SYNOPSIS OF

DISORDER INDUCED JAHN TELLER EFFECT AND EXCHANGE BIAS IN SPIN GLASS STATE OF THE MAGNETORESISTIVE Sr2FeCoO6

A THESIS

to be submitted by

PRADHEESH R

for the award of the degree

of

DOCTOR OF PHILOSOPHY

DEPARTMENT OF PHYSICS INDIAN INSTITUTE OF TECHNOLOGY MADRAS APRIL 2012

1 Introduction
The search for magnetoresistive materials for potential applications in room temperature spintronic devices have led to intense research in this eld [1]. The complex interplay of several degrees of freedom like spin, lattice and orbital lead to colossal effects in magnetoresistance (MR), as have been observed in manganites and related compounds [2]. A general feature of manganites is the occurrence of a metalinsulator transition exhibiting colossal magnetoresistance (CMR) [3]. Kobayashi et al., showed that fully ordered Sr2 FeMoO6 with Fe3+ (3d5 S = 5/2) and Mo5+ (4d1 S = 1/2) spins coupled ferrimagnetically exhibit CMR even at room temperature [4]. This discovery has led to a surge in research on double perovskites as an alternative to CMR materials, for example, La2 NiMnO6 , [5] ferromagnetic Sr2 FeMoO6 [6] SrFe1x Cox O3 [7] etc. For SrCoO3 , no MR is reported while for SrFeO3 MR as high as 90% in an applied eld of 9 T at 90 K has been observed [3]. Substitution of cobalt for iron in SrFeO3 leads to ferromagnetism and MR values of 6.5% in 7 T at 5 K, which was explained as due to the reduction of magnetic scattering of the charge carrier in a magnetic eld and grain boundary effects [7]. Signicant MR was observed in SrFe0.9 Co0.1 O3 due to cluster formation and blocking in the absence of long range order [8]. Similarly, a high MR in Sr doped LaCoO3 spin glass was found, which was due to the partial suppression of disorder in a magnetic eld [9]. Magnetic phase separation leads to negative giant magnetoresistance (GMR) along with spin glass behaviour as has been observed in cobaltites, especially in La1x Srx CoO3 [10]. Using small angle neutron scattering it was shown that the GMR in La1x Srx CoO3 is due to the granular heterostructure. An enhanced MR due to the magnetic disorder was also observed in layered iron-cobalt oxide Sr3 Fe2x Cox O7 [11], a member of the Ruddeldson-Popper (RP) series. An appreciable MR of 40 % was observed in Co doped Sr2 Fe1x Cox MoO6 (x = 0.1) which was attributed to the inhomogeneous magnetic behaviour that is responsible for spin glass behaviour, leading to the reduction in spin uctuations [12].

2 Motivation, Objectives and Scope

Most of the research were focused on double perovskite oxides where B and B are a combination of rst and third row transition metals (TM). Recently, few studies are aimed at combining the rst row TM of which Co and Mn based system attained prominence due to their varied valence states [13]. One of the reasons for a renewed interest is the fact that Mn3+ and Co3+ can have intermediate spin states (IS) leading to JahnTeller type distortions. This will lead to itinerant behaviour of the single electron which will contribute to magnetic and transport properties. Though double perovskite oxides in the A2 BB O6 family have been actively investigated, there are only a few reports on the Co based double perovskite, Sr2 FeCoO6 . [14, 15] Ab initio band structure calculations on Sr2 FeCoO6 showed that both Co and Fe make comparable contributions ) and Fe4+ (d4 L ) in high spin to ferromagnetism of the compound [16] where Co4+ (d5 L (HS) states can lead to metallicity and ferromagnetism. However, owing to the comparable ionic radii and valence states of Fe and Co (both in 4+ state), it is surprising that Co doped SrFeO3 showed ferromagnetism. The absence of a linear B OB O B chain consequent to tilts in the B O6 and B O6 octahedra can cause 90 and 180 superexchange interactions [17, 18]. Moreover, comparable ionic radii of the B site cations combined with antisite disorder can lead to magnetic frustration in the double perovskites. Cluster glass phenomenon in Sr2 Mn1x Fex MoO6 [17] was attributed to the local magnetic frustration developed due to the competing nearest neighbour (N N ) and next nearest neighbour (N N N ) superexchange interactions. These observations point to the fact that mixed valence state of the B and B ions and their crystallographic disorder can lead to a spin glass state as it would create mixed interactions and randomness. It is possible, if a frustration develop, that the MR can be enhanced by reducing the spin dependent scattering. Owing to the comparable ionic radii and similar charge difference SFCO should behave like a disordered structure. To the best of our knowledge a detailed study on the structure and magnetotransport properties have not been investigated and hence the aim of this thesis is to give a comprehensive analysis on SFCO double perovskite. Also, it would be interesting to see the effect of frustration on the MR properties and also the nature of valence state of Fe and Co and its role in magnetic properties.

