Graphical Abstract

Discover the SciOpen Platform and Achieve Your Research Goals with Ease.
Search articles, authors, keywords, DOl and etc.
Chemical vapor deposition (CVD) synthesis of large-domain hexagonal boron nitride (h-BN) with a uniform thickness is very challenging, mainly due to the extremely high nucleation density of this material. Herein, we report the successful growth of wafer-scale, high-quality h-BN monolayer films that have large single-crystalline domain sizes, up to ~72 μm in edge length, prepared using a folded Cu-foil enclosure. The highly confined growth space and the smooth Cu surface inside the enclosure effectively reduced the precursor feeding rate together and induced a drastic decrease in the nucleation density. The orientation of the as-grown h-BN monolayer was found to be strongly correlated to the crystallographic orientation of the Cu substrate: the Cu (111) face being the best substrate for growing aligned h-BN domains and even single-crystalline monolayers. This is consistent with our density functional theory calculations. The present study offers a practical pathway for growing high-quality h-BN films by deepening our fundamental understanding of the process of their growth by CVD.
Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Electric field effect in atomically thin carbon films. Science 2004, 306, 666–669.
Huang, X.; Qi, X. Y.; Boey, F.; Zhang, H. Graphene-based composites. Chem. Soc. Rev. 2012, 41, 666–686.
Huang, X.; Yin, Z. Y.; Wu, S. X.; Qi, X. Y.; He, Q. Y.; Zhang, Q.; Yan, Q.; Boey, F.; Zhang, H. Graphene-based materials: Synthesis, characterization, properties, and applications. Small 2011, 7, 1876–1902.
Gao, T.; Song, X. J.; Du, H. W.; Nie, Y. F.; Chen, Y. B.; Ji, Q. Q.; Sun, J. Y.; Yang, Y. L.; Zhang, Y. F.; Liu, Z. F. Temperature-triggered chemical switching growth of in-plane and vertically stacked graphene-boron nitride heterostructures. Nat. Commun. 2015, 6. 6835.
Hunt, B.; Sanchez Yamagishi, J. D.; Young, A. F.; Yankowitz, M.; LeRoy, B. J.; Watanabe, K.; Taniguchi, T.; Moon, P.; Koshino, M.; Jarillo-Herrero, P. et al. Massive Dirac Fermions and Hofstadter Butterfly in a van der Waals heterostructure. Science 2013, 340, 1427–1430.
Yang, W.; Chen, G. R.; Shi, Z. W.; Liu, C. C.; Zhang, L. C.; Xie, G. B.; Cheng, M.; Wang, D. M.; Yang, R.; Shi, D. X. et al. Epitaxial growth of single-domain graphene on hexagonal boron nitride. Nat. Mater. 2013, 12, 792–797.
Levendorf, M. P.; Kim, C. J.; Brown, L.; Huang, P. Y.; Havener, R. W.; Muller, D. A.; Park, J. Graphene and boron nitride lateral heterostructures for atomically thin circuitry. Nature 2012, 488, 627–632.
Liu, Z.; Ma, L. L.; Shi, G.; Zhou, W.; Gong, Y. J.; Lei, S. D.; Yang, X. B.; Zhang, J. N.; Yu, J. J.; Hackenberg, K. P. et al. In-plane heterostructures of graphene and hexagonal boron nitride with controlled domain sizes. Nat. Nanotech. 2013, 8, 119–124.
Wang, M.; Jang, S. K.; Jang, W. J.; Kim, M.; Park, S. Y.; Kim, S. W.; Kahng, S. J.; Choi, J. Y.; Ruoff, R. S.; Song, Y. J. et al. A platform for large-scale graphene electronics – CVD growth of single-layer graphene on CVD-grown hexagonal boron nitride. Adv. Mater. 2013, 25, 2746–2752.
Zhang, C. H.; Zhao, S. L.; Jin, C. H.; Koh, A. L.; Zhou, Y.; Xu, W. G.; Li, Q. C.; Xiong, Q. H.; Peng, H. L.; Liu, Z. F. Direct growth of large-area graphene and boron nitride heterostructures by a co-segregation method. Nat. Commun. 2015, 6, 6519.
Dean, C. R.; Young, A. F.; Meric, I.; Lee, C.; Wang, L.; Sorgenfrei, S.; Watanabe, K.; Taniguchi, T.; Kim, P.; Shepard, K. L.; Hone, J. Boron nitride substrates for high-quality graphene electronics. Nat. Nanotech. 2010, 5, 722–726.
Decker, R.; Wang, Y.; Brar, V. W.; Regan, W.; Tsai, H. Z.; Wu, Q.; Gannett, W.; Zettl, A.; Crommie, M. F. Local electronic properties of graphene on a BN substrate via scanning tunneling microscopy. Nano Lett. 2011, 11, 2291–2295.
