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Journal of Non-Crystalline Solids 204 (1996)202-203

Letter to the Editor

S o m e c o m m e n t s on so-called 'silicon m o n o x i d e '

Bernd Friede, Martin Jansen *
Institut fiir Anorganische Chemie der Unicersitiit Bonn, Gerhard-Domagk- Strafle 1, 53121 Bonn, Germany

Abstract

By XANES- and 29Si-MAS-NMR-spectroscopy, evidence has been obtained that commercially available solid silicon
monoxide is not really silicon(II)oxide. Instead, this SiO seems to be a composite of at least two compounds. This is in
contrast to a previous report in this Journal [M. Nagamori, J.-A. Boivin and A. Claveau, J. Non-Cryst. Solids 189 (1995)
270].

During our investigations on siliconsuboxides, we

decided to use SiO as a reference for 29Si-MASN M R - and XANES-spectroscopies. Encouraged by
the results of Nagamori et al. [1] who have asserted
that chemically pure SiO (amorphous) is available
from a number of commercial sources such as Merck,
Goodfellow (Brewyn, PA), and Cerac (Milwaukee,
WI), we have performed spectroscopic measurements on samples of SiO obtained from Merck
(Darmstadt, Germany).
Already in 1991 Belot et al. [2] have shown by
means of XANES-spectroscopy that commercial SiO
does not consist of chemically pure silicon(II)oxide,
but is, in fact, a mixture of Si and SiO~. Recently we
could confirm this statement, analyzing SiO obtained
from Alfa Products (Karlsruhe, Germany) by means
of X A N E S spectroscopy [3].
In the meantime we have recognized that also SiO
obtained from Merck (Darmstadt, Germany) is not
silicon(II)oxide. This is in contrast to the findings of
Nagamori et al. [1]. Fig. 1 shows a 29Si-MAS-NMR

* Corresponding author. Tel.: +49-228 733 ll4; fax: +49-228

735 660; e-mail: friede@plumbum.chemie.uni-bonn.de.

spectrum of SiO (Merck). The main signal at a

chemical shift of - I l0 ppm is a typical Q4-signal
belonging to S i O 4 tetrahedra as they would occur in
S i O 2. The broad signal at about - 6 1 ppm cannot be
assigned to any specific silicon oxide species. There
is no signal indicating the presence of pure silicon
that would be expected at a chemical shift of - 8 5
ppm.
X A N E S spectroscopy is sensitive to the electronic
structure and oxidation states of the respective probe
atom. The X A N E S spectrum of commercial SiO in
Fig. 2 was measured at the Si K-edge and shows two
absorption edges. These two features can be assigned
to pure Si and S i O 2 by comparison with the corresponding spectra of the pure compounds, and SiO
seems to be a mixture of Si and SiO 2. There exists
no significant indicating an oxidation state of + II
for silicon as would be expected for a silicon(II)oxide.
Thus none of the commercially available samples
of solid silicon monoxide seems to fulfil the necessary spectroscopic requirements that would allow
one
to a d d r e s s
them
as s i n g l e p h a s i c
'silicon(II)oxide'. On the other hand the samples
cannot be regarded as a simple macroscopic mixture
of Si and S i O 2. Chemical reactions aiming at the

0022-3093/96/$15.00 Copyright 1996 Elsevier Science B.V. All rights reserved.

PII S0022-3093(96)00555-8

E T T E R TO THE EDITOI

B. Friede, M. Jansen/Journal of Non-C~stalline Solids 204 (1996) 202-203

. . . .

. . . .

20

. . . .

. . . .

. . . . . . . . . . . .

-20

. . . .

. . . .

-40

. . . .

....

-60

....

....

-80

. . . . . . . .

-liO0

. . . . . . . .

-l~2O

. . . . . . . .

-i140

203

. . . . . . . .

-1~60

. . . . . . . . . . . . .

-liSO

ppm

Fig. 1. 29Si-MAS-NMR-spectrum of commercially available silicon monoxide. The spectrum was performed on a Varian Unity 400 device.
Spinning rate = 6035 Hz, pulse width = 3 /~s, spectrometer frequency = 79.224 Hz, relaxation delay time = 900 s, line broadening = 50 Hz.

Silizium - V e r b i n d u n g e n
on der $ i - K - K o n t e

diphasic, however, not a simple macroscopic mixture

of SiO 2 and Si or silicon(II)oxide.

3.5
3.0

Acknowledgements

2.5
o

2.o

1.5

The authors would like to thank Dr W. Hoffbauer

for measuring and discussing the 29Si-MAS-NMRspectrum and Dipl.-Phys. B. Peitz and Dipl.-Phys. S.
Bender for measuring the XANES-spectra.

!/_j//"

0.5

:" J

0.0
1830

1840

18150
Energie

18160

1870

18180

/ eV

Fig. 2. XANES-spectra of the respective silicon compounds,

measured at the SiK-edge. The spectra were performed at ELSA
Bonn.

cleavage of Si-Si-bonds via bases or at the alcoholic

complexation of S i O 2 have been tried using SiO
without success [4]. Thus commercial SiO is at least

References
[1] M. Nagamori, J.-A. Boivin and A. Claveau, J. Non-Cryst.
Solids 189 (1995) 270.
[2] V. Belot, R.J.P. Corriu, D. Leclerq, P. Lef~vre, P.H. Mutin
and A. Vioux, J. Non-Cryst. Solids 127 (1991) 207.
[3] M. Jansen and B. Friede, diploma thesis B. Friede, University
of Bonn (1995).
[4] U. Scubert and G. Donh~irl, diploma thesis G. Donh~irl, University of Wi.irzburg (1994).