Diamond and Related Materials 10 Ž2001.

519᎐525

Potassium adsorption on hydrogen- and oxygen-terminated

diamondž 100/ surfaces

Susana Petrick a , Carsten Benndorf b,U

a
Facultad de Ciencias, Uni¨ ersidad Nacional der Ingenieria, Lima, Peru
b
Department of Physical Chemistry, Uni¨ ersity of Hamburg, Bundesstr. 45, D-20146 Hamburg, Germany

Abstract

The adsorption of K at 298 K is a route for the titration of surface groups like O and OH. The experiments were performed on
a semi-conducting natural diamond Ž100. surface cleaned by a 480-W microwave hydrogen plasma at 750⬚C and a hydrogen
pressure of 20 mbar, resulting in a very clean, ordered Ž2 = 1. surface. A second type of CŽ100. surface was prepared by ex situ
oxidation, using a mixture of hydrochloric and nitric acids. The adsorption experiments were carried out in a UHV system
equipped with facilities for photoelectron spectroscopy ŽXPS and UPS.. K deposition was achieved using a dispenser source from
the SAES Getters Company. The K uptake of H-terminated CŽ100. at room temperature is marginal, with a sticking coefficient of
- 0.03. The acid-treated CŽ100. surface shows the presence of a broad O 1s spectrum with different oxygen states Ždifferent
binding energies. in the XPS region. The sticking coefficient for K adsorption at 298 K on this surface is nearly 1. The amount of
K accommodated on the surface correlates with the oxygen coverage and a stoichiometry of nearly KrO s 1 is reached for the
saturated K coverage. In the O 1s spectrum, the high-energy state Ž534.2 eV. disappears, whereas the overall O 1s intensity is
constant. Due to the K adsorption, the C 1s peak shifts by 0.5 eV to a higher binding energy. UPS He I spectra demonstrate a
lowering of the work function by y1.9 eV. 䊚 2001 Elsevier Science B.V. All rights reserved.

Keywords: Diamond; Surface; Oxygen; Alkalis; Photoemission

1. Introduction acterize the reactivity of diamond surfaces and look for

Processes on diamond surfaces play an important
role in the CVD synthesis of diamond. In the recent
past, studies from different groups worldwide have
contributed to the understanding of the gas-phase
processes occurring in the plasma of H 2rCH 4 gases
used for diamond deposition. However, processes oc-
curring on the diamond surface are, up to now, not well
understood. Our present target is to identify and char-
U metals onto diamond surfaces in the recent past. Hos-
Corresponding author. Tel.: q49-40-428384531; fax: q49-40-
428383452.
E-mail address: benndorf@chemie.uni-hamburg.de ŽC. Benndorf..
reactions which can be used to titrate different reactive
groups on this surface. For example, we recently stud-
ied the adsorption of halogens ŽCl 2 and F2 . on CŽ100.
and other low-indexed diamond surfaces w1x, demon-
strating that the H coverage plays an important role in
this reaction. In the present study, we have expanded
our investigation to potassium, which, in contrast to the
electronegative halogens, is an electropositive element.
We therefore expected to find a possible route for the
titration of acidic surface groups, like O and OH.
Several groups have studied the adsorption of alkali
sain et al. w2x studied the K adsorption at 90 K onto a B
doped-CVD CŽ100. surface epitaxially grown on a Ž100.

0925-9635r01r$ - see front matter 䊚 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 5 - 9 6 3 5 Ž 0 0 . 0 0 4 4 0 - 4
520 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525

diamond crystal. In order to obtain a clean surface,

they heated the crystal to 1400 K, removing the surface
H. The K adsorption was investigated using HREELS
and thermal desorption spectroscopy. Their results de-
monstrate that K can be accommodated Ževen at 298
K. on the H-free surface nearly up to ⌰ K ( 1. No
indications are found in this work of the adsorption of
K onto the H-terminated surface. Diederich et al. w3x
reported on the Cs adsorption on natural diamond
Ž100. surface, investigated with XPS and UPS. They
observed the uptake of Cs on the H-terminated, as well
as the H-free, surface. Special attention was directed to
changes in the band bending and the influence on the
negative electron affinity ŽNEA. effect. Furthermore,
the adsorption of K on polycrystalline CVD diamond Fig. 1. XPS overview spectra of different treated CŽ100. surfaces: Ža.
has recently been studied with photoelectron spectro- plasma-treated CŽ100.; Žb. acid-treated surface; Žc. 2 min; and Žd. 5
scopy by Benndorf et al. w4x. min K dosage.

