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Semiconductor-to-Metallic Flipping in a ZnFe 2 O4 - graphene based Smart
Nano System: Temperature/Microwave Magneto-Dielectric Spectroscopy
PII: S1044-5803(14)00358-1
DOI: doi: 10.1016/j.matchar.2014.11.018
Reference: MTL 7738
Please cite this article as: Ameer Shahid, Gul Iftikhar Hussain, Mahmood Nasir, Mu-
jahid Muhammad, Semiconductor-to-Metallic Flipping in a ZnFe2 O4 - graphene based
Smart Nano System: Temperature/Microwave Magneto-Dielectric Spectroscopy, Materi-
als Characterization (2014), doi: 10.1016/j.matchar.2014.11.018
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Shahid Ameer a,*, Iftikhar Hussain Gula, Nasir Mahmoodb, and Muhammad Mujahida
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a,*
School of Chemical and Materials Engineering (SCME), National University of Sciences and
Technology (NUST), H-12, Islamabad, Pakistan.
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E-mail: shahidameer@scme.nust.edu.pk Contact: +92-345-5963306
b
Department of Materials Science and Engineering, College of Engineering, Peking University,
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Beijing 100871, China.
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Abstract
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Zn-(FeO2)2 - graphene smart nano-composites were synthesized using a novel modified
resembling a maple leaf. To determine the composition, Energy Dispersive Spectroscopy and X-
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revealed the improved dielectric properties of the nano-composite compared to those of the
parent functional nanocrystals. Temperature gradient dielectric spectroscopy was used over the
spectral range from 100Hz to 5MHz to reveal the phenomenological effect that the nanosystem
flips from its usual semiconductor nature to a metallic nature with sensing temperature. Electrical
conductivity and dielectric analysis indicated that the dielectric loss and the dielectric
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functionalized graphene nanosystem opens up a new dimension for engineering advanced and
Keywords:
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Ceramic-graphene nanosystem; Smart materials; Temperature-gradient dielectric spectroscopy;
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Semiconductor / metal Flipping; Nano-electronics.
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1. Introduction MA
Graphene, atomically thin sheets of sp2 hybridized carbon atoms, has had a remarkable impact on
various areas of research and opened new horizons for researchers working in the
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nanotechnology field. The new phenomena's associated with graphene can be utilized in
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Graphene can be used in a variety of applications, including electronic nano-devices [1, 2], nano-
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medicine [3], optoelectronic engineering [4], green energy and fuels[5], environmental
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engineering [6], food technology and so on.[1, 7]. Transition metal based complex iron oxides
are functional nano materials used in a wide variety of technological applications such as nano-
photonics [8], advanced electronics, magnetic devices [9] and nano-medicine; in particular,
complex iron oxides have been used in many aspects of targeted drug delivery and anti-cancer
research, from diagnosis via cancerous cell imaging modalities to research on the treatment of
cancer(breast cancer MCF7, colon cancer HT29, and liver cancer HepG2, etc.) based upon their
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electrochemical, electronic, catalytic, and sensing applications, has shown huge potential.
Various strategies have been devised for the modification of graphene to improve the electro-
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catalytic properties and hence improve bio-sensing [14], drug delivery [15], and
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photoluminescence [16];reduce CO2 foot prints [17];improve mechanical integrity and reduce
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gas permeability [18]; produce efficient electrode materials for Li-ion batteries [5]; and improve
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the photo catalytic activity [19], efficiency of oil exploration [20], and solar energy harvesting
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[21]. Nano hybrids of both graphene and functional ferrite nanocrystals have been studied in
various aspects [22-24].There is growing interest to utilize the high magnetic permeability of
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graphene coupled with a complex iron oxide based formulation having high saturation
magnetization in conjunction with the dielectric environment supported by the carbon backbone
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[25]. However, all of the electronic and magnetic applications of such hybrid nanosystems are
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dependent upon the semiconductor nature derived from their unique electronic
configurations[10]. Graphene and its related derivatives can be modified electronically either by
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functionalizing with the appropriate chemical agent [26-28] or by choosing a proper method of
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graphene in terms of its structural manipulation along with magnetic inclusions provide a new
can address the need for smart materials and systems that provide unique functional responses,
superconductors[32]. Although different strategies have been slated to modify the functional
response of graphene and its associated derivatives, there is a need to evaluate the novel
graphene based nano-hybrids that can effectively be utilized in the next generation of green
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nano-electronics within a subset of flexibility as well as the ability to shape their response
devices. In the present work, smart nano-systems based on zinc-complex iron oxides were used
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to functionalize graphene sheets; the magneto-dielectric enhancement associated with the
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phenomenological effects imparted from graphene is discussed and the energy absorption is
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analyzed by varying the share of graphene in the synthesized nanosystems. The novelty of the
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work lies in the special growth of the flexible functional nanomaterial@graphene nanosystem
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with excellent switching of the electronic nature through solvent engineering. Novelty of the
synthesis lies in the nature of mixture of solvent (Ethanol: DI water) used in this research work
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which promotes the complete reduction of graphene oxide and also serves as the solvothermal
medium for the growth of ZnFe2O4 nanocrystals of low dimension and the attachments of the
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these nano crystals with the reduced graphene oxides sheets. In this particular experimental
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scheme, instead of using the pure ethanol, various proportions of Ethanol and DI water were
utilized with an aim to get uniformly functionalized reduced graphene oxide sheets with ZnFe2O4
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nano particles of low dimension as compared to facile hydrothermal synthesis which have very
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complex permittivity and high complex permeability. These functional particles, when anchored
semiconducting nature to a metallic nature above when room temperature. These new
phenomenological effects can open up new directions in tailoring the flexible nano-devices for
2. Experimental work:
2.1 Chemicals:
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Flake Graphite (3061) was provided by Asbury carbon, NJ, USA. Zn(NO3)2.6H2O and
chemicals, including Fe(NO3)2.6H2O, H2SO4, H3PO4, KMnO4, and NaOH, were purchased from
Sigma Aldrich. Double distilled DI water was used for synthesis and washing purposes. For
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solvothermal grafting and reduction of graphene oxide, an alumina modified-Teflon lined
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stainless steel (SS) autoclave was used.
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2.2 Synthesis of the graphene precursor:
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Graphene oxide was used as a source of graphene for the synthesis of the nanocomposite.
