Pro9msrin Sutfacc Scimce. 1979.Vol. 9, pp. 143-W. PergamonPress.

Printedin Great Britain

ULTRAVIOLET PHOTOEMISSION STUDIES OF

MOLECULAR ADSORPTION ON OXIDE SURFACES

VICTORE. HENRICH
Lkpatimmt of Engiwwing and Applied Science, Yale University,
New Haven, Connecticut06520.U.S.A.
Abstract-This paper reviews the current status of ultraviolet photoemission (UPS) measurementsof
the interaction of molecules with the surfaces of metal oxides. A brief summary of the ekctronic,
geometric and compositionalproperties of atomically ckan oxide surfaces is given, followed by a
survey of the various adsorbatelsubstrate systems that have been investigated by UPS. Essentially
all of that work to date has been on single-crystaloxide substrates. A brief description is also given
of the various theoretical methods that are being used to study molecule/oxide interactions.

content!3
1. Introduction 143

2. Structure of Clean Oxide Surfaces

A. Composition f:
B. Geometry 145
C. Electronic structure I46

3. YoleeOar Adsorption on Single-crystal Oxides 147

147
B: Adsorption of 02 on Ti02 and SrTia IS2
C. Adsorption of Hz0 on TQ and SrTia I56
D. Adsorption of Hz on TiO, lS8
E. Adsorption of 01 on TiO, (x - I) I59
F. Adsorption of Hz0 on Ala
G. Adsorption of C2H2on NiO E

4. Theoretical Calculations of Molecular ,Adsorption on Oxide .Surfaces 161

5. Future Directions 162

References 163

DV discrete variational
electron-energy-loss spectrosc y
linear combination of atomic or“k tats
local density of states
LEED low-energy-electron diffraction
self-comustent field
&F scattered wave
ultra-high vacuum
!z ultraviolet photoemission spcctros~~p~
XPS X-ray photoemission spectroscopy

1. Introduction molecules with oxide surfaces. Over the last few

The surface properties of metal oxides, and
particularly their interaction with adsorbed mole-
cules, have been technologically important for
‘many years. The poisoning of a thermionic emit-
ter: the activity and selectivity of an oxide cata-
lyst: the sensitivity of an electron multiplier to
ambient gases: the interaction of a small catalyst
particle with its support: the long-term stability of
MOS devices and negative-electron-affinity photo-
cathodes; the efficiency with which hydrogen
can be produced from sea water by photolysis-all
of these involve the interaction of atoms and
years, surface scientists have taken an increasing
interest in oxides, and oxide surfaces have been
studied using a wide range of techniques.
The present paper will review the current status
of research on molecular adsorption on metal
oxides by means of ultraviolet photoemission
spectroscopy (UPS). The reason for restricting the
scope of the paper to UPS studies is two-fold.
First is simply a space requirement; a comprehen-
sive treatise on studies of adsorption on oxides
would occupy an entire book. Secondly, UPS has
given us by far the most detailed information on

