RSC Advances

PAPER

Electrical and magnetic properties of the pulsed

laser deposited Ca doped LaMnO3 thin films on Si
Cite this: RSC Adv., 2015, 5, 69075
(100) and their electronic structures
Khalid Sultan,*a M. Ikram,*a Sanjeev Gautam,bc Han-Koo Lee,d Keun Hwa Chaeb
and K. Asokane

We report the effect of Ca doping on the structural, electrical, magnetic and electronic properties of
stoichiometric La1
xCaxMnO3 (x ¼ 0, 0.3, 0.5 and 0.7) (LCMO) thin films grown on Si (100) using a pulsed
laser deposition technique. All these films exhibit a single-phase orthorhombic structure with the space
group Pnma. Physical properties, such as surface roughness, grain size, Curie temperature ‘Tc’, activation
energy ‘Ea’ and magneto-resistance, were studied as a function of Ca doping. These properties were
correlated with the variation of the observed electrical transport and magnetic properties and their
Received 1st May 2015
Accepted 28th July 2015
electronic structures. The electronic structures of these films were studied by X-ray absorption
spectroscopy (XAS) at O K and at Mn L3,2-edges, which indicate an admixture of Mn2+, Mn3+, and Mn4+
DOI: 10.1039/c5ra08028b
ions and also an increase in the density of states with Ca doping. These mixed valence states of Mn ions
[Link]/advances in LCMO arise due to the doping of Ca in the La sites, which modifies the electrical and magnetic properties.

1. Introduction
a
Solid State Physics Lab, Department of Physics, National Institute of Technology,
Hazratbal, Srinagar, J & K-190006, India. E-mail: [Link]@[Link]; ikram@ Even aer ve decades of research, doping studies of divalent
[Link]; Tel: +91-8717000375 cations such as Ca ions in manganites still fascinate researchers
b
Advanced Analysis Center, Korea Institute of Science and Technology (KIST), Seoul as a result of the evolution of a complex phase diagram that
136-791, South Korea comprises a rich variety of crystallographic, magnetic, and
c
Dr S. S. Bhatnagar University Institute of Chemical Engineering and Technology (SSB electronic phases.1–3 These compounds exhibit a strong inter-
UICET), Panjab University, Chandigarh, 160-014, India
d
play between the spin, charge, orbital, and lattice degrees of
Beamline Research Division, Pohang Accelerator Lab (POSTECH), Pohang 790-834,
South Korea
freedom. All these properties are dependent on the doping
e
Materials Science Division, Inter University Accelerator Centre, New Delhi-110067, concentration and show drastic changes in the magnetic and
India transport properties even by subtle modications in the
chemical composition and external parameters such as
temperature and pressure.4 LaMnO3 was found to have an
Khalid Sultan did his [Link] at the orthorhombic structure with the space group Pnma. The devi-
University of Kashmir with 1st ation of this structure from the cubic structure is usually
division and obtained his attributed to the Jahn–Teller instability of the Mn3+ ions. On the
Master's degree in Physics from other hand, CaMnO3 is thought to have a structure closer to
the University of Kashmir (J & K), cubic as compared to LaMnO3 (LMO) because the Mn4+ ions do
India, with 1st division. He has not produce any Jahn–Teller distortion.5 The valency of Mn ions
qualied for the prestigious (Mn3+/Mn4+), the oxygen stoichiometry and the ratio between
Junior Research Fellowship (JRF) trivalent and divalent cations (R3+/A2+) determine the magnetic
and has qualied the National and electrical properties in the compound.5 The observed
Eligibility Test (NET) twice in behavior in these compounds is explained on the basis of a
Physical Sciences conducted by double exchange mechanism,6–8 Jahn–Teller distortion,9 lattice,
CSIR-UGC. He has submitted his charge and orbital degrees of freedom as well as phase sepa-
Ph.D thesis in Physics (Materials ration.10–12 The strong correlation between the observed trans-
Science) at the National Institute of Technology (NIT) Srinagar, J & port and the magnetic properties results in novel phenomena
K, India. His main research interests include the synthesis and with possible future applications.
characterization of Mn-based rare earth transition metal oxides Magneto-electronic devices are oen fabricated in the form
and their irradiation study. of thin lms. These applications require lms of high quality

