Diamond and Related Materials 10 Ž2001.

2049᎐2056

Chemisorption of O 2 and CO on the K-modified diamond

ž 100/ 2 = 1 surface

M.Z. Hossaina , T. Miki a , H. Okuyamaa , T. Arugaa , T. Tsuno b, N. Fujimori b,

T. Ando c , M. Nishijimad,U
a
Department of Chemistry, Graduate School of Science, Kyoto Uni¨ ersity, Kyoto 606-8502, Japan
b
Itami Research Laboratories, Sumitomo Electric Industries, Ltd., 1-1-1 Koyakita, Itami, Hyogo 664-0016, Japan
c
National Institute for Research in Inorganic Materials (NIRIM), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
d
Department of Chemistry, Graduate School of Science, Kyoto Uni¨ ersity, Kyoto 606-8502, Japan

Received 22 January 2001; accepted 4 April 2001

Abstract

The adsorption of O 2 and CO molecules on the K-modified CŽ100. surface has been studied mainly by electron energy loss
spectroscopy ŽEELS. and additionally by thermal desorption spectroscopy ŽTDS. and low-energy electron diffraction ŽLEED. at
300 K. Although O 2 does not react with the clean CŽ100. surface, it readily reacts with the K-modified surface. The adsorbed
species are characterized by the two loss peaks at 150 and 214 meV. The 150 and 214-meV losses are ascribed to the C᎐O stretch
of the C᎐O᎐C Žether. and ) C⫽O Žcarbonyl. species which are formed by breaking both ␴ and ␲ bonds of a surface dimer,
respectively. In contrast to SiŽ100., substrate oxidation mainly occurs at the top layer of CŽ100.. The CO molecule also reacts with
the K-modified surface, while it does not react with the clean CŽ100. surface. The adsorbed species are characterized by the loss
peaks at 154 meV with a shoulder at 192 meV. The 154-meV loss is tentatively assigned to the C᎐O stretch of the ŽC 2 O 2 . 2y 2Kq
complex formed on the K-modified CŽ100. surface. The shoulder at 192 meV is ascribed to the C᎐O stretch of either
ŽC 4O4 . 2y 2Kq or ) C⫽O, in which the ␲ bond is largely perturbed by the K adatoms. 䊚 2001 Elsevier Science B.V. All rights
reserved.

PACS: 82.65.My; 34.50.Dy; 81.65.Mq

Keywords: Chemisorption; Diamond; Electron energy loss spectroscopy; Oxygen

1. Introduction on the solid surfaces. The alkali promotion effect on

The effects of alkali metals on the physics and chem-
istry of the solid surface have attracted considerable
attention from both fundamental and technological
points of view w1x. Alkali metals are known to promote
the reactivity or selectivity of many chemical reactions
U
Corresponding author. Tel.: q81-75-753-3979; fax: q81-75-753-
4000.
E-mail address: nishijima@kuchem.kyoto-u.ac.jp ŽM. Nishijima..
the solid surface has been examined widely for a vari-
ety of coadsorption systems. Most of the coadsorption
studies have been performed on the metal and semi-
conductor ŽSi, GaAs, etc.. surfaces, but no works have
been done on the diamond surface to our knowledge.
While electron orbitals of the diamond surface are
significantly localized and unreactive towards many gas
molecules, whether the alkali promotion effect on the
diamond surface is different from those on the metal
and Si surfaces or not is fundamentally intriguing.
Furthermore, the alkali-modified diamond surface is

