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Structural, magnetic, and spin dynamical properties of the

polar antiferromagnets Ni_{3−x}Co_{x}TeO_{6}(x=1,2)
Stella Skiadopoulou, Maria Retuerto, Fedir Borodavka, Christelle Kadlec, Filip Kadlec,
Martin Míšek, Jan Prokleška, Zheng Deng, Xiaoyan Tan, Corey Frank, Jose A. Alonso, Maria
Tereza Fernandez-Diaz, Mark Croft, Fabio Orlandi, Pascal Manuel, Emma McCabe, Dominik
Legut, Martha Greenblatt, and Stanislav Kamba
Phys. Rev. B 101, 014429 — Published 21 January 2020
DOI: 10.1103/PhysRevB.101.014429
 Structural, magnetic and spin dynamics properties
of the polar antiferromagnets Ni3-xCoxTeO6 (x=1,2)
Stella Skiadopoulou,1,2,3 Maria Retuerto,4 Fedir Borodavka,1 Christelle Kadlec,1 Filip Kadlec,1 Martin
Míšek1, Jan Prokleška,5 Zheng Deng,4 Xiaoyan Tan,4ξ Corey Frank,4 Jose A. Alonso,6 Maria Tereza
Fernandez-Diaz,7 Mark Croft,8 Fabio Orlandi,9 Pascal Manuel,9 Emma McCabe,10 Dominik Legut,2 Martha
Greenblatt4 and Stanislav Kamba1
1
Institute of Physics,Czech Academy of Sciences, Na Slovance 2, 18221 Prague 8, Czech Republic
2
IT4Innovations, VSB Technical University of Ostrava, 17. listopadu 2172/15, CZ-708 00 Ostrava-
Poruba, Czech Republic
3
School of Physics, CRANN, Trinity College, Dublin 2, Ireland
4
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610
Taylor Road, Piscataway, NJ 08854, USA
5
Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Ke
Karlovu 5, 121 16 Prague 2, Czech Republic
6
Instituto de Ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco, E-28049 Madrid, España.
7
Institut Laue Langevin, BP 156X, Grenoble, F-38042, France
8
Department of Physics and Astronomy, Rutgers, the State University of New Jersey, 136 Frelinghusen
Road, Piscataway, NJ 08854, USA
9
ISIS Facility, STFC, Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire, OX11 0QX, UK
10
School of Physical Sciences, University of Kent, Canterbury, Kent, CT2 7NH, UK
ξ
Current address: Department of Chemistry and Biochemistry, George Mason University, 4400
University Dr, Fairfax, VA 22030

We present results of a multimethod investigation of the polar antiferromagnets Ni2CoTeO6 and NiCo2TeO6,
inspired by the colossal magnetoelectric effect present in Ni3TeO6. Both compounds crystalize in the same
polar space group R3 as Ni3TeO6, preserving the crystal symmetry at least from room temperature down to 2
K. Ni2CoTeO6 and NiCo2TeO6 undergo antiferromagnetic phase transitions at TN=55 and 52 K, and spin-
flop transitions at external magnetic field of approximately 8 and 4 T, respectively. Both compounds present
an incommensurate antiferromagnetic helical structure with spins lying in the ab-plane, in contrast to the
collinear one along c-axis in Ni3TeO6. Moreover, dielectric anomalies are observed at their
antiferromagnetic phase transitions, suggesting a magnetoelectric behavior. Spin and lattice dynamics
studies by a combination of infrared, Raman and terahertz spectroscopies were performed. Below TN, in
both Ni2CoTeO6 and NiCo2TeO6, low-frequency spin excitations extremely sensitive to external magnetic
field were observed. At least one of these magnons was simultaneously seen in Raman and THz spectra of
both compounds, therefore we propose to assign them to electromagnons.

electromagnons, i.e. electrically active

I. Introduction 2,4,5
magnons. Since Ni3TeO6 presents a collinear
The polar antiferromagnet Ni3TeO6 exhibits AFM spin structure, the spin-lattice coupling
static (colossal)1 and dynamical2 magnetoelectric mechanism (symmetric exchange striction) is
(ME) effects. A collinear antiferromagnetic most probably responsible for the emergent
(AFM) order appears below the Néel temperature dynamical ME effect. A similar polar
TN = 53 K,3 giving rise to spin-induced antiferromagnet Ni2MnTeO6, undergoes an AFM
polarization of up to 3280 µC/m2 (at 2 K).1 Two phase transition at TN≈70 K, almost 20 K higher
spin excitations observed simultaneously in than Ni3TeO6, while keeping the same polar
Raman and time-domain THz spectra emerge rhombohedral R3 space group symmetry.6 A
below TN.2 These magnons show high tunability in dielectric anomaly at TN suggests a ME behaviour,
external magnetic field. Due to symmetry and a magnetic field-sensitive spin excitation
considerations, these excitations are assigned to appears below TN in the THz range.

