communications materials Article

[Link]

Peculiar magnetotransport properties in

epitaxially stabilized orthorhombic Ru3+
perovskite LaRuO3 and NdRuO3
Check for updates
1 1 2 3 3,4
Lingfei Zhang , Takahiro C. Fujita , Yuuki Masutake , Minoru Kawamura , Taka-hisa Arima ,
Hiroshi Kumigashira 2,5, Masashi Tokunaga 3,6 & Masashi Kawasaki 1,3

Complex oxides are interesting materials where multiple physical properties and functionalities can be
realized by integrating different elements in a single compound. However, owing to the chemical
1234567890():,;
1234567890():,;

instability, not all the combinations of elements can be materialized despite the intriguing potential
expected from their magnetic and electronic properties. Here we demonstrate an epitaxial stabilization
of orthorhombic Ru3+ perovskite oxides: LaRuO3 and NdRuO3, and their magnetotransport properties
that reflect the difference between non-magnetic La3+ and magnetic Nd3+. Above all, an
unconventional anomalous Hall effect accompanied by an inflection point in magnetoresistance is
observed around 1.3 T below 1 K for NdRuO3, which we propose is possibly related to a non-coplanar
spin texture on Nd3+ sublattice. These studies not only serve as a new testbed for the interplay between
spin-orbit coupling and Coulomb interaction but also open a new avenue to explore topological
emergent phenomena in well-studied perovskite oxides.

The interplay between spin-orbit coupling (SOC) and Coulomb correlation oxides (orthorhombic Pbnm phase, as shown in Fig. 1b) are rare exceptions
has become a central topic in condensed-matter physics1–3. This crucial of an oxidation state of Ru3+. Because of difficulties in synthesis, however,
importance has been widely known, especially in 4d and 5d transition metal studies on LnRuO3 are quite limited; with bulk polycrystals13–16 and single
oxides, where SOC acts on an energy scale comparable to the other energy crystals17, and their electronic and magnetic properties have not been
scales such as bandwidth, crystal field, and Coulomb interaction, etc. This revealed well, in contrast to AeRu4+O3 (Ae: alkaline earth)18–21. Different
class of materials has attracted considerable attention since the discovery of from AeRu4+O3, LnRuO3 can accommodate magnetic Ln3+, which renders
Mott insulating state in Sr2IrO44. The study has expanded to other heavy this system an intriguing playground for the magnetic interaction between
transition metal oxides, especially with the d5 configuration under octahedral Ru-4d itinerant electrons and Ln-4f localized moments (Fig. 1c). In this
crystal field1,2,5. In such materials of interest, partially filled 4d or 5d t2g-band point of view, LnRuO3 is a unique system among Ln-M-O (M: transition
are split into an effective j = 1/2 doublet and effective j = 3/2 quartets as shown metal) complex oxides that can support magnetization from Ln-site and
in Fig. 1a. Indeed, a number of novel topological phenomena related to the metallic conduction on M-O network at the same time, which is critical for
effective j = 1/2 states have been reported not only in oxides with Ir4+ 5–8 but evaluating the magnetic interaction by magnetotransport properties. To
also in α-RuCl3 with Ru3+ as a possible candidate of Kitaev quantum spin address this issue, we summarize electrical conductivity of two well-studied
liquid9–11. Here, we pose a question whether it is possible to stabilize Ru3+ state structures: perovskite (LnMO3) and pyrochlore (Ln2M2O7) in Fig. 1d, where
in oxide thin films as in the case of well-studied Ir4+, providing more “knobs” metallic ones are limited to LaNiO3, LaCuO3, LRO, Pr2Ir2O7, and
to tune the physical properties by utilizing epitaxial strain or heterointerface. Ln2Mo2O7 (Ln = Nd, Sm, Gd)13,22–25.
From the chemistry point of view, the stable oxidation state of Ru is Among magnetotransport properties, the Hall effect in magnets has
generally +4 or higher in oxides12. LnRuO3 (Ln: lanthanide) perovskite been of great interest, especially after the discovery of topological Hall effect

1
Department of Applied Physics and Quantum Phase Electronics Center (QPEC), The University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-8656, Japan.
2
Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Katahira 2-1-1, Sendai, Miyagi 980-8577, Japan. 3RIKEN Center for
Emergent Matter Science (CEMS), Hirosawa 2-1, Wako, Saitama 351-0198, Japan. 4Department of Advanced Materials Science, The University of Tokyo,
Kashiwanoha 5-1-5, Kashiwa, Chiba 277-8561, Japan. 5Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization
(KEK), Oho 1-1, Tsukuba, Ibaraki 305-0801, Japan. 6The Institute for Solid State Physics, The University of Tokyo, Kashiwanoha 5-1-5, Kashiwa, Chiba 277-8581,
Japan. e-mail: fujita@[Link]