3 Summary of the Research Work

In spite of the intense activity in the area of double perovskite and its magnetoresistive behaviour much is to be understood regarding the interplay between the spin and the transport properties. Although double perovskites are known to be metallic or half metallic with a room temperature magnetoresistive behaviour it would be interesting to look into the transport properties of insulating or semiconducting double perovskites and the effect of magnetic eld on them. The present work focuses on the frustration induced due to the site disorder and hence reducing spin dependent scattering which in turn helps in increasing the magnetoresistivity.

3.1 Structural aspects

The electron in solids possess several degrees of freedom like charge, spin and orbital degrees of freedom. But all three degrees of freedom will be active based on the valence states and the structure of the system. The presence of charge, spin and orbital degrees of freedom led to manganites being pivotal in research in recent times due to the occurrence of colossal magnetoresistance. In this regard cobaltites are also interesting and in these systems the spin order depends strongly on the competition between the exchange interaction Eex (which includes the Hubbard U parameter and Hunds rule coupling JH ) and the crystal eld splitting 10Dq . When the energies are comparable the spin states vary even with a small change in energy. Hence the exact valence state of Co depends on various factors.

3.1.1

X-ray diffraction

Using the powder XRD data, the crystal structure of Sr2 FeCoO6 was rened in the tetragonal space group I 4/m (No. 87) with lattice constants a = 5.4568(2) and c = 7.7082(4) . Even though, following the earlier reports on SrFe1x Cox O3 [14] a renement in cubic P m 3m space group was undertaken initially, an improved t to XRD data was achieved using the tetragonal space group. The results of our Rietveld analysis are presented in Fig 1 (a) where the observed XRD pattern at 300 K, the calculated prole, difference prole and the Bragg peaks are shown. The inset (1) of Fig 1 (a)

compares the 2 (goodness-of-t) of the renement for I 4/m and P m 3m space groups and shows that the former gives a better t. The temperature evolution of unit cell volume is presented in Fig. 1 (b). The variation of cell volume was modeled using the Grneisen approximation [19], V (T ) = U (T )/K0 + V0 ; U (T ) = 9 N kB T (T /D )3
D /T 0

x3 /(ex 1)dx. Here, U(T) is the specic internal energy, is the Grneisen

parameter, K0 is the incompressibility, V0 is the volume at T = 0 K and D is the Debye temperature. The resulting t is shown as a solid line in Fig. 1 (b). Note that the t deviates from the data at T 75 K where the volume displays a hump-like feature (a magnied low-temperature region where the t deviates from the data is shown in the inset (1)). This is inferred as magnetoelastic or magnetovolume effect coinciding with the magnetic transition. The value of D obtained from the t is 463(21) K and
(x 10 counts)
25 20 15 10 5 0 5 10 20 30 40 50 60 70 80

(a)
2

2.0

Obs

1.5

(1)
100 200 T(K)

Pm-3m I4/m

I I

Calc

1.0 0

Obs

-I

Calc

300

Bragg peaks

300 K

Intensity

2
3 Unit cell volume ( )
229.5
228.2

(degree)
7.72

(1)
7.71

229.0

228.0

2a
228.5
227.8 0 50 100

data fit

7.70

c
228.0

(b)
0 50 100 150 200 250 300
0 100

(c)
200 300

7.69

T (K)