1
 The cryolite-related Co3TeO6 with the
monoclinic C2/c space group symmetry down to
1.9 K7 undergoes at least 3 magnetic phase
transitions within the range from 26 to 16 K.7–13
Two main competing reports on the complex
magnetic ordering in Co3TeO6 suggest either
switching from an incommensurate collinear AFM
(~26 K) to a commensurate noncollinear AFM
structure (~17 K) with multiple propagation
vectors,7,10 or a coexistence of two layers with
commensurate collinear and incommensurate
noncollinear AFM spin-orderings.12 In the lowest
temperature phase, a magnetically-induced
polarization of up to 160 µC/m2 ( , 5
K, 9 T) emerges,7,8 possibly via the spin-current
mechanism (antisymmetric exchange).11
The peculiar magnetoelectricity and complex
magnetic ordering of Co3TeO6, in combination
with the colossal magnetoelectric coupling in
Ni3TeO6, led to the concept of Ni-substitution by
Co in Ni3TeO6. For the current study, Ni2CoTeO6
and NiCo2TeO6 were synthesized for the first
time, in the form of single crystals and
polycrystalline samples. Partial Ni-substitution by
Co preserves the polar R3 crystal symmetry of
Ni3TeO6, while inducing a non-collinear helical
spin structure, in contrast to the collinear cases of
Ni3TeO6 and Ni2MnTeO6. The helical spin
configurations in Ni2CoTeO6 and NiCo2TeO6
Figure 1 Schematic representation of the
yield hysteretic spin-flop transitions; in
incommensurate helical magnetic structure of
comparison, spin-flop transitions in the collinear
Ni2CoTeO6 and NiCo2TeO6 (the magnetic Ni/Co
cases are non-hysteretic. In this article, we discuss
sites are presented as blue spheres, whereas Te
spin and lattice excitations with an emphasis on
atoms are shown in gold, oxygen atoms are not
the magnetic-field sensitive magnons in the THz
shown for clarity). The magnetic structures of
range.
both compounds are quite similar, with a small
II. Experimental Section difference between the magnetic propagation
Polycrystalline Ni2CoTeO6 and NiCo2TeO6 vectors: k1=(0, 0, 1.299(4)) and k2=(0, 0,
were prepared by solid state reactions. 1.2109(1)), for Ni2CoTeO6 and NiCo2TeO6,
Stoichiometric amounts of NiO, TeO2 and respectively.
MnCO3 were mixed, ground together and heated crystals were obtained with lateral dimensions of
in a tubular furnace under oxygen flux at 800 ºC ~2 mm for Ni2CoTeO6 and less than 1 mm for
with intermediate grindings between 700 ºC and NiCo2TeO6. (See Fig S1.1 in Supplemental
800 ºC. Materials (SM),14 see also references [15–19]
Single crystals of both materials were therein).
prepared by the flux method by mixing the The samples were initially characterized by
corresponding mixed oxide (Ni2CoTeO6 or powder X-ray diffraction (XRD) (Cu Kα = 1.5406
NiCo2TeO6) with V2O5, TeO2, NaCl and KCl in a Å). The structure of the single crystals was
molar ratio of the five compounds of 1:5:10:10:5. determined by single-crystal X-ray data collected
The mixture was heated to 830ºC and kept at this on a Bruker Smart APEX CCD diffractometer
temperature during three days. The crystals were with graphite-monochromatized Mo Kα radiation
cooled to 600ºC during five days. Plate-shaped (λ = 0.71073Å) at 100 K.

