3-Enhanced Magnetization in CoFe2O4 Through Hydrogen Doping

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Research Article
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Enhanced Magnetization in CoFe2O4 Through Hydrogen

Doping
Zhuolu Li, Yingjie Lyu, Zhao Ran, Yujia Wang, Yang Zhang, Nianpeng Lu, Meng Wang,
Michel Sassi, Thai Duy Ha, Alpha T. N’Diaye, Padraic Shafer, Carolyn Pearce,
Kevin Rosso, Elke Arenholz, Jenh-Yih Juang, Qing He, Ying-Hao Chu, Weidong Luo,*
and Pu Yu*
interest due to its high transition tempera-

Magnetic spinel oxides have attracted extensive research interest due to their ture (TC–790 K) as well as large saturated
rich physics and wide range of applications. However, these materials invari- magnetization,[1–3] enabling a wide variety
ably suffer suppressed magnetization, due to structural imperfections (e.g., of applications in magnetic reading media,
disorder, anti-site defects, etc.). Herein, a dramatic enhanced magnetiza- microwave devices, etc.[4–8] Moreover,
CFO processes a large spin-orbit coupling
tion is obtained with an increasement of 5 µB/u.c in CoFe2O4 (CFO) through
induced cubic magneto-crystalline anisot-
ionic liquid gating induced hydrogen doping. The intercalated hydrogen ions ropy owing to its unique trigonal crystal-
lead to both distinct lattice expansion of ≈0.7% and notable Fe valence state line field of the Co2+ cations, prompting a
reduction through electron doping, in which ≈17% Fe3+ is reduced into Fe2+. series of interesting studies on the strain
These facts collectively trigger a site-specific spin-flip on tetrahedrally coor- engineered magnetic state.[9–12] In a typ-
ical spinel crystalline structure, one third
dinated Co2+ sites that enhances the net ferrimagnetic moment nearly to its
cation sites are tetrahedrally coordinated
theoretical maximum for perfect CFO. (Td symmetry), and the other two thirds are
octahedrally coordinated (Oh symmetry).
In CFO, the majority of the Co2+ cations
1. Introduction occupy Oh sites, and the minority occupy Td sites, resulting in a
predominately inverse spinel structure (as shown in Figure 1a).
Spinel complex oxides represent an important class of material The theoretical saturated magnetization for CFO with perfectly
systems with fascinating magnetic and electronic states. Among inverse spinel structure is ≈24 µB/u.c.,[2,3,30] where a unit cell
all spinel structures, CoFe2O4 (CFO) has garnered particular contains 8 cobalt cations and 16 iron cations. However, when
Z. Li, Y. Lyu, Y. Wang, Y. Zhang, M. Wang, P. Yu T. D. Ha, J.-Y. Juang, Y.-H. Chu
State Key Laboratory of Low Dimensional Quantum Physics and Department of Electrophysics
Department of Physics National Yang Ming Chiao Tung University
Tsinghua University Hsinchu 30010, Taiwan
Beijing 100084, China A. T. N’Diaye, P. Shafer, E. Arenholz
E-mail: yupu@mail.tsinghua.edu.cn Advanced Light Source
Z. Ran, W. Luo Lawrence Berkeley National Laboratory
Key Laboratory of Artificial Structures and Quantum Control (Ministry of Berkeley, California 94720, USA
Education) Q. He
School of Physics and Astronomy Department of Physics
Shanghai Jiao Tong University Durham University
Shanghai 200240, China Durham DH1 3LE, UK
E-mail: wdluo@sjtu.edu.cn Y.-H. Chu
N. Lu Department of Materials Science & Engineering
Beijing National Laboratory for Condensed Matter Physics National Tsing Hua University
Institute of Physics Hsinchu 30013, Taiwan
Chinese Academy of Sciences W. Luo
Beijing 100190, P. R. China Institute of Natural Sciences
M. Sassi, C. Pearce, K. Rosso Shanghai Jiao Tong University
Physical and Computational Sciences Directorate Shanghai 200240, China
Pacific Northwest National Laboratory P. Yu
Washington 99354, USA Collaborative Innovation Center of Quantum Matter
The ORCID identification number(s) for the author(s) of this article Beijing 100084, China
can be found under https://doi.org/10.1002/adfm.202212298.
