Article [Link]

1038/s41467-026-72456-y

Observation of room-temperature
multiferroicity with strong magnetoelectric
coupling in hafnia thin films
Received: 17 December 2025 Haiyi Zhang1,6, Haifeng Bu1,6, Dehe Zhang2, Yuchen Tu1, Yaoxin Li1, Zhijian Shen1,
Weijin Pan1, Zeyu Guan1, Qinghua Zhang 3, Kai Chen 4, Yurong Yang 2,
Accepted: 16 April 2026
Shengchun Shen 1 , Yuewei Yin 1 & Xiaoguang Li 1,5

Check for updates HfO2-based ferroelectrics have emerged as promising candidates for next-
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generation information devices due to their excellent compatibility with

complementary metal oxide semiconductor technology. However, achieving
room-temperature multiferroicity in single-phase HfO2-based materials
remains a rewarding yet challenging goal. Here, we report the discovery of
room temperature multiferroicity in single-phase Cr-doped HfO2 films. We
demonstrate a direct correlation between ferroelectric and ferromagnetic
orders; films with stronger ferromagnetism exhibit enhanced ferroelectricity.
Crucially, the application of external magnetic fields induces a significant
boost in both ferroelectric polarization and piezoresponse amplitude. A giant
magnetoelectric coupling coefficient of ~100 Vcm-1Oe-1 is obtained, surpassing
those of most previously reported single-phase multiferroic materials at room
temperature. Our results not only establish Cr-doped HfO2 films as a promising
platform for exploring emergent multiferroic phenomena but also pave the
way for a new class of silicon-compatible magnetoelectric devices.

Multiferroic materials—systems that simultaneously exhibit two or nominal “empty” d orbitals and broken spatial inversion symmetry,
more ferroic orders (ferroelectricity, (anti-)ferromagnetism, ferroe- whereas robust ferromagnetism relies on partially filled d orbitals and
lasticity) with mutual coupling —have attracted sustained interest for broken time reversal symmetry1.
both fundamental condensed-matter physics and potential device Recently, hafnium oxide (HfO2)-based ferroelectrics have
applications such as nonvolatile memories, energy-efficient logic, and emerged as a transformative material platform. Since the discovery of
neuromorphic computing systems1–3. Flourished in the last two dec- ferroelectricity in 2011, hafnia has attracted significant attention owing
ades, plenty of works provided multiple routes to achieving multi- to its scalability and compatibility with CMOS technology8–12. Ferroe-
ferroicity, with demonstration in diverse material systems including lectricity in HfO2-based materials arises from a metastable non-
hexaferrites, rare earth orthoferrites, and van der Waals compounds4–7. centrosymmetric orthorhombic phase stabilized by factors such as
However, the realization of intrinsic single-phase multiferroics that doping, oxygen vacancy, strain13–17. In contrast to conventional per-
operate at room temperature remains an enduring challenge, primarily ovskite oxides, where ferroelectricity is primarily governed by a cation
because of the conflicting electronic and symmetry requirements: off-centering mechanism, the ferroelectricity in HfO2-based materials
strong ferroelectric polarization typically favors closed-shell or is mainly associated with oxygen anion displacements13,18. This

1
Hefei National Research Center for Physical Sciences at the Microscale, and Department of Physics, University of Science and Technology of China,
Hefei, China. 2Jiangsu Key Laboratory of Artificial Functional Materials, Department of Materials Science and Engineering, Nanjing University, Nanjing, China.
3
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China. 4National Synchrotron
Radiation Laboratory, University of Science and Technology of China, Hefei, China. 5Collaborative Innovation Center of Advanced Microstructures, Nanjing
University, Nanjing, China. 6These authors contributed equally: Haiyi Zhang, Haifeng Bu. e-mail: scshen@[Link]; yyw@[Link]; lixg@[Link]

Nature Communications | (2026)17:5776 1

Article [Link]

unconventional origin provides a unique opportunity to engineer amplitude are enhanced by applying magnetic field at room tem-
multiferroicity in HfO2-based systems beyond traditional ferroelectric perature, providing compelling evidence of magnetoelectric coupling
perovskites. between ferroelectricity and ferromagnetism. Room temperature
Prior to the discovery of ferroelectricity, efforts to introduce multiferroicity discovered in HfO2-based films therefore opens a new
ferromagnetism into dielectric HfO2 through chemical doping or area to explore the magnetoelectric functionality integrated into sili-
defect engineering had already been pursued19–21. Both experimental con electronics.
and theoretical studies reported signatures of room temperature fer-
romagnetism in HfO2 with transition-metal and rare-earth dopants or Results
with controlled oxygen vacancies, although the microscopic origin of Structural characterizations
ferromagnetism is still under debate19–25. On the other hand, the che- Cr-doped HfO2 films with varying Cr concentration (x%, x = 0, 5, 10, 20)
mical dopants or oxygen vacancies have been shown to facilitate sta- and different thicknesses (Supplementary Fig. S1) were deposited on
bilization of the ferroelectric orthorhombic phase13,26,27. More recently, (001)-oriented Nb:SrTiO3 (NSTO) or SrTiO3 (STO) substrates with a
theoretical works have proposed that the selective dopants (such as La0.67Sr0.33MnO3 (LSMO) buffer layer by the pulsed laser deposition
Nb, Ta and V) may enable the coexistence of ferroelectricity and fer- (see details in Methods). Figure 1a shows the X-ray diffraction (XRD) θ
romagnetism in doped HfO228,29. These points together establish −2θ patterns of ~7.5 nm-thick Cr(x%):HfO2 films (x = 0, 5, 10, 20). The
proof-of-principle routes toward realizing single-phase multiferroicity dominant ferroelectric orthorhombic phase is identified by a diffrac-
in hafnia-based systems. Nevertheless, the multiferroicity in HfO2- tion peak near 30.2° corresponding to the (111) plane reflection. While
based materials remains an open question. undoped HfO2 exhibits additional peaks at 2θ ~ 28.2° and 34.3°, cor-
In this work, we demonstrate room temperature multiferroicity in responding (111) and (020) planes of the non-ferroelectric monoclinic
single-phase Cr-doped HfO2 thin films. Cr dopants substantially phase. With Cr doping, the monoclinic phase is largely suppressed. The
enhance ferroelectricity by effectively stabilizing the orthorhombic stabilization of the ferroelectric orthorhombic phase is closely asso-
phase, while simultaneously inducing robust ferromagnetism with a ciated with Cr concentration and film thickness (Supplementary Note
high Curie temperature exceeding 400 K. Comprehensive investiga- S1). In Cr-doped HfO2 films, distinct Laue oscillations are observed
tions of the ferroelectric and magnetic properties in Cr-doped HfO2 around the orthorhombic phase peaks, indicative of high crystalline
films reveal a positive correlation between ferromagnetism and fer- quality and epitaxial growth. This conclusion is further supported by
roelectricity. The ferroelectric polarization and piezoresponse the narrow full width at half maximum (FWHM) of the orthorhombic

