ARTICLE

Received 18 Feb 2015 | Accepted 10 Sep 2015 | Published 7 Oct 2015 DOI: 10.1038/ncomms9607 OPEN

Fermi states and anisotropy of Brillouin zone

scattering in the decagonal Al–Ni–Co quasicrystal
V.A. Rogalev1,w, O. Gröning2, R. Widmer2, J.H. Dil1,3, F. Bisti1, L.L. Lev1,4, T. Schmitt1 & V.N. Strocov1

Quasicrystals (QCs) are intermetallic alloys that have excellent long-range order but lack
translational symmetry in at least one dimension. The valence band electronic structure near
the Fermi energy EF in such materials is of special interest since it has a direct relation to their
unusual physical properties. However, the Fermi surface (FS) topology as well as the
mechanism of QC structure stabilization are still under debate. Here we report the first
observation of the three-dimensional FS and valence band dispersions near EF in decagonal
Al70Ni20Co10 (d-AlNiCo) QCs using soft X-ray angle-resolved photoemission spectroscopy.
We show that the FS, formed by dispersive Al sp-states, has a multicomponent character due
to a large contribution from high-order bands. Moreover, we discover that the magnitude of
the gap at the FS related to the interaction with Brillouin zone boundary (Hume–Rothery gap)
critically differs for the periodic and quasiperiodic directions.

1 Department for Synchrotron Radiation and Nanotechnology (SYN), Swiss Light Source, Paul Scherrer Institute, Villigen CH-5232, Switzerland.
2 Department of Advanced Materials and Surfaces, EMPA, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, Dübendorf
CH-8600, Switzerland. 3 Institute of Condensed Matter Physics, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland. 4 National
Research Center Kurchatov Institute, Akademika Kurchatova Square 1, Moscow 123182, Russia. w Present address: Physikalisches Institut and Röntgen
Research Center for Complex Materials Systems, Universität Würzburg, Würzburg 97074, Germany. Correspondence and requests for materials should be
addressed to V.A.R. (email: victor.rogalev@physik.uni-wuerzburg.de).

NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications 1

& 2015 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607

D
ecagonal quasicrystals (QCs) are extremely tempting On the basis of these principles, Fig. 1c shows the section of the
structures to study due to the unique combination of 3D Fermi surface (FS) model of d-AlNiCo, where for clarity only
the periodic and QP orders in the same crystal. The lattice the strongest reciprocal lattice vectors with G|| ¼ {0 Å  1,
of such materials can be obtained by appropriate projection of the 2.7 Å  1} at GZ ¼ {  1.54 Å  1, 0 Å  1,  1.54 Å  1} were
periodic lattice in five-dimensional space to the three-dimen- chosen as the centres of FE-like spheres. The real FS could be
sional (3D) space1. The real and the reciprocal space (k-space) obtained by increasing the set of G-vectors and taking into
lattice vectors of decagonal QCs thus can be denoted by five account the structure factors as well as all possible Bragg
vectors2 (Fig. 1a), spanning a reciprocal lattice in aperiodic plane scattering effects at the q-BZ boundaries. The latter open multiple
and a set of discrete maxima with 2p/c spacing in the periodic gaps at the EF at certain points in k-space and transform the FS
(00001) direction, where cE4 Å is a lattice parameter for into a segmented FS that has a smaller surface area compared
d-AlNiCo in this direction3. The corresponding low-energy with the original one. Although the largest gaps
electron diffraction (LEED) pattern from the clean tenfold are expected to appear at the first q-BZ boundary where the
surface of d-AlNiCo measured at electron beam energy corresponding interaction potential Fourier components are
Ee ¼ 43 eV at room temperature is shown in Fig. 1b. The very the largest, due to the dense diffraction pattern the smaller gaps
existence of the decagonal QCs poses fundamental questions on are expected to appear also in the higher q-BZs. Theoretical FSs
how the duality between the periodic and QP orders manifests were calculated ab initio for Y-AlNiCo structural model6 and for
itself in electronic structure and how it is related to the orthorhombic approximant to the decagonal phase10, both
stabilization of their unusual structure. resulting in a highly anisotropic FS with a complex multiple-
These questions have been explored in a number of band structure.
theoretical articles4–11 and experimental works12–19. Angle- However, all previously reported VUV-ARPES investigations
resolved photoemission spectroscopy (ARPES) experiments did not succeed to establish the presence of dispersive states in the
utilizing vacuum ultraviolet (VUV) radiation established the region near the EF, as well as the shape of the FS itself, which is
general electronic structure of d-AlNiCo, showing that in the important for understanding the mechanism of QC phase
binding energy Eb range far from EF the Al sp-derived states stabilization. Electronic structure calculations4,29,30 predicted
have clear dispersive character and hence are effectively that the density of states (DOSs) near EF should have two
delocalized20,21. The observed dispersion character is close to features: a pseudogap at EF with its characteristic energy scale of
free-electron like (FE like) with the effective mass ratio m*/meE1. the order of 1 eV and much finer spikes and mini-pseudogaps
Moreover, k-space locations of the sp-bands observed in ARPES with their characteristic scale of the order of tens of meV. The
correspond to the reciprocal lattice vectors G dominant in LEED coexistence of these two types of the DOS features in decagonal
in both periodic and QP directions in agreement with theoretical QCs has been confirmed by various techniques13,15,16,31
calculations22,23. The survival of FE-like dispersion in the including photoemission spectroscopy and scanning tunnel
aperiodic QC media is similar in nature to the incommensurate spectroscopy. The eV-scale pseudogap at EF is believed to result
periodicities, found, for example, in one-dimensional Peierls from the destructive interference of Fermi states at the boundaries
compounds, where the same phenomena was observed in ARPES of the first q-BZ, which is referred as the Hume–Rothery (HR)
experiment24. The spectral weight in such structures is mechanism, and/or the hybridization between transition metal
redistributed in accordance with the strength of the crystal (TM) d-states and Al sp-states12 (sp-d hybridization), while the
potential and the structure factor in k-space and concentrated relative weight of these two mechanism has not been defined yet.
mainly on the FE-like parabola. The corresponding q-Brillouin In turn, the meV-scale pseudogaps could appear due to the
zone (q-BZ) in the tenfold plane could be defined as a boundary scattering of the Al sp-states at the boundaries of the higher-order
between the central diffraction maximum and the most intense q-BZs or due to the localized character of the electron wave
reflections in diffraction pattern25,26. According to the function near EF. Since the QC structure provides a higher
Spot Profile Analysis (SPA)-LEED study27, these high-intensity symmetry of the q-BZ comparing with the periodic lattice, the
spots are distributed over a circle with a radius k of B2.7 Å  1. HR mechanism could significantly contribute to the formation of
Along the periodic direction, the unit cell includes two non- this large pseudogap (HR gap), thus being a driving force
equivalent adjacent aperiodic planes, nevertheless the effective of QC phase stabilization. The HR electron concentration rule
size of the q-BZ along the periodic axis in k-space is doubled and recently was revised theoretically using full potential linearized
is equal to 4p/c due to the non-symmorphic space group augmented planewave method for QC approximants
symmetry of d-AlNiCo (analogous, for example, to graphite28). involving sufficient number of the plain waves expansion11.