Communications Materials | (2024)5:35 1

[Link] Article

eg only at very low temperatures below 1 K. These results altogether demon-

a
strate that epitaxial stabilization is a potent activator to push new frontiers of
Ru3+: 4d5 the playground for strongly correlated electrons28–30 with both sizeable SOC
and magnetic interaction that will facilitate new fundaments and high-end
Jeff = 1/2 applications31,32.
t2g
Crystal Results and discussion
Jeff = 3/2
field Spin-orbit Structural properties
splitting coupling Epitaxial LRO and NRO thin films were prepared on SrTiO3 (STO) (001)
substrates by pulsed laser deposition (PLD) and subsequent annealing
b c f-d process (See Methods, Supplementary Note 1, and Supplementary Figs. 1, 3
interaction for the details). X-ray diffraction (XRD) 2θ-θ scan profiles of the films are
O
presented in Fig. 2a, b. From the positions of (002) peaks (pseudocubic
Ru3+ setting), out-of-plane lattice constants of LRO and NRO are deduced to be
3.96 Å and 3.94 Å, respectively. The full width at half maximum (FWHM)
Ln3+ in rocking curves of (002) peaks (Supplementary Figs. 1d, g) is less than 0.1°
c for both LRO and NRO films, reflecting high orientation and crystallinity.
Itinerant Localized
Thicknesses of the LRO and NRO films are around 6 nm and 9 nm,
b Ru-4d electrons Ln-4f electrons respectively, which are deduced from x-ray reflectivity measurements at
a
lower incident angles (Supplementary Fig. 1b, e). The root-mean-square
d Conductivity of Ln(III)-M-O oxides
roughness of the films is as small as sub-nanometer order before the
Metallic / Insulating perovskite: M(III) annealing while the surface becomes several times rougher after the
Metallic / Insulating pyrochlore: M(IV) annealing, which is deduced from their atomic force microscope images
4 5 6 7 8 9 10 11 (Supplementary Fig. 2). The epitaxial relationship between the substrate and
the thin films is clarified by the reciprocal space mappings (RSM) presented
Ti V Cr Mn Fe Co Ni Cu in Fig. 2c (and Supplementary Fig. 5). The peak of LRO exhibits a slight
broadening toward smaller Qx from the peak position of STO. Since the
Zr Nb Mo Tc Ru Rh Pd Ag mismatch between bulk LRO (3.94 Å in pseudocubic setting) and STO
substrate (3.905 Å) is as large as 1%, this broadening indicates that the thin
Hf Ta W Re Os Ir Pt Au film near the interface is fully strained while the rest part is partially relaxed.
Fig. 1 | Concept of this study. a Band splitting and 4d5 electron configuration of On the other hand, NRO (3.92 Å in pseudocubic setting), which has less
Ru3+ ion. b Schematic of orthorhombic Pbnm perovskite structure illustrated by mismatch to STO substrate, does not show such a peak broadening and thus
VESTA43. c Schematic of the interaction between itinerant Ru-4d and localized Ln-4f is fully strained. The high quality of the films can be confirmed by TEM
moments with a non-coplanar ordering. d Summary of the electrical ground states of images presented in Fig. 2d, e as well. Lattice images in an atomic resolution
Ln(III)-M-O (M: transition metal) perovskite and pyrochlore oxides that have been are clearly seen for thin films epitaxially grown on STO substrate. The
reported13,22–25,44–50. The gray color indicates that there are no reports related to the formation of orthorhombic perovskite structure is also supported by elec-
elements. tron beam diffractions (Supplementary Fig. 4).

Oxidation state of Ru
(THE). In contrast to the conventional anomalous Hall effect (AHE) in As evidenced by the XRD and TEM measurements, it is apparent that LRO
magnets, which appears to be proportional to uniform magnetization M, and NRO films are stabilized as perovskite structures. However, as men-
THE originates from topological magnetic states such as magnetic vortex, tioned above, Ru3+ is generally unstable in oxides12. To further confirm the
skyrmion, and non-coplanar spin arrangement. Among various materials, oxidation state of Ru, XAS measurements are performed for both LRO and
perovskite oxide thin films and heterostructures have been serving as a NRO films. Figure 2f and its inset respectively show the wide and near-edge
fertile playground for investigating THE. However, an anomaly seen in XAS for these thin films in comparison with those for Ru metal (Ru0),
magnetic field dependence of AHE deviating from that of M cannot always SrRuO3 (Ru4+), and RuO2 (Ru4+) as references. As shown in the inset of
be assigned to THE originating from topological spin texture because the Fig. 2f, Ru K-edge energies of LRO and NRO are located at the lower energy
superposition of multiple contributions to conventional AHE can mimic (reduction) side than those of SrRuO3 and RuO2, indicating that the oxi-
THE signal, which often cannot be ignored in thin films due to the existence dation state of Ru in LRO and NRO is less than +4. The oxidation state is
of surface/interface, strain, and inhomogeneities26,27. semi-quantitatively evaluated by comparing the Ru K-edge energies of the
In this work, we report the fabrication of the epitaxial thin films of LRO films with those of reference compounds for Ru2+ or Ru3+, as shown in
and NdRuO3 (NRO) with utilizing solid phase epitaxy technique. X-ray Fig. 2g33,34. Here, Ru K-edge energy is defined as the energy at which the
absorption spectroscopic (XAS) studies support Ru3+ oxidation state in the normalized absorption intensity decreased by half. The Ru K-edge energies
films. We carry out systematic electrical transport studies in magnetic fields of LRO and NRO are represented by red and blue vertical lines, respectively,
up to 54 T and at temperatures down to 50 mK to investigate the veiled while the ones of other compounds are plotted by symbols with the reported
magnetotransport properties of LRO and NRO. We find that both LRO and oxidation states. Ru K-edge energies of LRO and NRO are located among
NRO are metallic though NRO shows a slight upturn below 20 K. LRO the ones of standard references for Ru3+; Ru3+Cl3, Ru3+I3, and [Ru3+(NH3)5]
exhibits only an ordinary Hall effect, while NRO exhibits a clear signature of Cl3. Therefore, we conclude that Ru predominantly exists as +3 oxidation
AHE, which is successfully deconvoluted from ordinary one with the aid of state in both LRO and NRO films.
the high-filed measurements up to 54 T. Especially below 1 K, an uncon-
ventional AHE emerges at around 1.3 T concomitantly with an anomaly in Comparison of magnetotransport properties between LaRuO3
magnetoresistance. We propose a possible mechanism of this unconven- and NdRuO3
tional AHE in the context of THE related to a non-coplanar spin texture Temperature dependence of longitudinal resistivity (ρxx − T curves) for
realized in the orthorhombic perovskite structure, while unambiguous LRO and NRO is presented in Fig. 3a, b. In Fig. 3a, ρxx is shown in a
assignment requires further challenging experiments due to its appearance logarithmic scale to compare with those in previous studies (dashed lines).