a base pressure of 5 = 10y1 0 mbar. For UPS measure-

2. Experimental
The experiments were carried out on a natural semi-
conducting CŽ100. surface Žsize 5 = 5 = 0.25 mm3 .. The
diamond surface was cleaned in a hydrogen plasma at
750⬚C Ž480 W microwave. and a hydrogen pressure of
20 mbar, resulting in a very clean, ordered surface of
low roughness. After 4 h of plasma treatment, the
original Ž1 = 1. LEED pattern of the ‘as received’ sur-
face changed to the pattern of two domains of a Ž2 = 1.
surface reconstruction, which were rotated by 90⬚. This
surface is believed to be monohydride terminated Ž2 =
1:H.. As we demonstrated recently, this preparation
method leads to a very good LEED pattern with sharp
Ž2 = 1. spots and a low background intensity w1x. It is
evident that this surface has a high hydrogen and a
decreasing oxygen concentration, as detected by X-ray
induced photoelectron spectroscopy ŽXPS.. K deposi-
tion was achieved using a well outgassed dispenser
source from the SAES Getters Company. In order to
calibrate the flux of the K source, the adsorption onto a
sputtered Au surface was measured at room tempera-
ture, measuring the K 2p intensity and the work func-
tion changes from the secondary electron onset in the
He I spectra. On the Au surface, an initial sticking
coefficient for K adsorption of S0 s 1 and a maximum
coverage ⌰ K s 0.4 Ž298 K. was assumed. After a
‘warm-up’ period of 1 min, the K flux from the dis-
penser was found to be constant. The K exposure
reported in this paper is in min of dosing time Žcon-
stant current through the K dispenser of 7.5 A., which
started after the warm-up period of 1 min. Under these
conditions, a saturated first-layer K coverage is reached
on Au after a 5-min dose Ž ⌰ K s 0.4..
The photoelectron spectroscopic measurements, us-
ing AlK ␣ for XPS excitation and He I and II for UPS,
were carried out in an ESCALAB 5 UHV system with
ments, the CŽ100. sample was biased with y2 to y4 V
in order to detect the onset of secondary electron
emission more clearly.
The oxygen-terminated surface was obtained by acid
treatment of the crystal in a hot Ž60⬚C. mixture of HCl
and nitric acids. The change in the surface atomic
structure can be visualized by the contact angle of
water droplets on the surface. Whereas the H-
terminated surface is hydrophobic, the acid-treated
surface shows good wettability Žhydrophilic..
3. Results
3.1. XPS o¨ er¨ iew spectra
Fig. 1 shows the overview spectra in the binding
energy range of 0᎐1000 eV obtained from: Ža. the
H-terminated surface; Žb. the acid-treated surface; and
Žc. the acid-treated surface after a K deposition of 5
min. The spectrum of the H-terminated surface after
5-min evaporation of K is not included, because the
changes due to K are marginal. The very small changes
due to the uptake of a very small amount of K are
discussed in the next section.
For the H-terminated surface, a very sharp C 1s peak
was detected at 284.0 eV. No contamination from oxy-
gen was present on this surface. For the acid-treated
surface, a broader oxygen signal at 532᎐534 eV was
detected beside the C 1s peak at 284.0 eV. We are not
yet able to determine the absolute oxygen coverage.
The analysis of the O 1s peak with higher resolution
Žpresented and discussed below. shows that this signal
is rather broad, and is probably due to at least three
different oxygen species on the surface. We assume
here, that the oxygen coverage is ⌰O s 1 Žequal num-
 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525
Table 1
Relative intensity of C 1s and O1s peaks at different K coverage
K dosing K 2p3r 2 C 1s
time Žmin.
0 0 100
2 72.7 90.6
5 94.4 83.4
ber of surface O and C atoms.. Fig. 1c was obtained
after a 5-min dosage of K, which leads to saturation of