DOI: 10.1002/adfm.202212298
Adv. Funct. Mater. 2023, 2212298 2212298 (1 of 8) © 2023 Wiley-VCH GmbH

16163028, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adfm.202212298 by Shanghai Jiao Tong University, Wiley Online Library on [12/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Figure 1. Ionic liquid gating induced proton intercalation and structural evolution in spinel CFO. a) Crystalline structure of spinel crystal. Gray and
blue represent metal cations at Td and Oh sites respectively, while the oxygen ions are labeled in red. The magnetic moments of cations at Td and Oh
sites are coupled antiferromagnetically with each other. b) Schematic illustration of the device geometry for the ionic liquid gating (ILG). The external
gating voltage promotes the electrolysis of residual H2O molecules within the ionic liquid and then further drives the protons to intercalate into the thin
films. c) XRD θ-2θ scans around CFO (004) peak as a function of gating voltage (VG). The red dashed lines outline the peak positions of CFO (004).
d) Depth profiles of H+ (blue and red solid lines) and Ti4+ (black dash line) ions of pristine CFO and gated HCFO samples measured with secondary-
ion mass spectrometry. The Ti4+ signal from the NSTO substrate was used as a marker for the interface position.
CFO is grown in thin film form on substrates (such as MgO and Here, we demonstrate a practical pathway to achieve
SrTiO3), its magnetization is dramatically suppressed from this enhanced magnetization in CFO thin films through hydrogen
bulk value due to the formation of antiphase boundaries (APBs) (H) doping. To achieve highly effective H doping, we employed
and disordered defects resulting from the symmetry and lattice the ionic liquid gating (ILG) method. ILG inserts protons into
mismatch between CFO and the employed substrates.[31,32] Due materials through the application of positive electric voltage,
to its great scientific and technological interests, various strate- which simultaneously result in electron doping to maintain
gies have been developed over the past decades, including ionic charge neutrality.[24–27] Consequently, the hydrogen (combina-
substitutions,[12,13] strain,[14] thermal treatment [15–17] and nano- tion of both proton and electron) doping modulates the local
structure fabrications,[18] to enhanced the magnetization of CFO electric environment of transition metal cations, which can
thin films. Besides thin film samples, CFO nanoparticles and rebalance the super-exchange interactions as well as enhance
nanocomposites have also obtained wide-range research atten- spin-orbit couplings yielding both enhanced magnetization and
tion due to its technical interests. Thermal treatment[19] was change of magnetic anisotropy. The strategy we demonstrate
demonstrated as a promising pathway to manipulate the mag- can readily be extended to other spinel structures, leading to
netization, in which the enhanced magnetization is attributed an effective pathway to engineer and design their magnetic and
to the change of occupation sites for Co ions. Furthermore, electronic states.
owing to the unique morphology of nanomaterials, particle size
and nanocomposites heterostructured with other antiferromag-
netic and ferromagnetic materials have been widely explored to 2. Results and Discussion
manipulate the total magnetization.[20–23] Among these studies,
it remains a great challenge to enhance the magnetization In our study, CFO (001) thin films were fabricated using pulsed
toward or even above its theoretical value, particularly in single laser deposition (see Experimental Section) on Nb doped SrTiO3
crystal thin film form. Therefore, discovering new pathways to (STO) and STO (for comparison) (001) substrates. Due to the
obtain an enhanced saturated magnetization in spinel ferrites sizable in-plane lattice mismatch (≈7%) between bulk CFO and
presents an important research topic in the field of magnetic the STO substrates, the growth leads to semi-coherent thin
complex oxides. films with high-density interfacial dislocations to fully release

the epitaxial strain, verified here by X-ray diffraction (XRD) θ-2θ in stark contrast to the pristine thin film, consistent with a
scans and reciprocal space mappings (Figure S1a,b, Supporting hydrogen intercalation dominated structural transformation.
