Skip to main content
Log in

Fourier transform infrared spectroscopy studies on thermal decomposition of tetrakis-dimethyl-amido zirconium for chemical vapor deposition of ZrN

  • Published:
Korean Journal of Chemical Engineering Aims and scope Submit manuscript

Abstract

The decomposition behavior of tetrakis (dimethylamido) zirconium (TDMAZ) under various ambient gases was studied by using in-situ Fourier transform infrared spectroscopy (FTIR) aimed at understanding the gas phase reactions and also at selecting the appropriate process conditions for ZrN chemical vapor deposition (CVD). The infrared absorbance of the stretching vibration at 933.37 cm-1 was employed to monitor the degree of dissociation of the gaseous TDMAZ. In the case of argon and nitrogen atmospheres, TDMAZ starts to decompose at above 300 °C, while in a hydrogen atmosphere it starts to decompose at above 350 °C. To evaluate the effect of the decomposition behavior of the precursor on CVD ZrN, the ZrN films were grown at 150–375 °C under Ar, N2, and H2. A clear difference in transition temperature of controlling from surface reaction to gas phase mass transfer was observed: The ZrN growth rate decreased rapidly at above 300 °C under Ar or N2 atmospheres, and increased continuously with increase of the deposition temperature under an H2 atmosphere.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Berndt, H., Zeng, A.-Q., Stock, H.-R. and Mayr, P., “Zirconium Carbonitride Films Produced by Plasma-assisted Metal Organic Chemical Vapor Deposition”,Surf. Coating Technol.,74, 369 (1995).

    Article  Google Scholar 

  • Chou, W.-J., Sun, C.-H., Yu, G.-P. and Huang, J.-H., “Optimization of the Deposition Process of ZrN and TiN Thin Films on Si(100) using Design of Experiment Method,”Mater. Chem. Phys.,82, 228 (2003).

    Article  CAS  Google Scholar 

  • Dauchot, J. P., Gouttebaron, R., Cornelissen, D., Wautelet, M. and Hecq, M., “Synthesis of Stoichiometric Zirconium Nitride by d.c. Reactive Magnetron Sputtering Pulsed at Low Frequency: Characterization by ESCA, SIMS and Electron Microprobe”,Surf. Interface Anal.,30, 607 (2000).

    Article  CAS  Google Scholar 

  • Dubois, L. H., Zegarski, B. R. and Girolami, G. S., “Infrared Studies of the Surface and Gas Phase Reactions Leading to the Growth of Titanium Nitride Thin Films from Tetrakis(dimethylamido)titanium and Ammonia,”J. Electrochem. Soc.,139, 3603 (1992).

    Article  CAS  Google Scholar 

  • Fix, R. M., Gordon, R. G. and Hoffman, D. M., “Solution-phase Reactivity as a Guide to the Low-temperature Chemical Vapor Deposition of Early-transition-metal Nitride Thin Films,”J. Am. Chem. Soc.,112, 7833 (1991).

    Article  Google Scholar 

  • Hoffman, D. M., “Chemical Vapor Deposition of Nitride Thin Films,”Polyhedron,13, 1169 (1994).

    Article  CAS  Google Scholar 

  • Jin, S., Wen, X. Y., Gong, Z. X. and Zhu, Y.C., “Structure and Adhesion of Zirconium Nitride Films Formed by Reactive Magnetron Sputtering Ion Plating and Dynamic Ion Mixing,”J. Appl. Phys.,74, 2886 (1993).

    Article  CAS  Google Scholar 

  • Kim, D.-H., Lim, G.-T., Kim, S.-K., Park, J.-W. and Lee, J.-G., “Characteristics of Chemically Vapor Deposited TiN Films Prepared using Tetrakis-ethylmethyl-amido-titanium”,J. Vac. Sci Technol. B,17, 2197 (1999).

    Article  CAS  Google Scholar 

  • Krusin-Elbaum, L. and Wittmer, M., “Oxidation Kinetics of Zirconium Mononitride Thin Films,”Thin Solid Films,107, 111 (1983).

