An et al.

NPG Asia Materials (2021) 13:69

https://doi.org/10.1038/s41427-021-00335-7 NPG Asia Materials

ARTICLE Open Access

Experimental realization of strain-induced room-

temperature ferroelectricity in SrMnO3 films via
selective oxygen annealing
Hyunji An1, Young-Gyun Choi1, Yong-Ryun Jo1, Hyo Jin Hong1, Jeong-Kyu Kim2, Owoong Kwon3, Sangmo Kim4,
Myungwoo Son1, Jiwoong Yang1, Jun-Cheol Park1, Hojoong Choi 1, Jongmin Lee1, Jaesun Song1, Moon-Ho Ham1,
Sangwoo Ryu5, Yunseok Kim3, Chung Wung Bark 4, Kyung-Tae Ko2,6, Bong-Joong Kim 1 and Sanghan Lee 1

Abstract
Antiferromagnetic-paraelectric SrMnO3 (SMO) has aroused interest because of the theoretical strong coupling
between the ferroelectric and ferromagnetic states with increasing epitaxial strain. In strained SMO films, the <110>
polarized state and polar distortions have been observed, although high leakage currents and air degradation have
limited their experimental verification. We herein provide a conclusive demonstration of room-temperature
ferroelectricity and a high dielectric constant (εr = 138.1) in tensile-strained SMO by securing samples with insulating
properties and clean surfaces using selective oxygen annealing. Furthermore, a paraelectricity and low dielectric
constant (εr = 6.7) in the strain-relaxed SMO film have been identified as properties of the bulk SMO, which directly
proves that the ferroelectricity of the tensile-strained SMO film is due to strain-induced polarization. We believe that
these findings not only provide a cornerstone for exploring the physical properties of multiferroic SMO but also inspire
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new directions for single-phase multiferroics.

Introduction been difficult to implement. Since Kimura demonstrated

Multiferroic materials exhibiting simultaneous ferro- multiferroicity in TbMnO35,6, significant progress has
electric and ferromagnetic properties have attracted much been made such that multiferroic systems can be classified
attention over the last decades as promising candidates into types I and II7,8. In type-I systems, an electric field
for next-generation devices such as multiple-state mem- can drive changes in the magnetization, although a rather
ory elements, electrical-field-controlled ferromagnetic weak coupling between ferroelectricity and magnetism
resonance devices, and transducers with magnetically was observed because ferroelectricity and magnetic order
modulated piezoelectricity1,2. In essence, ferroelectricity originate from two different cations9. Conversely, type-II
prefers the d0-ness configuration for transition metal off- multiferroics exhibit very strong magnetoelectric cou-
centering in a perovskite structure, whereas magnetism plings because the magnetic order breaks the inversion
stems from uncompensated spin magnetic moments of symmetry of the material and induces a ferroelectric
the occupied d electrons3,4. Owing to competing phase; however, their spontaneous polarization is gen-
requirements, multiferroicity with strong properties has erally small (~10−2 μC/cm2). Due to these limitations of
conventional multiferroics, a new multiferroic system is
urgently needed for practical device applications10.
Correspondence: Sanghan Lee ([email protected]) SrMnO3 (SMO) goes beyond the standard paradigm of
1
School of Materials Science and Engineering, Gwangju Institute of Science type I/type II multiferroics because both ferroelectric and
and Technology, Gwangju 61005, Republic of Korea
2 ferromagnetic properties are primary order parameters
Max Planck POSTECH/Hsinchu Center for Complex Phase Materials &
Department of Physics, POSTECH, Pohang 37673, Republic of Korea that in principle emerge independent of each other but
Full list of author information is available at the end of the article