Information). To provide further structure insight of the CFO Using a H-implanted SiO2 sample with known hydrogen
thin films, we carried out the scanning transmission electron dosage as reference, we quantitively estimated the hydrogen
microscope measurements as shown in Figure S2 (Supporting concentration as ≈0.1 H/Fe (the average dosage in the film
Information). Due to the large lattice mismatch between the bulk region), which is consistent with the relatively small lat-
film and substrate, a buffered atomic layer can be identified at tice expansion compared to previously studied systems.[24,26,27]
the interface to relax the epitaxial strain (Figure S2a, Supporting On this basis, we tentatively assigned the gated sample as
Information). Furthermore, we notice the existence of some HxCoFe2O4 (HCFO). Furthermore, we notice that the HCFO
regions with different contrast on cation sites, which can be shows a thermal transition temperature at ≈200 °C (Figure S4,
attributed to structural imperfections with distinct cation occu- Supporting Information), above that the HCFO changes back
pancies. Nevertheless, the spinel structure of CoFe2O4 can be into CFO through dehydrogenation process.
confirmed as shown in Figure S2b (Supporting Information). With the confirmed ILG-induced crystalline structural
With this obtained high-quality CFO thin films, we carried out transformation, we then investigated how H-doping changes
the ILG using the device geometry illustrated in Figure 1b. During the magnetic properties of the CFO thin films. Figure 2a,b
ILG, the residual water within the ionic liquid (DEME-TFSI) show the temperature dependent magnetic hysteresis loops
is electrolyzed into protons and hydroxyls through application of undoped CFO with the magnetic field applied along both
of an external voltage,[24] and the resulting protons accumulate out-of-plane and in-plane directions, respectively. A reduced
at the sample surface to enhance the corresponding chemical saturation magnetization (19 µB/u.c. at 10 K) was found for our
potential. The conducting Nb doped STO substrate served as pristine thin films, which is ≈25% lower than its theoretical
the working electrode, which leads to an effective electric-field bulk value (between 22 and 24 µB/u.c.) for a perfectly inverse
across the insulating CoFe2O4 to facilitate the proton intercala- spinel structure.[2,3,30] Furthermore, our measurements show a
tion from the film surface into the film bulk.[28,29] very small magnetocrystalline anisotropy evidenced by the great
Figure 1c shows the in situ XRD 2θ-ω scans around the CFO similarity between the in-plane and out-of-plane magnetic hys-
(004) diffraction peak during the ILG at different gate volt- teresis loops.
ages (VG). We observed a clear critical voltage to trigger the However, after ILG, the resulting HCFO film exhibits a dis-
ILG induced phase transformation, where the CFO (004) peak tinct modulation of the macroscopic magnetization, in which
remains unchanged with VG under 2 V and then shifts clearly both the out-of-plane and in-plane saturation magnetization
toward lower 2θ angles with voltage above 2.5 V, reflecting the are greatly enhanced at all measured temperatures (from 10 to
lattice expansion along the out-of-plane direction through ILG. 300 K) (Figure 2c,d). To clearly visualize the change of magneti-
The new structure reaches a saturated state with voltages up to zation, we summarized the temperature dependent saturated
3.5 V, which partially relaxes backward when the gating voltage magnetization (Ms) of both CFO and HCFO in Figure 2e, in
is turned off. Nevertheless, the distinct crystalline transforma- which the magnetization at room temperature increases ≈4 and
tion with the expanded out-of-plane lattice constant (≈0.7%) 5.5 µB/u.c. for out-of-plane and in-plane directions, respectively.
subsequently remains robust even at the zero voltage. To fur- Such a large enhancement in the magnetization to values close
ther evaluate the structural evolution through ILG, ex situ XRD to its theoretical maximum clearly demonstrates that the ILG
measurements through large-scale ω-2θ scans, reciprocal space approach is a promising pathway to engineer the magnetiza-
mapping (RSM) and phi scans were carried out on both pris- tion in CFO.
tine and gated (at 3.5 V for 30 mins) CFO samples (Figure S1, Furthermore, the magnetic anisotropy of CFO thin films is
Supporting Information); these measurements clearly reveal also greatly modulated by the hydrogen doping. For instance,
that the CFO film undergoes purely a lattice expansion along the out-of-plane M-H loops below 200 K are unsaturated even
the (001) axis without the emergence of any secondary phase, under 7 T. The magnetic anisotropy can be succinctly charac-
while in-plane lattice constant and quadruple symmetry of the terized by the saturation magnetic field (Hs) (Figure S5, Sup-
thin film remain unchanged. porting Information) and remanence ratio (Mr/Ms) (Figure 2f).