Graphene oxide was synthesized using the improved Hummer method [33, 34]. Typically, 3g of
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graphite flakes were added to 400ml of a 9:1 mixture of H2SO4 and H3PO4 and were then stirred.
KMnO4 (18g) was added slowly to the above mixture over a period of 20mins, and then, the
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solution was allowed to stir for three days at 50°C, during which the color of the mixture
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changed from dark green to brownish. Oxidation was stopped by quenching the mixture with ice
water containing a small amount of H2O2, which produced a brilliant yellow colored solution.
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The resulting solution was allowed to settle, and then, it was filtered/washed with a 20% HCl
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solution one time and with a 10% HCl solution twice, followed by a 5 % HCl solution (one time)
repeatedly with DI water to neutralize the pH. During centrifugation with DI water, graphite
oxide resulted in exfoliation. This GO suspension was then freeze dried at -50°C for 12hours to
obtain powdered graphene oxide, which was then used in the characterization and experimental
composite:
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involving the in-situ precipitation of Zn2+ and Fe2+ and the reduction of graphene oxide in the
supercritical state; the mechanism of which will be discussed later in the text. In a typical
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experiment, 0.967mg of graphene oxide powder was dissolved with another solution containing
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1.934g of zinc nitrate and iron nitrate in the stoichiometric ratio in ethanol and DI water. The
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suspension was transferred to the alumina modified-Teflon lined stainless steel autoclave
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(100ml) filled to 80% of its capacity. The reaction vessel was maintained at 160°C for 12 hour.
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After cooling, the supernatant was discharged, and then, the residue was washed repeatedly with
acetone and DI to neutralize the pH. This final suspension was dried at 70°C for 12 hours, and
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then, the obtained solid was grounded into fine powder, named ZnFe2O4-G8%, and used in
further studies. For comparison, the same procedure was used to grow the pristine Zn ferrite
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nano-crystals.
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2.4 Characterization
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The prepared nanomaterials were analyzed using X-ray diffraction (XRD) from an 8-80o (STOE
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spectral range of 190-800nm, and Fourier transform infrared (FTIR) spectroscopy over the
spectral range of 380 to 4000 cm-1 (Perkin Elmer spectrum 100) to determine their crystal
structure, bonding behavior and functional groups. The powdered sample was used for X-ray
spectroscopy, KBr pellets and suspensions of nano-powder in DI, respectively, were prepared.
For micro-structural growth, morphology, particle size and shape analysis, light suspensions
were prepared in DI water, casted onto Si substrates, and then analyzed using a JEOL 6490
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scanning electron microscope (SEM) and a FEI Tecnai T20 transmission electron microscope
(TEM). Compositional analysis was performed through in-situ energy dispersive X-ray
spectroscopy coupled with the JEOL 6490 SEM and a Kartos Axis Ultra X-ray photoelectron
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spectroscopy (XPS) system. Temperature gradient Dielectric spectroscopy was performed using
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an impedance analyzer (Wayne Kerr 6500B) coupled to a probe station with Cu electrodes over
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the frequency range of 100Hz to 5MHz and over the temperature range of 380K-543K using
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circular pellets of a nano-powder of diameter of 5mm and thickness of 1.5mm. Energy
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absorption and magneto-dielectric spectroscopy was performed using an Agilent E4991A
X-ray diffraction of graphite flakes, graphene oxide and Zn-(FeO2)2 - graphene nanocomposite
(Figure 1 a-c) were performed. It is clear from figure 1a that that after three days of oxidation,
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the characteristic peaks of graphite belonging to crystal planes (002) at 26O and (004) at 40O
disappear with the emergence of a new peak at 10.4O corresponding to the (001) plane of
graphene oxide [33]. The interlayer spacing for graphene oxide is increased from 0.86nm
compared to 0.33nm in the parent graphite crystal structure, and this apparent increase is due to
oxygen functional groups that are intercalated between the adjacent carbon layers. The inter-
planar spacing of synthesized graphene oxide is also consistent with other results that indicate
the higher degree of oxidation of graphene oxide. Figures 1b& 1c show the X-ray diffraction
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XRD patterns of ZnFe2O4 and Zn-(FeO2)2 - graphene nanocomposites agree well with JCPDS
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01-079-1150, i.e., face-centered cubic crystals. The XRD pattern of the functionalized material
exhibits no characteristic peak of graphene oxide, which demonstrates the complete reduction of
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the graphene oxide. Moreover, there is no prominent peak at 26o due to the uniform dispersion
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and anchoring of zinc ferrite nanocrystals on to the graphene layer, causing exfoliation and
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preventing further restacking of the graphene sheets to a greater extent. At the ratio of Ethanol:
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Di water of 7:1, we obtained the nanocrystals of lowest size attached with completely reduced
graphene oxide sheets with no peak of graphene oxide as shown in X-ray diffraction results.