a Cr(x%):HfO 2 (7.5 nm) b c 30.20 30.33 OOP

()
NSTO(001)

O(111) 15
45
M(111)
Intensity (arb. units )

Intensity (arb. units )

M(020) 75
x=0 105
135
165
x=5
195
225
x=10
255
285
x=20 315
345
20 25 30 35 40 28 29 30 31 32
2 Theta (deg.) 2 Theta (deg.)

d e

Fig. 1 | Structural characterization of Cr-doped HfO2 films. a XRD θ−2θ patterns respectively. d Cross-sectional HAADF-STEM image of Cr(10%):HfO2 film (~7.5 nm),
of ~7.5 nm-thick Cr(x%):HfO2 films. b Pole figure around the (111) peak of ~10 nm- viewed along [110] zone axis. e Plan-view HAADF-STEM image of Cr(10%):HfO2 film
thick Cr(10%):HfO2 film at 2θ = 30.2°. c 2θ scans of 12 diffraction points (χ = 71°) viewed along [111] zone axis. The insets in (d, e) are the FFT patterns of red square
extracted from pole figure, and the out-of-plane (111) plane (OOP, χ = 0°). The black regions.
and red dashed lines denote the peak positions of OOP (111) and (002) planes,

Nature Communications | (2026)17:5776 2

Article [Link]

a 20 b c
Cr(x%):HfO 2 (11.7 nm) Cr(x%):HfO 2 6.6 nm 8.5 Cr(x%):HfO 2 6.6 nm
60 7.5 nm 7.5 nm
11.7 nm 8.0 11.7 nm
10
45

2Pr ( C/cm 2)

Ec (MV/cm)
7.5
P ( C/cm 2)

0 30 7.0
x=0 6.5
-10
x=5 15
6.0
x=10
x=20 0 5.5
-20
-9 -6 -3 0 3 6 9 0 5 10 15 20 0 5 10 15 20
Electric field (MV/cm) Cr concentration (%) Cr concentration (%)
d 102 e f
Cr(10%):HfO 2 400
2Pr ( C/cm 2)

1 2Pr 180
10
300

Amplitude (pm)

Phase ()
100
200 90
101 Ec
Ec (MV/cm)

t -2/3
100
0
10 0 0
5 10 20 30 -12 -6 0 6 12
t (nm) V (V)

Fig. 2 | Ferroelectric properties of Cr doped-HfO2 films. a P-E loops for 11.7 nm- film. The dashed line denotes the scaling Ec ~ t−2/3. e Phase-contrast PFM images and
thick Cr(x%):HfO2 films (x = 0, 5, 10, 20). Cr-doping concentration dependence of (f) PFM amplitude (blue) and phase (red) hysteresis loops for the Cr(10%):HfO2
b remanent polarization 2Pr and c coercive field Ec for Cr(x%):HfO2 films with dif- film (~9.5 nm).
ferent thicknesses. d 2Pr and Ec as a function of film thickness (t) for Cr(10%):HfO2