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 1 . 0 0 4 8 4 - 8
2050 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
also attractive from the technological point of view.
Alkali-modified CŽ100. has been found to reduce the
substrate work function and exhibits negative electron
affinity ŽNEA. properties w2,3x. Therefore, the alkali-
modified CŽ100. surface has a potential to be used as a
NEA device for photocathodes, secondary electron
emitters and cold cathode emitters. In order to fabri-
cate the diamond-based device, it is important to eluci-
date the chemical reactivity of the alkali-modified
CŽ100. surface towards various gas molecules.
The recent development of the epitaxial-growth tech-
nique for high quality diamond films has stimulated a
large number of investigations related to this material.
Among the low index faces, the best diamond homoepi-
taxial growth occurs on the Ž100. surface w4᎐6x. As-
grown CŽ100.2 = 1 surface is H-terminated. The clean
CŽ100.2 = 1 surface can be obtained by heating the
sample at high temperature Ž; 1350 K.. The clean
CŽ100. surface is reconstructed into the 2 = 1 structure
in which the adjacent surface C atoms are paired to
form a symmetric dimer w7,8x. The surface dimer con-
sists of both ␴ and ␲ bonds. The strong ␲ bond of the
C⫽C dimer on clean CŽ100. makes the surface unreac-
tive towards many simple gas molecules, such as H 2 ,
O 2 , CO, CO 2 , N2 O, etc. w9x. Among the simple organic
molecules, acetylene ŽC 2 H 2 . and ethylene ŽC 2 H 4 . do
not react with the clean surface, whereas 1,3-butadiene
ŽC 4 H 6 . reacts with the C⫽C dimer of the clean surface
through the Diels᎐Alder reaction mechanism w10,11x.
The alkali adsorption on the clean CŽ100. surface is
expected to enhance the reactivity of the surface to-
wards various gas molecules.
In the present work, we studied the O 2 and CO
adsorption on the K-modified CŽ100. surface at 300 K.
Neither O 2 nor CO react with the clean Ž100.2 = 1
surface. On K-modified CŽ100., O 2 is found to be
dissociatively adsorbed, which is clearly indicated by
the appearance of the 150 and 214-meV loss peaks.
The 150 and 214-meV losses are assigned to the C᎐O
stretch of C᎐O᎐C and ) C⫽O species, which are
formed by breaking both ␲ and ␴ bonds of the surface
dimers, respectively. CO is also found to be adsorbed
on the K-modified surface, which is indicated by the
loss peaks at 154 meV with a shoulder at 192 meV.
Possible reaction mechanisms of O 2 and CO adsorp-
tion on the K-modified CŽ100. surface are discussed.
2. Experimental
The experiments were carried out in an ultrahigh
vacuum ŽUHV. system with a base pressure of - 1 =
10y1 0 Torr. The vacuum chamber was equipped with a
high resolution electron spectrometer for electron en-
ergy loss spectroscopy ŽEELS., an electron optics for
low-energy electron diffraction ŽLEED., and a
quadrupole mass spectrometer ŽQMS. for thermal de-
sorption spectroscopy ŽTDS. and gas analysis. For EELS
measurements, a primary energy Ep of 6.7 eV, an
energy resolution of 14᎐16 meV Žfull-width at half-
maximum, FWHM. and an incidence angle ␪ i of 60⬚
from the surface normal were used. All EELS spectra
were recorded in the specular mode at 300 K, i.e. the
reflection angle ␪ e Žs ␪ i . is 60⬚.
The B-doped diamond film Žthickness: ; 2 ␮m. was
epitaxially grown, using the microwave plasma-assisted
chemical vapor deposition ŽCVD. method, on the Ž100.
surface of synthesized single-crystalline diamond
w12,13x. Two of the present authors ŽTsuno and Fuji-
mori. showed, by scanning tunneling microscopy in air,
that the CVD-grown surface has a Ž2 = 1. structure
w14x. The size of the substrate was 4 = 4 = 0.3 mm3. The
CVD-grown diamond surface is H-terminated and,
hence, the clean surface was prepared by heating the
sample up to ; 1350 K by electron bombardment from
the rear. The clean surface was checked by LEED and
EELS. The sample temperature was measured by using
an alumel᎐chromel thermocouple attached to the sam-
ple edge.
K atoms were deposited at - 2 = 10y1 0 torr on the
surface at 300 K using a well-outgassed chromate dis-
penser ŽSAES Getters . which was located 5 cm away
from the sample surface. The K-modified CŽ100. sur-
face was prepared by the deposition of K more than
one monolayer Ž1 ML. at room temperature followed
by heating to 320 K to avoid any island formation.
Comparing with the TDS spectra of K from KrCŽ100.2
= 1 reported previously w3x, the K coverage of the
K-modified surface in the present study is assumed to
be a physical monolayer Ž1 ML.. All gases were intro-
duced into the UHV chamber through a variable leak
valve. The amounts of gas exposures are given in l Ž1
l s 1 = 10y6 Torr s.. The Bayard᎐Alpert ŽB᎐A. gauge
filament was turned off during the doses of O 2
molecules.
3. Results
Fig. 1 shows the EELS spectra of Ža. the clean
C 100. 2 = 1 surface; Žb. the K-modified surface; and
Ž
Žc᎐g. K-modified surface exposed to O 2 with increasing
exposure at 300 K. For the clean surface, a loss peak at
90 meV and a loss plateau at 120᎐180 meV are observed
which are the characteristics of the clean CŽ100.2 = 1
surface w9x. No loss peak related to the O 2 adsorption is
observed when the clean CŽ100.2 = 1 surface is ex-
posed to O 2 at 300 K Žnot shown.. When the clean
surface is exposed to 1 M of K, the loss peaks charac-
teristic of the clean surface disappear, instead a loss
continuum appears. The loss continuum is, perhaps,
attributed to the metallic character of the K-saturated
 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056 2051