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 69075–69085 | 69075
RSC Advances Paper

with homogeneous and smooth surface morphology. Many length ¼ 20 ns, repetition rate ¼ 10 Hz) was used to deliver a
novel techniques have been employed to synthesize LMO thin pulsed-laser beam of energy density ¼ 1.8 J cm
2 at the target
lms such as sol–gel, atomic layer deposition (ALD), molecular surface. The target–substrate distance was kept at 5 cm. The
beam epitaxy (MBE), and spray pyrolysis.13–17 Several studies substrate was placed at 750  C during the deposition to ensure
have focused on pulsed laser deposition (PLD) for the deposi- highly oriented growth. The ablation was carried out in oxygen at
tion of thin lms of Ca-doped LMO.18 PLD is a well-established a partial pressure of 330 mTorr. The deposition was carried out
technique for depositing high-quality thin lms, even those for 17 minutes using a laser energy of 200 mJ. Aer deposition,
with a complex stoichiometry. Due to the high energy of the the lms were cooled to room temperature under an ambient
laser and the short pulse duration (25 ns) the laser-target oxygen pressure at 20  C min
1. The lm thickness was estimated
material interaction is predominantly photonic with only a to be around 70  5 nm using an XP1 Tely step prolometer.
minimum of thermal heating. Moreover, when the material is The lms were characterized by X-ray diffraction (XRD)
fabricated as a thin lm, the crystal structure and chemical (Bruker AXS D8 Discover) (Cu-Ka radiation) at room temperature
composition at the surface can have a signicant inuence. in the 2q range of 20–80 . The surface morphology was studied
Commonly, SrTiO3 (STO) and LaAlO3 (LAO) single crystals, using an atomic force microscope (AFM) (Nanoscope E-digital
having the lattice constants aSTO ¼ 3.91 and aLAO ¼ 3.79  A, instrument. Inc., USA) in the contact mode. The magnetic
respectively, are used as substrates because their lattices match measurements were carried out using a 7 Tesla MPMS SQUID-
with that of bulk LMO. Theoretically, this allows the growth of VSM. Temperature dependent magnetization was carried out
single crystalline and epitaxial lms. On the other hand, thin from 5 K to 300 K under a eld of 100 Oe under both eld cooled
lms on Si (aSi ¼ 5.43  A) are expected to have a large lattice (FC) and zero-eld cooled (ZFC) conditions. Electrical resistance
mismatch and thus a polycrystalline nature. Therefore, depos- R(H) under a magnetic eld H was measured from 5 K to 300 K
iting LMO lms on Si causes strain due to large lattice using a standard four-probe technique. All these electrical and
mismatch and surface roughness. It is also well known that the magnetic measurements were carried out at IUC, CSR Indore.
surface composition of rare-earth manganites thin lms differs X-ray absorption spectra at O K and Mn L3,2 edges were
from the bulk sample due to segregation effects.19,20 In the case performed at the so X-ray beamline 10D XAS KIST (Korea
of LMO, the formal valencies are La3+Mn3+O32
, and for Institute of Science and Technology) of the Pohang light source
CaMnO3, they are Ca2+Mn4+O32
; thus, (La, Ca) MnO3 should (PLS), S. Korea, by operating at 2.5 GeV with a constant (top-up
