Applied Surface Science 37 (1989) 55-62 55

North-Holland, Amsterdam

CLEANING SURFACES OF SINTERED BERYLLIUM OXIDE

R.G. M U S K E T
Lawrence Livermore National Laboratory, Livermore, CA 94550, USA

Received 29 August 1988; accepted for publication 5 December 1988

A practical procedure for preparing atomically clean, debris-free surfaces on sintered beryllium
o',dde specimens has been developed. Chemical, ion-sputter, and UV/ozone cleaning techniqu,"
were examined in efforts to improve the surface cleanliness. Characterization of the surfaces were
performed using Auger electron spectroscopy (AES) to determine the level of cleanliaess and
scanning electron microscopy (SEM) to exataine the surface microtopography. In addition,
Rutherford backscattering (RBS) provided information on both bulk and surface contamination.
The essence of the practical procedure coasists of ultrasonic cleaning in dilute nitric acid followed
by a UV/ozone exposure. Such treatments reduced the surface impurity levels for elements with
Z > 4 to less than 1 at%. The described procedure should be directly applicable to other smtered
oxide materials.

1. |na'oducfion

Sintered beryllium oxide (Le. BeO) c o m p o n e n t s have b e e n used in a variety

of applications.. In m a n y cases BeO must be adhesively b o n d e d to other
materials or other BeO parts. F o r BeO specimens with surfaces defined by a
grinding process, b o t h the chemical cleanliness a n d the presence o f n o n - s i n t e r e d
grinding debris can affect adhesive bonds. Since the most logical " c o n t r o l "
surfaces for adhesive studies were deemed to be debris-free, atomically clean
surfaces, we have developed a practical procedure for obtaining such surfaces.

2. Experimental considerations

The puck-like BeO specimens were ground to a finish of 16 microinches

with final dimensions of 28.6 m m diameter × 12.5 m m thick. R u t h e r f o r d
backscattering (RBS) analysis [1] revealed the presence of the following
near-surface c o n t a m i n a n t s (in atomic percent (at%)): C > 30, Si < 1.7, Fe < 0.6,
Pb-like high-Z < 0.03. The shapes o f the Z > 13 RBS peaks suggested that
these c o n t a m i n a n t s were present in the particles and not c o n c e n t r a t e d in a fe',,:
atomic layers at the surface. Thus, the low levels of c o n t a m i n a t i o n found for
the Z > 13 elements were not considered to be significant from an a d h e s i o n /

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 R.G. Musket / Cleaning surfaces of sintered beryllium oxide

bonding viewpoint. However, the presence of significant carbon on the surface

established the need for surface cleaning procedures.
Auger electron spectroscopy (AES) [2] was used to assess the near-surface
( < 5 nm) composition of various BeO surfaces. Since BeO is an electrical
insulator, bombardment with electrons having energies typically used for AES
(i.e. 2-5 keV) led to charging of the surface and precluded useful measure-
ments. For a primary energy of 1 keV we f' ,und that charging was not a
problem, presumably because the secondary electron coefficient was greater
than one at our angle of incidence (i.e. 45°); however, the observed Auger
electron peak energies were about 12 eV below the expected values, indicating
that the surface was charged to about + 12 V. Sputter cleaning was achieved
using 5 keV Ar + ions with the ion-beam axis approximately perpendicular to
the electron beam axis. The actual surface composition was determined using
elemental sensitivity factors for 1 keV primary electrons obtained relative to
the AES peak of sputter-cleaned silver. For ,he carbon factor we used a
graphite specimen. A clean BeO surface was used for the beryllium and
oxygen factors. The measured, 1 keV sensitivity factors S were S ( B e ) = 0.29,
S(C) = 0.26, and S ( O ) = 9.17. The surface compositions were determined in
the standard way [2]. Since the characteristic loss peaks associated with the
Be KLL Auger peak occurred over an energy range that included the expected
position for the Li KLL Auger peak, the existence of lithium in the surface
re,,Jon of the specimens cannot be excluded. Thus, a " d e a n " surface was taken
to be one with less than 1 at% of surface impurities with Z > 4.
Since U V / o z o n e exposures have been shown to eliminate carbon con-
tamination from SiO2 surfaces [3], application of this cleaning/oxidizing
procedure to other oxide materials seemed logical. Our U V / o z o n e treatment
consisted of exposing the BeO surfaces to irradiation by a mercury vapor lamp
at a distance of about 7 mm for various times while flowing dry air at about
0.5 psi through the commercial U V / o z o n e unit [4], which was placed in an
exhausted hood to remove the unreacted ozone.