phase peak and the smooth surface morphology (Supplementary orthorhombic phase. Figure 1e shows a plan-view HAADF-STEM
Figs. S2 and S3). image of freestanding Cr(10%):HfO2 film along the [111] zone axis, and
To gain a deeper understanding of the phase structure of reveals the orthorhombic domains with distinct in-plane orienta-
Cr(10%):HfO2 film, the pole figure measurement was performed. Based tions, which is in agreement with the pole figure results. For com-
on the XRD patterns (Fig. 1a), the Cr(10%):HfO2 film is oriented along parison, the plan-view image of the undoped HfO2 film is shown in
[111] direction; accordingly, three additional reflections, (111), (111) and Supplementary Fig. S5, where the crystalline domain size is notably
(111), are expected to appear at a chi angle χ = 71° from the out-of-plane smaller than that of the Cr(10%):HfO2 film. These observations indi-
direction, with their azimuthal angles (φ) separated by 120°. As shown cate that Cr doping is critical for stabilizing the ferroelectric
in Fig. 1b, 12 clear diffraction spots are observed at the angle χ = 71°, orthorhombic phase and promoting the growth of larger domains.
corresponding to the projections of (111), (111) and (111) peaks. The
sharp spot at χ = 0° originates from the (001)-oriented NSTO substrate. Room temperature ferroelectricity in Cr-doped HfO2 films
The diffraction peaks can be grouped into four sets, highlighted in To verify the ferroelectricity of Cr(x%):HfO2 films, the ferroelectric
different colors (blue, green, orange, and brown). This suggests polarization versus electric field (P-E) loops were measured using the
Cr(10%):HfO2 film contains four crystallographic orthorhombic phase positive-up-negative-down (PUND) method (Supplementary Fig. S6),
domains with distinct in-plane orientations, matching with the fourfold which effectively eliminates non-ferroelectric contributions such as
symmetry of the (001)-oriented NSTO substrate. The corresponding 2θ leakage current and paraelectric response. Figure 2a shows well-
scans of the 12 diffraction spots (χ = 71°) are shown in Fig. 1c, which defined ferroelectric P-E loops for ~11.7 nm-thick Cr(x%):HfO2 films with
exhibit a slight shift toward larger angles compared to the reflection different Cr doping concentrations, demonstrating robust ferroelec-
position of the (111) peak, indicating a small rhombohedral distortion tricity. The ferroelectric polarization exhibits a non-monotonic
of the orthorhombic phase structure in Cr(10%):HfO2 film. dependence on doped Cr concentration, initially increasing and then
To further elucidate the microstructure and verify the epitaxial decreasing, with a maximum remanent polarization (2Pr ~ 30 µC/cm2)
growth nature of Cr(x%):HfO2 films, comprehensive high-angle at a doping level of 10%. Cr doping strongly influences not only the
annular dark-field scanning transmission electron microscopy polarization but also the coercive field (Ec). Figure 2b, c summarize 2Pr
(HAADF-STEM) investigations were carried out. Figure 1d presents and Ec as a function of Cr concentration for different film thicknesses,
the cross-sectional HAADF-STEM image of the 7.5 nm-thick Cr(10%): and the corresponding P-E loops are shown in Supplementary Fig. S7.
HfO2 film viewed along the [110] zone axis, which reveals a well- Both 2Pr and Ec reach their maximum values at 10% Cr doping for
defined interface between the Cr:HfO2 film and LSMO buffer layer different thicknesses. Such a dopant concentration dependence of
(Supplementary Fig. S4). The orthorhombic phase in Cr(10%):HfO2 polarization has been identified in different element-doped HfO2 films,
film was further confirmed by the fast Fourier transform (FFT) pat- which is mainly attributed to the stabilization of the orthorhombic
terns (the inset of Fig. 1d). In addition, the microstructures of phase13,30,31. Furthermore, Ec exhibits a consistent positive correlation
undoped HfO2 and Cr(20%):HfO2 films were also characterized by with 2Pr values, which may reflect the intrinsic coupling between
HAADF-STEM. As illustrated in Supplementary Fig. S4, sharp inter- polarization dynamics and domain reversal processes in ferroelectric
faces were observed between the HfO2-based film and the LSMO systems32. Importantly, the leakage current density remains nearly
layer. Undoped HfO2 film exhibits a mixture of orthorhombic and unchanged with varying Cr concentration (Supplementary Fig. S8),
monoclinic phases, while the Cr(20%):HfO2 film shows an indicating the good insulating characteristics of Cr-doped HfO2 films.

Nature Communications | (2026)17:5776 3

Article [Link]

a b c 4
Cr(x%):HfO 2 Cr(x%):HfO 2 60 Cr(x%):HfO 2
60 (11.7 nm) 60 (11.7 nm) (11.7 nm)
IP-300 K OOP-300 K 300 K 3
30 30 45
M (emu/cm 3)

M (emu/cm 3)

Hc (102 Oe)
Ms (emu/cm 3)
0 0 2
Amorphous Amorphous 30
x=0 x=0 IP
-30 -30 Ms
x=5 x=5 OOP 1
15
-60 x=10 -60 x=10 Hc
IP
x=20 x=20 OOP
0 0
-20 -10 0 10 20 -20 -10 0 10 20 0 5 10 15 20
H (kOe) H (kOe) Cr concentration (%)

d Cr(10%):HfO 2
4 e 40 Cr(10%):HfO IP FC ZFC
f 80
Cr(10%):HfO 2
60 2 7
300 K (11.7 nm) OOP FC ZFC (11.7 nm)
50 3 @500 Oe @20 kOe 6
IP 70

M (emu/cm 3)
Hc (102 Oe)

Hc (102 Oe)
30
Ms (emu/cm 3)

Ms (emu/cm 3)
Ms OOP
40 5
IP 2
30 Hc
OOP 60 4
20 IP
20 Ms
1 OOP 3
10 50 H IP
c OOP 2
10
0 0
10 15 20 25 30 35 0 100 200 300 400 0 100 200 300 400
t (nm) T (K) T (K)

Fig. 3 | Ferromagnetic properties of Cr-doped HfO2 films. a In-plane (IP) and measured at 300 K for different thickness Cr(10%):HfO2 films. e IP and OOP mag-
b out-of-plane (OOP) magnetization versus magnetic field (M-H) curves for ~11.7 netization versus temperature (M-T) curves of Cr(10%):HfO2 film measured at zero-
nm-thick Cr(x%):HfO2 films (x = 0, 5, 10, 20) and amorphous Cr(10%):HfO2 film, field-cooled (ZFC) and field-cooled (FC) modes. f Temperature dependence of Ms
measured at 300 K. c Saturated magnetization (Ms) and coercive field (Hc) as a and Hc for Cr(10%):HfO2 film, extracted from M-H curves at different temperatures.
function of Cr-doping concentration for Cr(10%):HfO2 film. d IP and OOP Ms and Ec

