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Oxygen Vacancy: The Invisible Agent on Oxide

Surfaces
Gianfranco Pacchioni*[a]

In Invisible Agent, a 1942 movie of the series of the invisible


man, an inventor of the invisibility potion becomes prey, during
World War II, to the Axis power who want the formula for
themselves. The smart inventor eludes them, becomes an
invisible agent and obtains top-secret information from the
enemy, playing a crucial role in a lot of subsequent events. This
story is reminiscent of the role played by oxygen vacancies, a
special class of point defects, in oxide materials. For a long time
oxygen vacancies have been the invisible agents of oxide
surfaces. People knew about their existence and properties, and
about their role in the chemistry of compound materials, but
nobody was able to see them nor to trace their reactivity in a
direct way. In a paper recently published in Science,[1] Flemming
Besenbacher and co-workers have been able, for the first time, to
study the migration of oxygen vacancies at the surface of a well-
ordered TiO2 surface. This has been possible thanks to the use of
atomically resolved scanning tunneling microscope (STM) im-
ages. It is not the first time that STM has been used to identify
vacancies on oxides (see e.g., Figure 1[2] or ref. [3]), and
spectacular advances have been obtained in the use of this
technique on oxide materials in the last decade.[4] But here the
authors have been able to follow a dynamic process, showing
that the migration of oxygen vacancies is catalyzed by transient
O2 molecules, and that the adsorbed O2 molecules diffuse across
the surface to find a vacancy, where they dissociate to fill the
vacancy, producing an O atom that adsorbs on the nearest Ti
atom, Figure 2. TiO2 is one of the most studied oxide materials,
partly because of its role both as a support for metal catalysts
and as a photocatalyst and electrocatalyst on its own, but also Figure 1. Empty states (a) and filled states (b) STM image of a vacancy on a NiO
because it is a model system.[5, 6] To understand the importance (100) surface. Reproduced from ref. [2], with permission of the American Physical
Society.
of this result better one has to make a step back and recall what
an oxygen vacancy is and what the role of these defect centers is
in materials science.
phenomena such as corrosion, which costs billions of dollars
each year, and catalysis by certain oxides, an activity which is the
basis of a large fraction of the whole chemical industry. In
Defects in Bulk Materials summary, there is no aspect of chemistry and physics of solids
which is not decisively affected by the presence of defects in a
During the course of the last century, and in particular in the last
material.
decades, it has been realized that several properties of solid
For these reasons, the study of the chemical, electrical and
materials are controlled not so much by their geometric and
optical properties of defects has attracted a continuously
electronic structure, but by faults or defects in the structure.[7, 8]
increasing interest in modern material science, to the point that
For instance, the strength of a metal is largely determined by the
presence of extended defects called dislocations; the color of a
gemstone is entirely related to the presence of impurity atoms in [a] Prof. Dr. G. Pacchioni
the lattice; even the electronic properties of the semiconductors Dipartimento di Scienza dei Materiali, Universita di Milano-Bicocca
and Istituto Nazionale per la Fisica della Materia
present in our electronic devices are connected to the level of
via R. Cozzi, 53, 20125 Milano (Italy)
doping introduced by the insertion of impurity atoms. Defects Fax: ( 39) 02-6448-5400
are also terribly important in chemistry, as they largely determine E-mail: gianfranco.pacchioni@unimib.it

CHEMPHYSCHEM 2003, 4, 1041 1047 DOI: 10.1002/cphc.200300835 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1041
conductor, or another oxide).[9, 10] This implies also a detailed
mapping of the surface defects, a difficult task because of their
low concentration and of the great variety of possible defect
situations. To give just one example of the variety of defects
present at oxide surfaces, we mention here the case of MgO.
Magnesium oxide is a particularly well-studied oxide because the
structure of the (100) single crystal surface is extremely flat,
clean, and stoichiometric. A great effort has been made in recent
years to characterize the MgO surface better, in particular for thin
films or polycrystalline forms,[11] and about a dozen different
types of defects and irregularities have been identified and
described in the literature, Figure 3 and Table 1. The identifica-
tion and classification of these defects is a formidable task, but is
Figure 2. STM images of oxygen vacancies (bright spots) at the (110) surface of
of fundamental importance. In fact, the presence of appreciable
TiO2 (courtesy of R. Schaub and F. Besenbacher)