143
144 VICTOR
E. HENRICH
the electronic nature of adsorbatelsubstrate inter-
actions. The method is inherently surface sen-
sitive, has good energy resolution and is parti-
cularly useful for studying electronic states in the
vicinity of the vacuum level (+-50eV). where the
action is in chemisorption. While techniques,
such as infrared absorption, electron-spin
resonance, thermal- and electron-stimulated
desorption, low-energy-electron diffraction
(LEED). X-ray photoemission (XPS), Auger and
electron-energy-loss spectroscopy (ELS), work
function measurements. etc., are also extremely
useful, we will only mention a few results as they
relate to UPS measurements.
The main technique that is used in ultraviolet
photoemission studies of adsorption is UPS
difference spectroscopy. This rather pretentious
title simply refers to subtracting the UPS spectrum
for a surface before adsorption (or some fraction
thereof, to compensate for adsorbate attenuation
of substrate emission) from the spectrum after
adsorption; the remainder is the “difference spec-
trum”.“’ In the limit of weak adsorbatelsubstrate
interaction, the difference spectrum reflects the
electronic structure of the adsorbed species; Since
the interactions are rarely very weak, care must be
taken in interpreting difference spectra, since fea-
tures arising from changes in substrate electronic
structure will also be present. Also, when working
with insulators or semiconductors, it is generally
necessary to shift the clean-surface spectrum in
energy relative to the adsorbed spectrum before
taking the difference to compensate for band
bending: determining the amount of this shift is
not,always trivial, and small differences in align-
ment can lead to large changes in the difference
spe+ra (see the discussion of adsorption on ZnO
in 53A).
In 52, we briefly summarize the properties of
atomically clean oxide surfaces, since these must
be understood in order to interpret adsorption
measurements. Section 3 reviews the particular
molecule/oxide systems that have been studied by
UPS: almost all of that work to date has been
performed on single-crystal substrates. Section 4
mentions the theoretical approaches that are being
taken to study adsorption of oxides, while
$5 discusses some of the most fruitful directions
for future research.
2. Structure of Clean Oxide Surfaces
Before discussing the adsorption of molecules
on oxide surfaces, we will briefly review what is
known about the properties of atomically clean
oxide surfaces. Due to the relatively small number
of surfaces that have been studied carefully to
date, it is not possible to draw very many general
conclusions. but some trends are beginning to
develop. The detailed properties of specific sur-
faces will be treated in $3 when we discuss ad-
sorption on those surfaces.
A. composition
One of the main difficulties in working with
oxides, as with any compound, is the possibility of
a wide range of composition in the surface region.
Many structures and compositions that cannot
exist in the bulk are allowed in the region of
reduced symmetry at a surface. Even surfaces that
are ideal terminations of the bulk can have
different atomic arrangements and compobitions
depending on which lattice plane is the topmost
one. In the perovskite (ABC&) lattice, for example,
there are two possible (100) surfaces, one consis-
ting of a B02 plane and the other consisting of a
plane with A0 composition.‘*’ Unlike the case of
the zincblende or wurtzite (A& lattices, where the
bond strengths are such that a crystal with (111)
faces will always have an A-face on one side and a
B-face on the other, there is an equal probability
of having either a B02 or an A0 face. An actual
fractured surface will thus contain equal areas of
each type. The two types of surfaces should have
quite different electronic and chemical proper-
ties,‘-’ and yet any experiment will sample both
surfaces simultaneously. It is then difficult, if pos-
sible at all, to separate the features due to each
type of surface.
The stoichiomctry of the surface of a com-
pound can be altered by the treatments that are
usually used in preparing nearly perfect surfaces:
chemical etching. ion bombardment, annealing,
etc. In the case of SrTiG, for example, it has been
found that simply rinsing a sample in distilled
water preferentially removes Sr ions from the
surface,“’ and it is very difficult to restore the
surface composition to that of the bulk by means
of further processing.‘6”’ Hence, the only reliable
method of preparing surfaces having the stoi-
chiometry of the bulk is to cleave them in an
ultra-high-vacuum (UHV) environment. Un-
fortunately, many oxides do not cleave in the
sense of preferential fracture along a particular
crystal plane, and we will use the word “fracture”
to describe such samples; we will consider the
geometry of fractured surfaces in 82 below. (Pho-
tographs of typical fractures for Ti02 and SrTiO,
are reproduced in Ref. 8.) However, regardless of
the geometric character of the fracture, one can
assume that the composition of the bulk is
retained. A surface prepared in any other manner
cannot be assumed u priori to have bulk stoi-
chiometry, and its Auger or X-ray photoemission
(XPS) spectra should be compared with those for
a vacuum-fractured surface in order to determine
its actual composition.
Ion bombardment is especially troublesome
with respect to altering surface composition.
The usual effect is a preferential removal of
oxygen, resulting in a reduced, metal-rich sur-
face.‘6.7.e151
In the case of Ti02 and SrTiO3.
this effect has been used to advantage to produce a
controlled density of surface defects’6*‘0’(see 03
 Ultraviolet photoemission studies of mokcular adsorption on oxide surfaces
below), but it complicates the preparation of
nearly perfect surfaces. For TiQ, it has been
found that annealing to about lOOOK in vacuum
after ion bombardment restores the surface to bulk
stoichiometry by diffusion of oxygen ions from the
bulk “a”) but a similar process does not work in
the iase of SrTi0,.f6*” The only procedure that has
been found to restore a SrTiG surface to bulk
composition is inert gas ion bombardment at about
900K; this process has only been used on the
SrTiG( I 11) surface.“’ For MgO, on the other
hand, ion bombardment does not change the sur-
face composition, and MgO(100) surfaces prepared
by 5OO-eV Ar’-ion bombardment are indis-
tinguishable from vacuum-cleaved surfaces.“~“~
Inert-gas ion bombardment has also been found
to remove oxygen preferentially from ZnO sur-
facesob”’ One procedure that has been adopted
for the preparation of presumably stoichiometric
ZnO surfaces is ion bombardment at 700 K fol-
lowed by cooling to room temperature and sub-
sequent annealing to 700 K.‘*’ An alternative pro-
cedure that has been used consists of room-tem-
perature ion bombardment followed by annealing
in vacuum at 1000K and s&sequent annea&g in
8 x IO-’ Torr 02 at 700 K.““‘) The latter treatment
was found to optimize the quality of LF$ED pat-
terns from the (lOi0) face.“” However, direct
comparisons between surfaces prepa& uaiug
these procedures and vacuw surfaces
have not yet been performed.
Damage produced by electron bombatdment
(electron energy b 5 keV) is also a serious problem
in the study of oxide surfaces.(~W’XHP-W As in
the case of ion bombardment, electron bombard-
ment tends to break cetion-anion bonds and
remove oxygen preferentially from the surface.
However, the response of a part&&u oxide to
electrons can be entirely di&eut from its res-
ponse to ions. A surface electronic state, which
probably consists of a surface oxygen vacancy (or
at least displacement of surface oxygen ions), can
be produced by electron bombardment of
MgWOO) surfaces, but no such state is produced
by ion bombardment (at least for ion energks less
than 1 keV).‘“’ Electron bombardment of SiO,
produces drastic changes in composition, releasing
oxygen and reducing much of the surface region to
elemental silicon.-’ Ion bombardment,
however, has essentially no dFect on the surface
stoichiometry of bulk SiO, samplc~.~ The tran-
sition-metal oxides and perovskites exhibit
changes in various electron emission spectra, due
also to preferential removal of oxygen, after
several minutes of exposure to the typical electron
beams used in Auger and energy-loss spectros-
copy: 1-5 keV, 10-50 ma/cmz~~~‘o*‘3*‘4’ However, it
is possible to measure Auger and ELS spectra on
TiO, and SrTi03 rapidly enough to obtain good
signal-to-noise without producing measurable
damage.'6.7.10,131
Electron-beam-induced changes in
145
surface composition have not been observed in
Zn()."9*l"
Another effect that can change the stoi-
chiometry of oxide surfaces is photodissociation
accompanied by the release of oxygen. This effect
seems to be strongest for photon energies close to
(but larger than) the bandgap and is seen in
ZIQ~’ TiG and a few other oxides. However, no
effects of photodissociation of oxides in the pho-
ton energy range generally used for UPS (i.e.
15-U) eV) have been reported.
Annealing of oxides to temperatures where
sublimation becomes appreciable can also alter
surface composition. In the case of ZnO, heating
to temperatures >750 K causes a preferential
sublimation of oxygen, resulting in O-deficient
surfaces.o”
In summary, anything that is done to an oxide
surface can, and often will, change its com-
position. In almost all cases, the surface will
become oxygen-deficient.
.
R- Gcawry
The atomic geometry of a number of oxide
surfaces has been examined qualitatively by low-
energy&c&on diBa&on (LEED), but only a few
surfaces have been studied quantitatively. LEED
intensity proflIes have been measured for
MgGWlO~~ and ZuO(OtKll)-Zn, woib0, (ioio)
and(1la),‘=‘- and these have been compared
with dynamkal nruhiploscettering calculations.‘*
y, For MgO(lOO),the LEED patterns exhibit the
symmetry of the bulk,Ws’ and calculations in-
corporating relax&m and rumpling (i.e. outward
motion of anions relative to cations in the surface
plane) indkate a relax&m of the top plane of less
than3%andarumphngofnomorethanaafew
percent.- The sensitivity of LEED spectra to
rumpling has not yet been thoroughly investigated,
howe~er.~’ For ZnO, comparison of LEED cal-
culations_with experimental I-V data indicates that
the @001)-0 and (11%) surfaces are very nearly
truncations of the bulk,- whik the (OOOl)-Znface
exhiits a relaxation of the top plane of Zn atoms
by about 0.2 A inward,W and the (ioio)surface
has the Zn ions relaxed 0.45 f 0.1 A inward and the
0 ions relaxed 0.05 &0.1 A inward.“” Reconstruc-
tion has been reported for the polar surfaces of
ZnO, and steps have been observed on both polar
and nonpolar faces*--”
Several Tiol surfaces have been studied quali-
tatively by LEED (i.e. only the symmetry of the
LEED patterns has been examined).““*‘3”’ The
(110) surface is stabk at all temperatures and
exhibits only (1 X 1) LEED pattems.“‘“*“’The (001)
surface is unstable and reconstructs on heating to
(110) and (100) facets.‘4’ The (100) surface exhibits
three different reconstructions depending on
annealing temperature: (1 x 3), (1 x 5) and (1 x 7)
for temperatures of 900, 1100 and 1500K, respec-
tively.“” The SrTiO,( 111) surface exhibits a (1 x 1)
146 vlcroa
pattern after annealing, but a complex, faceted
pattern can be produced by ion bombardment at
900 K.” The SrTi~(100) surface also exhibits (1 x
1) LEED patterns (Fii l(b)).@’
The LEED patterns from vacuum-fmctured
Tio2 and SrTiO, are generally poor (i.e. weak spot
intensities relative to the background, spots
somewhat difhlse). although they do exhiit the
basic symmetry of the nominal fracture plane. A
LEBD pattern for a fractured SfTiO3(100) surface
is shown in Fig. l(a). After anneahng to about
12OOK. the LEED pattern improves to that
expected for a nearly perfect surface [Fig. l(b)].
The poor quality of the LEED patterns on frac-
tured TiG and SrTiQ surfaces is consistent with
UPS determinations of the density of defect-
associated electronic states on those surfaces
(PZC).“‘”
FIG.I. LEED patterns(electron energy = 95 eV) for a vacuum-fractud SrTiOWO) surface (a) before
and (b) after annealing to about I#)0 K.
E. HENNCH
c. Elecmmk-
Compared to metals and semiconductors,
knowledge of the surface electronic properties of
oxides is meager. UPS and ELS measurements on
well characterized surfaces have only been pcr-
formed for a few oxides. We will consider each of
those surfaces in 03 when we discuss the UPS
data on adsorption, but we will make a few general
comments here. Nearly perfect surfaces of metal
oxides that have empty cation-derived bulk con-
duction (bands (e.e MI@, TX&, SrTii, ZnO,
St& AM) do not exhibit a gross transfer of
charge between surface anions and cations relative
to the bulk (i.e. if there is any transfer, it is less
than about 0.1 electron per surface ion). Such a
charge transfer would be seen in UPS spectra as
occwied states in the bandnarror conduction band
observed. Charge
 Ultraviolet photoemission studies of molecularadsorntion on oxide surfaces
transfer has been found to accompany defect
formation on those oxides,‘“*‘“.‘3’and that will be
discussed in 63 below. For oxides having partially
filled conduction bands (e.g. NiO, T&a, TiO, (X =
1). MnO, Fe& etc.), anion-cation charge transfer
between surface atoms would be much harder to
determine from UPS spectra, since it would ap-
pear only as a change in the intensity or width of
emission peaks due to bulk bands;“” no attempts
have been made to date to determine the extent of
any such transfer.
Very little is known about the spectra of empty
surface states on nearly perfect oxide surfaces.
Tia and SrTiO, do not exhibit any energy-loss
features corresponding to empty final states in the
bulk bandgap.‘6.‘o)In ZnO, one group has observed
an ELS peak at 2.8eV,‘&’ less than the bulk
bandgap of 3.2 eV, but that peak has not been seen
by other groups. MgO exhibits a strong surface
loss peak at 6.1 eV, less than the bandgap of
7.8eV, which clearly indicates an empty bandgap
surface state.“” For SQ, three energy-loss peaks
are observed at energies less than the bandgap on
oxidized silicon,‘“’ vacuum-fractured fused silica,
etc.,‘=’ but experiments have not yet been per-
formed on vacuum-fractured single-crystal quartz.
However, since the same three loss features are
seen on all other types of SiO, surfaces, there is
strong reason to believe that they do arise from
empty intrinsic surface states.‘u’ Simii loss
peaks have been observed for G& layers on
Ge.“”
8.MoleeukrAdsorp&mou~Gxkks
Although one of the main goals of the surface
scientist is to understand the mechanisms of
heterogeneous catalysis involving complex mole-
cules on real catalyst surfaces, basic studies begin
with systems that can be interpreted as completely
and unambiguously as possible-simple molecules
on nearly perfect single-crystal surfaces. With the
exception of the work on defect surfaces of TQ
and SrTiO3 described below, all of the UPS
studies to date of the changes in electronic struc-
ture during chemisorption have been performed
on nearly perfect surfaces. We will discuss each
oxide separately in the following sections.
A. ZOO
ZnO was the first oxide on which molecular
adsorption was studied by UPS. The changes that
are produced in its semiconducting properties by
the adsorption of various gases have been studied
by Tans of bulk. transport measurements for
many .years.‘46’ The first UPS measurements on
ZnO were made by Powell et al.“” in 1972, but
they only studied vacuum-cleaved (IOiO) surfaces.
Rubloff, Liith and Grobman at IBM began study-
ing the adsorption of hydrocarbons on ZnO in
1975.‘“’ All of their work to date has been on
as-grown, non-polar (ioio) “prism” surfaces
147
cleaned by direct resistive heating to about 1800 K
in UHV. This procedure was shown to give the
same ELS spectra as for (1010) surfaces cleaved in
vacuum,(&) although a preferential sublimation of
oxygen from (loio) surfaces at temperatures
above 750 K has been reported by G&XL”* Table
1 lists the molecules whose adsorption has been
studied by the IBM gro~p.‘~.‘~’
A sufficiently large number of molecuks has
been examined to show clearl_y the trends in
molecular adsorption on ZnO(1010).‘“s3’ Adsorp-
tion was studied at both 120 K and 300 K. Some
molecules (C&L, Ht, 02 and CO) produced no
changes from the UPS spectra of clean ZnO(lOi0)
at either temperature, except for 0.1-0.3 eV band
bending, indicating essentially no adsorption.
(Recent work by Gay et ul.“=‘isin disagreement with
those results for CO; this will be discussed below.)
Only C~HJN and HCOOH were found to adsorb at
300 K. The remainder of the molecules adsorbed
only at 120 K.
As an example of the changes in the molecular
orbital structure of molecules adsorbed on
ZnOGOiO), the results for C& adsorption from
Ref. 49 are shown in Fig. 2. Figure 2(a) shows the
UPS spectra for clean (dashed curve) and C&Is-
covered (solid curve) surfaces at 120 K. Figure 2(b)
shows the difference spectrum (with the clean-
surface spectrum attenuated by 50%) for adsorbed
Cd&, and Fig. 2(c) shows the gas-phase CsHs
spectrum, measured with the same resolution as for
the adsorbed spectra, for comparison. A uniform
extra-molecular relaxation/polarization shift,‘lJ2’
AE,,,, of 1.3 eV (toward smaller bindingenergy) is
found for all but the three highest-lying molecular
orbitals. The highest-lying (a) orbital is shifted
toward tighter binding by 0.4eV (A&), while the
next two orbitals, having mixed 7r and ‘a character,
have A& = 0.2 eV. The fact that the adsorbed
molecule clearly retains the basic molecular orbital
levels of the free molecule indicates that it does not
dissociate upon adsorption. Since the three orbitals
that are shifted toward tighter binding relative to the
rest of the molecular spectrum are presumably the
ones involved in bonding to the ZnO substrate, the
molecule is most likely lying flat on the surface.‘49’
The bonding shifts seen for the second and third
orbitals in Cd& are somewhat unusual in that only
the highest-lying orbital is shifted (in addition to
A&,) for most adsorbates. Figure 3 shows the
more typical case of C&O and CH3OH adsorbed
TAFILE 1. Molecules adsorbed on
Zn0(liOo) (Refs. 48-53)
C&N Co,
%
H(%$O &3$0
c&l (CH3)CCH
CH,OH C% HzCO
(CH3kCO HCOOH
148 VICTOR E. HENRIM