Obviously, the polarization and coercive field are closely corre- as clearly evidenced by the magnified view of the low-field region in the
lated with film thickness. Figure 2d summarizes the thickness depen- M-H curves (Supplementary Fig. S10). Compared with undoped HfO2,
dence of 2Pr and Ec for Cr(10%):HfO2 films, with the corresponding the values of magnetization for the Cr-doped HfO2 films are clearly
ferroelectric hysteresis loops shown in Supplementary Fig. S8a. The enhanced by Cr doping, as shown in Supplementary Fig. S11. With
increase of polarization with decreasing film thickness may be due to increasing Cr content, the magnetizations of Cr-doped HfO2 films
the enhanced stabilization and distortion of the orthorhombic phase initially increase and then decrease, suggesting the ferromagnetism is
in thinner films10,33. The variation of Ec with film thickness (t) approxi- strongly influenced by the dopant concentration. As summarized in
mately follows the Ec ~ t−2/3 scaling (Janovec-Kay-Dunn law), a behavior Fig. 3c, both saturated magnetization Ms and coercive field Hc exhibit a
commonly observed in ferroelectric perovskite and epitaxial HfO2- non-monotonic dependence on Cr doping, with the Cr(10%):HfO2 film
based films34–36. The thickness dependence of ferroelectricity in Cr- showing the most pronounced ferromagnetism. This non‑monotonic
doped HfO2 films involves a competition among various factors, such trend contradicts the expectation for extrinsic origins of ferro-
as ferroelectric phase ratio, strain relaxation and Cr doping (Supple- magnetism where higher concentrations of magnetic-ion clusters or
mentary Note S2)13,30. Furthermore, the ferroelectricity of Cr-doped induced defects would lead to a stronger ferromagnetism. Addition-
HfO2 films was characterized by piezoresponse force microscopy ally, at low Cr-doping concentrations (0%, 5%, and 10%), the in-plane Ms
(PFM). As shown in Fig. 2e, the phase image on Cr(10%):HfO2 film exceeds the out-of-plane Ms, whereas a larger out-of-plane Ms is
exhibits well-defined regions with 180° phase contrast switched under observed at a higher concentration (20%), suggesting a doping-
positive/negative applied bias, confirming the presence of ferro- induced change in magnetic anisotropy.
electric polarization. The corresponding amplitude image reveals clear As discussed above, the Cr(10%):HfO₂ film exhibits both opti-
domain walls at the boundaries between antiparallel domains (Sup- mized ferroelectric properties and the strongest ferromagnetism. The
plementary Fig. S9), indicative of stable bipolar remanent polarization parallel trends of ferroelectricity and ferromagnetism with varying Cr
states. Notably, the unpoled regions show the same phase contrast as concentration suggest a close interplay between the two ferroic
negatively poled regions, indicating spontaneous polarization in Cr- orders. To further substantiate this correlation, we conducted the
doped HfO2 films. Along with phase-contrast imaging, complementary following two studies: (1) A non-ferroelectric amorphous Cr(10%):HfO₂
local PFM switching spectroscopy further demonstrates the robust film (~11.7 nm) was synthesized, and its amorphous nature was con-
ferroelectricity in Cr-doped HfO2 films, as revealed by the square-like firmed by the XRD pattern as depicted in Supplementary Fig. S1d.
phase hysteresis loop and butterfly-shaped amplitude loop (Fig. 2f). Contrary to the crystallized film, room temperature ferromagnetism is
absent in the amorphous film (Fig. 3a, b). (2) Magnetization measure-
Room temperature ferromagnetism in Cr-doped HfO2 films ments of thicker films (20.3 and 33.4 nm) revealed a pronounced
Next, we turn to explore the ferromagnetism in Cr-doped HfO2 films. suppression of ferromagnetism (Fig. 3d and Supplementary Fig. S12). A
Figure 3a, b show the room temperature in-plane (IP) and out-of-plane detailed analysis of the XRD pattern indicated that the non-
(OOP) magnetizations versus magnetic field (M-H) hysteresis loops of ferroelectric monoclinic phase appears in these thicker films, coin-
Cr(x%):HfO2 films with different Cr doping levels, respectively. The ciding with diminished ferroelectricity. Collectively, these results
observed ferromagnetic hysteretic behaviors demonstrate the emer- provide evidence for the coupling between ferroelectricity and ferro-
gence of room-temperature ferromagnetism in Cr-doped HfO2 films, magnetism in Cr-doped HfO2 films.

Nature Communications | (2026)17:5776 4

Article [Link]

a c e
10 Cr(10%):HfO 2 800
Cr(10%):HfO 2 0T
0.4 T-IP Cr:HfO 2 (PFM)
5 Cr:HfO 2 (P-E)
ΔPr 600

Amplitude (pm)
P ( C/cm 2)

10
0 2Pr (H 0)
Pb2.48Fe2O5 [38]
2Pr (H=0)

-10
400
ΔPr
BiFeO 3 [5]
-5 ΔA
-2 0 2 200 SrCo 2Ti2Fe8O19 [48] @ 300 K
-10 A (H 0) A (H=0)
0T Bi5Ti3FeO 15 [49]
0.4 T-IP 0
-15 (TMCM) [FeCl 4] [50]
-8 -4 0 4 8 -15 -10 -5 0 5 10 15
E (MV/cm) E (MV/cm) Sr2Co2Fe24O41 [51]

b Cr(10%):HfO 2 0T 0.4 T-IP

d 3.0
Cr(10%):HfO 2
Na0.1Gd0.9FeO 3 [52]

