.1007/978-1-4939-4029-5_17, (523-589), (2016).
- Weitao Su, Naresh Kumar, Ning Dai and Debdulal Roy, Nanoscale mapping of intrinsic defects in single-layer graphene using tip-enhanced Raman spectroscopy, Chemical Communications, 10.1039/C6CC01990K, 52, 53, (8227-8230), (2016).
- Qing Tu, Björn Lange, Zehra Parlak, Joao Marcelo J. Lopes, Volker Blum and Stefan Zauscher, Quantitative Subsurface Atomic Structure Fingerprint for 2D Materials and Heterostructures by First-Principles-Calibrated Contact-Resonance Atomic Force Microscopy, ACS Nano, 10.1021/acsnano.6b02402, 10, 7, (6491-6500), (2016).
- Ryo Kato, Yuika Saito and Prabhat Verma, Near-field absorption imaging by a Raman nano-light source, RSC Advances, 10.1039/C6RA24428A, 6, 114, (113139-113143), (2016).
- Songpol Chaunchaiyakul, Takeshi Yano, Kamonchanok Khoklang, Pawel Krukowski, Megumi Akai-Kasaya, Akira Saito and Yuji Kuwahara, Nanoscale analysis of multiwalled carbon nanotube by tip-enhanced Raman spectroscopy, Carbon, 99, (642), (2016).
- Prompong Pienpinijtham, Sanpon Vantasin, Yasutaka Kitahama, Sanong Ekgasit and Yukihiro Ozaki, Nanoscale pH Profile at a Solution/Solid Interface by Chemically Modified Tip-Enhanced Raman Scattering, The Journal of Physical Chemistry C, 120, 27, (14663), (2016).
- Sitansu Sekhar Nanda, Min Jik Kim, Kwi Seok Yeom, Seong Soo A. An, Heongkyu Ju and Dong Kee Yi, Raman spectrum of graphene with its versatile future perspectives, TrAC Trends in Analytical Chemistry, 80, (125), (2016).
- D. Frank Ogletree, P. James Schuck, Alexander F. Weber‐Bargioni, Nicholas J. Borys, Shaul Aloni, Wei Bao, Sara Barja, Jiye Lee, Mauro Melli, Keiko Munechika, Stephan Whitelam and Sebastian Wickenburg, Revealing Optical Properties of Reduced‐Dimensionality Materials at Relevant Length Scales, Advanced Materials, 27, 38, (5693-5719), (2015).
- Lucas Langelüddecke, Prabha Singh and Volker Deckert, Exploring the Nanoscale: Fifteen Years of Tip-Enhanced Raman Spectroscopy, Applied Spectroscopy, 10.1366/15-08014, 69, 12, (1357-1371), (2015).
- S. Nilmoung, P. Kidkhunthod, S. Pinitsoontorn, S. Rujirawat, R. Yimnirun and S. Maensiri, Fabrication, structure, and magnetic properties of electrospun carbon/cobalt ferrite (C/CoFe2O4) composite nanofibers, Applied Physics A, 119, 1, (141), (2015).
- Ryan Beams, Luiz Gustavo Cançado, Ado Jorio, A Nick Vamivakas and Lukas Novotny, Tip-enhanced Raman mapping of local strain in graphene, Nanotechnology, 10.1088/0957-4484/26/17/175702, 26, 17, (175702), (2015).
- Farshid Pashaee, Faranak Sharifi, Giovanni Fanchini and François Lagugné-Labarthet, Tip-enhanced Raman spectroscopy of graphene-like and graphitic platelets on ultraflat gold nanoplates, Physical Chemistry Chemical Physics, 17, 33, (21315), (2015).
- Sanpon Vantasin, Yoshito Tanaka, Shohei Uemura, Toshiaki Suzuki, Yasunori Kutsuma, Daichi Doujima, Tadaaki Kaneko and Yukihiro Ozaki, Characterization of SiC-grown epitaxial graphene microislands using tip-enhanced Raman spectroscopy, Physical Chemistry Chemical Physics, 10.1039/C5CP05014F, 17, 43, (28993-28999), (2015).