contain both Mn3+ and Mn4+ ions. This mixed valency nature mode) storage current of 400 mA. The spectra were obtained
modies the magnetic and electronic properties of the system. using the sample drain current mode (TEY) at room tempera-
For instance, the parent compounds LaMnO3 and CaMnO3 are ture, and the vacuum in the experimental chamber was in the
antiferromagnetic insulators at low temperatures; however, low range of 10
9 Torr. The resolution of the spectra was better
La0.7Ca0.3MnO3 (LCMO) is a ferromagnetic metal. The mixed than 0.6 eV at O K-edge. The data is normalized to the edge-
valence states of Mn ions modify the electrical and magnetic jump at the post-edge region aer removing the background
properties of the LCMO system. To understand the local elec- at the pre-edge straight region.
tronic structure, including the valency of Mn and the hybrid-
ization of the Mn 3d–O 2p states, X-ray absorption spectroscopy 3. Results and discussions
(XAS) is a most suitable experimental technique and has been
used extensively in transition metal oxides. 3.1 Structural and morphological studies
The present study focuses on the structure, morphology, Fig. 1 shows the glancing incidence XRD (GIXRD) pattern of the
transport, magnetic and magnetoresistance properties of LCMO LCMO thin lms. All these lms were polycrystalline without
lms fabricated on Si substrates and the modications in their detectable secondary phases and were indexed with the ortho-
electronic structures. The emphasis is on understanding these rhombic structure of the space group Pnma. Abrashev et al.21
physical properties and electronic structures to correlate them reported that, unlike other perovskite manganites, the average
with the phase diagram of Ca-doped LaMnO3 thin lms fabri- crystal structure of La1
xCaxMnO3 remains orthorhombic in the
cated on Si substrates. entire range of Ca substitution at temperatures below 700 K.
With neutron and X-ray diffraction, Rodriguez et al.22 conrmed
2. Experimental details that LMO has an orthorhombic structure below 800 K. The
compositions with x ¼ 0.5 and x ¼ 0.83 can be indexed with the
Compounds with the compositions of La1
xCaxMnO3 (x ¼ 0.0, pseudocubic perovskite structure at room temperature and a
0.3, 0.5 and 0.7) (hereaer referred as LCMO) were prepared cubic to tetragonal structural phase transition arises on
using a conventional solid state reaction technique. Mixed lowering the temperature, as reported by Zheng et al.23 It has
powders of La2O3, Mn2O3 and CaCO3 in required stoichiometric been reported by Banerjee and Krishnan24 that LMO crystallizes
ratios were preheated at 1000  C for 12 hours, calcined again at into a rhombohedral structure (R3 c) with a small distortion.
1200  C for 12 hours and sintered. Thin lms of LCMO on Si Nagabbushane et al.25 reported that nanocrystalline LMO
(100) were prepared by the PLD method. The chamber was synthesized by a combustion process is in the cubic phase.
cleaned prior to PLD deposition and the base pressure was On calcination at 900  C, the structure of Ca-doped manga-
maintained at 1  10
5 Torr. A Lambda-Physik LPX210 nites changes to the rhombohedral phase, while pristine LMO
krypton–uorine excimer laser (wavelength ¼ 248 nm, pulse retains the cubic phase. All these studies show that the crystal