    Article  CAS  Google Scholar 

  • Motojima, S., Kani, E., Takahashi, Y. and Sugiyama, K., “Impurity Activated Whisker Growth of Zirconium Nitride by Chemical Vapor Deposition,”J. Mater. Sci.,14, 1495 (1979).

    Article  CAS  Google Scholar 

  • Murarka, S. P., “Metallization,” Butterworth-Heinemann, Stoneham, 15 (1993).

  • östling, M., Nygren, S., Petersson, C. S., Norström, H., Wiklund, P., Buchta, R., Blom, H.-O. and Berg, S., “Reactively Sputtered Zirconium Nitride (ZrN) used as an Aluminum/Silicon Diffusion Barrier in a Zirconium Contact to Silicon,”J. Vac. Sci. Technol. A,2, 281 (1984).

    Article  Google Scholar 

  • Puclin, T. and Kaczmarek, W A., “Formation of Zirconium Nitride Via Mechanochemical Processing”,J. Mater. Sci. Lett.,16, 1799 (1996).

    Article  Google Scholar 

  • Spillmann, H., Willmott, P. R. and Morstein, M. P., “ZrN, ZrxAlyN and ZrxGayN Thin Films,”Appl. Phys. A,73, 441 (2001).

    Article  CAS  Google Scholar 

  • Sproul, W. D., “Reactively Sputtered Nitrides and Carbides of Titanium, Zirconium, and Hafnium,”J. Vac. Sci. Technol. A,4, 2874 (1986).

    Article  CAS  Google Scholar 

  • Sugiyama, K., Pac, S., Takahashi, Y. and Motojima, S., “Low Temperature Deposition of Metal Nitrides by Thermal Decomposition of Organometallic Compounds”,J. Electrochem. Soc.,122, 1545 (1975).

    Article  CAS  Google Scholar 

  • Vab der Vis, M. G M., Konings, R. J. M., Oskam, A. and Walter, R., “Vibrational Spectra of Gaseous and Liquid Tetrakis(dimethylamido) titanium, and Tetrakis(diethylamido)titanium”,J. Mol. Struct.,93, 323 (1994).

    Google Scholar 

  • Weiller, B. H., “Chemical Vapor Deposition of TiN from Tetrakis(dimethylamido)titanium and Ammonia: Kinetics and Mechanistic Studies of the Gas-phase Chemistry,”J. Am. Chem. Soc.,118, 4975 (1996).

    Article  CAS  Google Scholar 

  • Wendel, H. and Surh, H., “Thin Zirconium Nitride Films Prepared by Plasma-enhanced CVD,”Appl. Phys. A,54, 389 (1992).

    Article  Google Scholar 

  • Yong, K. and Jeong, J., “Applications of Atomic Layer Chemical Vapor Deposition for the Processing of Nanolaminate Structures,”Korean J. Chem. Eng.,19, 451 (2002).

    Article  CAS  Google Scholar 

  • Yun, J.-H. Park, M.-Y. and Rhee, S.-W., “Effect of the Gas-phase Reaction in Metalorganic Chemical Vapor Deposition of TiN from Tetrakis(dimethylamido)titanium”,J. Electrochem. Soc.,145, 2453 (1998).

    Article  CAS  Google Scholar 

  • Yun, J.-Y. and Rhee, S.-W., “Effect of H2 and N2 in the Remote Plasma Enhanced Metalorganic Chemical Vapor Deposition of TiN from Tetrakis(diethylamido)titanium,”Thin Solid Films,320, 163 (1998).

    Article  CAS  Google Scholar 

  • Yun, J.-Y. and Rhee, S.-W., “Remote Plasma Enhanced Metal Organic Chemical Vapor Deposition of TiN for Diffusion Barrier,”Korean J. Chem. Eng.,13, 510 (1996).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Do-Heyoung Kim.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kim, IW., Kim, SJ., Kim, DH. et al. Fourier transform infrared spectroscopy studies on thermal decomposition of tetrakis-dimethyl-amido zirconium for chemical vapor deposition of ZrN. Korean J. Chem. Eng. 21, 1256–1259 (2004). https://doi.org/10.1007/BF02719504

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02719504

Key words

Navigation