Communications Materials | (2024)5:35 2

[Link] Article

10
10
a = STO sub. b d LRO1 e NRO1
8 = LRO (002)
10 = NRO
Intensity (arb. units)

(002)
6 (001)
10
LRO1
4
10

2
10 NRO1
(001) SrTiO substrate (001) SrTiO substrate
3 3
0
10 5 nm 5 nm
20 30 40 50 44 45 46 47 48 (100) (100)
2θ (deg.) 2θ (deg.)
c 7.8 LRO1 NRO1 f g
5
1.2 References RuO2

Oxidation State of Ru (Ru )

SrTiO3 This work

n+
Ru metal SrRuO3 RuO2 SrRuO3
(103) 4 From ref. 33
Intensity (arb. units)

1.0 From ref. 34

7.7 RuCl3
[Ru(NH3)6]Cl3 RuI3
Qz (nm )

0.8 3
-1

Near
0.6 edge
Film 2
LRO2 [Ru(NH3)5]Cl2
7.6 (103)pc 0.4 [Ru(NH3)6]Cl2
NRO2
Film 1
(103)pc 0.2 NRO2 LRO2
22.11 22.12 22.13 22.14 Ru metal
0
7.5 0.0
2.50 2.55 2.60 2.50 2.55 2.60 22.0 22.2 22.4 22.6 22.116 22.118 22.120 22.122
-1 -1
Qx (nm ) Qx (nm ) Photon Energy (keV) Ru K-Edge Energy (keV)
Fig. 2 | Structural properties and valence states of LaRuO3 and NdRuO3 with those of Ru0 metal, Ru4+O2 and SrRu4+O3 as references. The intensity was
thin films. XRD 2θ-θ scan profiles (a) and magnified data around the (002) peaks (b) normalized so that the averaged edge jump became unity. The inset shows the
of LaRuO3 and NdRuO3 thin films on SrTiO3 (001) substrates. Peaks for the sub- enlarged view of near-edge structures. g Oxidation state of Ru (Run+) versus Ru
strate, LaRuO3, and NdRuO3 are indicated by stars, triangles, and squares, respec- K-edge energy, which is defined as the energy where the normalized intensity equals
tively. c The XRD reciprocal space mappings around SrTiO3 (103) peak. The gray 0.5. The vertical red and blue lines correspond to the Ru K-edge energies of the
broken lines indicate the relaxation lines where a fully relaxed cubic film peak is LaRuO3 and NdRuO3 thin films, respectively. Symbols of stars, circles, and triangles
supposed to be located. TEM image of LaRuO3 (d) and NdRuO3 (e) thin films. The refer to the data from the present measurement, ref. 33, and SPring-8 BENTEN
red and blue arrows indicate the position of the interface between the film and database34, respectively.
substrate. f Ru K-edge XAS spectra of LaRuO3 and NdRuO3 thin films in comparison

For LRO, our thin film sample is metallic down to 5 K and ρxx slightly field. What is more, at 0.5 K, a unique bulge in MRR and a hump structure in
increases at lower temperatures. Compared with the works by refs. 13,14 for ρyx are observed at an identical magnetic field of ∼1.3 T (Also discussed later
polycrystalline samples, our LRO film has a lower ρxx by one order of on in relation to the unconventional Hall effect in NdRuO3). These distinct
magnitude. For NRO, in striking contrast to the insulating behavior behaviors observed only in NRO at low temperatures suggest an essential
reported in the bulk polycrystalline sample15, our thin film is metallic down role of an interaction between Nd-4f spins and Ru-4d electrons in magne-
to 20 K and shows a weak upturn in ρxx with further cooling. This totransport properties, compelling us to perform further measurements
improvement in conductivity, plausibly originating from the high crystal- with a pulsed high magnetic field.
linity and less grain boundary scattering in our epitaxial thin films, endows
an opportunity to examine magnetotransport properties of the two con- Magnetotransport properties of NdRuO3 under high
trasting LRO and NRO with non-magnetic La3+ and magnetic Nd3+, magnetic field
respectively. Magnetic field dependence of MRR and ρyx up to 54 T for NRO are pre-
Magnetic field (B) dependence of magnetoresistance ratio (MRR sented in Fig. 4a, b, respectively, together with the results measured with a
(%) ≡ [ρxx(B)/ρxx(0) − 1] × 100) and Hall resistivity (ρyx) up to 9 T mea- PPMS up to 9 T (thick lines). As presented in Fig. 4a, MRR increases
sured by Physical Properties Measurement System (PPMS, Quantum monotonically up to 54 T above 10 K. Below 10 K, MRR decreases at lower
Design Co.) are presented in Fig. 3c–f. For LRO, MRR increases mono- fields with a minimum at B ≈ 10 T and turns to increase at higher fields
tonically (Fig. 3c), and ρyx is linear (Fig. 3d) to the magnetic field down to similar to the ones above 10 K. This can be seen more clearly in Fig. 4d,
2 K. These behaviors suggest a paramagnetic and metallic state in LRO, where ρxx − T curves under different magnetic fields are shown. Intrigu-
which is consistent with previous reports13,14. On the other hand, NRO ingly, the slopes of ρyx saturate at a similar negative value at higher fields
exhibits peculiar behaviors at low temperatures in both MRR (Fig. 3e) and regardless of the measurement temperatures (Fig. 4b). Because of this,
ρyx (Fig. 3f). Negative MRR, which is a typical response in magnetic mate- ordinary Hall coefficient (RH) can be deduced from linear fittings of ρyx
rials, is observed below 5 K. Above 30 K, ρyx is linear but exhibits a sign between 45 T and 54 T. As presented in Fig. 4e, RH has little temperature
reversal at around 60 K. Below 30 K, ρyx is no longer linear to the magnetic dependence below 150 K. Therefore, with the help of the high-field

Communications Materials | (2024)5:35 3

[Link] Article

LRO3 NRO3
a c 1.0 e
7
2 10 K 20 K 30 K
10 Bulk T=2K
0.8 10 K 0
Thin film 5K
20 K 200 K
ρxx (μΩcm)

-2

MRR (%)

