Antiferromagnetic order in Co-doped Fe5 GeTe2 probed by resonant magnetic x-ray

scattering

Xiang Chen,1, 2, ∗ Enrico Schierle,3 Yu He,4, 2, 1 Mayia Vranas,5 John William Freeland,6 Jessica.
L. McChesney,6 Ramamoorthy Ramesh,7, 1, 2 Robert J. Birgeneau,2, 1, 7 and Alex Frano5, †
1
Materials Science Division, Lawrence Berkeley National Lab, Berkeley, California 94720, USA
2
Physics Department, University of California, Berkeley, California 94720, USA
3
Helmholtz-Zentrum Berlin für Materialen und Energie, BESSY II, D-12489 Berlin, Germany.
4
Department of Applied Physics, Yale University, New Haven, Connecticut, 06511, USA
5
Department of Physics, University of California, San Diego, California 92093, USA
6
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, USA
7
Department of Materials Science and Engineering,
arXiv:2207.14412v1 [cond-mat.mtrl-sci] 28 Jul 2022

University of California, Berkeley, California 94720, USA

(Dated: August 1, 2022)
The quasi-two-dimensional van der Waals magnet Fe5−δ GeTe2 has emerged as a promising plat-
form for electronic and spintronic functionalities at room temperature, owing to its large ferromag-
netic ordering temperature TC ∼ 315 K. Interestingly, by cobalt (Co) substitution of iron in F5GT,
i.e. (Fe1−x Cox )5−δ GeTe2 (Co-F5GT), not only can its magnetic transition temperature be further
enhanced, but the magnetic and structural ground states can also be tuned. Specifically, an anti-
ferromagnetic (AFM) order is induced beyond the Co doping level x ≥ 0.4. Here, we investigate
the magnetic properties of a Co-F5GT single crystal at x = 0.45(1), by utilizing the element spe-
cific, resonant magnetic x-ray scattering technique. Our study reveals an A-type, Ising-like AFM
ground state, with a transition temperature TN ∼ 340 K. In addition, our work unveils an impor-
tant contribution from Co magnetic moments to the magnetic order. The application of the in-plane
magnetic fields gradually polarize the spin moments along the field direction, but without inducing
incommensurate spin texture(s).

The unique nature of the cleavable, quasi-two- lar magnetic metal, which hosts a metastable, zero-field
dimensional (quasi-2D) van der Waals (vdW) materi- Néel-type skyrmion lattice at RT, was discovered at x =
als offers rich platforms for exploring both exotic phys- 0.5 of Co-F5GT [36, 37]. The aforementioned observa-
ical phenomena and technological applications [1–9]. A tions of the Co-F5GT system highlight its immense tun-
broad variety of intriguing physical phenomena have been ability and capacity for unusual magnetic properties and
reported in recent years by investigating the (atomi- could render applications in next-generation spintronics.
cally thin) vdW bonded compounds. Some exceptional Despite the reports of exotic magnetic textures such
phenomena include unconventional superconductivity in as the chiral soliton lattices and skyrmions in F5GT or
twisted graphene [10], nonlinear Hall effect in few-layer Co-F5GT [36, 38, 39], there is a scarcity of information
WTe2 [11, 12], 2D magnetism in monolayer Cr2 Ge2 Te6 from neutron scattering studies of these systems. The
[13, 14], CrI3 [15, 16] and the quantum anomalous Hall challenge of growing single crystals large enough for neu-
effect in insulating tellurides [17, 18]. Among the differ- tron experiments hinders the timely investigations of the
ent materials, the layered vdW, itinerant magnets rep- magnetic properties of Co-F5GT. Here, we demonstrate
resent ideal quasi-2D material systems which enable the the applicability of utilizing the element specific, resonant
coupling between the electronic and magnetic degrees of magnetic x-ray scattering (RMXS) technique [40–43] to
freedom [1, 4–7]. Therefore, vast opportunities arise be- investigate the bulk magnetic properties of a specific Co-
cause of the rich physical properties and the abundant F5GT single crystal at x = 0.45(1). By tuning the x-ray
possibilities for functional devices [19, 20]. energy E = h̄ω to either the Fe L edges or Co L edges,
Very recently, some promising quasi-2D magnetic tel- our study determines the contribution from both the Fe
lurides [21–33], such as Fe5 GeTe2 (F5GT) and CrTe2 , and Co spin moments to the magnetic order. In addition,
with atomically thin nanoflakes for promising room tem- our scattering data affirms the A-type AFM order, with
perature (RT) spintronics have been reported. The a Néel temperature TN ∼ 340 K and an out-of-plane mo-
F5GT compound has a ferromagnetic (FM) transition ment direction. The influence of external magnetic fields
above RT at TC ∼ 315 K [30, 31]. Intriguingly, on the AFM ground state is also explored and found to
with cobalt (Co) substitution of iron (Fe) in F5GT be consistent with magnetization measurements.
((Fe1−x Cox )5−δ GeTe2 , Co-F5GT), the magnetic transi- Single crystals of Co-F5GT at x = 0.45(1) (labeled
tion temperature is further increased up to ∼ 360 K, here as Co45-F5GT) were synthesized using the chem-
and the magnetic ground state switches from FM to an- ical vapor transfer technique [30, 31, 44]. The chemi-
tiferromagnetic (AFM) when the Co doping level reaches cal composition of the samples was verified by energy
x ≥ 0.4 [34, 35]. Interestingly, a novel wurtzite-type po- dispersive x-ray spectroscopy, with the cation deficiency
 2