CH,OH, respectively. The remainder of the orbi-

tals have a uniform A& of 1.5eV and 1.8eV,
respectively. Since only the O-lone-pair orbitals
are involved in the bonding, the molecules are
presumably standing on the surface with their 0
atoms down. There is clearly no dissociation of
either molecule upon adsorption.
The above examples show the usual situation
for molecules adsorbed on ZnO(10~0). The
highest-lying, unsaturated ?r or lone-pair orbitals,
which physically protrude from the molecule, are
the dominant bonding orbitals.‘4BJ” The uniform
relaxation/polarization shift of the remainder of
the orbitals varies from 0.3 eV to 2.0 eV, values
similar to those found for. adsorption on metals.‘s2’
With the exception of HCOOH, to be discussed
below, the molecules do not dissociate.
Three molecules studied-H&O, H(CHX0
and (CH,#O-exhibit non-xero bonding shifts of
deep-lying 0rbitaLs when adsorbed on ZnCXlOTO),
‘24 I ,b ,’ ,‘6 ,I ,’ ,I 3
23
ELEckmeALER&ul
I4 as well as on some metal surfaces.‘m Fii
shows data from Ref. 52 for chemisorbed
4

H(CH,)CO compared to the UPS spectrum of the

Fffi. 2. (a) UPS spectra (kv = 40.8 ev) for the ZnOf liOO1
face at 120 K. clean (dashed curve, No(E)) and in the gas-phase molecule. In addition to the bonding
presence of a C& ambient solid curve, N.&E)); (b) shift of the highest-lying, O-lone-pair orbital
diikrence spectrum N.&E)- I NdE): (c) UPS spectrum (which is expected), the peak at a binding energy
for gas-phase CA at hv = 40.8 eV (from Ref. 49). of about 16eV is also shifted toward tighter bind-
ing. That peak turns out to arise from an in-plane
7~ orbital (see the diagram of the molecule in Fig.
4(a)), which has a large component of 0(2p,)
character, as does the O-lone-pair orbital. It is thus
not unreasonable that such an orbital should shift
in a mater analogous to the lone-pair orbital.
However, upon chemisorption, the photoemission
peak at about 19 eV, shifts by 1 eV toward smuller
bindin& relative to the other orbitals. This rather

I ~H(CH&O hv=40.8eV 1 1 H
o=c’ -z

I CH,CtiW PHASE
I\ h I 1

FOG.3. (a) UPS difference sp@um for adsorbed C$&O

on ZnO(liO0) at 120 K and kv =40.8eV, compared to
the UPS spectrum of gas-phase CJGO at 40.8eV; 0~)
UPS difference spectrum for adsorbed CHaOH on
ZnO(l100) at 120K and hv = 40.8 eV compared to the
UPS spectNm of gas-phase CHsOH at hv = 40.8eV
(from Ref. 49).
Pm. 4. UPS spectra at hv - 40.8 eV for H(CH&O; (a)
on ZnO(lOiO) at 12OK.‘* only the most kkly chemisorbed on evaporated _W at 120K. 68 L exposure:
bound molecular orbital,
which for both of these (b) chemisorbed on ZnO(1100) at 120K. 5 x W’Torr
molecules is an O-lone-pair orbital, is shifted, ambient: (c) gas phase at hv = 40.8 eV (from Ref. 52).
with A&, = 0.6 eV and 0.4eV for GH.0 and
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces
unexpected behavior can he understood from the
fact that that orbital is a a& of purely s-charac-
ter-the only orbital in the spectrum that is not of
predominately p-character. It might therefore be
expected to behave in a different manner from the
others and more like the deeper-lying core ievels,
which generally exhibit larger relaxationlpolariza-
tion shifts than do valence levels.‘s2’
The dissociative chemisorption of HCOOH on
ZnO(lOi0) has also been studied by UPS,‘_“’and
Fig. 5(a) shows the spectra for a clean surface
(dashed curve) and that surface after exposure to
IO L (iL = 1 Langmuir = 10dTorr-set) of
Fw. 6. Model for chemisorbed CO and 0 on ZnO(liOO)
HCOOH at 120 K. The difference spectrum for
adsorbed HCOOH is the solid curve in Fig. 5(b).
Unlike the other hydrocarbons studied, this
difference spectrum does not resemble the gas-
phase HCOOH spectrum, suggesting that HCOOH
has dissociatively chemisorbed. In an attempt to
determine the nature of the adsorbed species, CO
and H2 were simultaneously adsorbed on a clean
(1010) surface at 120 K (the mixture would not
chemisorb at 3OOK), giving the difference spec-
trum shown by the dashed curve in Fig. 5(b).
(Recall that neither CO nor H2 alone would adsorb
at 120 K.) The difference spectra are compared to
the gas-phase spectrum for CO in Fig. 5(c). L&h et
al (” interpret the spectra as indicating that
H&XH decomposes into CO and atomic 0, the
Wer illkmd from the peak in the difference
specmun at lOeV, which is absent for CO alone.
Based on the observed bonding shifts, the authors
propose the adsorption geometry shown in Fig. 6.
ZnO (IiOO)HCOOH
10)
.H
1 1 / 180 K in the absence of H2. CO does not physisorb
24 20 16'li 8 '
ELECTRON BINDING ENERGY WI
FIG. 5. (a) UPS spectra of clean ZnO(l@IO) and after
IOL exposure to HCOOH; (b) difference spectra for
10 L HCOOH exposure at 300 K (solid curve) and co-
exposure to CO+ Hz ambient (2 x lo-‘Ton) at 120 K
(dashed curve); (c) UPS spectrum for gas-phase CO at
kv = 40.8 eV (from Ref. 51).
149
-C-AXIS-
(from Ref. 51).
The type of adsorption pictured in Fig. 6 points
up one of the main dil%ences between chem-
isorption on oxides and on metals or elemental
semiconductors. On non-polar oxide faces, both
cations and anions are available for bonding,
whereas elements offer only one type of substrate
atom. The presence of cations and anions offers
the possibility of more complex bonding inter-
actions, as well as charge transfer between the
adsorbate and both positive and negative ions. The
full implications of this additional degree of
freedom are far from being understood at present.
Recently, Gay cf u!.~*“’ have been studying
the adsorption of CO, NH,, 02, HI, COZ and
Hi0 on the (OOOl)-Zn, (OOU&O, (1010) and
(ll20) faces of ZnO by UPS. Their surfaces are
prepared by cutting, polishing and etching of the
desired face, followed by Ar+-ion bombardment at
7OOK. cooling to room temperature and sub-
sequently annealing to 7OOK in vacuum. This
procedure produces surfaces exhibiting excellent
LEED patterns. Since annealing is limited to
7OOK. the polar faces do not exhibit any of the
reconstruction that has been seen for the (WOl)-
Zn and (000&O faces annealed at temperatures
greater than 900K.‘2910’Gay ef al. have not yet
compared their LEED intensities to those for
either vacuum-cleaved surfaces or as-grown (1070)
surfaces; the latter is important in interpreting the
results for CO adsorption (or the lack thereof) on
ZnO. To date they have studied the adsorption of
CO and NH3 in detail on all four faces, for sub-
strate temperatures from 80 K to 450 K and am-
bient gas pressures up to 10m5Torr.
Gay et u/.~) find distinctly different results for
CO adsorption than do L&h d aL”” They find that
CO does chemisorb on all four faces up to about
down to 80 K, and H2 does not’adsorb at all over
the temperature range investigated. The amount of
CO adsorbed was found to depend on ambient CO
pressure rather than on exposure, necessitating
measurements over a wide pressure range.
Photoemission from the molecular orbitals of
adsorbed CO overlaps that from the strong Zn(3d)
150 VICTORE.
band, complicating the determination of accurate
UPS difference spectra. Slight shifts of the clean-
surface spectrum relative to the spectrum with
adsorbed CO can produce either a two- or three-
peaked difference spectrum for adsorbed CO, as
shown in Fig. 7. It is not obvious which is the
correct spectrum, since CO adsorption on metals
often results in a large bonding shift of the 50
orbital, placing it on top of the 1~ orbital and
giving a two-peaked difference spectrum.
However, weakly adsorbed CO should have a
three-peaked spectrum more like that of the free
CO molecule [see Fig. 5(c)]. The experimental
situation is further complicated by a narrowing of
the Zn(3d) band upon CO adsorption, which can
result in spurious peaks in the difference spectra.
(Such peaks are not spurious in the sense that they
do represent a real narrowing of the Zn(34 band;
they should not, however, be associated with the
molecular orbital structure of adsorbed CO.) The
narrowing is most likely due to depopulation of an
intrinsic surface state on the clean ZnO surface,
but the details of such a state have not been
investigated. A similar narrowing of the valence
band on adsorption, probably corresponding to
depopulation of a Wed intrinsic surface state at
the upper edge of the valence band, is also obser-
ved on the (OtlOl)_Zn face. The subtraction pro-
cedure finally adopted by Gay et al.‘” consists of
maximixing the overlap of structum in the valence-
FIG.7. -UPS difference spectra for CO chemisorbed on
ZnOUOlO) for various shifts of the abscissa of the clean
surface spectrum relative to the CO-covered Spectrum:
(a) -0.025eV; (b) -0.075;‘4; (c) -0.125eV (from Ref.
HENRICH
band region (Fig. 7(c)), which results in three-
peaked difference spectra similar to those of Liith
et al!” for adsorption on all four crystal faces.
Both groups thus agree that CO bonds to ZnO via
its So and la orbitals.
In spite of the complications discussed above,
the kinetics of CO adsorption can be studied by
monitoring the amplitude of the photoemission
peak due to the 4u orbital, which is well separated
from the ZnQd) band. Gay et d’= have studii
these kinetics for a wide range of temperatures
and pressures on all four faces, and Fig 8 shows a
plot of the intensity of the 4a photoemission peak
vs temperature for two different ambient CO
pressures forthe(lOi0) face. Measurementsofthe
change in work function with CO adsorption are
consistent with the intensity of the & peat’” The
adsorption kinetics were found to fit a Temkin
isotherm or isobar (i.e. Langmuir-type adsorption
plus a linear decrease of the heat of adsorption,
AH&, with coverage). and the solid lines are Ats to
such an isobar. In comparing the data from various
faces, it was necessary to assume that the
coverage dependence of AH,,,,,was the same on all
faces. It is then possible to compare the amount of
CO that would be chemisorbed at saturation
coverage on diierent faces. The results are given
in Table 2, where coverage is expressed as number
of CO molecules per surface ZnO molecule, nor-
malized to unity for the cioio)face. (The am-
0 60 60
FIG. 8. Intensity of the CO(4a) UPS peak for CO ad-
sorbed on Z&(1010) vs temperature for CO ambients of
(x) lo-6 TOITand (0) IO-’ Torr. SoIid curves arc fits to
Temkin isobars(fromRef. 20).
TABLET.
-~~
No. of CO molecules adsorbed
ZnO face
Surface ZnO molecule
(lOi0) (1.00)
(JlW
(0001 Zn :z!t
fooot-)-o 0:19
(from Ref. 20.)
 Uhviokt photoemission studies of molecular adsorption on oxide surfaces
plitude of the CO peaks relative to the substrate
emission for the non-polar faces also suggests
close to monolayer coverage at saturation.) The
heats of adsorption at zero coverage were nearly
the same for the four faces, ranging from 11.6 to
12.4 kcallmole.~’
The above results suggest an interesting pic%re
of CO ajsorption on ZnO.m’ The non-polar (1010)
and (I 120) faces, which adsorb a full monolayer of
CO, have both coordinatively unsaturated Zn and
0 ions in the surface plane. The much lower
saturation coverage on the polar (0001)_Zn and
(OOOi)-Ofaces, where only Zn or only 0 ions are
exposed, respectively, suggests that both a Zn and
an 0 site are necessary for CO chemisorption,
analogous to the dissociative chemisorption of
HCOOH in Fig. 6. But if both Zn and 0 sites are
required, then one would expect no adsorption on
the polar faces. However, it has been determined
that these faces contain a large Aumber of steps,
the height of which is predominately two double
layers (or a full lattice constant along the c-
axis).‘W’7s’ Such steps expose non-polar (IOiO)
facets, and CO could then adsorb at Zn-0 sites on
the facets. The amount of CO adsorbed at satura-
tion coverage would then be a measure of the
density of steps on the polar faces.
The reason that Gay d al. see chemisorption of
CO on ZnO, while Liith d al. do IX& has not been
dew. Subtle differences in surface structure
or composition arc probably the crucial factor.
Although both groups report excellent qualitative
LEED patterns, neither group has made I-V
qsurcments for comparison with theoretical
a&u&ions.
The adsorption of NH3 on all four faces of ZnO
Zn 0 KIOOl) -2n + NH,
FIG. 9. UPS difference spectra for NH3 on Zno(O001)-
Zn; (a) 246 K. 5 x IO4 Torr NH3 ambient; (b) 100 K. 2 L
NH3 exposure (from Ref. 20).
151
has also been studied by Gay et d~mJ*J5’ In ad-
dition to chemisorption, NH, physisorbs for tem-
peratures below about 110 K. Figure 9(a) shows
the di&rence spectrum for chemisorption of NH3
on a (OOOl)_Znface at 246 K and an ambient NH,
pressure of 5 X IOipTorr. The peaks corresponding
to emission from the le and 3~ molecular orbitals
of NH, are labelled (with 34: indicating the loca-
tion of the chemisorbed 3a, orbital). The two
peaks are shifted about 2eV closer together than
in the free molecule,‘=) suggesting bonding via the
3al N-lone-pair orbital. FQurc 9(b) shows the
spectrum for a combination of chemisorbed and
physisorbed NH3 for 2L exposure at 100 K. The 1e
orbital lies at essentially the same energy for both
adsorption states, but the 3a1 orbital for physisor-
bed NH2 is unshifted relative to the gas-phase
spectrum. (The other features in the difference
spectrum are “spurious” in that they arise from
narrowing of the ZnQd) band and changes in the
sfNcture of the valence band. As in the case of
CO adsorption, these changes have not yet been
thoroughly investigated.)
The kinetics of NH, chemisorption have been
i%WlyzediIltheSZUtle- as those of CO.‘2o’
They are found to fit a Temkin isotherm better
than a muir one, but there is significant scat-
ter in the data. The onset of physisorption below
110 K also restricts the range of data available.
Values of AH.,,, for chemisorbed NH, are difficult
to determine from the data, but they seem to lie in
the range of 25-U) k&/mole. It is difficult to
compare the ilitensities of the le orbital of NH3
adsorbed on the four faces of ZnO, due to the
difficulty of obtaining accurate difference spectra
and the possible variation of the magnitude of
A& between faces. UPS difftrence spectra in-
dictate that NH3 adsorbs not only on the step but
also on the terraces on the (ooOl)-Zn face, but
preliminary work function data do not corroborate
this conclusion.m)
An interesting aspect of NH, adsorption on ZnO
is that it “poisons” the surface for CO chemi-
sorption.@Ow~” Fiire lo(a) shows a UPS
difference spectrum for CO chemisorbed on the
(OOO&O face at 82 K and lo-‘Torr. When the
surface is exposed to 0.5 L of NH3 in the presence
of the CO ambient, the difference spectrum in Fig.
10(b) results. Emission from the Co(&) orbital
(the only CO orbital that does not overlap NH3
orbit&) drops as CO molecules are replaced by
NH1 molecules; the other two peaks in Fig. 10(b)
are combinations of CO and NHs orbitals. After I
L NH3 exposure, Fig. lo(c), the C0(4a) has
vanished, and the spectrum is purely that of NH,.
The surface is then completely inactive for ad-
ditional CO adsorption at any pressure-in other
words, it is poisoned.
Dmn et al.“’ have measured UPS spectra for 02
adsorption on the (ooOl)-Zn face of ZnO; their
results are shown in Fig. 11. Similar results have
152 VICIDR E. HENRICH

