Materials Science in Semiconductor Processing 135 (2021) 106130

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Transport properties, charge conduction mechanism and magnetic behavior

of La0.3Ca0.7MnO3:ZnO Nanocomposites
Neeta A. Bhammar a, Bhagyashree Udeshi a, Himanshu Dadhich a, Vidhi Dhokiya a,
Keval Gadani b, D. Venkateshwarlu a, R. Venkatesh c, V. Ganesan c, A.D. Joshi d, P.S. Solanki a, N.
A. Shah a, *
a
Department of Physics, Saurashtra University, Rajkot, 360005, Gujarat, India
b
Department of Physics, Indian Institute of Teacher Education, Gandhinagar, 382016, India
c
UGC–DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore, 452001, India
d
Department of Nanoscience and Advanced Materials, Saurashtra University, Rajkot, 360005, Gujarat, India

A R T I C L E I N F O A B S T R A C T

Keywords: Nanocomposites consist of ZnO and La0.3Ca0.7MnO3 (LCMO) nanoparticles, prepared by cost effective sol–gel
Transport method, have been studied for their transport and magnetoresistance (MR) behaviors. Different ZnO nano­
Charge conduction mechanism particles contents (weight ratio) were mixed with LCMO nanostructured manganite to understand the possible
Manganite
interactions between ZnO and LCMO nanoparticles. X–ray diffraction (XRD) measurement was performed for all
ZnO
Nanoparticles
composites and structural quality was verified by performing Rietveld refinements. Variation in an average
Nanocomposites crystallite size for LCMO and ZnO nanoparticles in different composites has been discussed. Temperature
dependent resistivity measurements under different applied magnetic fields suggest the semiconducting nature of
all nanocomposites under all applied magnetic fields. Mott type variable range hopping (VRH) mechanism has
been employed to understand the dependence of charge carrier localization in LCMO nanostructured manganite
lattice on the applied magnetic field and ZnO nanoparticles content within the nanocomposites. Observed MR
behavior has been understood under the influence of temperature and ZnO nanoparticles content in the context
of spin polarized tunneling (SPT) and magnetic field induced improved conduction across the manganite lattice.
Grain and grain boundary contributions to the MR behavior have been explained by using theoretical model fits
to obtained MR data at different temperatures for all studied LCMO:ZnO nanocomposites. Magnetic nature of
studied LCMO:ZnO nanocomposites has been understood by performing zero field cooled (ZFC) and field cooled
(FC) measurement protocols based magnetization and magnetic isotherms measurements that confirm the
coexisting magnetic phase in all studied nanocomposites. Magnetic nature has been understood on the basis of
weakening of zener double exchange (ZDE) mechanism within the magnetic lattice of LCMO manganite and
magnetic contribution from the free charge carriers within the ZnO clusters.

1. Introduction magnetic phase transition from ferromagnetic to paramagnetic (at

temperature TC) upon increase in temperature. They also show a large
Manganites are the members of ABO3 type perovskite family having change in resistance upon an increase in applied magnetic field, termed
interesting and attractive structural, optical, physical and chemical as MR behavior. MR may be positive or negative depending upon the
properties which can be useful for variety of applications on practical nature of the change in resistance either decrease in its value or increase
platform. This includes temperature sensors, magnetic field sensors, p–n in its value under application of magnetic field, respectively. ZDE
junction diodes, capacitors, field effect devices, magnetic tunnel junc­ mechanism has been employed to understand the conduction across the
tions, etc [1–6]. Mixed valent manganites are excellent candidates mixed valent manganite lattices [7,8]. Existence of a structural distor­
amongst the other phase transition oxides where they exhibit electronic tion inserts the strain in the manganite lattice thereby degrading the
phase transition from metal to insulator (at temperature TP) along with conduction across the lattice which can be understood on the basis of

* Corresponding author.
E-mail address: snikesh@yahoo.com (N.A. Shah).

https://doi.org/10.1016/j.mssp.2021.106130
Received 18 December 2020; Received in revised form 25 June 2021; Accepted 1 August 2021
1369-8001/© 2021 Published by Elsevier Ltd.
N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