For comparison, we also carried out the ILG measurement We note that for CFO thin films, the magnetic anistropy is
with CFO thin films grown directly on SrTiO3 substrates, where strongly correlated with the corresponding strain state.[12,33,35]
the CFO itself was employed as the working electrode. However, Hence it is not surprising that for our pristine CFO thin films
the crystalline structure of CFO thin films remains unchanged we observed a very small magnetocrystalline anisotropy with
even with large gating voltage up to 3.5 V (Figure S3, Sup- highly similar in-plane and out-of-plane magnetic hysteresis
porting Information). This result clearly highlights the effective loops, attributed to the relaxed epitaxial strain state in our sam-
tunability of ILG with external electric field applied through the ples (Figure S1b, Supporting Information). After the ILG, how-
sample, which provides a flexible pathway to manipulate the ever, we observed a large uniaxial magnetic anisotropy between
chemical potential for proton intercalation into the sample.[28] out-of-plane and in-plane directions. The magnetization along
To confirm the participation of protons (hydrogen ions) the out-of-plane direction becomes much harder to reach sat-
during the phase transformation, we preformed depth profile uration, and the remanence ratio simultaneously decreases
measurements of H+ ion concentrations in both pristine and significantly. Distinct from the out-of-plane data, the in-plane
gated CFO thin films using secondary ion mass spectroscopy saturation magnetic field and remanence ratio behave oppo-
(SIMS), as shown in Figure 1d. The results show a clearly sitely. All these results clearly indicate a great enhancement of
enhanced hydrogen concentration within the gated sample, magnetic anisotropy.

Figure 2. Evolution of the magnetization in CFO through ILG induced hydrogen doping. Temperature dependent a) out-of-plane and b) in-plane mag-
netic hysteresis loops for pristine CFO thin films. Temperature dependent c) out-of-plane and d) in-plane magnetic hysteresis loops for hydrogenated
HCFO thin films. Comparisons of e) saturation magnetization and f) remanent ratio (Mr/Ms) between CFO and HCFO along both out-of-plane and
in-plane directions at different temperatures. We note that the out-of-plane magnetic hysteresis loops below 200 K are not fully saturated with the
magnetic field of 7 T.
To obtain further insights into the enhanced magnetization XMCD spectra, it is completely suppressed in HCFO, which
upon ILG induced hydrogen doping, we then carried out room- leads to an enhanced magnetic moment from Co cations.
temperature X-ray absorption spectroscopy (XAS) and X-ray In contrast, at the Fe L-edges in the XAS spectra we observed
magnetic circular dichroism (XMCD) measurements on both a pronounced enhancement of spectral intensity at the low
CFO and HCFO thin films. Figure 3a shows the normalized Co energy shoulder of the L3 peak (≈708.15 eV; marked by a black
L-edge XAS (top panel) and the corresponding XMCD spectra triangle) and at the pre-edge region (marked by red arrows) for
(middle panel). The XAS spectra exhibit the two typical broad the HCFO sample (top panel in Figure 3b), clearly indicating
features in the range of 775–785 eV and 790–799 eV associated a reduced valency of Fe cations through electron doping. In
with, respectively, the Co 2p3/2 → 3d (L3) and 2p1/2 → 3d (L2) the corresponding XMCD spectra (middle panel in Figure 3b)
dipole transitions. Comparison between CFO and HCFO films three main site-specific features can be identified: b1 (Fe2+ at Oh
reveals only subtle changes of spectral intensity around the sites), b2 (Fe3+ at Td sites) and b3 (Fe3+ at Oh sites),[12,37,38] with
high-energy shoulder of the L3 peak attributed to hydrogen- the corresponding reference data shown in the bottom panel
doping induced evolution of site-specific contributions;[35,36] in Figure 3b.[39] Through simulating the Fe XMCD spectra for
there is no indication of Co valence change. While in the XMCD both CFO and HCFO with the reference data (Figure S6c,d,
spectra, two main characteristic features are clearly identified at Supporting Information), we observed a suppressed contribu-
Co L3 edge (labeled as a1 and a2), associated with tetrahedrally tion from Fe3+ at both Td sites and Oh sites, and a simultaneous
and octahedrally coordinated Co2+, respectively.[12,36,37] Using increase in Fe2+ at Oh sites for HCFO. We note that the reduced
reference data, site-specific spectra were extracted from the contribution from Td sites naturally leads to an increase of total
XMCD spectra as shown at the bottom panel of Figure 3a,[38] moment from Fe cations due to its intrinsic antiferromagnetic-
which highlight the opposite magnetic moments from Td and alignment between Td and Oh sites in CFO. This increase in the
Oh sites consistent with their antiparallel spin alignment and magnetic moment from the Fe sublattice comes in addition to
net ferrimagnetic order typical of the inverse spinel structure. the increase noted for the Co sublattice.