zno mooT)-o

hv m2l.W

(a)
+O.SL NH,

(b)

\ 21 l7 0 9 9
IS IO 5
Ilwal alstgy, lv Ekeon binding OMrgy M
FIG.10. UPS di&rence spectra for ZnO(OODi~ at82K FIG. 11. (a) UPS spectra of annealed ZnO(WOl~Zn
with a CO ambient of 1 x IO-’ Torr: (a) before exposure before (dashed curve) and after (solid curve) lti L
to NH,; (b) after 0.5 L NH, exposure; (cl after 1 L NH, exposure to Q; (b) dilTer~~cespectrum corresponding to
exposure (from Ref. 20). (a) (from Ref. 57).

been obtained in preliminary experiments by Gay
ef al.@“’No interpretation of the observed spectra
has been presented, but the 02 no doubt dis-
sociates, since the UPS spectrum for molecular a
exhibits four peaks over the energy range in-
vestigated.‘W
One additional UPS measurement should be
mentioned with regard to 2110. Cesiated ZnO has
been found to have an extremely low work func-
tion coupled with relative chemical stability!Ju”
properties of great interest for thermionic devices,
and Powell and Spice? have studii the cesia-
tion of ZnO by UPS. Figure 12 shows their spectra
for cleaved (lO’lo>ZnO, ZnO powder and cesiated
ZnO powder, all measured with a photon energy of
11.4eV. While showing clearly the reduction in
work function brought about by Cs adsorption, the
spectra provide no information about the elec-
tronic IeveIs of the adsorbate. The highest-lying
core levels of Cs are the 5pla and Sp,,,, with
binding energies (relative to I$) of 13.1 eV and
11.4eV, respectively, which are too deep to be
seen using this photon energy. The Cs(6s) electron
is presumably transferred to the substrate on ad-
sorption, giving rise to the low value of work
function. The two new peaks seen on the cesiated
surface, s3 and S.. have been attributed to a max-
imum in the ZnO conduction band density of
states and to inelastic scattering, respectively.‘60’
B. AdmrpthofChomTiOland!3rTiO,
The discovery in 1972 by Fujishima and
HomW6’) that TiOr @utile) could be used as a
catalytic electrode in the photodecomposition of