MRR (%)
5 NRO 0.6 60 K
10 LRO Ref. 15 200 K -4
0.4 2K
Ref. 14 -6
3 Ref. 13
10 0.2 -8
This work 0.0 -10 T = 0.5 K
1
10 -12
b 800 d 0.10 f 2
T = 0.5 K
2K
700 0.05 1 5K
LRO3 10 K

ρyx (μΩcm)
ρxx (μΩcm)

ρyx (μΩcm)
20 K
T = 200 K 30 K
600 0.00 0
60 K
200 K
500 -0.05 -1
NRO3
2K
400 -0.10 -2
0 50 100 150 200 250 300 -9 -6 -3 0 3 6 9 -9 -6 -3 0 3 6 9
Temperature (K) Magnetic Field (T) Magnetic Field (T)
Fig. 3 | Magnetotransport properties of LaRuO3 and NdRuO3 thin films. logarithmic (a) and linear (b) scales. Magnetic field dependence of magnetoresis-
a, b Temperature dependence of longitudinal resistivity (ρxx) compared with those in tance ratio (MRR) and Hall resistivity (ρyx) for LaRuO3 (c, d) and NdRuO3 (e, f) at
previous reports of polycrystalline bulk samples13–15. The data are plotted in selected temperatures.

measurements, the sign reversal of ρyx observed in Fig. 3f is revealed to be Since AHE is generally proportional to the magnetization M, it is
irrelevant to a carrier-type change. didactic to compare the observed AHE with the magnetic properties mea-
sured for another thick NRO film (NRO5) down to 2 K (See Supplementary
Anomalous Hall effect of NdRuO3 Note 5 and Supplementary Figs. 8, 9). As presented in Supplementary
Having clarified that the carrier-type of NRO is electron regardless of Fig. 9a, M becomes detectable at ∼100 K, which coincides with the emer-
temperatures, we can discuss the AHE of NRO. With using the deduced RH gence of the AHE shown in Fig. 4c. In the range of 30–100 K, M increases
in Fig. 4e, anomalous Hall resistivity ρAHE is defined as linearly to the magnetic field up to 7 T, indicating that NRO is in an AFM or
ρAHE(B) = ρyx(B) − RHB and presented in Fig. 4c. AHE is an important a paramagnetic (PM) phase. Considering that there is no anomaly in the
electrical transport phenomenon attracting extensive interest in both fun- ρxx − T curve usually concomitant with magnetic transitions, we speculate
damental physics and potential applications26,35. Indeed, NRO unveils var- that NRO may be PM in this temperature range, and magnetic moments of
ious AHE originating from different magnetic interactions depending on Ru3+ induced by the applied magnetic field lead to the AHE. At tempera-
temperatures and magnetic fields as we discuss below. tures lower than 20 K, M becomes non-linear to the magnetic field, which
At high temperatures, AHE emerges below ∼100 K while ρyx is linear to can be the reason for the steep increase in AHE at low fields in Fig. 4c, f. This
the magnetic field above 120 K. Since 100 K is too high for Ln3+ ions to be alludes to the existence of an additional magnetic component that is sen-
ordered in perovskite oxides36, AHE in this temperature range is supposed to sitive to magnetic field only at lower temperatures, which is attributable to
originate from the magnetism of Ru3+ induced by the applied magnetic field. Nd3+ moments, yet they may not be ordered in the temperature range. We
At lower temperatures, AHE at the high-field region shows almost no also compare the magnetic field dependence of magnetization (M − H
temperature dependence while it develops much faster at the low field curve) with the ρAHE − H curve for this thick NRO film, and find an almost
region below 20 K. This feature can be also confirmed clearly in the tem- perfect agreement between them above 10 K (Supplementary Fig. 9).
perature dependence of ρAHE at various magnetic fields (ρAHE(B) − T curve)
shown in Fig. 4f. Here, ρAHE increases dramatically below 20 K even at 1 T, Possible origin of unconventional anomalous Hall effect of
which is distinct from other curves measured at higher magnetic fields. NdRuO3
Finally, below 1 K, AHE starts to show a distinct behavior. Figure 5a Finally, we discuss the origin of the hump structure in AHE at lower tem-
shows ρAHE below 5 K and 4 T. At 0.8 K and 0.5 K, clear hump structures are peratures than 1 K. As previously reported, such a hump structure could
observed at ∼1.3 T while ρAHE almost monotonically increases as a function arise from the trivial superposition of multiple contributions to conven-
of B above 1.5 K. Furthermore, as presented in Fig. 5b, inflection points are tional AHE as we mentioned in Introduction, which has been reported in
observed for MRR at the same field range below 0.8 K. To compare the many studies of SrRuO3 thin films and heterostructures. At present, we
relationship between these two anomalies, we show the magnetic field cannot exclude the possibility that the hump structure in NdRuO3 also
derivatives of ρAHE and MRR at 0.5 K in Fig. 5c. The hump structure in ρAHE originates from such contributions from conventional AHE. On the other
and the inflection point in MRR appear almost at the same magnetic field, hand, LnRuO3 studied here are distinctive materials that can accommodate
which is indicative of the same origin for these two phenomena: plausibly a magnetic Ln3+ ions different from SrRuO3. Therefore, we attempt to pro-
magnetic one. pose an alternative mechanism in the framework of THE due to Nd3+

Communications Materials | (2024)5:35 4

[Link] Article

Fig. 4 | Magnetotransport properties of NdRuO3 PPMS

thin film measured with a pulsed high field mag- a Pulsed high field d
net. Magnetic field dependences of MRR (a), ρyx (b), 20 650
and anomalous Hall resistivity (ρAHE, c) at various 20 K B = 54 T
15 NRO3 30 K
temperatures. See the main text for the definition of
ρAHE. Both of the results measured with a PPMS
10 40 K 0T
T = 15 K