© The Author(s) 2021

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An et al. NPG Asia Materials (2021) 13:69 Page 2 of 10

are nevertheless strongly coupled11. Recent theoretical first time, and their dielectric properties can be investi-
studies have reported that the bulk antiferromagnetic- gated. We fabricated a 1.7% tensile-strained SMO thin
paraelectric ground state in some perovskites is driven to film with a thickness of 20 nm on an LSAT substrate
a new multiferroic state by increasing the epitaxial utilizing pulsed laser deposition (PLD) and fabricated
strain12–15. This multiferroic phase emerges from a strong films with various thicknesses (45, 69, 92, and 115 nm) to
interaction between the spin order and the lattice pho- systematically control the degree of strain. The samples
nons (so-called “spin-phonon coupling”) when the unit were then postprocessed using the SOA method. Com-
cell volume is increased16. Strain-induced multiferroicity pared with the semiconductor properties (current density >
based on spin-phonon coupling was first experimentally 10 A/cm2 and dielectric loss (tan δ) > 10) of the as-grown
demonstrated in the EuTiO3 of A-site rare-earth sys- films, the SOA-treated SMO films exhibited insulating
tems16,17; however, weak magnetoelectric coupling was properties (current density < 10−5 A/cm2 and tan
also observed because ferroelectricity and magnetism δ < 0.1). Based on these insulating properties, 1.7%
originated from different lattice sites16. For this reason, tensile-strained SMO films with a polarization hysteresis
the SMO of a B-site magnetic system was of particular loop (Ps = 1 μC/cm2) and a high dielectric constant (εr =
interest. In this material, strong magnetoelectric cou- 138.1) were demonstrated at room temperature for the
plings were expected since the off-centered Mn4+ (3d3) first time. Furthermore, the strain-induced ferroelectricity
ion carries both electric and spin magnetic moments15,18. of SMO was verified by examining the significant changes
According to density functional theory (DFT) calcula- in the polarization hysteresis loops and dielectric con-
tions, an epitaxial SMO film generates ferroelectric stants as the epitaxial strain increased.
polarization in the <110> direction at epitaxial tensile
strains above 1%, whereas high tensile strains above 4.5% Materials and methods
are required for ferromagnetism15. Because of the diffi- Sample preparation
culty of implementing high strain states, experimental The SrMnO3 ceramic was synthesized using a solid-
studies related to strain-induced ferroelectricity preceded state reaction method with the following starting binary
those of ferromagnetism. In particular, Becher and Guz- oxide powders as raw materials: SrCO3 (99.9%, Kojundo
man et al. fabricated epitaxial 1.7% tensile-strained SMO Chemical Lab.) and MnCO3 (99.9%, Kojundo Chemical
thin films with thicknesses of 10−20 nm using the Lab.). Based on the ceramic target, 1.7% tensile-strained
(LaAlO3)0.3(Sr2TaAlO6)0.7 (LSAT) substrate. They con- SrMnO3 (SMO) thin films (acubic = 0.3805 nm) were
firmed its <110> polarized state and polar distortions by grown on LSAT (001) substrates (acubic = 0.3869 nm).
second harmonic generation (SHG) and scanning trans- SMO thin films with thicknesses of 20, 45, 69, 92, and
mission electron microscopy (STEM)19,20. However, high 115 nm were fabricated at a high temperature of 900 °C,
leakage currents and the presence of oxygen vacancies oxygen pressure of 200 mTorr, and laser fluence of 1 J/cm2
were also observed19,20. More recently, surface and using PLD (KrF, λ = 248 nm). To perform SOA, we
internal cracks in SMO thin films were found under additionally grew SrRuO3 layers (acubic = 0.3926 nm) on
strained states9,21,22. These reports revealed that the the as-grown SMO films at a temperature of 750 °C,
strained SMO film could easily degrade in air so that oxygen pressure of 100 mTorr, and laser fluence of 2 J/cm2
cracks appeared due to partial epitaxial stress relief. Air using PLD. In a tube furnace, the SrRuO3 (SRO)-capped
degradation is an important challenge in the SMO SMO films were annealed under a high-purity oxygen
research field, as the intrinsic properties of thin films (99.995%, Sinil gas) atmosphere at a temperature of 600 °C
deteriorate due to chemical or mechanical instability when with an oxygen flow rate of 1.5 L/min in atmospheric
the thin film is exposed to air, consequently reducing the pressure for 2 h. Finally, the SRO capping layer was
device performance23–25. These issues make it difficult to selectively etched in a sodium metaperiodate (NaIO4)
directly investigate the intrinsic ferroelectric and dielectric etchant.
properties26, thus hampering the experimental verification
of strain-induced SMO thin films. Furthermore, in-depth Thin film characterizations
studies analyzing and solving high leakage current and air The structural properties were analyzed via XRD (D8
degradation issues have not been reported. Advance, Bruker) using Cu Kα radiation (λ = 1.5418 Å).
Herein, we propose a selective oxygen annealing (SOA) Reciprocal space mapping (RSM) was performed using
method as an innovative strategy to effectively suppress the 3 A beamline at the Pohang Light Source with a six-
the leakage current while protecting strained SMO films circle Paul Scherrer Institute (PSI) diffractometer. Surface
from air degradation. Because SOA imparts insulating morphologies were observed using a standard optical
properties and suppresses surface crack issues, the microscope with a CCD camera and an atomic force
intrinsic room-temperature ferroelectricity of tensile- microscope (Park Systems NX10). Atomic-scale structural
strained SMO thin films can be demonstrated for the characteristics and elemental mapping were investigated
An et al. NPG Asia Materials (2021) 13:69 Page 3 of 10