- Nina Mauser and Achim Hartschuh, Tip-Enhanced Raman Spectroscopy: Applications to Carbon Nanomaterials, Handbook of Enhanced Spectroscopy, 10.1201/b19175-13, (395-413), (2015).
- R. H. Rickman and P. R. Dunstan, Enhancement of lattice defect signatures in graphene and ultrathin graphite using tip‐enhanced Raman spectroscopy, Journal of Raman Spectroscopy, 45, 1, (15-21), (2013).
- Lucas Langelüddecke, Tanja Deckert‐Gaudig and Volker Deckert, Spectroscopic Imaging of Biological Samples Using Near‐Field Methods, Infrared and Raman Spectroscopic Imaging, (477-512), (2014).
- Dai Zhang and Alfred J. Meixner, Scanning Near‐Field Gap‐Mode Microscopy, Handbook of Spectroscopy, (911-940), (2014).
- Andreas M. Kern, Dai Zhang, Marc Brecht, Alexey I. Chizhik, Antonio Virgilio Failla, Frank Wackenhut and Alfred J. Meixner, Enhanced single-molecule spectroscopy in highly confined optical fields: from λ/2-Fabry–Pérot resonators to plasmonic nano-antennas, Chem. Soc. Rev., 10.1039/C3CS60357A, 43, 4, (1263-1286), (2014).
- Ichiro Tanabe, Masatoshi Egashira, Toshiaki Suzuki, Takeyoshi Goto and Yukihiro Ozaki, Prevention of Photooxidation of Deoxymyoglobin and Reduced Cytochrome c during Enhanced Raman Measurements: SERRS with Thiol-Protected Ag Nanoparticles and a TERS Technique, The Journal of Physical Chemistry C, 118, 19, (10329), (2014).
- Toshiaki Suzuki, Tamitake Itoh, Sanpon Vantasin, Satoshi Minami, Yasunori Kutsuma, Koji Ashida, Tada-aki Kaneko, Yusuke Morisawa, Takeshi Miura and Yukihiro Ozaki, Tip-enhanced Raman spectroscopic measurement of stress change in the local domain of epitaxial graphene on the carbon face of 4H-SiC(000–1), Phys. Chem. Chem. Phys., 10.1039/C4CP02078B, 16, 37, (20236-20240), (2014).
- Taka‐aki Yano and Satoshi Kawata, Tip‐Enhanced Raman Spectroscopy (TERS) for Nanoscale Imaging and Analysis, Frontiers of Surface‐Enhanced Raman Scattering, (139-161), (2014).
- Sanpon Vantasin, Ichiro Tanabe, Yoshito Tanaka, Tamitake Itoh, Toshiaki Suzuki, Yasunori Kutsuma, Koji Ashida, Tadaaki Kaneko and Yukihiro Ozaki, Tip-Enhanced Raman Scattering of the Local Nanostructure of Epitaxial Graphene Grown on 4H-SiC (0001̅), The Journal of Physical Chemistry C, 10.1021/jp508730y, 118, 44, (25809-25815), (2014).
- Toshihiro Mino, Yuika Saito and Prabhat Verma, Quantitative Analysis of Polarization-Controlled Tip-Enhanced Raman Imaging through the Evaluation of the Tip Dipole, ACS Nano, 10.1021/nn5031803, 8, 10, (10187-10195), (2014).
- Weigao Xu, Nannan Mao and Jin Zhang, Graphene: A Platform for Surface‐Enhanced Raman Spectroscopy, Small, 9, 8, (1206-1224), (2013).
- Thomas Schmid, Lothar Opilik, Carolin Blum and Renato Zenobi, Nanoscale Chemical Imaging Using Tip‐Enhanced Raman Spectroscopy: A Critical Review, Angewandte Chemie International Edition, 52, 23, (5940-5954), (2013).