2
 Time-of-flight neutron powder diffraction THz pulses radiated by a photoconducting switch
(NPD) data were collected for NiCo2TeO6 on the TeraSED (Giga-Optics). A gated detection
WISH diffractometer (target station 2) at the ISIS scheme based on electrooptic sampling with a 1
neutron and muon source;20 ~250 mg of powder mm thick [110] ZnTe crystal as a sensor allowed
were placed in a thin-walled, cylindrical vanadium us to measure the time profile of the electric field
can and cooled to 1.5 K. High quality data sets of the transmitted THz pulse. For low-
with angular steps equivalent to 40 µÅ in direct temperature THz and IR measurements, two
space were collected at 1.5 K, 32 K and 60 K. Oxford Instruments Optistat cryostats with mylar
Shorter scans with finer steps of 6.7 µÅ were and polyethylene windows, respectively, were
collected at intermediate temperatures, and the used. External magnetic field THz experiments
data at 100 K were obtained with 16.8 µÅ steps. with μoHext ≤ 7 T were conducted with an Oxford
Constant wavelength NPD data were collected for Instruments Spectromag cryostat in the Voigt
Ni2CoTeO6; 250 mg of powder were placed in a 6 configuration (with both Hext ∥ Eω and Hext ⊥
mm diameter vanadium can. High resolution scans Eω), where Eω denotes the electrical component
were collected on the D2B diffractometer (λ≈1.59 of the electromagnetic radiation.
Å) at 1.5 K and 300 K. Variable temperature data The IR reflectivity R(ω) and THz complex
were also collected on the high flux diffractometer permittivity spectra ε(ω) were fitted assuming a
D20 (λ ≈ 2.41 Å) to follow the magnetic ordering. sum of N independent damped harmonic
TopasAcademic21 software was used for initial oscillators, expressed as:25
refinements using data collected in the TOj
paramagnetic region to determine the Ni/Co ∑ (1)
TOj ωγTOj
distribution over 3a sites. The cation distribution where ∆ is the dielectric strength of the -th
was then fixed for refinements using Jana200622
mode, the frequencies of the -th transverse
using data collected at base temperature and on
warming. Group theory calculations and magnetic optical (TO) phonons, and are the
symmetry analysis were performed with the help corresponding damping constants. is the high-
of the ISODISTORT and ISOTROPY frequency (electronic) contribution to the
software.23,24 permittivity, determined from the room-
Radio-frequency dielectric measurements were temperature frequency-independent reflectivity
performed using a NOVOCONTROL Alpha-AN tail above the phonon frequencies. The complex
impedance analyser in conjunction with a JANIS magnetic permeability may be expressed in a
ST-100 cryostat. similar way, and then the reflectivity, the
Near-normal incidence IR reflectivity spectra complex dielectric function and the complex
of Ni3-xCoxTeO6 (x=1,2) ceramics were measured magnetic permeability are related by:
using a Fourier-transform IR spectrometer Bruker √ √
, (2)
IFS 113v in the frequency range of 20—3000 cm-1 √ √
(0.6 – 90 THz) at room temperature; the low- Raman studies of single crystals were
temperature spectral range was reduced to 20— performed with a Renishaw RM 1000 Micro-
650 cm-1 due to the limited transparency of the Raman spectrometer with Bragg filters, equipped
cryostat windows from polyethylene. A with an Oxford Instruments Microstat
pyroelectric deuterated triglycine sulfate detector continuous-flow optical He cryostat. The
was used for the room-temperature measurements, experiments were conducted in the backscattering
whereas a He-cooled (operating temperature 1.6 geometry in the 5–1800 cm-1 range. An Ar+-ion
K) Si bolometer was used for the low-temperature laser operating at 514.5 nm was used. The spectra
measurements down to 7 K. were carefully fit with a sum of independent
Time-domain terahertz experiments were damped harmonic oscillators multiplied by the
conducted in the spectral range from 3 to 60 cm-1 corresponding Stokes temperature factor.26
(0.09 – 1.8 THz), performed in the transmission III. Results and discussion
geometry with a custom-made time-domain
terahertz spectrometer. A train of femtosecond A. Structural Characterization
pulses was produced by a femtosecond
Single crystals and polycrystalline samples of
Ti:sapphire laser oscillator (Coherent, Mira),
Ni2CoTeO6 and NiCo2TeO6 were characterized by
which generated linearly polarized broadband