ρxx (μΩcm)
(thick lines below 9 T) and the pulsed high field 600

MRR (%)
10 K
magnet (thin lines) are shown. The vertical dotted 5
line indicates the position of B = 9 T. The oscillation
patterns appeared at 1.4 K are merely from noise 0 60 K
4.2 K 550 9T
because of the low measurement current which is
-5 80 K
employed to suppress the Joule heating (See Meth- 100 K
ods for details). d Temperature dependence of ρxx at 1.4 K 120 K
-10 0.5 K 150 K
B = 0, 9 (with a PPMS) and 54 T (with the pulsed 200 K
high field magnet). e Temperature dependence of -15 500
1 10 100
Hall coefficient (RH) deduced by a linear fitting of ρyx Temperature (K)
between 45 and 55 T. An optical image of the device b 2 e 6
structure for the transport measurements. Ni/Au
electrodes (dark areas) are deposited on the film and 1 5

−RH (10 cm C )
-1
then it is scribed (white dotted lines indicate the
ρyx (μΩcm)

3
scribed lines) to fabricate a Hall bar structure high-
lighted by the red colored area. f Temperature
0

-4
dependence of ρAHE at selected magnetic field. The T= 3
curves for B = 1 and 54 T are presented by lines with -1 0.5 K 20 K
open and filled circles. 1.4 K 30 K 100 K 2
-2 4.2 K 40 K 120 K
10 K 60 K 150 K 1
15 K 80 K 200 K 1 mm
-3 0
c 4 f 4

3 3 B = 54 T
40 T
ρAHE (μΩcm)

ρAHE (μΩcm)
30 T
2 2 20 T
15 T
10 T
1 1 7T
5T
3T
0 0
1T
0 5 10 15 20 25 30 35 40 45 50 55 0 50 100 150 200
Magnetic Field (T) Temperature (K)

moments. Here, we assume THE characteristic of the “non-coplanar” transition is indeed reported in GdFeO3, where Gd3+ moments take GbAa
magnetic structure with finite scalar spin chirality defined as χS = Si·(Sj×Sk) ground state and turn into FM state at about 5 T and 2 K41. As mentioned
(See inset of Fig. 5a)35. Actually, non-coplanar spin textures are ubiquitous in above, the spin structure of GbAa order is coplanar, where Nd3+ moments
M-site of orthorhombic LnMO3 including NdMO3 (M: 3d transition are confined within the ab-plane of orthorhombic setting. In our NRO film,
metal)36. For example, in NdMO3 (M = Cr, Fe, etc.), employing Bertaut’s the ab-plane is perpendicular to the film surface, which is confirmed by
notation37, a non-coplanar GbAaFc spin texture of M3+ moments has been electron beam diffraction and RSM (See Supplementary Note 3 and Sup-
widely confirmed. On the other hand, for Nd3+ moments, GbAa (M = Sc, In) plementary Table 3). Thus, when a magnetic field is applied perpendicular
or Cc (M = Cr, Co, Ga) textures are commonly observed while both are to the film surface, it is parallel to the ab-plane. With increasing the magnetic
coplanar36,38–40. Considering the more itinerant nature of Ru-4d electron, field, Nd3+ moments are aligned toward the field direction, leading to an
realization of the non-coplanar GbAaFc spin structure of Ru3+ moments is induced FM order. We suggest, during this transition, Nd3+ moments point
unlikely in NRO, thus we speculate that finite χS is mediated by the spin toward the c-axis and form a non-coplanar spin texture as presented in
texture of Nd3+ moments. We are aware that this speculation should be Fig. 5d (Also see Supplementary Fig. 10d) instead of simply rotating in the
supported by direct observation of magnetic structure or measurements of ab-plane, which we conjecture can be a source of finite χS. Here in NRO,
elemental-sensitive techniques such as neutron diffraction and x-ray mag- because of the square lattice, the definition of χS is not as straightforward as
netic circular dichroism. However, because of the thin film nature of the in the case of well-known triangular lattices. Yet, by summing up χS from all
sample and the low ordering temperature (~1 K), they are not feasible at the possible combinations of the three spins, it can be achieved. Although a
present. Therefore, we propose a possible mechanism based on the crystal more detailed discussion is provided in Supplementary Note 7, χS from each
symmetry as discussed below (Also see Supplementary Notes 6 and 7). contribution is indeed canceled out when the crystal structure has a high
As a starting point, we hypothesize that Nd3+ moments in NRO have symmetry (See Supplementary Table 4, and Supplementary Figs. 11, 12).
GbAa order as the ground state (Supplementary Fig. 10c) and turn into We thus speculate that there must be some causes for breaking the bulk
ferromagnetic (FM) order (Supplementary Fig. 10e) at ∼2.5 T, where THE crystal symmetry, which will be clarified by further studies for direct
disappears (Fig. 5a), since χS should vanish in the FM state. This type of evidence.

Communications Materials | (2024)5:35 5

[Link] Article

a 4.5 b c T = 0.5 K
0
4 2.0

dρAHE/dB (μΩcmT )
NRO3

dMRR/dB (10 T )
-1
T=5K
4.0 3 1.5
-2
T=5K 2 1.0
3.5
1 0.5
2K -4

-6 -1
3.0 0
0.0
2K
ρAHE (μΩcm)