using a high-resolution transmission electron microscope toward the reference line as the thickness increased to
(TecnaiTM G2 F30 S-Twin, 300 KeV, FEI). SRO inter- 115 nm. Moreover, the RSM results confirmed that the in-
digitated electrodes (IDEs) were patterned on the surface plane lattice parameters of the thinnest SMO film (20 nm
using a lift-off technique to minimize damage to the thick) were coherently strained on the LSAT substrate
surface. The finger length (L = 1000 μm), finger width (Fig. 1b), and the tensile strain was relaxed with increasing
(w = 6 μm), gap spacing (g = 6 μm), and electrode period film thickness (Fig. S2 and Table S1). These XRD results
(P = 12 μm) of the IDE pattern were confirmed according demonstrate that the 20-nm thick SMO thin film was
to Fig. S1 (Supplementary information). The total number 1.7% tensile-strained by the LSAT substrates; the epitaxial
of finger pairs was N = 30. The current density J–V curve strain was gradually relaxed as the thickness increased
was investigated under ambient conditions using a semi- from 20 nm to 115 nm. The rocking curves for the SMO
conductor parameter analyzer (Keithley, 4200-SCS). The (002) reflection were measured to determine the out-of-
dielectric constant and dielectric loss were measured plane mosaic spread and the crystalline quality. As shown
using an LCR meter (Agilent, 4294A). The P–E loop was in Fig. 1c–e, the full widths at half maximum (FWHM) of
measured using a ferroelectric analyzer (Precision Multi- the (002) reflection rocking curves of the SMO thin films
ferroic, Radiant Technologies Inc.). with thicknesses of 20 nm, 45 nm, 69 nm, 92 nm, and
115 nm were 0.032°, 0.055°, 0.109°, 0.164°, and 0.227°,
Results and discussion respectively. This indicates that the thinnest SMO film
Tensile-strained SrMnO3 thin films has a high out-of-plane crystallinity and that the crystal-
Tensile-strained SrMnO3 (SMO) thin films with thick- linity gradually deteriorates as the thickness increases.
nesses of 20, 45, 69, 92, and 115 nm were grown on an Microcracks were identified on the surface of the as-
LSAT substrate by PLD. LSAT substrates were used to grown SMO films, similar to previous experimental
achieve a nominal in-plane epitaxial strain of +1.7% for results (Figs. S3a–c)9,22. For these films, high leakage
the bulk SMO. As shown in Fig. 1a, X-ray diffraction currents and dielectric losses were also confirmed by
(XRD) θ−2θ patterns revealed that the SMO thin films investigating the leakage current density (J) and dielectric
with a cubic phase were highly (0 0 l)-oriented. The SMO loss (tan δ) versus voltage curves, as shown by the dotted
(002) peak of the thinnest SMO film (20 nm) shifted to a lines in Fig. 2e, f. Consequently, both the high leakage
higher angle based on the black dotted reference line for current19 and surface crack9,22 issues were similarly
the bulk SMO. Additionally, this peak gradually returned observed in our as-grown SMO films.

