Hexagonal Nano-Crystalline BCN Films Grown on Si (100) Substrate Studied by X-Ray Absorption Spectroscopy

Md. Abdul Mannan, Yuji Baba, Norie Hirao, Tetsuya Kida, Masamitsu Nagano, Hideyuki Noguchi

Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering, Saga University, Saga, Japan.
Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering, Saga University, Saga, Japan; Synchrotron Radiation Research Unit, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Ibaraki, Japan.
Synchrotron Radiation Research Unit, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Ibaraki, Japan.

DOI: 10.4236/msa.2013.45A003                

Abstract

Hexagonal nano-crystalline boron carbonitride (h-BCN) films grown on Si (100) substrate have been precisely investigated. The films were synthesized by radio frequency plasma enhanced chemical vapor deposition using tris-dimethylamino borane as a single-source molecular precursor. The deposition was performed by setting RF power at 400 - 800 W. The reaction pressure was at 2.6 Pa and the substrate temperature was recorded at 700°C - 800°C. Formation of the nano-crystalline h-BCN compound has been confirmed by X-ray diffraction analysis. The diffraction peaks at 26.3° together with a small unknown peak at 29.2° were elucidated due to the formation of an h-BCN structure. The films composed of B, C, and N atoms with different B-N, B-C, C-N chemical bonds in forming the sp²-BCN atomic configuration studied by X-ray photoelectron spectroscopy. Orientation and local structures of the h-BCN hybrid were studied by near-edge X-ray absorption fine structure (NEXAFS) measurements. The dominant presence of p* and s* resonance peaks of the sp²-hybrid orbitals in the B K-edge NEXAFS spectra revealed the formation of the sp²-BCN configuration around B atoms like-BN₃ in h-BN. The orientation was suggested on the basis of the polarization dependence of B K-edge and N K-edge of the NEXAFS spectra.

