Journal of Magnetism and Magnetic Materials 499 (2020) 166174

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Journal of Magnetism and Magnetic Materials

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Research articles

Giant ac magnetoconductivity in rGO-Fe3O4 composites T

a,b b b b
Khush Bakhat Akram , Syed Mohsin ul Hassan , Awais Ahmed , Muhammad Asif Hamayun ,
⁎
Mohsin Rafiqueb,c, Sadia Manzoorb,
a
School of Applied Sciences and Humanities, National University of Technology, Main IJP Road, Sector I-12, Islamabad 42000, Pakistan
b
Magnetism Laboratory, Department of Physics, COMSATS University Islamabad, Islamabad Campus, Park Road, Islamabad 45550, Pakistan
c
State Key Laboratory of Low-Dimensional Quantum Physics, Department of Physics, Tsinghua University, Beijing 100084, China

A B S T R A C T

In this work we report detailed investigations of structural, ac transport and magnetotransport properties of composites of reduced graphene oxide (rGO) and
magnetite nanoparticles measured in the frequency range 10 Hz–2 MHz and in static magnetic fields upto 500 mT. AC conductivity of composite samples was
enhanced by a factor of ~3 over that of the pure rGO even though the conductivity of magnetite is five orders of magnitude lower than that of rGO. We attribute this
to charge transfer effects between the magnetite nanoparticles and the rGO matrix. Evidence of this is also observed in detailed Raman analysis of all samples.
Further, we find a giant magnetoconductivity in the ac transport behavior of the composite samples. The rGO sample showed a negative magnetoconductivity of
~−15% at room temperature, while all composite samples showed positive magnetoconductivity with weak frequency dependence between 10 Hz and 254 kHz. We
report a room temperature ac magnetoconductivity of 57% (at f = 254 kHz) and 40% (at f = 10 Hz) in a magnetic field B = 500 mT for the sample with 40 wt%
magnetite nanoparticles. This is much larger than that obtained in dc magnetotransport, where room temperature magnetoconductivities in similar composites are
typically 10% or less in comparable magnetic fields.

1. Introduction supercapacitors [22], etc. These systems exhibit very interesting, di-
verse properties and rich physics that merits deeper investigation.
The unique properties of graphene, such as ballistic charge trans- Introducing ferromagnetism in graphene has been a long-standing
port, high electrical and thermal conductivity, exceptional optical and very attractive goal for scientists, particularly in view of spintronics
transmission, high mechanical strength and its 2D nature make it a applications. Pristine graphene, consisting entirely of sp2 bonded
promising candidate for futuristic applications in ultrafast electronics, carbon, is essentially diamagnetic, and weak ferromagnetism is only
optoelectronics and spintronics [1–3]. Single layer graphene (SLG) has introduced extrinsically through defects or dopants [23–25]. Ferro-
been used successfully in many devices [4–6], though there are still magnetism in rGO has been reported to be up to an order of magnitude
some unresolved challenges that need to be addressed in order to widen stronger than in graphene [26,27], and is attributed to its high defect
and optimize its applications. These are a relatively high conductivity density. Still, room temperature magnetization of rGO remains below
minimum and metallic nature with no bandgap even at the charge 1 emu/g. In this context, hybrid materials consisting of magnetic and
neutrality point [7,8]. Furthermore, these devices are also sensitive to graphitic nanostructures, present an attractive means of introducing
substrate dependent charge carrier in-homogeneities which severely magnetic functionality in graphene and graphene-like materials. It has
influences their transport behavior [9]. been found that when a transition metal atom is placed on graphene,
An alternative approach to approximating some of the excellent charge transfer occurs from the d-orbitals of the transition metal atoms
properties of graphene is to produce it in the form of reduced graphene to the p-orbitals of grapheme [28], and affects both transport [29,30] as
oxide (rGO) [10,11] or as three-dimensional (or 3D) grapheme [12]. well as magnetotransport [31–33] behavior. The relation between the
These materials offer the possibility of intercalating different metals or interfacial charge transfer and electronic transport in these 2D systems
metal oxides in between the graphene sheets. These not only act as needs to be further investigated for a complete understanding of
spacer agents but can also provide functionality to these multilayered transport and magnetotransport properties of these systems.
graphene-like nanostructures. Such functionalized graphene based na- Among magnetic materials, magnetite (Fe3O4) occupies a unique
nocomposites have many applications in the fields of nanoelectronics position due to its large saturation magnetization (MS = 87 emu/g),
[13–15], environmental remediation [16,17], biomedicine [18,19] and high Curie temperature (TC = 845 K), high degree of spin polarization
energy applications such as solar cells [20], lithium ion batteries [21], [34] and low toxicity and biocompatibility in physiological

⁎
Corresponding author.
E-mail address: [email protected] (S. Manzoor).