a new discipline has emerged; defect


engineering. Defect engineering is aimed
at manipulating the nature and the con-
centration of defects in a material so as to
tune its properties in a desired manner or
to generate completely new and unex-
pected behavior. For instance, by chang-
ing the defect concentration, one can
turn a colorless insulator into a black
material with metallic conductivity or an
ordinary copper oxide into a high tem-
perature superconductor. While this is
well-known in the field of bulk materials,
it is only more recently that attention has
been given to the problem of defects at
the surface of solids. On a metal the
defect can consist of an impurity or
dopant atom, or can be an extended
morphological irregularity like a step. In
an ionic compound, the complexity of Figure 3. Schematic representation of vacant sites at the surface of an ionic crystal such as MgO. On the left
defects is at least one order of magnitude Mg and O divacancies are shown at a terrace and at a step; on the right are shown oxygen vacancies located
higher than in metals because of the at terrace, step, and corner sites.
presence of anions and cations, which can
assume a variety of charged states. This
situation is particularly pronounced in metal oxides, also concentrations of defects can completely change the chemical
because of the very large number of these compounds. Oxide behavior of the MgO surface. For instance, while a single crystal,
surfaces are finding continuous new applications in advanced nearly defect-free, (100) MgO surface is totally inert towards
technologies such as in corrosion protection, coating for thermal carbon monoxide,[12] the surface of a polycrystalline MgO sample
applications, in catalysis as inert supports or directly as catalysts, reacts at low temperature with the same molecule, with
in sensors, in microelectronics for their dielectric properties. formation of complex carbonate species.[13]
Films of magnetic oxides are integral components in magnetic Among all the defects identified at the surface of MgO, (see
recording devices and many microporous materials are based on Table 1), the oxygen vacancy is one of the most important and is
oxides. supposed to be the prevalent defect in many oxides. Depending
on the material, the structure and properties of oxygen
vacancies can vary substantially. One could say that the oxygen
vacancy is a fingerprint of the electronic structure of the oxide.
Oxygen Vacancies: Fingerprints of the Oxide
Let us consider two simple binary oxides such as MgO and SiO2 .
Electronic Structure
In MgO, a missing O atom from the bulk or from the surface
For all the reasons mentioned above, there is a considerable results in two trapped electrons localized in the cavity center
effort to better characterize the surface of oxides or the interface (see Figure 4). The driving force for the localization of the
between an oxide and another materials (a metal, a semi- electrons in the cavity is the Madelung potential of the highly

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Oxide Surfaces

Table 1. Summary of most important point defects at the surface of MgO

Defect Symbol[a] Schematic description

anion vacancy Fmnc (m 0,1,2; n 3,4,5) missing oxygen with trapped electrons[3134]
cation vacancy Vm nc (m 0,1,2; n 3,4,5) missing cation with holes at O neighbors[35]
Mg and O divacancy VMgO cation and anion vacancy[36]
anion vacancy aggregate Mm (m 0,1) aggregate of two or more O vacancies[37]
low-coordinated cation Mg2nc (n 3,4) coordinatively unsaturated cation[38]
low-coordinated anion O2 nc (n 3,4) coordinatively unsaturated anion[39]
hydroxy group OH proton attached to O2 [40]
impurity atoms Mn/On ; Mg2/X2 substitutional cation (M Li, Ni, etc.) or anion (X S)[41]
oxygen radical O nc (n 3,4,5) hole trapped at O anion[42]
shallow electron traps MgOcorner(e ) trapped electrons at morphological sites (e.g., Mg23c)[43]
deep electron traps (M)(e ) pairs cation (H, Na, etc.) and electron pairs[44]

[a] nc is the coordination number of the center; 5c five-coordinated (100) terrace sites; 4c four-coordinated step or edge sites; 3c three-coordinated
corner sites.