Keywords

Nano-Crystalline; h-BCN Films; Synchrotron Radiation; XPS; NEXAFS; Orientation

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	I. Jiménez, A. F. Jankowski, L. J. Terminello, D. G. J. Sutherland, J. A. Carlisle, G. L. Doll, W. M. Tong, D. K. Shuh and F. J. Himpsel, “Core-Level Photoabsorption Study of Defects and Metastable Bonding Configurations in Boron Nitride,” Physical Review B, Vol. 55, No. 18, 1997, pp. 12025-12037. doi:10.1103/PhysRevB.55.12025
[2]	M. Wibbelt, H. Kohl and Ph. K. Redlich, “Multiple-Scattering Calculations of Electron-Energy-Loss Near-Edge Structures of Existing and Predicted Phases in the Ternary System B-C-N,” Physical Review B, Vol. 59, No. 18, 1999, pp. 11739-11745. doi:10.1103/PhysRevB.59.11739
[3]	A. Y. Liu, R. M. Wentzcovitch and M. L. Cohen, “Atomic Arrangement and Electronic Structure of BC2N,” Physical Review B, Vol. 39, No. 3, 1989, pp. 1760-1765. doi:10.1103/PhysRevB.39.1760
[4]	W. R. L. Lambrecht and B. Segall, “Anomalous BandGap Behavior and Phase Stability of c-BN-Diamond Alloys,” Physical Review B, Vol. 47, No. 15, 1993, pp. 9289-9296. doi:10.1103/PhysRevB.47.9289
[5]	J. Yu, X. D. Bai, J. Ahn, S. F. Yoon and E. G. Wang, “Highly Oriented Rich Boron B-C-N Nanotubes by BiasAssisted Hot Filament Chemical Vapor Deposition,” Chemical Physics Letter, Vol. 323, No. 5-6, 2000, pp. 529-533. doi:10.1016/S0009-2614(00)00546-7
[6]	M. Kawaguchi, “B/C/N Materials Based on the Graphite Network,” Advanced Materials, Vol. 9, No. 8, 1997, pp. 615-625. doi:10.1002/adma.19970090805
[7]	M. C. Polo, E. Martinez, J. Esteve and J. L. Andujar, “Preparation of B-C-N Thin Films by r.f. Plasma Assisted CVD,” Diamond and Related Materials, Vol. 7, 1998, pp. 376-379. doi:10.1016/S0925-9635(97)00167-2
[8]	L. Liu, Y. Wang, K. Feng, Y. Li, W. Li, C. Zhao and Y. Zhao, “Preparation of Boron Carbon Nitride Thin Films by Radio Frequency Magnetron Sputtering,” Applied Surface Science, Vol. 252, No. 2-5, 2006, pp. 4185-4189. doi:10.1016/j.apsusc.2005.06.025
[9]	A. Essafti, E. Ech-chamikh and J. L. G. Fierro, “Structural and Chemical Analysis of Amorphous B-N-C Thin Films Deposited by RF Sputtering,” Diamond and Related Materials, Vol. 14, No. 10, 2005, pp. 1663-1668. doi:10.1016/j.diamond.2005.06.005
[10]	C. Popov, K. Saito, B. Ivanov, Y. Koga, S. Fujiwara and V. Shanov, “Chemical Vapour Deposition of BC2N Films and Their Laser-Induced Etching with SF6,” Thin Solid Films, Vol. 312, 1998, pp. 99-105. doi:10.1016/S0040-6090(97)00694-9
[11]	M. Mieno and T. Satoh, “Study of BCN Compounds Prepared by the Chemical Vapor Deposition with Dimethylamineborane,” Journal of Materials Science, Vol. 36, No. 16, 2001, pp. 3925-3931. doi:10.1023/A:1017966004367
[12]	T. Yuki, S. Umeda and T. Sugino, “Electrical and Optical Characteristics of Boron Carbon Nitride Films Synthesized by Plasma-Assisted Chemical Vapor Deposition,” Diamond and Related Materials, Vol. 13, No. 4-8, 2004, pp. 1130-1134. doi:10.1016/j.diamond.2004.01.005
[13]	S. Ulrich, A. Kratzsch, H. Leiste, M. Stuber, P. Schloβmacher, H. Holleck, J. Binder, D. Schild, S. Westermeyer, P. Becker and H. Oechsner, “Variation of Carbon Concentration, Ion Energy, and Ion Current Density of Magnetron-Sputtered Boron Carbonitride Films,” Surface and Coating Technology, Vol. 116-119, 1999, pp. 742-750. doi:10.1016/S0257-8972(99)00353-9
[14]	V. P. Filonenko, V. N. Khabashesku, V. A. Davydov, I. P. Zibrov and V. N. Agafonov, “Synthesis of a New Cubic Phase in the B-C-N System,” Inorganic Materials, Vol. 44, No. 4, 2008, pp. 395-400. doi:10.1134/S0020168508040122
[15]	M. A. Mannan, M. Nagano, N. Hirao and Y. Baba, “Hexagonal BCN Films Prepared by RF Plasma-Enhanced CVD,” Chemistry Letter, Vol. 37, No. 1, 2008, pp. 96-97. doi:10.1246/cl.2008.96
[16]	M. A. Mannan, M. Nagano, T. Kida, N. Hirao and Y. Baba, “Characterization of BCN Films Synthesized by Radiofrequency Plasma Enhanced Chemical Vapor Deposition,” Journal of Physics and Chemistry of Solids, Vol. 70, No. 1, 2009, pp. 20-25. doi:10.1016/j.jpcs.2008.08.013