https://doi.org/10.1016/j.jmmm.2019.166174
Received 20 August 2019; Received in revised form 18 November 2019; Accepted 18 November 2019
Available online 25 November 2019
0304-8853/ © 2019 Elsevier B.V. All rights reserved.
K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

environments. In this work, Fe3O4-rGO composites have been synthe- All samples were characterized using XRD (Panalytical X’Pert PRO
sized, whereby the content of magnetite in the composites has been diffractometer using Cu-Kα radiation having wavelength
varied from 20 wt% to 80 wt%. Raman spectroscopy of the samples λ = 1.5045 Å) to determine phase purity. The morphology of the
provides clear evidence of charge transfer from the magnetite nano- samples was studied using a field-emission electron microscope
particles to the rGO matrix. We investigate effects of this charge (TESCAN VEGA3). Raman spectroscopy was carried out using a
transfer on the ac conductivity of Fe3O4-rGO composites in the fre- Ramboss spectrometer with Ar laser of excitation wavelength 514 nm.
quency range 10 Hz–2 MHz in presence of static magnetic fields upto The magnetization hysteresis loops of all samples were measured at
500 mT. The Fe3O4-rGO composites displayed exceptionally large room temperature with a Quantum Design SQUID magnetometer. After
magnetoconductivity in ac magnetotransport, much larger than that initial characterizations, all sample powders were pelletized under a
observed in dc magnetotransport. Here we define ac magneto- pressure of 300 bar for 45 min. in a circular die having diameter
conductivity as the change in the real part of the complex conductivity 13 mm. Both faces of the pellets were painted with silver paste to form
(
in the presence of a static magnetic field, i.e. Δσ 'ac =
σ 'ac (B ) − σ 'ac (0)
σ 'ac (0) ).
% the electrodes for ac conductivity measurements. The ac conductivity
was measured using a 7600 Plus precision LCR meter operating in a
Magnetotransport of graphene or rGO based composites has been
widely investigated in scientific literature in terms of the dc magne- frequency range from 10 Hz to 2 MHz with measurement accuracy
toresistance (MR), which is defined as the change in resistance upon ~0.05%. The complex impedance in an ac field is expressed as
application of a dc current in a static magnetic field normalized by the Z (ω) = Z′ (ω) + iZ″ (ω) , where ω = 2πf is the angular frequency in rad/
R (B ) − R (0) s, f is the frequency and Z' and Z" are real and complex parts of the
zero-field resistance, i.e. ΔRdc = dc R (0)dc %. Liao et al. [31] have
dc impedance, also known as the resistance and reactance respectively. In
measured the magnetoresistance of graphene-Fe3O4 junctions and
the following, the real part of the ac conductivity has been obtained as
found it to be just over −4% at in B = 5 T at room temperature.
′ = ′l , where l is the is the thickness of the pellet, i.e. distance
σac
Bhattacharya et al. [32] obtain a large value of ~67% for the magne- |Z |A
between the two electrodes and A is its cross-sectional area. For the ac
toconductance (MC) of rGO-CoFe2O4 composites in B = 1.8 T at room
magnetoconductivity measurements, a static magnetic field was applied
temperature. Similarly Baskey et al. [33] report a 23% magnetoresis-
parallel to the ac field (i.e. across the sample thickness) and measured
tance of rGO-ZnCo2O4 composites in a field of 1.8 T. In all these studies,
using a Lakeshore 475 DSP gaussmeter.
the magnitude of magnetoresistance (or magnetoconductance) at room
temperature is typically ~5% or less at fields ≤500 mT. This renders
3. Results and discussion
applications of these magnetoresistive effects largely impractical. In
this work, we find that the ac conductivity of Fe3O4-rGO composites
Structural and morphological characteristics of all samples were
changes by a maximum value of 51% at room temperature in dc
examined by X-ray diffraction (XRD), Raman spectroscopy and scan-
magnetic fields as low as 500 mT and frequency as low as 10 Hz. The
ning electron microscopy (SEM). XRD patterns of reduced graphene
magnetoconductance shows a very weak frequency dependence,
oxide (rGO), Fe3O4-rGO composites and Fe3O4 nanoparticles are shown
reaching a maximum of 57% when the frequency is increased to
in Fig. 1(a).
254 kHz. Though there is extensive work on dc magnetotransport in a
