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Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652

Multiple atom resonant photoemission: A new technique for

studying near-neighbor atomic identities and bonding
a,b , b,c a,b b,1 a,b
A.W. Kay , E. Arenholz , B.S. Mun , J. Garcia de Abajo , C.S. Fadley ,
a,b,2 b b
R. Denecke , Z. Hussain , M.A. Van Hove
Department of Physics, University of California, Davis, CA 95616, USA
Materials Sciences Division and Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
The Miller Institute, University of California, Berkeley, CA 94720, USA
A new multi-atom resonant photoemission (MARPE) effect between core levels of neighboring atoms in multi-element
samples has been observed. Experimental evidence for the effect and several possible applications are considered. In the
metal oxides MnO, Fe O , and La Sr MnO , we have observed a signicant enhancement in the core-level photoelectron
2 3 0.7 0.3 3
peak intensity associated with one element in the sample (e.g. O1s) when the excitation energy is tuned through an
energetically deeper absorption edge of a second element (e.g. Mn2p or Fe2p or La3d). The effects observed are up to a
105% increase in peak intensity, and a 29% increase in energy-integrated intensity. A generalization of the theory of
single-atom resonant photoemission has also been applied to MARPE, and is found to be in semiquantitative agreement with
our experimental results. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Resonant photoemission; Metal oxides
1. Introduction useful as a new tool for studying near-neighbor
atomic identities, bonding, and magnetism.
In recent experiments, we have provided evidence The mechanism involved in what we have termed
of a previously unconsidered interatomic resonant multi-atom resonant photoemission (MARPE) is best
photoemission process between core electronic levels introduced by comparison with the familiar single-
of neighboring atoms [1]. The process is conceptual- atom resonant photoemission (SARPE) case. In
ly similar to the well-known resonant phenomenon SARPE, it is known that, as the photon energy is
between electronic levels within a single atom. tuned across a given core level in an atom, the
However, the interatomic and multi-atom nature of photoemission from another less deeply bound level
this phenomenon is expected to make the process may be signicantly enhanced, following the form of
a Fano prole [26]. As an example, consider the
case of atomic Mn shown in Fig. 1. Here, the Mn3d
*Corresponding author.
photoemission is rst decreased, and then markedly
Permanent address: Departamento de CCIA y Departamento de
enhanced, as the photon energy crosses the excitation
Fisica de Materiales, Universidad del Pais Vasco/ EHU, 20080 San
threshold of the deeper Mn3p level at about 50 eV. A
Sebastian, Spain
Mn3p electron is excited into an unoccupied Mn3d
Present address: MAXLAB, Lund University, S-22100 Lund,
Sweden level, but decays via an autoionization process,
0368-2048/ 99/ $ see front matter 1999 Elsevier Science B.V. All rights reserved.
PI I : S0368- 2048( 98) 00329- 6
648 A.W. Kay et al. / Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652
complex valence bands (see for example, papers on
the highly correlated materials elsewhere in these
In the case of MARPE, we nd that the two levels
involved in the resonance do not need to be associ-
ated with the same atom. In Fig. 2, a diagram of the
process is shown for the case of O1s resonating with
Mn2p , as would be possible in the compound
3 / 2,1 / 2
MnO. As depicted in the gure, the photon energy
must be sufcient to excite Mn2p and 2p
3 / 2 1 / 2
electrons into an unoccupied band state of primarily
Mn3d character. This resonant process couples to the
direct O1s excitation when the Mn3d excitation
decays back to Mn2p via an interatomic autoioniza-
tion transition, simultaneously producing an electron
with the same energy as if the photon had directly
excited an O1s electron.
In this article, we present rst experimental results
exhibiting the MARPE effect, compare experiment
Fig. 1. Single-atom resonant photoemission (SARPE) for the case
of Mn3d emission from atomic Mn. The resonance occurs via the
Mn3p level. The direct excitation is indicated by the solid dark
arrow and the resonant process by the solid light arrow and dashed
arrows (autoionization decay). The key quantum mechanical
dipole and coulomb matrix elements involved are also indicated.