Jahn–Teller (JT) effect [9,10]. electrode in field effect studies for different manganites in few hetero­
Mixed valent manganites have attracted attention of researchers and structures [35–38]. Das et al. [39] have observed an enhancement in MR
scientists since they exhibit complex characteristics such as charge due to addition of ZnO within the lattice of mixed valent manganite.
ordering, orbital ordering, spin ordering, phase separation scenario, Modifications in transport properties and enhancement in MR value has
phase segregation, phase coexistence, etc. Modifications and improve­ been reported for ZnO doped La0.67Ca0.33MnO3 manganite composites
ment in these physical phenomena can be coined through application of [40]. Kang et al. [41] have also studied nanocomposite films consist of
external parameters such as temperature, magnetic field, electric field, 50% (wt %) La0.7Sr0.3MnO3 manganite with 50% (wt %) ZnO.
artificial defects through ion irradiation, current, voltage, pressure, light By considering all these reports on high concentrated divalent doped
illumination, ion implantation, etc [11–16]. One of the easiest way to mixed valent manganites (R0.3A0.7MnO3; basically n–type semi­
modify the structure of mixed valent manganites and, hence, their conductor as well as electron doped manganite system) for their various
physical properties is to use dopant at A site or B site in R1–xAxMnO3 studies as well as conventional well studied R0.7A0.3MnO3 manganites
mixed valent manganites, where R is rare earth ion/s and A is dopant/s with ZnO in their composite forms, in the present study, transport and
such as divalent ion/s (Ca, Sr, Pb, Ba, etc), tetravalent ion/s (Ce, Th, etc) magnetotransport properties have been investigated for n–type ZnO
and/or monovalent ion/s (Na, K, etc) and x is the measure of doping incorporated n–type LCMO manganite nanocomposites. Most of the re­
level at R site in R1–xAxMnO3 system. Undoped RMnO3 manganites are ports on manganite and ZnO based composite studies deal with their
antiferromagnetic insulators. Also, for lower doping levels (x < ~0.15) main aim to enhance the MR values through the addition of ZnO within
in R1–xAxMnO3 system, manganites become insulators. Upon the use of the mixed valent manganites wherein only hole doped manganites have
divalent ion/s as dopant/s (between x ~ 0.15 to 0.40 in R1–xAxMnO3 been targeted for these studies [39,40]. To the best of our knowledge, till
system), mixed valent manganites become ferromagnetic metal through date, there does not exist any report on electron doped mixed valent
the transformation of manganese ions valence state from Mn+3 to Mn+4 manganite combined with nanostructured ZnO oxide prepared in its
in their lattices. This supports the ZDE mechanism across the Mn–O nanostructured form. In this context, present report explains an inter­
magnetic lattice of mixed valent manganites thereby enhances the esting effect of addition of ZnO nanoparticles on the modifications of
conduction and providing the ferromagnetism. For x ~0.50, mixed transport, magnetoresistive and magnetic properties of electron doped
valent manganites possess strong charge ordering state that makes mixed valent LCMO manganite nanoparticles. Combination of these two
mixed valent manganites antiferromagnetic insulator. For the higher oxides, which are n–type semiconductors, becomes interesting in their
contents of x > 0.50, physical states of these materials are represented powder composite form due to the fact that ZnO and LCMO provide
by respective phase diagrams in Refs. [17,18] due to fact that each drastically different energy states, magnetic states, electrical properties
physical property of mixed valent manganites is strongly dependent on and charge conduction mechanisms. As a consequence, one can identify
ionic radii of rare earth ion/s used and dopant ion/s employed in the the role of ZnO nanoparticles content within the lattice of LCMO
system [19,20]. nanoparticles in modifying the magnetic and transport properties of
For higher dopant level x ~0.70, mixed valent manganites become these electron doped manganite nanoparticles. In this context, present
electron doped in which content of Mn+4 is larger than Mn+3 and their study opens new possibilities of designing potential devices for their
properties are drastically modified [21–28]. Few reports exist on practical applications through band gap engineering and charge con­
R0.3A0.7MnO3 mixed valent manganites for their various studies duction processes across manganite lattice.
[21–28]. Auslender et al. [21] have reported weak ferromagnetic state
coexisting with paramagnetic state in La0.3Ca0.7MnO3 compound having 2. Experimental details
low temperature improved ferromagnetism. Sudyoadsuk et al. [22] have
studied resistivity behavior of La0.3Ca0.7Mn0.8Cr0.2O3 manganite com­ ZnO nanoparticles were synthesized by using low cost sol–gel tech­
pound and reported semiconducting behavior up to 300 K under zero nique wherein zinc acetate (make: Sigma–Aldrich; purity: 99.999%) was
and 5 T magnetic field. Calvet et al. [24] have investigated the low used as a starting material (i.e. precursor). Its solution was prepared
temperature resistivity minimum behavior of La0.3Sr0.7MnO3 nano­ using acetic acid and double distilled water (1:1 vol ratio) with its 0.3 M
–patterned thin films with thicknesses less than 30 nm and reported molarity. Solution was stirred at 90 ◦ C for 1 h till a clear transparent
electron–electron interaction as a conduction mechanism for minimum solution was obtained. Obtained gel state of the material was, then,
behavior at low temperature. Guo et al. [26] have performed resistivity dried at 150 ◦ C followed by calcination at 600 ◦ C for 12 h in high
measurements under different applied magnetic fields and found semi­ temperature muffle furnace (make: Therelek; model: TES–14). Well
conducting behavior for La0.3Sr0.7MnO3 manganite film from 150 to calcined powder was then sintered at 900 ◦ C for 12 h in its pellet form (in
350 K with reasonable reduction in resistivity upon increase in magnetic its disc shape with 10 mm diameter).
field up to 5 T. Similar semiconducting nature has been reported for LCMO manganite nanoparticles were also prepared using the same
Pr0.3Sr0.7MnO3 compound between the temperatures 140 and 300 K cost effective sol–gel method wherein lanthanum acetate (make: Sig­
[27]. Zhang et al. [28] have studied Gd0.7Ca0.3MnO3 manganite system ma–Aldrich; purity: 99.999%), calcium acetate (make: Sigma–Aldrich;
wherein observed semiconducting behavior has been governed through purity: 99.99%) and manganese acetate (make: Sigma–Aldrich; purity:
the VRH mechanism. 99.999%) were employed as starting precursors which were dissolved in
Other than dopant/s (such as monovalent, divalent, tetravalent, etc) double distilled water and acetic acid with the same volume ratio of 1:1.
in manganites, one can also consider the preparation of composites The solution was kept at 0.3 M with continuous stirring at 90 ◦ C for more
consist of manganites (as a one component) to modify the transport than 1 h till a clear transparent solution was obtained. The solution was,
properties and MR behaviors of these manganites. Reports already exist then, heated at 150 ◦ C followed by its calcination at 700 ◦ C for 12 h. Well
on the preparation and studies on powder and thin film composites calcined powder was pressed into pellet form with the disc diameter of
consist of manganite and metal oxide as components of composites 10 mm followed by its sintering at 1200 ◦ C for 24 h.
[29–33]. Few reports also exist on the studies on transport and mag­ Nanocomposites were prepared by mixing weight ratio of (i) LCMO:
netotransport properties of manganite and ZnO based thin film hetero­ ZnO = 100:0, (ii) LCMO:ZnO = 90:10, (iii) LCMO:ZnO = 80:20 and (iv)
structures and composites wherein ZnO serves as supporting oxide to LCMO:ZnO = 70:30 in a single sample form followed by their grinding
enhance physical properties of manganites for targeted practical appli­ for longer time. All these powders (i.e. mixtures of ZnO and LCMO) were
cations [2,5,34–41]. Some of these reports deal with ZnO and manganite pressed into pellet form with 10 mm disc diameter. All samples were,
based heterostructures wherein ZnO has been employed as n–type finally, sintered at 700 ◦ C for 12 h to provide proper strength to each
semiconducting electrode in p–n junctions for possible current–voltage sample pellet. Hereafter, samples (i) LCMO:ZnO = 100:0, (ii) LCMO:
characteristics [2,34,35,37,38]. ZnO has also been used as polarizable ZnO = 90:10, (iii) LCMO:ZnO = 80:20 and (iv) LCMO:ZnO = 70:30 will