The lowermost panel shows the XRD pattern of reduced graphene
variety of materials, we have not come across any study of the effect of
oxide (rGO) with its characteristic (0 0 2) peak at 2θ = 26.4°. Its pre-
a magnetic field on ac transport measurements. The giant ac magne-
sence indicates that the graphene oxide (GO) has been successfully
toconductive effects found in this study at low magnetic fields have not
reduced and an ordered crystalline structure with π-π stacking has been
been previously reported and could be very useful for a variety of
developed. The XRD pattern of magnetite revealed a prominent peak
magnetoelectric applications.
around 2θ ~ 35° corresponding to the (3 1 1) planes. Smaller peaks at
2θ ~ 30°, 43°, 57° and 63° corresponding to the (2 2 0), (4 0 0), (4 2 2)
2. Experimental details and (5 1 1) planes respectively have been identified using the reference
card ICPDS: 01-071-4918. Fig. 1(b) shows the average crystallite size
For synthesis of Fe3O4-graphene nanocomposites, first graphene for Fe3O4 nanoparticles obtained using the Scherrer formula, as a
oxide (GO) was synthesized using the modified Hummer’s method [35]. function of magnetite content. It will be shown in the SEM images
High quality expandable graphite powder of mean particle size 25 µm below that Fe3O4 nanoparticles are well-separated and intercalated
(Aldrich, purity 99.99%) was used as precursor. rGO was prepared by between the sheets of rGO in samples with low magnetite content
drying the graphene oxide in an oven and then thermally reducing it at (F20G80 and F40G60). In these samples the magnetic phase is well-
800 °C for 1 hr. under 300 sccm flow of forming gas (95% N2 + 5% H2). dispersed within the rGO matrix, so that the Fe3O4 nuclei can grow to
To prepare the Fe3O4-rGO composites, appropriate amounts of form larger crystallites. In the synthesis technique followed by us, the
FeCl3·6H2O, FeCl2·4H2O and graphene oxide (GO) powders were ferric and ferrous salts are added to the graphene oxide (GO) in solu-
weighed for each composition. Stoichiometric quantities of FeCl3·6H2O tion. The GO nanosheets have randomly distributed functional groups
and FeCl2·4H2O were dissolved in 25 mL de-ionized (DI) water to obtain (e.g. hydroxyl) that act as nucleation sites for the growth of magnetite
their 0.04 and 0.02 M aqueous solutions respectively. The required nanoparticles. It has been shown by Baumgartner et al. [36], that
amount of GO was dispersed in DI water for each composition. In order during the co-precipitation reaction, growth of magnetite nanoparticles
to transform the attached carboxylic acid groups to carboxylate anions, proceeds through the formation of primary particles, which then grow
the dispersion was sonicated for 1 h. Then 0.02 mol of FeCl2·4H2O and into crystallites by agglomeration. At high concentrations of the ferric
0.04 mol of FeCl3·6H2O were dissolved in DI water and added dropwise and ferrous salts in the solution, these nucleation sites are larger in
to the GO solution at room temperature under vigorous stirring. On number and closer together, so that the growing primary particles may
completion of the ion exchange reaction, 32 vol% NH3 solution was form clusters in which the growth of individual crystallites is frustrated.
added drop by drop until a pH of 10 was obtained. All samples were Such large clusters can be seen in the SEM image of sample F80G20
oven-dried and thermally reduced as described above. The composite (Fig. 2d). Lower concentrations of the iron salts result in fewer nu-
samples were labeled F(x)G(100 − x) with the nominal weight per- cleation sites that are well dispersed on the GO layers. This provides
centage of Fe3O4 nanoparticles, x = 20, 40, 60 and 80 wt%. So, for easier kinetic pathways for agglomeration of primary particles as well
example, sample F20G80 contains 20 wt% magnetite nanoparticles and as for crystallite growth by atomic accretion.
80 wt% rGO. Magnetite nanoparticles were prepared in exactly the Fig. 2 shows scanning electron microscopy (SEM) images of the rGO
same manner, except that the precursor salts were dissolved in DI water and some selected composite samples. The pure rGO sample (Fig. 2a)
without GO. shows good exfoliation and layered flake-like structures. The effect of