Fig. 1 Tensile-strained SrMnO3 thin films. a XRD θ–2θ patterns of the SMO thin films on the LSAT (001) substrates with thicknesses of 20–115 nm.
Cubic SMO (002) in bulk, the reference, is denoted by the black dotted line (JCPDS no.: 23-1413). b RSM data for the SMO thin film with a thickness of
20 nm. c, d Rocking curves and FWHMs for the 20 nm and 115 nm films, respectively. e FWHMs of SMO films with various thicknesses (20, 45, 69, 92,
and 115 nm).
An et al. NPG Asia Materials (2021) 13:69 Page 4 of 10

Fig. 2 Selective oxygen annealing method and improved insulating properties. a–d Schematics of the selective oxygen annealing process
including the interdigitated electrode (IDE) manufacturing process for the SMO thin films. a Tube furnace annealing of the SRO-capped SMO film on
LSAT at a high temperature (600 °C) and an oxygen-rich atmosphere (O2 flow: 1.5 L/min in atmospheric pressure). b Typical photolithography process
with an interdigitated photoresist (PR) pattern on the sample. c Selective etching of SRO on the SMO film using a NaIO4 solution. d Patterned SRO IDE
on the SMO films after removing the PR pattern using an acetone solution. e Current density versus voltage curves and f dielectric loss (tan δ) versus
voltage curves of the as-grown SMO (applied with processes b–d) and SOA-treated SMO films (applied with processes a–d) with thicknesses of 20
and 115 nm.

Selective oxygen annealing solution27,28. Last, SRO can also be used as a top elec-
To overcome the high leakage current and air degra- trode, thus avoiding additional processing for electrical
dation issues, we devised a SOA method. This method measurements.
entails fabricating epitaxial SrRuO3 (SRO) capping layers After applying the SOA method, we ascertained the
(20 nm) on the as-grown SMO thin films and performing purity of the SMO thin film; the complete removal of SRO
ex situ annealing at a temperature of 600 °C under an is shown in Fig. S3 (surface morphological aspect), Fig. S4
oxygen-rich atmosphere, followed by removal of the SRO (chemical aspect), and Fig. S5 (structural aspect), and
capping layer, as shown in Fig. 2a, c. The overall process, significant suppression of the surface crack issues is shown
including the interdigitated electrode (IDE) manufactur- in Fig. S3. Notably, a significant reduction in the leakage
ing process, is illustrated in detail in Fig. 2a−d. The use of current and dielectric loss of the SOA-treated SMO films
a capping layer was recently proposed by several research was observed, as shown by the solid lines in Fig. 2e and f.
groups to prevent air degradation of strained SMO thin In these figures, to show the dramatic effect of SOA on the
films9,22. Consequently, they confirmed the ferroelectric electrical properties, we plotted the J–V and tan δ–V
polarization hysteresis loop for the DyScO3 (DSO)-capped switching curves of both the as-grown SMO films (thick-
SMO thin film at a low temperature (10 K). However, the ness: 20 nm, 115 nm) and SOA-treated SMO films
ferroelectric hysteresis loops of the DSO-capped SMO (thickness: 20 nm, 115 nm). Figure 2e shows that the
thin film may also include the interfacial characteristics of semiconductor loops of the as-grown SMO films were
the DSO layer (such as the strain effect) as well as the equally transformed to insulating butterfly loops after
characteristics of SMO. For a more accurate investigation, SOA, which exhibit typical metal-insulator-metal capaci-
we used the SRO capping layer, which can be removed tors29,30. The strain-relaxed film (115 nm) has a larger
after oxygen annealing, and then the room-temperature insulating butterfly loop than the fully strained film
ferroelectricity of the single SMO thin films was investi- (20 nm), which indicates the amount of charge trapping by
gated. The advantages of the SRO capping layer can be gate bias sweeping31. Such a difference between the two
summarized as follows: First, coherent growth is expected films may be attributed to the thickness dependence or the
on SMO films because SRO has the same cubic perovskite emergence of ferroelectric phases in strain-relaxed films
structure as SMO, and its larger lattice parameter (acubic (20 nm). Note that after performing SOA, the leakage
= 0.3926 nm) than SMO (acubic = 0.3805 nm) can stabilize current density of the fully strained SMO film (20 nm) was
the films over a large range of strain states22. Second, only reduced by eight orders of magnitude from 180 A/cm2 to
SRO can be selectively etched by the NaIO4 etching 3.8×10−6 A/cm2 at 5 V. Similarly, the strain-relaxed SMO
An et al. NPG Asia Materials (2021) 13:69 Page 5 of 10