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Figure 2 shows the micro-Raman spectra of graphite, graphene oxide and Zn-(FeO2)2
functionalized graphene. From figure 2(a), the characteristic peaks for graphite materials are the
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D band at 1371 cm -1, the G band at 1590 cm -1, and the 2D band or G’ band at 2748 cm -1[35]. In
graphene oxide, the intensity of the D band is significantly higher because of the defects induced
and both the G and D bands became broader. There is a small hump around the same wave
number as that of the 2D and D+G band, indicating the presence of single-layered graphene
oxide sheets, which is in agreement with the literature. The intensity ratio of the ID/IG is on the
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In the Raman spectrum of Zn-(FeO2)2 functionalized graphene, all of the peaks in the range of
375-1200 cm -1 are indicative of zinc ferrite nanocrystals. The characteristic peak approximately
653-671 cm -1 is because of the movement of oxygen within the MO4 of the tetrahedral structure
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(symmetry type A1g); the G and D bands in the ranges of 1347-1368 cm -1 and 1588-1611 cm -1,
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respectively, are typical of graphene sheets. The red shift of G, D peaks compared to graphene
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oxide spectra is due to the charge exchange between the graphene sheet and oxygen containing
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Zn-Fe complex and can also be attributed to stress-induced phonon hardening due to
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nanoparticle formation [36]. Moreover, the Raman shifts (red shift) associated with the G- and
D- bands are regarded as a good indicators of the reduction process [22, 36]. Here, the position
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of the G-band shifted from 1680 to 1585 cm -1, and the D-band shifted from 1370 to 1347 cm -
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for the Zn-(FeO2)2 -graphene nanocomposite compared with GO. In addition, the observation of
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the diminished 2D band at 2692 cm -1also validates the complete reduction and formation of the
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graphene structure. This position of the 2D band is almost identical to that reported for
monolayer graphene. [37, 38]. The Raman spectra of Zn-(FeO2)2 - graphene nanocomposite and
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pure ZnFe2O4 show identical features in the range of 375 to 1200 cm -1, which indicates the
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presence of pristine ZnFe2O4 in the nanocomposite. The peaks in the range of 653 to 671 cm -1
are of the A1g vibrations linked to O motion in tetrahedral AO4 groups. Normally, the phonon
modes at low wave number indicate metal ions involved within octahedral groups (BO6). These
modes reveal the oxygen’s symmetric and anti-symmetric bending in M-O bond within
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Figure 3 and Figure 4 show the SEM and TEM images of graphene oxide, pristine ferrite
nanocrystals and their nanocomposite. Figure 3(a-d) shows the SEM images of graphene oxide
sheets. It is evident that graphene sheets have a sheet-like morphology and have a fairly large
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diameter, confirming the synthesis of large area graphene oxide sheets. It is clear from Figure
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3(a-d) that the some of the graphene oxide sheets are almost transparent, while others are
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overlapping, thereby increasing the thickness and making them appear opaque. The EDX
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analysis shows that the amount of oxygen in GO is approximately 45%, with no notable
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impurities. Figure 3(e-h) shows the SEM images of prepared pristine ZnFe2O4 nanocrystals and
homogenous, almost spherical in shape. Figure 3(i-l) shows the overall growth pattern of both
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pristine ZnFe2O4 and one of the nano-composites, ZnFe2O4-G25%. Note that this beautiful self-
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similar to a maple leaf. It is evident that some of the nanocrystals have grown in the form of a
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beautiful leaf in the samples, with the individual vein being the region rich in nanoparticles.
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Figures 4(a) and 4(b) show the TEM images of pristine ZnFe2O4 nanoparticles, which exhibit
almost spherical shaped crystals, and figures 4(c) and 4(d) show the ZnFe2O4-G25% sample,
which exhibits a mixed morphology. EDX analysis confirmed that the Zn:Fe is in the ratio of
1:2, and the percentage of graphene sheets of 8%, 14%, and 25% functionalized content of
graphene sheets were found in the ZnFe2O4-G8%, ZnFe2O4-G14% and ZnFe2O4-G25% samples,
respectively, as presented in Table 1. The particle size of the composite samples lies in the range
of 20 to 30nm based upon SEM and TEM analysis (see Table 1).
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The in-situ grafting of the ZnFe2O4 to graphene sheets (nano-compositing), which is also formed
in-situ by the reduction of graphene oxide at high alkaline pH under solvothermal condition, can
be explained as the precipitation of Zn2+ and Fe2+ ions onto the surface, edges, and gap in-
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between the individual sheets of GO, as shown in figure 5, thereby promoting and facilitating the
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further exfoliation and reduction. Subsequent growth and nucleation enables the grafting to be
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completed, creating a leaf-like microstructure.
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3.4 XPS Analysis:
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X-ray photoelectron spectroscopy was used to investigate the elemental composition along with
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the valence states of the various chemical species involved in the nano-system. Figure 6 (a)
shows the XPS spectra, Zn 2p, Fe 2p, O1s, and C1s spectra, which are in good agreement with
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the EDX results. In the case of the Zn 2p spectra (Fig. 6b), two peaks at binding energies of
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1044.4eV and 1021.4eV, corresponding to Zn 2p1/2 and Zn 2p3/2, respectively, which is the same
as that of pristine ZnFe2O4[40], indicate the presence of the Zn2+ valence state. Fig. 6(c) shows
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the Fe 2p spectra, there are two major peaks centered at 725.2eV and 711.2eV corresponding to
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Fe 2p1/2 and Fe 2p3/2, respectively, which indicate the valence states of Fe3+ and Fe2+. There are
also two satellite peaks at 734eV and 719.6eV, which is the result of shakeup of 2p1/2 (2p3/2) [22,
41, 42]. In the O1s spectra shown in Fig. 6(d), the only major peak occurs at 530.4eV, which
corresponds to the M-O bond energy. In the C1s spectra, a diminished peak at 288.5eV
corresponds to the C=O bond, and a dominant peak at 284.4eV corresponds to the C=C bond as
shown in Fig. 6(e). The low concentration of the C=O bond indicates the good progress of the
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Figure 7 shows the Ultraviolet-Visible spectra of graphene oxide and pristine ZnFe2O4 and Zn-
(FeO2)2 functionalized graphene samples. In the graphene oxide UV-Vis spectrum, the peak at
228 nm corresponds to graphene oxide, which is in agreement with the reported literature [34];
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this peak is due to electronic transition in C-C bonds related to π-π* transition [41]. There is
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another shoulder peak at approximately 305nm that is related with electronic transitions (n-π*) in
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the C=O species in graphene oxide. The absorption peak at 228nm also confirms the higher
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degree of oxidation, demonstrating that graphene oxide contains a large number of oxygen-
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related functional groups that are uniformly distributed on the basal plane and that there is