[17]	M. A. Mannan, H. Noguchi, T. Kida, M. Nagano, N. Hirao and Y. Baba, “Chemical Bonding States and Local Structures of the Oriented Hexagonal BCN Films Synthesized by Microwave Plasma CVD,” Materials Science and Semiconductor Processesing, Vol. 11, No. 3, 2008, pp. 100-105. doi:10.1016/j.mssp.2009.04.003
[18]	M. A. Mannan, H. Noguchi, T. Kida, M. Nagano, N. Hirao and Y. Baba, “Growth and Characterization of Stoichiometric BCN Films on Highly Oriented Pyrolytic Graphite by Radiofrequency Plasma Enhanced Chemical Vapor Deposition,” Thin Solid Films, Vol. 518, No. 15, 2010, pp. 4163-4169. doi:10.1016/j.tsf.2009.11.086
[19]	M. A. Mannan, Y. Baba, T. Kida, M. Nagano, I. Shimoyama, N. Hirao and H. Noguchi, “Orientation of B-C-N Hybrid Films Deposited on Ni (111) and Polycrystalline Ti Substrates Explored by X-Ray Absorption Spectroscopy,” Thin Solid Films, Vol. 519, No. 6, 2011, pp. 17801786. doi:10.1016/j.tsf.2010.09.052
[20]	J. H. Scofield, “Theoretical Photoionization Cross Section from 1 to 1500 keV,” Lawrence Livermore Laboratory, Livermore, 1973.
[21]	R. Franke, St. Bender, H. Jungermann, M. Kroschel and M. Jansen, “The Determination of Structural Units in Amorphous Si-B-N-C Ceramics by means of Si, B, N and C K-XANES Spectroscopy,” Journal of Electron Spectroscopy and Related Phenomenon, Vol. 101-103, 1999, pp. 641-645. doi:10.1016/S0368-2048(98)00328-4
[22]	D. Li, G. M. Bancroft and M. E. Fleet, “B K-edge XANES of Crystalline and Amorphous Inorganic Materials,” Journal of Electron Spectroscopy and Related Phenomenon, Vol. 79, 1996, pp. 71-73. doi:10.1016/0368-2048(96)02805-8
[23]	J. Stohr, “XEXAFS Spectroscopy, Springer Series in Surface Sciences,” Vol. 25, Springer, Berlin, 1996.
[24]	R. Torres, I. Caretti, R. Gago, Z. Martín and I. Jiménez, “Bonding Structure of BCN Nanopowders Prepared by Ball Milling,” Diamond and Related Materials, Vol. 16, No. 4-7, 2007, pp. 1450-1454. doi:10.1016/j.diamond.2007.01.009
[25]	Z. F. Zhou, I. Bello, M. K. Lei, K. Y. Li, C. S. Lee and S. T. Lee, “Synthesis and Characterization of Boron Carbon Nitride Films by Radio Frequency Magnetron Sputtering,” Surface and Coating Technology, Vol. 128-129, 2000, pp. 334-340. doi:10.1016/S0257-8972(00)00600-9
[26]	A. Perrone, A. P. Caricato, A. Luches, M. Dinescu, C. Ghica, V. Sandu and A. Andrei, “Boron Carbonitride Films Deposited by Pulsed Laser Ablation,” Applied Surface Science, Vol. 133, No. 4, 1998, pp. 239-242. doi:10.1016/S0169-4332(98)00207-4
[27]	C. Morant, P. Prieto, J. Bareno, J. M. San and E. Elizalde, “Hard BCxNy Thin Films Grown by Dual Ion Beam Sputtering,” Thin Solid Films, Vol. 515, No. 1, 2006, pp. 207-211. doi:10.1016/j.tsf.2005.12.063
[28]	M. O. Watanabe, S. Itoh, K. Mizushima and T. Sasaki, “Bonding Characterization of BC2N Thin Films,” Applied Physics Letter, Vol. 68, 1996, pp. 2962-2964. doi:10.1063/1.116369
[29]	W. J. Pan, J. Sun , H. Ling, N. Xu, Z. F. Ying and J. D. Wu, “Preparation of Thin Films of Carbon-Based Compounds,” Applied Surface Science, Vol. 218, No. 1-4, 2003, pp. 298-305. doi:10.1016/S0169-4332(03)00622-6
[30]	M. O. Watanabe, T. Sasaki, S. Itoh and K. Mizushima, “Structural and Electrical Characterization of BC2N Thin Films,” Thin Solid Films, Vol. 281-282, 1996, pp. 334-336. doi:10.1016/0040-6090(96)08656-7
[31]	M. N. Uddin, I. Shimoyama, Y. Baba, T. Sekiguchi and M. Nagano, “X-Ray Photoelectron Spectroscopic Observation on B-C-N Hybrids Synthesized by Ion Beam Deposition of Borazine,” Journal of Vacuum Science and Technology A, Vol. 23, No. 3, 2005, pp. 497-502. doi:10.1116/1.1894667
[32]	Yu. G. Andreev and T. Lundstrom, “High-Temperature Synthesis and Investigation of Hexagonal Boron Carbonitride,” Journal of Alloys and Compounds, Vol. 210, No. 1-2, 1994, pp. 311-317. doi:10.1016/0925-8388(94)90155-4
[33]	M. Dinescu, A. Perrone, A. P. Caricato, L. Mirenghi, C. Gerardi, C. Ghica and L. Frunza, “Boron Carbon Nitride Films Deposited by Sequential Pulses Laser Deposition”, Applied Surface Science, Vol. 127-129, 1998, pp. 692-696. doi:10.1016/S0169-4332(97)00727-7