the K coverage. A K 2p doublet at the high-energy side
of the C1s peak Žat approx. 293 eV., as well as the K 1s
at approximately 385 eV, is evident. From the inte-
grated peak areas of the oxygen 1s and the K 2p 3r2 and
the atomic sensitivity factors ŽO 1s s 0.63 and K 2p 3r2
s 0.55., we calculated a stoichiometry for KrO of
0.94:1. The oxygen intensity for three different K dosage
times Ž0, 2 and 5 min. was constant within 3%, whereas
the C 1s signal decreased continuously with increasing
K coverage. The relative peak intensities and their
changes during K adsorption are summarized in Table
1. For the acid-treated surface, the O 1s and C 1s
relative intensities are referred to as 100%. The K
2p 3r2 intensity is related to that of O 1s, corrected with
the ASF factors.
The nearly constant O 1s intensity is in accordance
with the assumption that the oxygen is located on top
of the surface. The decrease in the C 1s intensity
reflects the attenuation of the C 1s signal from the K
overlayer.
3.2. XPS C1s and K 2p spectra
Fig. 2 shows the C 1s and the region of the K 2p
doublet obtained by XPS using a higher resolution
Žpass energy 20 eV.. Spectrum Ža. shows the C 1s
Fig. 2. C 1s spectra of: Ža. the H-terminated; and Žb. the acid-treated
CŽ100. surface. The difference spectrum Žb. y Ža. was obtained after
alignment of the positions and correction of the peak intensities.
521
O 1s
100
100
100
Fig. 3. C 1s and K 2p spectra of the acid-treated CŽ100. surface with:
Ža. 0; Žb. 2; and Žc. 5 min of K dosing.
spectrum for the H-terminated surface and Žb. is the
spectrum of the acid-treated surface. A shift of ⌬ Es
0.4 eV for the C 1s peak from the acid-treated surface
to a higher binding energy is evident. In order to detect
changes due to C᎐O bonding, we also plotted the
difference spectrum Žb. y Ža. after alignment of both
peaks and correction for differences in the peak height.
The procedure is not unambiguous and will be dis-
cussed later in more detail. The difference spectrum
shows a broad positive peak Žhalf-width approx. 4.0 eV.
centered at 286.8 eV and a smaller negative peak at
approximately 283.5 eV. The broad peak at approxi-
mately 286.8 eV possibly arises from surface carbon
atoms bound to oxygen. Possible oxygen species with
these binding energies will be discussed later. After the
evaporation of a 5-min K dose on the H-terminated
CŽ100., a small shift of the C 1s peak from 284.0 to
284.3 eV is evident Žthis spectrum is not shown in Fig.
2.. No measurable intensity from the K 2p doublet was
detected with XPS. However, some small changes were
found in the UPS spectra. We conclude that the K
coverage on the H-terminated surface is negligible,
below the detection limit of approximately 3% of a K
monolayer. Therefore, we conclude that the sticking
coefficient S0 on the H-terminated CŽ100. surface at
298 K is below 0.03.
The C 1s and K 2p spectra on the acid-treated
surface are summarized in Fig. 3. On the acid-treated
surface, spectrum Ža., the C 1s peak is evident at 284.4
eV. After evaporation of K ŽFig. 3b,c. two peaks from
the K 2p doublet at 294.0 Ž2p 3r2 . and 296.8 eV Ž2p1r2 .
are evident, which reach saturation for a 5-min dose of
K. With the increase in K coverage, the C 1s peak
shifts by 0.5 eV to a higher binding energy. In order to
detect possible changes in the C᎐O bonding Ždif-
ference spectrum Fig. 2. andror to see bonding between
C and K, we again analyzed the difference spectrum
between the K-covered and uncovered acid-treated sur-
522 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525
face; this spectrum is not given in Fig. 3. This analysis
suggests that the C᎐O bonding is not changed due to
the presence of K and, furthermore, that no C᎐K
bonding occurs.
3.3. XPS O 1s spectra