The clearly decreased peak intensity at a1 peak of HCFO sug- Based on the simulations of both Co and Fe XMCD spectra
gests a suppressed spin contribution from tetrahedrally coordi- of CFO (Figure S6, Supporting Information), we can assign
nated sites as compared to the octahedrally coordinated ones. the pristine CFO sample as having a partially inverse spinel
Indeed, a careful fitting of the Co XMCD spectra (Figure S6a,b, structure with about 20% Co cations occupied at Td sites. Fur-
Supporting Information),[38] reveals that while for the CFO the thermore, the XMCD data for HCFO also reveal that ≈17% Fe3+
tetrahedrally coordinated Co2+ ions contribute ≈20% of the is reduced into divalent state (Fe2+). Assuming one hydrogen

Figure 3. Modulated electronic states and microscopic magnetism within CFO through hydrogen doping. a) Co L3, 2-edge XAS spectra (top panel), the
corresponding XMCD spectra (middle panel), and the site-specific XMCD contributions (bottom panel). Td-site and Oh-site related peaks are labeled as
a1 and a2 at XMCD spectra (middle panel). b) Fe L3, 2-edge XAS spectra (top panel), the corresponding XMCD spectra (middle panel), and the referenced
data of site-specific XMCD contributions (bottom panel). The hydrogen doping leads to the presence of divalent Fe2+ in the HCFO as indicated by the
extra features at the pre-edge region (with the red arrows) and low-energy shoulder at L3 edge (with black triangle) of the XAS spectra. Characteristic
peaks labeled as b1, b2, and b3 at the XMCD spectra, represent the main contribution from Fe2+ cations at Oh sites, Fe3+ cations at Td sites and Fe3+
cations at Oh sites, respectively (middle panel).
atom leads to the doping of one electron inside the sample, we 300 K (the experimental condition used during the XMCD
can estimate the hydrogen concentration as 0.17 H/Fe, which is measurements).