Fig. 1. EELS spectra in the specular mode of: Ža. the clean CŽ100. 2 = 1 surface; Žb. the clean surface exposed to 1 ML of K; and Žc᎐g.
K-modified surface exposed to O 2 with increasing exposure at 300 K. All spectra are normalized by the elastic peak intensities. The primary
energy Ep s 6.7 eV. The inset shows changes of the intensities of the 150 and 214-meV losses normalized by the elastic peak intensities with
increasing O 2 exposure.

surface w3x, and is produced when electrons at the
Fermi level are excited into the continuum of empty
states w15x. No loss related to the C᎐K vibration is
observed due to the low vibrational energy.
When the K-modified surface is exposed to 0.9 l O 2 ,
two intense loss peaks at 150 and 214 meV are clearly
observed. No energy shifts of the loss peaks are
observed with increasing coverage within the experi-
mental error of "12 meV. The appearance of the loss
peaks due to O 2 exposure clearly indicates that O 2
molecules react with the K-modified surface. Changes
of the intensities of the 150 and 214-meV loss peaks
with increasing O 2 exposure are shown in the inset of
Fig. 1. The intensity of the 214-meV loss increases with
increasing coverage tip to 32-l exposure. The intensity
of the 150-meV loss remains almost the same from 0.9
to 182 l of exposure. It is noted that the absolute count
rate of the elastic peak Ž1.7= 10 5 cps. drastically de-
creases Ž5.3= 10 3 cps. when the clean surface is modi-
fied by K exposure. When the K-modified surface is
exposed to O 2 , the absolute count rate of the elastic
peak increases significantly Ž3.9= 10 4 cps for 0.9 l
exposure. compared with that of the K-modified sur-
face.
Fig. 2 shows the annealing temperature dependence
of the EELS spectra of the K-modified CŽ100. surface
exposed to 182 l of O 2 at 300 K. It is observed that the
intensities of the 150 and 214-meV losses do not de-
crease up to 700 K. The intensities of both losses
significantly decrease at 900 K. At 1000 K, a further
decrease in intensity is observed. At 1300 K, the loss
peaks at 150 and 214 meV completely disappear and
the losses characteristic of the clean CŽ100.2 = 1 sur-
face reappear. These results indicate that the adsorbed
species associated with the loss peaks are strongly
bonded with the substrate.
It is noted that, after the O 2 adsorption and desorp-
tion processes, the intensity of the 2 = 1 LEED pattern
becomes weaker with high background. After three
cycles of O 2 adsorption and desorption processes, the
2 = 1 LEED pattern completely disappears. Hence,
getting a series of the TDS spectra requires many
sample surfaces, which limits the detailed TDS mea-
surements. These results are similar to those observed
in the case of atomic oxygen adsorption and desorption
processes on clean CŽ100. 2 = 1 w16x. In order to get
some information about the desorption products, TDS
spectra of masses 28, 32 and 44 were recorded after the
K-modified surface exposed to 182 l of O 2 was heated
to 1000 K. The results are shown in the inset of Fig. 2.
2052 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
Fig. 2. EELS spectra in the specular mode of the K-modified surface
exposed to 182 l of O 2 at 300 K and of the same surface with
increasing heating temperature. The primary energy Ep s 6.7 eV.
The inset shows the TDS spectra of masses 32, 44, 28 and 39. The
spectra corresponding to the masses 32, 44 and 28 are recorded after
the K-modified surface exposed to 182 l of O 2 is heated to 1000 K.
The spectra corresponding to the mass 39 is recorded after the
K-modified surface is exposed to 30 l of O 2 at 300 K Žheating rate: 8
Krs..