3
XRD and NPD, revealing pure phases with the compounds is the periodicity of the helix along c,
non-centrosymmetric R3 space group symmetry. which increases with Co2+ content approaching k
The XRD and NPD patterns, unit cell parameters, = (0 0 ). The incommensurate nature of the
atomic positions and bond distances, are presented
magnetic structures suggests some frustration in
in sections S2 and S3 in SM.14 Both compounds
magnetic exchanges along the c-axis and a lack of
present layers of edge-sharing NiO6, CoO6 and
a clear anisotropy direction in the ab-plane.
TeO6 octahedra, where the central Ni, Co and Te
Details of the structure refinements, Rietveld
ions are slightly (by ~ 0.1 Å) displaced from the
plots, values of the magnetic moments as well as
centers of the oxygen octahedra cages.
the temperature evolutions of the magnetic
B. Magnetic Structures structures are reported in section S3 in
Supplemental Materials.14
The magnetic structures of both compounds, Note that the related materials Ni2-xCoxScSbO6
determined by NPD, correspond to an (x=0-1.5) and Mn2InSbO6 have similar polar R3
incommensurate AFM helical with the magnetic crystal structures, but their magnetic structures
moments lying in the ab-plane, in clear contrast differ substantially. The helical spin structure of
with the collinear out-of-plane spin structure of Ni2ScSbO6 is incommensurately modulated with
Ni3TeO6 and Ni2MnTeO6.1,3,6. The magnetic an in-plane propagation vector k=[0 0.036(1) 0],
propagation vectors are k1=(0, 0, 1.299(4)) and corresponding to an almost 40 times longer helix
k2=(0, 0, 1.2109(1)), for Ni2CoTeO6 and than that in the Ni3-xCoxTeO6 compounds.27 With
NiCo2TeO6 at 3 K and 1.5 K, respectively. In both the addition of Co, the Ni2-xCoxScSbO6 (x=0.5-
compounds the magnetic structure is described by 1.5) compounds present a series of long-
the superspace group R31'(00γ)ts, corresponding periodicity commensurate helices with k=[0 0
to the mΛLE2 irreducible representation. The 1/3n], where n=5, 6, 8 and 10 for x=0.5, 1, 1.5,
helical structure is characterized by ferromagnetic and 2, thus the helix length increases with
(FM) ab layers rotating along the c-axis (Figure 1) increasing Co contents.28
yielding an AFM structure. It is interesting to note
that the sole difference between the two

Figure 2 (a) Temperature dependences of magnetization (at 0.1 T; logarithmic scale) and permittivity (at 0.1
MHz) for Ni2CoTeO6 and NiCo2TeO6 ceramics, presenting AFM phase transition at 54 and 49 K,
respectively. The dielectric anomalies also appear at the same temperatures for each compound. (b)
Magnetic field dependences of magnetization with Hext ∥ ab-plane at 2 K for Ni2CoTeO6 and NiCo2TeO6
single crystals, revealing spin flop transitions at approximately 8 and 4 T, respectively.
4
 Finally, the double-corundum compound to provide a comparison with the dielectric
Mn2InSbO6 exhibits three magnetic phase measurements done exclusively on ceramics.
transitions below 38 K, and the structure may The magnetic transitions in both samples
exhibit a commensurately modulated helix with a resemble that of Ni3TeO6, unlike Ni2MnTeO6,
propagation vector k=[0 0 0], an incommensurate which orders antiferromagnetically at around 70
one with k=[0 0 kz], or a commensurate one with K.6 The single crystals were measured after
kz=1/8.29 applying 0.1 T, at zero field cooling, and for two
different magnetic field configurations: Hext ∥ c-
C. Magnetic and dielectric properties axis and Hext ∥ ab-plane. In contrast to
The temperature dependences of the Ni2MnTeO6 exhibiting a c-easy-axis
magnetization in Ni2CoTeO6 and NiCo2TeO6 magnetization, both Co compounds present ab-
polycrystalline samples reveal AFM phase easy-plane magnetization, confirming the
transitions at 54 and 49 K, respectively (Figure 2 magnetic structure indicated by the NPD
(a)). Similarly, the single crystals of Ni2CoTeO6 experiments. An additional anomaly at around 35
and NiCo2TeO6 exhibit AFM orderings at slightly K is present in the Ni2CoTeO6 single crystal
higher temperatures of 55 and 52 K, respectively (Figure S5(a) in SM),14 possibly due to another
(Figure S2(a) and (b) in SM).14 Here we chose to magnetic phase transition.
show the results of the ceramic samples, in order

Figure 3 Temperature dependences of IR reflectivity spectra for (a) Ni2CoTeO6 and (d) NiCo2TeO6
ceramics, at selected temperatures. The reflectivity spectra calculated using the THz range data are also
shown, for frequencies below 70 cm-1, by dense dotted lines. Insets: Temperature dependences of IR
reflectivity of the modes near (a) 220 cm-1 and (d) 215 cm-1, showing conspicuous decrease in damping on
cooling, accompanied by frequency increase. (b), (e) Real and (c), (f) imaginary parts of the product of
complex permittivity and complex magnetic permeability, as obtained from the fits.

