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Germanium Deposition on Silicon: Surface Chemistry of (CH3CH2)2GeH2 and GeC14

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Abstract

Diethylgermane, (CH3CH2)2GeH2, and germanium tetrachloride, GeCl4 may be useful precursors for chemical vapor deposition (CVD) or atomic layer controlled deposition of germanium. To explore the surface chemistry of these alternative precursors, the adsorption and desorption kinetics of (CH3CH2)2GeH2 (DEG) and GeCl4 on Si(111) 7x7 have been examined using laser-induced thermal desorption (LITD), and temperature programmed desorption (TPD) techniques. Fourier transform infrared (FTIR) spectroscopy has also been employed to monitor the decomposition of DEG on porous silicon surfaces. The FTIR spectra revealed that DEG dissociatively adsorbs on porous silicon surfaces at 200 K to form SiH, GeH, and SiCH2CH3 surface species. No spectral features were observed for GeCH2CH3 surface species. The TPD studies following DEG exposures on Si(111) 7x7 observed CH2=CH2 and H2 desorption products at 700 and 800 K, respectively. The production of CH2=CH2 (ethylene) was consistent with a β-hydride elimination mechanism from surface ethyl species, i.e. SiCH2CH3(ad) —> SiH(ad) + CH2=CH2 (g). Similar TPD experiments following GeCl4 exposures monitored the desorption of only SiCl2 at approximately 920 K. Desorption of SiCl2 indicates that the chlorine on GeCl4 has transferred to the silicon surface. Atomic Ge was also observed to desorb at 1200 K following both DEG and GeCl4 adsorption. LITD experiments measured initial reactive sticking coefficients of So ∼0.05 for DEG and So ∼1.0 for GeCl4 at 200 K. As expected from a precursor-mediated adsorption model, the sticking coefficients decreased versus increasing surface temperature. The sticking coefficients for these germanium containing precursors were higher than the corresponding sticking coefficients for (CH3CH2)2SiH2 and SiCl4. Possible recipes for the CVD or atomic layer controlled deposition of germanium on silicon can be proposed based on the surface chemistry and adsorption and desorption kinetics for DEG and GeCl4.

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Acknowledgement

This work was supported by the Office of Naval Research under Contract No. N00014-92-J-1353. We thank Dr. David A. Roberts of Schumacher for providing the diethylgermane and for numerous helpful discussions. MLW gratefully acknowledges the AT&T Bell Laboratories for a graduate fellowship. SMG acknowledges the National Science Foundation for a Presidential Young Investigator Award.

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Authors and Affiliations

  1. Dept. of Chem. and Biochem., Univ. of Colorado, Boulder, Colorado, 80309, USA

    P. A. Coon, M. L. Wise, A. C. Dillon & S. M. George

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  1. P. A. Coon
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  2. M. L. Wise
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  3. A. C. Dillon
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  4. S. M. George
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Coon, P.A., Wise, M.L., Dillon, A.C. et al. Germanium Deposition on Silicon: Surface Chemistry of (CH3CH2)2GeH2 and GeC14. MRS Online Proceedings Library 282, 413–419 (1992). https://doi.org/10.1557/PROC-282-413

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