These indicate that adsorbed oxygen desorbs as CO
Žmass 28. at ; 1030 K. Desorption of CO from the
oxygenated CŽ100. surface is in agreement with the
previous studies w16᎐20x. The origin of the minor CO 2
Žmass 44. desorption peak at 1030 K is not known at
the present stage. The uppermost curve in the inset
shows the TDS spectrum of K Žmass 39. from the
K-modified surface exposed to 30 l of O 2 at 300 K. Two
K desorption peaks are observed at 760 and 860 K. The
desorption peaks at 760 and 860 K may be related to
the ␣ and ␤ peaks of the K-modified surface observed
at 400 and 525 K in the previous study on K-modified
CŽ100., respectively w3x. These results suggest that K is
highly stabilized due to the coadsorbed O species.
In addition to O 2 exposure to the K-modified CŽ100.
surface wO 2rKrCŽ100.x, we also briefly studied the K
adsorption on the OrCŽ100. surface wKrOrCŽ100.x.
The OrCŽ100. surface was produced by atomic O
exposure to the clean CŽ100. surface w16x. For the
KrOrCŽ100., the loss peaks characteristic of the
OrCŽ100. surface Ždiscussed later. are not observed
and a spectrum similar to that shown in Fig. 1b appears
at 300 K. When the KrOrCŽ100. is heated to 500 K,
the loss peaks at 150 and 214 meV similar to those
shown in Fig. 1c᎐g appear. These observations suggest
that K atoms simply adsorb on the OrCŽ100. and
thereby screen the C᎐O vibrational losses at 300 K.
The adsorbed K may partly desorb at 500 K and the
losses related to the C᎐O vibration appear. Thus, the
structures of KrOrCŽ100. and O 2rKrCŽ100. at 300 K
are not the same.
Fig. 3 shows the EELS spectra of Ža. the clean
CŽ100. 2 = 1 surface; Žb. the K-modified surface; and
Žc,d. K-modified surface exposed to CO at 300 K.
Unlike O 2 exposure, the absolute count rate of the
elastic peak does not increase due to CO exposure to
the K-modified surface. Hence, the signal-to-noise ratio
in the spectra for the CO-exposed surface is low. When
the K-modified surface is exposed to CO, a loss peak at
154 meV with a shoulder at ; 192 meV is clearly
observed.
Fig. 4 shows the annealing-temperature-dependent
EELS spectra of the K-modified CŽ100. surface ex-
posed to 15 l of CO. It is observed that the intensity of
the loss peak at 154 meV with the shoulder at 192 meV
does not decrease at 500 K. When the surface is heated
to 900 K, the 154-meV loss with the shoulder at 192
meV almost disappears. Comparing with the EELS
spectra in Fig. 2, it is obvious that chemisorbed species
formed by O 2 and CO exposures to the K-modified
surface are not the same. Unlike the case of the O 2
adsorption᎐desorption processes, the LEED patterns
show the 2 = 1 structure even after several cycles of
CO adsoption and desorption processes. An attempt
has been made to measure the desorption products by
Fig. 3. EELS spectra in the specular mode of: Ža. the clean CŽ100.
2 = 1 surface; Žb. clean surface exposed to 1 ML of K; and Žc,d.
K-modified surface exposed to CO with increasing exposure at 300 K.
The primary energy Ep s 6.7 eV.
 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
Fig. 4. EELS spectra in the specular mode of the K-modified surface
exposed to 15 l of CO at 300 K and of the same surface with
increasing heating temperature. The spectra were recorded at 300 K.
The primary energy Ep s 6.7 eV. The inset shows the TDS spectra of
K from: Ži. the K-modified surface; and Žii. K-modified surface
exposed to 15 l of CO at 300 K Žheating rate: 8 Krs..
TDS. Unfortunately, no clear CO desorption peak was
observed due to the simultaneous CO desorption from
the sample holder. TDS spectra of K from the K-mod-
ified surface were recorded before and after CO expo-