2.5 PbZr 0.52 Ti0.48 O3 Cr2O3 [53]

4
2.0
ΔPr/Pr(H=0) (%)

H-IP PbFe 0.5Nb0.5O3 [54]

ΔA/A(H=0)
0 1.5 Na0.5Bi0.5TiO3 [55]
1.0
GdFe 0.94Mg0.06O3 [56]
PbZr 0.52 Ti0.48 O3 0T 0.4 T-IP 0.5
4 Bi3.7Sm0.3Ti2.7Fe0.3O12 [57]
0.0
(Sm0.25 Ho0.25 Yb0.25 Lu0.25 )FeO 3 [58]
0
-0.5
0 2 4 6 8 10 12 14 16 0.0 0.1 0.2 0.3 0.4 10-4 10-3 10-2 10-1 100 101 102 103 104
Cycles H (T) ME coefficient αΜΕ (V cm -1 Oe -1)

Fig. 4 | Coupling of ferroelectricity and ferromagnetism in Cr-doped HfO2 films. defined as A. d Variation of remanent PFM amplitude (ΔA(H)/A(H = 0), normalized
a P-E loops of Cr(10%):HfO2 film measured without and with an IP magnetic field of by its value at 0 T) of Cr(10%):HfO2 and PZT films measured under various IP
0.4 T. The inset shows the enlarged view of the P-E loops. b Magnetic field induced magnetic fields. Multiple measurements were performed at each fixed magnetic
variation of remanent polarization Pr (ΔPr(H)/Pr(H = 0), normalized by its value at field. Error bars in (b, d) denote the standard deviation from the mean value.
0 T) of Cr(10%):HfO2 (upper panel) and PZT (bottom panel) films. The presented e Comparison of the magnetoelectric coupling coefficient (αME) of Cr-doped HfO2
PFM amplitude curve is the result of averaging ten independent measurements (as film with those of previously reported single-phase multiferroic materials at room
shown in Fig.S20). c PFM amplitude loops of Cr(10%):HfO2 measured without and temperature5,38,48–58. The αME of Cr-doped HfO2 film was estimated from the mag-
with an IP magnetic field of 0.4 T. Remanent PFM amplitude at zero voltage bias is netic field-induced variations in polarization (P-E) and piezoresponse (PFM).

To further study the ferromagnetic behavior, the temperature interplay between these two ferroic orders. As a characteristic probe of
dependence of magnetization was investigated. Figure 3e presents the ferroelectricity, the ferroelectric polarization (P-E) loops of Cr-doped
temperature dependences of IP and OOP magnetizations under zero- HfO2 films were measured under external magnetic fields. Meanwhile,
field-cooling (ZFC) and field-cooling (FC) conditions. Notably, ferro- ferroelectric PbZr0.52Ti0.48O3 (PZT) films without ferromagnetism were
magnetic ordering persists beyond 400 K, suggesting a high Curie also characterized under the same conditions for comparison.
temperature (TC) for Cr-doped HfO2 films. A kink feature observed in Figure 4a shows the P-E loops of the Cr(10%):HfO2 film measured
the ZFC M-T curves at low temperatures may indicate the presence of a without and with an in-plane magnetic field of 0.4 T. The application of
spin glass state37, which becomes smeared when measured at a higher a magnetic field enhances the ferroelectric polarization of
magnetic field (Supplementary Fig. S13). The M-H loops of Cr(10%):HfO2 film, whereas the polarization of PZT film remains nearly
Cr(10%):HfO2 film recorded at different temperatures reveal that both unchanged (Supplementary Fig. S16a). To quantify this effect, the
saturated magnetization Ms and coercive field Hc decrease as the variation in remanent polarization (ΔPr/Pr(H = 0), normalized by its
temperature increases (Fig. 3f and Supplementary Fig. S14). For com- value at 0 T) is plotted as a function of applied magnetic field, as shown
parison, the IP and OOP M-H loops of undoped HfO2 film at different in Fig. 4b (also see Supplementary Note S4). Cycling the in-plane
temperatures were also measured (Supplementary Fig. S15). The non- magnetic field between 0 T and 0.4 T results in periodic variations of
zero ferromagnetic response in undoped HfO2 film is primarily remanent polarization for Cr(10%):HfO2 film. In contrast, the remanent
attributed to intrinsic point defects, specifically oxygen vacancies, polarization of the PZT film is insensitive to the magnetic field. At each
which can induce localized magnetic moments by creating unpaired fixed magnetic field, the P-E loops were repeatedly measured multiple
electrons or modulating the electronic structure (Supplementary Note times (Supplementary Figs. S17 and S18). In addition, similar polar-
S3)19,20. The saturated magnetization (Ms) and remanent magnetization ization enhancement was observed under out-of-plane magnetic fields
(Mr) values are systematically summarized in Supplementary Fig. S15e, (Supplementary Fig. S19a). Furthermore, measurements performed
f. The magnetization of Cr(10%):HfO2 film consistently exceeds that of under larger in-plane and out-of-plane magnetic fields of 2 T further
the undoped HfO2 film across the entire measured temperature range, confirm the magnetic field control of ferroelectric polarization (Sup-
which demonstrates that ferromagnetism is significantly enhanced plementary Fig. S19b, c). The coercive field remains essentially unaf-
with Cr doping. fected by the applied magnetic field (Supplementary Fig. S19d). These
results unambiguously demonstrate that ferroelectric polarization in
Coupling of ferroelectricity and ferromagnetism Cr(10%):HfO₂ films is enhanced by magnetic fields, in sharp contrast to
Having established the coexistence of room-temperature ferroelec- PZT films.
tricity and ferromagnetism in Cr-doped HfO2 films, we next investigate To further verify the coupling between ferroelectricity and fer-
their magnetoelectric coupling, which fundamentally arises from the romagnetism, the PFM technique was utilized, which offers a way to