5
The same anomaly is absent in the ceramic Ni3TeO6, Ni2CoTeO6/NiCo2TeO6 and Ni2MnTeO6
samples (neither was it observed in NPD), due to respectively.
random orientations of the grains. As anticipated The magnetic field dependences of
due to the multiferroic behavior of Ni3TeO6 and magnetization of Ni2CoTeO6 and NiCo2TeO6
Ni2MnTeO6, also Ni2CoTeO6 and NiCo2TeO6 single crystals at 2 K and for Hext // ab-axis are
evidence an interplay of magnetic and dielectric shown in Figure 2 (b). Ni2CoTeO6 presents a spin-
properties, as indicated by the dielectric anomaly flop transition at approximately 8 T, similarly to
seen at TN (Figure 2 (a)). The critical temperatures Ni3TeO6,1 however NiCo2TeO6 exhibits a
amount to at 53 and 47 K for Ni2CoTeO6 and dramatic decrease in the spin-flop critical field
NiCo2TeO6 ceramic samples, respectively, slightly down to about 4 T. Such a behavior can be
lower (~1-2 K) than the magnetic anomalies. Such explained by the helical spin structure (Figure 1),
discrepancy, which lies close to the experimental and by the lack of a strong anisotropy direction of
error, may also originate in thermo-lag effect at the FM layers in the ab plane. The famous non-
the sample-thermocouple contact during the hysteretic behavior of Ni3TeO6 is absent in both
measurements. The permittivity values of the two compounds, which manifest a strong hysteresis in
compounds differ, with Ni2CoTeO6 close to the magnetic field-dependent magnetization. The
Ni3TeO6,1 whereas NiCo2TeO6 present a two- ceramic samples demonstrate similar magnetic
times higher value, thus nearing that of phase transitions, albeit at slightly lower values of
Ni2MnTeO6.6 However, one may only make a magnetic field, possibly due to grain boundary
rough comparison between the static permittivity contributions (Figures S3 in SM).14 In addition,
values, since they were measured at different the hysteretic behavior becomes more pronounced
frequencies: 44 kHz, 0.1 MHz and 1 MHz, for for both samples on cooling (see Figure S5.2).

Figure 4 Temperature dependences of Raman spectra for (a) Ni2CoTeO6 and (b) NiCo2TeO6 single crystals,
measured at polarization configuration. A spin excitation appears below TN at ~15 cm-1 for both
compounds.

6
Figure 5 (a),(e) Temperature dependences of the low frequency Raman spectra, (b),(f) temperature
and (c),(d),(g),(h) magnetic field dependences of the imaginary part of the index of refraction from THz
measurements for Ni2CoTeO6 (a-d) and NiCo2TeO6 (e-h). At least five spin excitations appear below TN for
both compounds, and the one at ~15 cm-1 is simultaneously seen in the Raman spectra. The arrows in parts
(a), (b), (e) and (f) indicate the temperature decrease from 300 to 5 K, whereas in (c), (d), (g) and (h), they
show the increase of the external magnetic field from 0 to 7 T.
group, at least from RT down to 4 K and it is
D. Spin and lattice excitations known that Ni3TeO6 keeps the same rhombohedral
The family of the four Ni-based tellurates, structure up to 1000 K.30 As expected, all
Ni3TeO6, Ni2MnTeO6, Ni2CoTeO6 and compounds present almost identical vibrational
NiCo2TeO6, crystalize in the polar R3 space spectra.2,6,18 All 18 vibrational modes predicted by

7
factor group analysis (9 E(x,y,x2-y2,xy,xz,yz) and the phonon to a spin excitation may take place
9 A(x2+y2,z2,z)), both IR and Raman active, are when the magnetic ordering occurs and the
present in the IR reflectivity spectra of both magnon becomes electrically active (i.e., it
compounds (see Figure 3(a) and 3(d)). The contributes to the permittivity), which is a typical
corresponding mode frequencies are listed in signature of electromagnons.
Table S6 in SM.14 The anticipated weak The spectra were fit assuming a sum of
temperature dependence of the IR reflectivity independent harmonic oscillators, as mentioned in
spectra of Ni2CoTeO6 and NiCo2TeO6 confirms section II. The products of the complex
the resemblance among the four compounds and permittivity ε and permeability μ spectra obtained
the stability of the crystal structure in the whole by the fits for both compounds are plotted in
temperature range studied. Naturally, the damping Figures 3(b), (c), (e) and (f). Although, the THz
constants of the modes decrease on cooling. In spectra are analysed below in detail, here it is
analogy to the mode at 310 cm-1 in Ni3TeO6, the worth mentioning that the IR spectra were fit
modes seen in Ni2CoTeO6 and NiCo2TeO6 at 224 simultaneously with the THz spectra. In the low-
and 211 cm-1, respectively, exhibit a conspicuous frequency spectra (Figures 3(c) and (f)) one
frequency hardening, accompanied by a decrease can notice weak spin excitations appearing below
in damping. The observed phenomenon of mode TN, as measured by the THz spectroscopy. Since
intensity loss below TN might be related to a we do not know, whether they contribute only to
coupling between the phonon and a lower energy permittivity or permeability, we present their
magnon. As we show below, both compounds product.
evidence several spin excitations in the THz
range, thus a transfer of dielectric strength from