1.5 K -1

MRR (%)
2.5 -0.5 -6
-2 0 1 2 3 4
Magnetic Field (T)
0.8 K
2.0 -3 1.5 K d
0.5 K -4
1.5
-5
0.8 K c
1.0 S -6
Itinerant a b
-7 electron S
0.5 Sk
Si Sj -8 of Ru3+ B
0.5 K
0.0 -9
0 1 2 3 4 0 1 2 3 4
Magnetic Field (T) Magnetic Field (T) Non-coplanar spin texture of Nd3+
Fig. 5 | Unconventional Hall effect in NdRuO3 thin film. Magnetic field depen- curve, right axis) at 0.5 K. The square and triangle in (c) indicate the zero point in
dence of ρAHE (a) and MRR (b) in the NRO film below 5 K at low-field region dρAHE/dB (i.e., peak in ρAHE) and the peak in dMRR/dB (i.e., an inflection point in
(B ≤ 4 T) with vertical offsets for clarity. The results of 0.5, 2, and 5 K are identical to MRR) around 1.3 T, respectively. The red-colored areas in (a–c) highlight the field
the ones presented in Fig. 3e, f. For each curve in (a, b), its origin at B = 0 is indicated region where the anomalies are observed at 0.5 K. d Schematic of a possible
by a thick horizontal bar. Inset of (a) is a schematic of a non-coplanar spin texture mechanism to generate the topological Hall effect. Itinerant electrons of Ru3+
that produces scalar spin chirality χS. The peak position of AHE and inflection point interact with localized Nd3+ moments and acquire χS induced by non-coplanar spin
of MRR are indicated by square and triangle, respectively. c Magnetic field depen- texture of Nd3+. Note that Ru3+ locates at the body center of the deformed cube
dence of magnetic field derivatives of ρAHE (red curve, left axis) and MRR (blue formed by Nd3+.

Conclusion 600 °C and an oxygen pressure of 10−4 Torr after the optimization of growth
In conclusion, we have successfully stabilized perovskite LRO and NRO conditions (See Supplementary Fig. 1a). KrF excimer laser (λ = 248 nm)
with Ru3+ in the epitaxial thin film form as a new materials platform to pulses with a frequency of 5 Hz and a fluence of ∼2 J cm−2 were employed to
investigate the interaction between Ru−4d and Ln-4f electrons. Magneto- ablate the targets. After deposition, the as-grown thin films were annealed
transport measurements highlight the clear difference between LRO and with RuO2 powder in a tube furnace at 1000 °C for 2 h under 160 ml min−1
NRO reflecting the absence/presence of magnetic moments on Ln-site as we N2 flow (Supplementary Fig. 3). RuO2 powder works as a supplying source
designed. Especially, only NRO exhibits an anomalous Hall effect, wherein for compensating Ru into the as-grown thin films to form the perovskite
interaction among Ru3+ moments below 100 K, and between Nd3+ and Ru3+ structure.
moments below 20 K play important roles. Above all, we capture an
unconventional AHE below 1 K. We propose a possible mechanism to Structural characterization
realize the unconventional AHE in the framework of topological spin tex- The structural properties of the samples were characterized by XRD (Smart
ture based on the common spin configuration of orthorhombic per- Lab, Rigaku) and transmission electron microscope (TEM) at room tem-
ovskite NdMO3. perature. The oxidation state of Ru in the films was analyzed by X-ray
absorption spectroscopy (XAS) measurements around the Ru K-edge. The
Methods XAS measurements were conducted in the fluorescence mode at BL14B2
Sample Preparation beamline, SPring-8.
Epitaxial LRO and NRO thin films were prepared on STO (001) substrates
by pulsed laser deposition (PLD) and subsequent annealing process. This Magnetotransport measurements
procedure is the so-called solid phase epitaxy, where the precursor seed layer For the magnetotransport measurements, a Hall bar structure was fabri-
is epitaxially crystallized by annealing42. Targets for LRO and NRO were cated by a scriber, and Ni (10 nm) and Au (50 nm) electrodes were deposited
prepared by solid-phase reaction using Ln2O3 (Ln = La or Nd) and RuO2 by electron beam evaporation. Aluminum wires were attached to the six
powders as starting materials. To avoid the deficiency of Ru, Ln2O3 and electrodes to obtain longitudinal (ρxx) and Hall (ρyx) resistivities by four-
RuO2 were mixed by the molar ratio of Ln:Ru = 1:1.25. The mixed powders terminal measurements. A typical device structure is presented in the inset
were milled and calcined for 24 h at 1,150 °C in air. Powder X-ray diffraction of Fig. 4e. The magnetic field was applied perpendicularly to the film surface;
(XRD) confirmed that La3.5Ru4O13 and Nd2Ru2O7 were respectively ρxx and ρyx were deduced by conventional symmetrization and anti-
formed in LRO and NRO targets. The excess Ru remained as RuO2 in both symmetrization procedures, respectively. Magnetotransport measurements
targets. Before deposition, STO substrates were annealed in-situ at 950 °C were performed with a 9 T superconducting magnet equipped with a liquid
under 10−5 Torr oxygen to obtain a clear step-terrace structure with single- He cryostat (PPMS, Quantum Design Co.) down to 0.5 K. Above 2 K, the
unit-cell height. The films were deposited at a substrate temperature of measurement current Im was set to 50 μA. Below 2 K, Im was reduced to