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

Fig. 1. (a) XRD patterns of rGO (lowermost panel), Fe3O4-rGO composites, and magnetite nanoparticles (topmost panel). The (0 0 2) peak of rGO is indicated with
(*). (b) The average crystallite size < D > of magnetite nanoparticles as a function of magnetite content in the composite samples.

increasing magnetite content can be seen in Fig. 2(b)–(d), where the charge transfer for the sample F40G60. The weak intensity of the 2D
magnetite nanoparticles appear as bright clusters often embedded be- peak in this sample also confirms that electron-phonon scattering is
tween the layers of rGO. In sample F80G20 (Fig. 2d), which contains being suppressed by enhanced electron-electron scattering [38]. We
80 wt% magnetite, agglomerated clusters of Fe3O4 nanoparticles are will show below that this charge transfer plays a crucial role in en-
interspersed in the rGO matrix. Fig. 2(e) shows the edge of a flake of hancing the conductivity and magnetoconductivity of the composite
rGO which is almost electron transparent at position D1. This high samples. The Raman spectrum of magnetite (topmost panel in Fig. 3a)
magnification image also shows several magnetite nanoparticles em- show three of the five theoretically predicted bands. These include the
bedded onto and possibly between the layers of graphene. A1g (668 cm−1) and T2g(2) (481 cm−1) bands arising respectively due to
Raman spectra of all samples were measured at room temperature. the symmetric and asymmetric stretching of oxygen atoms along the Fe-
The Raman spectrum of rGO (Fig. 3a) lowermost panel) shows the O bonds. The Eg band at 352 cm−1 band is due to the symmetric
characteristic D, G and 2D bands of graphene at 1335 cm−1, 1576 cm−1 bending motion of O with respect to Fe ions.
and 2720 cm−1 respectively. Fig. 4 shows the M(H) curves for all samples measured at room
In rGO, as in graphene, the D and G-band phonon frequency, in- temperature using a Quantum Design VersaLab vibrating sample mag-
tensity, and line shape are strongly influenced by surface or edge de- netometer in the field range up to 2 T. The M(H) loop of rGO (inset
fects and by doping. The D-band is absent in pristine graphene, and its bottom right) shows strong (for rGO) ferromagnetic response as has
occurrence in defective graphene samples or rGO indicates sp3 hy- been reported earlier [26,27], and a tendency towards diamagnetism at
bridization in an otherwise sp2 bonded structure. The ratio of the peak high fields. sp2 bonded carbon networks are intrinsically diamagnetic
intensities ID/IG of the G- and D-bands is inversely proportional to the and the ferromagnetism observed in rGO or graphene is known to arise
average distance between defects [37] of graphene monolayers. due to defects, which may be chemical or topological in nature. This is
Fig. 3(b) (left axis) shows that the ID/IG ratio increases with increasing corroborated by the high ID/IG ratio in our rGO sample.
content of magnetite nanoparticles, reaching a maximum at 40 wt% We note that the saturation magnetization MS does not decrease
magnetite nanoparticle loading. This indicates that for low magnetite monotonically as the magnetite content in the composite is reduced.
content, the Fe3O4 nanoparticles are well dispersed between the sheets The inset at the top left in Fig. 4 shows MS as a function of magnetite
of rGO leading to an increase in the sp3 defects in the rGO matrix. At content in the sample. Although a general decrease in MS is observed,
higher magnetite content (> 40 wt%), clustering of the Fe3O4 (as seen the sample F40G60 clearly lies out of this trend. This is possibly due to
also in the SEM images) results in the rGO and Fe3O4 growing as two the large crystallite size of Fe3O4 in this sample, as shown in Fig. 1(b).
separate phases, so that ID/IG is again reduced. Our Raman spectra also The magnetic behavior of a magnetic component dispersed in a non-
provide strong evidence of charge transfer from Fe3O4 to the rGO ma- magnetic matrix depends not only on the quantity of the magnetic
trix [38]. In pristine graphene the in-plane Raman G peak at 1580 cm−1 component but also on how it is dispersed within the matrix. This af-
arises due to the doubly degenerate E2g phonon mode at the Γ-point. In fects not only the size of individual crystallites, but also the inter-
our rGO sample this peak is slightly red-shifted at 1576 cm−1, due to particle dipolar interactions.
'
stacking of layers as has been shown to occur for rGO and multilayer The real part of the ac conductivity σac of rGO, Fe3O4-rGO compo-
grapheme [39]. In the composite samples, charge transfer from the d- sites and pure Fe3O4 was measured at room temperature in the fre-
orbitals of Fe (2+ or 3+) ions to the p-orbitals of graphene changes the quency range 10–2 × 106 Hz in static magnetic fields upto 500 mT. The
Fermi-level, leading to an increase in the energy of this phonon mode frequency dependent response of the ac conductivity is shown in Fig. 5.
because of non-adiabatic electron-phonon coupling. Fig. 3(a) shows a The conductivity of the pure rGO sample is largely independent of
clear blue-shift in the G-peak position of rGO in the composite samples. frequency up till the cut-off limit is reached at f ~ 250 kHz. Such be-
This is plotted as a function of magnetite content in Fig. 3(b) (right axis) havior has been reported for carbon nanotube polymer composites
and reaches a maximum at 40 wt% magnetite, indicating maximum [40], as well as for composites of 3D graphene and noble metals [12]

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

(a) (b)

(c) (d)

(e)

Fig. 2. SEM images of (a) rGO, (b) sample F20G80, (c) sample F40G60, (d) sample F80G20. Magnetite nanoparticles have been encircled in black in (b) and (c). (e)
Shows a high magnification cross-sectional view of sample F40G60.

and rGO-ZnS nanocomposites [41]. The weak frequency dependence in samples as well as magnetite increase in the presence of a magnetic
our sample may arise due to defect states, which are also deemed to be field. We will return to this point later in the discussion of the mag-
responsible for the very small ferromagnetic signal of this sample (inset, netoconductivity.
Fig. 4). Pure rGO displays a negative magnetoconductivity of ~15% at The frequency dependence of the ac conductivity of all composite
all applied frequencies, while the conductivities of all composite samples follows that of pure rGO, indicating the non-percolative nature

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

Fig. 3. (a) Room temperature Raman spectra of rGO (lowermost panel), rGO-magnetite composites and pure magnetite (Fe3O4) nanoparticles (uppermost panel).
Dashed vertical line at 1576 cm−1 indicates the position of the G-peak of the rGO sample, and also shows the shift in its position in the composite samples. (b) Ratio
of intensities of the D and G bands (ID/IG) (left-axis) and G-peak position (right axis) as a function of the weight percentage of magnetite (Fe3O4) dispersed in the rGO
matrix.

of the magnetic component in these composites. This holds true even particularly at low frequencies (see Fig. 5f). This trend of conductivity
upto sample F80G20 which contains 80 wt% magnetite. The large enhancement persists upto 40 wt% magnetite, after which there is a
difference in the densities of rGO and magnetite ensures that Fe3O4 decrease in σ'ac . These results are summarized in Fig. 6 which shows the
nanoparticles actually occupy a very small volume of the sample, so dependence of σ'ac on magnetite content for B = 0 and 500 mT at
that the the rGO matrix is essentially contiguous even in sample f = 10 kHz. The largest conductivity and magnetoconductivity are
F80G20, and entirely determines the conduction pathways in all com- observed for the sample F40G60, in which σ'ac increases by a factor of 3
posite samples. An interesting observation is that addition of even 20 wt over that of pure rGO. This is also the sample for which the Raman
% magnetite nanoparticles to the rGO matrix increases the conductivity spectrum shows the largest G-peak shift (Fig. 3b), indicating the highest
of the composite over that of pure rGO in the entire frequency range. degree of charge transfer from magnetite to graphene among all com-
This is a striking result considering that the conductivity of the Fe3O4 posite samples. Baykal et al. also report enhancement in ac conductivity
sample is at least six orders of magnitude smaller than that of rGO, of acid functionalized multiwall carbon nanotube (CNT)/magnetite

Fig. 4. Magnetization hysteresis loops measured at room temperature. Inset (top left) shows the values of saturation magnetization MS as a function of magnetite
content. Inset (bottom right) shows the magnified M(H) loop of rGO.

