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Article history: The prospects for converting angle-resolved photoemission data from reciprocal space to real space are
Available online 12 March 2010 evaluated. Examples are given for one- and two-dimensional systems, where wave functions have been
obtained for quantum well states conned between steps and for planar molecules adsorbed at a surface.
Keywords: The extension to three-dimensional systems via variable photon energies is discussed. The uncertainty
Photoemission relation between position and momentum makes such a capability complementary to imaging in real
Angle-resolved
space by scanning tunneling microscopy. Angle-resolved photoemission provides access to the internal
Wave function
structure of an electronic orbital and penetrates below the surface.
Fourier transform
Imaging 2010 Elsevier B.V. All rights reserved.
It was recognized as early as 1970 by Siegbahn and coworkers state effect when the electron escape depth becomes small com-
[1,2] that photoelectrons have a distinct momentum distribution. pared to the electronphonon scattering length. That eliminates
Early results are shown in Fig. 1 (from [1]), where the angular electronphonon scattering, which scrambles the momentum
dependence of the photoemission intensity from a NaCl single crys- information without changing the energy signicantly.
tal is plotted versus the polar angle . The Na 1s and Na 2s core For truly elastic photoelectrons it becomes possible to deter-
levels, as well as the Cl 3p valence band, exhibit distinct modula- mine the momentum distribution of the valence electrons in the
tions of up to 30% which seem to be tied to the crystal lattice in initial state and measure their E(k) band dispersion and Fermi sur-
real space. It was quickly found [3] that this phenomenon was not face (for early work see [11] and references therein, for reviews
restricted to ionic insulators but rather wide spread. Such obser- see [1214]). Initial and nal state effects can be separated using
vations eventually led to the concepts of photoelectron diffraction tunable synchrotron radiation, which allows constant initial state
[46] and photoelectron holography [7]. The angular distribution of spectra (CIS) and constant nal state spectra (CFS) to be taken [15].
elastic photoelectrons from a core level is explained by scattering Synchrotron radiation also makes it possible to tune the momen-
of the outgoing photoelectrons at neighbor atoms. In the forward tum perpendicular to the surface, k , which can be varied with
direction this leads to a focusing effect along rows of atoms which the photon energy. An example is shown in Fig. 3 for LiF(1 0 0),
explains the connection with the crystal lattice in real space rather now at energies high enough to avoid electronphonon scattering
than the Brillouin zone in reciprocal space. By appropriate model- (from [16]). The angular distribution is shown for several initial
ing [46] or by direct holographic inversion [7] it is now possible state energies E across the F 2p valence band. E is measured rel-
to determine the positions of atoms at surfaces. This is particularly ative to the valence band maximum which lies at k = 0 ( -point).
useful for nding the location of adsorbed molecules relative to the The valence band minimum lies at the X-point of the Brillouin zone
substrate lattice. boundary at 3.5 eV. The upper row of images is taken at a photon
When going from X-rays to the vacuum ultraviolet and from energy where k corresponds to the (3 0 0) X-point in normal emis-
core levels to valence electrons one nds again a strong angu- sion (with k in units of 2/a). Consequently, one sees a bright dot at
lar dependence of the photoemission intensity, as shown in Fig. 2 the center when E is set to 3.4 eV, close to the X-point (left end of
for NaCl(1 0 0) (from [810]). The angular dependence is shaped the upper row). In the lower row of images the photon energy is set
by the outgoing photoelectrons for the data in Figs. 1 and 2, for the (4 0 0) -point in normal emission. Consequently, one sees
i.e., one observes predominantly a nal state effect. This can be a bright dot at the center when E is set to +0.2 eV, near the -point
veried by varying the photon energy with synchrotron radia- (right end of the lower row).
tion and exciting the same nal state from different initial states. While the photoelectrons in the nal state behave like a nearly
With valence electrons, however, there is also a strong initial free electron with an inner potential at higher energies, the elec-
trons in the initial state are strongly affected by the crystal potential
and exhibit correlations with the other electrons in the solid. There-
Tel.: +1 608 263 5590; fax: +1 608 265 2334. fore, a more sophisticated theory is required to describe initial state
E-mail address: fhimpsel@wisc.edu. effects. In Fig. 3 a many-body, quasiparticle approach was used
0368-2048/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.elspec.2010.03.007
F.J. Himpsel / Journal of Electron Spectroscopy and Related Phenomena 183 (2011) 114117 115
Fig. 1. Observation of angular (momentum) dependence of the photoemission signal from a NaCl single crystal using MgK radiation with a photon energy = 1.25 keV.