- Thomas Schmid, Lothar Opilik, Carolin Blum and Renato Zenobi, Chemische Bildgebung auf der Nanometerskala mittels spitzenverstärkter Raman‐Spektroskopie, Angewandte Chemie, 125, 23, (6054-6070), (2013).
- Toshiaki Suzuki, Xinlei Yan, Yasutaka Kitahama, Harumi Sato, Tamitake Itoh, Takeshi Miura and Yukihiro Ozaki, Tip-Enhanced Raman Spectroscopy Study of Local Interactions at the Interface of Styrene–Butadiene Rubber/Multiwalled Carbon Nanotube Nanocomposites, The Journal of Physical Chemistry C, 10.1021/jp309217y, 117, 3, (1436-1440), (2013).
- Lothar Opilik, Thomas Schmid and Renato Zenobi, Modern Raman Imaging: Vibrational Spectroscopy on the Micrometer and Nanometer Scales, Annual Review of Analytical Chemistry, 10.1146/annurev-anchem-062012-092646, 6, 1, (379-398), (2013).
- Satoshi Kawata, Plasmonics: Future Outlook, Japanese Journal of Applied Physics, 52, 1R, (010001), (2013).
- Manola Moretti, Remo Proietti Zaccaria, Emiliano Descrovi, Gobind Das, Marco Leoncini, Carlo Liberale, Francesco De Angelis and Enzo Di Fabrizio, Reflection-mode TERS on Insulin Amyloid Fibrils with Top-Visual AFM Probes, Plasmonics, 10.1007/s11468-012-9385-x, 8, 1, (25-33), (2012).
- Lilin Li, Baoshan An, Abhishek Lahiri, Peijie Wang and Yan Fang, Doublet of D and 2D bands in graphene deposited with Ag nanoparticles by surface enhanced Raman spectroscopy, Carbon, 65, (359), (2013).
- Weitao Su and Debdulal Roy, Visualizing graphene edges using tip-enhanced Raman spectroscopy, Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, 31, 4, (041808), (2013).
- Jun Ando, Taka-aki Yano, Katsumasa Fujita and Satoshi Kawata, Metal nanoparticles for nano-imaging and nano-analysis, Physical Chemistry Chemical Physics, 10.1039/c3cp51806j, 15, 33, (13713), (2013).
- Norihiko Hayazawa and Taka-aki Yano, Tip-Enhanced Spectroscopy at the Nanoscale, Nanoscale Spectroscopy with Applications, 10.1201/b15615-2, (1-40), (2013).
- D.A. Schmidt, I. Kopf and E. Bründermann, A matter of scale: from far‐field microscopy to near‐field nanoscopy, Laser & Photonics Reviews, 6, 3, (296-332), (2011).
- A. K. Sood and Biswanath Chakraborty, Understanding Graphene via Raman Scattering, Graphene, (49-90), (2012).
- Marcel Lucas and Elisa Riedo, Invited Review Article: Combining scanning probe microscopy with optical spectroscopy for applications in biology and materials science, Review of Scientific Instruments, 10.1063/1.4720102, 83, 6, (061101), (2012).
- Viviane Uzayisenga, Xiao-Dong Lin, Li-Mei Li, Jason R. Anema, Zhi-Lin Yang, Yi-Fan Huang, Hai-Xin Lin, Song-Bo Li, Jian-Feng Li and Zhong-Qun Tian, Synthesis, Characterization, and 3D-FDTD Simulation of Ag@SiO 2 Nanoparticles for Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy , Langmuir, 10.1021/la3005536, 28, 24, (9140-9146), (2012).
- Ado Jorio, Raman Spectroscopy in Graphene-Based Systems: Prototypes for Nanoscience and Nanometrology, ISRN Nanotechnology, 2012, (1), (2012).
- V. Le Nader, J.-Y. Mevellec, T. Minea and G. Louarn, Gold Nanoparticles as Probes for Nano-Raman Spectroscopy: Preliminary Experimental Results and Modeling, International Journal of Optics, 2012, (1), (2012).