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

Fig. 5. Ac conductivity of (a) rGO, (b–e) rGO-Fe3O4 composite samples, and (f) Fe3O4 (magnetite) (inset shows data on a log–log plot), measured at room temperature
in magnetic fields upto 500 mT applied parallel to the electric field.

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

sample, the moments of individual grains point in random directions,

giving zero net magnetization of the material. This represents a high
resistance state. As the applied field exceeds the coercivity
(BC = 15 mT), the increasingly parallel alignment of the intragranular
magnetic moments allows for spin dependent tunneling across the grain
boundaries, leading to enhanced conductivity. Ferromagnetism in
Fe3O4 is due to the double-exchange interaction between the octahedral
sites, mediated by the shared electron of the mixed-valence state of
Fe+2/Fe+3. This shared electron is spin polarized and responsible for
conduction. We obtain Δσ 'ac = 550% in B = 500 mT at f = 10 Hz, and
this increases to 730% at f = 2 MHz. This is orders of magnitude larger
than that reported for dc magnetotransport [34,45,46]. To the best of
our knowledge, we have not come across studies of how dc magnetic
fields may affect ac transport in magnetite or other spinel ferrites. Room
temperature values of the (negative) dc magnetoresistivity are gen-
erally low (10–15%), and these are achieved at magnetic fields of
several tesla, which is clearly unfeasible for device applications. This
behavior of the dc magnetoconductivity is generally attributed to the
intergrain tunneling magnetoresistance (ITMR) and spin-dependent
Fig. 6. Ac conductivity at f = 10 kHz as a function of magnetite content transport across antiphase boundaries in magnetite as well as intrinsic
without magnetic field and in B = 500 mT. Dotted lines are guide to the eye. effects related to the peculiar band structure of magnetite.
The pure rGO sample shows a small decrease in ac conductivity in
composites [42] over that of the CNT’s. Similar enhancement of ac B = 500 mT. In all reviewed literature, we could only find reports of dc
conductivity has been reported for composites of three-dimensional (or magnetoresistance of rGO, which has been found to be both positive as
3D) graphene doped and Pt or Ag nanoparticles [12], but these noble well as negative [47–50], depending upon the temperature and degree
metals have typically much higher conductivities than that of magne- of disorder in graphene. In most of these studies the magnetic field is
tite. DFT computations by Liu et al. [28] to study the adsorption of applied perpendicular to the direction of current, while in our work
transition metal atoms on graphene have shown strong covalent they are collinear. Though our measurements are not made in a typical
bonding between the dx2−y2 and dyz orbitals of Fe and the pz orbitals of Hall configuration, the high degree of disorder in rGO may cause
graphene. These strong covalent bonds can create in-plane distortions electrons to scatter in directions in which they may experience a Hall-
in the graphene lattice, evidence of which is seen in the Raman spectra like effect, resulting in negative magnetoconductivity. Electron-electron
in Fig. 3. The resulting charge transfer from the d-orbitals of Fe to the p- scattering is also known to be responsible for negative magneto-
orbitals of graphene enhances the conductivity of the composite sam- conductivity [32].
ples over that of graphene. For samples with high magnetite content, The Fe3O4 sample and all composite samples exhibit conductivity
clustering of magnetite nanoparticles (as seen in Fig. 2d) reduces the enhancement in magnetic field. The magnetoconductivity of the pure
rGO-magnetite interfacial area, resulting in decreased conductivity. rGO, magnetite, and all composite samples was calculated from data
The conductivity of magnetite remains independent of frequency shown in Fig. 5 and are shown in Fig. 7 for Fe3O4, rGO and sample
upto about 10 kHz, after which there is a sharp increase. The inset of F40G60 sample at f = 10 Hz and 254 kHz (the highest frequency before
Fig. 5(a) shows the conductivity on a log–log scale, which follows the the cut-off regime). Δσ 'ac values measured at the intermediate fre-
typical behavior of disordered solids as described by Jonscher’s power quencies lie systematically between these two limits but are not shown
law [43] and explained by Koops’ model [44]. Applying a dc magnetic here for clarity.
field of 50 mT increases the conductivity by about an order of magni- An important feature of these data is that even though the con-
tude throughout the entire frequency range. The Fe3O4 sample has a ductivity of all composite samples follows the behavior of pure rGO, the
coercivity BC of about 15 mT as obtained from the magnetization data magnetoconductivity is clearly determined by their magnetite content.
shown in Fig. 4. An applied magnetic field of 10 mT (< BC) has neg- The field dependences of Δσ 'ac for Fe3O4 and sample F40G60 are very
ligible effect on σ'ac , but the conductivity changes abruptly by about an similar (Fig. 7(a) and (c)), indicating that it is the magnetic component
order of magnitude when the magnetic field is increased to 50 mT, i.e. that is responsible for the enhanced magnetoconductivity of the com-
greater than BC (see inset Fig. 5a). At the coercive field of the magnetite posites. (Δσ 'ac for other composite samples also shows similar magnetic
field dependence). The inset of Fig. 7(c) shows the variation of Δσ 'ac as a

Fig. 7. Magnetoconductivity of (a) Fe3O4, (b) rGO and (c) sample F40G60 measured at f = 10 Hz and f = 254 kHz. Curves for intermediate frequencies lie
systematically between these limits but are not show for clarity. Fig. (c) Inset shows the magnetoconductivity at B = 500 mT as a function of the weight percentage of
Fe3O4 nanoparticles in the rGO matrix. Lines are guide to the eye.

