Article

Cite This: Cryst. Growth Des. 2018, 18, 4388−4394 pubs.acs.org/crystal

Exchange Bias Effect along Vertical Interfaces in La0.7Sr0.3MnO3:NiO

Vertically Aligned Nanocomposite Thin Films Integrated on Silicon
Substrates
Jijie Huang,† Adam Gellatly,† Alexander Kauffmann,† Xing Sun,† and Haiyan Wang*,†,‡
†
School of Materials Engineering and ‡School of Electrical and Computer Engineering, Purdue University, West Lafayette, Indiana
47907, United States
*
S Supporting Information

ABSTRACT: Silicon (Si) integration is a critical step toward

Downloaded by MARTIN LUTHER UNIV HALLE WITT at 08:03:32:464 on June 19, 2019

future applications of multifunctional oxides as nanoscale

electronics and spintronic devices, because of the low cost and
scalability of silicon substrates. As a demonstration, self-
assembled (La0.7Sr0.3MnO3)x: NiO1−x (LSMO:NiO) vertically
aligned nanocomposite (VAN) thin films with exchange bias
from https://pubs.acs.org/doi/10.1021/acs.cgd.8b00366.

(EB) properties have been successfully deposited on buffered

Si substrates. To enable the epitaxial growth of LSMO:NiO
VAN, SrRuO3/TiN was first grown as the buffer layers on Si
substrates. The composition of the two-phases has been varied
with x = 0.25, 0.5, 0.75, and 1 to explore the electrical transport and magnetic properties of the VAN system on Si. The
irreversible temperature Tirr was found to increase with increasing NiO composition, with the highest for (LSMO)0.25(NiO)0.75
of ∼275 K, when the field was applied in the out-of-plane direction. In addition, the EB effect has been observed for all the
nanocomposite films, with the highest HEB value of 300 Oe for (LSMO)0.25(NiO)0.75. The integration of the VAN system on Si
with pronounced EB properties presents a promising approach toward future practical devices using oxide VANs on Si.

■ INTRODUCTION
Exchange bias (EB) is the phenomenon that the magnetization
curve of a ferromagnetic thin film shifts from the origin by the
spin interactions between ferromagnetic (FM) and antiferro-
magnetic (AFM) layers.1−3 EB has been widely used in various
applications, such as magnetic memory, magnetic field sensors,
and recording heads for hard disk drives.4−6 To date, most of
the exchange bias effect has been demonstrated as an in-plane
FM-AFM pinning effect in a bilayer or multilayer fashion.7−11
For example, an apparent EB effect has been detected in
various FM-AFM material systems fabricated by different
techniques, such as magnetron sputtered Co/CuMn,8 pulsed
laser deposition (PLD) deposited La0.7Sr0.3MnO3/BiFeO3,7,9
as well as the molecular beam epitaxy (MBE) deposited Fe/
FeO.10 However, such an in-plane exchange bias effect has
strong thickness dependence, i.e., as predicted by the
traditional theory of HEB ∝ 1/tFM (tFM is the thickness of the
FM layer).12 For example, the HEB value of the IrMn/Co
bilayer was found to follow a smooth 1/tCo curve where HEB
reduces with increasing Co layer thickness and to near zero
beyond a particular thickness.13
Taking advantage of the unique vertical interface structure of
vertically aligned nanocomposites (VAN),14−16 the concept of
EB along the vertical interface has been introduced with its
potential to overcome such thickness limitations by coupling
an FM oxide and an AFM oxide along their vertical
interfaces.16,17 EB effects along the vertical interface have
been demonstrated in several VAN systems17−20 and are
considered more attractive for the next-generation high-density
nonvolatile memory devices, which require good thermal
stability and high density.21,22 However, most of the VAN
systems were obtained on single crystal oxide substrates (e.g.,
SrTiO3),17−20 which are expensive and limited for large-scale
device integration. Silicon is an ideal substrate for future device
applications and the integration of oxide-based devices with
complementary metal-oxide semiconductor (CMOS) devices.
To enable the integration of oxides on Si-substrates, much
effort has been devoted to overcome the challenges of the
epitaxial growth of oxides on Si. Different buffer layers have
been developed to establish the epitaxial relationship under
such large mismatch between the oxides and the Si substrates
and to minimize the interdiffusion between the oxides and
Si.23−25 Specifically, BiFeO3−CoFe2O4 nanocomposite thin
film has been demonstrated on Si substrate with PLD
deposited Sr(Ti0.65Fe0.35)O3/CeO2/YSZ buffer layers, or
molecular beam epitaxy (MBE) grown STO.23
In this work, FM La0.7Sr0.3MnO3 (LSMO) and AFM NiO
are selected as the novel FM-AFM VAN system for the
demonstration of EB oxides integrated with Si substrates. The
LSMO:NiO system on STO substrate has been demonstrated
to have high epitaxial quality and an obvious exchange bias
effect.17,20 Through the proper design of the buffer layer stack,
Received: March 8, 2018
Revised: May 14, 2018
Published: June 15, 2018