qualitatively consistent with the bulk averaged value obtained To reveal the underlying mechanism for the enhanced mag-
from SIMS data. netization from both Co cations and Fe cations in HCFO, we car-
We further calculated both the spin and orbital momen- ried out density functional theory (DFT) calculations. To simulate
tums of Co and Fe cations through the XMCD sum rule,[40–42] the partially inverse spinel structure as revealed from the XAS
in which the moments can be calculated from the integrals of studies, we constructed a pristine unit cell with the chemical
XAS and XMCD spectra (as shown in Figure S7, Supporting composition of [CoFe7]Td[Co7Fe9]OhO32. We further considered
Information). The calculated magnetic moments (Table 1) in two typical cation occupations around the oxygen ion bonded
CFO and HCFO are ≈5.21 and 7.91 µB/u.c., respectively. It is with a proton (Figure 4). In the first case, all Oh sites are occu-
important to note that the magnetic field (0.5 T) used during pied by Fe ions, while Td sites are occupied by Co ions, forming a
the XMCD is not enough to fully saturate the magnetization, typical spinel structure. The calculations reveal that the addition
and therefore the magnetization obtained here should be com- of hydrogen atoms into the lattice leads to the direct bonding
pared with the remanent magnetization measured along out- between the hydrogen ion with the oxygen ion, associated with
of-plane direction. The calculated moment for HCFO is ≈52% both local lattice deformation and charge doping. Specifically, the
larger than value of CFO, which is qualitatively consistent with valence state and magnetic moment of one Oh Fe ion is greatly
the change (37%) of experimental value obtained at 0.5 T and reduced toward Fe2+, and consequently the antiferromagnetic
coupling between this Oh Fe and Td Co ion is dramatically sup-
pressed, which results in the spin-flip of the Co ion at the Td
Table 1. Spin and orbital magnetic moments of Co and Fe cations at
CFO and HCFO samples calculated through XMCD sum rules. site. Importantly, the flipped spins of Co ions reduce the spin
moments at Td sites but contribute to an enhancement of total
Sample Element Morb [µB/ Mspin [µB/ Sum [µB/ MS (Cal.) MS (Exp.) net moment for ≈4.85 µB/H. Subsequently, we considered the
atom] atom] atom] [µB/u.c.] [µB/u.c.] structure with two Fe ions and one Co ion at Oh sites, and one Fe
CoFe2O4 Co 0.081 0.216 0.297 5.21 5.53 ion at Td site, forming a perfect inverse spinel structure. When
Fe -0.004 0.181 0.177 hydrogen is doped into this structure, although the spin orienta-
tion of Td Fe ions remains unchanged, the valence state and mag-
HxCoFe2O4 Co 0.097 0.356 0.453 7.91 7.60
netic moment of the Td Fe ion is also clearly reduced, which also
Fe -0.003 0.271 0.268
results in the enhancement of total magnetization.

Figure 4. Theoretically calculated electronic and magnetic properties of CFO through hydrogen doping with two typical atomic configurations. a) Simu-
lated crystalline structure with Td site occupied by Co cation. In this configuration, one of the Fe ions at Oh site is reduced. In this case, the spin-flip
results in an enhancement of magnetization by 4.85 µB. b) Simulated crystalline structure with Td site occupied by Fe cation, while Co cation locates at
one of three Oh site. In this configuration, the valence state of Fe at Td site is dramatically reduced, which results in an enhancement of magnetization
by 0.93 µB. BVS, stands for bond valence sum; M, stands for magnetic moment, in unit of µB.
3. Conclusion sample and gate electrode were then put into a quartz-bowl filled with
the ionic liquid (DEME-TFSI). Both in situ and ex situ 2θ-ω scan and
To summarize, we successfully achieved an electric-field reciprocal space mapping measurements were carried out at room
induced hydrogen doping into CFO thin films through ILG. temperature, using a high-resolution X-ray diffractometer (Smartlab,
Rigaku) with monochromatic Cu Kα1 radiation (λ = 1.5406 Å). For in situ
With the hydrogen doping, the magnetization is clearly
VG dependent 2θ-ω scans, the sample was first aligned with the SrTiO3
enhanced as compared with the pristine sample toward the (002) peak and then covered by a thin layer of ionic liquid, and the time
theoretical value for perfect CFO. We further revealed that the interval for each VG dependent scans was set as 10 min.
intercalated hydrogen atoms lead to a clear modulation of local Secondary Ion Mass Spectroscopy Measurements: To probe the
chemical environment for both Fe and Co cations, which results hydrogen concentration in the HCFO samples, SIMS measurements
in the spin-flip of Co cations and reduced magnetic moment of were carried out using a TOF SIMS 5–10 instrument (IONTOF GmbH).