69076 | RSC Adv., 2015, 5, 69075–69085 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

cation within the oxygen octahedra. The present study follows

the former (rA < a/O2
ro) relation between its contributing
ions, thus the distortion probably occurs as a result of the
rotation of oxygen octahedra at room temperature. This varia-
tion has been attributed to the decrease in the effective ionic
radii of La and Mn on Ca doping. The distortion of MnO6
octahedra depends not only on the ionic radii of the dopants
but also on the amount of doping.
Fig. 2 shows the AFM images of LCMO thin lms. The
surface roughness of these lms are approximately 1.86 nm,
2.64 nm, 2.27 nm and 2.62 nm for x ¼ 0, 0.3, 0.5 and 0.7,
respectively. The values listed in Table 2 suggest that the lms
are extremely smooth in general. There are very small grains
with an average diameter of about 44 nm, 46 nm, 45 nm and 51
nm for x ¼ 0.0, 0.3, 0.5 and 0.7, respectively. The observed grain
diameters of these lms, which were prepared by PLD, were less
Fig. 1 The GIXRD pattern of LCMO thin films. Inset shows the XRD compared to those prepared by other groups17 using ALD. This
pattern with the substrate. implies that deposition techniques have a considerable role in
grain formation. This study shows that with Ca doping, there is
structure of LMO is highly sensitive to preparation conditions a change in the surface roughness and grain sizes of the LCMO
and that the physical properties are highly dependent on the lms.
structure.
Furthermore, the strain (3) was calculated using the Wil- 3.2 Magnetic measurements
Kl
liamson Hall equation: b ¼ þ 43 tan q. Rearranging this The ZFC and FC magnetization as a function of temperature at
D cos q
equation, one obtains 100 Oe eld are shown in Fig. 3. The large difference between FC
and ZFC curves at low temperatures suggests an
Kl
b cos q ¼ þ 43 sin q inhomogeneous mixture of a ferromagnetic and anti-
D
ferromagnetic ordering rather than a distinct long range
order. This also indicates the presence of magnetic ordering in
By linear extrapolation of the plot of b cos q vs. 4 sin q along the lm. The appearance of peaks in the ZFC curves is charac-
the y and x axes, the crystallite size is obtained at the intercept teristic of a blocking mechanism, because of the competition
of Kl/D and the strain (3) from the slope. Here, b and q are taken between the thermal energy and the magnetic anisotropy
in radians.
The lattice parameters, full width at half maximum (FWHM)
calculated from peak (121) and strain are presented in Table 1.
With Ca doping, it is observed that the calculated strain and
FWHM increases but the intensity decreases marginally, indi-
cating changes in the crystallinity of the LCMO thin lms. In
addition, there was deviation in the lattice parameters.
The cations, La and Ca, have almost identical ionic radii and
are randomly substituted on the A site. The size of the ions
determines the extent of distortion in the compound. If the size
of the A site cation, rA, <a/O2
ro (here ‘a’ is the cubic lattice
parameter and ro is the radius of oxygen ion), the distortion will
most probably be due to rigid tilts of oxygen octahedra. On the
contrary, if rB < a/2
ro (rB is the radius of the B site cation), the
distortion is most likely to be due to the movement of the B site

Table 1 The lattice parameters of LCMO films deposited on Si (100)

substrates

Film a (
A) b (
A) c (
A) FWHM (degrees) Strain ( 10
1)

x ¼0 5.521 7.712 5.541 0.416 1.07

x ¼ 0.3 5.413 7.733 5.489 0.431 1.11
x ¼ 0.5 5.425 7.669 5.431 0.425 1.09
x ¼ 0.7 5.312 7.570 5.391 0.496 1.20 Fig. 2 AFM images (size: 1 mm  1 mm) of LCMO films on Si (100): (a) x
¼ 0.0, (b) x ¼ 0.3, (c) x ¼ 0.5, and (d) x ¼ 0.7.

This journal is © The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 69075–69085 | 69077
RSC Advances Paper

Table 2 The values of various calculated parameters, such as grain diameter, surface roughness, ferromagnetic Curie temperature (Tc), blocking
temperature (TB), saturation magnetization (Ms), retentivity (Mr) coercivity (Hc) and activation energy, for LCMO films are summarized

Film Surface roughness (nm) Grain diameter (nm) Tc (K) TB (K) Ms (emu g
1) Hc (Oe) Mr (emu g
1) Ea (eV)

x ¼ 0.0 1.86 44 150 75 721 200 455 0.21

x ¼ 0.3 2.64 46 240 179 763 410 589 0.15
x ¼ 0.5 2.27 45 245 169 288 940 199 0.16
x ¼ 0.7 2.62 51 a
48 756 20 14 0.18
a
No sharp transition.

energy. The values of magnetic transition temperature ‘Tc’ (the The absence of such anomalies may be attributed to a different
temperature at which the maximum slope dM/dT occurs) for x ¼ preparation technique (PLD) and may possibly be due to a
0.0, 0.3 and 0.5 are 140 K, 230 K and 235 K, respectively. The different calcination temperature being used in this study
values of the ferromagnetic Curie temperature (Tc), blocking during the preparation of lms. The shi in transition
temperature (TB), saturation magnetization (Ms), retentivity (Mr) temperature “Tc” of different doping concentrations may arise
and coercivity (Hc) for the LCMO lms are presented in Table 2. due to the presence of lattice disorder and/or strain in the lms.
It is observed that the value of Tc increases with Ca doping in The value of the magnetic moment increases progressively with
the LCMO system up to x ¼ 0.5. For the composition x ¼ 0.7, no Ca doping but decreases for higher doping (x ¼ 0.7). Magneti-
sharp magnetic transition is observed. The calculated magnetic zation (M), both FC and ZFC, increases rapidly below Tc. At
parameters Ms, Mr and Hc show an increase with Ca doping, lower temperatures, M becomes saturated in the FC case due to
indicating magnetic ordering in lms with Ca doping. No the fully ordered Mn3+ and Mn4+ pairs. However, in the case of
anomaly was observed in MT spectra of LMO, as observed by ZFC magnetization, M does not become saturated even at lower
Khanduri et al.;17 they reported that LMO shows broad anom- temperatures.
alies at 44 K and 211 K in magnetization vs. temperature curves.