[34]	V. Linss, S. E. Rodil, P. Reinke, M. G. Garnier, P. Oelhafen, U. Kreissig and F. Richte, “Bonding Characteristics of DC Magnetron Sputtered B-C-N Thin Films Investigated by Fourier-Transformed Infrared Spectroscopy and X-Ray Photoelectron Spectroscopy,” Thin Solid Films, Vol. 467, No. 1-2, 2004, pp. 76-87. doi:10.1016/j.tsf.2004.03.009
[35]	I. Shimoyama, G. Wu, T. Sekiguchi and Y. Baba, “Study of Electronic Structure of Graphite-Like Carbon Nitride,” Journal of Electron Spectroscopy and Related Phenomenon, Vol. 114-116, 2001, pp. 841-848. doi:10.1016/S0368-2048(00)00306-6
[36]	X. Li, J. Zhang, L. Shen, Y. Ma, W. Lei, Q. Cui and G. Zou, “Preparation and Characterization of Graphitic Carbon Nitride through Pyrolysis of Melamine,” Applied Physics A, Vol. 94, 2009, pp. 387-392. doi:10.1007/s00339-008-4816-4
[37]	P. Hammer and F. Alvarez, “Influence of Chemical Sputtering on the Composition and Bonding Structure of Carbon Nitride Films,” Thin Solid Films, Vol. 398-399, 2001, pp. 116-123. doi:10.1016/S0040-6090(01)01456-0
[38]	R. A. Rosenberg, P. J. Love and V. Rehn, “PolarizationDependent C(K) Near-Edge X-Ray Absorption Fine Structure of Graphite,” Physical Review B, Vol. 33, 1986, pp. 4034-4037. doi:10.1103/PhysRevB.33.4034
[39]	R. Gago, I. Jiménez, I. García and J. M. Albella, “Growth and Characterisation of Boron-Carbon-Nitrogen Coatings Obtained by Ion Beam Assisted Evaporation,” Vacuum, Vol. 64, No. 3-4, 2002, pp. 199-204. doi:10.1016/S0042-207X(01)00314-1
[40]	I. Caretti and I. Jiménez, “Point Defects in Hexagonal BN, BC3 and BCxN Compounds Studied by X-Ray Absorption Near-Edge Structure,” Journal of Applied Physics, Vol. 110, No. 2, 2011, Article ID: 023511. doi:10.1063/1.3602996
[41]	I. Caretti and I. Jiménez, “Composition and Bonding Structure of Boron Nitride B1-xNx Thin Films Grown by Ion-Beam Assisted Evaporation,” Chemical Physics Letters, Vol. 511, No. 4-6, 2011, pp. 235-240. doi:10.1016/j.cplett.2011.06.001
[42]	R. Gago, I. Jiménez, T. Sajavaara and J. M. Albella, “XRay Absorption Studies of Cubic Boron-Carbon-Nitrogen Films Grown by Ion Beam Assisted Evaporation,” Diamond and Related Materials, Vol. 10, No. 3-7, 2001, pp. 1165-1169. doi:10.1016/S0925-9635(00)00414-3
[43]	S. C. Ray, H. M. Tsai, J. W. Chiou, J. C. Jan, K. Kumar, W. F. Pong, F. Z. Chien, M. H. Tsai, S. Chattopadhyay, L. C. Chen, S. C. Chien, M. T. Lee, S. T. Lin and K. H. Chen, “X-Ray Absorption Studies of Boron-Carbon-Nitrogen (BxCyNz) Ternary Alloys,” Diamond and Related Materials, Vol. 13, No. 4-8, 2004, pp. 1553-1557. doi:10.1016/j.diamond.2003.11.052
[44]	J. Kouvetakis, T. Sasaki, C. Shen, R. Hagiwara, M. Lerner, K. M. Krishnan and N. Bartlett, “Novel Aspects of Graphite Intercalation by Fluorine and Fluorides and New B/C, C/N and B/C/N Materials Based on the Graphite Network,” Synthetic Metals, Vol. 34, No. 1-3, 1989, pp. 1-7. doi:10.1016/0379-6779(89)90355-X
[45]	Z. Weng-Sieh, K. Cherrey, N. G. Chopra, Y. Miyamoto, A. Rubio, M. L. Cohen, S. G. Louie, A. Zettl and R. Gronsky, “Synthesis of BxCyNz Nanotubules,” Physical Review B, Vol. 51, No. 16, 1995, pp. 11229-11232. doi:10.1103/PhysRevB.51.11229
[46]	R. Gago, I. Jiménez and J. M. Albella, “Identification of Ternary Boron-Carbon-Nitrogen Hexagonal Phases by XRay Absorption Spectroscopy,” Applied Physics Letter, Vol. 78, No. 22, 2001, pp. 3430-3432. doi:10.1063/1.1376428
[47]	I. Caretti, R. Torres, R. Gago, A. R. Landa-Canovas and I. Jiménez, “Effect of Carbon Incorporation on the Microstructure of BCxN (x = 0.25, 1, and 4) Ternary Solid Solutions Studied by Transmission Electron Microscopy,” Chemical Materials, Vol. 22, No. 6, 2010, pp. 1949-1951. doi:10.1021/cm9038472
[48]	T. Hagio, M. Nakamizo and K. Kobayashi, “Studies on X-Ray Diffraction and Raman Spectra of B-Doped Natural Graphite,” Carbon, Vol. 27, No. 2, 1989, pp. 259-263. doi:10.1016/0008-6223(89)90132-2
[49]	A. C. Ferrari and J. Robertson, “Interpretation of Raman Spectra of Disordered and Amorphous Carbon,” Physical Review B, Vol. 61, No. 20, 2000, pp. 14095-14107. doi:10.1103/PhysRevB.61.14095
[50]	S. Ulrich, T. Theel, J. Schwan and H. Ehrhardt, “Magnetron-Sputtered Superhard Materials,” Surface and Coating Technology, Vol. 97, No. 1-3, 1997, pp. 45-69. doi:10.1016/S0257-8972(97)00159