The lower panel (from Refs. [3] and [4]) also shows the measured
variation of the Mn3d intensity with photon energy, together with
theoretical calculations. The solid and cross-hatched areas repre-
sent the resonant and non-resonant contributions to intensity,
producing an electron of the same energy as if a
Mn3d electron had been directly excited by the
photon. This resonant process thus provides a second
coherent channel for the Mn3d-to-photoelectron
excitation. The gure presents experimental [3] and
theoretical [4] results for this particular process in
Mn, which is by now well understood. SARPE is
thus a well-known phenomenon that has been ob- Fig. 2. Multi-atom resonant photoemission (MARPE) in the case
of O1s emission from MnO, with the resonance occurring via the
served both between an outer valence level and a
Mn2p and Mn2p levels. The direct excitation and resonant
3 / 2 1 / 2
core level (as shown in Fig. 1), and between two
processes are indicated as in Fig. 1. Our measured variation of the
core levels. This effect has often been used in vuv/
O1s intensity over the Mn2p and Mn2p regions is also
3 / 2 1 / 2
soft X-ray studies, where it can e.g. be employed to
shown, with resonant and non-resonant contributions again indi-
emphasize the contributions of a certain orbital to cated as in Fig. 1.
A.W. Kay et al. / Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652 649
with theory, and discuss some possible applications on-resonance and off-resonance excitation. This in-
of this effect. tensity as a function of excitation energy is plotted in
Fig. 2 (lower panel), and the enhancement due to
MARPE (grey area) is evident as a deviation from a
2. Experiment smooth non-resonant background intensity (cross-
hatched area). As a nal step in analysis, we remove
All experimental data were recorded with the the contribution of the non-resonant background by
Advanced Photoelectron Spectrometer / Diffractome- subtraction of a smooth polynomial tted to it and
ter (APSD) on beamline 9.3.2 of the Advanced Light set the new baseline to unity, as shown in Fig. 3C;
Source in Berkeley [7,8]. This beamline allows this last step permits comparing our data more
photon energy to be selected between 30 and 900 eV directly to the X-ray absorption coefcient of the
and polarization to be varied from linear to left or material. Note in Fig. 3A that the O1s peak lies on
right circular, but for these experiments, only linearly an inelastic background whose magnitude varies
polarized light was used. The APSD further allows across the Mn2p edge due to secondary processes
signicant degrees of freedom in the experimental associated with Mn2p excitation. The variation of
geometry. A specially built sample manipulator this background with photon energy can thus be used
permits selecting arbitrary takeoff angles and as a measure of the X-ray absorption coefcient of
azimuthal angles of electron emission relative to the the Mn2p levels, as illustrated in Fig. 3B, where the
spectrometer acceptance (or photon incidence). Fur- background level as a function of photon energy is
thermore, a rotatable Scienta ES200 analyzer allows compared to a previous measurement of the X-ray
the photon incidence and electron takeoff angles to absorption coefcient by Butorin, et al. [9], and
be adjusted independently. The photon incidence excellent agreement is seen. Comparing Fig. 3B and
angle with respect to the surface is denoted by u C also shows that the MARPE effect in MnO follows
and the electron takeoff angle with respect to the very closely the X-ray absorption coefcient of the
surface by u. material.
The samples used in this study were single crystal
MnO(001), single crystal Fe O (001), and sol-gel
2 3
produced La Sr MnO with (001) orientation.