Fig. 3 Temperature dependence of ZFC and FC magnetization plots (in the presence of 100 Oe magnetic field) of LCMO films for (a) x ¼ 0.0, (b) x
¼ 0.3, (c) x ¼ 0.5, and (d) x ¼ 0.7. It is observed that the value of Tc increases with Ca doping in the LCMO system up to x ¼ 0.5. For the
composition x ¼ 0.7, there is no sharp magnetic transition.

69078 | RSC Adv., 2015, 5, 69075–69085 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

In LCMO, there are three basic phases: insulating- room temperature (300 K) is almost paramagnetic. However,
paramagnetic, ferromagnetic (with metallic-like conductivity) below the transition temperature, the lms show strong ferro-
and charge-ordered antiferromagnetic insulating phase. The magnetic behavior. It is seen that the value of the saturation
parent compound, LMO, is an antiferromagnetic insulator and magnetization increases up to x ¼ 0.3 and then decreases with
Ca doping at La sites results in the phenomenon of colossal doping. For the composition of x ¼ 0.7, the lms show an
magneto-resistance (CMR) for the doping range 0.2 < x < 0.5. antiferromagnetic nature with ordering of doped charge
CMR occurs in these compositions as a consequence of a rapid carriers. The maximum hysteresis is observed for the compo-
shi of the ferromagnetic transition temperature (Tc) to a sition of x ¼ 0.5. The observed large hysteresis is also reported
higher temperature region in the presence of a magnetic eld. in the literature for these compounds.28,29
The compound La0.5Ca0.5MnO3 shows the coexistence of two
totally dissimilar ground states, i.e. ferromagnetic-metallic and
3.3 Electrical transport measurements
antiferromagnetic-charge ordered, which is also consistent with
earlier reports.26,27 For the doping value of x ¼ 0.7, the The electrical resistivity (r) of the thin lms, x ¼ 0–0.7, at both H
compound is an antiferromagnetic insulator with ordering of ¼ 0 and H ¼ 8 T as a function of temperature (range, 5–300 K)
doped charge carriers. There is no sharp magnetic transition are shown in Fig. 6. The activation energy (Ea) was calculated
and the magnetic signal is also very low. Mathur et al.28 reported from the slope of the curve of log r vs. 1000/T (K
1) using the
that when x ¼ 0.7, the crystal structure of manganite interacts relation r ¼ r0e
Ea/kT and the values are shown in Table 2. Here,
strongly with the corresponding magnetic and electronic r0 is the conductivity at innite temperature, k is Boltzmann's
structures, and any imposed physical discontinuities in the constant and Ea is the activation energy. The pre-factor r0 is of
actual samples are likely to create or destroy the delicate phase the order of 1.5 mU, implying that the holes are localized in the
balance. paramagnetic phase. This localization is most probably due to
The plots of magnetization vs. eld (MH) curves at 300 K the coulombic attraction of the divalent cation or lattice
(Fig. 4) show paramagnetic behavior at room temperature, distortion around it. It is clear from Table 2 that the value of Ea
whereas at 5 K, (Fig. 5, except for the composition of x ¼ 0.7) rst decreases with doping but later increases for higher doping
they show ferromagnetic behavior, which is consistent with M (x ¼ 0.7). The observed trend is consistent with magnetic data,
vs. T data discussed above. The magnetic hysteresis loop at in which magnetization rst increases with doping for x ¼ 0.3
and then decreases for higher doping concentrations.