the regular lattice to 2.4 2.5 in the


defect) and the associated optical transi-
tion involves localized excitations from a
bonding to an antibonding state in the
gap.[14] The nature of the oxygen vacancy in
the two oxides, therefore, is completely
different as the result of the different
electronic structure and bonding in the
two materials; highly ionic in MgO, cova-
lent polar in SiO2 .
What about intermediate cases like the
Figure 4. Electron density difference plots for an oxygen vacancy at the surface of MgO. Left: a neutral O TiO2 surface investigated in the STM study
vacancy, with two electrons trapped in the cavity (F center); center: a charged oxygen vacancy with one
electron trapped in the cavity (F center); right: a doubly charged oxygen vacancy with no trapped electrons
of Schaub et al.[1] ? Recent first principle and
(F2 center). Reproduced from ref. [34], with permission of the American Institute of Physics. experimental studies agree about the fact
that TiO2 has a degree of ionicity inter-
mediate between fully ionic (Ti4 and O2 )
and fully covalent; a rough estimate indi-
ionic crystal. In this way, the place occupied by the O2 anion in
the regular lattice is taken by two free electrons in the
defective crystal, and the energetic cost of the vacancy
formation is minimized. For the same reason, the removal of a
neutral O atom from the MgO surface results in a very small local
relaxation (the crystalline potential is only moderately perturbed
and the distances around the vacancy change by less than 1 %).
The electrons trapped at an oxygen vacancy in MgO give rise to
typical excitations in the visible region of the spectrum, which
thus changes the color of the defective material, as shown in
Figure 5. For this reason these centers are called F centers, from
Farbe, the German word for color.
The situation is completely different in SiO2 , a crystalline or
amorphous solid characterized by covalent polar bonds. In SiO2
the removal of an O atom from a Si O Si linkage results in
two Si dangling bonds, Si . , which recombine to form a Si Si
covalent bond with two electrons occupying a localized state
Figure 5. Two samples of polycrystalline MgO powder with low (left) and high
with Si Si bonding character, as shown in Figure 6.[14] The
(right) concentrations of trapped electrons (color centers). The presence of
process is accompanied by a strong geometrical relaxation electrons trapped at the surface of the material leads to a drastic color change
around the defect (the Si Si distance decreases from 3.06 in (courtesy of M. Chiesa and E. Giamello).

CHEMPHYSCHEM 2003, 4, 1041 1047 www.chemphyschem.org 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1043
G. Pacchioni