film (115 nm) was also reduced by nine orders of magni- films reveal that only the SMO (002) peaks equally shifted
tude from 29 A/cm2 to 6.9 × 10−8 A/cm2 at 5 V. Figure 2f to a higher angle without a remarkable change in the SRO
shows that a tan δ of less than 0.1 was found for the SOA- (002) peaks after oxygen annealing. As shown in Figs.
treated SMO films, which was also significantly reduced S6a−c, this peak shift of SMO (002) occurred for all
compared to the high tan δ (102–103) of the as-grown samples. Additional RSM data of both the as-grown SMO
films. These results revealed that the SOA method can not and SOA-treated SMO films also demonstrated that a
only significantly suppress the high leakage current of the fully strained in-plane lattice parameter of SMO on the
strained SMO film but also protect the surface from LSAT substrate was maintained after oxygen annealing
cracks. Moreover, the J–V resistive switching and low tan (Fig. S6d, e). Therefore, the peak shift results of SMO
δ measured for the SOA-treated SMO films indicate that indicate that a large amount of oxygen was selectively
the samples are suitable for investigating intrinsic ferro- incorporated into SMO rather than into SRO during SOA
electric and dielectric properties and that they can be so that only the c-lattice parameter of SMO was changed.
applied in a typical capacitor without leakage issues. Based on the XRD data, the c-lattice parameters of the as-
grown SMO and SOA-treated SMO films were calculated
Improved crystal structure using Bragg’s law, as shown in Fig. 3c. The results show
To thoroughly verify the SOA effect in reducing the that the c-lattice parameters of SMO were consistently
high leakage current, structural analyses of the SMO thin contracted after SOA. In particular, it was confirmed that
films before and after oxygen annealing were carried out. the c-lattice parameter of the SOA-treated fully strained
As shown in Fig. 3a, b, the XRD θ−2θ patterns for the SMO thin film (20 nm) was reduced to 3.769 Å compared
SRO (20 nm)-capped SMO (thickness: 20 nm, 115 nm) to the 3.775 Å of the as-grown SMO thin film (20 nm).

Fig. 3 Comparative structural analyses before and after SOA. XRD θ–2θ patterns of SRO (20 nm) capped SMO thin films before and after oxygen
annealing with a thickness of a 20 nm and b 115 nm. Comparison of the c c-lattice parameters, which were calculated from the XRD θ–2θ data using
Bragg’s law (2dsinθ = nλ) and d FWHM intensities of the SMO (002) peaks for both the as-grown and SOA-treated SMO films depending on their
thickness (20, 45, 69, 92, and 115 nm).
An et al. NPG Asia Materials (2021) 13:69 Page 6 of 10