3. Results and discussion

Fig. la shows the AES spectrum of an as-received surface of BeO. The

surface composition is clearly dominated by carbon; the shape of the carbon
peak is indicative of graphitic carbon, not carbidic carbon. Using the mea-
sured sensitivity factors, the surface composition was calculated to be Be = 10,
O = 34, and C = 56 at%. In table 1 the average surface composition for four
different spots on two as-received specimens is displayed.
3.1. Sputter cleaning

We used Ar + sputtering in an attempt to reduce the carbon and found that

most of the carbon was removed within the first 20 rain of sputtering. The
 R.G. Musket / Cleaning surfaces of sintered beryllium oxide

(Eo = 1 keV, 45 =) (Eo = 1 keV, 45 °)

:etu
-g zw
}

c
8 b
O 200 400 600 800 1000 0 200 4()0 600 800 1000
Electron e n e r g y (eV) Electron energy (eV)

Fig. 1. Auger electron spectrum of sintered BeO specimen in (a) the as-received condition and (b)
after sputter cleaning with 5 keV argon ions.

Table 1
Summary of AES analyses
Specimen condition Specimens/spots Ave (std dev)
Be (at%) O (at%) C (at%)
As-received 2/4 11 (4) 35 (2) 55 (5)
As-received + sputter clean 2/4 46 (4) 50 (3) 4 (1)
As-received + nitric clean 1/2 41 (0) 48 (2) 10 (2)
Nitric 4-sputter clean 1/2 49 (0) 50 (1) 2 (1)
Nitric+ 20 h air 1/2 50 (1) 50 (1) 1 (0)
+ 1 h UV/ozone
As-received+ 1 h UV/ozone 1/2 49 (1) 50 (1) 1 (1)
Nitric + 15 min UV/ozone 2/lst side 45 (4) 49 (0) 6 (5)
2/2nd side 48 (2) 50 (1) 2 (2)
Nitric + 30 min UV/ozone 2/lst side 50 (1) 50 (0) 1 (0)
2/2nd side 50 (0) 50 (0) 0 (0)

s p e c t r u m of fig. l b s h o w s the surface of fig. l a after s p u t t e r cleaning. In this

case the c o m p o s i t i o n , neglecting the argon, is Be = 48, O = 49, a n d C = 3 at%.
T h e s p u t t e r i n g w a s n o t effective for c o m p l e t e r e m o v a l o f the c a r b o n seen by
the electron b e a m because, p r e s u m a b l y , s u r f a c e r o u g h n e s s a n d debris particles
protected s o m e of the surface areas f r o m t h e ions, w h o s e b e a m axis was
p e r p e n d i c u l a r to that of t h e electron b e a m . T h e average s u r f a c e c o m p o s i t i o n
for as-received s p e c i m e n s after s p u t t e r i n g is listed in table 1.
S c a n n i n g electron m i c r o s c o p y revealed t h e m i c i o t o p o g r a p h y of the as-re-
ceived BeO surfaces. Since the BeO h a d a t e n d e n c y to charge u p d u r i n g
 R.G. Musket / Cleaning surfaces of sintered beryllium oxide

electron irradiation, a thin gold coating was routinely applied to all specimens
prior to SEM measurements. The micrographs of fig. 2 give representative
views of a typical as-received surface. In the x 100 micrograph there is clear
evidence for the grinding direction. Both the x 1K and x 3K photo~ show the
presence of small, apparently loose particles or debris and of large particles
with grinding marks. In the × 10K view, small, apparently adherent particles
are present on the surface of a large particle. These micrographs support the
suggestion that both the surface roughness and debris contributed to the
shadowing phenomena during ion b o m b a r d m e n t cleaning.

Fig. 2. Scanning electron micvographs ef sintered BeO specimen of fig. la in the as-received
condition.
 R.G. Musket / Cleaning surfaces of sintered beryllium oxide 59

3.2. Ultrasonic cleaning

For removal of the debris, we investigated the effect of ultrasonic cleaning
on the specimens in both a 5% nitric acid solution and pure ethanol. Our
process consisted of the following steps: (1) ultrasonic cleaning in either the
nitric acid or ethanol for 15 rain; (2) ultrasonic rising in distilled water for 5
min; and (3) immersion in ethanol to displace water and enhance drying. For
both the ultrasonic steps the specimens were on edge to permit easy exit of any

Fig. 3. Scanning electron n'ficrographs of the sintered BeO specimen of fig. 2 after ultrasonic
cleaning in 5% nitric for 15 min.
60 R.G. Musket / Cleaning surfaces of sintered beryllium oxide

dislodged particles. Fig. 3 shows the results for the nitric acid cleaning
procedure. Relative to the corresponding as-received surface of fig. 2, fig. 3
shows that the nitric acid cleaning removed essentially all the gebris, including
the small apparently adherent particles in the × 10K view of fig. 2. There is
also evidence that this cleaning removed some of the larger BeO particles. In
contrast to these results for nitric acid cleaning, the ethanol cleaning removed
the loose debris, but did not remove the small, apparently adherent particles.
AES showed the nitric-acid cleaned surfaces to be much cleaner than the
as-received surfaces (table 1). In addition, removal of the debris reduced the
ion-beam shadowing and led to more efficient sputter cleaning (i.e. nitric +
sputter clean in table 1).