Fig. 4 Magnetization vs. field curves at 300 K for LCMO thin films.

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RSC Advances Paper

Fig. 5 Magnetization vs. field curves at 10 K for LCMO films. The value of saturation magnetization increases up to x ¼ 0.3 and then decreases
with doping.

All these LCMO thin lms are paramagnetic insulators and shown in Fig. 7(a)–(d) for lms with (a) x ¼ 0.0, (b) x ¼ 0.3, (c) x
have an orthorhombic crystal structure at room temperature ¼ 0.5 and (d) x ¼ 0.7.
(300 K).30 There is a decrease in resistivity with Ca doping but For x ¼ 0.0 and x ¼ 0.7, the MR values are only shown at 200
the resistivity increases for more highly doped lms (x ¼ 0.7). K and 300 K because the resistivity of these lms are too high at
The data from Miller et al.31 shows a sharp increase in the lower temperatures. It is observed that at all doping concen-
resistivity for both end members: LaMnO3 and CaMnO3. This is trations, resistivity decreases with temperature and is consis-
reminiscent of the large change in resistivity observed in tent with resistivity data discussed above. The MR also increases
semiconducting materials when donor or acceptor levels are with magnetic eld for all doping concentrations. The value of
introduced by doping with small quantities of atoms with a MR% is maximum (70–80%) for intermediate doping concen-
different valency. It is likely that the LMO lm used in this trations (x ¼ 0.3 and 0.5) at H ¼ 8 Tesla. There is a visible
investigation contains an excess of oxygen, which introduces a similarity in the nature of the change of resistivity with Ca
mixed valency into the system (sometimes this process is doping to that of the dependence on magnetic Tc. Resistivity
referred to as ‘self-doping’); this could reduce the resistivity by decreases sharply with Mn content, reaches a minimum at x ¼
an order of magnitude. The observed trend in resistivity is 0.5 and then increases; magnetization also increases with
consistent with the magnetic data as well as with Ea values. A doping, reaches a maximum at x ¼ 0.5 and then decreases. The
possible explanation for the high resistivity for x ¼ 0.7 is based variation of these transport properties with Ca doping reects
on grain boundaries. It is clear from Table 2 that the grain changes in conduction band structure, which are evident from
diameter is larger for higher doping concentrations. The X-ray absorption spectroscopy studies.
observed trend is also consistent with the reports of Edwards
et al.,32 where it was found that the grain diameter has consid- 3.4 Electronic structure by XAS
erable dependence on the resistivity of the samples. In the
To understand the element-specic electronic structure and
studied polycrystalline samples, well dened grain morphology
chemical environment of Mn and O ions in the compound
on a Si substrate was observed. The zero-eld resistivity
LCMO thin lms, XAS studies were carried out. The normalized
increases systematically with increasing grain size due to
XAS spectra at O K edge at 300 K is shown in Fig. 8(a). The
enhanced scattering at the grain boundaries.
electronic structure close to the Fermi level (EF) is dominated by
The eld-dependent resistivity (magnetoresistance MR% ¼
Mn 3d and O 2p states in manganites. The O K edge probes the
(r
r0/r0)  100) of the lms at 5 K, 100 K, 200 K and 300 K are
unoccupied density of states with the O 2p symmetry due to

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Paper RSC Advances

Fig. 6 Temperature dependence of resistivity of LCMO films for (a) x ¼ 0.0, (b) x ¼ 0.3, (c) x ¼ 0.5, and (d) x ¼ 0.7. These films show a decrease in
resistivity with Ca doping but the resistivity increases for more highly doped samples (x ¼ 0.7).