Initial state energy relative ta valwm bgtd mamum

FIG. 12. UPS spectra for hv = 11.4eV for heat-clcancd ZnO powder. (Cs)ZnO powder and single-
crystal ZnO(1010) cleaved in vacuum (from Ref. 60).
 Ultraviolet photoemission studies of mokcukr adsorption on oxide surfaces
water @hotoelectmlysis) aroused a great deal of
interest in the surface electronic properties of
transition-metal oxides. The first UPS studies of
the adsorption of G on Tiol and SrTiG were
performed by Henrich ef (II.“Oa’Subsequently, Lo
et al.“” studied other surfaces of Tio2. Before the
results of those experiments can be discussed, the
electronic properties of atomically clean Ti02 and
SrTiOs surfaces must be described in some detail.
The bulk band structures of Tio2 and SrTiO, are
very similar, because the Ti ions are in an octa-
hedral oxygen environment in both the rutile
(Ti0.J and perovskite (SrTiG) lattices, and the
ions in both materials have a Ti4’(3dq electronic
configuration.“~’ Figure 13 shows a schematic
energy-level diagram for SrTiOa?*) the structure
of TiG is essentially identical, except for the
absence of Sr bands. Both filled and empty Sr
bands in SrTiG are too far from the Fermi level to
play a significant role in chemisorption bond-
ing.(~45)The room-temperature bulk bandgaps for
SrTiO, and TiOr are 3.17 and 3.05 eV, respectively.
The bulk Fermi level lies in the bandgap, and both
materials are insulators when stoichiometric. Their
bulk stoichiometry can be varied slightly by heat-
ing to several hundred K in vacuum (or a reducing
atmosphere); 0 then diffuses to the surface and is
released, resulting in a small number of 0 vacan-
cies in the bulk (up to about 1019/cm3at 900 K).‘W’
These 0 vacancies act as donors, resulting in
n-type material. (A bulk density of IO” elec-
trons/cm3 is too small to be seen in a UPS
e&@ment.)
R&e 14 shows the UPS spectrum of a
nmum-fractured surface of SrTi@ [roughly
tM@)),measured with hv = 21.2 eV.“’ The zero of
&s&l-state energy has been taken as the Fermi
kvel, EF, which is pinned at the bottom of the
conduction band by bulk 0 vacancies. The bulk
valence band, which is predominately of O(2p)
Sr(56)
10
-_---_----_ VACUUM
Ti (3d)
E/O
O(2p)
e Sr(4p)
-20 O(2s)
-30
Ti(3p)
FM. 13. Schematic energy-level diagram of SrTiO, (from
Ref. 6).
153
1 FRACTURED SrTiO, (I@01
hv l 21.2eV
w
c
E, 2 b-0
x10
(a)
0 t 1 I
10 6 6 42, 2 E,=O
INITIAL ENERGY, E (rV1
PK. 14. UPS spectra for vacuum-fractured SrTiO,(loO)
(a) before and (b) after subtraction of 23.1 eV “ghost”
spectrum (from Ref. 6). ’
origin, extends from 3 eV to 9eV. The small
amount of emission in the bandgap region, which
is shown in Fig. 14(b) after correct&r for the
presence of a 23.1 eV line in the photon spectrum,
is believed to arise from surface &fee& present
on fmchued surfaces (32B); as ‘shown. it virtually
pisappears upon 02 adsorption., The UPS spectra
for vacuum-fractured TiO, are similar to Fig. 14.
Since the active states on TG and SrTii ph+
toelectrolysis elec&odes are believed, from elec-
trochemical measurements,‘“‘~ to lie near the
middle of the bulk bandgap. Henrich er (ll.“*‘O)
studied the electronic structure of surface defects
on TioS and SrTiO,. They created defects in a
controlled manner by Ar’-ion bombardment and
found that several different surface defect phases
occurred as the defect density was varied. Figure
15 shows the mannerinwhichtheUPSspectrafor
vacuum-fractured SrTQ change with bombard-
ment by 500 eV Ar’ ions for the times ~hown;‘~
the t = 0 curve is essentially the same as Fig. 14.
Fortimesgreaterthan6OOsec,therearenofurther
changes in the UPS spectra; a steady-state has
been reached and the sample surface is just being
etched away by the ions. Emission from the
valence band decreases in intensity with ion born
bardment, and an emission peak appears in the
regionofthebulkbandgapandgrowswithbom-
bardment time. When steady state has been
reached, the amplitude of the bandgap emission
peak corresponds to l-l.5 electrons per surface
unit cell (see Ref. 6 for a complete discussion).
The LEEDpattems disappear by t==3Osec, and
Auger spectra show a loss of both 0 and Sr from
the surface as a result of ion bombardment.
Sii effects are seen for TiG (see Refs. 10 and
 VICTORE. HENRICH
FIG. IS. UPS spectra for vacuum-fractured SrTiQ(lO0)
for various SOOeV Ar+-ion-bombardment times. Spectra
are aligned at EF (from Ref. 6).
13). with Auger spectra indicating a loss of 0 from
the surface.
The defect surface states created on both
SrTii and Tiol by ion bombardment correspond
to a transfer of electrons from surface 0 ions to
surface ‘Ii ions, resulting in a Ti’+(3d’) electronic
con@uration.‘WW Henrich e? (Il.‘*ln in-
vestigated the SrTi~(100) and TiO4 10) surfaces,
while Chung d u!.~*” studied the TiilOO) and
(110) and SrTiO,(lll) surfaces. On the TiO#OO)
surface, defects were produced not only by ion
bombardment, but also by evaporation of sub-
monolayer amounts of Ti.“” The defect surface
states produced by both methods were consistent
with the transfer of electrons to surface Ti ions;
we refer to such defects as Ti”/O-vacancy com-
plexes.
Since the defect surface states involve 0
vacancies, they should interact strongly with OZ
molecules; this is just what is obser~ed.“‘~’
figure 16 shows three UPS spectra for Tior(110)
after various treatments.“” Figure 16(a) is for a
nearly perfect surface, while Fig. 16(b) gives the
steady-state spectrum after H)OeV AC-ion bom-
bardment. Figure 46(c) shows the surface in (b)
after exposure to lp L of 0~. The adsorption of
02 restores the valence-band emission to some-
thing resembling that for the perfect surface, and
the bandgap surface state has been completely
depopulated. (Geometric order is not restored to
the surface by 02 adsorption, of course, and the
surface in Fig. 16(c) exhibits no LEED patterns.)
This behavior upon 02 adsorption is characteristic
of all SrTit& and Ti02 surfaces studied to date.
The amount of 02 exposure necessary to com-
X10
ES
(c) ly
i
-4 E"=O 4
INITIAL EN&Y W)
FIG. 16. UPS spectra for (a) annealed (nearly perfect)
Ti02(110); (b) 500 eV Ar+-ion-bombarded TiO?( I 10) at
steady state (solid curve); (c) surface in (b) after
exposure to lo’ L Oz(from Ref. IO).
pletely depopulate the bandgap surface state is
smaller on SrTiO, (about 30 L) than on TiO,
(about lo’ L).‘=’
Detailed studies of the adsorption of 0, on Ti02
and SrTia as a function of exposure at room
temperature have been carried out by Henrich et
al.‘=’ Figure 17 shows a family of UPS spectra for
AC-ion-bombarded SrTiO,( 100) before exposure
to a (0 L) and after exposures of 0.5 L to 108L;
the spectra have been aligned at the top edge of
the valence band, E,, to eliminate the effects of
band bending during adsorption. The increase in
valence band emission and the depopulation of the
bandgap surface state can be clearly seen, indicat-
ing electron transfer from the surface defect states
to the adsorbed species. More detailed information
can be obtained from difference curves (always
subtracting the clean-surface spectrum), as shown
in Fig. 18. These spectra show that two distinct
adsorbed phases are formed at different
exposures. The initial phase (I) is obtained for
exposures up to about 100 L; its difference spectra
exhibit two peaks, separated by about 2.5 eV,
overlapping the bulk valence band [see also Fig.
19(a)]. The similarity of these difference spectra to
the valence-band emission suggests that the ad-
sorbed species may be ti-, since the bulk valence
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces 155

band is derived predominately from 02- ions. The

depopulation of the Ti’+/O-vacancy surface state
is consistent with the formation of a negatively
I\ 0, ON BOMBARDED SrTi03(100)

charged adsorbed species. However, the data do

not rule out other negatively charged species, such
as a-.
For exposures greater than IOOL. a second
phase (II) appears, whose difference spectra are
characterized by a third peak below the bulk
valence band (7-g eV) and by changes in the rela-
tive heights of the peaks near 2 eV and 4eV. If
one assumes that phase II adsorbs in addition to
phase I, its difference spectrum can be obtained by

II / 1 I>, 8 s 4, I iI
e 6 4 2 E,.O -2 -4
INITIAL ENERGY IW

FIG. 19. UPS difference spectra for Ar+ -ion-bombarded

SrTiO,(loO): (a) phase I (30 L-O L); (b) phase II (10’
L - 30 L) (from Ref. 62).

subtracting the UPS spectrum for 30L 02

exposure from that for IO’L; this has been done in
Fig. 19(b). We have not been able to identify the
adsorbed species in phase II. It is probably not
neutral 02, since the free molecule has a four-
peaked UPS spectrum,c16)although we cannot rule
out a severely perturbed (or perhaps dissociated)
02 molecule.
The difference between 02 adsorptiok on high-
0 a 6 4 2 qeo -2 -4 defect-density surfaces and on nearly perfect sur-
INITIAL ENERGY (&‘I faces can be seen from Fig. 20, which presents a
Fffi. 17. UPS spectra (hv-5 21.2eV) for Ar’-ion-bom- family of difference spectra for 02 adsorption on
Wded SrTi~(lO0) after successive exposures to Q vacuum-fractured SrTiOs( IOO).~) Two adsorbed
(from Ref. 62). phases are seen here also, with phase I identical to
that on a highdefectdensity surface. (The ab-

h\
4 ON SCMARDED
solute intensity of photoemission from the ad-
SrTi4(1Wl sorbed phase on the fractured surface is less than
that on the defect surface, however.) The features
in the difference spectra for 100 L and greater are
quite diierent in Fig. 20 than in Fig. 18, however.
On the fractured surface, the peak near 1 eV has
completely vanished by lb L, and the difference
spectrum for lo’ L in Fii. 20 is very similar to the
spectrum for phase II alone in Fig. 19(b). It there-
fore appears that the same two adsorbed phases
are present on both surfaces, but that phase II
displaces phase I on nearly perfect surfaces. A
third case has been seen for ol adsorbed on ion-
bombarded and annealed SrTi6 (100) surfaces.
There, a similar initial adsorbed phase is seen, but
no second phase adsorbs.
The adsorption of 02 on TiG is more complex
than on SrTio3, and has not been as thoroughly
studied.‘~ The same initial phase (I) is observed,
but exposures greater than about 100 L give com-
plicated spectra, perhaps consisting of more than
INITIAL ENERGY WI one additional phase.‘=’ Charge transfer from the
FIG. 18. UPS difference spectra for Ar’-ion-bombarded bandgap surface state is observed for these other
SrTiQ(100) after successive exposures to 02 (from data phases, as well as for phase I.
in Fig. 17) (from Ref. 62). Lo et al.“” have studied the adsorption of G on
JPSS Vol. 9. No. J/6-B
156 VKZTORE. HENRICH

studies of Hz0 adsorption have been carried out

a, ON FRACTURED
by Lo et al!“’ on Ti02(100) and by Henrich et
S r TI O,(lOO)
al v”*7’1on TX&(110) and SrTQ( 100).
Lo et al.“” measured UPS spectra for ICYL of
Hz0 on the TiGWtV-(l x 3) surface (which has
no T?+ surface ions), the Ti02(100)41 x 7) surface
(which exhibits a small concentration of Ti’+ sur-
face ions) and on Tideposited and Ar’-ion-bom-
barded Tio2(100) surfaces (both of which have a
large number of surface Ti’+ ions and exhibit
similar UPS difference spectra). Figure 22 shows
the UPS spectra for the TiO#OOHl x 3) surface
before and after lo’ L Hz0 exposure. Three peaks
are seen, two overlapping the substrate valence
, band and one lying below it. The difference spec-
tra for l@ L Hz0 on the three different surfaces
are shown in Fig. 23. While the Ti01(100Hl x 3)
and Ar’-ion-bombarded (or Tideposited) surfaces
both give three-peaked difference spectra, the
Ti02(100)-(1 x 7) surface exhibits four peaks in the

I t I I I
INITIAL ENERGY (cv)
a+ - 0.8 rv
FIG. 20. UPS ditference spectra for vacuum-fractured T.3OtY.K
SrTii(100) after successive exposures to 4 (from Ref. qUctGl-G~3)+lo’Ln*O
62). 9 =4.9*v

k
A+* * 0.2 lv
T.300.K

I
-12 -6 -4 WO
2tectron Binding Enwgy. eV

FIG. UPS spectra of Tio2(100)-(1 x 3) surface before

22.
and after l@ L Hz0 exposure at 300 K (from Ref. 15).

v
-16
I
-12 -6
I
-4
I
-0
I

-11.2
I 1
TiO@Ol<l~3) +IO’L%O

Ektron 6imsq Enugy. rv

FIG. 21. UPS spectra for TiO&OOHl x3) surface

before and after 10’ L 4 exposure at 3C0K (from Ref.
15).