Nature Communications | (2026)17:5776 5

Article [Link]

a O K-edge t2g HfO 2 c Cr 2p Exp. Fitting d Hf 4f Exp. Fitting

eg Cr(5%):HfO 2 HfO 2
Cr(5%):HfO 2
Cr(10%):HfO 2 Hf 4+ 94.0%
Intensity (arb. units )

Cr 3+ 62.5%
Cr(20%):HfO 2 Hf (4-)+ 6.0%
Cr (3+n)+ 37.5%

Cr(5%):HfO 2
Hf 4+ 93.8%
Hf (4-)+ 6.2%

Intensity (arb. units )

Intensity (arb. units )

Hf 5d Hf 6sp
Cr(10%):HfO 2
Cr 3+ 70.8%
520 528 536 544 552 Cr (3+n)+ 29.2%
Photon energy (eV) Cr(10%):HfO 2
b Cr L-edge Cr(5%):HfO 2
Hf 4+ 91.9%
Hf (4-)+ 8.1%
Cr(10%):HfO 2
L3
Cr(20%):HfO 2
Intensity (arb. units )

L2
Cr(20%):HfO 2
Cr 2p3/2
Cr 3+ 65.4% Cr(20%):HfO 2
Cr (3+n)+ 34.6% Hf 4f7/2 Hf 4f5/2
Cr 2p1/2 Hf 4+ 92.8%
Hf (4-)+ 7.2%
Cr 3+ (Ref.)

572 576 580 584 588 592 570 576 582 588 594 14 15 16 17 18 19 20 21
Photon energy (eV) Binding energy (eV) Binding energy (eV)

Fig. 5 | XAS and XPS characterizations of the Cr(x%):HfO2 films. Normalized XAS spectra are also presented in (b). XPS spectra of c Cr 2p and d Hf 4 f core levels.
spectra at a O K-edge and b Cr L-edge for Cr-doped HfO2 films with varying Cr Black dot: original spectra, red line: fitted spectra. All film thicknesses are identical
concentrations. The data are vertically offset for clarity. Referenced Cr3+ L-edge at 11.7 nm.

probe local magnetoelectric coupling behavior in multiferroics38–40. demonstrating magnetic field control of ferroelectric polarization and
Figure 4c exhibits the PFM amplitude-voltage butterfly loops of piezoelectric amplitude, we confirmed robust room temperature
Cr(10%):HfO2 film measured at 0 T and an in-plane magnetic field of multiferroicity in single-phase Cr-doped films.
0.4 T. The application of the magnetic field markedly enhances the
PFM amplitude for Cr(10%): HfO2 film, whereas the response of PZT Discussion
remains essentially unaffected (Supplementary Fig. S16b). These To illustrate the possible mechanisms underlying room temperature
observations are well consistent with the P-E loop measurements, multiferroicity and magnetoelectric coupling in Cr-doped HfO2 films,
further demonstrating magnetoelectric coupling in Cr-doped HfO2 X-ray absorption spectroscopy (XAS) and X-ray photoelectron spec-
films. To evaluate the magnetic field dependence, PFM amplitude troscopy (XPS) characterizations were performed. XAS spectra pro-
loops were studied under different in-plane magnetic fields, as vide insight into the electronic structure of Cr-doped HfO2 films.
revealed in the Supplementary Fig. S20. For quantitative analysis, the Figure 5a displays the O K-edge XAS spectra for films with varying Cr
variation in remanent piezoelectric amplitude ΔA at zero voltage was concentration. Two prominent peaks at 536.6 eV and 540.9 eV corre-
extracted (Fig. 4c and Supplementary Note S4). As shown in Fig. 4d, the spond to the eg and t2g components of the Hf 5 d manifold, arising from
variation in remanent amplitude (ΔA/A(H = 0), normalized by its value crystal field splitting and associated with the hybridization of O 2p and
at 0 T) increases systematically with applied magnetic field in Hf 5 d orbitals. Additional weaker peaks at higher energies originate
Cr(10%):HfO2 film, while that of PZT film exhibits negligible changes. from O 2p-Hf 6sp orbital hybridization. In case of Cr doping, the Cr 3 d
Similar field-dependent behavior was also observed in Cr(x%):HfO₂ and 4 s orbitals also hybridize with O 2p orbital, leading to modifica-
films with other doping levels (Supplementary Figs. S20 and S21), with tions in the O K-edge spectra. For the undoped HfO2 film, a two-fold
the strongest effect occurring at 10% doping, consistent with the degeneracy in the eg component is observed, which is related to the
enhanced ferroelectric and ferromagnetic properties at this con- monoclinic phase41,42. In contrast, Cr-doped HfO2 films display only a
centration. Remarkably, Cr-doped HfO2 films exhibit a giant magne- single eg peak, suggesting suppression of the monoclinic phase by Cr
toelectric coupling coefficient αME of ~100 V cm–1 Oe–1 at room doping. This point is well consistent with the XRD results (Supple-
temperature (Supplementary Fig. S22), surpassing most previously mentary Fig. S1b). Furthermore, the increase in eg peak intensity with
reported single-phase multiferroics (Fig. 4e). The αME is estimated higher Cr concentration may reflect enhanced structural distortion, as
using two distinct methods: the changes in polarization (P-E) and the ionic radius of Cr is smaller than that of Hf. Figure 5b shows the Cr
piezoelectric response (PFM) under an applied magnetic field (Sup- L-edge XAS spectra of Cr-doped HfO2 films, along with reference
plementary Note S4). The discrepancy between the two derived αME spectra for Cr3+43. The spectra clearly resemble those of Cr3+, indicating
values is likely attributed to the inherent differences between global (P- that Cr3+ is the dominant oxidation state in Cr-doped films. The dom-
E) and local (PFM) measurement techniques, which arise from different inance of Cr³⁺ might arise from charge compensation via oxygen
physical observables and boundary conditions (Supplementary Note vacancies and its ionic radius (0.62 Å), which is closer to that of Hf⁴⁺
S4). PFM measurement quantifies local magnetoelectric coupling by (0.76 Å) than the Cr ion with a higher valence state. Additionally,
probing strain-mediated modulation of the piezoelectric coefficient, to pinpoint the source of magnetism, we performed Cr L-edge
whereas P-E measurements reflect the global response by integrating X-ray magnetic circular dichroism (XMCD) measurements on the
changes in macroscopic polarization under a magnetic field. By Cr(x%):HfO2 thin films (Supplementary Fig. S23). This provides solid