Xue, J. M.; Sanchez-Yamagishi, J.; Bulmash, D.; Jacquod, P.; Deshpande, A.; Watanabe, K.; Taniguchi, T.; Jarillo-Herrero, P.; LeRoy, B. J. Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride. Nat. Mater. 2011, 10, 282–285.
Watanabe, K.; Taniguchi, T.; Kanda, H. Direct-bandgap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. Nat. Mater. 2004, 3, 404–409.
Liu, Z.; Gong, Y. J.; Zhou, W.; Ma, L. L.; Yu, J. J.; Idrobo, J. C.; Jung, J.; MacDonald, A. H.; Vajtai, R.; Lou, J. et al. Ultrathin high-temperature oxidation-resistant coatings of hexagonal boron nitride. Nat. Commun. 2013, 4, 2541.
Lee, G. H.; Yu, Y. J.; Cui, X.; Petrone, N.; Lee, C. H.; Choi, M. S.; Lee, D. Y.; Lee, C.; Yoo, W. J.; Watanabe, K. et al. Flexible and transparent MoS2 field-effect transistors on hexagonal boron nitride-graphene heterostructures. ACS Nano 2013, 7, 7931–7936.
Song, L.; Ci, L. J.; Lu, H.; Sorokin, P. B.; Jin, C. H.; Ni, J.; Kvashnin, A. G.; Kvashnin, D. G.; Lou, J.; Yakobson, B. I. et al. Large scale growth and characterization of atomic hexagonal boron nitride layers. Nano Lett. 2010, 10, 3209–3215.
Shi, Y.; Hamsen, C.; Jia, X. T.; Kim, K. K.; Reina, A.; Hofmann, M.; Hsu, A. L.; Zhang, K.; Li, H. N.; Juang, Z. Y. et al. Synthesis of few-layer hexagonal boron nitride thin film by chemical vapor deposition. Nano Lett. 2010, 10, 4134–4139.
Zhang, C.; Fu, L.; Zhao, S.; Zhou, Y.; Peng, H.; Liu, Z. Controllable co-segregation synthesis of wafer-scale hexagonal boron nitride thin films. Adv. Mater. 2014, 26, 1776–1781.
Gao, Y.; Ren, W. C.; Ma, T.; Liu, Z. B.; Zhang, Y.; Liu, W. B.; Ma, L. P.; Ma, X. L.; Cheng, H. M. Repeated and controlled growth of monolayer, bilayer and few-layer hexagonal boron nitride on Pt foils. ACS Nano 2013, 7, 5199–5206.
Lu, G. Y.; Wu, T. R.; Yuan, Q. H.; Wang, H.; Wang, H. S.; Ding, F.; Xie, X. M.; Jiang, M. H. Synthesis of large single-crystal hexagonal boron nitride grains on Cu-Ni alloy. Nat. Commun. 2015, 6, 6160.
Caneva, S.; Weatherup, R. S.; Bayer, B. C.; Brennan, B.; Spencer, S. J.; Mingard, K.; Cabrero-Vilatela, A.; Baehtz, C.; Pollard, A. J.; Hofmann, S. Nucleation control for large, single crystalline domains of monolayer hexagonal boron nitride via Si-doped Fe catalysts. Nano Lett. 2015, 15, 1867–1875
Park, J. H.; Park, J. C.; Yun, S. J.; Kim, H.; Luong, D. H.; Kim, S. M.; Choi, S. H.; Yang, W.; Kong, J.; Kim, K. K.; Lee, Y. H. Large-area monolayer hexagonal boron nitride on Pt foil. ACS Nano 2014, 8, 8520–8528
Camilli, L.; Sutter, E.; Sutter, P. Growth of two-dimensional materials on non-catalytic substrates: h-BN/Au(111). 2D Mater. 2014, 1, 025003.
Kim, K. K.; Hsu, A.; Jia, X. T.; Kim, S. M.; Shi, Y. S.; Hofmann, M.; Nezich, D.; Rodriguez-Nieva, J. F.; Dresselhaus, M.; Palacios, T. et al. Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition. Nano Lett. 2012, 12, 161–166.
Tay, R. Y.; Griep, M. H.; Mallick, G.; Tsang, S. H.; Singh, R. S.; Tumlin, T.; Teo, E. H.; Karna, S. P. Growth of large single-crystalline two-dimensional boron nitride hexagons on electropolished copper. Nano Lett. 2014, 14, 839–846.