Fig. 4 shows the O 1s spectra from the acid-treated
CŽ100. surface Žcurve a. and its changes after 2- and
5-min K doses Žcurves b and c, respectively.. The oxy-
gen peak from the acid-treated surface is located at
approximately 532.4 eV, and is rather broad, with a
half-width of 3.4 eV. The broadness suggests that dif-
ferent oxygen species are present on the CŽ100. sur-
face. In order to quantify the changes observed due to
K adsorption, the O 1s peak was deconvoluted into
three single peaks with half-width between 1.7 and 2.5
eV. As will be discussed below, no yet complete de-
scription of the different oxygen species under these
conditions has been reached, so the deconvolution is
arbitrary.
From the overview spectra and the integrated peak
areas, it can be concluded that the oxygen peak inten-
sity does not change by more then 3% on K adsorption.
After a 2-min K dosage, it is evident ŽFig. 4 b. that the
half-width of the O 1s peak decreases. The deconvolu-
tion shows that this is mainly due to the decrease in
intensity of the high-energy part at 534.2 eV, whereas
the O 1s peaks at lower binding energy Ž531.1 and
532.4 eV. increase in intensity. For the 5-min K dose,
the 534.2-eV peak has nearly disappeared. As already
noted above, the analysis of the overview spectra re-
sulted in a nearly stoichiometric ratio for KrO of 1:1.
3.4. UPS spectra
Fig. 5 summarizes the UPS He I results obtained for
Fig. 4. Oxygen 1s spectra of: Ža. the acid-treated surface; Žb. after 2
min; and Žc. after 5 min of K dosing. The broad O 1s spectrum is
deconvoluted into three Gaussian peaks.
Fig. 5. He I spectra of the H-terminated CŽ100. surface after: Ža. 0;
Žb. 2; and Žc. 4 min of K dosing. As a reference, the spectrum of an
Au surface is included.
the H-terminated CŽ100.. Fig. 5a shows the spectra
obtained from the clean plasma-treated surface, and
Žb. and Žc. spectra after a K dosing of 2 and 4 min,
respectively. For comparison and alignment, the UPS
spectrum of a sputtered polycrystalline Au surface was
measured under the same conditions. As already men-
tioned above, the K uptake of the H-terminated sur-
face is negligible. Some minor changes in the ‘bulk’
peak located at 8.0 eV and a slight shift of the sec-
ondary electron onset at higher binding energies were
observed. The secondary electron onset shifts by ⌬ Es
0.3 eV for the 4-min dose and suggests a small increase
in the work function. The onset of electron emission
from the CŽ100. surface is detected at 1.1 eV and is
related to the location of the valence band of diamond.
The secondary electron peak for the plasma-treated
surface is split into two peaks. The relatively sharp
high-energy peak at approximately 17 eV arises from
the electron emission due to the negative electron
affinity ŽNEA. of the H-terminated CŽ100. w5x.
The UPS He I spectra of the acid-treated CŽ100. and
the changes observed for K adsorption are shown in
Fig. 6. On the acid-treated surface the ‘bulk’ peak is
shifted to a lower binding energy and is now located at
approximately 7 eV. Also, the onset of emission from
the valence band is shifted to 0.9 eV. From the onset of
the secondary electron emission at approximately 16.3
eV, it can be concluded that the work function of the
acid-treated surface is lower compared to the H-
terminated one. The sharp shoulder on the high-energy
side of the secondary electron peak suggests that the
NEA effect has not yet completely disappeared. After
evaporation and uptake of K, a shift of the secondary
electron onset to a higher binding energy Žlowering of
⌬⌽ by 2 eV. and a disappearance of the NEA effect is
observed. Due to the presence of K, some extra inten-
 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525
Fig. 6. UPS He I spectra of the acid-treated CŽ100. surface after: Ža.;