negligible pi-conjugation in the graphene oxide lattice. The calculated intensity ratio of π-π* and
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n-π* is 3.59, which is higher than the reported values (~3.2) of all of the prepared large area
graphene oxide structures; this intensity ratio is usually ~2 for wet-chemically prepared graphene
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derivatives [34]. In UV-Vis spectra of pristine ZnFe2O4 nano crystals and Zn-ferrites-graphene
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nanocomposite samples, there is a strong absorption in the UV range, which is typical of ferrite-
based materials. The absorption behavior between 300-400nm is due to electronic transitions
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involving 3d5 and 3d4-4s1 orbital's in Fe ions, where the conduction band contribution comes
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Figure 8 shows the FTIR spectra of the graphene oxide, pristine ZnFe2O4 and Zn-(FeO2)2
functionalized graphene. In the case of graphene oxide, the peaks correspond to oxygen-related
functionalities, indicating the complete oxidation of graphite. The graphene oxide FTIR
spectrum mostly contains hydroxides, epoxides and carboxylic groups. It is evident that the peak
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at approximately 1625 cm is due to the bending vibrations of the structural O-H functional
groups [22, 34]. The peak at 1102cm-1 is due to the C-O stretching vibration, and the major peak
at 1386cm-1 is characteristic of the C-OH stretching vibration. The stretching vibration of C=O
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of carboxyl groups lies at 1730 cm-1[46-48]. The peaks in-between 2800-3400 cm-1 arise from O-
H groups of adsorbed water molecules and of structural addends [46]. These oxygen related
functionalities (O-H, C-O, and C-OOH) acts as nucleation sites where fine crystals of ferrites can
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grow. In the FTIR spectrum of pristine ZnFe2O4 nanocrystals, there are normally four sets of
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lattice vibrations, corresponding to lower and higher frequencies. The lattice vibrations involving
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oxygen and cations at octahedral and tetrahedral positions in the base lattice appear in the high
frequency region, namely, ν1 and ν2 at 600-540 cm-1 and 400-460 cm-1, respectively. The low
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frequency bands in the vicinity of 320 cm-1 are due to divalent oxygen vibrations. The typical M-
O bond corresponds to a major band in the range of 550 to 553cm-1(tetrahedral) and a faint peak
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at 430cm-1 (octahedral lattice vibrations) [49]. The peak at 1387cm -1 is due to the asymmetrical
stretching vibrations of adsorbed carbonate ions CO32- on the lattice [50]. The peak at 790cm-1 is
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due to the Zn-O bond [51], and the peaks at 1627cm -1, 890cm -1 and between 2800-3500cm -1 are
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due to O-H bending vibration and physically adsorbed moisture [52]. The small peaks between
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1000-1260 cm and at approximately2800 cm-1 may be due to C-H or N-H bonds due to
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impurities from the precursor [53]. In the FTIR spectrum of the graphene-ZnFe2O4
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nanocomposite, the distinct peak corresponding to the M-O bond appeared in the range of 500 to
540cm-1. The apparent red shift of the position of the M-O bond vibration is often related with
the size of the particles formed. From figure 8, it is clear that the wave number corresponding to
the M-O bond vibration decreased in the ZnFe2O4-G25% sample compared to that of the pristine
ZnFe2O4 nanoparticles, which is consistent with the SEM results, which can be correlated with
the increased average particle size of ZnFe2O4-G25% [54] as one of the factor (not necessarily
the only factor) which can cause this shift. Although The absence of most of the oxygen-related
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functional groups in the graphene oxide pattern confirms the reduction of GO. The slight peak at
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The microwave magneto dielectric properties of the pristine ZnFe2O4 and the Zn-(FeO2)2 -
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graphene nanocomposite were evaluated from 15MHz to 3GHz. Figure 9(a-d) shows the
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microwave magneto-dielectric spectroscopy results of all of the samples. The real and imaginary
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parts of both the complex permittivity and the complex permeability were measured using the
impedance analyzer. The expressions characterizing [55-57] the nature of the relations between
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these properties are as follows:
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Where ε' and μ' are the real parts of the complex permittivity and the complex permeability,
respectively, and ε'' and μ'' are the imaginary parts of the complex permittivity and the complex
permeability, respectively.
The real part ε' exhibits a decreasing trend with the increase in the frequency from 15MHz to
3GHz for all of the samples. The value of dielectric constant of pure ZnFe2O4 decreases from 8.9
at 15MHz to approximately 3.20 at 1GHz, and finally terminates at 3.17 at 3GHz following a
region of being constant, with only a minor fluctuation in-between 2 and 2.7GHz. The dielectric
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constant increases with the increase in the graphene content from 0% to 25% and remains high at
all of the frequencies. For the ferrite-nanocrystals-graphene nano-composite, the real part of the
dielectric permittivity increased from 8.9 for pristine particles to 10.0, 10.4 and 14.2 for
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ZnFe2O4-G8%, ZnFe2O4-G14% and ZnFe2O4-G25%, respectively at 15 MHz, and remains high
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afterwards. A similar trend was observed for the magnetic permeability, the real part of which
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also decreases with increasing frequency. The main reason of this apparent decrease is because
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of the nature of the real part of the complex permittivity, as it depicts the dipolar and electric
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polarization of the sample at a microwave frequency; with the increase in the loading of
graphene sheets, the overall conductivity and hence the electric polarization of the resulting
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strained lattice increases, resulting in the overall high dielectric constant and high dielectric
losses. The increased dielectric loss can also be explained on the basis of electron hopping
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between Fe2+ and Fe3+ and electron spin and charge polarization [23]. The obtained values of
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both the real and imaginary parts of permittivity are way too smaller than the reported literature
which are crucial for better microwave absorption [58-61], same is the case of high real and
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imaginary parts of permeability of pristine nonmagnetic nano particles synthesized via this
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method.
Moreover, it is clear from Figure 9b and Figure 9d that the dielectric losses are greater than the
[62, 63]. The fundamental cause of microwave attenuation in graphene is the effects of the
electron spin. During the reduction and exfoliation process and the subsequent precipitation of
ferrites particles, various defects can be induced in the original rGO sheets. These defects can act
as polarization centers and also induce various delocalized energy states near the Fermi states
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that cause the attenuation during microwave irradiation. In Zn-(FeO2)2 functionalized graphene,
various polarization centers due to the reconstructed graphene lattice that exhibit a varying
dipolar polarization ability causes the electron motion hysteresis to attenuate the microwave path
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within the sample [62, 64, 65].