Communications Materials | (2024)5:35 6

[Link] Article

3 μA to prevent the Joule heating. Additional transport properties at lower 15. Sinclair, A. et al. Synthesis and properties of lanthanide
temperatures and higher magnetic fields were measured with a dilution ruthenium(III) oxide perovskites. Angew. Chem. Int. Ed. 53,
refrigerator down to 50 mK (See Supplementary Note 4 and Supplementary 8343–8347 (2014).
Figs. 6, 7) and a pulsed magnet up to 54 T, respectively. For the high field 16. Ji, K. et al. YRuO3: a quantum weak ferromagnet. Phys. Rev. Mater. 4,
measurements, Im was set to 400 μA above 4.2 K and 60 μA at 1.4 K to 091402 (2020).
suppress the Joule heating. For the dilution refrigerator measurements, to 17. Patel, B. K., Kolambage, M. T. K., McMillen, C. D. & Kolis, J. W.
minimize the Joule heating, Im was set to 0.1 μA. Hydrothermal synthesis of lanthanide ruthenate single crystals. J.
Cryst. Growth 602, 126979 (2022).
Magnetic measurements 18. Koster, G. et al. Structure, physical properties, and applications of
Magnetization measurements for NRO were performed with a super- SrRuO3 thin films. Rev. Mod. Phys. 84, 253–298 (2012).
conducting quantum interference device magnetometer (MPMS3, Quan- 19. Cheng, J. G. et al. High-pressure synthesis of the BaIrO3 perovskite: A
tum Design Co.) down to 2 K and up to 7 T. Since it was challenging to Pauli paramagnetic metal with a Fermi liquid ground state. Phys. Rev.
detect the magnetic moment signal in an ultra-thin film, a 37-nm-thick B 88, 205114 (2013).
NRO film was prepared for the magnetic measurements. A bare SrTiO3 20. Matsuno, J. et al. Interface-driven topological Hall effect in SrRuO3-
substrate was also measured to subtract the diamagnetic contribution ori- SrIrO3 bilayer. Sci. Adv. 2, e1600304 (2016).
ginating from the substrate. The summary of magnetic properties is pre- 21. Takiguchi, K. et al. Emergence of Weyl fermions in an epitaxial
sented in Supplementary Note 5, and Supplementary Figs. 8, 9. ferromagnetic oxide. Nat. Commun. 11, 4969 (2020).
22. Torrance, J. B., Lacorre, P., Nazzal, A. I., Ansaldo, E. J. & Niedermayer,
Summary of samples C. Systematic study of insulator-metal transitions in perovskites
Several LRO and NRO films were employed for the various measurements RNiO3 (R = Pr, Nd, Sm, Eu) due to closing of charge-transfer gap.
mentioned above. See Supplementary Note 2 and Supplementary Tables 1, 2 Phys. Rev. B 45, 8209–8212 (1992).
for the summary of these samples. 23. Arima, T., Tokura, Y. & Torrance, J. B. Variation of optical gaps in
perovskite-type 3d transition-metal oxides. Phys. Rev. B 48,
Data availability 17006–17009 (1993).
All data are available in the main text or the supplementary materials. 24. Matsuhira, K., Wakeshima, M., Hinatsu, Y. & Takagi, S. Metal-
insulator transitions in pyrochlore oxides Ln2Ir2O7. J. Phys. Soc. Japan
Received: 24 June 2023; Accepted: 28 February 2024; 80, 094701 (2011).
25. Greedan, J. E., Sato, M., Ali, N. & Datars, W. R. Electrical resistivity of
pyrochlore compounds R2Mo2O7 (R = Nd, Sm, Gd, Tb, Y). J. Solid
References State Chem. 68, 300–306 (1987).
1. Witczak-Krempa, W., Chen, G., Kim, Y. B. & Balents, L. Correlated 26. Wang, H., Dai, Y., Chow, G.-M. & Chen, J. Topological Hall transport:
quantum phenomena in the strong spin-orbit regime. Annu. Rev. Materials, mechanisms and potential applications. Prog. Mater. Sci.
Condens. Matter Phys. 5, 57–82 (2014). 130, 100971 (2022).
2. Rau, J. G., Lee, E. K. H. & Kee, H. Y. Spin-orbit physics giving rise to 27. Kimbell, G., Kim, C., Wu, W., Cuoco, M. & Robinson, J. W. A.
novel phases in correlated systems: iridates and related materials. Challenges in identifying chiral spin textures via the topological Hall
Annu. Rev. Condens. Matter Phys. 7, 195–221 (2016). effect. Commun. Mater. 3, 19 (2022).
3. Maryenko, D. et al. Interplay of spin–orbit coupling and Coulomb 28. Fujita, T. C., Zhang, L. F. & Kawasaki, M. Antiferromagnetic metallic
interaction in ZnO-based electron system. Nat. Commun. 12, state as proved by magnetotransport in epitaxially stabilized
3180 (2021). perovskite PbRuO3. Phys. Rev. Mater. 4, 031401 (2020).
4. Kim, B. J. et al. Novel Jeff = 1/2 Mott state induced by relativistic spin- 29. Maruyama, T., Chikamatsu, A., Onozuka, T. & Hasegawa, T.
orbit coupling in Sr2IrO4. Phys. Rev. Lett. 101, 076402 (2008). Magnetotransport properties of perovskite EuNbO3 single-crystalline
5. Bertinshaw, J., Kim, Y. K., Khaliullin, G. & Kim, B. J. Square lattice thin films. Appl. Phys. Lett. 113, 032401 (2018).
iridates. Annu. Rev. Condens. Matter Phys. 10, 315–336 (2019). 30. Kozuka, Y. et al. Epitaxially stabilized EuMoO3: a new itinerant
6. Yamada, R. et al. Field-induced multiple metal-insulator crossovers of ferromagnet. Chem. Mater. 24, 3746–3750 (2012).
correlated Dirac electrons of perovskite CaIrO3. npj Quantum Mater. 7, 31. Huang, J. K. et al. High-κ perovskite membranes as insulators for two-
13 (2022). dimensional transistors. Nature 605, 262–267 (2022).
7. Kitagawa, K. et al. A spin-orbital-entangled quantum liquid on a 32. Hong, C. et al. Anomalous intense coherent secondary
honeycomb lattice. Nature 554, 341–345 (2018). photoemission from a perovskite oxide. Nature 617, 493–498 (2023).
8. Takagi, H., Takayama, T., Jackeli, G., Khaliullin, G. & Nagler, S. E. 33. Fujiwara, K. et al. Insulator-to-Metal Transition of Cr2O3 Thin
Concept and realization of Kitaev quantum spin liquids. Nat. Rev. Films via Isovalent Ru3+ Substitution. Chem. Mater. 32,
Phys. 1, 264–280 (2019). 5272–5279 (2020).
9. Banerjee, A. et al. Neutron scattering in the proximate quantum spin 34. Matsumoto, T. et al. Experimental data collection and data access
liquid α-RuCl3. Science 356, 1055–1059 (2017). software through internet at SPring-8. AIP Conf. Proc. 2054,
10. Kasahara, Y. et al. Majorana quantization and half-integer thermal 060076 (2019).
quantum Hall effect in a Kitaev spin liquid. Nature 559, 35. Nagaosa, N., Sinova, J., Onoda, S., MacDonald, A. H. &
227–231 (2018). Ong, N. P. Anomalous Hall effect. Rev. Mod. Phys. 82,
11. Yokoi, T. et al. Half-integer quantized anomalous thermal Hall effect in 1539–1592 (2010).
the Kitaev material candidate α-RuCl3. Science 373, 568–572 (2021). 36. Bousquet, E. & Cano, A. Non-collinear magnetism in multiferroic
12. Greenwood, N. N. & Earnshaw, A. Chemistry of the elements. perovskites. J. Phys. Condens. Matter 28, 123001 (2016).
(Butterworth-Heinemann, 1997). 37. Bertaut, E. F. Magnetism, Vol. 3. (New York: Academic, 1963).
13. Bouchard, R. J. & Weiher, J. F. LaxSr1-xRuO3: a new perovskite series. 38. Palacios, E., Bartolome, J., Luis, F. & Sonntag, R. Nuclear polarization
J. Solid State Chem. 4, 80–86 (1972). of Nd in the pseudocubic perovskite NdAlO3 studied by neutron
14. Sugiyama, T. & Tsuda, N. Electrical and magnetic properties of diffraction below 1 K. Phys. Rev. B Condens. Matter Mater. Phys. 68,
Ca1-xLaxRuO3. J. Phys. Soc. Japan 68, 3980–3987 (1999). 224425 (2003).