Žb. 2; and Žc. 5 min of K dosing. As a reference, the spectrum of a
clean polycrystalline Au surface is included.
sity in the regime is evident, at approximately 4, 5 and
13.5 eV.
The presence of K is seen more clearly in the UPS
He II spectra shown in Fig. 7. Curve Ža. in Fig. 7 shows
the H-terminated surface with a ‘bulk’ peak at approxi-
mately 8 eV and a smaller peak at approximately 14.5
eV. This spectrum is in accordance with results from
w7x. The onset of emission from the valence band is
detected at 1.2 eV. On the acid-treated surface Žcurve
b., the emission intensity between 0 and 2.5 eV is
greatly reduced. The ‘bulk’ peak has shifted to lower
energy, probably due to the contribution of emission
from oxygen 2p states. After 5-min K exposure onto the
acid-treated surface, spectrum Žc. was observed Fig. 7.
New emission intensity at approximately 3.8 and 17 eV
is evident. The latter peak is attributed to the emission
from the K 3p level. The peak at 13.5 eV corresponds
to the 14.5-eV peak from the H-terminated surface,
and suggests that the diamond surface structure is still
present. Reinke and Oelhafen recently demonstrated
that graphtiziation of the diamond surface is accom-
panied by the disappearance of this peak, although the
bulk contributions are nearly unchanged w6x.
4. Discussion
The results demonstrate that the adsorption of K is
very different for the H- and the O-terminated sur-
faces. It is proposed that these results are not in
contrast to the observations of Hossain et al. w2x for the
uptake of K on H-free CŽ100. surfaces. That study
desorbed the hydrogen at a higher substrate tempera-
ture Ž1400 K.. The abstraction of H leads to the forma-
tion of CsC bonding, which could have a considerable
influence on the interaction with KŽad.. Alkali adsorp-
tion ŽCs. onto a H-terminated CŽ100. surface was stud-
523
Fig. 7. UPS He II spectra of: Ža. the H-terminated; and Žb. the
acid-treated CŽ100. surface. Spectrum c shows changes in the acid-
treated surface after K adsorption Ž5 min..
ied by Diederich et al. at room temperature w3x. Al-
though the K sticking coefficient was not reported, the
authors were able to obtain a high Cs concentration on
a H-terminated surface. The differences observed on
the H-terminated CŽ100. for the K and Cs is assumed
to be due to different behavior of the alkali metals.
The ionic radius and the polarizability of Cs is larger
than that of K. It is noted that the sticking coefficient
of metals on polymer surfaces ŽH-terminated. is gener-
ally rather small.
Informations about the chemical state of the surface
oxygen can be gained from the O 1s, as well as the C
1s, spectra. However, as already stated, we are not yet
able to arrive at an absolute value for the O coverage.
The acid treatment with strong oxidizing acids should
lead to the following surface groups:
We believe that these species are present on the
acid-treated surface and give rise to the broad O 1s
spectrum observed from this surface ŽFig. 4a.. The O 1s
peak is located at approximately 532.4 eV with a half-
width of 3.4 eV. Table 2 gives a correlation between
the O 1s peak position measured by Siegbahn et al. w7x
for gas-phase species and the corresponding position
on CŽ100.. In order to achieve the alignment, it was
assumed that the position of H 2 O adsorbed on solid
surfaces is at 533.2 eV w8x. The three O 1s peaks in Fig.
4 can thus be interpreted as being due to two different
oxygen states from the acidic group Žat 531.1 and 533.4
eV.; the intermediate peak at 532.4 eV can arise from
<
᎐ C ᎐H or _rCsO groups.
<
Upon K adsorption, there was evidence in the C 1s
spectrum that the C᎐O bonding still exists Ždiscussion
524 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525