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evidence that the Cr ions possess a net magnetic moment and are the ferromagnetic and antiferromagnetic orders are very close. This sug-
dominant source of the observed ferromagnetism. The ferromagnet- gests that the two orders could coexist in large supercells with a dis-
ism in Cr(x%):HfO2 films fundamentally differs from defect-induced ordered distribution of Cr atoms, potentially leading to a ferrimagnetic
background magnetism, such as that induced by oxygen vacancies ground state in the Cr-doped HfO2 system. The partial density of states
(Supplementary Note S5). (PDOS) shows a significant overlap of Cr 3 d and O 2p orbitals, and the
XPS was further employed to investigate the effects of Cr-doping band structures are mainly composed of Cr 3 d and O 2p components
on the valence states and defect configurations in Cr-doped HfO2 films. near the Fermi level (Supplementary Figs. S26 and S27), indicating the
Figure 5c, d present the XPS spectra of Cr 2p and Hf 4 f core levels, strong orbital hybridization between Cr 3 d and O 2p. The magnetic
respectively. The Cr 2p spectrum can be deconvoluted into contribu- reorientation induces a redistribution of electronic charge due to this
tions from Cr3+ (2p3/2 and 2p1/2) and Cr(3+n)+ (2p3/2 and 2p1/2) species. As strong p-d orbital hybridization (Supplementary Fig. S28), which sub-
shown in Fig. 5c, Cr3+ is the dominant portion, and a noticeable fraction sequently modulates the ferroelectric polarization, demonstrating
of Cr(3+n)+ portion is also present, consistent with the XAS results, which that the Cr-doped HfO2 system can possess strong magnetoelectric
might be responsible for the multiferroicity of Cr-doped HfO2 films. coupling.
Similarly, Hf 4 f spectrum can be decomposed into two components: In summary, we demonstrate the room temperature multi-
Hf4+ related to Hf–O bonding and Hf(4-δ)+ associated with weaker ferroicity in single-phase Cr-doped HfO2 thin films. With the intro-
bonding and reduced valence state. The O 1 s spectra further support duction of Cr dopant, the ferroelectric phase is stabilized with
these assignments (Supplementary Fig. S24a). With increasing Cr enhanced ferroelectricity. Concurrently, intrinsic room temperature
concentration, the relative proportions of Cr3+, Hf(4-δ)+ and non-lattice O ferromagnetism emerges, which is positively correlated with ferroe-
increase (Supplementary Fig. S24b). Additionally, the binding energy lectricity. More importantly, the strong magnetoelectric coupling
positions of Hf 4 f and O 1 s spectra in Cr-doped films exhibit slight between these two ferroic orders is verified, with a giant coupling
shifts to the higher energy compared with undoped HfO2, reflecting coefficient of 10 ~ 100 Vcm–1Oe–1, which is superior to that of the
changes in oxidation state and local chemical environment. Taken majority of single-phase multiferroic materials. The discovery of room-
together, the XAS and XPS analyses demonstrate that Cr doping alters temperature multiferroicity in HfO2-based materials marks a sig-
both the electronic structure and local chemical environment of Hf. In nificant advance, opening new opportunities for integrating magne-
addition, the XPS spectra of thicker Cr(10%):HfO2 films (20.3 and toelectric functionality into silicon-based electronics.
33.4 nm), which exhibit weaker ferroelectric and ferromagnetic
responses, reveal a pronounced increase in the Cr(3+n)+ fraction (Sup- Methods
plementary Fig. S24c). This evolution may be attributed to the higher Thin-film growth
formation energy of oxygen vacancies in the monoclinic phase that HfO2 targets with different Cr-doping concentrations were prepared
becomes dominant in thicker films44. by spark plasma sintering (SPS) system using high-purity HfO2
The coexistence of Cr3+/Cr(3+n)+ ions and oxygen vacancies likely (99.99%) and Cr2O3 (99.99%) powders. Cr-doped HfO2 thin films were
plays a central role in establishing room temperature multiferroicity in grown on (001)-oriented Nb-doped SrTiO3 (NSTO, 0.7 wt%) and SrTiO3
Cr-doped HfO2 thin films. Ferroelectricity arises from the stabilization (STO) substrates with a La0.67Sr0.33MnO3 (LSMO) buffer layer by the
of the ferroelectric orthorhombic phase facilitated by Cr doping and pulsed laser deposition (PLD). Specifically, the thin LSMO buffer layer
oxygen vacancy. Simultaneously, the Cr mixed valence states and (~3 u.c.) was first deposited on (001) NSTO substrate using a KrF
oxygen vacancies can mediate exchange interactions, enabling long- excimer laser (λ = 248 nm) with 1 Hz frequency and 1.3 J/cm2 energy
range ferromagnetism45. As proposed by Coey et al., the observed density, at 650 °C under an oxygen pressure of 20 Pa. The Cr-doped
ferromagnetism may originate from long-range magnetic order HfO2 layer was then deposited at 825 °C under an oxygen pressure of
mediated by shallow donor electrons, which form bound magnetic 13 Pa with a frequency of 2 Hz. Following deposition, the films were
polarons capable of overlapping to produce a spin-split impurity cooled to room temperature at a cooling rate of 10 °C/min in a 1000 Pa
band46. The strong magnetoelectric coupling can be realized through oxygen atmosphere. For the preparation of freestanding films used in
the interplay between ferroelectricity and ferromagnetism. Polar dis- plan-view HAADF-STEM measurements, a thicker LSMO buffer layer
tortions associated with ferroelectricity modify Cr-O bond lengths and (~25 nm) was grown to serve as a sacrificial layer. Finally, circular Au top
angles, thereby tuning magnetic exchange interactions28. Under an electrodes with 20 ~ 100 μm diameters were prepared by magnetron
applied magnetic field, spin reorientation mediates Cr-O bonding sputtering and patterned using lift-off lithography for subsequent
changes, which in turn influence the displacement of oxygen ions and ferroelectric characterization.
consequently modify the ferroelectric properties. In addition, the
Dzyaloshinskii-Moriya (DM) interaction may provide another Structural characterizations
mechanism for magnetoelectric coupling2,47. The inversion symmetry The phase structure and thickness of the films were probed by X-ray
breaking in the non-centrosymmetric orthorhombic phase, together diffraction (XRD, Rigaku Smartlab 9 kW) with Cu Kα1 radiation
with the strong spin–orbit coupling from heavy Hf atoms, can induce (λ = 1.5406 Å) in θ−2θ scanning, X-ray rocking curves (RC) and X-ray
significant antisymmetric exchange interactions between localized reflectivity (XRR) modes. Pole figure and corresponding 2θ scans were
magnetic moments introduced by Cr dopant or oxygen vacancies. As obtained using the χ-φ pole figure measuring method. The surface
the DM vector is intimately tied to the polar lattice distortion, an morphology of Cr(x%):HfO2 films (x = 0, 5, 10, 20) was examined by
external magnetic field can indirectly affect polarization by reorienting atomic force microscope (AFM, Asylum Research MFP-3D Infinity). The
the spin structure, thereby enhancing the ferroelectric polarization atomic lattice structures of films were investigated by high-angle
and piezoresponse in Cr-doped HfO2 films. annular dark-field high-resolution transmission electron microscopy
To gain deeper insights into the underlying mechanism of mag- (HAADF-HRTEM, JEM-ARM200F, JEOL).
netoelectric coupling in single-phase multiferroic Cr-doped HfO2 films,
we performed density functional theory (DFT) calculations (Supple- Ferroelectric characterizations
mentary Note S6). Compared with undoped HfO2, the energy differ- The macroscopic ferroelectric properties of the Au/Cr(x%):HfO2/
ence between orthorhombic and monoclinic phases is reduced in Cr LSMO/NSTO capacitors were measured by a semiconductor parameter
doped HfO2 (Supplementary Fig. S25 and Table S1), indicating that Cr analyzer (4200A-SCS, Keithley). Ferroelectric P-E hysteresis loops of
doping facilitates the stabilization of the ferroelectric orthorhombic Cr(x%): HfO2 films (x = 0, 5, 10, 20) were characterized by positive-up-
phase. Intriguingly, our calculations reveal that the energy values of negative-down (PUND) mode under triangular electric pulses with a