0.7 0.3 3
Photoelectron diffraction measurements conrmed 3. Results
each sample to have a highly ordered surface and
allowed precise orientation of the sample geometry The three samples used in this investigation
during subsequent measurements [8]. allowed us to observe interatomic resonance between
For clarity, we will discuss the experimental a variety of levels.
method in the specic case of an MnO sample where In the MnO sample, we measured the previously
the O1s level (binding energy |530 eV) is in discussed O1s resonance with the Mn2p and 2p
3 / 2 1 / 2
resonance with the Mn2p and 2p levels (bind- levels. As indicated in Fig. 3B and discussed above,
3 / 2 1 / 2
ing energies |639 and 650 eV). The details may be our measured X-ray absorption coefcient exhibits
trivially modied to apply to subsequent examples. excellent agreement with previous work, and it also
We are interested in the variation of the O1s peak closely follows the MARPE enhancement in O 1s
intensity as the photon energy is scanned through the intensity. Referring to Fig. 3C, the resonance en-
Mn2p edges. We thus recorded O1s spectra at hances the O 1s intensity by up to 43% and yields an
various increments in photon energy, for energies overall enhancement of 11% as integrated across the
across the Mn 2p range 634 to 657 eV. For each entire Mn2p absorption peak.
3 / 2
peak, an inelastic background of Shirley type was In the Fe O sample, we observe the O1s reso-
2 3
then subtracted and the remaining peak t with nance with the Fe2p and 2p as shown in Fig.
3 / 2 1 / 2
analytical Voigt functions in order to nally obtain 3D and E [1]. Again, our X-ray absorption coef-
the peak intensity (as an area). Fig. 3A shows cient matches previous work, in this case by Kuiper
examples of such ts for the particular cases of et al. [10]. The resonant enhancement of the O1s
650 A.W. Kay et al. / Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652
Fig. 3. (A) MnO:O1s photoelectron spectra from MnO for normal photoelectron emission and photon incidence at 208 with respect to the
surface:off-resonance at hn5637.6 eV (solid data points and lower curve) and on-resonance at hn5640.2 eV (open data points and upper
curve). The Shirley-type inelastic backgrounds are shown as dashed curves, and the solid curves are ts of Voigt functions to the data. Note
the increased inelastic background on-resonance due to secondary processes following Mn2p excitation. (B) MnO:X-ray absorption
coefcient for MnO, as measured in this study from the energy dependence of the inelastic background under the O1s spectra (solid curve)
and from Ref. [9] (data points). (C) MnO:O1s intensities (peak areas) above inelastic background for normal emission as a function of
photon energy, with the smoothly varying non-resonant intensity at each energy (compare Fig. 2, lower panel) being subtracted and set to
unity. Data are shown for photon incidence angles of 208 (solid curve) and 408 (dashed curve). (D) Fe O :X-ray absorption coefcient for
2 3
Fe O over the Fe2p and Fe2p levels, as determined e from inelastic background (solid curve) and with higher energy resolution in
2 3 3 / 2 1 / 2
Ref. [10] (dashed curve). (E) Fe O :As (C), but O1s intensity in resonance with Fe2p and Fe2p for Fe O , after normalization of the
2 3 3 / 2 1 / 2 2 3
non-resonant intensity. Data are shown for two experimental geometries: 208 photon incidence with 908 electron exit angle (solid curve) and
658 photon incidence with 458 electron exit (dashed curve), but with a xed x-ray-to-electron angle of 708.
A.W. Kay et al. / Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652 651
intensity is here as large as 62% and integrates to some obvious differences. Furthermore, although
24% across the Fe2p portion of the effect. both directions show essentially the same peak
3 / 2
The La Sr MnO sample provided another enhancement over Fe2p of about 6062%, the
0.7 0.3 3 3 / 2
example of O1s resonating with the Mn2p levels, energy-integrated magnitude of the effect differs
although this data is not shown here [1]. In this case, over this portion of the curve. The normal emission
the effect was as large as 33% in peak intensity and case (u5908) shows an enhancement of 24%, as
integrated to 17% over the Mn2p peak. In addi- compared to 17% for the off-normal emission case
3 / 2
tion, resonance between the O1s and the La3d , (u5458).