I
TiqLlOOl-W7l+lO’Ln,O

the Ti~lOO)-(l x 3) surface, and Fig. 21 shows -IO.8

their UPS spectra for the clean surface and for

lol L of 02 at room temperature. The three peaks
due to 0, adsorption in Fig. 21 are similar to the
spectra for comparable exposure in Fig. 19(b) and
Fig. 20. Similar structure was seen for G ad-
sorption on Ar+-ion-bombarded TiOz(lOO).“nLo et
ol. only used a single 02 exposure of lo’, and no
model for the adsorbed species was postulated.
J
-12 -6 -4
C. A&rptkmef&Oor~TiO,andSrl’KI, Cktron 6indiq Lnu~y. *V IEpOb
Clearly, the most important mokcule to study in Fro. 23. UPS difference spectra for Hfi adsorption on
an attempt to understand the role Of the electrode three d&&rent TQ surfaces. Dashed curve is UPS
surface in photoelectrolysis is HzO. Photoemission spectrum of gas-phase Hz0 (from Ref. 15).
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces 157

difference spectrum. The spectrum for the (1 X 3) r\ H-0 ON BOMBARDEDTiO, (110) 1

surface is compared with the UPS spectrum for
gas-phase Hz0 (dashed curve) in Fig. 23(a). Lo er
al.“” concluded that Hz0 is adsorbed molecularly
on the (1 x 3) surface, with the b, orbital dominant
in binding to the surface. They interpret the spec-
tra for the other two surfaces as indicating dis-
sociative chemisorption, resulting in adsorbed
hydroxyl groups (OH or OH-). They base the
latter conclusion on thermal- and electron-stjmu-
lated desorption measurements and i&a-red stu-
dies, as well as UPS data.“”
Henrich et ul:m*7”have studied Hz0 adsorption
on Ti%(!!O) and SrTiO&OO) surfaces for a wide
range of exposures. Figure 24 shows a family of
UPS spectra for Hz0 on an Ar’-ion-bombarded
TiMllO) surface. The changes that occur upon
HD adsorption are similar to those for 4 on
Ar+-ion-bombarded SrTia(100) shown in Fig. 17,
but there is no depopulation of the bandgap sur-
face state for Hz0 adsorption. The detailed
changes c+n be seen more ckarly in Fig 25, which
presents the difference spectra corresponding to
FQ. 24. For exposures up to 10 L, the difference I,, 1 I

4 2 E,=D -2 -4
10 8 6
spectra exhibit two broad, weak peaks in the
INITIAL ENERGY (eV)
region of the bulk valence band. We believe that
FIG. 25. UPS difference spectra for Ar+-ion-bombarded
these peaks most likely correspond to adsorbed TiWllO) after successive exposuns to Hz0 (from data
OH radicals, and that the Ha mole&es are dis- in Fig. 24) (from Ref. 70).
so&%&y chemisorbed in that regime. Gas-phase
UPS spectra of OH radicals exhibit two peaks
having ionization potentials of 13.01 and temperature.m’ If the adsorbed species is assumed
152OcV,” the same spacing as the observed to be OH, the polarixatiqnlrelaxation shift
peaks. Also, i&a-red absorption spectra show ob&ined is close to that found for molecularly
thnt OH is a stable species on Ti% at room adsorbed HD at higher exposures (see below).
The same two-peaked spectrum is seen on nearly
perfect TiwllO) surfaces, but it is not present on
Hz0 ON BOMBARDED TI02 11101
any of the SrTiO, surfaces studied, suggesting that
hv * 21.2 lV
Hz0 is not dissociatively chemisorbed on SrTioS.
This is a surprising result, and it must be examined
in more detail before reliable conclusions can be
drawn.
For HzO exposures greater than about 3OL, a
thirdpe.akappearsabout7eVbelowE,andgrows
until at lb L a three-peaked spectrum, similar to
that for gas-phase H20, is obtained. This three-
E
peaked spectrum has been observed on all TioZ
_
I and SrTia surfaces studied,~’ as shown in Fig.
26. (A background emission has been subtracted in
Fig. 26 to facilitate peak location. The three-
peaked spectra at 1o”L are sufhciently more in-
tense than the two-peaked spectra for low
exposures that essentially the same lb L difference
spectra are obtained whether the clean surface
spectrum or that for 10 L is subtracted. Also, note
the change in the labelling of the b, and b2 orbitals
in Fig 26 compared to Fig. 23; this corresponds to
different conventions for labelling the x- and y-
INITIAL EWEWY (WI .
axes of the molecule.) The four difference spectra
FIG. 24. UPS spectra
(hu = 21.2eV) for ~k+-ion-bon+ are aligned with the b, orbital of the gas-phase
barded Tio2(110) after successive exposures to H~O Hz0 spectrum in Fig. 26(a). We interpret all of
(from Ref. 70). these spectra as arising from molecularly adsorbed
 VICTORE. HENRICH

TABLE 3. Work functions and relaxation-

polarization shifts for Hz0 on TiQ and SrTi4

(energies in eV) (from Ref. 70.)

@ckm @HP A4w10 A&

Bombarded
Tia( 110) 5.06 4.56 -0.50 3.6
Annealed
TI02(110) 5.32 4.80 -0.44 2.5
Bombarded
BOMBARDED SrTii(lO0) 2.79 3.80 1.01 3.7
Bombarded
and annealed
SrTiQ( 100) 3.15 4.05 0.90 3.7

ANNEALED

al.“” on ion-bombarded TiO.#lO) are virtually

identical to those measured by Lo ef al.“” on
ion-bombarded TiMlOO), and yet the data have
been interpreted as due to molecular HiO in the
Hz0 (GAS1 former case and OH radicals in the latter. We feel
hv * 21.2 lV that data of the type shown in Fig. 25, which show
two adsorbed phases, support the interpretation of
three-peaked difference spectra as due to molecular
H,O. However, the difference spectrum in Fig.
23(b) for the TiO#OO)-(l x 7) surface”” most
20 10 16 14 12 likely results from more complicated adsorption
INITIAL ENERG’f WI products.
The work function changes and
FIG. 26. UPS difference spectra for various Ti0~ and
SrTi4 surfaces exposed to 10’ L Ha (b-c) and (a) UPS polariultion/relaxation shifts measured for mole-
spectrum of gas-phase Hz0 from Ref. 56 (from Ref. 70). cular HZ0 adsorbed on Ti02 and SrTiO, by Hen-
rich el al!‘“” are given in Table 3. (All values are
for 1O’L exposure.) HZ0 is seen to decrease the
H10 rather than OH.“O*“’For both nearly perfect work function of Tit& which is consistent with
TiOr(l10) (Fig. 26(b)) and Ar’-ion-bombarded the orientation of the adsorbed molecules as
Tio2(110) (Fig. 26(c)), the spacing of the outermost determined above from binding energy shifts. On
two peaks in the difference spectra is very nearly SrTiOJ, the work function is increased by HZ0
the same as that for the b, and b2 orbitals of adsorption; we have no interpretation for this
gaseous Hto, but the central peak is shifted effect at present. The polarization/relaxation shifts
toward tighter binding relative to the free-mokcuk in Table 4 exhibit an interesting dependence on the
al orbital. The shift is l.OeV for the defect surface presence of d-electron surface states. Those sur-
and 0.7 eV for the annealed surface. The b2 orbital faces that have filled Ti”(3d’) surface states have
for adsorption on the nearly perfect TiwllO) similar shifts (3.7 2 0.2 eV), even though the work
surface is also shifted about 0.2eV toward larger functions before HZ0 exposure differ by as much
binding energy. We interpret these shifts as bond- as 2.3eV. The one surface having no d-electron
ing of the H1O molecule predominately via its surface states has a shift of only 2.5 eV. It there-
in-plane O-lone-pair (a,) orbital, particularly on the fore appears that, even when there is no charge
defect surface. The molecule would then be bound transfer between surface states and adsorbed
to the surface with its 0 ion down and is H ions molecules, these states have a pronounced effect
away from the surface. The b2 orbital, cor- on the polarization/relaxation of the molecules.
responding to the O-lone-pair normal to the mole-
cular plane, also enters in bonding on nearly per- D. Adsorption of HZon TiG
fect surfaces. For defect SrTiG(100) surfaces, Lo et aL”5’ have also studied HZ adsorption on
both the ul and b2 orbitals are shifted by OJeV the TQ( 100X1 x 3) and Ar’-ion-bombarded
relative to the b, orbital: there is also some (but TiC)2(100) surfaces, and their difference spectra for
not total) depopulation of the bandgap surface 10 L HZ are shown in Fig. 27. Both are three-
state. No shifts relative to gaseous Hz0 are seen peaked spectra, and both look very much like the
for adsorption on Ar’-ion-bombarded and spectra for HZ0 adsorbed on the same surfaces
annealed SrTiO,(loO) surfaces: this is a com- (Fig. 23). Lo et al.“” interpret the two lowest-lying
plicated surface (see Ref. 6). however, and we peaks as due to OH formed by dissociative chemi-
have not tried to interpret the result. sorption of HZ, with the H atoms bonding to
Comparison of Fig. 23 with Fig. 26 shows that surface 0 ions. The highest-lying peak is attributed
the difference spectra measured by Henrich el to a negative charge on the OH (i.e. OH-).
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces 159

TABLE 4. d-Electron confi.guration vs crystal structure for fourth-period transition-metal

oxides

Bixbyite Rutile Corundum Rocksalt Spine1 Other

TQ@natase)
Ti02 - - - V20Y(orthorhombic)
CrO,(orthorhombic)

3d’ - wh(Tr340 K) TiG - -

3d2 - v203 TiO,(x * 1) -
3d’ - ,9%&r Crz03 vo,tx= I) -
3d’ MnrOr - -
3d” - - a-FeG3
3d6 - - -
3d7 - -
3ds - - - NiO - -
- I - - - CuO(monoclinic)
- - - Cur0 (cubic)
- 1 ZnO Wurtzite)