sure. The results are shown in the inset of Fig. 4. The
spectra Ži. and Žii. show the TDS spectra of K from the
K-modified surface w3x and the K-modified surface ex-
posed to CO at 300 K, respectively. It is observed that
the K desorption edge is shifted by ; 70 K towards
higher temperature by CO exposure. This observation
suggests that the adsorbed K is stabilized by the coad-
sorbed CO molecules.
4. Discussion
4.1. O2 exposure to the K-modified C(100) surface
In order to assign the observed losses, first we briefly
discuss several studies concerning the vibrational spec-
tra of the oxidized CŽ100. surface. Investigations of
acid-treated diamond powder by the infrared technique
have shown peaks at 212᎐220 and 136᎐155 meV, which
have been assigned to the stretching mode of the
surface carbonyl Ž) C⫽O. and ether ŽC᎐O᎐C. species,
2053
respectively w21,22x. Studies on the adsorption of water
on CŽ100. by multiple-internal-reflection spectroscopy
have assigned the observed peaks at 155 and 149 meV
to the ether-type C᎐O᎐C structure w23x. Theoretical
calculations on the monolayer O on CŽ100. have shown
multiple peaks at 145᎐155 meV, which are assigned to
the C᎐O stretching mode of the surface ether species
w24x. A recent study on the atomic O adsorption on the
clean CŽ100.2 = 1 surface by EELS has shown the loss
peaks at 113, 150, 215 and 261 meV w16x. The 113 and
215-meV losses are assigned to the bending and
stretching modes of the ) C⫽O species Žon-top O.
which is formed by the dimer ␲ and ␴ bond breaking,
respectively. The 150-meV loss is attributed to the
C᎐O᎐C species, which is also formed by the dimer
bond breaking. The 261-meV loss indicates the exis-
tence of minority O atoms almost triple bonded to the
substrate defect sites.
Since K atoms are highly reactive in nature, one
might think of ascribing the observed losses to peroxide
andror superoxide species formed on the K-modified
CŽ100. surface by the O 2 dose. According to the in-
frared studies of K oxides in the Ar matrix, the K᎐O
stretching mode is observed at 38᎐62 meV depending
on the valency of O 2 w25x. The O᎐O stretching energy
is observed at 98᎐116 meV for the peroxide ŽK 2 O 2 .
species w26x. For the superoxide ŽKO 2 . species, the
O᎐O stretching energy is observed at 137 meV w25x.
The observed loss peaks at 150 and 214 meV in the
present study are obviously out of these ranges and can
be related with the oxide species associated with the
substrate. No additional loss peak related with the
peroxide or superoxide species is observed in Figs. 1
and 2. These observations are similar to the study on
the K-promoted oxidation of the SiŽ100. surface at 300
K w27x. For K-modified SiŽ100. Ž1 ML of K., it is found
due to O 2 doses at 300 K, that oxidation of the Si
substrate takes place and K-oxides are not formed.
The 150 and 214-meV losses in the present study are
very similar in energy with those observed for the
atomic O adsorption on clean CŽ100. w16x. Hence, the
150 and 214-meV losses are assigned to the C᎐O
stretching energy of the C᎐O᎐C and ) C⫽O species,
respectively, which are formed by breaking the ␲ and
␴ bonds of the surface dimer. A schematic view of the
oxidized surface is shown in Fig. 5. The bending mode
of the ) C⫽O species has not been observed on the
K-modified CŽ100.. Formation of the ) C⫽O and
C᎐O᎐C species on the K-modified CŽ100. surface sug-
gests that O 2 molecules dissociatively adsorb on the
surface. On the K-modified SiŽ100., the Si᎐O᎐Si species
are most favorably formed and the oxidation is found
to be extended up to a few monolayers of the SiŽ100.
surface which is indicated by the significant shift of the