dipole selection rules that arise mainly from the hybridization observed from the difference spectra that the density of states
of O 2p states with various states of neighboring atoms, namely, increases with Ca doping (the spectral peaks from ‘A’ to ‘D’).
3d states of Mn as well as the 4d states of La.33 These spectra Fig. 9(a) shows XAS at Mn L3,2-edges of LCMO lms. Due to
show main features ‘A’, ‘B’, ‘C’ and ‘D’ at 527.5, 530.6, 534.1 and the spin–orbit splitting of the 2p core level, 2p / d-symmetry
541.4, respectively. The peaks ‘A’ and ‘B’ arise from the transitions give rise to two edges, namely, the 2p3/2 (L3-edge)
hybridized O 2p–Mn 3d states and are split into t2g and eg at 639 eV and the 2p1/2 (L2-edge) at 650 eV, separated by 11 eV.
orbitals under the inuence of an octahedral crystal eld.34 The Each spectral edge has sharp peaks due to the large number of
peak ‘C’ in Fig. 8(a) is attributed to the hybridization of the O 2p conduction band 3d-states. Compared to 2p1/2, a higher number
orbital with La 5d-states. The broad peak ‘D’ is attributed to the of electrons is available in 2p3/2; therefore, the intensity of the
bands of higher energy metallic states, e.g. Mn 4sp and La 6sp L3-peak is expected to be higher compared to the L2-peak. It has
bands. The well-resolved peaks marked as ‘A’ and ‘B’ in pure been reported earlier that the energy position of spectral
LaMnO3 correspond to a crystal eld splitting energy of 10 Dq ¼ features in the Mn L3,2 XAS study are very sensitive to the
2.9 eV for eg and t2g orbitals of the 3d energy level of Mn. All oxidation state of Mn atoms and can be used to determine the
these features are commonly observed in perovskites,35 Mn valency.40–44 The double peak feature of the L3-edge changes
including nickelates,36 titanates37 and manganites.38,39 as the Ca-concentration increases. The changes in the spectral
The changes in the spectral features of the compound LMO features of the compound LMO with the inclusion of Ca are
with the inclusion of Ca is depicted in the O K-edge difference depicted in the L3,2-edge difference spectra, as shown in
spectra, as shown in Fig. 8(b). The intensity of peak B provides a Fig. 9(b). The multiplet feature L3-edge are marked as ‘A1’ and
measure of the Mn 3d-state occupancy. From Fig. 8(b), it is ‘B1’. With an increase in Ca-concentration, there is a change in
observed that the intensity of peak ‘B’ increases with Ca concen- the mixed valent states of Mn2+/Mn3+ in the system. It is also
tration. An increase in peak intensity indicates lower Mn 3d-state seen that the L3-edge shis towards higher energy and there is
occupancy, i.e. higher Mn valency. The origin of Mn2+ is inter- corresponding modication in the spectral shape, which is
preted by suggesting a charge disproportionation model based on suggestive of the fact that the valency of Mn changes with Ca
the instability of Mn3+ with respect to Mn2+ formation via 2Mn3+ / doping.42 It is also observed from Fig. 9 that the peak at 638.8
Mn2+ + Mn4+ by Hundley et al.33 and de Jong et al.34 It is also eV, shown by ‘A1’, is typical for Mn2+ and the peak around 640.3
eV is typical for Mn3+. Therefore, if Mn is in a mixed valency

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RSC Advances Paper

Fig. 7 Magnetoresistance values for LCMO thin films for (a) x ¼ 0.0, (b) x ¼ 0.3, (c) x ¼ 0.5, and (d) x ¼ 0.7. The value of MR% is maximum (70–
80%) for intermediate doping concentrations (x ¼ 0.3 and 0.5) at H ¼ 8 Tesla.

state, a mixture of Mn2+ and Mn3+, a double peak Mn L3-feature (Mn2+–O–Mn3+ and Mn3+–O–Mn4+) may be favored. This
is expected. With these insights, one concludes that LCMO implies that the mixed valence state of Mn ions is responsible
lms contain both Mn2+ and Mn3+ ions. Due to this mixed for modifying the magnetic and other transport properties of
valence state of Mn induced by the introduction of Ca in the the LCMO system.
LCMO system, a multichannel double exchange mechanism

Fig. 8 (a) Normalized O K-edge XAS spectra of La1
xCaxMnO3 (x ¼ 0.0, 0.3, 0.5, and 0.7) thin films. (b) Difference spectra for the same films at O K
edge. It is observed that the intensity of peak ‘B’ increases with Ca concentration, implying a change in density of states.