in oxides (not only vacancies) is essential for the understanding


of their structure properties relationships. The problem is that
defects are often elusive species, highly diluted, and therefore
difficult to detect. It is as if one wanted to identify all the men
with a beard among the population of Europe from a satellite
which is a few hundreds of kilometers away from the earth
surface: the task is difficult, and it is easy to get confused. The
same happens with the identification of defects and vacancies at
oxide surfaces. Very often the proofs of their existence are
indirect, based on the change of a property or of a spectroscopic
response as a function of the number of defects present in the
sample. For instance, I mentioned above that oxygen vacancies
often result in peculiar optical properties and in a specific color
of the sample. Sometimes one can use more sophisticated
techniques to prove the presence of defects. Some defects
Figure 6. The structure of amorphous silica as obtained from first principle consist of single electrons trapped in special sites (including
density functional calculations. In the unit cell an oxygen has been removed from oxygen vacancies). The resulting centers are paramagnetic, and
the structure, leading to the formation of a direct Si Si bond typical of oxygen their presence can be detected by electron paramagnetic
vacancies in this class of materials (courtesy of M. Bernasconi).
resonance (EPR).[18] This technique is rather sensitive to the
presence of unpaired electrons, being able to reveal 1012 spins;
cates a charge of about 2 on Ti and 1 on O. An additional this means that for a high surface area polycrystalline sample of
complication comes from the presence of d orbitals on Ti. This 200 m2g 1, the lower limit of sensitivity is 107 spins cm 2, that is,
complication, in fact, opens up new possibilities to redistribute about a paramagnetic center every 108 surface atoms. This level
the electrons involved in the bonding with the oxygen atom is much better than the sensitivity of optical measurements
which has been removed to form the vacancy. A characteristic of which, for high dilutions, cannot detect the electronic states
many transition-metal oxides is the possibility to change the associated with the defect.
oxidation state of the metal. It is no surprise that the creation of In this respect, the novelty of the result of Schaub et al.[1]
an oxygen vacancy in TiO2 leads to a situation which differs from becomes more clear in the context of understanding dynamic
those described above for non-transition metal oxides such as phenomena. The dynamics of surface oxygen vacancies are
MgO and SiO2 . In TiO2 in fact, the electrons associated with the essential for the understanding of numerous reactions in
lattice O atom removed from the structure are neither trapped in catalysis by transition-metal oxides. For example, the oxidation
the cavity (as in MgO) nor lead to the formation of a Ti Ti bond of an organic substrate at an oxide surface usually occurs at the
(as in SiO2). Rather, they are transferred to the empty 3d levels at expense of a surface lattice oxygen atom, and results in the
the bottom of the conduction band belonging to the adjacent Ti formation of a surface vacancy. The role of gas-phase O2 in the
atoms.[15] Since the 3d states are rather localized, this corre- process is to react with the surface to regenerate the surface
sponds to a change of the formal oxidation state, from Ti4 to oxygen atom. At an atomistic level, this implies that the O2
Ti3. This change in oxidation state results in two observable molecule dissociates at the vacancy site, with formation of highly
consequences: a shift in the core level binding energies of the reactive atomic oxygen and of the regular surface. The study of
reduced Ti atoms,[16] and the presence of an unpaired electron in Schaub et al.[1] provides a direct proof and a detailed interpre-
the 3d shell of the Ti atom with formation of paramagnetic tation of the mechanism of this process on the TiO2 surface.
centers.[15] Recently the same group has shown the role of oxygen
The three examples illustrated here, MgO, SiO2 , and TiO2 , are vacancies on the TiO2 surface in dissociating water, Figure 7.[19]
paradigmatic of the great variety of behavior and characteristics Using STM images and DFT calculations they showed that the
of oxygen vacancies in simple binary oxides. This complexity amount of water dissociation is limited by the density of oxygen
increases when one considers ternary oxides such as spinels vacancies and that the dissociation takes place as soon as
(e.g., MgAl2O4) or perovskites (e.g., BaTiO3). Here the distribution molecular water is able to diffuse to the active site. Another
and electronic structure of the bulk defects forms the basis, example of the unusually high chemical activity of oxygen
which is not completely understood, for very peculiar and vacancies is that of the adsorption of molecular N2 on a MgO
important collective phenomena, such as for instance, high Tc surface activated by the presence of paramagnetic color
superconductivity in cuprates. Even less is known about the centers.[20] In this case, electrons trapped at oxygen vacancies
surface vacancies of these materials, despite the use of some of cause a special reactivity of the surface. N2 is a notoriously
them in catalysis (e.g., perovskites).[17] unreactive molecule, and it is quite surprising that the activated
MgO surface reacts by transferring one electron from the
vacancy to the N2 molecule, with formation of the radical anion
Detection of Point Defects at Surfaces
N2 , as shown in Figure 8.[20] EPR measurements have unambig-
In general, a detailed understanding and a control at the uously proven the formation of this unique surface complex,
atomistic level of the nature (and concentration) of point defects which can be seen as a first step in nitrogen fixation. Notice that