Si᎐O stretch energy with increasing O 2 exposure w27x.
2054 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
Fig. 5. Schematic structural models of: Ža. the K-modified CŽ100.
surface exposed to O 2 molecules; and Žb. possible products formed
by the CO exposure to the K-modified CŽ100. surface. The average of
˚ . and metallic Ž2.35 A
ionic Ž1.33 A ˚ . radii of K was considered in Ža..
In the present study, oxidation seems to occur only at
the top layer of the CŽ100. surface.
Although the crystal structure of silicon is similar to
that of diamond, the difference in the structural
parameters, electronic states, etc. seems to result in the
different oxidation process. A recent periodic density
functional calculation on the oxidation of H-terminated
CŽ100. reveals that insertion of an O atom into the
second layer distorts the crystal structure markedly and
the process is endothermic w28x. In contrast to the
diamond, previous experiments and calculations re-
vealed that an O atom can be easily inserted into the
backbone of the SiŽ100. surface w29᎐31x.
Although two losses Ž150 and 214 meV. appear si-
multaneously, changes of the peak intensities of the
150 and 214-meV losses with O 2 exposure Žinset of Fig.
1. suggest that the formation of the C᎐O᎐C species is
energetically more favorable than that of the ) C⫽O
species at 300 K.
The desorption peaks corresponding to the C᎐O᎐C
and ) C⫽O species have not been observed separately
Žinset of Fig. 2.. The single desorption peak may be
explained by considering that the desorption process
proceeds through a single transition state, e.g. the
conversion between the ether and carbonyl species
occurs prior to the desorption or that the adsorption
energy difference per O atom between the two species
is small, as calculated by Whitten et al. w32x. Recent
calculations on the oxidation of H-terminated CŽ100.
predicts that the ether species are priorily formed at
the initial stage of the oxidation of H-terminated CŽ100.
and the formation of the ) C⫽O structure becomes
easier as the O coverage is increased w28x. It is noted
that the EELS intensities of the C᎐O᎐C and ) C⫽O
species formed by atomic O exposure on the clean
CŽ100. surface at 300 K increase simultaneously with
exposure w16x.
With the experimental resolution used here, the C᎐O
stretch energies Ž150 and 214 meV. observed in the
present study are similar to those Ž150 and 215 meV.
observed for oxygenated CŽ100.. This apparently sug-
gests that the C᎐O bond strength, compared with the
oxygenated CŽ100., is not largely affected by the K
adatoms. It is difficult to understand this, as there is no
theoretical work on the electronic states involved in the
bonding of O and K with CŽ100. at the present stage. It
may be related to the contribution of the polarized
covalent bond in the bonding of alkali metal with the
substrate w33x. In the present study, the O atoms are
strongly bonded to the substrate C atoms and ulti-
mately desorb as CO at ; 1000 K. Hence, the strong
C᎐O bond strength largely dominates over the K᎐O
interaction and the K-oxides are not formed w34x.
While O 2 molecules do not react with the clean
CŽ100. surface, the dissociative chemisorption of O 2 on
the K-modified surface implies that K adatoms play a
crucial role in the dissociation of the O 2 molecules.
The role of adsorbed K in the dissociation of O 2
molecules can be explained by the alkali promotion
effect.
A large number of studies related to the alkali pro-
motion effect have been done by various experimental
techniques on both metal and semiconductor surfaces
w1x. The alkali promotion effect is generally explained
