Abstract
In this study, the effect of alkyl chain length in amine-based compounds on the work function of graphene was investigated. The graphene was synthesized by the chemical vapor deposition method. The graphene layers were functionalized by amine-based groups using a simple spin-coating method. The amine-based compounds were composed of phenyl amine and methyl-, ethyl-, propyl-, n/t-butyl-, and octyl-phenyl amine groups. Materials were confirmed by X-ray photoelectron spectroscopy to show the C and N bonding. The work function of the doped graphene layers decreased because of the effect of the doping agents. Among the doped graphene samples, t-butyl-phenyl amine functionalized graphene achieved the lowest work function of 3.89 eV (compared with 4.43 eV for pristine graphene). Further, the sheet resistance of n-doped graphene increased, confirming the high concentration of n-doping agents on the graphene layers. These results suggest the best alkyl chain is the t-butyl group to reduce the work function of graphene, and promise the use of these materials as cathodes for opto-electronic applications.
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Geim, A.K.: Graphene: status and prospects. Science 324, 1530–1534 (2009)
Du, X., Skachko, I., Barker, A., Andrei, E.Y.: Approaching ballistic transport in suspended graphene. Nat. Nanotechnol. 3, 491–495 (2008)
Novoselov, K.S., Jiang, Z., Zhang, Y., Morozov, S., Stormer, H.L., Zeitler, U., Maan, J., Boebinger, G., Kim, P., Geim, A.K.: Room-temperature quantum hall effect in graphene. Science 315, 1379 (2007)
Obraztsov, A., Obraztsova, E.A., Tyurnina, A.V., Zolotukhin, A.: Chemical vapor deposition of thin graphite films of nanometer thickness. Carbon 45, 2017–2021 (2007)
Im, H., Kim, J.H.: Thermal conductivity of a graphene oxide–carbon nanotube hybrid/epoxy composite. Carbon 50, 5429–5440 (2012)
Kwon, K.C., Son, H.J., Hwang, Y.H., Oh, J.H., Lee, T.-W., Jang, H.W., Kwak, K., Park, K., Kim, S.Y.: Effect of amine-based organic compounds on the work-function decrease of graphene. J. Phys. Chem. C 120, 1309–1316 (2016)
Bae, S., Kim, H.K., Lee, Y.B., Xu, X., Park, J.-S., Zheng, Y., Balakrishnan, J., Lei, T., Kim, H.R., Song, Y.I., Kim, Y.-J., Kim, K.S., Ozilmaz, B., Ahn, J.H., Hong, B.H., Iijima, S.: Roll-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 5, 574–578 (2010)
Kim, K.S., Zhao, Y., Jang, H., Lee, S.Y., Kim, J.M., Kim, K.S., Ahn, J.-H., Kim, P., Choi, J.-Y., Hong, B.H.: Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706–710 (2009)
Li, X., Cai, W., An, J., Kim, S., Nah, J., Yang, D., Piner, R., Velamakanni, A., Jung, I., Tutuc, E., Banergee, S.K., Colombo, L., Ruoff, R.S.: Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009)
Kwon, K.C., Choi, K.S., Kim, B.J., Lee, J.-L., Kim, S.Y.: Work-function decrease of graphene sheet using alkali metal carbonates. J. Phys. Chem. C 116, 26586–26591 (2012)
Kwon, K.C., Choi, K.S., Kim, C., Kim, S.Y.: Effect of transition-metal chlorides on graphene properties. Phys. Status Solidi a 211, 1794–1800 (2014)
Kwon, K.C., Choi, K.S., Kim, S.Y.: Increased work function in few-layer graphene sheets via metal chloride doping. Adv. Funct. Mater. 22, 4724–4731 (2012)
Kwon, K., Kim, B.J., Lee, J.-L., Kim, S.Y.: Role of ionic chlorine in the thermal degradation of metal chloride-doping graphene sheets. J. Mater. Chem. C 1, 253–259 (2013)
Christodoulou, C., Giannakopoulos, A., Nardi, M.V., Ligorio, G., Oehzelt, M., Chen, L., Pasquali, L., Timpel, M., Giglia, A., Nannarone, S., Norman, P., Parvez, K., Mullen, K., Deljonne, D., Koch, N.: Tuning the work function of graphene-on-quartz with a high weight molecualr acceptor. J. Phys. Chem. C 118, 4784–4790 (2014)
Gholizadeh, R., Yu, Y.-X.: Work function of pristine and heteroatom-doped graphenes under different external electric fields:an ab initio DFT study. J. Phys. Chem. C 118, 28274–28282 (2014)
Yu, Y.-X.: A dispersion-corrected DFT study on adsorption of battery active materials anthraquinone and its derivatives on monolayer graphene and h-BN. J. Mater. Chem. A 2, 8910–8917 (2014)
Yu, Y.-X.: Binding energy and work function of organic electrode materials phenanthraquinone, pyromellitic dianhydride and their derivatives adsorbed on graphene. Appl. Mater. Interfaces 6, 16267–16275 (2014)
Basko, D.M., Piscanec, S., Ferrari, A.C.: Electron–electron interactions and doping dependence of the two-phonon Raman intensity in graphene. Phys. Rev. B 80, 165413 (2009)
Dong, X., Fu, D., Fang, W., Shi, Y., Chen, P., Li, L.-J.: Doping single-layer graphene with aromatic molecules. Small 5(12), 1422 (2009)