1044 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org CHEMPHYSCHEM 2003, 4, 1041 1047
Oxide Surfaces

have assisted spectacular advances in the deposition of metal


clusters on oxide surfaces in the last five years.[21] These systems
represent well-defined models of the more complex and often
not well-understood catalysts consisting of small particles
deposited by chemical impregnation on inert supports (silica,
alumina, etc.). The key problem in this research area is the
control of the size of the particles, in order to generate a system
with a narrow distribution of the particle dimensions. Thanks to
new experiments designed to nucleate clusters under controlled
conditions[21] or even to deposit by using soft-landing techni-
ques on mass-selected clusters generated in the gas-phase,[22] it
has been possible to produce collections of nanosized particles,
Figure 7. Ball-and-stick model and corresponding simulated STM image of the all having the same dimensions. For many years this has been
TiO2 surface showing the appearance of a) vacancy-free surface, b) bridging the dream of people working on supported metal clusters. The
oxygen vacancy, c) bridging OH group, and d) water molecule on top of a Ti atom. conditions in which this has been realized are very far from the
Red atoms: O; yellow atoms: Ti; blue atoms H. Reproduced from ref. [19], with
permission of the American Physical Society. actual working conditions of the practical catalysts. Still, these
experiments offer the unique opportunity to study the cluster
reactivity as a function of the particle size,[23] opening up new
perspectives for the understanding of the basic principles of
catalysis by metal particles.
What is the connection between the field of supported
nanoclusters and the problem of oxygen vacancies at oxide
surfaces? Here we have to think about what happens when the
metal atoms are deposited onto the oxide surface from the
vapor phase. The atoms impinging on the surface can stick to it,
diffuse on the surface, or re-evaporate, depending on the
strength of the interaction with the substrate, of their kinetic
energy, and of the amount of thermal energy in the system. In
the process of diffusing on the surface, it can happen that the
atoms encounter a specific site where the interaction is stronger
and the diffusion barrier is higher. On these sites the atoms
remain trapped and there is a given probability that a second
atom diffusing on the surface binds to the first one, which gives
rise to the nucleation and growth of the metal cluster. It is a
general belief that oxygen vacancies are among the most likely
sites for the nucleation to occur. For instance, the group of
Besenbacher has shown recently that on the rutile TiO2(110)
surface the active nucleation sites for Au clusters are the
bridging oxygen vacancies; see Figure 9.[24] Even when the

Figure 8. EPR spectra of an activated MgO surface exhibits the typical signal
assigned to trapped electrons (top); after exposure to N2 at 77 K the spectra
changes dramatically indicating the formation of a new species (center); the
simulated spectrum (bottom) indicates that the new species corresponds to the
N2 radical anion formed by electron transfer from the surface. Reproduced from
ref. [20], with permission of the American Chemical Society.

Figure 9. a) STM image of a small Au clusters on TiO2 . Vacancies are marked


on a defect-free MgO surface, N2 does not stick even at a very with squares. b) Simulated STM image of a single Au atom trapped in a oxygen
vacancy. c) Line profiles comparing DFT theoretical results and experiment.
low temperature. Reproduced from ref. [24], with permission of the American Physical Society.

clusters are generated in the gas-phase and soft-land on the


Point Defects and Supported Metal Clusters
oxide surface there is indication that oxygen vacancies are
Oxygen vacancies are relevant not only in catalysis by oxides. important for their stabilization. The binding of a metal atom or a
Recently it has been suggested that they can play an important cluster to an oxygen vacancy can be three to four times larger
role in tuning the activity of supported metal nanoparticles. We than on the regular sites.[25, 26] It is not surprising that these are

CHEMPHYSCHEM 2003, 4, 1041 1047 www.chemphyschem.org 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1045
G. Pacchioni

the most likely sites for the nucleation to occur, as demonstrated of the static and dynamic behavior of point defects at oxide
in Figure 10. It should be mentioned, however, that some surfaces.
theoretical studies cast doubts on this view, at least for the
transition-metal atoms at the right of the periodic table.[27] But
there is also another reason why these centers are important. For Acknowledgements

Work supported by the Italian Institute of Condensed Matter


Physics (INFM) through the PRA-ISADORA project. The author
thanks Annalisa Del Vitto, Cristiana Di Valentin, Livia Giordano,
and Davide Ricci for their valuable input, and thanks R. Schaub, F.
Besenbacher, M. Chiesa, D. Donadio, E. Giamello, M. Bernasconi,
and M. R. Castell for making available some original and some
unpublished pictures from their work.

Keywords: defects materials science oxides surfaces

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