a b c

ky || (00110)
kz , 2/c || e5

e2 (01000) 2
e3 (00100)
e1 (10000), 1
ky
kx 0
e5 (00001)
e4 (00010)
–2 4
kx 0 2
kx , –1
2 0
Å –1 ,Å
ky

Figure 1 | Quasicrystaline lattice basis and the model of electronic structure. (a) Set of reciprocal lattice base vectors. (b) LEED from the clean tenfold
surface measured at electron beam energy Ee ¼ 43 eV. (c) Section of the theoretical FS model in k-space in the simplest case that implies only central FE-
like sphere and set of tenfold surrounding spheres with strongest diffraction intensity.

2 NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications

& 2015 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607 ARTICLE

At the same time, although the sp-d hybridization may indeed Increase of the photoelectron mean free path l at higher
form a pseudogap at EF, it is less likely to stabilize the photoelectron energies make the SX-ARPES experiment more
QC structure because, with the d-states beingD localized, E bulk sensitive33, which is essential for the QC samples because
the interaction integral between sp- and d-states jsp jH jjd their surface stoichiometry may be distorted by structural defects
(where H is the Hamiltonian) that contributes to the system total and surface segregation. In addition, SX-ARPES reduces the final-
energy, responds only smoothly to a variance of the atomic state effects distorting the photoemission response of the valence
positions. states, in particular because the increase of l scales down electron
In this study, we endeavour to observe the 3D FS of a bulk QC momentum broadening in the surface normal direction34, thus
and to understand the role of pseudogap in stabilization allowing accurate resolution of the native 3D bulk dispersions
mechanism of QC structure. We demonstrate that FS consists E(k). The tenfold (00001) surface of the sample was oriented
of dispersive Al sp-states with large contribution from high-order normal to the analyser axis. We varied the surface perpendicular
bands. We show that FS–BZ interaction is highly anisotropic, momentum kz of the probed valence states through the photon
which results in a different magnitudes of HR gaps along QC and energy hv and their k|| through the emission angle (refer also to
periodic directions. the Methods section).
The entire set of our experimental results is presented in Fig. 2.
Results The sketch in Fig. 2a shows the main features of the
FS contours in QC planes. In ARPES, the HR gap should be experimentally observed 3D FS. It differs from the one presented
clearly observed as bending of the band dispersions closer to EF32 in Fig. 1c because of the specific structure factor due to the non-
at the q-BZ boundary, which leads to the formation of a symmorphic space group symmetry of d-AlNiCo. In addition,
pseudogap at EF. As a consequence, the FS should be not a sphere previous theoretical simulations of the photoemission from QCs
anymore but should break into a set of discrete pockets. To suggested that there is a certain threshold for the relative strength
observe the 3D FS, we performed soft X-ray ARPES (SX-ARPES) of the lattice potential35, which significantly reduces the number
experiments in the vicinity of EF on decagonal AlNiCo QCs. of observable bands in the typical photoemission experiment.