by the large decrease in the work function of both
metal and semiconductor surfaces due to the
alkali᎐metal adsorption. The lowering of the substrate
work function enhances the electron flow into the
anti-bonding molecular orbitals of the gas molecules
w35,36x. In our recent study, it was observed that the
work function of clean CŽ100.2 = 1 also drastically de-
creases Ž3.25 eV. when 1 ML of K is adsorbed on the
surface w3x. At 1 ML K coverage, the CŽ100. surface
becomes metallic with the vacuum level lying 2.2 eV
above the Fermi level. Thus, the electron flow into the
2 ␲U anti-bonding orbital of molecular O 2 is highly
facilitated on the K-pre-adsorbed surface resulting in
the dissociation of O 2 molecules.
4.2. CO on the K-modified C(100) surface
The ŽK q CO. coadsorption system has been exten-
sively investigated on various transition metal surfaces
w1x. Many studies have shown that coadsorbed K atoms
enhance the metal᎐CO bonding, weaken the C᎐O
bonding and promote the CO dissociation. Vibrational
 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
energies of CO coadsorbed with K on various metals
have been reported to be as low as 174 meV on Pt
Ž111. w37x, 174 meV on RuŽ100. w38x and 175 meV on
NiŽ100. w39x surfaces. Molecular orbitals of gas phase
CO are considered to explain the observed losses for
CO adsorption on the K-modified surface w1x. The
highest occupied state of CO is the 5␴ orbital and the
lowest unoccupied state is the 2 ␲U anti-bonding or-
bital. According to the traditional Blyholder model, the
CO molecules can bind through the donation of elec-
trons in the 5␴ orbital to the substrate, and also
through the back-donation of electrons from the sub-
strate to the empty 2 ␲U orbital w40x. If back-donation
to the 2 ␲U anti-bonding orbital is large, a CO structure
similar to the organic carbonyl with the double bond
between C and O can be formed. The lowering of the
vibrational energy Ž174 meV. of adsorbed CO on the
K-modified surface is largely explained by filling of the
2 ␲U anti-bonding orbital where the bond order be-
comes less than 2 w41x. It is noted that the C᎐O stretch
energies of the gas phase and carbonyl CO are 266 and
; 212 meV, respectively w42x.
The loss energy at 154 meV observed in the present
study is much lower than that observed on the metal
surfaces mentioned above. Possible explanations for
such a low C᎐O stretch energy are: Ži. the CO molecule
completely dissociates into C and O atoms upon ad-
sorption; Žii. the CO molecule forms a CO᎐K complex
or CŽ100. ᎐CO᎐K complex in which the C᎐O bond is
largely perturbed by the adsorbed K. If CO molecules
completely dissociate into C and O atoms, then O
atoms would react with the dimers underneath, result-
ing in the formation of the ) C⫽O and C᎐O᎐C species
as we observed in the case of O 2 adsorption ŽFig. 1..
However, no loss peak at 215 meV is observed in Fig. 4,
as well as no degradation of the LEED pattern is
observed even after several cycles of CO adsoption and
desorption processes. Hence, the possibility of the dis-
sociation of CO molecules into C and O atoms can be
ruled out.
Since the ␲ bond which is formed by the overlap of
two dangling orbitals of the clean CŽ100. surface is
largely perturbed by the adsorbed K, it is likely that
CO molecule reacts with the dimer to form a bridging
) C⫽O species as shown in Fig. 5b Ži.. Depending on
the strength of the interaction of the ) C⫽O species
with K-adatoms, the C⫽O bond can be weakened or a
complex like C᎐OyKq might be formed. It is noted,
however, that in order to form the COyKq, the C has