I It has a wide range of stoichiometry (0.6 IX 5

Ti 4 000) -II 13)t Id LH2
1.28) and has the NaCl structure for all com-
A+:-0.4+0leV
positions except those close to x = 1; it then has a
AN(E) monoclinic structure. Over the entire composition
range, the crystal structure contains an extremely
high density of lattice vacancies. For x = I, about
I
15% of both cation and anion sites are vacant,
I resulting in a rather open structure.‘6J’
Ar s’~ttered TIQ 000) + IO5 LH2
Interest in the adsorption of 02 on TiO, arose
A$= Olf0.1 eV
indirectly because of a theoretical paper by Jen-
ANyI\ , ~1 nison and Kunzo‘) on the bulk band structure of
TiO. Their results indicated that there should not
be a partially filled TiQd) band above the O(2p)
valence band, in disagreement with other cal-
-12 -8 -4 culations.“’ Their results agreed, however, with
Electron Bindmg Energy, eV (EF = 0) XPS measurements of Ichikawa et ~1.~) on five
FIG. 27. UPS difference spectra for Ti02(1OOHl X3) TiO, samples (0.84~ x Z=1.22). which showed no
surface and A?-ion-bombarded TiOr(lOO) surface after electron emission from the region above the
16’ L H2 exposure at 300 K (from Ref. IS). valence band. This surprising result prompted
Wertheim and Buchananm’ to perform XPS
measurements on samples of arc-melted TiO,.,
Henrich et uL’~’ have tried to study HI ad- (whose surfaces had been abraded in the pre-
sorption on TiQ and SrTiO, at room temperature, paration chamber of the XPS spectrometer) and
but with little success. In all cases, the difference Henrich et 01.~’ to take UPS spectra for vacuum-
spectra obtained were much weaker than, but fractured polycrystalline TioO., and TiOl.,s. Both
essentially the same shape as, those for Hz0 ad- of these measurements showed strong emission
sorption. Examination of the ambient in the from a Ti(3d) band lying 2.5 eV above the valence
vacuum system with a quadropole mass spec- band. The question then arose of why Ichikawa et
trometer during Hz exposure showed an increase al. ‘76’had not seen this band. After having studied
in the mass 18 (H20) peak whenever HZ was the effects of O2 on Tf+ defect states on TiOz, Hen-
admitted to the vacuum system, even when the Hz rich et aLm) suspected that the exposure of the
was passed through a liquid nitrogen trap prior to Ichikawa et nl. samples to air before measurement
admission and the system had been thoroughly had resulted -in oxidation of Ti ions near the sur-
baked. Presumably Hz was reacting with residual face to a Ti“(3dq co&uration. The open struc-
O-containing molecules somewhere in the vacuum ture of TiO, might allow 0 atoms or ions to
system, but the exact cause was never determined. migrate far enough into the sample (30 A or SO) to
oxidize all of the Ti ions within the XPS sampling
IL AdsorptionofOtonTiO.(x=l) depth. Thus, they exposed the vacuum-fractured
TiO, (x = 1) is an interesting compound in surfaces to various amounts of 02. As seen in Fig.
several respects. ‘=’ From its stoichiometry, the Ti 28 for TiOl.lJ, the Ti(3d) band disappears upon
ions would be expected to have a Ti2+(3d2) exposure to G.m’ (It should be noted that
configuration, which is rather unusual for Ti ions. exposure of T&O,, which is a “tight” lattice, to O2
160 VKTOR E. HENRICH

decreases but does not eliminate the Ti’+ emission

peak.‘=) The UPS spectra in Fig. 28 are remark-
ably like those for % adsorption on Ar’-ion-bom-
barded Tia (Fig. 6 of Ref. 62) for all exposures.
Wertheim and Buchanan also reported the absence
of the Ti(3d) band for TiO,., samples prepared in
air.”
F. Adsorption of I&O on AId&
One study of the room temperature adsorption
of Hz0 on Al$&(OOOl)has been reported by Ahny
et al.‘ml AIla is of particular interest because of
its widespread use as a catalyst as well as a
catalyst support. The surfaces studied were orien-
ted to within 25” of the (0001) face, cut and
polished (no mention was made of subsequent
etching, either chemical or ion-bombardment). The 0 4 a I2 16 .20 24
sample was then heated for 14 hours in 5 x lo-’
Torr 02 at 850 K before adsorption. Fii 29(a) Kinotk omqy, eV

shows the UPS spectrum for that surface, and Pii.
29(b) shows the difference spectrum after
exposure to 2 x IO L of HsO. The results are
ditTtcult to interpret, since the A&O, sampk may
not have been thoroughly dehydrated before ad-
sorption.‘m
UPS measurements of CHtOH adsorption on
AltO, have also been reported by Rogers and
White.‘”
G. Adso@enefC~~onNlO
In the course of studying the chemisorption of
Fm. 29. Experimental and theoretical UPS spectra of a
p&ally hydrated cr-Al& surface. The lower abscissa
gives the measured electron kinetic energy while the
upper scale gives the electron binding energy with res-
pect to the experimental Fermi level of the substrate.
The four spectra represent (a) reference surface pn-
pamdbyhcating14hin5x10-~Torr4atJU)C;(b)
cm from reference after 7Smin exposure to 5X
IO-’Tow Hfl vapor at room tew: (cl shifted
SCF-G-SW spectrum for A&(OHh (from Ref. 7!J).

!:
C2Hz on single-crystal Ni surfaces, Demuthg”
oxidized a NitIll) surface at room temperature to
obtain an epitaxial NiO layer consisting of NiO
islands having the (111) surface exposed and the
same crystallographic orientation as the substrate.
He then adsorbed CzHl on the NiO(ll1) surface
and obtained the UPS spectra shown in Fig 30.
I.

02 ON FRACTURED Ti O,,,,
I

h*s 21.2rV ,!
I / i_
I6 14 12 IO 6 6 4 2 I
4
ELECTRON 6lNOlNG ENERGY t&I

FIG. 30. (a) UPS spectra (hv-40.8.eV) for NiO (on

thermally oxidized Ni( I I I)) before (solid curve) and after
3 L exposure of &Hz; (b) UPS difference spectrum from
(a) for hv = 40.8 cl!; (c) UPS difference spectrum for
hv = 21.2 eV (from Ref. 81).

The main features of the difference spectrum in

Fig 30(b) are two peaks at 10.2eV and 16.8eV
.below EF. By comparison with experimental UPS
results of CzHz adsorption on Ni, and by using
molecular orbital arguments, the peaks were
INITIAL ENERGY, E WI identified as arising from CH radicals adsorbed at
FIO. 28. UPS spectra for vacuum-fractured TiOl.lJ after
Ni sites.“‘) C2H2 thus appears to chemisorb dis-
various Q exposures. Spectra have been aligned at EF sociatively on NiO(l1 l), unlike the associative
(from Ref. 78). chemisorption observed for C2H2on ZnO(lOiO).‘m
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces
4. Theo&W Calculationsof Mohxdar
Adsorption on Oxide Surfaces
Several groups have considered the adsorption
of molecules on oxide surfaces theoretically, and
some of those calculations are sufficiently detailed
to permit direct comparison with UPS data. We
will not attempt to describe the theoretical results
in detail, but rather we will summarize the various
approaches and conclusions.
Morin and Wolframq’ considered molecular ad-
sorption on the (100) surfaces of d-band perov-
skites qualitatively, using a simple linear-com-
bination-of-atomic-orbitals (LCAO) energy band
calculation. Wolfram and Ellialtioght’4’ later
extended the method to calculate the local density
of states (LDOS) for atomic planes in the surface
region, including Coulomb repulsion among d-
electrons, and these results agree favorably with
experimental UPS data for atomically clean sur-
faces.m’ They then calculated the LDOS for a
molecule consisting of one bonding and one anti-
bonding level with a Ti ion on a (100) perovskite
surface;“’ Fig. 31 shows the results of this cal-
culation. The antibonding molecular orbital is
assumed to hybridize with the Ti(d,) orbital and
the bondmg molecular orbital with the Tiid~)
orbital, as shown in Fig. 32. (They have not yet
sr TQ
AEpO
0
3*
3 orbital cluster calculations for clusters represent-
10
c: 2
w the presence of an adsorbed molecule.
Lo
0 culations on the Al&OHh
2
0 -4 -8 -12
Ftc. 31. Local densities of states (LDOS) for a chemi-
sorption process. (a) LDOS for the xz-component of a
cation on a (100) oerovskite surface with A& = 0. where
AE,, is a surface &rturbation parameter representing the
deviation of a surface from ideal truncation of the bulk
(A& = 0); Same as (a), but for A& = - 2 eV (represent-
ing presence of surface defects): (c) LDOS for surface
cation (AI?,+= - 2 eV) after interaction with an antibond-
ing molecular orbital; (d) LDOS for the interacting orbi-
tal of an adsorbed molecule. E,, and Ee are the anti-
bonding and bonding states of the molecule-surface
complex and EM is the energy of the molecular state
prior to interaction with the surface (from Ref. 65).
161
Gkii’
8
I e -+-+
1 83
-------X2
(al (bl
pHn 7
0nn
+
d+
e
I +
IL
0
0
+
ii 2
z
(c 1 (d)
hG. 32. Schematic of orbit& and geometries of typical
molecular orbit& that interact witit x2 and z2 orbitals of
a transition-metal ion. (a) and fb) illustrate overlap of the
xz state with antibonding molecular orbitals, and (c) and
(d) show the overlap between the z2 state and bonding
molecular orbitals. Arrows indicate tbe usual direction of
charge transfer when these orbitals hybridize to form a
surface complex (from Ref. 65).
c&tWeti the LDOS for specific molecules ad-
sorbed on the perovskite surface.) Their cai-
culations indicate that the adsorbed molecule par-
ticipates in delocalized anface energy band states,
which provides a mechanism for adsorbed mole-
cules to communicate electronically over large
distances with each other or with substrate atoms.
Wolfram et al.‘“’ have also performed molecular
ing the surface electronic levels of Tii, SrTiO3
and BaTicX, but they have not explicitly included
Almy d af.m have performed self-consistent-
field (SCF)-Xa-scattered-wave (SW) cluster cal-
cluster (simulating
Al& + HsO), shown in Fig. 33, in order to inter-
pret their experimental results for Hz0 adsorbed
on A120&t001). The results of the calculation are
shown in Fii. 29(c). The calculation, while show-
ing moderate agreement with experiment, was not
ddinitive, since some probable adsorption
geometries were not considered.~’ Foyt and
Whitea’ have also performed SCF-Xa-SW Cal-
culations of CHJ(OH) adsorbed on Al&
Lee and Wang@) have calculated the LDOS for
an ordered monolayer of both H-like and Cl-like
atoms adsorbed on MgO(lOO), using an LCAO
interpolation scheme. Figure 34 shows the results
of their calculations for H-like atoms, along with
the bulk energy bands for MgO. There are, as yet,
no expciimentaf UPS data with which. to compare
their calculations.
162 VICTORE. HENRICH
o/0
H
FIG. 33. Geometry of the Al&(OHk cluster used to
calculate interactions of Ha with AI& (from Ref. 79).
FIG. 34. Energy-band structure for a monolayer of H-
like atoms on MgO(IaO). Shaded area represents sub-
strate continua (from Ref. 84).
Kunz and co-workers have investigated the ad-
sorption of H on Mg@=’ and Ni@=’ by means of
SCF-unrestricted-Hartree-Fock cluster caicula-
tions. These systems have not yet been studied
experimentally by UPS, so no comparison of
theory and experiment is possible.
Clwter calculations of OH- adsorbed onto a
defect site on TiG have beep performed by Kawai
et al.,“) using the discrete-variational (DV)_Xa
method. They have performed calculations for
both an atomically clean surface (TiO, cluster) and
for a surface with adsorbed OH- (TiOrOH- clus-
ter), and taken the difference between them to
simulate UPS difference spectra. The results are
shown in Fig. 35 along with the UPS data of
Henrich et al.“O’ Since their calculations yielded
essentially a three-peaked spectrum, they con-
cluded that only OH is adsorbed on TQ and
SrTia surfaces, as opposed to the interpretation
given by Henrich et d.(m) They did not perform
calculations for a cluster simulating adsorbed
molecular H20.
Kowalski and Johnson’p’ have performed scat-
tered-wave (SW)-Xa calculations for both Hz0 and
OH adsorption on TiO. clusters that simulate both
perfect and defect surfaces of Ti(x and SrTia.
They find ‘that molecular Hz0 gives the expected
three-peaked spectrum, but that the peaks are at
larger binding energies than those seen by UPS.
Adsorbed OH gives a two-peaked spectrum, which
v8lence band
FIG.35. (a) Calculated state density difference (4) for
OH- adsorbed on a TiO, cluster; (b) UPS difference
spectrum for 10’ L Ha on Ar+-ion-bombarded TiQ
(adapted from Henrich ef a/., Ref. 70) (from Ref. 87).
agrees quite well with the initial stages of ad-
sorption seen by UPS. They are currently extend-
ing their method to larger clusters (T&OS) to in-
clude the effects of Ti-Ti interactions in both bulk
and surface geometries.
J.FutureDirWtions
It is clear from the work reviewed above that
the study of molecular adsorption on oxide sur-
faces by means of photoemission spectroscopy is
a rather young field. Relatively few oxide surfaces
have been studied, and little is known about the
details of adsorption sites. Only on the Zno(lOi0)
surface have a wide enough range of adsorbed
molecules been studied to see trends in adsor-
bate/substrate interactions,‘-” and even then the
details of bonding are not well understood. The
field is ripe for expansion in a number of different
directions.
Space limitations in the present paper have
prevented us from discussing surface analysis
techniques other than UPS in any detail. Most of
those techniques, such as the ones mentioned in
$1, have been applied in at least some degree to
oxides, and a coupling of the various methods is
obviously necessary in order to gain as complete
an understanding of adsorption on oxides as pos-
sible. Most groups already employ a number of
dierent techniques, and that trend is continuing.
Just within the field of ultra-violet photoemis-
sion spectroscopy, however, there are several
directions of research that should greatly increase
our understanding of molecule/oxide interactions.
One is to perform more detailed UPS measure-
ments on a few selected systems. At@e-resolved
photoemission, using tunable synchrotron radia-
tion, should be applied to relatively simple sys-
 Ultraviolet photoemission studies of molecular adsorption on oxide surfaces 163