Min Max

b e h
0
1

E–EF, eV
0 –4
ky , Å–1

–1
–8
–2
a
–12
12 –2 –1 0 1 2 –2 –1 0 1 2 –3 –2 –1 0 1
k|| , Å–1
kz , 2/c

c f j
10 ⎡10 0
0
E–EF, eV
ky , Å–1

⎡9 –2
8 –1

–2 –4
–2 2
kx 0 0 –1
, Å –1 2 Å
–2 k y , –2 –1 0 1 –2 –1 0 1 –1 0 1
kx , Å–1
i d g k
0 0
10 ⎡10
E–EF, eV

–2
E–EF, eV
kz (2/c)

–5
–4

–10 9 ⎡9 –6
–1
–2 –1 0 1 2 –2 –1 0 1 2 –8
k 0
x ,Å 1 1 9.2 9 8.8
–1 0 kx , Å–1 kx , Å–1
–1 –1 kz (2/c)
ky , Å

Figure 2 | SX-ARPES data. (a) Sketch of the 3D FS observed in the current experiment with the planes corresponding to the different cuts represented in
b–g. Red arrows denote the possible directions where eV-scale HR gap can appear in addition to the one observed along the periodical direction. (b–d)
Constant binding energy maps (CEMs) corresponding to the FS cut acquired along the planes parallel to the sample surface at kz ¼ 10  (2p/c) denoted as
G10-point (b) kz ¼ 9  (2p/c) denoted as G9-point (c) and perpendicular to the sample surface at ky ¼ 0 (d). (e–g) CEMs at Eb ¼  0.6 eV acquired at the
same planes as (b–d). The blue and green circles are the guide for the eye lines of Al sp-dispersion contours. (h,j,k) The ARPES intensity (logarithmic
grayscale for h and j) maps I(Eb, k||) measured along the directions shown with red arrows in e–g, respectively. (i) The 3D sketch of the sp-band dispersion
parabola Eb (kx,ky) hybridized with the TM-d flat band.

NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications 3

& 2015 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607

Photoelectron intensity maps at constant Eb (constant energy circles. It again confirms that the energy scale of the HR gap in QP
maps, CEMs) were acquired in planes in k-space shown in the plane (if present) should be in sub-eV scale.
sketch in Fig. 2a. These CEMs are reported for two different Eb:
corresponding to the FS (Fig. 2b–d) and halfway between EF and
SX-ARPES along periodic direction. The FS character along the
TM d-bands maximum (Fig. 2e–g). Surprisingly, in CEM
periodic direction is different however. In CEMs measured along
measured parallel to the surface at kz in the G10-point (centre
the periodic axis (Fig. 2d,g), we observe sharp features at kz at the
of the tenth BZ along the periodic axis, hv ¼ 875 eV), we observed
G10- and G9-point, whereas between them we find a continuum of
a sharp and almost unaltered contour of FE-like Al sp-bands
states without any well-defined dispersions. From the I(Eb, k||)
at EF (Fig. 2b) with the Fermi momentum k0FE1.57 Å  1 (shown
measured in the same plane along kz near the G9-point (Fig. 2k),
as a blue circle at lower Eb in Fig. 2e). Apart from the circle-like
it becomes clear that there are also no dispersive Al sp-states from
contour of dispersive Al sp-states centred at surface parallel
EF to TM d-band at kx ¼ 0 near G9-point. This observation
momentum k|| ¼ 0, there is a small hole-like pocket at k|| ¼ 0 with
unveils the occurrence of the Bragg scattering of Al sp-states close
kFE0.3 Å  1 and a manifold of surrounding electron-like pockets
to the EF at the effective q-BZ boundary between two even
with k1FE0.7 Å  1 with tenfold symmetry (green circles in
G-points in periodic direction since the Fermi momentum k0F
Fig. 2e). The centres of these latter e-pockets are distributed on
matches 2p/c ¼ 1.54 Å  1—the periodicity along kz. The observed
a circle with kE2.7 Å  1, which corresponds to the radius of the
gap of the eV-scale reduces the integrated DOS of the occupied
ð00110Þ reflections in the LEED pattern27. These directions
states at EF, minimizing the total energy of the system. Formation
belong
P to the set of twofold D axes rotated by p/10 from the
of such a gap is a keystone of HR mechanism and should indeed
axes, both having different intensity distribution patterns in
electronically stabilize the sample structure, but unexpectedly this
diffraction26.
eV-scale gap was observed only in periodical direction. With this
The ARPES intensity map at G10-point as a function of Eb
observation, we can conclude that the HR mechanism in
and k|| (I(Eb, k||)) along the axis, which belongs to the set of
d-AlNiCo exhibits strong anisotropy: the eV-scale HR gap
D axes is shown in Fig. 2h, where to enhance the figure contrast,
appears along the periodic direction, while the energy scale of the
we applied the background subtraction procedure (refer to the
HR gap in QP planes has to be in the sub-eV range. We
Methods section). The map appears to be quite complex in
emphasize that these experimental results are consistent with the
dispersion, especially in a region from EF to 3 eV in binding
scanning tunnel spectroscopy studies, which found a manifold of
energy, due to the contribution of the higher-order dispersions
locally dependent sets of small (20–50 meV) gaps in the occupied
that originates from other points of the dense reciprocal
DOS of d-AlNiCo16,31. The theoretical calculations of the spectral
lattice. Nevertheless, one can recognize that the FE-like parabola
density along the D axis of the 2D Penrose tiling22 also revealed
of Al sp-band is effectively divided in two energetic regions
the gaps near centre of the bands due to the localized character of
as a result of the sp-d hybridization, which is schematically shown
the states rather than scattering at the q-BZ boundary.
in Fig. 2i in 3D (see the Methods section and Supplementary
It is interesting as well to correlate the observed energy scale
Fig. 3). In this figure, the lower part of the sp-band paraboloid
anisotropy with well-studied vibrational spectra of the QCs. A
Eb (kx,ky) is shown in green and the upper part near the EF in
larger pseudogap between the optic and acoustic excitation was
blue. The high-Eb part of the Al sp-band in Fig. 2h appears
observed in 1/1 approximant comparing with the QC counter-
to be more blurred than its near EF counterpart due to the effects
part36, suggesting the stronger Bragg-plane reflection for the
of electron momentum broadening in the surface normal
periodic structure. On the other hand, inelastic neutron
direction and increased DOSs of TM d-bands at higher Eb. In
scattering37 did not reveal a significant anisotropy between the
addition, the sp-d hybridization slightly reduces the value
vibrational modes along the QP and periodic directions in
of kF of the Fermi states, but does not affect the FS continuity.
d-AlNiCo.
The survival of the FE-like FS contour and the absence of
We note that the previous VUV-ARPES data21, presented in
dispersion bands bending near EF suggest that the energy scale of
the high-Eb sector of electronic structure, have certain differences
the pseudogap, induced by the HR mechanism in QP plane,
respective to our SX-ARPES data in the number of the bands
is either vanishingly small or at least less than B70 meV, which
observed. Contributing to these differences can be, first,
is half of our actual experimental resolution. This value is
the highly different degree of surface sensitivity. Second,
significantly smaller than the reported value of the pseudogap of
VUV-ARPES poorly defines the kz component, which is
1 eV order31.
intrinsically limited by non-FE character and kz broadening of
Due to the non-symmorphic space group symmetry, completely
low-energy final states34. Finally, the final-state wavevector kf in
different CEMs were observed at kz in the G9-point (hv ¼ 720 eV),
VUV-ARPES is much smaller than in SX-ARPES. If we treat the
which would otherwise be identical to G10-point. Figure 2c,f f
ARPES final state as a plane wave jkf ðr Þ ¼ ekf r with weak
reveals very intense central ring with k1F (green circle in Fig. 2f)
damping towards the crystal interior, the photoemission intensity
and less pronounced tenfold large circles with radius k0F f
appears essentially as a matrix element hjkf ðr ÞjHint jjik ðr Þi
surrounding this circle (blue circles in Fig. 2f). The former ring i
between the initial state jk ðr Þ transformed by the
corresponds to an electron-like pocket with band minimum f
dipole operator Hint and the final state jkf ðr Þ. Therefore, the
around EbE  2 eV as can be seen from I(Eb, k||) acquired parallel
VUV- and SX-photoemission probe different low- and high-k
to kx through G9-point (Fig. 2j). Obviously, this electron-like
Fourier components, respectively, of the transformed initial state.
pocket is a result of intersection of FE-like Fermi spheres formed
by Al sp-states and centred at G-points at nearest even BZs along
the periodic axis. The 2p/c shift of small and large e-pockets along Simulation of the FS contours in QC planes. To simulate the
the kz (blue and green circles in Fig. 2e,f) is consistent with the stronger in-QP-plane HR gap at the EF, we utilized a 3D theo-
results of the SPA-LEED experiment27, where the same shift in the retical model that consists of the single near-EF part of Al sp-d
periodicity along kz of the full width at half maximum of the hybridized bands (blue part of the hybridized sp-d band in Fig. 2i)
central and kE2.7 Å  1 diffraction spots was observed. In centred at the same spots in k-space as observed in the present
addition, we note that the large circles that surround the central experiment (see the Methods section). We simulated the FS cuts
electron-like pocket in Fig. 2c do not show any significant gaps at along k|| at kz in the even and odd G-points with and without
EF at intersection points and one can see the crossing arcs of these Bragg scattering at the q-BZ boundaries in the QP and periodic