Figure 6 Magnetic field dependence of spin-wave frequencies for (a) Ni2CoTeO6 and (b) NiCo2TeO6, at 5
K. In the latter, the spin-flop transition is clearly seen at approximately 3 T (designated by the violet stripe),
by the steps on the magnon branches, as well as both the appearance of new modes and extinction of ones
present in the low-field phase.

8
Note that these modes are very weak, therefore NiCo2TeO6 (TN≈49 K). All excitations sharpen
they are not visible in the real part of spectra. All and harden on cooling, with evident splitting for
the modes seen above 150 cm-1 are polar phonons, the broader ones. The spectra were fit together
i.e. they contribute only to permittivity and 1 with those of IR reflectivity, and the
in this range. corresponding frequencies, damping constants and
For both compounds a significant number of mode strengths are listed in Table S6.2.1 in SM.14
sharp modes can be seen in the temperature At the lowest temperature of 5 K the THz
dependent Raman spectra of single crystals at all spectrum of Ni2CoTeO6 displays five modes,
possible polarization configurations ( , whereas NiCo2TeO6 presents six of them. The
, , , , ) taken in rapid strengthening of these modes upon cooling
the backscattering geometry. Here we present only below TN, especially of the sharp ones, suggests
spectra (Figure 4), where the magnetic that they correspond to spin excitations. As
excitation is more pronounced comparing to the mentioned above, the 15 cm-1 mode is
other configurations. simultaneously seen in the Raman spectra of both
All above-mentioned configurations measured compounds. Magnons are mostly very weak or
at 4 K are plotted in Figure S6 in the SM.14 The inactive in Raman spectra. Nevertheless, in some
temperature dependence of , and magnetic materials like orthoferrites, the magnons
polarization configurations for both are clearly observed in Raman spectra31 and they
compounds are presented in the Figures S6.1.2 are also IR-active, despite their centrosymmetric
and S6.1.3, together with a schematic crystal structure. Ni2CoTeO6 and
representation of the configurations used and their NiCo2TeO6 have a noncentrosymetric R3 crystal
respective Porto notations (Figure S6.1) in the structure, so the phonons and magnons can be
SM.14 The Raman modes from all possible both IR and Raman active. Since the magnons
polarization configurations for Ni2CoTeO6 and were observed in the and Raman
NiCo2TeO6 are listed together with the IR modes spectra, they belong to the E symmetry. As the
in Table S6.2.1 in the SM.14 Both compounds phonons near 210 - 220 cm-1 reduce their
show an additional mode in the low-frequency oscillator strengths on cooling below TN, they
range, at approximately 15-16 cm-1, which turns probably transfer their dielectric strengths to the
up below the AFM transition, therefore we assume strongest Raman-active magnons near 17 cm-1 and
it is of magnetic origin. This low frequency therefore we assume that these excitations can be
excitation appears in most polarization called electromagnons. Note the small strengths of
configurations, as seen in SM,14 however the all our spin excitations in the THz spectra
strongest intensity corresponds to , measured in transmission using a 1.9 mm thick
reflecting the ab-plane-sensitivity of the magnon. sample. The broader mode near 60 cm-1 (Figure 3)
Note that the observed low-intensity modes is also seen in Raman spectra (Figures S6.1.2 and
observed in other polarized spectra may also S6.1.3), but it most probably corresponds to two-
originate in polarization leakage, due to slight magnon scattering.
sample misalignments. In addition, for ´ in Spectra of the extinction coefficient obtained
Ni2CoTeO6, a broader mode is seen at around 67 by time-domain THz measurements in the Voigt
cm-1, which might be of two-magnon scattering configuration with external magnetic field Hext ⊥
origin. As we show below in more detail, both Eω up to 7 T and at temperatures of 30 and 5 K are
modes are also observed in the THz spectra. presented in Figures 5(c),(d) and (g),(h) for each