to be three-coordinated with the substrate, which seems
unlikely on the CŽ100. surface where the electron or-
bital is significantly localized and highly directional. In
the complex like ) C᎐OyKq, the C᎐O stretch energy
is expected to be approximately 136 meV, as observed
in the CH 3 ᎐O᎐K complex w1x.
The lowest vibrational energy of coadsorbed CO is
2055
observed using EELS on the K-adsorbed Cu Ž110.
surface by Lackey et al. w43x. They reported that CO
exposed to Cu Ž110. covered with 1 ML K shows the
C᎐O stretch energy at 151 and 195 meV, which may be
associated with the C᎐O bond order of approximately
1.2 and 1.7, respectively w44x. By comparison with the
infrared spectra of solid salts of alkali metals and C᎐O,
Lackey et al. suggested the formation of adsorbate
complex containing polymeric CO anions of the form
ŽC qOq . 2y with q s 2 or 4 wFig. 5b Žii,iii.x.
The loss energies observed in the present study are
very close to those observed for the COrKrCuŽ110.
system w43x. Thus, it is expected that a similar kind of
complex is formed by CO exposure to the K-modified
CŽ100. surface. The inorganic chemistry of alkali met-
als has been extensively studied and it is now accepted
that, under favorable conditions, sodium and potassium
can react with CO to give salts of the general formula
mentioned above. At 1 ML K coverage on CŽ100.
Žwithout CO., it is found that the adsorbed K is nearly
neutral in the charge state w3x. From this point of view,
the formation of the CO᎐K complex on the KrCŽ100.
surface is likely. Thus, we suggest that the 154-meV
loss is due to the C᎐O stretch of the ŽC 2 O 2 . 2y 2Kq
complex formed on the K-modified surface. The
shoulder at 192 meV can be ascribed to the C᎐O
stretch of either the ŽC 4 O4 . 2y 2Kq complex or ) C s O
species where the ␲ bond is perturbed by the K
adatoms as observed on metal surfaces.
5. Conclusion
Chemisorption of the O 2 and CO molecules on the
K-modified CŽ100. surface has been studied by EELS,
TDS and LEED at 300 K. The important results are
summarized as follows:
1. Although O 2 does not react with the clean CŽ100.
surface, it readily reacts with the K-modified sur-
face at 300 K. Two different chemisorbed species
are observed which are characterized by the loss
peaks at 150 and 214 meV. The loss peaks at 150
and 214 meV are ascribed to the C᎐O stretch of
C᎐O᎐C Žether. and ) C⫽O Žcarbonyl. species,
which are formed by breaking both ␴ and ␲ bonds
of the surface dimer, respectively.
2. The K atoms are active essentially in the dissocia-
tion of the O 2 molecules, but not in the CŽ100. ᎐O
bond. The large decrease of the work function of
CŽ100. due to the K adsorption Ž3.2 eV at 1 ML K.
facilitates the electron transfer to the 2 ␲U anti-
bonding orbitals of O 2 resulting in the dissociative
adsorption of O 2 molecules. In contrast to the
SiŽ100., the K-induced oxidation occurs mainly at
the top layer of CŽ100..
2056 M.Z. Hossain et al. r Diamond and Related Materials 10 (2001) 2049᎐2056
3. The CO molecule reacts with the K-modified sur-
face while it does not react with the clean CŽ100.
surface. The adsorbed species are characterized by
the loss peak at 154 meV with a shoulder at 192
meV. The 154-meV loss is tentatively assigned to
the C᎐O stretch of the ŽC 2 O 2 . 2y 2Kq complex
formed on the K-modified CŽ100. surface. The
shoulder at 192 meV is ascribed to the C᎐O stretch
of either the ŽC 4 O4 . 2y 2Kq or ) C⫽O in which
the ␲ bond is largely perturbed by the K adatoms.
Acknowledgements
This work was supported in part by Grants-in-Aid
from the Ministry of Education, Science, Sports and
Culture ŽJapan..
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