4 NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications

& 2015 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607 ARTICLE

4.5
a c e

ky , Å–1
0

–4.5
4.5
b d f
ky , Å–1

–4.5
–4.5 0 4.5 –4.5 0 4.5 –4.5 0 –4.5
kx , Å–1 kx , Å–1 kx , Å–1

Figure 3 | Simulation of FS contours. (a,b) Simulation results of the CEMs at EF at kz in the G10- and G9-points, respectively, in (kx,ky) plane without the
Bragg scattering at the q-BZ boundaries. (c,d) Same as a and b, but with the Bragg scattering allowed at the q-BZ boundaries only in periodical direction.
(e,f) Same as a and b, but with the Bragg scattering allowed at the q-BZ boundaries in both QP and periodical directions.

directions (Fig. 3). These cuts reflect the measured CEMs shown the periodic and aperiodic planes of d-AlNiCo. With our results,
in Fig. 2b,c with different parameters of the scattering strength at we hope to stimulate the advanced theories capable of explaining
q-BZ boundaries taken into account. The value of the scattering the observed anisotropy from first principles.
strength was chosen to provide the HR gap of eV-order for the
QP and periodic directions to match the experimentally observed Methods
value of the HR gap along the kz axis (Fig. 2k). Corresponding Samples and SX-ARPES measurements. Single crystals of decagonal AlNiCo
dispersion relations Eb (kx,ky ¼ 0) for different cases shown in with the bulk composition Al70Ni20Co10 were grown by means of Czochralski
method. Slow growth out of the melt over 300 h at the solidification temperature
Fig. 3a–f are presented in Supplementary Fig. 4a–f, respectively. ensured high sample quality. The (00001)-oriented surface (tenfold) of AlNiCo was
From Fig. 3, it becomes clear that the experimentally observed FS cleaned by cycles of Ar þ ion sputtering and subsequent annealing up to 750 °C
(Fig. 2b,c) corresponds better to the case when the eV-scale HR leading to sharp tenfold symmetric LEED (Fig. 1b) and the single metallic com-
gap is present along the periodic direction only (Fig. 3c,d), while ponent in Al2p core level photoemission spectrum. The measurements were con-
the same HR gap present in both periodic and QC planes should ducted at the ADRESS beamline at Swiss Light Source synchrotron facility, Paul
Scherrer Institute, Switzerland, using photon energy range hv ¼ 315–1,000 eV and
significantly alter the FS contours (Fig. 3e,f). different polarizations of incident X-rays33. The temperature of the samples during
the measurements was around 12 K. The combined (beamline þ analyser) energy
resolution was down to 70 meV. The analyser entrance slit was oriented along the
Discussion X-ray beam incident on the sample at a grazing incidence angle of 20° (for further
It is commonly believed that there are two main alternative experimental details see ref. 33).
mechanisms for stabilization of the QP phase: the energy
stabilization with the QC ground state and the entropy Data processing. Due to the absence of the translational periodicity in the QC
stabilization with a crystalline phase at low temperature38. The lattice and a small Al-sp cross-section at the given photon energies, the quasi-
observed energy scale of the HR gap along the QC direction is particle peaks in valence band maps are rather weak and broadened along the
momentum axis. Nevertheless, the raw data itself allowed us to recognize imme-
significantly lower or even vanishing compared with the one diately the Al sp-bands at main high-symmetry points (Supplementary Fig. 1a). To
along periodic direction, suggesting that the in-QC-plane increase the quality of the observed dispersions, we applied several procedures to
(aperiodic) structure does not lead to a significant Peierls-type the measured ARPES intensity maps I (Eb, k||). First, the background from the
energy contribution to the structural stability. On the other hand, charge-coupled device was taken into account and subtracted from the raw image.
At the second step, the non-dispersive intensity from TM d-states was suppressed
there could be an additional contribution to the 3D structure by subtraction of the substantially smoothed in momentum directions ARPES
stabilization via the HR gaps along the ‘off-symmetry’ directions intensity map I (Eb, k||) from the original raw images. The resulting processed
shown in Fig. 2a with red arrows. In fact, the distance in k-space image is shown in Supplementary Fig. 1b. The subtraction of the strongly
between centres of FE-like sphere at k|| ¼ 0 at G10-point and smoothed image was also applied for the contrast enhancement in constant binding
energy maps (CEMs).
tenfold FE-like spheres observed on a radius k|| ¼ 2.7 Å  1 at
G9-point (Fig. 2a) matches the diameter of these spheres
d ¼ 2  k0F, thus enabling the possibility for the eV-scale HR gap Polarization dependencies and sp-d hybridization. All the data presented in the
paper were measured using the p-polarized light. The valence band maps measured
to appear. For the icosahedral QC, due to the presence of only at G9-point in s-polarized and p-polarized light are shown in Supplementary
aperiodic planes, we suppose that the energy scale of HR gaps is Fig. 2a,b, respectively. Interestingly, the photoemission intensity from the dis-
more likely to be uniform. persive Al states vanishes in s-polarized light (anti-symmetric in the given
We note that the direct observation of the FS–BZ scattering experimental geometry) confirming the symmetric nature of these states with
respect to the measurement plane. The degree of hybridization between Al sp- and
anisotropy has only been possible by the virtue of accurate TM d-states could be estimated from the angle integrated spectra measured at
definition of 3D electron momentum achieved with SX-ARPES. G-points at kz ¼ 6  (2p/c) (hvE315 eV) and kz ¼ 10  (2p/c) (hvE875 eV) shown
This has been essential to disentangle the electron dispersions in in Supplementary Fig. 1c. Two spectra almost coincide however the relative

NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications 5

& 2015 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607

cross-section of Al sp-states to TM d-states increases significantly with the photon new Hume-Rothery electron concentration rule. Philos. Mag. 92, 1691–1715
energy39. Moreover, the sp-d hybridization is clearly observed in Fig. 2h as a (2012).
bending of Al sp-bands closer to the original TM d-states to avoid crossing. This 12. Belin-Ferré, E. Electronic structure of quasicrystalline compounds. J. Non-Cryst.
effectively divides the dispersion of Al sp-states into two regions with different Eb Solids 334-335, 323–330 (2004).
range (Fig. 2i). As a consequence, at G9-point, there is an additional spectral weight 13. Stadnik, Z., Purdie, D., Garnier, M. & Baer, Y. Electronic structure of
at EbB4.5 eV near kx ¼ 0 that comes from higher Eb part of the Al sp-dispersion at quasicrystals studied by ultrahigh-energy-resolution photoemission
G10- and G8-points (Supplementary Fig. 2a). spectroscopy. Phys. Rev. B 55, 10938–10951 (1997).
14. Okada, J. & Watanabe, Y. Electron momentum distribution of decagonal
The theoretical model and simulation results. The model to simulate the Al72Ni12Co16 studied by Compton scattering. J. Phys. Condens. Matter 14,
dispersion of the sp-bands in the d-AlNiCo structure is based on multiple Bragg L43–L48 (2002).
reflections of the nearly free electrons on a set of the major components of the 15. Suzuki, T. et al. Electronic structure of the topmost tenfold surface of decagonal
reciprocal quasi-lattice {Gi}. For a given k-vector, the corresponding tight binding Al-Ni-Co quasicrystal. Phys. Rev. B 72, 115427 (2005).
Hamiltonian can be written as follows: 16. Mäder, R., Widmer, R., Gröning, P. & Deloudi, S. High-resolution scanning
X X   tunneling microscopy investigation of the (12110) and (10000) two-fold
H ðk Þ ¼ eðk  Gi Þcyk;Gi ck;G

i
þ ^ Gj  Gi cy ck;G
V k;Gj

i
: ð1Þ symmetric d-Al-Ni-Co quasicrystalline surfaces. Phys. Rev. B 80, 035433
Gi hGi ;Gj i (2009).
17. Soda, K. et al. Spectroscopic study of Ni-rich Al–Co–Ni quasicrystal. Philos.
Here cyk;Gj and ck;G