is found below.. From the peak changes after K ad- by Baumann and Nemanich w5x is y1.9 eV. On the
sorption Ždecrease of the O 1s intensity at 534.2 eV, acid-treated surface in the present study, a small struc-
Fig. 4b,c. it can be concluded that the acidic oxygen ture was still observed at the high-energy side of the
Žcontaining the OH groups. is involved. This interpre- secondary electron peak. The NEA has not completely
tation favors the build-up of a salt-like structure, where disappeared, although ␹ f 0. For the K-covered acid-
two positively charged K ␦q are bonded to the two treated surface, ␹ is found to be positive. In the XPS C
oxygens of the acidic group. In this structure, both 1s spectra, a shift in the C 1s peak of ⌬ Es 0.4 eV was
oxygen atoms are now equivalent. observed for the acid-treated surface, and a further
The difference spectrum between the acid-treated shift due to K adsorption of ⌬ Es 0.5 eV. In an en-
and the H-terminated CŽ100. surface revealed a rather ergy-level diagram, these shifts correspond to a down-
broad Ž4 eV half-width. new C 1s intensity centered at ward shift of the bulk levels due to positive surface
286.8 eV. Furthermore, a rather small negative peak charges.
was observed at 283.8 eV. The new intensity at approxi-
mately 286.8 eV is supposed to arise from C bonded to
oxygen species. Table 2 shows the possible energy 5. Conclusions
positions, again derived from gas-phase values of Sieg-
bahn et al. w7x. In order to compare the gas-phase
We briefly summarize the main conclusions of our
values with the energy position on solid surfaces, the
present work as follows:
value for CH 4 was first shifted by ⌬ Es 0.3 eV to a
higher B.E. to obtain a value for C᎐H. The position of
䢇 K adsorption at room temperature onto H-
this hydrogen-terminated carbon is assumed to be at
terminated CŽ100. is negligible. The adsorption of
284.0 eV. Bonding of acid groups should give rise to a
K requires the formation of a K ␦q species, which is
new C 1s peak located at 287.2 eV. A similar shift
hindered on the H-terminated surface.
should occur for CsO bonding. C᎐OH groups should
䢇 The acid treatment of CŽ100. leads to the formation
shift the C 1s peak to approximately 285.6 eV. These
of surface groups, like
contributions are supposed to be the reason for the
䢇 K adsorption on the acid-treated CŽ100. surface
new weak structure observed in the difference spec-
takes place with a sticking coefficient S0 f 1. The
trum Fig. 2.
oxygen coverage does not change after K adsorp-
The sharp negative structure could arise from H
tion. However, changes in the O 1s spectrum sug-
abstraction from the H-terminated CŽ100. surface due
gest the formation of salt-like species.
to the treatment with acids. For example, a shift to
䢇 C 1s spectra support the presence of different oxy-
higher B.E. occurs for the C 1s position for H 2 CsCH 2
gen-containing surface groups on the acid-treated
compared to H 3 C᎐CH 3 w7x.
CŽ100. surface. They demonstrate that K adsorption
In accordance with the observation of other authors,
does not lead to the formation of KOH or K oxides.
a sharp peak in the secondary electron emission was
observed in the UPS He I spectra from the H-
terminated surface ŽFig. 6.. This peak has been at-
tributed to the negative electron affinity of the H-
terminated CŽ100. surface w4x. The value for ␹ derived
 S. Petrick, C. Benndorf r Diamond and Related Materials 10 (2001) 519᎐525
䢇 The adsorption of K at room temperature can be
used to determine Žtitrate . surface oxygen species.
Our results contribute to the understanding of sur-
face reaction on diamond surfaces. They clarify the
nature of oxygen species on diamond surfaces.
Acknowledgements
This investigation was supported by the Deutsche
Forschungsgemeinschaft and the tri-national German,
Austrian and Swiss ŽD-A-CH. ‘synthesis of super-hard
materials’ co-operational project. We further ac-
knowledge the financial support by the Volkswagen-
Stiftung.
525
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