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

be referred as Z0, LZ10, LZ20 and LZ30, respectively. content up to 20 wt % and reduction in these parameters and cell volume
To understand the structural behavior of the nanocomposites un­ for higher studied content of ZnO nanoparticles.
derstudy, XRD measurement was performed using Cu Kα X–ray source in To justify the variations in lattice parameters and cell volume with
X–ray diffractometer (make: Philips; model: PW 3040/60 X’Pert PRO). ZnO nanoparticles content, Rietveld refinements were carried out for all
The range of 2θ was kept between 20 and 80◦ for all nanocomposites. four studied nanocomposites using FULLPROF code program. Fig. 2
XRD patterns were analyzed by performing Rietveld refinements using shows the Rietveld refined XRD patterns of all studied nanocomposites:
FULLPROF code. Transport and MR properties were studied through the (a) Z0, (b) LZ10, (c) LZ20 and (d) LZ30. Refinements were performed by
performance of temperature and magnetic field dependent resistance using the line shape of the diffraction peaks, generated by modified
measurements using cryogenic based low temperature physical property Lorentzian function for, both, ZnO and LCMO phases, separately, for
measurement system (PPMS; make: Quantum Design) in the tempera­ each studied nanocomposite. It can be observed that dual phase added
ture ranges: 75–300 K under the field range of 0–13 T. Temperature and Rietveld refinements confirm the good quality structure (i.e. high
magnetic field dependent magnetization has been studied by performing structural purity) for all nanocomposites. Values of cell parameters, cell
ZFC and FC measurement protocols based temperature (15–300 K) volume, R–factors and goodness of fitting parameter for all LCMO:ZnO
dependent magnetization under 1 kOe fixed magnetic field and applied nanocomposites are listed in Table 1. It can be observed from Table 1
magnetic field (0 to + 1.5 T to 0 to – 1.5 T to 0) dependent magnetization that cell parameters and cell volume for LCMO orthorhombic phase
(M − H loop) at 15 and 300 K for all studied nanocomposites using the (with Pnma space group no. 62) get enhanced with increase in ZnO
vibrating sample magnetometer (VSM; make: cryogenics; model: nanoparticles content up to 20 wt % followed by reduction in their
J4330). values for 30 wt % ZnO based nanocomposite sample. For ZnO phase,
having hexagonal structure having P63mc space group no. 186, lattice
3. Results and discussion parameters and cell volume nonmonotonically get modified with in­
crease in ZnO wt %, i.e. values of parameters increase first up to LZ20
Fig. 1 shows the XRD patterns of all LCMO:ZnO nanocomposites then after decrease in LZ30 nanocomposite. By considering the Scher­
consist of different contents of ZnO nanoparticles within LCMO rer’s formula, eq. (1), one can state that crystallite size of LCMO nano­
manganite lattice. All peaks in these patterns are identified and indi­ particles or LCMO phase is found to be enhanced from Z0 to LZ30
cated by respective (hkl) parameters for both the phases (i.e. LCMO and nanocomposite however crystallite size of ZnO phase content in the
ZnO) present in the nanocomposites. ZnO nanoparticles were studied for nanocomposites gets reduced from LZ10 to LZ30 nanocomposites.
their structural aspects by performing XRD measurement (not shown Enhancement in LCMO crystallite size from Z0 to LZ30 can be ascribed
here) with an average crystallite size of ~23.14 nm [calculated using the to the agglomeration effect upon increase in ZnO nanoparticles content
Scherrer’s formula, eq. (1): within LCMO nanostructured manganite lattice. Reduction in ZnO
crystallite size can be attributed to the fine distribution of the particles
CS = 0.9 λ / B cosθ (1) within the LCMO nanostructured manganite lattice. LCMO manganite
crystals are larger than ZnO crystals thereby it hinders the possibility of
where λ is the X–ray wavelength used, B is the width of the XRD peak
agglomeration effect between two or more smaller ZnO crystallites, even
(only most intense peak was considered) and θ is the angle of reflection
upon increase in its content. Crystallite sizes of LCMO nanoparticles are
noted in the pattern]. From Fig. 1, it is clear that all nanocomposites
found to be ~25.23 nm (Z0), ~29.07 nm (LZ10), ~30.66 nm (LZ20) and
possess dual phase (of ZnO and LCMO) nature without any unwanted
~31.66 nm (LZ30) whereas crystallite sizes for ZnO nanoparticles are
impurity within the measurement range studied. However, dual phase
found to be ~30.10 nm, ~28.86 nm and ~28.25 nm for LZ10, LZ20 and
consists of ZnO hexagonal phase and LCMO orthorhombic phase within
LZ30 nanocomposites, respectively.
the studied 2θ range in each nanocomposite. Observed peaks of ZnO and
Fig. 3 shows the temperature dependent variation in resistivity under
LCMO get shifted toward lower 2θ upon increase in ZnO nanoparticles
zero magnetic field for LCMO:ZnO nanocomposites having different
content from 0 to 20 wt % followed by considerable enhancement in 2θ
contents of ZnO nanoparticles. It can be observed that resistivity de­
upon addition of 30 wt % ZnO nanoparticles within the LCMO nano­
creases with increase in temperature for all studied nanocomposites.
structured manganite lattice. This indicates that lattice parameters and
This suggests a semiconducting nature of all LCMO:ZnO nanocomposites
unit cell volume get enhanced with increase in ZnO nanoparticles
throughout the temperature range studied which can be ascribed to the
paramagnetic nature of the nanocomposites for the studied temperature
[21]. However, Auslender et al. [21] have reported that there exists
coexisting ferromagnetic state with the paramagnetic state due to
presence of pairs of Mn+3 and Mn+4 ions within the lattice of their
studied LCMO manganite. This provides comparatively lower resistivity
value than any pure insulator. In other words, there exists combination
or phase coexistence of ferromagnetic (metallic) phase and para­
magnetic (insulating/semiconducting) phase in the manganite lattice
[21]. Similar semiconducting behavior has been reported for different
R0.3A0.7MnO3 manganites [22,26–28]. Presently studied Z0 nano­
composite (i.e. pure LCMO manganite) exhibits maximum resistivity
~200 Ωcm which is lower than other reported La0.3Ca0.7Mn0.8Cr0.2O3
manganite [22] as well as Gd0.3Ca0.7MnO3 manganite [28]. This can be
ascribed to the doping of Cr employed by Sudyoadsuk et al. [22] and
smaller ionic size of Gd+3 ion (as compared to larger size of La+3) used
by Zhang et al. [28]. However, resistivity of Z0 nanocomposite (i.e. pure
LCMO manganite) (Fig. 3) is much higher than La0.3Sr0.7MnO3 thin film
[26] as well as Pr0.3Sr0.7MnO3 manganite compound [27] which can be
Fig. 1. XRD patterns of nanocomposites consist of ZnO and La0.3Ca0.7MnO3
manganite nanoparticles having different ZnO nanoparticles contents. Inset: An attributed to the larger Sr+2 ion employed for these reports than pres­
enhanced view of XRD patterns of most intense peaks of nanocomposites consist ently studied Ca+2 ion in LCMO manganite. Larger size of the Sr+2 ion as
of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles having different ZnO compared to Ca+2 ion supports the itinerant eg electrons to provide
nanoparticles contents. better conduction across the manganite lattice (through an

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Fig. 2. Rietveld refined XRD patterns of (a) Z0, (b) LZ10, (c) LZ20 and (d) LZ30 nanocomposites consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles.

Table 1
Values of lattice parameters, cell volume and R–Factors obtained from the
Rietveld refinements for XRD patterns (raw data) for nanocomposites consist of
ZnO and La0.3Ca0.7MnO3 manganite nanoparticles having different ZnO nano­
particles contents.
Parameters Z0 LZ10 LZ20 LZ30

a (Å) (LCMO) 5.3426 (2) 5.3557 (1) 5.3865 (4) 5.3742 (5)
a (Å) (ZnO) NA 3.2365 (3) 3.2369 (2) 3.2005 (1)
b (Å) (LCMO) 7.5465 (3) 7.5487 (2) 7.5520 (5) 7.5342 (6)
b (Å) (ZnO) NA 3.2365 (3) 3.2369 (2) 3.2005 (1)
c (Å) (LCMO) 5.3671 (6) 5.3747 (8) 5.3780 (7) 5.3270 (9)
c (Å) (ZnO) N.A. 5.1841 (1) 5.1858 (2) 5.1422 (5)
V (Å3) (LCMO) 216.390 217.291 218.526 215.691
V (Å3) (ZnO) N.A. 53.851 54.262 53.330
Bragg R–Factor 15.39 33.13 30.99 25.85
R– Factor 13.14 31.26 24.38 21.62
χ2 2.18 2.96 3.70 4.36

enhancement in the Mn–O–Mn bond angles in MnO6 octahedra) that

enhances the one electron bandwidth and reduces the resistivity of the
manganite. Upon increase in ZnO nanoparticles content from Z0 to Fig. 3. Temperature dependent resistivity under zero magnetic field for
nanocomposites consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles
LZ10, resistivity of the nanocomposite gets enhanced throughout the
having different ZnO nanoparticles contents.
temperature range studied. This can be understood as: when ZnO
nanoparticles are added within the LCMO nanostructured manganite
lattice, they occupy either the grain positions of LCMO or grain nonmagnetic or poor magnetic semiconductor in nature that adds its
boundary positions of LCMO. In both these cases, overall ZnO nano­ own resistivity to LZ10 nanocomposite thereby one can consider an
particles break the exchange interactions among the manganese ions enhancement in the resistivity of LZ10 upon addition of 10 wt % ZnO
thereby either weakens the ZDE mechanism (when occupying the po­ nanoparticles within 90 wt % LCMO nanostructured manganite lattice.
sitions within grains; which reduces the conduction across the manga­ Upon further increase in ZnO nanoparticles content, i.e. LZ20 and
nite lattice) or modifies the resistance of the grains when occupying their LZ30, resistivity of LCMO:ZnO nanocomposites gets suppressed from
positions across the boundaries. However, later possibility (occupation LZ10 nanocomposite. One can expect an enhancement in the resistivity
of grain boundary regions) can be intricate to consider at present due to for LZ20 and LZ30 nanocomposites due to weakening of ZDE mechanism
fact that, both, ZnO and LCMO nanoparticles are comparable in size and in the LCMO manganite lattice of respective nanocomposites. However,
thickness/size of the grain boundaries of LCMO manganite is too small this is not the case in present study since one can observe in Fig. 3 that
as compared to the size of the ZnO nanoparticles. In the regard of first resistivity gets suppressed from LZ10 to LZ20 and further reduced in
possibility (i.e. occupation of ZnO nanoparticles within grain regions of LZ30 nanocomposite. This suggests that a weakening of ZDE process
LCMO manganite), ZnO induced weakening of ZDE mechanism en­ (which is responsible for resistivity enhancement) is overcome by role of
hances the resistance of the LZ10 nanocomposite as compared to Z0 oxygen vacancies in the ZnO nanoparticle. ZnO nanoparticles possess
compound, as shown in Fig. 3. In addition, ZnO nanoparticles are also their reduced sizes in LZ20 (~28.86 nm) and LZ30 (~28.25 nm),