Chen, Z., Santoso, I., Wang, R., Xie, L.F., Mao, H.Y., Huang, H., Wang, Y.Z., Gao, X.Y., Chen, Z.K., Ma, D., Wee, A.T.S., Chen, W.: Surface transfer hole doping of epitaxial graphene using MoO3 thin film. Appl. Phys. Lett. 96, 213104 (2010)
Han, C., Lin, J., Xiang, D., Wang, C., Wang, L., Chen, W.: Improving chemical vapor deposition graphene conductivity using molybdenum trioxide: an in-situ field effect transistor study. Appl. Phys. Lett. 103, 263117 (2013)
Panchakarla, L., Subrahmanyam, K., Saha, S., Govindaraj, A., Krishnamurthy, H., Waghmare, U., Rao, C.N.: Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 21, 4726–4730 (2009)
Hwang, J.O., Park, J.S., Choi, D.S., Kim, J.Y., Lee, S.H., Lee, K.E., Kim, Y.-H., Song, M.H., Yoo, S., Kim, S.O.: Workfunction-tunable, N-doped reduced graphene transparent electrodes for high-performance polymer light-emitting diodes. ACS Nano 6, 159–167 (2011)
Deng, Y., Li, Y., Dai, J., Lang, M., Huang, X.: An efficient way to functionalize graphene sheets with presynthesized polymer via ATNRC chemistry. J. Polym. Chem. 49, 1582–1590 (2011)
Ren, L., Huang, S., Zhang, C., Wang, R., Tjiu, W.W., Liu, T.: Functionalization of graphene and grafting of temperature-responsive surfaces from graphene by ATRP “on water”. J. Nanopart. Res. 14, 940 (2012)
Shanmugharaj, A., Yoon, J., Yang, W., Ryu, S.H.: Synthesis, characterization, and surface wettability properties of amine functionalized graphene oxide films with varying amine chain lengths. J. Colloid Interface Sci. 401, 148 (2013)
Kim, C., Yoon, M.-J., Hong, S.H., Park, M., Park, K., Kim, S.Y.: Aromatic substituents for prohibiting side-chain packing and π–π stacking in tin-cored tetrahedral stilbenoids. Electron. Mater. Lett. 12, 388–398 (2016)
Song, S.M., Park, J.K., Sul, O.J., Cho, B.J.: Determination of work function of graphene under a metal electrode and its role in contact resistance. Nano Lett. 12, 3887–3892 (2012)
Shi, Y., Kim, K.K., Reina, A., Hofmann, M., Li, L.-J., Kong, J.: Work function engineering of graphene electrode via chemical doping. ACS Nano 4, 2689–2694 (2010)
Jo, I., Kim, Y., Moon, J., Park, S., Moon, J.S., Park, W.B., Lee, J.S., Hong, H.: Stable n-type doping of graphene via high-molecular-weight ethylene amines. Phys. Chem. Chem. Phys. 17, 29492–29495 (2015)
Ishikawa, R., Bando, M., Morimoto, Y., Sandhu, A.: Doping graphene films via chemically mediated charge transfer. Nano Res Lett 6, 111 (2011)
Lee, W.H., Suk, J.W., Lee, J., Hao, Y., Park, J., Yang, J.W., Ha, H.-W., Murali, S., Chou, H., Akinwande, H., Kim, K.S., Ruoff, R.S.: Simultaneous transfer and doping of CVD-grown graphene by fluoropolymer for transparent conductive films on plastic. ACS Nano 6, 1284–1290 (2012)
Podila, R., Rao, R., Tsuchikawa, R., Ishigami, M., Rao, A.M.: Raman spectroscopy of folded and scrolled graphene. ACS Nano 6, 5784–5790 (2012)
Sun, T., Wang, Z., Shi, Z., Ran, G., Xu, W., Wang, Z., Li, Y., Dai, L., Qin, G.: Multilayered graphene used as anode of organic light emitting devices. Appl. Phys. Lett. 96, 55 (2010)
Ferrari, A.C.: Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun. 143, 47–57 (2007)
Kwon, K.C., Son, P.K., Kim, S.Y.: Ion beam irradiation of few-layer graphene and its application to liquid crystal cells. Carbon 67, 352–359 (2014)
Oh, J.H., Choi, G.J., Kwon, K.C., Bae, S.-R., Jang, H.W., Gwag, J.S., Kim, S.Y.: Ion-beam-irradiated CYTOP-transferred graphene for liquid crystal cells. Electron. Mater. Lett. 13, 277–285 (2017)
Zafar, Z., Ni, Z.H., Wu, X., Shi, Z.X., Nan, H.Y., Bai, J., Sun, L.T.: Evolution of raman spectra in nitrogen doped graphene. Carbon 61, 57–62 (2013)
Ramanathan, T., Fisher, F., Ruoff, R., Brinson, L.C.: Amino-functionalized carbon nanotubes for binding to polymers and biological systems. Chem. Mater. 17, 1290–1295 (2005)
Jansen, R., Bekkum, H.V.: XPS of nitrogen-containing functional groups on activated carbon. Carbon 33, 1021–1027 (1995)
Acknowledgements
This research was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIP) (Nos. 2018R1A4A1022647); and this research was supported by the Chung-Ang University Research Scholarship Grants in 2015.
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Bae, SR., Lee, T.W., Park, K. et al. Tuning of Graphene Work Function by Alkyl Chain Length in Amine-Based Compounds. Electron. Mater. Lett. 15, 141–148 (2019). https://doi.org/10.1007/s13391-018-00109-4
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DOI: https://doi.org/10.1007/s13391-018-00109-4