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Figure 9e and Figure 9f show the tanδε and tanδm data, in which a resonance peak appears for the
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sample without any graphene addition, while there is also a small hump for the sample with the
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lowest amount of graphene, which disappears for samples with increasing graphene content
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because of the negligible magnetic characteristic of the graphene in the overall composite. In the
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graph showing the imaginary part of the complex permeability, the value of μ'' of ZnFe 2O4 is
quite high because of the super paramagnetic nature of the material; however, the value of μ'' of
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except for some defect contribution, due to which the ZnFe2O4 particles exhibit slightly
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increased magnetic loss when attached to the graphene lattice [66]. To evaluate the
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electromagnetic absorption characteristic, the reflection loss and input impedance [23] were
The microwave absorption of any material depends upon magnetic loss, dielectric loss and
impedance matching properties, all of which depend upon the intrinsic crystal structure and the
electronic and magnetic orientations as well as the size of the resulting particles and the absorber
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thickness. Any variation in any of these factors can be used to tune the microwave absorption
and to vary its bandwidth and effectiveness [66]. Because of the resonance phenomenon, a
vortex appears at 1GHz for pure ZnFe2O4. This vortex is indicative of microwave absorbance
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and characterizes the consumption of microwave irradiated on magnetic/dielectric nanohybrid,
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due to which eddy currents are converted in heat losses at any particular frequency. With an
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increase in the graphene content of the samples, no particular absorbance peak appears in the
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frequency region studied, and the reflection loss reduces with increasing graphene content (a
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reflection loss of -10dB corresponding to 90% loss of incident power). However, this decreasing
trend of reflection loss shows not only the onset of the vortex but also indicates that we can tune
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the threshold frequency by using the amount of graphene loading and adjusting other factors,
such as the size of the filler particles and the specific surface area.
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Figure 10a shows the dielectric constant at room temperature of the pristine Zn-(FeO2)2 and
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functionalized graphene sample at room temperature in the frequency range from 100Hz to
1MHz. The relations characterizing these parameters are discussed elsewhere [57, 67, 68].
It is evident from figure 10a that the dielectric constant increased with increasing graphene
concentration in the samples, while it decreased with increasing frequency. Figure 10(b-c) shows
that dielectric loss decreased ,while the ac conductivity increased with increasing concentration
of graphene from 0%-25%. Because the major mechanism responsible for ferrites is the charge
hopping between Fe2+ and Fe3+ ions at the octahedral lattice sites, this correlation between the
increased polarization and the conduction process can be explained by the local displacement
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caused by charge movement [69]. Graphene (rGO) consist of an sp2 hybridized, hexagonal lattice
of carbon atoms, which may contain certain defects induced either during the deoxygenating
process or due to the presence of sparsely populated oxygenated islands that are somehow left
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behind during reduction. Thus, the main conduction that occur in these rGO sheets is due to 2D
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variable range hopping involving conductive carbon sheets with defects islands, while with the
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increase in frequency, the relaxation process of the molecular species causes the dielectric
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constant to decrease. With the increase in the graphene content, the charge content increased,
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causing an increase in polarization due to their drift under the applied field; as a result, the
dielectric constant increased and remained high in high graphene content samples because the
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high density of charges causes increased charge accumulation, thereby increasing the interfacial
polarization. The dielectric loss follows the same dispersion behavior as that of the dielectric
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constant. The origin of the dielectric constant can partly be explained using Maxwell Wagner
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theories, which address a heterogeneously arranged dielectric structure [69, 70]. Because ferrite
relatively less conducive grains boundaries, the grain boundary behavior is the major factor at
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low frequencies, while the grain response becomes more effective at higher frequencies, enabling
us to correlate the decrease in the dielectric permittivity and loss with the increasing reversal rate
Figure 10d shows the temperature dependence of the ZnFe2O4-G25% with temperature. This
trend indicates that there is a major transition from semiconductor to metallic behavior at the
temperature of 380K [73]. As the temperature increases, the conductivity increased, with an
increase in temperature and decreased in frequency, which is a very unusual trend in ferrite based
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semiconductor systems. With the increase in temperature, the conductivity follows a state
Electrical conductivity of ferrite based nano systems are often related with semiconductor
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behavior [74]. The ac conductivity of ZnFe2O4 increases with increase in frequency which is
explained based upon the grain and grain boundary activation and their relative contribution
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towards the overall conductivity of ferrites as explained earlier. The case of semiconductor to
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metallic transition has recently been reported in some ferrites nano structured systems [73, 75,
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76]. In case of semiconductor behavior with temperature, the ac conductivity decreases with
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increases in frequency and when the conductivity behavior overlaps that of the metallic behavior,
the conductivity decreases with increase in frequency over and above a certain transition
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temperature. In case of our sample of ZnFe2O4 with 25 % graphene, the ac conductivity follows
the typical behavior of semiconductor nature as depicted by data curves in Fig. 10c and as the
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temperature increases, above the room temperature, the nature of curves reverses and it shows
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the decreasing trend with increases in temperature which is typical to metallic behaviour. This
frequency dependence at low temperature follows the Jonscher power law. At higher
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temperatures, since the charge transfer process increases as the development of semi-elastic
properties makes the metal bonds mechanically soft and flexible for overlapping electronic
orbitals from functionalized graphene content and adjacent ions. Hence the delocalization of
electrons increases which causes the materials to show a reverse trend of electrical conductivity
This type of modification and alteration in the nature of the materials (semiconductor-to-metal
transition) at such a relatively low temperature indicates new directions for the manipulation of
these nanoceramics for sensing at a relatively low temperature. As shown recently in research on
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BiSe, a topological insulator [31], the metal to semiconductor transition can be induced by using
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4. Conclusion
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Zn-(FeO2)2-graphene nanocomposites were synthesized solvothermally by varying the graphene
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amount and were characterized. These functional material embedded sheets from solvothermal
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synthesis exhibit unique structural and morphological features, such as uniformity of shape and
dispersion, small particle size, well-reduced nanocomposite structure and leaf-like morphology.
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Microwave magneto-dielectric spectroscopy revealed the improved dielectric properties of these
nanocomposites. The energy absorption vortex was not visible in the range of frequency
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graphene percentage increased from 0% in the parent nanosystem to 25% in the highest
functionalized sample, along with the same trend in both the dielectric loss and the dielectric
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electrical behavior from the usual semiconductor-like nature at room temperature to a metallic
nature at 380K and remained metallic until 543K; the remarkable feature of this new smart
5. Acknowledgments
The authors thank Dr. N. M. Huang, Low-Dimensional Materials Research Center, University of
Malaya, Malaysia, for the useful discussions, Dr. Arshad Bhatti, Director Centre for Micro and
Nano Devices (CMND) COMSATS Islamabad for Raman anaysis, Mr. Albert V. Tamashausky,
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Director of Research, Asbury Carbons, USA for providing the various grades of flake graphite
for the initial study. The authors also acknowledge the financial support of the Higher Education
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References
S
[1] M.F. El-Kady, R.B. Kaner, Scalable fabrication of high-power graphene micro-supercapacitors for
flexible and on-chip energy storage, Nat Commun, 4 (2013) 1475.