- Johannes Stadler, Thomas Schmid and Renato Zenobi, Developments in and practical guidelines for tip-enhanced Raman spectroscopy, Nanoscale, 10.1039/C1NR11143D, 4, 6, (1856-1870), (2012).
- Taka-aki Yano, Taro Ichimura, Shota Kuwahara, Prabhat Verma and Satoshi Kawata, Subnanometric stabilization of plasmon-enhanced optical microscopy, Nanotechnology, 23, 20, (205503), (2012).
- Joanna M. Atkin, Samuel Berweger, Andrew C. Jones and Markus B. Raschke, Nano-optical imaging and spectroscopy of order, phases, and domains in complex solids, Advances in Physics, 10.1080/00018732.2012.737982, 61, 6, (745-842), (2012).
- Ado Jorio and Luiz Gustavo Cançado, Perspectives on Raman spectroscopy of graphene-based systems: from the perfect two-dimensional surface to charcoal, Physical Chemistry Chemical Physics, 14, 44, (15246), (2012).
- Marcos Ghislandi, Günter G. Hoffmann, Evgeniy Tkalya, Lijing Xue and Gijsbertus De With, Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets, Applied Spectroscopy Reviews, 47, 5, (371), (2012).
- Yuika Saito, Yoshiro Ohashi and Prabhat Verma, Optimization ofs-Polarization Sensitivity in Apertureless Near-Field Optical Microscopy, International Journal of Optics, 2012, (1), (2012).
- Rodolfo V. Maximiano, Ryan Beams, Lukas Novotny, Ado Jorio and Luiz Gustavo Cançado, Mechanism of near-field Raman enhancement in two-dimensional systems, Physical Review B, 85, 23, (2012).
- Valentinas Snitka, Raul D. Rodrigues and Vitas Lendraitis, Novel gold cantilever for nano-Raman spectroscopy of graphene, Microelectronic Engineering, 88, 8, (2759), (2011).
- Johannes Stadler, Thomas Schmid and Renato Zenobi, Nanoscale Chemical Imaging of Single-Layer Graphene, ACS Nano, 10.1021/nn2035523, 5, 10, (8442-8448), (2011).
- Guangfu Luo, Lu Wang, Hong Li, Rui Qin, Jing Zhou, Linze Li, Zhengxiang Gao, Wai-Ning Mei, Jing Lu and Shigeru Nagase, Polarized Nonresonant Raman Spectra of Graphene Nanoribbons, The Journal of Physical Chemistry C, 115, 50, (24463), (2011).
- Laurence A. Nafie, Recent advances in linear and nonlinear Raman spectroscopy. Part IV, Journal of Raman Spectroscopy, 41, 12, (1566-1586), (2010).
- Hacksung Kim, Kathryn M. Kosuda, Richard P. Van Duyne and Peter C. Stair, Resonance Raman and surface- and tip-enhanced Raman spectroscopy methods to study solid catalysts and heterogeneous catalytic reactions, Chemical Society Reviews, 10.1039/c0cs00044b, 39, 12, (4820), (2010).
- Yuika Saito, Mitsuhiro Honda, Yoshikiyo Moriguchi and Prabhat Verma, Temporally dynamic photopolymerization ofC60molecules encapsulated in single-walled carbon nanotubes, Physical Review B, 81, 24, (2010).
- V. Deckert, Tip‐Enhanced Raman Spectroscopy, Journal of Raman Spectroscopy, 40, 10, (1336-1337), (2009).
- Kirsty F. Gibson and Sergei G. Kazarian, Tip‐enhanced Raman Spectroscopy, Encyclopedia of Analytical Chemistry, (1-30), (2014).
- Miguel Valcárcel and Ángela I. López‐Lorente, The Third Way in Analytical Nanoscience and Nanotechnology, Encyclopedia of Analytical Chemistry, (1-26), (2016).