j
are denoting the creation and annihilation operators, Mag. 91, 2510–2518 (2011).
respectively, hGi ; Gj i denotes the pairwise sum for Gi 6¼ Gj and V ^ represents the 18. Nayak, J. et al. Bulk electronic structure of quasicrystals. Phys. Rev. Lett. 109,
valence electron potential in reciprocal space. The kinetic energy term of the model 216403 (2012).
Hamiltonian was chosen to match the lower-Eb part of the hybridized sp-d band 19. Nayak, J. et al. Bulk electronic structure of Zn-Mg-Y and Zn-Mg-Dy
(blue curve in Supplementary Fig. 3) with k0F ¼ 1.57 Å  1, which was fitted with the icosahedral quasicrystals. Phys. Rev. B 91, 235116 (2015).
polynomial equation: 20. Rotenberg, E., Theis, W., Horn, K. & Gille, P. Quasicrystalline valence bands in
decagonal AlNiCo. Nature 406, 602–605 (2000).
eðk  Gi Þ ¼ a0 þ a1 ðk  Gi Þ2 þ a2 ðk  Gi Þ4 þ a3 ðk  Gi Þ6 ; ð2Þ 21. Rotenberg, E., Theis, W. & Horn, K. Electronic structure investigations of
quasicrystals. Prog. Surf. Sci. 75, 237–253 (2004).
where a0 ¼  1.34, a1 ¼ 0.25, a2 ¼  0.03 and a3 ¼ 0.06. The selection of a finite set
22. Niizeki, K. & Akamuatsu, T. The reciprocal space properties of the electronic
of {Gi} for the calculation was made according to the most intense spots in the
wave functions of the Penrose lattice. J. Phys. Condens. Matter 2, 7043–7047
LEED. The set of {Gi} consists of an alternating stack in kz at (kx,ky) ¼ (0,0)
with kz ¼  3.08, 0 and 3.08 Å  1 and a tenfold rings with |k| ¼ 2.71 Å  1 at (1990).
kz ¼  4.62,  1.54, 1.54 and 4.62 Å  1. This gives a total of 43 reciprocal vectors. 23. Niizeki, K. & Akamatsu, T. Special points in the reciprocal space of an
The strength of the potential V ^ ðqÞ was modelled as a Gaussian centred at k0: icosahedral quasi-crystal and the quasi-dispersion relation of electrons. J. Phys.
Condens. Matter 2, 2759–2771 (1990).
 2 24. Voit, J., Perfetti, L., Zwick, F. & Berger, H. Electronic structure of solids with
V ^ 0  exp  ðjqj  k0 Þ ;
^ ð qÞ ¼ V ð3Þ
2s 2 competing periodic potentials. Science 290, 501 (2000).
^ 0 stands for the strength 25. Niizeki, K. A classification of special points of quasilattices in two dimensions.
where q is the difference between pair of G-vectors, V J. Phys. A Math. Gen. 22, 4281–4293 (1989).
of the potential, k0 ¼ 2.7 Å  1 and s ¼ 0.84 Å  1. The parameter values were
26. Niizeki, K. The diffraction pattern of a non-Bravais-type quasicrystal with
chosen to induce a gap of 1-eV order at EF at q-BZ boundaries. Figure 3a,b shows
application to a decagonal quasicrystal. J. Phys. Soc. Jpn 63, 4035–4043 (1994).
the simulation result for the CEMs at EF at G10- and G9-points along the kz,
^ 0 set to zero, which corresponds to 27. Gierer, M., Mikkelsen, A., Gräber, M., Gille, P. & Moritz, W. Quasicrystalline
respectively, with the strength of the potential V
surface order on decagonal Al72.1Ni11.5Co16.4: An investigation with spot profile
the absence of the Bragg scattering at the q-BZ boundaries. Figure 3c,d shows the
^ 0 had a value of  0.7 eV for analysis LEED. Surf. Sci. 463, L654–L660 (2000).
simulation result when the strength of the potential V
the periodic direction, while for the QP direction it was set to zero. This case 28. Chung, D. D. L. Review graphite. J. Mater. Sci. 37, 1–15 (2002).
corresponds to the occurrence of the Bragg scattering at the q-BZ boundaries along 29. Fujiwara, T. & Yokokawa, T. Universal pseudogap at Fermi energy in
the periodic direction only. Finally, Fig. 3e,f shows the simulation result when the quasicrystals. Phys. Rev. Lett. 66, 333–336 (1991).
strength of the potential V^ 0 was set to  0.7 eV for both QP and periodic direction. 30. Smith, A. & Ashcroft, N. Pseudopotentials and quasicrystals. Phys. Rev. Lett. 59,
The corresponding cuts Eb (kx,ky ¼ 0) for different cases shown in Fig. 3a–f are 1365–1368 (1987).
presented in Supplementary Fig. 4a–f, respectively. 31. Mäder, R., Widmer, R., Gröning, P., Steurer, W. & Gröning, O. Correlating
scanning tunneling spectroscopy with the electrical resistivity of Al-based
quasicrystals and approximants. Phys. Rev. B 87, 075425 (2013).
References 32. Trambly de Laissardière, G., Nguyen-Manh, D. & Mayou, D. Electronic
1. Yamamoto, A. Crystallography of quasiperiodic crystals. Acta Crystallogr. A 52, structure of complex Hume-Rothery phases and quasicrystals in transition
509–560 (1996). metal aluminides. Prog. Mater. Sci. 50, 679–788 (2005).
2. Steurer, W., Haibach, T., Zhang, B., Kek, S. & Lück, R. The structure of 33. Strocov, V. N. et al. Soft-X-ray ARPES at the Swiss Light Source: From 3D
decagonal Al70Ni15Co15. Acta Crystallogr. B B49, 661–675 (1993). Materials to Buried Interfaces and Impurities. Synchrotron Radiat. News 27,
3. Steurer, W. Twenty years of structure research on quasicrystals. Part I. 31–40 (2014).
Pentagonal, octagonal, decagonal and dodecagonal quasicrystals. Z. Kristallogr. 34. Strocov, V. N. Intrinsic accuracy in 3-dimensional photoemission band
219, 391–446 (2004). mapping. J. Electron Spectrosc. Relat. Phenom. 130, 65–78 (2003).
4. Trambly de Laissardière, G. & Fujiwara, T. Electronic structure and transport in 35. Rotenberg, E., Theis, W. & Horn, K. Model simulations of momentum-resolved
a model approximant of the decagonal quasicrystal Al-Cu-Co. Phys. Rev. B 50, photoemission from quasicrystals. J. Alloys Compd. 342, 348–351 (2002).
9843–9850 (1994). 36. De Boissieu, M. et al. Lattice dynamics of the Zn-Mg-Sc icosahedral
5. Krajčı́, M., Hafner, J. & Mihalkovič, M. Atomic and electronic structure of quasicrystal and its Zn-Sc periodic 1/1 approximant. Nat. Mater. 6, 977–984
decagonal Al-Ni-Co alloys and approximant phases. Phys. Rev. B 62, 243–255 (2007).
(2000). 37. Dugain, F. et al. Inelastic neutron scattering study of the dynamics of the
6. Smontara, A., Smiljanić, I., Ivkov, J. & Stanić, D. Anisotropic magnetic, AlNiCo decagonal phase. Eur. Phys. J. B 7, 513–516 (1999).
electrical, and thermal transport properties of the Y-Al-Ni-Co decagonal 38. Steurer, W. & Deloudi, S. Decagonal quasicrystals - What has been achieved? C.
approximant. Phys. Rev. B 78, 104204 (2008). R. Phys. 15, 40–47 (2014).
7. Inukai, M., Soda, K., Kato, M., Yagi, S. & Yokoyama, Y. Cluster study of 39. Yeh, J. & Lindau, I. Atomic subshell photoionization cross sections and
Al–Co–Ni decagonal quasicrystal. Z. Kristallogr. 223, 851–854 (2008). asymmetry parameters:1oZo103. At. Data Nucl. Data Tables 32, 1–155 (1985).
8. Mizutani, U. et al. e/a Determination for the transition metal element TM in
Al–Cu–TM–Si (TM ¼ Fe and Ru) approximants and B2-compounds by means
of the FLAPW-Fourier method. Z. Kristallogr. 224, 17–20 (2009).
9. Komelj, M., Ivkov, J., Smontara, A. & Gille, P. Origin of the Hall-coefficient Acknowledgements
anisotropy in the Y–Al–Ni–Co periodic approximant to the decagonal phase. V.A.R. was supported by Swiss Federal Commission for Scholarship FCS. We thank
Solid State Commun. 149, 515–518 (2009). Professor P. Gille for preparing the Al–Ni–Co single crystal used in this study. We are
10. Dolinšek, J. et al. Anisotropic magnetic and transport properties of also thankful to Professor K. Horn, Professor R. Claessen, Professor P. Aebi and S. Moser
orthorhombic Al13Co4. Phys. Rev. B 79, 184201 (2009). for the promoting discussions and encouragement. Experiments were performed at the
11. Mizutani, U., Inukai, M., Sato, H. & Zijlstra, E. S. Hume-Rothery stabilization Advanced Resonance Spectroscopy beamline of the Swiss Light Source synchrotron
mechanism and e/a determination in MI-type Al–Mn, Al–Re, Al–Re–Si, facility within the Paul Scherrer Institute, Switzerland. The technical support from
Al–Cu–Fe–Si and Al–Cu–Ru–Si 1/1-1/1-1/1 approximants – a proposal for a M. Kropf, F. Dubi, C. Hess and L. Nue is gratefully acknowledged.

