Vapor Phase Epitaxy of Magnesium Oxide on Silicon

Using Methylmagnesium Alkoxides

Myung M. Sung, Sung Yong Lee, Chang G. Kim, Sun
Sook Lee, Young Kuk Lee, Eun Ju Nah, Chuleui Kim,
Sang Heon Lee, and Yunsoo Kim
Advanced Materials Division
Korea Research Institute of Chemical Technology
Yusong P. O. Box 107, Taejon 305-600, Korea
Vapor phase epitaxy of magnesium oxide has been
accomplished on both Si(001) and Si(111) substrates
using the precursors methylmagnesium tert-butoxide and
methylmagnesium isopropoxide. The deposition was
carried out, mainly with methylmagnesium tert-butoxide,
in the temperature range 400-850 C under high vacuum
conditions. From x-ray crystallographic analysis, the
precursor methylmagnesium tert-butoxide was found to
exist as a tetramer in the crystalline state. It had to be
heated at 140 C to give a reasonable vapor pressure,
whereas the precursor methylmagnesium isopropoxide
was heated at 100 C, indicating that the two precursors
have the same degree of association in the gas phase. The
films were characterized by reflection high energy
electron diffraction (RHEED) in situ in the growth
chamber, and x-ray diffraction (XRD), x-ray pole figure
analysis, scanning electron microscopy (SEM), and x-ray
photoelectron spectroscopy (XPS) after the growth.
Epitaxial growth of magnesium oxide on Si(111) was
achieved by raising the substrate temperature only,
however, on Si(001), it was necessary to grow a silicon
carbide buffer layer prior to the deposition of MgO.
Magnesium oxide is thermodynamically very
stable, has a low dielectric constant and a low refractive
index, and has been widely used as substrate for growing
various thin film materials, particularly oxides of the
perovskite structure. There has been a considerable
interest in integrating the physical properties of these
oxides with semiconductor materials such as GaAs and
Si.1-8 In this regard, it is considered very important to be
able to grow MgO buffer layers epitaxially on the
semiconductors. Various oxide films can then be grown
on such buffer layers, eliminating the need for using MgO
single crystal substrates. On the other hand, magnesium
oxide is used as a protective coating in plasma display
panels (PDPs). To be useful for the manufacturing of
PDPs, the growth rate must be improved.
There have been several reports on chemical
vapor deposition (CVD) of MgO using various
magnesium compounds such as diethylmagnesium,
bis(2,2,6,6-tetramethyl-3,5-heptanedionato)magnesium,
bis(acetylacetonato)magnesium, magnesium acetate,
magnesium 2-ethylhexanoate, bis(cyclopentadienyl)magnesium, and methylmagnesium tert-butoxide. These
compounds must be vaporized at temperatures higher than
100 C, and except for methylmagnesium tert-butoxide,
generally need an additional oxygen source such as H2O
or O2.
In our experiments, stainless-steel ultrahighvacuum (UHV) chambers were employed for the growth
of MgO thin films. The precursors were synthesized
according to the method described previously.9 The base
pressures of the deposition chambers were below 1 x 10-8
Torr, and the chamber pressures increased to 3-5 x 10-6

Torr after the introduction of the precursors.

Thin films of MgO tend to grow preferentially in
the [111] direction by CVD of metal organic compounds,
and therefore its growth in that direction is anticipated on
Si(111). The MgO films grown at low temperatures using
methylmagnesium tert-butoxide are polycrystalline, and
epitaxy on this substrate could only be achieved around
800 C. XRD and pole figure analysis of the films clearly
revealed their epitaxial nature. X-ray photoelectron
spectra of the films indicated formation of stoichiometric
films and were almost identical with those of MgO single
crystals. SEM plan-view images of the films showed flat,
featureless surfaces. To elucidate the pyrolysis
mechanism of the precursor methylmagnesium tertbutoxide, it was adsorbed onto a Si substrate and flash
evaporated toward a quadrupole mass analyzer attached to
the UHV chamber. The mass spectrum indicated that the
precursor is pyrolyzed by -hydrogen elimination
between the methyl group and the tert-butyl group.
On clean Si(001) substrates on the other hand, all
efforts to grow epitaxial MgO films have failed. The
lattice mismatch of MgO with respect to Si is -22.4 %.
Since magnesium oxide has a lattice mismatch of -3.3 %
with respect to cubic silicon carbide and the latter grows
epitaxially on Si(001) relatively easily, it was decided to
grow a silicon carbide buffer layer on Si(001) prior to the
deposition of MgO. SiC buffer layers were deposited on
clean Si(001) substrates using 1,3-disilabutane as the
source compound. After the formation of a SiC buffer
layer was confirmed by RHEED, a magnesium oxide film
was deposited on it. A corresponding RHEED pattern
indicated epitaxial growth of MgO, although a certain
degree of twinning was evident judging from the
appearance of extra diffraction spots. This twinning
phenomenon became much less pronounced when 4-off
Si(001) substrates were used. XRD, rocking curve
measurement, and pole figure analysis also indicated that
the films were epitaxially grown in the [100] direction at
the growth temperatures of 700-850 C. When the growth
temperature was lowered, below 600 C for example,
there always appeared ring structures in the RHEED
patterns indicating polycrystalline growth of the films.
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