NU
[2] K.S. Novoselov, V.I. Falko, L. Colombo, P.R. Gellert, M.G. Schwab, K. Kim, A roadmap for graphene,
Nature, 490 (2012) 192-200.
[3] H.Y. Mao, S. Laurent, W. Chen, O. Akhavan, M. Imani, A.A. Ashkarran, M. Mahmoudi, Graphene:
MA
Promises, Facts, Opportunities, and Challenges in Nanomedicine, Chem Rev, 113 (2013) 3407-3424.
[4] T.J. Echtermeyer, L. Britnell, P.K. Jasnos, A. Lombardo, R.V. Gorbachev, A.N. Grigorenko, A.K. Geim,
A.C. Ferrari, K.S. Novoselov, Strong plasmonic enhancement of photovoltage in graphene, Nat Commun,
2 (2011) 458.
ED
[5] N. Mahmood, C. Zhang, F. Liu, J. Zhu, Y. Hou, Hybrid of Co3Sn2@Co Nanoparticles and Nitrogen-
Doped Graphene as a Lithium Ion Battery Anode, Acs Nano, 7 (2013) 10307-10318.
[6] A.K. Mishra, S. Ramaprabhu, Carbon dioxide adsorption in graphene sheets, AIP advances, 1 (2011)
PT
032152
[7] W.B. Hu, C. Peng, W.J. Luo, M. Lv, X.M. Li, D. Li, Q. Huang, C.H. Fan, Graphene-Based Antibacterial
Paper, Acs Nano, 4 (2010) 4317-4323.
CE
[8] S. Yarga, K. Sertel, J.L. Volakis, Chiro-ferrites for low-loss magnetic photonic crystals, Antennas and
Propagation Society International Symposium, 2005 IEEE, 2005, pp. 208 vol. 202B.
[9] D.M. Jnaneshwara, D.N. Avadhani, B. Daruka Prasad, B.M. Nagabhushana, H. Nagabhushana, S.C.
Sharma, S.C. Prashantha, C. Shivakumara, Effect of zinc substitution on the nanocobalt ferrite powders
AC
for nanoelectronic devices, Journal of Alloys and Compounds, 587 (2014) 50-58.
[10] T.K. Indira, P.K. Lakshmi, Magnetic nanoparticles- A review, International Journal of pharmasuitical
sciences and nanotechnology, 3 (2010) 1035-1042.
[11] A.G. Roca, R. Costo, A.F. Rebolledo, S. Veintemillas-Verdaguer, P. Tartaj, T. Gonzalez-Carreno, M.P.
Morales, C.J. Serna, Progress in the preparation of magnetic nanoparticles for applications in
biomedicine, J Phys D Appl Phys, 42 (2009).
[12] V.B. Bregar, J. Lojk, V. Sustar, P. Veranic, M. Pavlin, Visualization of internalization of functionalized
cobalt ferrite nanoparticles and their intracellular fate, Int J Nanomed, 8 (2013) 919-931.
[13] M.S. Al-Qubaisi, A. Rasedee, M.H. Flaifel, S.H.J. Ahmad, S. Hussein-Al-Ali, M.Z. Hussein, E.E.M. Eid, Z.
Zainal, M. Saeed, M. Ilowefah, S. Fakurazi, N.M. Isa, M.E. El Zowalaty, Cytotoxicity of nickel zinc ferrite
nanoparticles on cancer cells of epithelial origin, Int J Nanomed, 8 (2013) 2497-2508.
[14] Y. Wang, Y. Shao, D.W. Matson, J. Li, Y. Lin, Nitrogen-doped graphene and its application in
electrochemical biosensing, ACS nano, 4 (2010) 1790-1798.
[15] L. Feng, Z. Liu, Graphene in biomedicine: opportunities and challenges, Nanomedicine, 6 (2011)
317-324.
[16] J.W. Chiou, S.C. Ray, S.I. Peng, C.H. Chuang, B.Y. Wang, H.M. Tsai, C.W. Pao, H.J. Lin, Y.C. Shao, Y.F.
Wang, S.C. Chen, W.F. Pong, Y.C. Yeh, C.W. Chen, L.C. Chen, K.H. Chen, M. Tsai, A. Kumar, A. Ganguli, P.
24
ACCEPTED MANUSCRIPT
T
[18] C. Xiang, P.J. Cox, A. Kukovecz, B. Genorio, D.P. Hashim, Z. Yan, Z. Peng, C.C. Hwang, G. Ruan, E.L.
IP
Samuel, P.M. Sudeep, Z. Konya, R. Vajtai, P.M. Ajayan, J.M. Tour, Functionalized low defect graphene
nanoribbons and polyurethane composite film for improved gas barrier and mechanical performances,
CR
Acs Nano, 7 (2013) 10380-10386.
[19] Y. Yang, L. Ren, C. Zhang, S. Huang, T. Liu, Facile fabrication of functionalized graphene sheets
(FGS)/ZnO nanocomposites with photocatalytic property, ACS applied materials & interfaces, 3 (2011)
2779-2785.
S
[20] D.V. Kosynkin, G. Ceriotti, K.C. Wilson, J.R. Lomeda, J.T. Scorsone, A.D. Patel, J.E. Friedheim, J.M.
NU
Tour, Graphene oxide as a high-performance fluid-loss-control additive in water-based drilling fluids,
ACS applied materials & interfaces, 4 (2012) 222-227.
[21] J.D. Roy-Mayhew, D.J. Bozym, C. Punckt, I.A. Aksay, Functionalized graphene as a catalytic counter
MA
electrode in dye-sensitized solar cells, Acs Nano, 4 (2010) 6203-6211.
[22] Y.S. Fu, X. Wang, Magnetically Separable ZnFe2O4-Graphene Catalyst and its High Photocatalytic
Performance under Visible Light Irradiation, Ind Eng Chem Res, 50 (2011) 7210-7218.
[23] H.L. Xu, H. Bi, R.B. Yang, Enhanced microwave absorption property of bowl-like Fe3O4 hollow
ED
25
ACCEPTED MANUSCRIPT
[35] A.C. Ferrari, Raman spectroscopy of graphene and graphite: Disorder, electron-phonon coupling,
doping and nonadiabatic effects, Solid State Commun, 143 (2007) 47-57.