From Siegbahn et al. [1].
to describe the initial states and a nearly-free-electron model for The same problem is currently receiving a lot of attention for
the nal states [16]. Sophisticated many body theory is required the reconstruction of a coherent X-ray diffraction pattern from an
to get the correct band width for correlated electrons, such as the isolated nano-object. One faces the usual problem of X-ray crys-
localized F 2p electrons in the valence band of LiF. In Fig. 3 the tallography: only the intensity distribution in reciprocal space is
calculated angular pattern is shown in the bottom half of each known, not the phases. For periodic crystals there are several stan-
image and compared to the experiment in the top half. All the dard ways to overcome the phase problem, such as substitution
experimental features are reproduced by this rst-principles the- by heavy atoms and anomalous scattering at an absorption edge.
ory, and even the intensities can be compared in semi-quantitative For an aperiodic object, such as a single protein molecule or a sin-
fashion. gle nanocrystal, the phase problem can be overcome as long as the
With both initial and nal states under control, one can ask object is located in a well-dened spatial region (for example inside
whether it is possible to extend the concept of photoelectron a small aperture) and isolated from neighboring objects [1720]. In
diffraction from core levels (where the initial state is a simple - such a situation one can employ an iterative method to retrieve the
function) to valence states (where one has to deal with extended phases. To begin, the measured intensities in reciprocal space are
orbitals). Experimentally, the analogy is rather straightforward: combined with arbitrary phases to enable an inverse Fourier trans-
just measure the angular photoemission pattern of valence elec- form into real space. The spurious intensity outside the aperture is
trons instead of core levels. Due to the nite energy width of the then set to zero and the rest of the data is Fourier transformed into
valence band one obtains a set of data at several initial state ener- reciprocal space. The resulting diffraction intensities are corrected
gies across the band width, as shown in Fig. 3. These correspond to the experimental values while keeping the phases. A second
to different initial state wave functions. Can a straightforward inverse Fourier transform leads back into real space. This procedure
inversion procedure, such as the reconstruction of a hologram [7], can be iterated many times, and it eventually converges to the cor-
produce a reasonable initial state wave function? In contrast to pho- rect result. Quite a few renements have been devised, but there is
toelectron holography, one cannot use the spherical wave emitted a common condition for this method to work: The diffraction pat-
from a core level as reference wave. tern needs to be oversampled in reciprocal space, i.e., the k-points
116 F.J. Himpsel / Journal of Electron Spectroscopy and Related Phenomena 183 (2011) 114117
Fig. 2. Angle-dependent photoemission from the Cl 3p valence band of NaCl(1 0 0), Fig. 4. Momentum-resolved photoemission data are transformed from reciprocal
varying both the nal energy Ef an the initial energy Ei = Ef and of the photo- space (left) to real space (right), thereby revealing the wave functions of quantum
electrons using synchrotron radiation. From [8] (see also [9,10]). well states conned to a terrace on the stepped Au(23 23 21) surface. This provides
proof of principle that the phase problem can be overcome by utilizing the knowl-
edge that the wave function is conned to nite region in space (here a terrace).
need to be dense enough that diffraction features from the aper-
From [24].
ture are still well-sampled. Using electrons instead of X-rays for
coherent imaging is analogous, except for the multiple scattering
problem at low energies. Various techniques have been developed as long as the electrons do not scatter coherently between different
by electron microscopists ever since Gabors invention of hologra- terraces. The short mean free path of low energy electrons provides
phy. A recent example is the coherent imaging of carbon nanotubes a rather efcient cutoff that serves as affective aperture. The tran-
and the electric potential around the tip of a nanotube eld emitter sition from coherent to incoherent electrons scattering between
[2123]. different terraces has been investigated systematically in [25]. The
While X-rays and high energy electrons image the core electrons reconstruction of electron wave functions from a regular array of
and thereby provide structural information, one has to use lower terraces can be performed in the same way as for coherent X-ray
energy photons with angle-resolved photoemission to image the diffraction by over-sampling and iterative phase retrieval. By set-
valence electrons and their orbitals. This has been demonstrated ting the energy of the spectrometer to the three lowest quantum
for quantum well states residing on a terrace of a stepped Au(1 1 1) well states and mapping their intensity distributions in k-space,
surface [24], as shown in Fig. 4. A coherent diffraction experiment is three different wave functions are obtained. Even when the wrong
ideally performed with a single nano-object, but an array of identi- phase is chosen as starting point (for example the phase of the
cal terraces is sufcient to reconstruct meaningful wave functions, n = 2 state with the intensity data for the n = 1 state) the iteration
Fig. 3. Comparison between experiment (top half of the images) and theory (bottom half) for angular photoemission patterns from LiF(1 0 0). The momentum perpendicular
to the surface k is varied by changing the photon energy. The upper row of images has the (3 0 0) X-point at the center (Ei = 3.5 eV), and the lower row the (4 0 0) -point
(Ei = 0 eV). From [16].
F.J. Himpsel / Journal of Electron Spectroscopy and Related Phenomena 183 (2011) 114117 117
Acknowledgment
References