6 NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications

& 2015 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms9607 ARTICLE

Author contributions Reprints and permission information is available online at http://npg.nature.com/

V.A.R., V.N.S. and O.G. developed project conception and planned the experiment. O.G., reprintsandpermissions/
R.W., V.A.R. and F.B. prepared sample surface for measurements. V.A.R., F.B., L.L.L. and
How to cite this article: Rogalev, V. A. et al. Fermi states and anisotropy of
V.N.S. performed SX-ARPES experiment. V.A.R., V.N.S. and O.G. analysed the data and
Brillouin zone scattering in the decagonal Al–Ni–Co quasicrystal. Nat. Commun. 6:8607
wrote the manuscript draft. All authors extensively discussed the results and the
doi: 10.1038/ncomms9607 (2015).
manuscript.

This work is licensed under a Creative Commons Attribution 4.0

International License. The images or other third party material in this
Additional information
article are included in the article’s Creative Commons license, unless indicated otherwise
Supplementary Information accompanies this paper at http://www.nature.com/
naturecommunications in the credit line; if the material is not included under the Creative Commons license,
users will need to obtain permission from the license holder to reproduce the material.
Competing financial interests: The authors declare no competing financial interests. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

NATURE COMMUNICATIONS | 6:8607 | DOI: 10.1038/ncomms9607 | www.nature.com/naturecommunications 7

& 2015 Macmillan Publishers Limited. All rights reserved.