3.3. U V / ozone cleaning

Although the combination of the nitric-ac~.d cleaning and sputter cleaning

yields a surface suitable for adhesive bonding, the sputter cleaning step was
deemed too complicated for routine preparation of the BeO surfaces. Conse-
quently, we investigated the application of U V / o z o n e cleaning. AES showed
that one hour of U V / o z o n e cleaning was sufficient to reduce the carbon
contamination level to about 1 at% for both as-received and nitric-acid cleaned
(after 20 h air exposure) specimens (table 1).
Further studies were pursued to establish the minimum time of U V / o z o n e
exposure necessary to provide clean specimens on a routine, reproducible
basis. For these studies the nitric-acid cleaned specimens were placed in a

(E o = 1 keV, 45 °}

Be

o 200 4~o 6o~ 8oo looo

Electron energy (eV)
Fig. 4. Auger electron spectrum of sintered BeO specimen after ultrasonic cleaning in 5% nitric
acid solution for 15 min and UV/ozone cleaning in slightly flowingdry air for 30 min.
 R.G. Musket / Cleaning surfaces of smtered beryllium oxide 61

clean, sorption-pumped chamber, which was evacuated to less than 100 mTorr
to remove residual water vapor prior to the U V / o z o n e cleaning step. Since
cleaning of both sides of each specimen was needed for the bonding studies,
first one side was given the specified U V / o z o n e exposure and then the
specimen was turned over and the second side was given the same exposure.
AES measurements of the two sides showed that 15 min of U V / o z o n e
cleaning of nitric~acid cleaned specimens was not sufficient to reduced the
carbon contamination to 1 at% in all regions of the specimens, but 30 rain
exposure of each side of the puck-like specimens leads to acceptably clean
surfaces (table 1). Fig. 4 is the AES spectrum from the second side of a
specimen cleaned in U V / o z o n e after the nitric-acid cleaning procedure.
Although this specimen was exposed to air for about 10 min after the
U V / o z o n e cleaning (before it was under vacuum in the AES analysis cham-
ber), there was no evidence for carbon contamination.

4. Practical cleaning procedure

Coz:sidering the above results, we have defined a practical procedure for

preparing debris-free, atomically clean surfaces of sintered BeO. With minor
changes these procedures can be applied in a production environn~ent. For
adhesive bonding studies, the sequence of steps can be summarized as follows:
(1) Ultrasonic cleaning in a fresh, 5% nitric acid solution for 15 rain with each
specimen on edge in individual glass beakers.
(2) Ultrasonic rinsing in fresh, distilled water for 5 rain v'ith the specimens on
edge in individual beakers.
(3) Immersion rinsing in ethanol to enhance water evaporation.
(4) Evacuation to below 100 mTorr in a clean, sorption-pumped system to
remove residual water.
(5) Storage in clean < 100 rnTorr vacuum until needed for bon~ing s~.~dies
(6) U V / o z o n e cleaning in slightly flowing dry air for 30 rain on each side
with the exposed surface about 7 mm from the UV lamp.
(7) Application of adhesive within 10 rnin after the U V / o z o n e cleaning.
Steps 1-3 leave fine BeO particles ill the beakers. These residual solutions
must be handled with care and disposed of according to hazard control
procedures.

5. Concluding remarks

Although the described procedure was developed for sintered beryllium

oxide, essentially the same steps should be appropriate for the preparation of
debris-free, atomically clean surfaces of other sintered oxides. However, the
62 R.G. Musket / Cleaning surfaces of sintered beryllium oxide

U V / o z o n e exposure w o u l d p r o b a b l y result in o x i d a t i o n of n o n - o x i d e m a t e r i -
als and, thus, m a y n o t be a n a p p r o p r i a t e cleaning step for s u c h materials.

Acknowledgements

It is a pleasure to a c k n o w l e d g e the technical assistance of J. T h o u r n i r for

the A E S m e a s u r e m e n t s a n d the cleaning e x p e r i m e n t s , J. Y o s h i y a m a for t h e
SEI',4 m e a s u r e m e n t s , a n d S. B a u m a n n of C. E v a n s a n d Associates for the R B S
m e a s u r e m e n t s . W o r k p e r f o r m e d in part u n d e r the auspices of the U S D e p a r t -
m e n t of E n e r g y b y Lawrence L i v e r m o r e N a t i o n a l L a b o r a t o r y u n d e r c o n t r a c t
N o . W-7405-Eng-48.

References

[1] W.K. Chu, J.W. Mayer and M.A. Nicolet, Backscanering Spectrometry (Academic Press, New
York, 1978).
[2] L.E. Davis, N.C. MacDonald, P.W. Palmberg, G.E. Riach and R.E. Weber, Handbook of
Auger Electron Spectroscopy, 2nd ed. (Physical Electronics Industries, Eden Prairie, MN,
1976).
[31 J.R. Vig, in: Surface Contamination, Vol. 1, Ed. K.L. Mittal (Plenum, New York, 1978) p. 235.
[4] Model 0306 UV/ozone unit, UVOCS Inc., Montgomery~lle, PA 18936, USA.