FIG. 1. (Color online) (a) The schematic of the res-

onant magnetic x-ray scattering (RMXS) experiment on
a Co doped Fe5 GeTe2 single crystal at x = 0.45(1)
((Fe0.55 Co0.45 )5−δ GeTe2 , Co45-F5GT). (b) The crystal struc-
ture of Co45-F5GT, with the AA stacking order [34, 36, 37].
(c) Temperature dependent magnetization of Co45-F5GT. (d)
In-plane isothermal magnetization of Co45-F5GT at varying
temperatures. The H ∗ is the saturation field, beyond which
the spin moments are fully polarized along the field direction
with a saturation magnetization Msat .

FIG. 2. (Color online) Photon energy dependence of the (0, 0,

|δ| ≤ 0.1. The RMXS experiments were performed at the
0.5) peak at T = 300 K or 350 K. (a) The (0, 0, 0.5) peak at T
UE46− PGM-1 beamline at Helmholtz-Zentrum Berlin = 300 K near the Fe L edges. Maximum intensity is observed
(HZB) and the 29-ID IEX beamline at Advanced Pho- at Fe LIII edge (E = 707.7 eV). (b)-(c) Energy dependent
ton Source (APS) at Argonne National Laboratory. A integrated area of the (0, 0, 0.5) peak at both 300 K and 350
horizontal scattering geometry is utilized with the sam- K, near the Fe L edges (b) and Co L edges (c), respectively.
ple lattice c direction lying within the scattering plane
(Fig. 1(a)). The Bragg peaks Q = (H · 2π 2π 2π
a ,K · b ,L· c )
are defined in reciprocal lattice units (r.l.u.) with lattice
parameters a = b ≈ 4.02 Å and c ≈ 9.80 Å. The data The F5GT compound is composed of three identical
are collected near the Fe and Co L edges to enhance the layers with the rhombohedral layer stacking (space group
magnetic scattering signal [45–47]. The incoming x-ray R3̄m), labelled as ABC-stacking [30]. It was experimen-
is either horizontally polarized (H-pol or π-pol) or verti- tally established that the stacking order in F5GT is sus-
cally polarized (V -pol or σ-pol), but the scattered x-rays ceptible to external perturbations [34, 36, 48]. Upon re-
are not analyzed. Therefore, both outgoing σ 0 -pol and placing Fe with Co in F5GT, when x ≥ 0.4, the crystal
π 0 -pol channels will contribute to the scattered intensity, structure undergoes a transition from ABC-stacking to
which can be written as [42, 43]: AA-stacking (space group P3̄m1, as shown in Fig. 1(b))
[34]. Meanwhile, the magnetic ground state evolves from
X FM at x < 0.4 to AFM when x ≥ 0.4. Our magneti-
Iµν ∝ | eiQ·rj (eµ × e∗ν ) · mj F (E)|2 , (1) zation measurements on the Co45-F5GT sample confirm
j an AFM order, with TN = 341(2) K (Fig. 1(c)). It is
worth emphasizing that a unique type of stacking or-
to first order in the magnetic moment mj of the ion der, labelled as AA0 -stacking, was reported recently at
located at site rj within the unit cell. eµ (µ = σ or π) and x = 0.5 [36, 37]. Néel-type skyrmions were identified
eν (ν = σ 0 or π 0 ) are unit vectors along the polarization at this doping, because of the AA0 -stacking order which
of the electric field component of the incident and out- breaks the inversion symmetry and therefore features a
going x-ray beams, respectively. F (E) is the non-local, bulk Dzyaloshinskii–Moriya interaction [49, 50]. The spin
photon energy dependent scattering tensor. Since the structures of Co-F5GT, however, have not yet been in-
polarization of the scattered light is not analyzed, the vestigated by bulk scattering techniques. Particularly,
measured intensities are IH = Iπ ≡ Iπσ0 + Iππ0 and IV the magnetic ground state, including the spin moment
= Iσ ≡ Iσσ0 + Iσπ0 . direction, shows a strong dependence on the Co doping
 3