69082 | RSC Adv., 2015, 5, 69075–69085 This journal is © The Royal Society of Chemistry 2015
Paper RSC Advances

Fig. 9 (a) Normalized Mn L3,2-edge XAS spectra of LCMO thin films. (b) Difference spectra for Mn L3,2-edge. Note that the Mn L3-edge shifts
towards higher energy and there is corresponding modification in the spectral shape, which is suggestive of the fact that the valency of Mn
changes with Ca doping.

The overall magnetic and electrical behavior depends on the epitaxial lms. It is speculated that stress is most effectively
interactions between the different Mn ions. Four counteracting propagated through the lm thickness in the absence of grain
processes determine the behavior of the Mn 3d valence elec- boundaries. For the LaAlO3 substrate, MR is maximized for a
trons. These are double exchange interaction, super exchange lm thickness of 1000 A. In this study, the fact that LCMO lms
interaction, Jahn–Teller effect and charge ordering. Parameters, were deposited on Si (100), which has a larger lattice mismatch
such as temperature, doping, strain and crystal structure, with LCMO at room temperature (as discussed in the Intro-
determine the dominant mechanism. Deformation of the duction), may induce additional strain in the lms. Pristine
oxygen octahedron causes energy differences within the other- LMO is in an anti-ferromagnetic insulating (AFI) state up to 150
wise degenerate t2g and eg electron states. The orbitals that are K and then changes into a paramagnetic state (PM). The lm
compressed by the deformation gain energy, while the orbitals with the composition of x ¼ 0.3 was found to be in the ferro-
that are elongated by the deformation loose energy. When the eg magnetic region up to 240 K, above which it changed into a PM
shell is half lled, it is energetically favorable to create a state. The lm with composition of x ¼ 0.5 was found to be in a
deformation because one of the orbitals will lose energy. The FM state up to 245 K, above which they changed to a PM state.
electrons in the eg shell will then occupy this lower energy state. The lms with a composition of x > 0.5 (x ¼ 0.7) were found to
Creating a deformation of the oxygen octahedrons without be in a mixture of charge ordered insulating (COI) and AFI
altering the overall crystal lattice leads to typical Jahn–Teller states. Ramirez46 reported the Tc for concentration of x ¼ 0.3
distortions. During the double exchange interaction, two to be around 220 K, while in this study, it was observed to be
neighboring Mn ions and their connecting O ion play an around 240 K. Therefore, the large lattice mismatch between Si
important role. The Mn ion in this system has one unoccupied and LCMO results in a change in the phase diagram of the
3d orbital. Thus, one electron from the O 2p orbital tunnels to LCMO system when it is deposited on Si substrates. The mixed
this Mn 3d orbital. With the formation of the unoccupied O 2p valent LCMO exhibits a large variety of states. Such variation
orbital, the electron from the other Mn 3d orbital moves. The occurs because of the presence of various competing and
net result is the movement of one electron from one Mn ion to cooperating interactions that involve the charge, orbital, spin
another Mn ion. The qualitative image of this behavior in the and lattice degrees of freedom. In the present study, the inter-
mixed-valent manganite, namely, La0.5Ca0.5MnO3, has been actions are described using a simple ionic image of Mn 3d
attributed to the concept of Zener double exchange.6,30 orbitals. The Mn4+ ion contains three electrons in the t2g state,
The inuence of substrate strain is the main factor that which are localized and have collinear spins because of the large
distinguishes manganite thin lms from bulk ceramic samples. Hund's coupling. With Ca doping in the parent compound
LaAlO3 is a commonly used substrate that has least lattice LaMnO3, the extra electron goes into the eg orbitals. There is
mismatch to LCMO at room temperature and hence low strain. also a large Hund's coupling between the eg electron and the
The effect of various substrates, as well as lm thickness, on MR immobile t2g spin. As a result, the metallic ground state in
has been studied by Jin et al.,45 and it was observed that the manganites is also ferromagnetic. In the LCMO system, oxygen
strain effect, expressed through the MR, is most pronounced for 2p orbitals play an essential role and are strongly hybridized

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RSC Advances Paper

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