This value is closer to the theoretically expected c-lattice the <110> polar domain orientation of SMO using a
parameter (3.624 Å) of the fully constrained SMO film on focused ion beam, as depicted schematically in Fig. 4b.
the LSAT substrate9, allowing us to predict that oxygen Figure 4a and c show the high-resolution TEM (HRTEM)
vacancies are additionally filled by SOA treatment. This images of the as-grown SMO film (20 nm) and SRO
c-lattice contraction was also observed in a previous paper (20 nm)-capped SMO (20 nm) film after oxygen anneal-
of oxygen-annealed La0.84Sr0.16MnO3-δ (LSMO)32, which ing, respectively. The HRTEM image with the corre-
proved that the lattice contraction was due to the sponding fast Fourier transform (FFT) patterns in Fig. 4a
increased ratio of Mn4+ ions with a smaller ionic radius shows that the SMO film is a single crystal with planar
than Mn3+ ions by oxygen incorporation. Moreover, all defects (i.e., stacking faults)33, as indicated by the streaks
FWHMs of the SMO (002) peaks were also reduced after along the (001) direction of the SMO FFT pattern (upper
SOA, indicating that the crystallinity of the SOA-treated inset of Fig. 4a).
SMO films was improved (Fig. 3d). In contrast, the HRTEM image of the SRO (20 nm)-
Indeed, it is known that the c-axis lattice parameter of capped SMO (20 nm) film on the LSAT substrate after
strained SMO thin films is elongated due to air degra- oxygen annealing (Fig. 4c) shows that the SRO is a single
dation21,22. This elongation results from structural defects crystal and grows epitaxially on the SMO without obser-
such as surface and internal cracks for epitaxial-strain vable defects, as the selective area diffraction (SAD) pat-
relief of the strained SMO thin film. Since these structural tern of the three layers in Fig. 4d presents discrete
defects were also observed in our as-grown SMO thin diffraction spots with no streaks, in contrast to the pattern
films (Figs. S3a–c), their c-lattice parameters may be more from the SMO layer in Fig. 4a. Specifically, it was found
elongated than the genuine lattice parameter. However, that the (001) lattice spacings of the three layers are
compared to the c-lattice parameters of the as-grown 3.805 Å (SMO), 3.868 Å (LSAT) and 3.926 Å (SRO), while
films, those of the SOA-treated SMO films were con- those of the (110) lattice of the three layers are the same.
versely contracted, and furthermore, the film crystal- Furthermore, the HRTEM image (Fig. 4e) taken from the
linities were improved for all samples. Therefore, the boxed area in Fig. 4c shows off-centering of the Mn
structural defects of SMO were considerably reduced by cations (Δx: 96 pm) along the [110] direction from the
suppressing air degradation and incorporating additional intrinsic centrosymmetric positions, which is consistent
oxygen during SOA. with the polar distortions previously identified in the
To confirm the effects of the capping layer and oxygen strained SMO thin films on LSAT19,20. We presume that
annealing, we also performed oxygen annealing for the as- such crystallinity with no large-scale defects in the SMO
grown SMO thin films (thickness: 20 nm, 115 nm) with- layer is attributed to the SOA process. Thus, the SMO
out the SRO capping layer. In this case, there were no thin film exhibited insulating properties with no defect-
changes in the c-lattice parameter and conductivity of driven leakage current.
SMO compared to those of the as-grown SMO (Fig. S7).
Therefore, in situ SRO capping should follow SMO Strain-induced ferroelectricity
growth and precede oxygen annealing to achieve the SOA To confirm strain-induced ferroelectricity, we measured
effect. Moreover, the electrical properties of the as-grown the polarization hysteresis loops (P–E loops) and dielec-
SMO, which are SRO-capped SMO thin films without tric constant (εr)–V curves for the SOA-treated SMO
oxygen annealing, exhibited high leakage currents, as films with various thicknesses. Based on the verified
shown in Fig. 2e, f. Thus, these results demonstrate that insulating properties (Fig. 2e, f), the SOA-treated SMO
oxygen annealing plays a prominent role in suppressing films with thicknesses of 20, 45, 69, 92, and 115 nm were
the leakage current and that the capping layer plays a role found to exhibit polarization hysteresis loops at room
in preventing air degradation of the films. Through a temperature, as shown in Fig. 5a. The P–E loop shapes of
comparative analysis of each SOA process, we identified the 69, 92, 115 nm thick films are close to the linear
that each process should be performed sequentially; thus, capacitor, and the 20 nm and 45 nm thick films are similar
this is the optimized method to effectively suppress both to the ferroelectric capacitor34. As the SMO thickness
aforementioned issues of SMO. We call this method SOA, decreased, it was confirmed that the change in P–E loop
which includes both selective oxygen incorporation for shapes from the linear capacitor to the ferroelectric
SMO and selective etching of the SRO capping layer. capacitor, as well as both the remnant polarization (Pr)
and coercive field (Ec), decreased. (The saturation polar-
Atomic-scale observation ization (Ps) of the 45 nm thick film, which is slightly larger
For atomic-scale structural analysis, we performed a than that of the 20 nm thick film, might be due to the
cross-sectional transmission electron microscopy (TEM) slightly higher dielectric loss (but less than 0.1) of the
analysis of the as-grown SMO and SOA-treated SMO 45 nm thick film than those of the other samples in
films. The cross-sectional samples were prepared along Fig. 5c.) In particular, the fully strained SMO film (20 nm)
An et al. NPG Asia Materials (2021) 13:69 Page 7 of 10