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

respectively, as compared to LZ10 nanocomposite case having ZnO CS is Fig. 4 shows the variation in resistivity with temperature under
~30.10 nm. Reduced size of ZnO granular structure possesses larger different applied magnetic fields up to 13 T for (a) Z0, (b) LZ10, (c) LZ20
defect density including oxygen vacancies [42,43]. Oxygen vacancies and (d) LZ30 nanocomposites. All samples possess semiconducting na­
act as electron donor in the ZnO nanoparticles lattices thereby enhances ture without any electronic phase transition (i.e. semiconducting to
the conduction across the lattices within nanocomposite structures of metallic state) upon application of a magnetic field up to 13 T which
LZ20 and LZ30. In this context, ZnO nanoparticles with reduced sizes suggests that strong magnetic field cannot transform the semiconducting
possess larger oxygen vacancies (as well as other defects inside their or insulating phase to metallic phase in any studied LCMO:ZnO nano­
lattices) thereby larger density of free charge carriers. This provides composite. For all studied nanocomposites, magnetic field mono­
excess conduction to the composites, instead of enhancement in re­ tonically suppresses the resistivity throughout the temperature range
sistivity through weakening of ZDE mechanism. In this regard, ZDE studied. This shows the presence of negative MR at all temperatures and
weakening process is overcome by oxygen vacancy induced enhance­ magnetic fields. Reduction in resistivity due to an applied magnetic field
ment in conduction thereby suppression in resistivity of LCMO:ZnO can be ascribed to the field induced reduction in the scattering of the
nanocomposites for LZ20 and LZ30 samples having higher ZnO nano­ charge carriers at the grain boundaries as well as field induced reduction
particles contents. In addition, nanostructured ZnO possesses larger in the magnetic disorder across the Mn–O magnetic lattice of LCMO
defect density including oxygen vacancies which improves the magnetic manganite [45,46]. Also, there exists considerable effect of magnetic
nature of ZnO nanoparticles [44]. There may be possibility of favorable field on the charge conduction across ZnO nanostructured phase which
magnetic exchange between the particles of LCMO (having ferromag­ also contributes to the reduction in resistivity upon increase in magnetic
netic phase coexisting with paramagnetic phase) and ZnO (having field [47], as shown in Fig. 4. To understand the charge conduction
considerable ferromagnetism at low temperatures) that encourages the mechanism, responsible for the semiconducting nature of all LCMO:ZnO
ferromagnetism in complete structure of nanocomposites of LZ20 and nanocomposites and its dependence on applied magnetic field, tem­
LZ30 samples having larger contents of ZnO nanoparticles. As a result, perature (range: 75–300 K) dependent resistivity has been fitted theo­
for higher ZnO nanoparticles content based LZ20 and LZ30 nano­ retically to Mott type VRH model, eq. (2) (as shown in Fig. 4 by black
composites, resistivity is expected to be reduced as compared to LZ10 lines):
nanocomposite, as shown in Fig. 3. One possibility of reduction in re­
sistivity from LZ10 to LZ30 can also be considered as: with increase in ρ (T) = ρo exp (To / T)1/4 (2)
ZnO nanoparticles content from LZ10 to LZ30, an average crystallite size where ρo is the residual resistivity and To is the characteristic temper­
of LCMO manganite nanoparticles gets enhanced from 29.07 nm (LZ10) ature that defines the degree of charge carrier localization. Another way
to 30.66 nm (LZ20) and 31.66 nm (LZ30) which suggests that grain to perform this theoretical fits is to plot ln (ρ) versus T− 1/4 followed by
boundary density in LCMO manganite lattice gets suppressed effectively. derivation of slope of straight line fits to this plot where slope is directly
As result, one can expect an improved conduction through LCMO proportional to, a characteristics temperature of charge carriers within
manganite lattice in higher ZnO content based nanocomposites since the manganite lattices understudy [48,49]. However, very few reports
grain boundaries are disordered in nature in the manganites that weaken exist on the use of direct formula, eq. (2), for fitting theoretically the
the ZDE mechanism across the lattice of LCMO manganite [19]. As a resistivity data through non–linear fitting process using Origin software
result, one can realize the improved ZDE mechanism in LCMO manga­ [37,46,50]. Both these fitting processes provide almost similar values of
nite lattices having larger grain sizes and lower density of grain characteristic temperatures. However, one can expect better perfection
boundaries (i.e. in the case of higher ZnO nanoparticles content based in deriving characteristic temperature (To) values using non–linear
nanocomposites). fitting process since it covers larger temperature range studied as well as

Fig. 4. Temperature dependent resistivity under different applied magnetic fields with theoretical fits using Mott type VRH model for (a) Z0, (b) LZ10, (c) LZ20 and
(d) LZ30 nanocomposites consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles.

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

it provides exact derivation of fitting parameters where slope process is from VRH model fits to resistivity data under different applied magnetic
an average mathematical exercise based process of fittings. As shown in fields for all studied nanocomposites are listed in Table 2. From Table 2
Fig. 4, one can state that resistivity of all studied nanocomposites follows and Fig. 5, one can realize a larger localization length (in K) of charge
the VRH model throughout the temperature range studied with negli­ carriers in the range of 107 K which is in accordance with reported
gibly small difference between the experimental and theoretical fitting values of To for different R0.3A0.7MnO3 mixed valent manganites [22,
lines under all applied magnetic fields. Variation in To, derived from the 28]. Variation in residual resistivity obtained from the fittings (as
theoretical fits of VRH model to experimental resistivity data (Fig. 4), tabulated in Table 2) can also be correlated with the effect of ZnO
with an applied magnetic field for all LCMO:ZnO nanocomposites is nanoparticles contents within LCMO manganite lattice with its effect of
shown in Fig. 5. To is found to decrease with increase in applied mag­ weakening of ZDE mechanism and contribution to conduction through
netic field for all LCMO:ZnO nanocomposites which can ascribed to the free charge carriers donated by oxygen vacancies within the ZnO
field induced reduction in the charge carrier localization length thereby nanoparticle lattice in different LCMO:ZnO nanocomposites understudy.
enhancement in the movement of charge carriers across the LCMO One can also realize an interesting role of an average crystallite size of
manganite lattice and, hence, reduction in the resistivity (with increase LCMO manganite in governing the values of To for all studied nano­
in applied magnetic field), as shown in Fig. 4. Upon addition of ZnO composites as: To [a characteristic temperature in eq. (2)] signifies an
nanoparticles within LCMO nanostructured manganite lattice, To gets average energy required to hop localized d electrons of Mn ions from one
enhanced from Z0 to LZ10 followed by reduction in its values from LZ10 site to another nearest site at a certain distance within a manganite
to LZ20 and further to LZ30 nanocomposite under each applied mag­ lattice. It is apparent that grain boundaries in manganite possesses
netic field employed. This can be understood as: upon addition of ZnO higher energy requirement to hop these localized charge carriers across
nanoparticles content with weight fraction of 10 wt % in LZ10, ZnO its lattice [51–53]. In this regard, presently studied nanocomposites with
nanoparticles agitates the charge carrier flow across the lattice of LZ10 lower contents of LCMO manganite possess higher average crystallite
nanocomposite as well as Mn–O–Mn magnetic lattice gets interrupted sizes thereby lower density of grain boundaries within the studied
due to removal of LCMO phase at the cost of addition of ZnO phase. As a nanocomposites. As a consequence, lower LCMO content based nano­
consequence, ZDE becomes weak in LCMO thereby ferromagnetic frac­ composites possess lower values of To as compared to higher LCMO
tion within LCMO manganite lattice in LZ10 nanocomposite gets sup­ content based nanocomposites, i.e. To decreases monotonically from
pressed (probably converted into paramagnetic state). In this regard, LZ10 to LZ30 under all applied magnetic fields.
charge carrier localization becomes larger under each applied magnetic To understand the magnetotransport properties of presently studied
field upon addition of 10 wt % ZnO nanoparticles within 90 wt % LCMO LCMO:ZnO nanocomposites, applied magnetic field (range: 0–13 T)
nanostructured manganite lattice. For higher ZnO nanoparticles con­ dependent resistance of all nanocomposites was recorded at 100, 200
tents (with weight fractions of 20 and 30 wt %) in LZ20 and LZ30 and 300 K. Using these isothermal resistance (i.e. resistivity), MR has
nanocomposites, ZnO nanoparticles possess lower average crystallite been estimated using the formula, eq. (3):
sizes where these smaller crystals consist of larger possible defect den­
sity including oxygen vacancies. These oxygen vacancies donate larger MR (%) = [{ρ (H) – ρ (0)} / ρ (0)] × 100 (3)
free charge carrier densities to the lattices of LCMO:ZnO nano­ where ρ (H) and ρ (0) are the values of resistivity recorded during
composites which take participation in the conduction across the lattices magnetotransport measurements (i.e. isothermal resistance measure­
of LZ20 and LZ30 nanocomposites. Due to higher addition of ZnO ments) under applied magnetic field and zero magnetic field, respec­
nanoparticles contents in LZ20 (i.e. 20 wt % ZnO) and LZ30 (i.e. 30 wt % tively. Fig. 6 shows the variation in MR with applied magnetic field at
ZnO), higher oxygen vacancy density gets generated thereby large 100, 200 and 300 K for (a) Z0, (b) LZ10, (c) LZ20 and (d) LZ30 nano­
number of free charge carriers take part into the conduction and, hence, composites. It is clear that all studied nanocomposites show negative
localization length gets suppressed from LZ10 to LZ20 followed by LZ30 MR, i.e. reduction in resistivity upon increase in applied magnetic field.
nanocomposite understudy (Fig. 5). Values of fitting parameters derived Also, observed negative MR increases monotonically with applied
magnetic field for each studied temperature and for all nanocomposites.
Overall MR increases with increase in applied magnetic field which can
be attributed to the field induced suppression in scattering of the charge
carriers and reduction in magnetic disorder across the Mn–O magnetic