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K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

function of magnetite content for all samples. We report a giant room References
temperature ac magnetoconductivity Δσ 'ac = 57% at f = 254 kHz at
B = 500 mT for sample F40G60. This decreases slightly to Δσ 'ac = 50% [1] K.S. Novoselov, A.K. Geim, The rise of graphene, Nat. Mater. 6 (2007) 183–191.
at f = 10 Hz , indicating a very weak frequency dependence. This is also [2] A.K. Geim, Graphene: status and prospects, Science 324 (2009) 1530–1534.
[3] M.S. Fuhrer, C.N. Lau, A.H. MacDonald, Graphene: materially better carbon, MRS
the sample with the largest conductivity (Fig. 6) and for which the Bull. 35 (2010) 289–295.
Raman spectrum shows the largest G-peak shift (Fig. 3b), indicating the [4] G. Wang, M. Zhang, Y. Zhu, G. Ding, D. Jiang, Q. Guo, S. Liu, X. Xie, P.K. Chu, Z. Di,
highest degree of charge transfer from magnetite to graphene among all X. Wang, Direct growth of graphene film on germanium substrate, Sci. Rep. 3
(2013) 2465–2469.
composite samples. This charge redistribution can induce a magnetic [5] W. Han, W.H. Wang, K. Pi, K.M. McCreary, W. Bao, Y. Li, F. Miao, C.N. Lau,
moment in grapheme [28], which would respond to a magnetic field. R.K. Kawakami, Electron-hole asymmetry of spin injection and transport in single-
Furthermore, in the presence of magnetic field, the increased con- layer graphene, Phys. Rev. Lett. 102 (2009) 137205–137208.
[6] F. Withers, M. Dubois, A.K. Savchenko, Electron properties of fluorinated single-
ductivity of the Fe3O4 nanoparticles facilitates a more effective charge layer graphene transistors, Phys. Rev. B 82 (2010) 073403.
transfer to the rGO matrix. In such composite systems, spin-orbit cou- [7] A. Sagar, E.J. Lee, K. Balasubramanian, M. Burghard, K. Kern, Effect of stacking
pling at interfaces is particularly strong due to broken inversion sym- order on the electric-field induced carrier modulation in graphene bilayers, Nano
Lett. 9 (2009) 3124–3128.
metry. This can lead to splitting of the spin bands of the surface states of
[8] N.O. Weiss, H. Zhou, L. Liao, Y. Liu, S. Jiang, Y. Huang, X. Duan, Graphene: an
magnetite leading to positive magnetoconductivity. emerging electronic material, Adv. Mater. 24 (2012) 5782–5825.
We have not come across any experimental or theoretical reports on [9] P. Zomer, S. Dash, N. Tombros, B.V. Wees, A transfer technique for high mobility
graphene devices on commercially available hexagonal boron nitride, Appl. Phys.
enhancement of ac conductivity in magnetic field. Such large magneto-
Lett. 99 (2011) 232104.
conductivities achieved at room temperature in relatively low magnetic [10] J. Zhao, S. Pei, W. Ren, L. Gao, H.M. Cheng, Efficient preparation of large-area
fields and frequencies are very interesting from the point of view of graphene oxide sheets for transparent conductive films, ACS Nano 4 (2010)
applications, e.g. magnetoresistive sensors for static magnetic fields. It 5245–5252.
[11] M. Park, S.J. Hong, K.K. Ho, H. Kang, M. Lee, D.H. Jeong, W.P. Yung, H.K. Byung,
is yet not completely clear why these effects are much larger in ac Electrical and thermoelectric transport by variable range hopping in reduced gra-
transport than in dc. This merits an investigation into the role of a static phene oxide, Appl. Phys. Lett. 111 (2017) 173103.
magnetic field in ac transport measurements, as well as further ex- [12] P.K. Sahoo, R. Aepuru, H.S. Panda, D. Bahadur, Ice-templated synthesis of multi-
functional three dimensional graphene/noble metal nanocomposites and their
periments for a deeper understanding of this effect. mechanical, electrical, catalytic, and electromagnetic shielding properties, Sci. Rep.
5 (2015) 17726.
[13] X. Ou, P. Chen, L. Jiang, Y. Shen, W. Hu, M. Liu, π-conjugated molecules crosslinked
4. Conclusions graphene-based ultrathin films and their tunable performances in organic nanoe-
lectronics, Adv. Funct. Mater. 24 (2014) 543–554.
[14] J.M. Tour, Top-down versus bottom-up fabrication of graphene-based electronics,
We have shown that incorporating magnetite nanoparticles in an Chem. Mater. 26 (2013) 163–171.
rGO matrix enhances both the ac conductivity and magneto- [15] Z. Tan, S. Ohara, H. Abe, M. Naito, Synthesis and processing of graphene hydrogels
conductivity of the composite samples over that of pure rGO. The best for electronics applications, RSC Adv. 4 (2014) 8874–8878.
[16] P.K. Sahoo, B. Panigraphy, D. Bahadur, Facile synthesis of reduced graphene oxide/
results are obtained for sample F40G60 in which σ'ac increases to 3