Fig. 4 Atomic-scale observation before and after SOA. a HRTEM image of the as-grown SMO film with a thickness of 20 nm on the LSAT substrate
with the FFT of each layer. b Schematic of the ideal SMO structure along the [−110] direction. c HRTEM image of the SRO (20 nm) capped SMO thin
film after oxygen annealing with a thickness of 20 nm on LSAT with the FFT of each layer. d Diffraction pattern of the area in panel c. e Magnified
image of the boxed area in panel c showing the polar SMO structure where the Sr and Mn cations are indicated by green and purple, respectively.

exhibited a ferroelectric hysteresis loop with a saturation constant can be increased by 20 times or more when a
polarization (Ps) of 1 μC/cm2 and a remnant polarization tensile strain of 1.7% is applied. Although the dielectric
(Pr) of 0.8 μC/cm2. Bulk SMO is known as a paraelectric constant of the 1.7% strained SMO thin film is not as high
material, and the phase transition to ferroelectric material as those observed in BaTiO341, PbTiO342, and several
that appears as an in-plane tensile strain above 1% has ferroelectric perovskite oxides found in capacitors, it is
been verified through many theoretical11,15 and experi- comparable to that of typical perovskite multiferroics such
mental results19,20. In this regard, we have sufficiently as BiFeO3 (BFO)43. Additionally, since SMO can optionally
confirmed Mn off-centering of the 1.7% tensile-strained become a low-κ or a high-κ material, it can be applied to a
SMO thin film (20 nm) using XRD and HRTEM analysis. wide range of capacitors or memory devices.
Therefore, we believe that such a change in P–E loop In our cases, a significant difference in εr arising from
shapes was due to the strain-induced ferroelectricity of the leakage issue is not expected because tan δ of all the
SMO. thin films is less than 0.1 (right-hand side of Fig. 5c). The
The measured εr for each SMO thin film is shown in thickness dependence of εr can be neglected (εr increases
Fig. 5c. The εr values of the SMO were extracted from the due to the nonferroelectric dead layer between the film
capacitance data using a Gevorgian approximation model, and the electrode when the thickness increases44–46) since
which is suitable for very thin films of 20–115 nm34–38. the current path length of 6 μm is the same for all films, as
The low dielectric constant of LSAT (εr: 22.5)39 reduces shown in Fig. S1 (Supplementary information). Moreover,
field penetration in the substrate and facilitates modeling to rule out the effects due to IDE geometry and film
of the εr of the SMO films when IDEs are used12,40. The εr thickness dependence, we calculated the dielectric con-
results revealed that the strain-relaxed SMO film (115 nm) stant using the Gevorgian model. Therefore, we believe
has a low εr (6.7), whereas the fully strained SMO film that this significant increase in the dielectric constant with
(20 nm) has a relatively high εr (138.1). The low εr of the decreasing film thickness was due to experimentally
strain-relaxed SMO film is consistent with the paraelec- identified strain-induced polarization. This indicates that
tricity of bulk SMO, while it seems that the dielectric the considerable changes in both the polarization and
An et al. NPG Asia Materials (2021) 13:69 Page 8 of 10