Table 2
Values of studied magnetic fields, residual resistivity and charge carrier locali­
zation parameter (To) obtained from the Mott type VRH model fits for resistivity
data for nanocomposites consist of ZnO and La0.3Ca0.7MnO3 manganite nano­
particles having different ZnO nanoparticles contents.
Nanocomposite H (T) ρ0 (Ωcm) To (K) ( × 107) χ2
Z0 0 2.5487 02.15 1.32E–7
1 2.4873 01.89 3.02E–6
7 2.1257 01.54 0.01458
13 1.8952 01.21 3.58E–4
LZ10 0 8.2451 11.25 3.05E–6
1 –– –– ––
7 7.0198 09.49 0.00738
13 5.0298 08.15 0.00255
LZ20 0 5.2198 07.59 1.31E–7
1 4.2658 07.21 0.07404
7 3.8945 06.45 7.96E–7
13 3.1284 05.91 0.0101
Fig. 5. Variation in characteristic temperature To or charge carrier localization LZ30 0 3.2654 04.28 0.0521
To with applied magnetic field obtained from Mott type VRH model for nano­ 1 3.0158 03.27 0.06921
7 2.8971 02.87 4.01E–4
composites consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles having
13 2.5127 02.01 2.04E–5
different ZnO nanoparticles contents.

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

Fig. 6. Applied magnetic field dependent MR isotherms collected at 100, 200 and 300 K temperatures for (a) Z0, (b) LZ10, (c) LZ20 and (d) LZ30 nanocomposites
consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles.

lattice of LCMO nanostructured manganite [51–53]. For all LCMO:ZnO parameter B which justifies that MR at higher studied temperatures is
nanocomposites, maximum high field MR (under 13 T) is found at 100 K mainly governed by grains of LCMO as well as ZnO nanoparticles. At all
which gets suppressed monotonically with increase in temperature from studied temperatures for MR isotherms (i.e. 100, 200 and 300 K), MR
100 to 300 K. This suggests that present MR behavior is mainly governed gets enhanced from Z0 to LZ10 nanocomposite which can be attributed
by SPT process wherein spin polarization gets suppressed with increase to the field induced improved ZDE mechanism across the LCMO nano­
in temperature that results in the decrease in MR from 100 to 300 K, for structured manganite lattice (which gets weakened due to addition of
all studied nanocomposites [54–56]. Interestingly, it is observed that ZnO nanoparticles). Upon further increase in ZnO nanoparticles con­
MR at 100 K behavior crossover from its lower value (well below 3 T) to tents (i.e. 20 and 30 wt % in LZ20 and LZ30 nanocomposites, respec­
higher value as compared to 200 and 300 K MR behaviors for Z0, LZ10 tively), MR values (at all respective temperatures) get suppressed
and LZ20 nanocomposites. This low field high temperature MR value of slightly which can be ascribed to the improved conduction across the
the nanocomposites can be ascribed to the field induced modifications in nanocomposite lattices as well as reduced effect of magnetic field on the
the interactions between poor ferromagnetic ZnO and paramagnetic oxygen vacancy created free charge carriers in the same high ZnO
LCMO nanoparticles. Above 3 T applied magnetic field, role of grain nanoparticles content based nanocomposites.
boundary becomes dominant over this interactions and extrinsic MR To understand the magnetic properties of presently studied nano­
behavior can be realized by these three nanocomposites (i.e. Z0, LZ10 structured mixed valent LCMO manganite and its nanocomposites with
and LZ20). For LZ30 nanocomposite, no cross over can be observed different contents of ZnO nanoparticles, temperature dependent
which may be due to a dominant SPT mechanism throughout the mag­ magnetization was recorded under 1 kOe applied magnetic field using
netic field range studied. All MR isotherms have been fitted theoretically ZFC and FC measurement protocols for the temperature range between
using the formula, eq. (4): 15 and 300 K. Obtained magnetization behaviors (ZFC and FC curves)
for (a) Z0 (i.e. pure LCMO manganite nanoparticles), (b) LZ10 (with 10
MR (%) = A × exp (B × H) + C × H + D × Hm (4) wt % ZnO and 90 wt % LCMO nanocomposite), (c) LZ20 (with 20 wt %
where A is the initial resistivity response under first applied magnetic ZnO and 80 wt % LCMO nanocomposite) and (d) LZ30 (with 30 wt %
field value used for measurements, first exponential term deals with the ZnO and 70 wt % LCMO nanocomposite) are shown in Fig. 7. Reported
grain boundary contributions to the MR behavior, second and third magnetic behavior of pure LCMO electron doped mixed valent manga­
terms deal with the MR contribution from grain structures (i.e. core of nite [57–60] exhibits: (i) paramagnetic state well above ~ 260 K (i.e.
the grains) of LCMO nanostructured manganite lattice. In this formula, charge ordered temperature; TCO) (ii) charge ordered state between ~
small but considerable contributions from grains and grain boundaries 160 K (i.e. Néel’s temperature; TN), and ~260 K (i.e. TCO) (iii) antifer­
of ZnO nanoparticles are also involved at all temperatures and for the romagnetic state well below 160 K (i.e. TN), and (iv) weak ferromagnetic
three LCMO:ZnO nanocomposites, namely, LZ10, LZ20 and LZ30. It can clusters coexisting with antiferromagnetic and charge ordered states at
be observed that at all temperatures for all four nanocomposites, above low temperatures well below ~ 250 K. This clearly suggests that pres­
formula (that differentiates the grain boundary and grain contributions ently studied LCMO electron doped mixed valent manganite sample
for MR) fits well throughout the magnetic field range studied, as shown consists of a complex magnetic (spin) orderings where orderings of spins
in Fig. 6. At 100 K, parameters B is larger than parameters C and D for all are strongly governed by the temperature within the studied manganite
studied nanocomposites which suggests that grain boundaries lattice. However, all these samples were prepared in their poly­
contribute more effectively to MR for all studied nanocomposites. At 200 crystalline bulk form using conventional solid state reaction route [21,
and 300 K, parameters C and D are dominant over the value of 22,28,57]. Presently studied nanostructured LCMO electron doped
mixed valent manganite sample was synthesized by low cost sol–gel