Pt–Ni nanocatalysts: their magnetic and catalytic properties, RSC Adv. 4 (2014)
times its value in pure rGO. Our Raman spectra point towards charge 48563–48571.
transfer due p-d mixing between the orbitals of graphene and Fe3O4 as a [17] S. Thangavel, N. Raghavan, K. Krishnamoorthy, G. Venugopala, Visible-light driven
possible cause of the observed effects. The giant room temperature ac photocatalytic degradation of methylene-violet by rGO/Fe3O4/ZnO ternary nano-
hybrid structures, J. Alloys Compd. 665 (2016) 107–112.
magnetoconductivity of 57% (at f = 254 kHz) and 50% (at f = 10 Hz) [18] Y. Wang, Y. Shao, D.W. Matson, J. Li, Y. Lin, Nitrogen-doped graphene and its
in a static magnetic field of 500 mT is far more attractive for magne- application in electrochemical biosensing, ACS Nano 4 (2010) 1790–1798.
toelectric applications compared to the low dc magnetoconductivity [19] J. Gupta, A. Prakash, M.K. Jaiswal, A. Agarrwal, D. Bahadur, Superparamagnetic
iron oxide-reduced graphene oxide nanohybrid-a vehicle for targeted drug delivery
which is generally less than 10% at room temperature for B ~ 1 T. and hyperthermia treatment of cancer, J. Magn. Magn. Mater. 448 (2018) 332–338.
[20] E. Jokar, Z.Y. Huang, S. Narra, C.-Y. Wang, V. Kattoor, C.-C. Chung, E.W.-G. Diau,
Anomalous charge-extraction behavior for graphene-oxide (GO) and reduced gra-
CRediT authorship contribution statement phene-oxide (rGO) films as efficient p-contact layers for high-performance per-
ovskite solar cells, Adv. Energy Mater. (2017) 1701640.
[21] J. Su, M. Cao, L. Ren, C. Hu, Fe3O4–graphene nanocomposites with improved li-
Khush Bakhat Akram: Conceptualization, Investigation, thium storage and magnetism properties, J. Phys. Chem. C 115 (2011)
Visualization, Writing - original draft, Funding acquisition. Syed 14469–14477.
Mohsin ul Hassan: Investigation, Validation, Visualization. Awais [22] Y. Zhou, L. Guo, W. Shi, X. Zou, B. Xiang, S. Xing, Rapid production of Mn3O4/rGO
as an efficient electrode material for supercapacitor by flame plasma, Materials 11
Ahmed: Investigation, Validation. Muhammad Asif Hamayun:
(2018) 881.
Investigation, Validation. Mohsin Rafique: Investigation. Sadia [23] R. Singh, Unexpected magnetism in nanomaterials, J. Magn. Magn. Mater. 346
Manzoor: Supervision, Formal analysis, Resources, Writing - review & (2013) 58–73.
editing, Project administration, Funding acquisition. [24] O.V. Yazyev, Emergence of magnetism in graphene materials and nanostructures,
Rep. Prog. Phys. 73 (2010) 056501.
[25] C.N.R. Rao, H.S.S.R. Matte, K.S. Subrahmanyam, U. Maitra, Unusual magnetic
properties of graphene and related materials, Chem. Sci. 3 (2012) 45.
Declaration of Competing Interest [26] S. Qin, X. Guo, Y. Cao, Z. Ni, Q. Xu, Strong ferromagnetism of reduced graphene
oxide, Carbon 78 (2014) 559–565.
The authors declare that they have no known competing financial [27] J. Peng, Y. Guo, H. Lv, X. Dou, Q. Chen, J. Zhao, C. Wu, X. Zhu, Y. Lin, W. Lu, X. Wu,
Y. Xie, Superparamagnetic reduced graphene oxide with large magnetoresistance: a
interests or personal relationships that could have appeared to influ- surface modulation strategy, Angew. Chem. 55 (2016) 3176–3180.
ence the work reported in this paper. [28] X. Liu, C.Z. Wang, Y.X. Yao, W.C. Lu, M. Hupalo, M.C. Tringides, K.M. Ho, Bonding
and charge transfer by metal adatom adsorption on graphene, Phys. Rev. B 83
(2011) 235411.
Acknowledgements [29] T.N. Narayanan, Z. Liu, P.R. Lakshmy, W. Gao, Y. Nagaoka, D.S. Kumar, J. Lou,
R. Vajtai, P.M. Ajayan, Synthesis of reduced graphene oxide–Fe3O4 multifunctional
freestanding membranes and their temperature dependent electronic transport
The authors (KBA and SM) gratefully acknowledge the Higher properties, Carbon 50 (2012) 1338–1345.
Education Commission (HEC) of Pakistan for financial support under [30] H. He, C. Gao, Supraparamagnetic, conductive, and processable multifunctional
graphene nanosheets coated with high-density Fe3O4 nanoparticles, ACS Appl.
research grant for Indigenous 5000 Ph.D. fellowship (PhaseII) PIN no.
Mater. Interfaces 2 (2010) 3201–3210.
112-22494-2PS1-385. The Center for Micro and Nanodevices (CMND) [31] Z.M. Liao, H.C. Wu, J.J. Wang, G.L.W. Cross, S. Kumar, I.V. Shvets, G.S. Duesberg,
and Applied Thermal Physics Lab. (ATPL) are gratefully acknowledged Magnetoresistance of Fe3O4-graphene-Fe3O4 junctions, Appl. Phys. Lett. 98 (2011)
for providing support for Raman and ac conductivity measurements 052511.
[32] S. Bhattacharya, R. Maiti, M.B. Sen, S.K. Saha, D. Chakravorty, Anomalous
respectively.