[36] J.N. Tiwari, K. Nath, S. Kumar, R.N. Tiwari, K.C. Kemp, N.H. Le, D.H. Youn, J.S. Lee, K.S. Kim, Stable
platinum nanoclusters on genomic DNA-graphene oxide with a high oxygen reduction reaction activity,
Nature Communications, 4 (2013).
[37] K.S. Vasu, B. Chakraborty, S. Sampath, A.K. Sood, Probing top-gated field effect transistor of
T
reduced graphene oxide monolayer made by dielectrophoresis, Solid State Commun, 150 (2010) 1295-
IP
1298.
[38] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri, S. Piscanec, D. Jiang, K.S.
CR
Novoselov, S. Roth, A.K. Geim, Raman spectrum of graphene and graphene layers, Phys Rev Lett, 97
(2006).
[39] Z.W. Wang, D. Schiferl, Y.S. Zhao, H.S.C. O'Neill, High pressure Raman spectroscopy of spinel-type
ferrite ZnFe2O4, J Phys Chem Solids, 64 (2003) 2517-2523.
S
[40] Z.W. Wang, P. Lazor, S.K. Saxena, G. Artioli, High-pressure Raman spectroscopic study of spinel
NU
(ZnCr2O4), J Solid State Chem, 165 (2002) 165-170.
[41] M. Wang, Z.H. Ai, L.Z. Zhang, Generalized preparation of porous nanocrystalline ZnFe2O4
superstructures from zinc ferrioxalate precursor and its superparamagnetic property, J Phys Chem C,
MA
112 (2008) 13163-13170.
[42] L.B. Yang, Y. Zhang, W.D. Ruan, B. Zhao, W.Q. Xu, J.R. Lombardi, Improved surface-enhanced Raman
scattering properties of TiO2 nanoparticles by Zn dopant, J Raman Spectrosc, 41 (2010) 721-726.
[43] J.P. Singh, R.C. Srivastava, H.M. Agrawal, Optical Behaviour of Zinc Ferrite Nanoparticles, AIP
ED
graphene sheets as an anode material for lithium-ion batteries, Electrochim Acta, 55 (2010) 3909-3914.
[47] Y.X. Xu, H. Bai, G.W. Lu, C. Li, G.Q. Shi, Flexible graphene films via the filtration of water-soluble
noncovalent functionalized graphene sheets, J Am Chem Soc, 130 (2008) 5856-+.
AC
[48] S. Stankovich, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Synthesis and exfoliation of isocyanate-treated
graphene oxide nanoplatelets, Carbon, 44 (2006) 3342-3347.
[49] M. Thomas, K.C. George, Infrared and magnetic study of nanophase zinc ferrite, Indian J Pure Ap
Phy, 47 (2009) 81-86.
[50] M.M.K. Motlagh, A.A. Youzbashi, L. Sabaghzadeh, Synthesis and characterization of Nickel
hydroxide/oxide nanoparticles by the complexation-precipitation method, International Journal of the
Physical Sciences, 6 (2011) 6.
[51] K. Namratha, K. Byrappa, S. Rajesh, V.R. Rai, Hydrothermal and Solvothermal Syntheses, In situ
Surface Modification and Antioxidant Activity of Codoped Advanced ZnO Nanoparticles, Proccedings:
10th International Symposium on Supercritical Fluids, 1 (2013) 1-8.
[52] R. Frost, H.Y. Zhu, P. Wu, T. Bostrom, Synthesis of acicular goethite with surfactants, Mater Lett, 59
(2005) 2238-2241.
[53] F.E. Rasmussen, B. Geilman, M. Heschel, O. Hansen, A.M. Jorgensen, Development and
characterization of KOH resistant PECVD silicon nitride for microsystem applications, Electrochemical
Society Proceedings 1(2003) 218-229.
26
ACCEPTED MANUSCRIPT
[54] K.N. Harish, H.S.B. Naik, P.N.P. Kumar, R. Vishwanath, G.S.Y. Kumar, Optical and photocatalytic
properties of CdFe2O4 nanocatalysts: Potential application in water treatment under solar light
irradiation, Archives of Applied Science Research, 5 (2013) 42-51.
[55] A.M. Gama, M.C. Rezende, Complex permeability and permittivity variation of radar absorbing
materials based on MnZn ferrite in microwave frequencies, Materials Research, 16 (2013) 997-1001.
[56] U.C. Hasar, Unique permitivity determination of low loss dielectric materials from transmission
T
measurements at microwave frequencies, Progress In Electromagnetics Research, 107 (2010) 16.
IP
[57] S. Ameer, A. Maqsood, Powder synthesis and electrical, dielectric spectroscopic characterizatio nof
rare earth disilicates (D-Er2Si2O7): Transistor scaling-22nm or beyond, Solid State Commun, 152 (2012)
CR
1811-1816.
[58] Z. Yang, Y. Wan, G. Xiong, D. Li, Q. Li, C. Ma, R. Guo, H. Luo, Facile synthesis of ZnFe2O4/reduced
graphene oxide nanohybrids for enhanced microwave absorption properties, Mater. Res. Bull., 61 (2015)
292-297.
S
[59] Y. Li, R. Yi, A. Yan, L. Deng, K. Zhou, X. Liu, Facile synthesis and properties of ZnFe2O4 and
NU
ZnFe2O4/polypyrrole core-shell nanoparticles, Solid State Sci., 11 (2009) 1319-1324.
[60] S. Tyagi, P. Verma, H.B. Baskey, R.C. Agarwala, V. Agarwala, T.C. Shami, Microwave absorption study
of carbon nano tubes dispersed hard/soft ferrite nanocomposite, Ceram. Int., 38 (2012) 4561-4571.
MA
[61] S. Tyagi, H. Baskey, R. Agarwala, V. Agarwala, T. Shami, Synthesis and Characterization of
Microwave Absorbing SrFe12O19/ZnFe2O4 Nanocomposite, Trans. Indian Inst. Met., 64 (2011) 607-614.
[62] C. Wang, X.J. Han, P. Xu, X.L. Zhang, Y.C. Du, S.R. Hu, J.Y. Wang, X.H. Wang, The electromagnetic
property of chemically reduced graphene oxide and its application as microwave absorbing material,
ED
[64] F. Qin, C. Brosseau, Comment on "The electromagnetic property of chemically reduced graphene
oxide and its application as microwave absorbing material" [Appl. Phys. Lett. 98, 072906 (2011)], Appl
Phys Lett, 100 (2012).