T (K)

Figure 1: (a) X-ray diffraction pattern of Sr2 FeCoO6 at 300 K rened in tetragonal I 4/m space group. Quality measures of renement are RwP = 1.52 %, RP = 1.18 %, 2 = 1.23. (b) Shows the analysis of unit cell volume using Grneisen approximation. Note the anomaly in volume indicated by arrow. Inset (1) shows the enlarged view of the anomaly near 75 K. (c) Shows temperature evolution of lattice parameters 2a and c (the error bars were smaller than the size of the data markers). V0 = 227.89 3 . The D of Sr2 FeCoO6 lies in the range of values estimated for double perovskites like Sr2 FeTeO6 assuming two different D s for light and heavy atoms. [20] In Fig 1 (c) we show the temperature variation of the lattice parameters a and c. An important structural parameter characterizing the double perovskites, and having 4

Lattice parameters ()

a bearing on the magnetic properties is the cationic site disorder. However, since the X-ray atomic structure factors of Fe and Co are comparable, an accurate evaluation of atomic occupancies was not possible from the present XRD data.

3.1.2

Neutron diffraction

The analysis of neutron diffraction data was performed using tetragonal I 4/m space group, presented in gure 2. A completely random occupancy of Fe and Co in the ) sites, as previously done in the case of X-ray investigations 2a (0,0,0) and 2b (0,0, 1 2 were assumed in the renement procedure. The rened lattice parameters, unit cell volume and atomic positions of Sr2 FeCoO6 (SFCO) determined from the Rietveld analysis are presented in Table 1. A completely disordered arrangement of cations were also reported in the case of double perovskites like Sr2 MnNbO6 , Sr2 MnRuO6 [21], where I 4/mcm space group also was suggested for a completely disordered cationic arrangement. Hence, renement of the structure in I 4/mcm space group with , 1 ); Fe/Co(4c) (0,0,0); O(4a) (0,0, 1 ); O(8h) (x,x + 1 ,0) was also performed Sr(4b) (0, 1 2 4 4 2 for SFCO. IS Co3+ is a Jahn-Teller active ion and hence it distorts the CoO6 octaI I I
obs

(a)

calc

12 K

diff

Bragg pos.

Intensity (arb. units)

(b)

65 K

(c)

325 K

20

40
2

60
(deg)

80

100

Figure 2: Neutron powder diffraction patterns of Sr2 FeCoO6 at (a) 12 K, (b) 65 K and (c) 325 K are presented along with the results of Rietveld renement. The structure was rened in I 4/m space group at all temperatures. In the gure, a vertical down-arrow indicates the region of 2 = 61.4 to 64.1 which was excluded from the renement. hedra to further remove the degeneracy of the triply degenerate t2g and doubly degenerate eg states. The experimentally determined bond lengths for SFCO, given in Table 2, show the presence of two long and four short bond lengths for CoO6 and 5

Table 1: Structural parameters of Sr2 FeCoO6 at different temperatures. The Wyckoff 1 1 1 positions are Sr 4d(0, 2 , 4 ); Fe1 2a(0,0,0); Fe2 2b(0,0, 2 ); Co1 2b(0,0, 1 ); Co2 2 2a(0,0,0); Oap 4e(0,0,z ) and Oeq 8h (x, y , z ). The agreement factors of the renement are quantied as 2 and RBragg . 12 K I 4/m 5.4360(1) 7.7010(3) 227.569(3) 4e (0, 0, z) 0.2592(1) 8h (x, y, 0) 0.2491(9) 0.2507(6) 3.5 4.2 0.2548(1) 0.2433(7) 3.4 4.2 0.2581(9) 0.2400(3) 3.37 3.97 0.2498(2) 0.2541(7) 3.83 3.63 0.2502(2) 0.2495(1) 0.2530(4) 30 K I 4/m 5.4390(2) 7.6982(3) 227.736(2) 65 K I 4/m 5.4381(1) 7.7037(3) 227.826(1) 300 K I 4/m 5.4554(3) 7.7319(1) 230.115(5)