Communications Materials | (2024)5:35 7

[Link] Article

39. Plaza, I. et al. Neutron diffraction study of NdScO3 below 1 K Magnetic Author contributions
structure and hyperfine enhanced polarization of Nd. Phys. B Conceptualization: L.F.Z., T.C.F. Methodology: MinoruK, H.K., M.T.
Condens. Matter 234–236, 635–636 (1997). Investigation: L.F.Z., T.C.F., Y.M., MinoruK, H.K., M.T. Visualization: L.F.Z.
40. Plaza, I. et al. Neutron diffraction study of the magnetic ordered Nd3+ Supervision: T.C.F., M.K. Writing—original draft: L.F.Z., T.C.F. Writing—
in NdCoO3 and NdInO3 below 1 K. Phys. B Condens. Matter 234–236, review & editing: T.C.F., MinoruK, T.A., H.K., M.T., M.K.
632–634 (1997).
41. Tokunaga, Y. et al. Composite domain walls in a multiferroic Competing interests
perovskite ferrite. Nat. Mater. 8, 558–562 (2009). The authors declare no competing interests.
42. Evans, P. G., Chen, Y., Tilka, J. A., Babcock, S. E. & Kuech, T. F.
Crystallization of amorphous complex oxides: New geometries and Additional information
new compositions via solid phase epitaxy. Curr. Opin. Solid State Supplementary information The online version contains
Mater. Sci. 22, 229–242 (2018). supplementary material available at
43. Momma, K. & Izumi, F. Vesta 3 for three-dimensional visualization of [Link]
crystal, volumetric and morphology data. J. Appl. Crystallogr. 44,
1272–1276 (2011). Correspondence and requests for materials should be addressed to
44. Zhou, H. D. & Goodenough, J. B. Localized or itinerant TiO3 electrons Takahiro C. Fujita.
in RTiO3 perovskites. J. Phys. Condens. Matter 17, 7395–7406 (2005).
45. Liu, B. et al. Electrical transport properties of La1-xSrxCoO3 thin films. Peer review information Communications Materials thanks Felix Gunkel
J. Appl. Phys. 120, 154103 (2016). and the other, anonymous, reviewers for their contribution to the peer review
46. Dabrowski, B. et al. Structural, transport, and magnetic properties of of this work. A peer review file is available.
RMnO3 perovskites (R = La, Pr, Nd, Sm, Eu, Dy). J. Solid State Chem.
178, 629–637 (2005). Reprints and permissions information is available at
47. Niwa, E. et al. Dependence of crystal symmetry, electrical conduction [Link]
property and electronic structure of LnFeO3 (Ln: La, Pr, Nd, Sm) on
kinds of Ln3+. J. Ceram. Soc. Japan 123, 501–506 (2015). Publisher’s note Springer Nature remains neutral with regard to
48. Subramanian, M. A., Aravamudan, G. & Subba Rao, G. V. Oxide jurisdictional claims in published maps and institutional affiliations.
pyrochlores - A review. Prog. Solid State Chem. 15, 55–143 (1983).
49. Sakai, T., Adachi, G., Shiokawa, J. & Shin-ike, T. Electrical conductivity of Open Access This article is licensed under a Creative Commons
LnVO3 compounds. Mater. Res. Bull. 11, 1295–1299 (1976). Attribution 4.0 International License, which permits use, sharing,
50. Hallas, A. M. et al. Coexistence of metallic and nonmetallic properties adaptation, distribution and reproduction in any medium or format, as long
in the pyrochlore Lu2Rh2O7. npj Quantum Mater. 4, 9 (2019). as you give appropriate credit to the original author(s) and the source,
provide a link to the Creative Commons licence, and indicate if changes
Acknowledgements were made. The images or other third party material in this article are
This work is supported by JSPS Grants-in-Aid for Scientific Research (S) No. included in the article’s Creative Commons licence, unless indicated
JP22H04958, by JSPS Grant-in-Aid for Early-Career Scientists No. otherwise in a credit line to the material. If material is not included in the
JP20K15168, by The Mitsubishi Foundation, by The Izumi Science and article’s Creative Commons licence and your intended use is not permitted
Technology Foundation, and by The Tokuyama Science Foundation. The by statutory regulation or exceeds the permitted use, you will need to
XAS measurements at SPring-8 were done under approval of the Japan obtain permission directly from the copyright holder. To view a copy of this
Synchrotron Radiation Research Institute (Proposal No. 2022B0504). The licence, visit [Link]
magnetic measurements were performed using the facilities of the Cryo-
genic Research Center, the University of Tokyo. © The Author(s) 2024

Communications Materials | (2024)5:35 8