Wang, L. F.; Wu, B.; Chen, J. S.; Liu, H. T.; Hu, P. A.; Liu, Y. Q. Monolayer hexagonal boron nitride films with large domain size and clean interface for enhancing the mobility of graphene-based field-effect transistors. Adv. Mater. 2014, 26, 1559–1564.
Li, X.; Magnuson, C. W.; Venugopal, A.; Tromp, R. M.; Hannon, J. B.; Vogel, E. M.; Colombo, L.; Ruoff, R. S. Large-area graphene single crystals grown by low-pressure chemical vapor deposition of methane on copper. J. Am. Chem. Soc. 2011, 133, 2816–2819.
Chen, S. S.; Ji, H. X.; Chou, H.; Li, Q. Y.; Li, H. Y.; Suk, J. W.; Piner, R.; Liao, L.; Cai, W. W.; Ruoff, R. S. Millimeter-size single-crystal graphene by suppressing evaporative loss of Cu during low pressure chemical vapor deposition. Adv. Mater. 2013, 25, 2062–2065.
Fang, W. J.; Hsu, A. L.; Caudillo, R.; Song, Y.; Birdwell, A. G.; Zakar, E.; Kalbac, M.; Dubey, M.; Palacios, T.; Dresselhaus, M. S. et al. Rapid identification of stacking orientation in isotopically labeled chemical-vapor grown bilayer graphene by Raman spectroscopy. Nano Lett. 2013, 13, 1541–1548.
Frueh, S.; Kellett, R.; Mallery, C.; Molter, T.; Willis, W. S.; King'ondu, C.; Suib, S. L. Pyrolytic decomposition of ammonia borane to boron nitride. Inorg. Chem. 2011, 50, 783–792.
Reina, A.; Son, H.; Jiao, L.; Fan, B.; Dresselhaus, M. S.; Liu, Z.; Kong, J. Transferring and identification of single- and few-layer graphene on arbitrary substrates. J. Phys. Chem. C 2008, 112, 17741–17744.
Pacilé, D.; Meyer, J. C.; Girit, C. O.; Zettl, A. The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes. Appl. Phys. Lett. 2008, 92, 133107.
Gorbachev, R. V.; Riaz, I.; Nair, R. R.; Jalil, R.; Britnell, L.; Belle, B. D.; Hill, E. W.; Novoselov, K. S.; Watanabe, K.; Taniguchi, T.; Geim, A. K. et al. Hunting for monolayer boron nitride: Optical and raman signatures. Small 2011, 7, 465–468.
Blase, X.; Rubio, A.; Louie, S. G.; Cohen, M. L. Quasiparticle band structure of bulk hexagonal boron nitride and related systems. Phys. Rev. B 1995, 51, 6868–6875.
Vanin, M.; Mortensen, J. J.; Kelkkanen, A. K.; Garcia-Lastra, J. M.; Thygesen, K. S.; Jacobsen, K. W. Graphene on metals: A van der Waals density functional study. Phys. Rev. B 2010, 81, 081408(R).
Joshi, S.; Ecija, D.; Koitz, R.; Iannuzzi, M.; Seitsonen, A. P.; Hutter, J.; Sachdev, H.; Vijayaraghavan, S.; Bischoff, F.; Seufert, K. et al. Boron nitride on Cu(111): An electronically corrugated monolayer. Nano Lett. 2012, 12, 5821–5828.
Kim, G.; Jang, A. R.; Jeong, H. Y.; Lee, Z.; Kang, D. J.; Shin, H. S. Growth of high-crystalline, single-layer hexagonal boron nitride on recyclable platinum foil. Nano Lett. 2013, 13, 1834–1839.
van der Zande, A. M.; Huang, P. Y.; Chenet, D. A.; Berkelbach, T. C.; You, Y.; Lee, G. -H.; Heinz, T. F.; Reichman, D. R.; Muller, D. A.; Hone, J. C. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 2013, 12, 554–561.
Lee, J. H.; Lee, E. K.; Joo, W. J.; Jang, Y.; Kim, B. -S.; Lim, J. Y.; Choi, S. H.; Ahn, S. J.; Ahn, J. R.; Park, M. H. et al. Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium. Science 2014, 344, 286–289.
Zhang, X.; Xu, Z.; Hui, L.; Xin, J.; Ding, F. How the orientation of graphene is determined during chemical vapor deposition growth. J. Phys. Chem. Lett. 2012, 3, 2822–2827.
Gao, L.; Guest, J. R.; Guisinger, N. P. Epitaxial graphene on Cu(111). Nano Lett. 2010, 10, 3512–3516.
Liu, Y.; Zou, X. L.; Yakobson, B. I. Dislocations and grain boundaries in two-dimensional boron nitride. ACS Nano 2012, 6, 7053–7058.