Semiconductor-to-Metallic Flipping in a ZnFe 2 O4 - graphene based Smart
Nano System: Temperature/Microwave Magneto-Dielectric Spectroscopy

Shahid Ameer, Iftikhar Hussain Gul, Nasir Mahmood, Muhammad Mu-

jahid

PII: S1044-5803(14)00358-1
DOI: doi: 10.1016/j.matchar.2014.11.018
Reference: MTL 7738

To appear in: Materials Characterization

Received date: 19 July 2014

Revised date: 3 November 2014
Accepted date: 15 November 2014

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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 ACCEPTED MANUSCRIPT

Semiconductor-to-Metallic Flipping in a ZnFe2O4 - graphene based Smart

Nano System: Temperature/Microwave Magneto-Dielectric Spectroscopy

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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

solvothermal synthesis with different percentages of graphene. The structure of the

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nanocomposite was confirmed through X-ray diffraction, Micro-Raman scattering spectroscopy,

Ultraviolet-Visible spectroscopy, and Fourier Transform Infrared spectroscopy. The structural

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growth and morphological aspects were analyzed using scanning/transmission electron

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microscopy, revealing marvelous micro-structural features of the assembled nano-system

resembling a maple leaf. To determine the composition, Energy Dispersive Spectroscopy and X-
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ray photoelectron spectroscopy were used. Microwave Magneto-Dielectric spectroscopy

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

permittivity increased at room temperature. This extraordinary switching capability of the

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functionalized graphene nanosystem opens up a new dimension for engineering advanced and

efficient smart composite materials.

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-based systems to further enhance the performance of nano-devices and nano-systems.

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

electronic and magnetic sensitivity [10-13].

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The flexibility in the tailoring of the characteristics of graphene, such as in chemical,

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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its formation by controlling its structural modifications[29]. Therefore, the flexibility of

graphene in terms of its structural manipulation along with magnetic inclusions provide a new

dimension to engineer nano-devices with improved functionality; such engineered functionality

can address the need for smart materials and systems that provide unique functional responses,

such as super insulators [30], topological insulators [31], or even room-temperature

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

according to changing conditions to maximize efficiency in the ever-miniaturizing hybrid

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

to graphene sheets, exhibited an extraordinary transition of the nanosystem from a

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

nano-electronics to address specific technological needs.

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)

using centrifugation at 13,500 × g. The graphite-oxide-HCl suspension was then washed

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

work regarding the nano-composite synthesis.

2.3 Synthesis of pristine ferrite nanocrystals and Zn-(FeO2)2 - graphene

composite:

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Graphene–Zn-(FeO2)2 nano-composites were synthesized using the solvothermal approach

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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Diffractometer using Cu-Kradiation, MicroRaman (Horiba LabRam, 512nm),

ULTRAVIOLET-Visible spectroscopy (Perkin Elmer Lambda 950 UV/Vis/NIR) over the

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

diffraction and micro-Raman analysis; for FTIR spectroscopy and ULTRAVIOLET-Vis

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

microwave magneto-dielectric spectroscopy apparatus with torus-shaped material samples

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prepared with an inner diameter of 3.1mm and outer diameter of 7mm.
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3. Results and Discussions:

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3.1 X-ray diffraction studies:

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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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pattern of zinc-ferrite nanocrystals and Zn-(FeO2)2 - graphene nanocomposites with different

graphene loadings, as presented in Table 1.

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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3.2 Micro-Raman Analysis:

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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

order of 1, which agrees well with the literature [34, 35].

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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

octahedral groups [39, 40].

3.3 Micro-structural Analysis:

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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

ZnFe2O4-G8%, ZnFe2O4-G14% and ZnFe2O4-G25% nanocomposite samples. It is clear from

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the images that the ZnFe2O4 nanocrystals are fully functionalized to graphene sheets and are

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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assembled pattern in all of the solvothermally synthesized nano-systems involving ZnFe2O4 is

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

GO reduction process under solvothermal conditions [22].

3.5 Ultraviolet-Visible and Fourier Transform Infrared analyses:

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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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from the 4s orbital [43-45].

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

approximately 1570cm-1corresponds to the deoxygenated carbon backbone [22].

3.6 Microwave Magneto-Dielectric Spectroscopy:

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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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εr = ε'- j ε'' (1)

tanδε = ε'' / ε' (2)

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μr = μ' - jμ'' (3)

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tanδm = ε'' / ε' (4)

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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

magnetic losses in Zn-(FeO2)2 functionalized graphene, so the electromagnetic

absorption/attenuation is largely dependent upon dielectric loss due to graphene incorporation

[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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the composite sample exhibits no considerable difference because graphene is nonmagnetic,

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

calculated from the expression below and are shown in Figure 8 g:

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Zin = tanh(j ) (5)

RL (in dB) =20log (6)

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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3.7 Temperature-Gradient Dielectric Spectroscopy and

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Phenomenological Semiconductor-to-Metal Flipping:

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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

nanocrystals are thought to consist primarily of conducting grains contributing separated by

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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

of the applied oscillation [71, 72].

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

reversal and follows the metallic behavior from 380 K to 543K.

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

verses frequency as compared to room temperature [73, 76].

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

laser-induced polarization. The observed temperature-induced electrical characteristics opens up

new application of these nanomaterials in nano-electronics [31, 32, 77].

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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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(15MHz– 3GHz) studied. Room temperature ac conductivity exhibited an increase as the

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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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permittivity. Temperature-gradient dielectric spectroscopy exhibited extraordinary flipping of its

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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

system can be utilized in developing novel applications, especially in nano-electronics.

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

Commission (HEC) of Pakistan that enabled this research work.

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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. 8 Fourier Transform Infrared 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) tanm 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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Fig. 2a
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Fig. 2b
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Fig. 3a-d
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Fig. 6a-2
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Fig. 10
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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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