© 2018 American Chemical Society 4388 DOI: 10.1021/acs.cgd.8b00366

Cryst. Growth Des. 2018, 18, 4388−4394
Crystal Growth & Design
it is believed that this system could be a good candidate to
integrate on Si to explore its exchange bias effect. A bilayer
buffer structure SrRuO3 (SRO)/TiN was adopted to establish
the epitaxial growth of oxides on Si. TiN is selected because of
its domain epitaxy growth with Si, i.e., 4 of TiN (002)
matching with 3 of Si (004) enables a direct cube-on-cube
growth despite the very large lattice mismatch (f ≈ 24%),26 as
illustrated in the right panel of Figure 1. SRO is selected to
Figure 1. Schematic illustration of LSMO-NiO nanocomposite
integrated on SRO/TiN buffered Si substrate; the right panel shows
the lattice/domain matching between the buffers and Si substrate, and
the upper panel shows the out-of-plane matching between the LSMO
and NiO phases.
further reduce the lattice parameter from 4.24 to 3.93 Å to
enable the high quality growth of the oxide VAN. The SRO/
TiN buffer stack also provides a conducting bottom electrode
for the electrical measurements. Illustrated in the left panel of
Figure 1 is the overall three-dimensional (3-D) structure of the
FM-AFM VAN with NiO nanopillars embedded in the LSMO
matrix on buffered Si. The exchange coupling occurs at the
LSMO (FM) /NiO (AFM) vertical interface areas and
produces the EB effect along the vertical interface. A
composition dependent study is conducted to explore the
composition of the AFM phase on the overall microstructural,
magnetic, and electrical transport properties of (LSMO)x:
(NiO)1−x VANs on Si.
■
EXPERIMENTAL SECTION
Thin Film Growth. Pure LSMO thin film, as well as LSMO:NiO
with different compositions were deposited by a PLD system with a
KrF excimer laser (Lambda Physik Compex Pro 205, λ = 248 nm, 5
Hz) on SRO/TiN buffered Si substrates. The laser energy density was
3 J/cm2. The deposition temperature was kept at 700 °C, and the
target-substrate distance was 4.5 cm for all the depositions. The base
pressure for all the depositions reached less than 1 × 10−6 Torr in a
vacuum. The multilayer thin films were prepared by alternative laser
ablation of the TiN, SRO, and LSMO:NiO nanocomposite targets.
Microstructure and Physical Property Characterizations.
The microstructure of the films was characterized by X-ray diffraction
(XRD) (Panalytical X’Pert X-ray diffractometer) and transmission
electron microscopy (TEM) (FEI Talos-200X). Resistance in
dependence of temperature (R−T) measurement was conducted by
a physical property measurement system (PPMS: Quantum Design).
Temperature dependence of ZFC and FC magnetization and
magnetic hysteresis curves were done by a SQUID magnetometer
(MPMS: Quantum Design).
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■
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RESULTS AND DISCUSSION
Figure 2 shows the typical θ−2θ X-ray diffraction (XRD) scans
of (LSMO)x:(NiO)1−x nanocomposite thin films with different
Figure 2. θ−2θ XRD scans of LSMO:NiO thin films with different
compositions, as well as a pure LSMO sample as the reference.
LSMO compositions (x = 0.25, 0.5 and 0.75), as well as a pure
LSMO film as reference, all on SRO/TiN buffered Si
substrates. First, for the SRO/TiN buffer layer, SRO (00l)
peaks can be identified, which indicates the highly textured
growth of the SRO layer on Si. However, no obvious TiN peak
was observed, while the TiO2 (004) peak was identified,
possibly due to the partial oxidation of the TiN layer during
deposition of the SRO buffer layer and the following VAN
layer. Both NiO (002) and LSMO (002) peaks were identified
in (LSMO)x:(NiO)1−x nanocomposite thin films, which
indicates the formation of both textured NiO and LSMO
phases. This further demonstrates that the epitaxial growth of
SRO/TiN buffer can provide an effective template for the
following VAN epitaxial growth. Furthermore, the peak
intensity of NiO (002) increases with decreasing x, while the
LSMO (002) peak intensity decreases accordingly.
To explore the microstructure characteristics of the