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

Fig. 7. Temperature dependent variation in magnetic moment recorded during FZC and FC measurement protocols performed under 1 kOe magnetic field for (a) Z0,
(b) LZ10, (c) LZ20 and (d) LZ30 nanocomposites consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles.

method and possesses smaller sized crystallites (with an average size of possesses paramagnetic state well above 300 K, similar to pure LCMO (i.
~25.23 nm) at nanoscale level. Due to nanostructured phase of targeted e. Z0) sample, (ii) an effective irreversibility gets started at TIR ~ 228 K,
LCMO manganite, this sample possesses large number of crystal which is considerably higher than pure Z0 sample. Presence of higher
boundaries and various defects and disorder including oxygen vacancies TIR in LZ10 nanocomposite can be ascribed to the fact that addition of
within its lattice. All these defects and oxygen vacancies act as free ZnO nanoparticles within LCMO manganite nanoparticles creates an
charge carrier donors. As a result, magnetic behavior of presently effective coexisting magnetic phase based clusters having paramagnetic
studied LCMO manganite can be found completely different than other or poor ferromagnetic ZnO clusters along with paramagnetic LCMO
reported magnetic behavior in different studies [21,22,28]. Magnetic manganite clusters, (iii) upon decrease in temperature from 228 K to 15
behavior of studied pure LCMO electron doped mixed valent manganite K, magnetic moment recorded during FC measurement protocol gets
can be explained as: (i) present LCMO nanoparticles possess para­ enhanced monotonically whereas magnetic moment recorded during
magnetic state well above 300 K, as depicted from Fig. 7 (a), (ii) one can ZFC measurement protocol gets suppressed continuously. This indicates
observe from these plots of ZFC and FC behaviors in Fig. 7 (a) for pure that thermal fluctuations and thermal agitation within the spin order­
LCMO sample that it possesses large irreversibility, which gets started at ings get suppressed during FC protocol whereas ZFC based results sug­
temperature TIR ~ 211 K, between ZFC and FC curves which can be gest an improved phase coexistence and freezing effect within the LZ10
ascribed to the presence of magnetic clusters, (iii) below TIR at ~ 211 K nanocomposite lattice [52], (iv) ZFC curve indicates that there exists
for pure LCMO manganite sample, one can observe an enhancement in, small amount of antiferromagnetic state (well below ~ 211 K from
both, ZFC and FC based magnetic moments up to the lowest employed where magnetic moment during ZFC protocol starts to decrease with
temperature of 15 K which can be attributed to the suppression in spin decrease in temperature towards 15 K) within the LZ10 lattice which
fluctuations and thermal agitation upon decrease in temperature, (iv) may be created due to magnetic interactions between ZnO and LCMO
unlike to reported magnetic behaviors of LCMO polycrystalline bulk nanoparticles, (v) overall magnetic moments of, both, ZFC and FC
compound [21,22,28], no confirmation of an existence of charge or­ magnetic behaviors for LZ10 nanocomposite are found to be smaller
dered state or antiferromagnetic state can be acquired from these plots than pure Z0 sample, i.e. LCMO manganite, which can be attributed to
of ZFC and FC for pure LCMO manganite, which validates that high the role of paramagnetic or poor ferromagnetic ZnO nanoparticles that
temperature paramagnetic state gets converted into the low temperature weaken the possible ZDE mechanism between Mn+3 and Mn+4 ions
magnetic clusters that consist of ferromagnetic spin ordering upon across Mn–O–Mn magnetic lattice of LZ10 nanocomposite. This also
decrease in temperature, due to possible ZDE mechanism between Mn+3 supports to one’s belief that poor magnetic response (i.e. lower magnetic
and Mn+4 ions through oxygen ions across Mn–O–Mn magnetic lattice, moment) in LZ10 nanocomposite is an indication of coexisting phases of
(v) however, overall lower magnetic moment in this sample confirms the antiferromagnetic state (only below TIR), ferromagnetic state and
coexistence of paramagnetic and ferromagnetic clusters within a single paramagnetic state throughout the temperature range studied and (vi)
lattice of LCMO manganite throughout the temperature range studied one can realize from the reduction in magnetic moment during ZFC
and (vi) it is important to note that below TIR in LCMO sample, bifur­ protocol and monotonic enhancement in magnetic moment during FC
cation in ZFC and FC curves gets enhanced with decrease in temperature protocol for LZ10 nanocomposite that irreversibility below TIR ~ 228 K
which can be ascribed to the short range spin ordering of ferromagnetic becomes stronger in LZ10 nanocomposite as compared to pure LCMO
cluster type coexisting with paramagnetic clusters [52]. manganite which can be ascribed to the presence of coexisting magnetic
Upon addition of 10 wt % ZnO nanoparticles within 90 wt % LCMO states including paramagnetic LCMO clusters, ferromagnetic LCMO
manganite nanoparticles lattice, overall magnetic behavior [as shown in clusters and ZnO paramagnetic or poor ferromagnetic clusters within a
Fig. 7 (b)] gets modified due to change in LCMO crystallite size as well as single lattice of LZ10 nanocomposite.
possible magnetic interactions between ZnO and LCMO nanoparticles. Fig. 7 (c) shows the ZFC and FC curves for LZ20 nanocomposite
Following magnetic aspects can be highlighted from the magnetic where following aspects of magnetic behavior of the same can be
behavior of LZ10 nanocomposite [Fig. 7 (b)]: (i) LZ10 nanocomposite identified: (i) LZ20 also possesses paramagnetic state well above 300 K,