5 / 2 3 / 2
levels exhibited O1s enhancements of up to |105% Finally, we point out that a rst attempt at
and an integrated effect of 29% over the La3d modifying the theory of single-atom resonant photo-
5 / 2
peak. Finally, resonance between the Mn2p and the emission so as to apply to MARPE has yielded
La3d , levels showed maximum and integrated results in reasonable agreement with our experimen-
5 / 2 3 / 2
enhancements of 60% and 20%, respectively, in tal data for MnO [1]. In particular, with simple
going over the La3d peak. In each case, we were atomic wave functions describing initial and nal
5 / 2
again able to demonstrate close agreement of our states, the O1sMn2p resonance via the inter-
3 / 2
measured X-ray absorption coefcient with previous atomic coulomb interaction that is responsible for the
results, and with the associated MARPE enhance- autoionization step (cf. top panel of Fig. 2) is found
ments in photoelectron intensities [1,1113]. to produce an energy-integrated effect for Mn2p
3 / 2
of 2.5% that is within a factor of 4.4 of the observed
11%. These calculations also suggest that the effect
4. Discussion is inherently multi-atom in character, extending over
the rst few spheres of neighbors around a given
For each case considered above, the resonance emitter, although with strongest emphasis on nearest
enhancement or MARPE signal is seen to be a neighbors. Further desired improvements in theory
signicant contribution as judged relative to the non- are discussed elsewhere [1].
resonant intensity. At least for these metal oxides,
such effects are thus expected to be relatively easy to
measure and use. We have also found that, simply by 5. Conclusions
monitoring the inelastic background intensity upon
which the photoelectron peak lies is a reliable We have thus observed a new interatomic multi-
method for extracting form of the X-ray absorption atom resonant photoemission effect (MARPE) that is
coefcient associated with the resonating levels. It is rather large in magnitude in transition metal oxides
also noteworthy that the MARPE enhancement fol- and appears to extend over several near-neighbor
lows very closely, although perhaps not identically, atoms around a given emitter. Future studies of this
the X-ray absorption coefcient in each case studied. effect are thus interesting and promising in several
In Fig. 3C, we also note that the resonance prole respects. Better understanding the large magnitude
has been measured for two cases differing only in the observed for the effect in oxides, as well as its
photon incidence angle u . Within the statistics of occurrence/ non-occurrence in other systems (e.g.,
the experiment, the curves are indistinguishable. This metals, adsorbates, free molecules) is clearly im-
provides convincing evidence that the effect is in fact portant. Improving the theoretical modeling of the
due to MARPE and not to any X-ray attenuation effect is also crucial. Further investigations of the
length changes as the edge of the deeper level is effect are therefore called for in order to better
crossed, with further discussion of these data appear- understand the basic processes involved.
ing elsewhere [1]. Even more interesting is the potential of this effect
In Fig. 3E, we show evidence for dependence of to be used as a new tool for determining element-
these resonance effects on the photoelectron emis- specic information about near-neighbor atoms. Our
sion direction. For two different emission directions, initial theoretical calculations have indicated that the
the resonance curves have similar shapes, but also resonance will be primarily between near-neighbor
652 A.W. Kay et al. / Journal of Electron Spectroscopy and Related Phenomena 101103 (1999) 647652
atoms and that the magnitude of the effect will be D.F.G-Germany (R.D.), and the Basque Government
very sensitive to atomic separations [1]. Thus, direct- (F.J.G. deA.) is gratefully acknowledged.
ly determining near-neighbor atomic identities
(atomic numbers), as well as subtle changes in
bonding type or magnetic interactions seems pos- References
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references therein.
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We are indebted to M.P. Klein and J. Kortright for
[11] A. Kay et al., data not shown
helpful discussions, and to S.A. Chambers and K.
[12] M. A. Brewer et al., Advanced Light Source Compendium of
Krishnan for providing samples. This work has been
User Abstracts and Technical Reports, Report LBNL-39981,
supported by the Ofce of Energy Research, Materi- UC-411 (Lawrence Berkeley National Laboratory, Berkeley,
CA, 1997), p. 411; K. Krishnan, personal communication
al Sciences Division, of the U.S. Department of
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Energy, under contract DE-AC03-76F00098. Addi-
tional support from the Miller Institute (E.A.), the