The sputtering area was set as 350 µm × 350 µm and the detecting
Fe cations at Td sites. The net result of these spin and electronic
area was 150 µm × 150 µm in order to avoid the disturbance from
state changes is a profoundly enhanced magnetization. On this the crater edge. Both pristine samples and ILG gated HCFO samples
basis, for a much broader set of complex oxide systems we envi- were measured under the same conditions. The interface position was
sion that hydrogen doping comprises an effective pathway for marked by the profile of Ti element, and the concentration of H was
controlling the magnetic properties through the modulation of estimated by profiling H-implanted SiO2 with known hydrogen dosage.
local electronic environments. Macroscopic Magnetism Measurements: Both in-plane and out-of-
plane temperature-dependent magnetization (M-T) measurements and
magnetic hysteresis loops were carried out with a SQUID magnetometer
(Quantum Design), in which the maximum magnetic field was 7 T.
4. Experimental Section X-Ray Absorption Spectra and X-Ray Magnetic Circular Dichroism
Measurements: XAS and XMCD measurements were carried out in a total
Sample Fabrication: CoFe2O4 thin films were deposited on Nb electron yield (TEY) mode at beamlines 4.0.2 and 6.3.1 of Advanced Light
(0.5 wt.%) doped SrTiO3 (001) and SrTiO3 (001) substrates with a home- Source at room temperature. The incident X-ray was set perpendicular
built pulsed laser deposition system (KrF, λ = 248 nm), at a growth to the film surface, with a magnetic field of 0.5 T applied along the
temperature of 700 °C and oxygen pressure of 1 m Torr. The laser energy beam incident direction. To gain high beam intensity, the polarity of the
density was fixed at 0.6 J cm−2 at the target surface with the repetition circular polarized X-rays was set at 90%. The XAS spectra were deduced
rate at 10 Hz, which results in a growth rate of 1.4 nm min−1. After the from the average of XAS spectra with positive and negative magnetic
deposition, the samples were cooled down to room temperature at a fields, and the XMCD spectra were calculated as the difference between
cooling rate of 10 °C min−1 in 100 m Torr oxygen. the spectra at these two magnetic states. The XAS spectra at Co and Fe
Scanning Transmission Electron Microscopy: STEM samples were L-edges were normalized by the main peak of L3 edge.
prepared using a focused ion beam (FIB) instrument. The samples Density Functional Theoretical Calculations: The density function theory
were thinned down to 50 nm using an accelerating voltage of 30 kV (DFT) simulations were carried out using the Vienna ab initio simulation
with a decreasing current from 240 to 50 pA, followed by a fine polish package (VASP 5.4.4).[42–45] Spinel CoFe2O4 (space group: Fd-3m (#227))
with an accelerating voltage of 5 kV with a current of 20 pA. The STEM- in cubic cell with a = 8.39 Å was used in our calculations. To simulate the
HAADF images were acquired on an FEI Titan Cubed Themis 60–300 experimental condition, in which the lattice only expands along the OOP
(operated at 300 kV), capable of recording high-resolution STEM images through the ILG, the lattice constants of a and b axis were fixed during
spatial resolution of ≈0.059 nm. The microscope was equipped with a the simulation, while the lattice constant in c direction was relaxed
high brightness electron gun (X-FEG with monochromator), a spherical to obtain converged crystalline structure and atomic positions. The
aberration corrector, and a post-column imaging energy filter (Gatan projected augmented wave (PAW) potentials were used and the wave
Quantum 965 Spectrometer). The collection angle of the HAADF and functions were expanded in the plane-wave basis with a kinetic energy
ABF detector was 48–200 mrad. cutoff of 500 eV.[46,47] The generalized gradient approximation (GGA) was
Ionic Liquid Gating Device and X-Ray Diffraction Measurements: Before used to describe the exchange-correlation interaction of electrons.[48]
the ionic liquid gating (ILG) study, the bottom electrode was formed GGA+U with a spherically averaged scheme was employed to deal
by painting the silver conductive adhesive at the sample edge, which with the transition metal Iron (Fe) and Cobalt (Co) atoms, with U and
forms a direct electrical connection with the conducting substrate. A J values set as 3.0 and 0.0 eV, respectively.[49] Monkhorst-Pack k-point
conductive platinum slice was employed as the gate electrode. Both with 6 × 6 × 6 mesh was used to sample the Brillouin zone during the

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Enhanced Magnetization in CoFe2O4 Through Hydrogen

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