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

similar to Z0 and LZ10 samples, (ii) irreversibility can be identified from free charge carrier density within the clusters of ZnO nanoparticles
the separation between ZFC and FC curves at ~ 193 K which is much which support the magnetism in ZnO clusters and make them better
lower than LZ10 sample. This indicates reduction in magnetic disorder ferromagnetic in nature thereby improves overall magnetic moment for
in the LZ20 lattice. Reduction in the magnetic disorder can be under­ this nanocomposite and (vi) in addition to the higher magnetic moment
stood as: addition of ZnO nanoparticles (20 wt %) within 80 wt % LCMO in LZ30, this nanocomposite consists of a complex phase coexistence
nanoparticles lattice creates the considerably high coexisting magnetic consists of ferromagnetic clusters of ZnO (due to free charge carrier
clusters within the LZ20 lattice. (iii) as a result, one can expect an density), ferromagnetic LCMO (due to reduced thermal fluctuations and
enhancement in TIR as compared to Z0 and LZ10 samples. However, this thermal agitation effects) and paramagnetic LCMO and ZnO nano­
is not the case which can be due to fact that magnetic disorder due to particles at higher temperatures within the LZ30 lattice.
addition of ZnO nanoparticles gets overcome by free charge carriers One can correlate the magnetic moment of the studied LCMO:ZnO
(provided by nanoscale based ZnO particles and oxygen vacancies nanocomposites with the resistivity behavior of the same as: from pure
therein) within the LZ20 lattice. These free charge carriers improves the LCMO (i.e. Z0) to LZ10, resistivity of the nanocomposite gets enhanced
ferromagnetic nature of ZnO clusters and, hence, overall magnetic dis­ upon addition of 10 wt % ZnO nanoparticles within the 90 wt % LCMO
order gets suppressed and TIR shifts towards lower temperature ~193 K nanoparticles lattice. At the same state, magnetic moment gets sup­
in LZ20 lattice, (iv) similar to LZ10 nanocomposite, LZ20 nano­ pressed effectively. For the case of LZ20, resistivity values are found to
composite also exhibits an enhancement in magnetic moment for FC be lower in LZ20 (due to an effective role of free charge carriers)
protocol whereas ZFC protocol has initially enhancement in magnetic whereas magnetic moment of LZ20 gets continuously suppressed from
moment followed by reduction in it well below ~ 179 K which corre­ Z0 to LZ10 followed by reduction in LZ20 which can be ascribed to the
sponds to the temperature below which development of antiferromag­ fact that free charge carriers supports the conduction across a complete
netic clusters can be expected within the lattice of LZ20. However, this lattice of LZ20 thereby resistivity gets suppressed in LZ20 nano­
temperature is much lower than that for LZ10 nanocomposite, which composite, however these free charge carriers can modify only 20 wt %
can be due to an important role of free charge carriers (created through ZnO nanoparticles for their possible magnetic orderings. For higher ZnO
ZnO nanoparticles based oxygen vacancies) induced magnetic moment based LZ30 nanocomposites, both, conduction and magnetic moments
contribution to total magnetic moment of LZ20 nanocomposite, (v) get improved mainly due to smaller crystallite sized ZnO nanoparticles
although, there exists a strong role of free charge carriers within the thereby enhanced free charge carrier density within the LZ30 lattice. It is
lattice of LZ20 nanocomposite for improving magnetic nature of the expected to have an effective role of an average crystallite size of LCMO
same sample, overall magnetic moment is found to get suppressed in manganite nanoparticles in governing the magnetic properties of pres­
LZ20 as compared to LZ10 nanocomposite which can be due to fact that ently studied LCMO:ZnO nanocomposites. Since, an average crystallite
free charge carrier contribution to total magnetic moment (for ZnO size increases from 25.23 nm (Z0, i.e. pure LCMO manganite nano­
nanoparticles clusters) is overcome by weakening of ZDE mechanism particles) to 29.07 nm (LZ10), 30.66 (LZ20) and 31.66 nm (LZ30) with
within the magnetic clusters of LCMO manganite and (vi) observation of increase in ZnO nanoparticles contents, magnetic moment is found to
magnetic moment reduction in ZFC curve well below ~ 179 K and decrease from Z0 to LZ10 and further to LZ20 followed by an effective
monotonic enhancement in magnetic moment for FC curve in LZ20 enhancement in magnetic moment in LZ30 nanocomposite. This non­
nanocomposite strongly suggest that LZ20 nanocomposite consists of monotonic variation in magnetic moment of LCMO:ZnO nano­
antiferromagnetic clusters (below ~ 179 K) in coexistence with low composites with ZnO nanoparticles content can be understood on the
temperature ferromagnetic clusters of LCMO and ZnO and high tem­ basis of two possible mechanisms: (i) free charge carriers in ZnO
perature paramagnetic clusters of both these components of nano­ nanoparticles, created due to oxygen vacancies in the ZnO nanoparticles
composite understudy. lattice, get enhanced in number from Z0 to LZ30 (i.e. with increase in
Fig. 7 (d) depicts the magnetic moment dependence on temperature ZnO nanoparticles content). These free charge carriers provide their
recorded for, both, ZFC and FC protocols of measurements for LZ30 magnetic moment to total magnetic moment of studied nanocomposites.
nanocomposite. Following observations can be highlighted for the same: As a consequence, one can expect an enhancement in total magnetic
(i) similar to all other three studied samples, LZ30 also exhibits para­ moment of nanocomposites with increase in ZnO nanoparticles content
magnetic state well above 300 K, (ii) enhanced FC protocol based from Z0 to LZ30 and (ii) with increase in ZnO nanoparticles content from
magnetic moment across the LZ30 nanocomposite can be attributed to Z0 to LZ30, an average crystallite size of LCMO nanoparticles within the
the reduction in thermal fluctuations for the spins of the oxide sample nanocomposite lattice gets enhanced monotonically. As a result of which
understudy and reduced thermal agitation upon reduction in tempera­ one can expect a suppressed magnetization from Z0 (i.e. pure LCMO) to
ture towards 15 K, (iii) irreversibility between ZFC and FC curves can be LZ30. Strong but complex competition between these two processes/
identified at TIR ~ 173 K which suggests the presence of magnetic mechanisms based on an effect of an average crystallite size of LCMO
clusters consists of different magnetic/spin orderings within the LZ30 manganite and an effect of free charge carrier density in ZnO nano­
lattice. Value of TIR for LZ30 is found to be lower than all other three particles lattice, one can expect a nonmonotonic variation in magnetic
samples which can be ascribed to the presence of improved magnetic moment of studied nanocomposites with increase in ZnO nanoparticles
orders and comparatively reduced magnetic disorder in the lattice. This content (Fig. 7). In other words, from Z0 to LZ10 and LZ20 nano­
may be mainly due to improved free charge carrier density within ZnO composites, effective role of crystallite size can be considered as a
clusters and stronger effect of ZnO and LCMO magnetic interactions dominant process over the role of free charge carrier density however for
within the studied lattice of LZ30, (iv) monotonic increase in FC protocol LZ30 nanocomposite, dominant role of free charge carrier density can be
based magnetic moment and reduction in ZFC protocol based magnetic considered as an effective mechanism. This can be expected since
moment (well below TIR) upon decrease in temperature towards 15 K maximum possible free charge carrier density is possessed by LZ30
can be ascribed to the creation of small amount of antiferromagnetic nanocomposite sample since it has higher ZnO nanoparticle content
clusters well below TIR and improved coexisting ferromagnetic clusters among all other three samples understudy.
within the LZ30 lattice, (v) although, added content of ZnO nano­ Fig. 8 shows the variation in inverse susceptibility with temperature
particles within the LCMO nanoparticles lattice is highest among all for (a) Z0 (i.e. pure LCMO manganite), (b) LZ10, (c) LZ20 and (d) LZ30
other samples, this LZ30 nanocomposite exhibits higher magnetic nanocomposites. Linear fits have been performed for the linear regions
moment recorded during, both, ZFC and FC protocols performed which in these plots using the Curie–Weiss law for all studied nanocomposites
can be understood on the basis of the smallest crystallite size of ZnO as eq. (5):
nanoparticles in LZ30 lattice, as compared to other two nanocomposites
χ = C / (T – θP) (5)
with lower ZnO contents. Smaller size of crystallites can provide higher

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

Fig. 8. Variation in inverse susceptibility with temperature having straight line fits using Curie–Weiss law for (a) Z0, (b) LZ10, (c) LZ20 and (d) LZ30 nanocomposites
consist of ZnO and La0.3Ca0.7MnO3 manganite nanoparticles.