FIG. 3. (Color online) Temperature dependence of the (0, 0, FIG. 4. (Color online) Magnetic field dependence of the (0,
0.5) peak, at different energies: (a) Fe LIII edge, E = 708 0, 0.5) peak on resonance. (a) The (0, 0, 0.5) peak at T =
eV, (b) Co LIII edge, E = 778.2 eV. Solid lines in (a)-(b) are 300 K and E = 708 eV, collected under select magnetic fields.
Lorentzian fits to the peak intensity. (c) Power law fits to the Solid lines are Lorentzian fits to the peak intensity. (b) Field
integrated area of the (0, 0, 0.5) peak at both Fe and Co LIII dependence of the integrated area of the (0, 0, 0.5) peak at
edges. For better comparison, the data is normalized to 1 at 300 K, at both Fe and Co LIII edges. The peak intensity is
T = 300 K. completely suppressed beyond H ∗ = 2.4(1) T. The green line
is a fit to the data by assuming the intensity is proportional
to the c component of the magnetization squared m2c . For
level x [30, 31, 36, 38]. Consequently, it is important better comparison, the data is normalized to 1 at zero field.
(c) Phase diagram of the temperature dependent H ∗ , from
to investigate the magnetic properties of Co-F5GT by
both the magnetization and RMXS measurements.
using a direct, bulk-sensitive, element-specific scattering
technique such as RMXS.
Our RMXS experiments were performed on Co45-
F5GT single crystals with the AA-stacking sequence also examined, as shown in Figs. 2-3. With increasing
(P3̄m1, Fig. 1(b)). A strong peak is identified at the temperature, the peak intensity at either the Fe or the Co
structurally forbidden Bragg peak position Q0 = (0, 0, LIII edge is becoming vanishingly small and independent
0.5) below the magnetic onset temperature. To under- of temperature above the transition temperature TN =
stand fully the nature of this reflection, we present a 337(3) K (Fig. 3) [44].
thorough study of its dependence on x-ray energy, po- Both the energy and temperature dependent studies
larization, temperature and magnetic field. Fig. 2 shows in Figs. 2-3 demonstrate the magnetic nature of the
the x-ray energy dependence of the Q0 reflection. Res- (0, 0, 0.5) peak, which is in agreement with the AFM
onant peak profiles were recorded near both the Fe and behavior from the magnetization in Fig. 1(c). This is
Co LIII or LII edges (Fe LIII ∼ 708 eV, Fe LII ∼ 720 further supported by studying the magnetic field H de-
eV, Co LIII ∼ 778 eV and Co LII ∼ 793 eV) [45–47]. A pendence of the Q0 peak on resonance (at both Fe and
single energy dependent peak profile is evident near both Co LIII edges), examined at select temperatures (Fig. 4).
the Fe and Co LIII (LII ) edges. This resonance in photon The field was applied in the ab plane of the sample (Fig.
energy is a strong signature of the magnetic nature of 1(a)). With increasing magnetic field, the Q0 peak in-
the Q0 peak [42, 43, 45–47]. To support this argument tensity is gradually suppressed and reaches almost zero
further, the temperature dependence of the Q0 peak at when H ≥ H ∗ . This can be easily understood since the
the resonance energies (both Fe and Co LIII edges) was applied magnetic fields are polarizing the spins along the
 4

Another important piece of information is the magnetic

moment direction, specifically the magnetic structure be-
low TN . This can be inferred from the representational
analysis [51], the photon polarization and azimuthal de-
pendence of the RMXS data. The magnetic represen-
tation of the crystallographic sites of Fe or Co can be
decomposed in terms of the irreducible representations
(IRs) [51], with the propagation vector Q0 = (0, 0, 0.5)
(Table I): ΓMag = 1Γ12 + 1Γ13 + 1Γ25 + 1Γ26 , where Γ2 , Γ3
are one-dimensional IRs with moments pointing parallel
to the c axis and Γ5 , Γ6 are two-dimensional IRs with
basis vectors lying in the ab-plane.
Considering the AFM nature, only the solutions from
Γ3 and Γ5 are possible. Experimentally, the magnetic
peak intensity at the Q0 position remains the same with
either σ or π polarized incoming x-rays (Fig. 5(a)), which
implies Iπ = Iσ :