LSMO:NiO nanocomposites on Si substrate, a detailed
TEM/STEM analysis was carried out. Figure 3a shows a
low-magnification cross-sectional TEM image of a
(LSMO)0.25(NiO)0.75 film. Two buffer layers and the VAN
layer can be clearly identified, and NiO nanopillars are
embedded in the LSMO matrix structure. The corresponding
selected area electron diffraction (SAED) pattern is shown in
the inset of Figure 3a to identify the epitaxial growth and the
orientation relationships between LSMO and NiO in the
nanocomposite and the underlying SRO layer, which are
LSMO (002) ∥ NiO (002) ∥ SRO (002) and LSMO [200] ∥
NiO [200] ∥ SRO [200]. The high-resolution TEM image of
the LSMO/NiO interface area in Figure 3b confirms the
epitaxial matching relationship and the high epitaxial quality of
the nanocomposite film. Scanning transmission electron
microscopy (STEM) image in Figure 3c and its corresponding
EDX mapping image shown in Figure 3d further demonstrate
the well separated NiO and LSMO phases without obvious
interdiffusion. Microstructure of the (LSMO)0.5(NiO)0.5 film is
DOI: 10.1021/acs.cgd.8b00366
Cryst. Growth Des. 2018, 18, 4388−4394
Crystal Growth & Design
Figure 3. TEM micrographs of a typical (LSMO)0.25(NiO)0.75 nanocomposite thin film on Si substrate. (a) Cross-sectional low magnification TEM
image to show the overall film stack and its corresponding selected area diffraction pattern as the inset; (b) high resolution TEM image taken at the
interface area to show the epitaxial quality of both LSMO and NiO phases; (c) STEM image and (d) its corresponding EDS mapping to show the
two-phase VAN structure.
shown in Figure S1, and lower density NiO nanopillars with
smaller size were observed, because of the less amount of NiO
in the sample compared to the case of x = 0.25 above.
To explore the EB effect of the LSMO:NiO nanocomposite
thin films, magnetization hysteresis measurement was carried
out for all the nanocomposite films, and the pure LSMO film
for comparison. The measurements were taken after a field
cooling of 1 T down to 5 K, and both OP and IP
measurements were conducted, as shown in Figure 4, panels
a and c, respectively. Figure 4, panels b and d are the enlarged
plot near zero field regime for L0.75N0.25 and L0.25N0.75, to show
the horizontal shift of the hysteresis loop. Here, the HEB value
can be calculated by HEB = |H+ + H−|/2 (where H+ and H−
represent the positive and negative values of coercivity as the
magnetization goes to zero). Specifically, L0.25N0.75 exhibits
high HEB values of 300 and 175 Oe for OP and IP
measurements, respectively. L0.5N0.5 obtains a HEB (OP)
value of 275 Oe, which is higher than the previous reported
value of 77 Oe for the L0.5N0.5 on STO substrate.17 It is noted
that the measurement of the HEB values was conducted under 5
K for the samples on Si substrates in this work, while the
measurement was done at 10 K for the STO ones.17 The
results suggest that the Si integration could even lead to
enhanced physical properties in certain nanocomposites
compared to those on STO substrates. The HEB values of all
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the samples can be obtained from the M−H curves in Figure
S2, and the results are plotted and compared in Figure 4e.
When the applied field was perpendicular to the film surface, as
illustrated in the inset in Figure 4e, the M−H curves of all the
nanocomposite films exhibit an obvious horizontal shift, with
the highest value of 300 Oe for L0.25N0.75 and no shift for the
pure LSMO film. The general trend is that the HEB value
increases with increasing NiO composition, as more vertical
FM/AFM interface was generated with increasing NiO ratio
and thus leads to a stronger FM-AFM coupling. Furthermore,
with more NiO, an increased out-of-plane tensile strain is
applied on LSMO because of the larger lattice parameter of
NiO (a = 4.17 Å) compared to that of LSMO (a = 3.88 Å).
Such enhanced tensile strain on the LSMO domains could
stabilize the FM ordering in LSMO and results in higher
exchange bias value.27 However, no EB shift was observed
when the measurement was taken after zero-field cooling