Fig. 5 Strain-induced ferroelectricity at room temperature. a In-plane P–E loops for the SOA-treated SMO films with thicknesses of 20, 45, 69, 92,
and 115 nm at 2 kHz. b Remnant polarization values according to the film thickness extracted from the P–E loops of panel a. c In-plane dielectric
constants (εr = 138.1, 45.2, 14.5, 8.7, and 6.7) and dielectric losses (tan δ = 0.019, 0.079, 0.039, 0.028, and 0.015) of the SOA-treated SMO films with
thicknesses of 20, 45, 69, 92, and 115 nm, respectively at 100 kHz. d Out-of-plane lattice parameters of the SOA-treated SMO films calculated based on
the XRD data.

dielectric constant were dominantly affected by strain- dramatic increase in the dielectric constant when the
induced polar distortion. Consequently, the intrinsic fer- thickness changed from 45 and 69 nm may be attributed
roelectric hysteresis loop (Ps = 1 μC/cm2) and dielectric to this phase transition. Finally, we anticipate that a
constant (εr = 138. 1) of the 1.7% tensile-strained SMO stronger ferroelectric polarization of the SMO thin films
thin film was experimentally verified for the first time. accompanying dielectric switching, which was limited in
Increasing the thickness of the films to control the our case due to the large current path length of the in-
epitaxial strain enabled observation of the phase transition plane electrodes (Fig. S8 for details), can be realized at
from paraelectric to ferroelectric SMO. As shown in room temperature in the near future.
Fig. 5d, the 20 nm thick SMO film had the most con-
tracted c-lattice parameter, which gradually elongated due Conclusion
to strain relaxation as the thickness increased. Conversely, To conclude, we have successfully investigated the
the remnant polarization (0.81, 0.63, 0.12, 0.09, 0.07) and intrinsic ferroelectric and dielectric properties of strained
dielectric constant (138.1, 45.2, 14.5, 8.7, and 6.7) expo- SMO thin films using our SOA method. The experimental
nentially decreased as the thickness increased, as shown in results confirmed that SOA was able to effectively sup-
Figs. 5b, c, respectively. In particular, the gradual increase press the high leakage current and air degradation of
in the polarization values and dielectric constants when SMO thin films. Of particular importance is that SOAs
the thickness changed from 115 nm to 69 nm evolved to a not only allow direct investigation of the intrinsic multi-
rapid increase when the thickness changed from 69 nm to ferroicity of strained SMO thin films but also allow device
20 nm. The overall results shown in Fig. 5b–d are con- applications without leakage issues. Based on their insu-
sistent with the theoretically calculated diagram, in which lating properties, we can determine the ferroelectric
the polarization rapidly increases at more than 1% of the polarization loop (Ps = 1 μC/cm2) and the dielectric
epitaxial in-plane strain because of the phase transition constant (εr = 138.1) of 1.7% tensile-strained SMO thin
from paraelectric to ferroelectric SMO, although the films. Moreover, the polarization and dielectric constant
c-lattice parameter gradually decreases15. Therefore, the of the SMO films can be significantly increased from 6.7
An et al. NPG Asia Materials (2021) 13:69 Page 9 of 10

to 138.1 via strain engineering. These findings are not 7. Khomskii, D. Classifying multiferroics: mechanisms and effects. Physics 2, 20
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Publisher’s note 27. Weber, D., Vőfély, R., Chen, Y., Mourzina, Y. & Poppe, U. Variable resistor made
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