terns, such as CO on the four major faces of ZnO. T. WOLFRAM,E. A. Krutrt and F. J. MORIN, Phys.
These techniques are now sufficiently well Rev:B7, 1677 (1973).
developed, as a result of work on metal and semi-. F. J. MOJUNand T. WOLFRAM,.P~~~.Rev. L&r. 30,
1214 (1973).
conductors, that they can easily be applied to Ti W&MM and S. ELLLUI~CLU,
A&. Ms. 13,
oxides. Such measurements would give infor-
mation about both filled and empty surface and D. M. TENCHand D. 0. RALEIGH,Elrctmotalysis on
molecular levels as well as bonding geometry. Non-h&aNic Surfaces, Natl. Bur. Stand. Spec.
Publ. No. 455, p. 229 (U.S. GPO, Washin%on, D.C.,
Quantitative LEED measurements and com- 1976).
parison with theoretical calculations would also be 6. V. E. HENRICH,G. I)RESSELHAUS and H. J. ZEIGER,
necessary on those systems in order to better Phys. Rev. B17,4988 (1978).
define the surface geometry. 7. W. J. LQ and G. A. SOMORIAI. Phys. Rev. B17,4942
Another general approach that should prove (1978).
8. G. F. DEREIENWICK.Ph.D. thesis (Stanford Uni-
very useful is the study of a number of different versity, 1970) (unpublished).
crystal faces of the same oxide. Since adsorption 9. S. THOMAS,Surf. Sci. 55,754 (1976).
sites on oxides, or on any compound, can involve 10. V. E. HENRICH,G. DRESSELHAUS and H. J. ZEIGER,
two or more different types of atoms, it is im- Phys. Rev. Lerr. 36, 1335 (1976).
11. M. L. KNOTEK,in Proceedings of the Symposium on
portant to examine the effect of changes in the Eiecrtvde Marerkk and Ptvcesses for Eneqy Con-
relative position of the substrate atoms, the direc- version and storage. eds. J. D. E. MCINTYRE,S.
tion of their bonding and antibonding orbitals, etc., SRINIVASANand F. G. WILL, p. 234, (Tbc Elec-
on adsorption. To date, only the adsorption of CO trochemical Society, Princeton, NJ, 1977).
and NH3 on ZnO have been studied in such a 12. M. L. KNUIXKand J. E. HOUSTON,Phys. Rev. B15,
4588 (1977).
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cule/oxide systems. 14. H. J. MATHIELJ, J. B.. MAIXIEU,D. E. MCCLUREand
In addition to varying the surface geometry (i.e. D. LANDOLT,J. Vat. Sci. Technof. 14. 1023 (1977).
15. W. J. Lo, Y. W. CHIJNGand G. A. !SOMORJAI, Srtrf
crystal face) on a single oxide, it is possible in Sci. 71. 199 (1978).
some oxide systems to vary the electronic 16. V. E. HENRICH,G. DRESELHAUS and H. J. ZEIGER,
configuration of the surface without changing its Phys. Rcu. L&r. 36. 158 (1976).
crystal structure. The fourth-row transition-metal 17. P. W. PALMBERG, personal communication.
oxides are an excellent case in point. The cation 3d18. w. OPEL. surf. sci. 62.165 f1977).
19. R. R. GAY; personal c&nun&ati~n.
levels fill progressively as one moves across the 20. R. R. GAY, E. 1. SOLOMON,V. E. HENRICHand H. J.
periodic table from SC203to ZnO. The fourth-row ZEK~ER,(unpublished).
@&ion-metal oxides are organized according to W. G~PEL, J. Vat. Sci. TechnoL 15. 1298 (1978).
their d-electron configuration and crystal structureg: C. C. CHANG,Surf Sci. 25,53 (1971).
23. S. THOMAS.J. ADD!.Phvs. 48. 161 (1974).
in Table 4. Large isostructural families exist in this
24. V. M. B&&‘and V. H. Rtti! (&pubJisbcd).
system, and it should be posstble to vary the 25. V. E. HENRICH,G. DRI%SEL.HAUS and H. J. ZEIGER
cation d-electron population for a particular sur- (unpublished).
face geometry. Such studies have not been per- 26. G. HENAND, P~vceedings of the Second Inremarional
formed, and the structure of a particular crystal Confemnceon Ekcrrophorog~hy, p. 117.
27. K. 0. Leon, M. PR~JT~~Nand C. KINNIBURGH,1.
face may well turn out to be sensitive to dclec- Phys. C7,4236 (1974).
tron configuration, but it is certainly a promising 28. S. C. CHANGand P. MARK,Surf. Sci. 45,721 (1974).
direction in which to proceed in order to determine 29. S. C. CHANGand P. MARK.Surf. Sci. 46,293 (1974).
the role of d-electrons in chemisorption and 30. A. R. L~JBINSKY, C. B. DUKE, S. C. CHANG.B. W.
LEE and P. MARK, J. Vat. Sci. Tech&. 13, 189
catalysis. (1976).
The study of the interaction of molecules with 31. C. B. DUKE and A. R. LUBINSKY,Surf. Sci. 50, 685
defects on oxide surfaces is also an important (1975).
direction for future research. Some work of this 32. C. B. DUKE. A. R. LUBNSKY, S. C. CHANG, B. W.
type. has already been done on Ti02 and LEE and P. MARK,Phys. Rev. BlS. 4865 (1977).
srTiO~,‘6.‘O.‘Sb2.~II) 33. C. B. DUKE, R. J. MI&R, A. PA&N and P. ‘MARK,
but much more is needed, par- Phys. Rev. B18.4225 (1978).
ticularly on well-defined defect sites. Unless the 34. C. G. KINNIBU~H, /. ‘Phyi. C8.2382 (1975).
geometry of defect sites is fairly well understood, V. E. HENRICH,Surf. Sci. 57,385 (1976).
it will be difficult to make meaningful contact z: hf. R. WELTQN-COOK and M. PRWTON, Surf Sci. 74,
276 (1978).
between experimental results and theoretical cai- 37. M. HENZLER,Surf Sci. 36, 109 (1973).
culations. This is a difficult area of research, but it
38. D. KOHL, M. HENZLERand G. HEILAND,Surf Sci.
is one that must be tackled in order to gain an 41,403 (1974).
understanding of real oxide surfaces. 39. B. J. HOPKINSand P. A. TAYLOR,J. Phys. C9, 571
(1976).
40. H. VANHOVEand R. LEYSEN,Phys. Status Soridi (a)
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