(ZFC), as shown in Figure S3. Furthermore, the IP HEB values
of the nanocomposite films are lower than their OP HEB values,
regardless of the different compositions. The reason is that the
spins of NiO align along the [112̅] direction,28 as illustrated in
Figure 5a,b, and therefore the OP spin component is larger
than the IP spin component, which results in larger OP HEB
values. The result demonstrates the anisotropic nature of the
LSMO:NiO films and the EB effect dominated along the
DOI: 10.1021/acs.cgd.8b00366
Cryst. Growth Des. 2018, 18, 4388−4394
Crystal Growth & Design
Figure 4. Magnetic hysteresis curves of the pure LSMO and LSMO:NiO films after 1 T FC to 5 K in (a) OP and (c) IP directions. (b) and (d) are
the enlarged regimes of L0.25N0.75 and L0.75N0.25, to show the bias shift; (e) HEB and (f) HC in dependence of NiO ratio in both OP and IP
directions.
vertical interface. Furthermore, coercivity (HC) values of all the
samples were also compared in Figure 4f, which was calculated
by HC = |H+ − H−|/2. The general trend is that OP HC is
higher than its corresponding IP HC, which further confirms
the anisotropic nature of the nanocomposite thin films with the
preferred out-of-plane anisotropy. Overall, the LSMO:NiO
nanocomposite thin films on Si exhibit obvious EB effect by
the FM-AFM vertical interface coupling and demonstrate
enhanced coercivity, which suggests the VAN on Si is very
promising for potential applications such as read heads in
magnetic storage devices with reduced dimensions.
To further understand the magnetic spin structures, the
magnetization as a function of temperature (M−T) under both
zero-field cooling (ZFC) and 1000 Oe field cooling (FC) was
measured for all the samples, in both OP and IP directions, as
shown in Figure 5, panels c and d, respectively. First, the Curie
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temperature TC for pure LSMO is ∼355 K, for both OP and IP
directions, which is close to previous reports.29,30 The TC value
of LSMO:NiO VANs slightly decreases to ∼315 K, possibly
due to the lower degree of magnetic ordering after introducing
NiO in the film,31 as well as the lattice mismatch strain from
LSMO−NiO interfaces, which causes the distortion of MnO6
octahedra and thus suppresses the TC.32 More interestingly,
when the field was applied OP, two bifurcations between the
FC and ZFC curves (which determines the irreversible
temperature Tirr) were observed in the VAN films, while
only one bifurcation appears in that of the pure LSMO film.
Obviously, the lower one at ∼140 K is attributed to the LSMO
phase, which indicates that the LSMO phase has a lack of long-
range FM ordering and becomes possible spin-glass states, spin
clusters, or superparamagnets under such temperature. The
higher Tirr in the nanocomposite films is believed to be
DOI: 10.1021/acs.cgd.8b00366
Cryst. Growth Des. 2018, 18, 4388−4394
Crystal Growth & Design
Figure 5. Schematic illustration to show the spin states for (a) OP and (b) IP; temperature dependence of ZFC and FC magnetization of pure
LSMO and LSMO:NiO films measured with (c) OP and (d) IP magnetic field of 1000 Oe.
originated from the spin-frustration in the FM-AFM interface
area, evidenced by its value increasing with increasing NiO
composition, e.g., (LSMO)0.25(NiO)0.75 of ∼275 K. With more
NiO included, the motion of the domain wall in LSMO under
a magnetic field was hindered, and thus Tirr increases.33 Such
interface ferromagnetic contributions could be from the
following: (1) the finite-size effect could result in magnetic
NiO due to the ultrathin NiO nanopillars (<10 nm), suggested
by prior reports;34,35 (2) potential interfacial defects could also
contribute to the FM structure at the interface, as reported
previously.36 In comparison, the IP measurements for all the
samples only present one Tirr of ∼145 K, similar to that of the
lower Tirr in OP caused by the LSMO phase, as shown in
Figure 5d. This is because the FM effects contributed by the
LSMO:NiO vertical interfaces is not evident in the IP case, and
thus only one bifurcation is observed.