The temperature dependence of the imaginary compound, respectively. The spectra of the real
part of the index of refraction in the THz range is parts of the index of refraction are presented in
shown in Figures 5(b) and (f) for Ni2CoTeO6 and Figure S6.2.2 in SM.14 In both compounds, the
NiCo2TeO6, respectively (ceramics of ∼1.9 mm magnons can be tuned by applying external
thickness). The real part of the index of refraction magnetic field, upon which they exhibit noticeable
for both compounds is presented in Figure S6.2 in peak sharpening and frequency shifts. The
SM.14 The spectra were measured from 300 down magnetic field dependences of the spin-wave
to 5 K. An initial decrease in the real part of the frequencies at 5 Κ, obtained by the fits, are
index of refraction on cooling is observed, summarized in Figures 6(a) and (b). In
followed by the appearance of two modes below Ni2CoTeO6, the sharp mode seen at 30 K around
TN for both Ni2CoTeO6 (TN≈54 K) and 17 cm-1 (0 T) (Figure 5(c)) softens down to 14 cm-
9
1
at 7 T, whereas the higher-frequency modes near are electrically active and can be called
30 cm-1 are less sensitive to Hext. The 17 cm-1 (0 electromagnons.
T) mode was also seen in Raman spectra, as The discrepancies in the TN values observed by
mentioned above. The small discrepancy between Raman spectroscopy (the magnetic modes
the frequencies can be explained by the disappear already at ~40 K, more than 10 K below
experimental error and it may also slightly vary in the AFM phase transition) could be explained by
different experimental setups. The sharpening and thermo-lag effects, laser-heating, and/or random
softening of the latter mode is even more crystallite orientation in the polycrystalline
pronounced at 5 K (Figure 5(d)). samples.
The changes in the magnons response in
external magnetic field are even more pronounced
in NiCo2TeO6. At 30 K (Figure 5(g)), the two
strongest modes near 7 and 23 cm-1 at 0 T, harden
to 13 and 28 cm-1 respectively, with rising field up
to 7 T. At 5 K the spectra are much richer (Figure
5(h)). The magnon frequency-shifts due to
external magnetic field can be seen in Figure 6(b).
The marked discontinuities which occur at ~4 T in
the frequencies of at least four of the excitations,
are probably linked to the spin-flop transition,
observed also by the magnetization measurements
(Figure 2(b)). Two new modes seem to appear at
around 30 cm-1 above 3 T. These new excitations
might also correspond to a splitting of the
neighboring singlet mode, triggered by the spin-
flop transition. The convoluted non-collinear
magnetic behavior of the Co-rich compounds was
foreseen due to the intriguing magnetism of
Co3TeO6,7,8,10 as well as the spin-orbit coupling
(SOC) contribution from Co3+ (3d6).
The 15 cm-1 mode seen in Raman spectra
(Figure 5(e)), possibly corresponds to the one in
the THz spectra at ~17 cm-1 (0 T), and it shows a
strong magnetic field dependence. Since this
mode (together with its higher-frequency
component near 22 cm-1) increases its strength Fig. 7. Comparison of THz extinction coefficient
below TN in THz spectra (Figure 5f) and the spectra k for Ni3-x(Co,Mn)xTeO6 (x=0, 1, 2)
phonon mode near 215 cm-1 reduces its dielectric compounds taken at 5 K at (a) zero magnetic field
strength on cooling below TN (Figure 3), these and (b) 7 T.
modes are probably coupled. It strongly suggests
that the spin excitation seen near 17 and 22 cm-1
Table 1 Overview of main characteristics of magnetic phase transitions and spin orders for the Ni3-
x(Co,Mn)xTeO6 (x=0-2) compounds: paramagnetic to AFM phase transition at TN, spin-flop transition at
external magnetic field HSF, type of spin order and spin orientation, and spin order propagation vector k. The
metamagnetic phase transitions observed in Ni3TeO6 at higher magnetic fields (up to 92 T)32–34 are not
included here.
Ni3TeO61,3 Ni2MnTeO66 Ni2CoTeO6 NiCo2TeO6
TN (K) 53 70 55 52
HSF (T) 8.2 4.5 8 4
Spin-order collinear c-axis collinear c-axis helical ab-plane helical ab-plane
k [0, 0, 0.5] [0, 0, 0.5] [0, 0, 1.299(4)] [0, 0, 1.2109(1)]