8
K.B. Akram, et al. Journal of Magnetism and Magnetic Materials 499 (2020) 166174

enhancement in the magnetoconductance of graphene/CoFe2O4 composite due to nanocomposite, ChemPhysChem 17 (2016) 1518–1523.
spin–orbit coupling, J. Phys. D: Appl. Phys. 48 (2015) 435002. [42] A. Baykal, M. Senel, B. Unal, M. Toprak, Acid functionalized multiwall carbon
[33] M. Baskey, R. Maiti, S.K. Saha, D. Chakravorty, Superior magnetic, dielectric, and nanotube/magnetite (MWCNT)-COOH/Fe3O4 hybrid: synthesis, characterization
magnetodielectric effects in graphene/ZnCo2O4 nanocomposites, J. Appl. Phys. 115 and conductivity evaluation, J. Inorg. Organomet. P.s 23 (2013) 726–735.
(2014) 094306. [43] A.K. Joncher, The 'universal' dielectric response, Nature 267 (1977) 673–679.
[34] H. Zeng, C.T. Black, R.L. Sandstrom, P.M. Rice, C.B. Murray, S. Sun, [44] C.G. Koops, On the dispersion of resistivity and dielectric constant of some semi-
Magnetotransport of magnetite nanoparticle arrays, Phys. Rev. B 73 (2006) 020402. conductors at audiofrequencies, Phys. Rev. B 83 (1951) 121.
[35] W.S. Hummers Jr., R.E. Offeman, Preparation of graphitic oxide, JACS 80 (1958) [45] D. Serrate, J.M.D. Teresa, P.A. Algarabel, M.R. Ibara, J. Galibert, Intergrain mag-
1339. netoresistance up to 50 T in the half-metallic (Ba0.8Sr0.2)2FeMoO6 double per-
[36] J. Baumgartner, A. Dey, P.H. Bomans, C.L. Coadou, P. Fratzl, N.A. Sommerdijk, ovskite: spin-glass behavior of the grain boundary, Phys. Rev. B 71 (2005) 104409.
D. Faivre, Nucleation and growth of magnetite from solution, Nat. Mater. 12 [46] A.S. Tarasov, M.V. Rautskii, A.V. Lukyanenko, M.N. Volochaev, E.V. Eremin,
(2013) 1–5. V.V. Korobtsov, V.V. Balashev, V.A. Vikulov, L.A. Solovyov, N.V. Volkov, Magnetic,
[37] M.S. Dresselhaus, A. Jorio, A.G.S. Filho, R. Saito, Defect characterization in gra- transport, and magnetotransport properties of the textured Fe3O4 thin films reac-
phene and carbon nanotubes using Raman spectroscopy, Philos. Trans. R. Soc. A tively deposited onto SiO2/Si, J. Alloys Compnd. 688 (2016) 1095–1100.
(2010) 5355–5377. [47] A. Vianelli, A. Candini, E. Treossi, V. Palermo, M. Affronte, Observation of different
[38] A.C. Crowther, A. Ghassaei, N. Jung, L.E. Brus, Strong charge-transfer doping of 1 to charge transport regimes and large magnetoresistance in graphene oxide layers,
10 Layer graphene by NO2, ACS Nano 6 (2012) 1865–1875. Carbon 89 (2015) 188–196.
[39] A. Gupta, G. Chen, P. Joshi, S. Tadigadapa, P.C. Eklund, Raman scattering from [48] V.N. Matveev, V.I. Levashov, O.V. Kononenko, V.T. Volkov, Large positive mag-
high-frequency phonons in supported n-graphene layer films, Nano Lett. 6 (2006) netoresistance of graphene at room temperature in magnetic fields up to 0.5 T, Scr.
2667–2673. Mater. 147 (2018) 37–39.
[40] S. Barrau, P. Demont, A. Peigney, C. Laurent, C. Lacabanne, DC and AC conductivity [49] S. Qin, X. Guo, Y. Cao, Z. Ni, Q. Xu, Strong ferromagnetism of reduced graphene
of carbon nanotubes−polyepoxy composites, Macromolecules 36 (2003) oxide, Carbon 78 (2014) 559–565.
5187–5194. [50] B. Muchharla, T.N. Narayanan, K. Balakrishnan, P.M. Ajayan, S. Talapatra,
[41] K. Chakraborty, P. Das, S. Chakrabarty, T. Pal, S. Ghosh, AC conduction and Temperature dependent electrical transport of disordered reduced graphene oxide,
time–temperature superposition scaling in a reduced graphene oxide–zinc sulfide 2D Mater. 1 (2014) 011008.