In addition, electrical transport measurement was also
carried out to explore the potential magnetoresistance (MR)
properties in both OP and IP directions for all the
nanocomposite samples, and pure LSMO for comparison.
Figure S4a,b plots the normalized resistivity in dependence of
temperature (R−T) in the range of 5−380 K for (LSMO)0.5-
(NiO)0.5 VAN and pure LSMO thin films, respectively. The
SRO buffer was used as the bottom electrode, and a magnetic
field of 1000 Oe was applied perpendicular to the film surface.
For the VAN film, a relatively broad metal-to-insulator (MI)
transition was observed at ∼250 K in the IP direction, while no
transition was found in the OP direction. The IP MI transition
was considered to be originated from the strong suppression of
double exchange interaction between the neighboring LSMO
domains decoupled by NiO. However, for pure LSMO, its
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resistivity decreases continuously with decreasing temperature,
which indicates its metallic-like nature under its Curie
temperature. In addition, temperature independence magneto-
resistance (MR) for all the samples in the IP direction is shown
in Figure S5 (a magnetic field of 1 T was applied perpendicular
to the film surface), and the largest MR value of ∼7.5% was
obtained at ∼320 K for (LSMO)0.5(NiO)0.5 VAN film.
VAN nanostructure design provides a significant amount of
vertical interface area depending on the pillar size and
density.16,37 Because of the versatile combination of oxide−
oxide multifunctional thin film systems and the strong coupling
of the two phases and the heterointerface effect, unique
properties have been obtained beyond exchange bias along
vertical interfaces, such as multiferroic,38,39 magnetoresist-
ance,40−42 enhanced flux pinning for superconductors,43−45
and enhanced ionic conductivity in electrolytes for solid oxide
fuel cells (SOFC).46,47 Integrating many of these multifunc-
tional VAN systems on silicon substrates could lead to
practical applications of these new materials. Thus, the
successful demonstration of Si integration for the VANs with
the EB effect and MR property is not only critical for
spintronic and magnetic storage applications, but also has
broader impacts on other multifunctional VAN systems and
their future applications.
■
CONCLUSION
Epitaxial (LSMO)1−x(NiO)x vertically aligned nanocomposites
have been successfully integrated on SRO/TiN buffered Si
substrates. NiO nanopillars were embedded uniformly in the
LSMO matrix to form a VAN structure with excellent epitaxial
quality, confirmed by TEM/STEM analysis. An obvious
DOI: 10.1021/acs.cgd.8b00366
Cryst. Growth Des. 2018, 18, 4388−4394
Crystal Growth & Design
exchange bias effect along vertical AFM/FM interfaces was
observed for all the nanocomposite films, with the highest HEB
value of 300 Oe for L0.25N0.75. Such exchange bias effects are
attributed to the interface coupling between the LSMO (FM)
and NiO (AFM) phases. The anisotropic nature of the
nanocomposite films has been demonstrated by both electric
transport and magnetic property measurements. The irrever-
sible temperature T irr increases with increasing NiO
composition, with (LSMO)0.25(NiO)0.75 of ∼275 K, when
the field was applied in the OP direction. The VAN thin films
with pronounced EB properties grown on Si substrates present
a promising approach for future VAN based device integration
on Si as spintronics and magnetic data storage applications.
■
ASSOCIATED CONTENT
* Supporting Information
S R. P.; Yarotski, D.; Sheldon, M.; Chen, H.; Jacob, Z.; Zhang, X.;
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.cgd.8b00366.
Figures S1−S5 (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: hwang00@purdue.edu.
ORCID
Haiyan Wang: 0000-0002-7397-1209
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the U.S. National Science
Foundation (DMR-1643911). The TEM/STEM imaging
effort was funded by the U.S. National Science Foundation
(DMR-1565822).
■
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4394 DOI: 10.1021/acs.cgd.8b00366

Cryst. Growth Des. 2018, 18, 4388−4394