10
 Note that the observed excitations cannot substitution of Ni in Ni3TeO6 preserves the ME
correspond to crystal field splitting caused by the properties of the parent structure, and it enhances
octahedral coordination geometry in Ni, Co and the dynamical ME coupling. The non-
Te, since the 3d-related crystal field splitting centrosymmetric rhombohedral R3 structure is
values lie in the UV and visible range,35 whereas maintained at least up to RT for both Ni2CoTeO6
the 4f-related splitting reaches down to the FIR and NiCo2TeO6, even though Co3TeO6 has a
range.36 monoclinic non-polar structure with the space
Substitution of Ni by Mn and Co in the Ni3- group C2/c. Unfortunately, evidence of
x(Co,Mn)xTeO6 (x=0-2) compound family ferroelectricity is still missing, since our single-
preserves the polar R3 crystal structure. However, crystalline samples were too small for pyrocurrent
the different magnetic anisotropies introduced by or ferroelectric hysteresis loops measurements.
the magnetic cations Ni(II)(3d8), Mn(II)(3d5) and The magnetic ordering appears in single crystals
Co(II)(3d7) dramatically affect the magnetic phase (ceramics) at TN=55 (54) and 52 (49) K for
transitions and the spin order (see Table 1). The Ni2CoTeO6 and NiCo2TeO6, respectively.
differences in the spin modulations of the In contrast to the magnetic ordering in
compounds are reflected in the THz spectra Ni3TeO6 and Ni2MnTeO6, which are collinear
(Figure 7). Very recent neutron studies of the along the c-axis, the two compounds under study
magnetic ordering of Ni3TeO6 single crystals have present a helical non-collinear structure with the
revealed that the commensurately modulated spins in the ab-plane. Hysteretic spin-flop
collinear antiferromagnetic structure changes transitions were observed in both compounds,
above 8.6 T to an incommensurately modulated near 8 T (Ni2CoTeO6) and 4 T (NiCo2TeO6), in
conical spiral one with significant spin contrast to Ni3TeO6 and Ni2MnTeO6, which did
components in the ab-plane.34 One can expect that not show any hysteretic behavior.
the THz spectra of Ni3TeO6 taken above 8.6 T Below TN in the THz range both compounds
should resemble the spectra of NiCo2TeO6 at zero demonstrate numerous spin-excitations, which are
magnetic field. Unfortunately, the magnetic markedly influenced by external magnetic field,
cryostat used for measuring the THz spectra with clear modifications at the spin-flop transition
operates up to 7 T. In addition, the absence of of ∼4 T for the case of NiCo2TeO6. The Co-
evidence of the exact spin order at external richer compound NiCo2TeO6 prevails, manifesting
magnetic field for all compounds (except for six magnons unusually strongly dependent on
Ni3TeO6) and the fact that the THz experiments magnetic field. Both compounds present at least
were performed with polycrystalline samples one magnetic excitation simultaneously seen by
prevents us from drawing a detailed comparison Raman spectroscopy, thus they can be assigned to
between compounds. electromagnons.
Large enough single crystals are required for
more extensive THz measurements, in order to Acknowledgements
resolve the relation between crystal symmetry and The work of MG, ZD and MR was supported
magnon symmetry and propagation. Also the by the NSF-DMR – 1507252 grant. MR also
alternative of studying directional dichroism is acknowledges the Juan de la Cierva program of
currently not feasible due to the small size of the the Spanish Ministry of Economy and
available crystals, and because the pyroelectric Competitiveness for a grant FPDI-2013-17582.
polarization is most likely non-switchable.37 The work of SK, SS, FB, CK and FK was
Finally, single crystals could also serve for supported by the Czech Science Foundation
performing pyrocurrent measurements in external (Projects No.18-09265S) and by Operational
magnetic field, in order to examine the static ME Programme Research, Development and
coupling, and compare it with the colossal ME Education financed by European Structural and
effect observed in Ni3TeO6. Investment Funds and the Czech Ministry of
IV. Conclusions Education, Youth and Sports (Project SOLID21 -
CZ.02.1.01/0.0/0.0/16_019/0000760). This project
New compounds from the family of Ni-based
has received funding from the European Union’s
tellurates, Ni2CoTeO6 and NiCo2TeO6, were
Horizon 2020 research and innovation programme
successfully synthesised for the first time, in the
under the Marie Sklodowska-Curie grant
form of single crystals and ceramics. Co-
agreement No 838220. DL and SS acknowledge
11
the European Regional Development Fund in the project No. 17-27790S of Czech Science
IT4Innovations national supercomputing centre- Foundation. The authors acknowledge the Science
Path to Exascale (Project and Technology Facility Council (STFC, UK) for
CZ.02.1.01/0.0/0.0/16_013/0001791) within the the provision of neutron beam time on the WISH
Operational Programme Research, Development diffractometer.
and Education, and DL acknowledges also the

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