Carbon nitride formation by low-energy nitrogen implantation into graphite

Abstract Recently, some attempts to produce the new β-C 3 N 4 phase withhardnes higher than diamond have been reported. In this paper, a model study of carbon nitride formation by low-energy nitrogen implantation into graphite is presented. Room temperature (RT) and hot (500°C) nitrogen implantations were performed at saturation and low doses. The formation of chemical bonds between implanted nitrogen and carbon atoms was assessed by in situ X-ray photoelectron spectroscopy. It was found that two dominant nitrogen bonding states are formed in the implanted layer. The relative distribution of these states depends on the implantation temperature, dose and post-annealing process. Hot nitrogen implantation results in a predominant population of the more covalent (higher binding energy) nitrogen bonding state which has been suggested to be characteristic of the β-C 3 N 4 phase. Post-annealing of a low-dose nitrogen-implanted graphite results in a distribution of the nitrogen bonding states similar to the hot implantation case. RT implantation at saturation doses followed by annealing leads to a different distribution of the nitrogen bonding states. The implantation-induced damage was investigated by means of electron-excited C(KVV) Auger line shape measurements. Hot implantation results in point defect formation, although the graphite structure is not completely amorphized. The experimental results suggest that hot nitrogen ion beam-assisted deposition can lead to the formation of the new β-C 3 N 4 phase.

[1]  J. Petruzzello,et al.  Transmission electron microscopy and Auger electron spectroscopy of silicon‐on‐insulator structures prepared by high‐dose implantation of nitrogen , 1985 .

[2]  W. Sproul,et al.  Growth and characterization of C-N thin films , 1992 .

[3]  I. Gouzman,et al.  POSSIBILITY OF CARBON NITRIDE FORMATION BY LOW-ENERGY NITROGEN IMPLANTATION INTO GRAPHITE : IN SITU ELECTRON SPECTROSCOPY STUDIES , 1994 .

[4]  Vinayak P. Dravid,et al.  Synthesis and Tribological Properties of Carbon Nitride as a Novel Superhard Coating and Solid Lubricant , 1993 .

[5]  Kiyoshi Ogata,et al.  Properties of carbon nitride thin films prepared by ion and vapor deposition , 1993 .

[6]  Yip-Wah Chung,et al.  Nano‐indentation studies of ultrahigh strength carbon nitride thin films , 1993 .

[7]  J. M. Wilson,et al.  The diamond surface: I. The structure of the clean surface and the interaction with gases and metals , 1977 .

[8]  J. Ashley Taylor,et al.  Chemical reactions of N 2+ ion beams with group IV elements and their oxides , 1978 .

[9]  Yoshio Bando,et al.  A graphitic carbon nitride , 1990 .

[10]  Sin‐Shong Lin.  Surface characterization of ion beam modified graphite , 1993 .

[11]  Vinayak P. Dravid,et al.  Analytical electron microscopy and Raman spectroscopy studies of carbon nitride thin films , 1993 .

[12]  Kiyoshi Ogata,et al.  Formation of Carbon Nitride Films by Means of Ion Assisted Dynamic Mixing (IVD) Method , 1993 .

[13]  R. Hezel,et al.  Room Temperature Formation of Si‐Nitride Films by Low Energy Nitrogen Ion Implantation into Silicon , 1982 .

[14]  Hong-Gyu Kang,et al.  Silicon nitride formation by low energy N+ and N+2 ion beams , 1992 .

[15]  J. Rabalais,et al.  Interactions of nitrogen (N2+) and nitrosyl (NO+) ions with surfaces of graphite, diamond, teflon, and graphite monofluoride , 1978 .

[16]  A. Liu,et al.  Prediction of New Low Compressibility Solids , 1989, Science.

[17]  Charles M. Lieber,et al.  Experimental Realization of the Covalent Solid Carbon Nitride , 1993, Science.

[18]  O. Björneholm,et al.  Core level spectroscopy of physisorbed molecules on graphite , 1993 .

[19]  S. Hasegawa,et al.  Formation and bonding structure of silicon nitride by 20-keV N + ion implantation , 1985 .

[20]  Liu,et al.  Structural properties and electronic structure of low-compressibility materials: beta -Si3N4 and hypothetical beta -C3N4. , 1990, Physical review. B, Condensed matter.

[21]  Cohen,et al.  Calculated quasiparticle band gap of beta -C3N4. , 1993, Physical review. B, Condensed matter.

[22]  J. Roth,et al.  Damage and deuterium trapping in highly‐oriented pyrolytic graphite , 1993 .

[23]  Marton.,et al.  Auger-electron-spectroscopy analysis of chemical states in ion-beam-deposited carbon layers on graphite. , 1991, Physical review. B, Condensed matter.

[24]  Sunil Kumar,et al.  Growth and structure of CN thin films prepared by radio frequency reactive sputtering , 1993 .

[25]  S. Prawer,et al.  Effect of low energy argon ion irradiation on the secondary electron emission spectrum of highly oriented pyrolytic graphite , 1990 .

[26]  D. Cole,et al.  Carbon–Nitrogen Pyrolyzates: Attempted Preparation of Carbon Nitride , 1991 .

[27]  M. Wixom.  Chemical Preparation and Shock Wave Compression of Carbon Nitride Precursors , 1990 .

[28]  Steffen,et al.  Displacement energy threshold for Ne+ irradiation of graphite. , 1992, Physical review letters.