Space Group a() c() 3 V ( ) Oap z Oeq x y 2 RBragg

two short and four long bonds for FeO6 suggesting the distortion of CoO6 octahedra owing to Jahn-Teller (JT) activity. The bond distances FeO increase with increasing temperature while CoO distances show the opposite trend. The Jahn-Teller distortion has three sets of modes namely, breathing mode (Q1 ), basal distortion (Q2 ) and octahedral stretching (Q3 ). From the bond length calculation, two long and four short, it is obvious that Co3+ shows Q3 distortion mode [22]. The distortions of the octahedra are reected in the octahedral tilting of M O6 from the z axis dened as 1 = (180 - )/2 where is the M OM bond angle along z axis. The rotation angle in the xy -plane, dened as 2 = (90 - )/2 where is the angle among three oxygen ions between two corner-shared oxygen octahedra, also quanties the degree of distortion. The tilt angle 1 and the rotation angle 2 of SFCO at different temperatures are given in Table 2. The values of average bond angles <Fe-O-Co> and the distances of FeO and CoO bonds and various distortion parameters are also presented in the table. Interestingly 1 (2 ) shows high (low) values in the intermediate temperature range where an anomaly in lattice constants is observed. The octahedral tilting and the distortions are also quantied through empirical parameters like, cp /ap (cp = c/2 and ap = a/ 2) which denote the ratio of equivalent primitive perovskite lattice parameters; and the distortion parameter d , dened as (1/6)n=16 [(dn < d >)/ < d >]2 . From Table 2, it is clear that the tetragonal strain dened as, et = (cp ap )/(cp + ap ), also shows an increase with increasing temperature. In order to signify the distortions of the octahedra, we have calculated the lattice parameters and the bond parameters at room 6

Table 2: Main bond distances () and selected angles (deg) of Sr2 FeCoO6 at different temperatures. The distortion parameter of the octahedra is dened as d = (1/6)n=16 [(dn < d >)/ < d >]2 . < d > is the average MnO distance. The strain parameter is et = (cp ap )/(cp + ap ). cp and ap are the equivalent primitive perovskite lattice constants given by c/2 and a/ (2) respectively. The structural parameters in the absence of distortions as calculated using SPuDS are also shown. 12 K 30 K CoOap (2) 1.9961(2) 1.9267(1) CoOeq (4) 1.9217(3) 1.9164(5) FeOap (2) 1.8543(5) 1.9224(1) FeOeq (4) 1.9221(5) 1.9305(2) FeOCo 179.64(1) 177.38(1) d 104 3.25 0.064 cp /ap 1.001 1.0 et 104 8.7 4.1 1 (deg) 0.18 1.31 2 (deg) 1.03 0.84 SPuDS a() c() FeO 5.3684 7.5921 1.9260 65 K 300 K 1.9221(6) 1.9227(5) 1.913(4) 1.9107(5) 1.9297(1) 1.9329(5) 1.934(4) 1.9695(5) 176.04(2) 177.92(1) 0.77 0.52 1.001 1.002 8.4 13 1.98 1.04 0.07 1.94 CoO FeOCo 1.8700 179.99

temperature using the program SPuDS [23] (see, Table 2). A comparison between the ideal values calculated by SPuDS and the experimentally determined values for SFCO indicates the major role played by lattice distortions in this double perovskite.