Nature Communications | (2026)17:5776 7

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frequency of 10 kHz. For magnetoelectric coupling measurements, P-E repulsion associated with the localized Cr 3 d orbitals. All structures
loops of ~10.6 nm-thick Cr(10%):HfO2 film and referenced ~80.0 nm- were fully relaxed until the force on each atom was less than 1 meV Å–1
thick PZT film (with ~25 nm-thick LSMO buffer layer as bottom elec- and the total energy difference of the supercell between two adjacent
trode) were measured by PUND mode under in-plane or out-of-plane steps was less than 10–6 eV. An oxygen vacancy was introduced in the
magnetic field cycled between 0 T and 0.4 T/2 T. Multiple P−E loops vicinity of the trivalent Cr3+ ions to maintain charge neutrality for the
were measured in each fixed magnetic field to ensure reproducibility. 12.5 at.% Cr3+ doping system. The spontaneous polarization was
determined via the Berry phase method.
Magnetization characterizations
The temperature and magnetic field dependences of magnetization Data availability
were measured by a superconducting quantum interference device The data generated in this study are provided in the Supplementary
(SQUID, MPMS3). For zero field cooling (ZFC) measurements, samples Information/Source Data file. Source data are provided with this paper.
were cooled from 400 K to 2 K without a magnetic field; whereas for
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