CE
[65] C. Wang, X.J. Han, P. Xu, X.L. Zhang, Y.C. Du, S.R. Hu, J.Y. Wang, X.H. Wang, Response to "Comment
on 'The electromagnetic property of chemically reduced graphene oxide and its application as
microwave absorbing material'" [Appl. Phys. Lett. 100, 046101 (2012)], Appl Phys Lett, 100 (2012).
AC
[66] J.J. Fang, W.K. Zha, M. Kang, S.H. Lu, L. Cui, S.F. Li, Microwave absorption response of
nickel/graphene nanocomposites prepared by electrodeposition, J Mater Sci, 48 (2013) 8060-8067.
[67] S. Ameer, A. Faraz, A. Maqsood, N.M. Ahmad, Synthesis, structural, electrical, magnetic and
dielectric spectroscopic characterization of C-Er2Si2O7, Journal of Nano Research, 14 (2012) 85-98.
[68] S. Ameer, A. Maqsood, Electrical and Dielectric Spectroscopic Characterization of Polycrystalline
Dy2Si2O7, Key Engineering Materials Vols. 510-511, 510-511 (2012) 194-200.
[69] A. Faraz, A. Maqsood, N.M. Ahmad, F.Z. Rehman, S. Ameer, Mg0.50Cu0.5-xNixFe2O4 Spinel
Nanoferrites: Structural, Electrical, Magnetic and Y-K angle Studies, Journal of Nano Research 17 (2012)
99-114.
[70] C.A. Z. Yua, Maxwell–Wagner polarization in ceramic composites BaTiO3– (Ni0.3Zn0.7)Fe2.1O4, J
Appl Phys, 91 (2002) 794-797.
[71] S. Choudhury, M.A. Bhuiyan, S.M. Hoque, Effect of sintering temperature on apparent density and
transport properties of NiFe2O4: synthesized from nanosize powder of NiO and Fe2O3, International
Nano Letters, 1 (2011) 111-116.
[72] S.N. Anuar, Z. Zalita, R. Shamsudin, Effect of Different Weight Fraction on Dielectric Properties of
Barium Ferrite-Barium Titanate Composites, Journal of Physics: Conference Series 431 (2013) 012007.
27
ACCEPTED MANUSCRIPT
[73] R.N. Bhowmik, Observation of plastoferrite character and semiconductor to metal transition in soft
ferromagnetic Li0.5Mn0.5Fe2O4ferrite, Condensed Matter Materials Science, arXiv:1309.7956 (2013).
[74] N. Gandhi, K. Singh, A. Ohlan, D.P. Singh, S.K. Dhawan, Thermal, dielectric and microwave
absorption properties of polyaniline–CoFe2O4 nanocomposites, Composites Science and Technology, 71
(2011) 1754-1760.
[75] A. Pradeep, P. Priyadharsini, G. Chandrasekaran, Structural, magnetic and electrical properties of
T
nanocrystalline zinc ferrite, Journal of Alloys and Compounds, 509 (2011) 3917-3923.
IP
[76] A.u. Rahman, M.A. Rafiq, S. Karim, K. Maaz, M. Siddique, M.M. Hasan, Semiconductor to metallic
transition and polaron conduction in nanostructured cobalt ferrite, J. Phys. D: Appl. Phys., 44 (2011)
CR
165404.
[77] T. Sujatha, G.B. Devidas, T. Sankarappa, S.M. Hanagodimath, Dielectric and AC Conductivity Studies
in Alkali Doped Vanadophosphate Glasses, International Journal of Engineering Sciences, 2 (2013) 302-
309.
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Table 1. Sample designation scheme and their along with average particle sizes
Sample Name ZnFe2O4(%) Graphene(%C) Particle size(nm)
ZnFe2O4 100 -- 24
ZnFe2O4-G8% 92 08 26
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ZnFe2O4-G14% 86 14 25
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ZnFe2O4-G25% 75 25 27
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Figure Captions
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Figure 1. X-ray Diffraction analysis: (a) graphene oxide (inset shows the short range analysis of
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(001) peak), (b) Pristine ZnFe2O4 and (c) Zn-(FeO2)2 functionalized graphene samples with 8%,
14% and 25% graphene.
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Figure. 2 MicroRaman (a) Pristine ZnFe2O4, graphene oxide and graphite precursor and (b) Zn-
(FeO2)2 functionalized graphene samples with 8%, 14% and 25% graphene (rGO).
Figure 3. Scanning Electron Microscope images (a)-(d) graphene oxide sheets (e-h) ZnFe2O4
nanocrystals and ZnFe2O4-G8%, ZnFe2O4-G14%, ZnFe2O4-G25% samples and (i)-(l) Growth
morphology of ZnFe2O4 nanocrystals and ZnFe2O4-G25%
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Figure. 4 Transmission electron microscopic images (a)-(b) ZnFe2O4 nanocrystals and (c)-(d)
ZnFe2O4-G25%
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Figure 5. In situ functionalization of graphene
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Figure 6. X-ray photoelectron spectroscopic analysis of ZnFe2O4-G25% (a) full spectra (b) Zn
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2p, (c) Fe 2p, (d) O1s and (e) C1s
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Figure 7. Ultraviolet-Visible spectroscopy spectroscopic analysis
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Figure 9. Dielectric spectroscopy from 15MHz-3GHZ at room temperature (A) Real part, (B)
Imaginary part of relative permittivity, (C) Real part, (D) imaginary part of relative permeability,
(E) tan(F) tanm and (G) reflection loss
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Figure 10. Dielectric and electrical properties at room temperature (a) Dielectric constant, (b)
Dielectric loss, (c) AC conductivity and (d) temperature gradient dielectric spectroscopy of
ZnFe2O4-G25% sample
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Highlights
Zn-(FeO2)2 - graphene smart nano-composites were synthesized using a novel modified
solvothermal synthesis.
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The synthesized nano system exhibits marvelous leaf like microstructure.
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These nano composites shows improved magneto dielectric response.
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This engineered smart nano system shows phenomenological flipping from
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semiconductor like nature to metallic behavior.
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Graphical Abstract
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