where C is the Curie constant and θP is the paramagnetic Curie–Weiss To understand the magnetic isotherms at low and high temperatures,
temperature. Linear fits to χ− 1 vs. T plots suggest that pure LCMO applied magnetic field dependent magnetic moment (i.e. magnetic iso­
nanoparticles exhibit θP ~67 K which gets enhanced to ~198 K for LZ10 therms) were recorded at (a) 15 K and (b) 300 K for all studied LCMO:
nanocomposite. Enhancement in the Curie–Weiss temperature from ZnO nanocomposites, as shown in Fig. 9. One can observe that magne­
~67 K to ~198 K upon addition of ZnO nanoparticles can be ascribed to tization (i.e. magnetic moment) increases monotonically with increase
the improved free charge carriers within the ZnO nanoparticles based in applied magnetic field for both the studied temperature for all studied
clusters. Further increase in ZnO nanoparticles content from 10 wt % for nanocomposites. No saturation can be observed for any magnetic
LZ10 to 20 wt % for LZ20, value of Curie–Weiss temperature gets further isotherm curve up to 1.5 T applied magnetic field which can be ascribed
enhanced which can be again ascribed to the more number of free to the lack of complete ferromagnetic state in the nanocomposites un­
charge carriers within the clusters of ZnO nanoparticles. However, for derstudy. This observation confirms the phase coexisting nature (i.e.
higher ZnO content based LCMO:ZnO nanocomposite (i.e. LZ30), this coexisting paramagnetic, ferromagnetic and antiferromagnetic phases)
temperature gets shifted towards lower temperature which can be of all studied nanocomposites, as discussed from ZFC and FC protocols
ascribed to the weakening of ZDE mechanism between Mn+3 and Mn+4 based magnetic behaviors of the same. Small M − H loop observed at 15
ions of manganese through oxygen ions within Mn–O–Mn magnetic K for all studied nanocomposites suggest presence of weak ferromag­
lattice due to addition of ZnO nanoparticles and, hence, reduction in netism at this temperature for all studied nanocomposites. At 300 K, no
total possible number of pairs of these manganese ions. It is necessary to effective M − H loop can be observed from Fig. 9 (b) for any studied
highlight here that ZDE weakening is overcome by free charge carrier nanocomposite which strongly suggests that each nanocomposite pos­
density based enhancement in magnetic ordering within the ZnO clus­ sesses dominant paramagnetic state at 300 K. Importantly, one can
ters for LZ10 and LZ20 nanocomposites whereas charge carrier density notice that magnetic moment at 15 K gets suppressed from pure LCMO
based enhancement in magnetic ordering within ZnO nanoparticles is nanoparticles sample (i.e. Z0) to LZ10 followed by further reduction in
overcome by ZDE weakening effect in LZ30 nanocomposite. In addition, magnetic moment in LZ20 sample. This can be ascribed to the poor
all studied LCMO:ZnO nanocomposites exhibit positive sign for Curi­ magnetic interactions between ZnO and LCMO nanoparticles and ZnO
e–Weiss temperature which indicates that all nanocomposites possess nanoparticles induced weakening of ZDE mechanism that suppress the
ferromagnetic ordering of spins at low temperatures. magnetic moment in LZ10 and furthermore in LZ20 nanocomposites, as

Fig. 9. Applied magnetic field dependent magnetic moment (magnetic isotherms) recorded at (a) 15 K and (b) 300 K for nanocomposites consist of ZnO and
La0.3Ca0.7MnO3 manganite nanoparticles having different ZnO nanoparticles contents.

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N.A. Bhammar et al. Materials Science in Semiconductor Processing 135 (2021) 106130

shown in Fig. 9 (a). For higher ZnO nanoparticles based LCMO:ZnO coexistence in the lattices of LCMO:ZnO nanocomposites. Interesting
nanocomposite, i.e. LZ30, magnetic moment is found to be enhanced, as role of weakening of ZDE mechanism and free charge carriers based
compared to LZ20 which can be attributed to the free charge carriers contribution to the magnetism in the nanocomposites has been discussed
induced magnetic moment within the ZnO nanoparticles based clusters in detail. Magnetic isotherms have been understood on the bases of role
where ZnO nanoparticles in LZ30 nanocomposite possess lowest crys­ of magnetic interactions between ZnO and LCMO nanoparticles, weak­
tallite size among all studied nanocomposites. For higher temperature ening of ZDE mechanism within the LCMO manganite lattice and free
magnetic isotherms at 300 K, magnetic moment is found to increase charge carriers based magnetic contribution within the ZnO nano­
monotonically with increase in ZnO nanoparticles content from Z0 (i.e. particles clusters.
LCMO nanoparticles) to LZ10, LZ20 and LZ30 nanocomposites. This can
be understood as: with increase in ZnO nanoparticles content from Z0 to Author statement
LZ30, size of the ZnO nanoparticles gets suppressed monotonically
which provides more free charge carrier density in the nanocomposites All persons who meet authorship criteria are listed as authors, and all
having higher ZnO nanoparticles contents. These free charge carriers authors certify that they have participated sufficiently in the work to
contribute effectively to the total magnetic moment of the nano­ take public responsibility for the content, including participation in the
composites where pure LCMO content of the nanocomposites is para­ concept, design, analysis, writing, or revision of the manuscript.
magnetic in nature that does not contribute effectively to the total Furthermore, each author certifies that this material or similar material
magnetic moment of the nanocomposites. One can also notice that at has not been and will not be submitted to or published in any other
300 K, recorded magnetic moments are almost similar to the magnetic publication before its appearance in the Materials Science in Semi­
moments recorded at 15 K which clearly confirms that magnetic mo­ conductor Processing.
ments in the studied nanocomposites are mainly supported by the free
charge carriers and their contribution to the magnetic behavior of Author contribution
nanocomposites.
Category 1: Conception and Design of Study: Neeta A. Bhammar,
4. Conclusion Bhagyashree Udeshi, A.D. Joshi, P.S. Solanki, N.A. Shah. Category 1:
Acquisition of Data: Neeta A. Bhammar, Bhagyashree Udeshi, Himanshu
In conclusion, LCMO:ZnO nanocomposites were successfully pre­ Dadhich, R. Venkatesh, V. Ganesan. Category 1: Analysis and/or Inter­
pared by employing low cost and easy sol–gel method. Different con­ pretation of Data: Neeta A. Bhammar, Bhagyashree Udeshi, Himanshu
tents of ZnO nanoparticles were added within the LCMO nanostructured Dadhich, P.S. Solanki, N.A. Shah. Category 2: Drafting the Manuscript:
manganite lattice to understand the effect of ZnO nanoparticles content Neeta A. Bhammar, Vidhi Dhokiya, Keval Gadani, D. Venkateshwarlu, A.
on the structural, transport, MR and magnetic behaviors at different D. Joshi. Category 2: Revising the Manuscript Critically for Important
temperatures under different applied magnetic fields. XRD patterns and Intellectual Content: N.A. Shah, P.S. Solanki. Category 3: Approval of
their Rietveld refinements confirm the dual phase nature of all nano­ the Version of the Manuscript to be Published: Neeta A. Bhammar,
composites without presence of any unwanted impurity phase (other Bhagyashree Udeshi, Himanshu Dadhich, Vidhi Dhokiya, Keval Gadani,
than ZnO and LCMO). In nanocomposites, ZnO nanoparticles with D. Venkateshwarlu, R. Venkatesh, V. Ganesan, A.D. Joshi, P.S. Solanki,
hexagonal structure and LCMO nanoparticles with orthorhombic struc­ N.A. Shah.
ture remain structurally and chemically separated. Average crystallite
size of LCMO phase in nanocomposites is found to increase with increase
in ZnO nanoparticles content whereas ZnO phase possesses reduced Declaration of competing interest
average size of crystallites for higher ZnO nanoparticles content based
LCMO:ZnO nanocomposites. Resistivity behavior under different The authors declare that they have no known competing financial
applied magnetic fields show semiconducting nature for all studied interests or personal relationships that could have appeared to influence
magnetic fields as well as for all nanocomposites due to strong para­ the work reported in this paper.
magnetic nature of the LCMO wherein ferromagnetic clusters are phase
coexisting due to ZDE mechanism. Resistivity is found to increase for the Acknowledgement
addition of 10 wt % ZnO nanoparticles within LCMO nanostructured
manganite lattice whereas for higher ZnO nanoparticles contents (i.e. 20 Authors are thankful to Department of Science and Technology
and 30 wt %), it gets reduced which has been understood on the basis of (DST), New Delhi, India for the financial support in the form of Vibrating
weakening of ZDE mechanism and creation of free charge carriers Sample Magnetometer (VSM) set–up under DST–FIST Phase II grant at
through oxygen vacancies within ZnO phase. Magnetic field suppresses Saurashtra University, Rajkot, India.
the resistivity that suggests an existence of negative MR which has been
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