X X X
FIG. 5. (Color online) (a) The (0, 0, 0.5) peak, collected at | eiQ·rj kf ·mj |2 = | eiQ·rj ki ·mj |2 +| eiQ·rj eσ ·mj |2
708 eV and 300K, with the incoming x-ray either horizontally j j j
(π-pol) or vertically (σ-pol) polarized. Iσ = Iπ is observed. (2)
(b) The intensity ratio Iσ /Iπ ≈ 1 in a wide range of azimuthal
where ki and kf are the unit vectors along the incom-
angle Ψ, where Ψ = 0 is defined when the [1 0 0] direction is
parallel to the scattering plane. ing and reflected photon wave-vector directions, respec-
tively. The azimuthal Ψ dependence of the Q0 peak was
performed by rotating the sample about the Q0 direction,
which is parallel to the c-axis (Fig. 1(a)), and measuring
field direction. When the magnetic moments are fully the peak intensity for both polarizations. Clearly, Iσ ≈
polarized under H ≥ H ∗ , the magnetic structure enters Iπ is maintained over a broad range of the Ψ angle (Fig.
into the polarized FM state and hence the peak inten- 5(b)). This rules out the possible contribution from Γ5
sity at Q0 disappears. By assuming that the measured since the presence of in-plane moments will manifest as
peak intensity is proportional to the c component of the an angle-dependent azimuthal scan by virtue of rotat-
magnetic moment squared m2c , which equals Msat 2
− Mab2
ing the projections shown in Equation (2). It is evident
from the magnetization data in Fig. 1(d), an excellent that only the solution from Γ3 satisfies Equation (2) (Iπ
agreement is found between the field dependence of the = Iσ ), regardless of the Ψ angle, since the magnet mo-
resonant peak intensity at Fe LIII edge and the measured ments pointing along the c direction are parallel to the
magnetization squared (green line in Fig. 4(b)). Specif- rotation axis along the Q0 direction. From these argu-
ically, the H ∗ values at different temperatures inferred ments, the experimental data determine an A-type AFM
from both the RMXS data and the magnetization data order with Ising moments in Co45-F5GT, as depicted in
also match each other excellently, which are summarized Fig. 1(b).
and plotted as the phase diagram in Fig. 4(c). Our RMXS study together with the magnetization
Combining all evidence, our study confirms the AFM data on the Co45-F5GT single crystals confirm the long-
nature of Co45-F5GT with a propagation vector Q0 = range AFM ground state. Under moderate magnetic
(0, 0, 0.5) and a transition temperature TN ∼ 340 K. fields (H < H ∗ ), this AFM state is still maintained, since
The similar behavior of the magnetic peak at both the the (0, 0, 0.5) magnetic peak is only gradually weakened
Fe or Co L edges indicates an important contribution in magnitude, but without becoming incommensurate or
from the Co spin moments in Co-F5GT. This explains significantly broadened in peak width. This suggests that
why the saturation moment of Co45-F5GT at 10 K (Fig. it is unlikely to have the magnetic field induced exotic
1(d))–Msat ∼ 8 µB per formula unit (f.u.)–is only slightly spin textures in Co45-F5GT with the AA-stacking order,
smaller than the value of Msat ∼ 10 µB per f.u. in F5GT unlike the novel AA0 -stacked structure hosting Néel-type
(x = 0). By assuming the average Fe magnetic moment skyrmion lattices in Co-F5GT at x = 0.50 [36, 37]. The
is unchanged (∼ 2 µB /Fe) [30, 31, 36, 48], the average contrasting magnetic textures in Co-F5GT, albeit with
Co spin moment contribution to the magnetization is es- the similar Co doping level x = 0.45 or x = 0.5, high-
timated to be ∼ 1.1 µB /Co in Co45-F5GT. Clearly, iden- light the essential role of the underlying lattice symmetry,
tifying the presence of an ordered magnetic moment at as well as the contribution from the Co spin moments.
the Co site is an important result of our work. Additionally, the Co magnetic moments appear to play
 5

IR BV Atom BV components HZB for the allocation of synchrotron radiation beam-

mka mkb mkc time. A.F. was supported by the Alfred P. Sloan Foun-
Γ2 ψ 1 1 0 0 1
dation (FG-2020-13773) and the Research Corporation
2 0 0 1
Γ3 ψ 2 1 0 0 1
for Science Advancement via the Cottrell Scholar Award
2 0 0 -1 (27551).
Γ5 ψ 3 1 0 -1 0
2 0 1 0
ψ4 1 -2 -1 0
2 2 1 0
∗
Γ6 ψ 5 1 2 1 0 [email protected]
†
2 2 1 0 [email protected]
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