3.2 AC susceptibility
Sharpness of the peak in ac susceptibility curves and its shift to high temperature with increasing frequency are typical features exhibited by spin glass systems. [24, 25] In order to probe this, ac susceptibility measurements were performed in the temperature range 5 250 K, with a driving eld of 3 Oe. Fig 3 (a) shows the temperature dependence of the real part of ac susceptibility, (T ), at different applied frequencies in the range 33 - 1333 Hz. (T ) attains a maximum at Tf , the freezing temperature, that shifts to higher temperature as the frequency is increased. The shift of the peaks as a function of frequency is clear in Fig 3 (b) and is characteristic of spin glasses. [25] A t of the ac susceptibility data to the Arrhenius relation, = 0 exp[Ea /kB T ], where Ea is the activation energy, yielded unphysical values of 0 = 1082 Hz and Ea = 14301 eV. The failure of Arrhenius relation points to spin glass behaviour, since a description of mere energy-barrier blocking and thermal activation will not suit the spin glass transition.

In order to conrm the spin glass behaviour, analysis of the susceptibility data using the dynamical scaling relation at Tc was performed. For a spin glass, the maximum of (T ) (freezing temperature, Tf ) depends on the applied frequency and the characteristic time, t = 1/ , is equal to the maximum relaxation time . Thus, a spin glass phase can be judged if follows a power law divergence of the form, = 0
23.16
x 10 (emu/g)

Tf Tct Tf

133Hz 337Hz 667Hz 967Hz

x 10 (emu/g)

(a)

33Hz

(b)

33 Hz 133 Hz 1333 Hz

17.37

-4

11.58

ac

5.79

ac

1333Hz

-4

50

100
T (K)

150

200

70

75

80
T (K)

85

90

-1.6

3
Log

-2.0 -2.4 -2.8 -3.2

4.88
(emu/g)

50 Oe 100 Oe 500 Oe 1000 Oe

(s)

X10

2.44

-2

-1.60

-1.52

-1.44
ct ct

-1.36

X 10

-6

Log (|T - T |/T )

(d)
0.00

(c)
77.0 77.5 78.0
T (K)

78.5

''

ac

100
T (K)

200

Figure 3: (a) Temperature dependence of AC susceptibility of Sr2 FeCoO6 at different frequencies. (b) The peak in (T ) 75 K which shifts to higher temperature as the frequency is increased, signifying glassy magnetism. (c) The t using the power law for critical slowing down, where the best t gave z = 6.2 , 0 = 1012 s. The inset presents the same plot but in log-log scale. (d) Displays (T ) at different values of superimposed magnetic elds. where Tct is the critical temperature and z and 0 are the critical exponents and microscopic time scale respectively. [25] The best t to the above equation, as shown in Fig 3 (c) (inset presents the same graph in log-log scales), yields z = 6.2(2), Tct = 75.14(8) K and 0 1012 s. The values of 0 and z are consistent with that of conventional 3D spin glasses [26] and Fe doped cobaltites [27]. In order to probe whether the FM state coexist with the frozen spin glass state as in reentrant spin glasses, we performed ac susceptibility measurements with superimposed dc elds. The result is presented in Fig 3 (d) which shows the out of phase susceptibility in an external dc eld varying from 50 - 1000 Oe at a frequency of 33 Hz with an ac amplitude of 3 Oe. Emergence of a second peak as observed in certain reentrant systems [28] was not observed, instead, the intensity of the peak at Tc in (T ) diminishes with increasing eld indicating FM nature of the compound. The ac susceptibility studies conrm the presence of canonical spin glass state in Sr2 FeCoO6 in turn suggests the presence of disorder. 8

3.3 Magnetoresistance
The electrical resistance of SFCO in 0 and 6 T applied magnetic eld is presented in Fig. 4 (a). It exhibits a monotonic increase as the temperature is lowered below the spin glass transition temperature. The variation of electrical resistance indicates semiconducting behaviour. The inset of the gure shows the log-log representation of the main panel and suggests that thermally activated behaviour of carrier hopping does not hold in SFCO. The resistivity does not follow Arrhenius law and a real energy gap opening being the reason for the upturn of resistance at low temperature is ruled out since no divergence in the derivative of resistivity is observed. The temperature evolution of MR is presented in Fig. 4 (b). The MR is positive for a small range at high temperatures and then begins to decrease with decreasing temperature and goes to negative values. Negative magnetoresistance observed in semiconductors was compared with the effects observed in dilute alloys such as Cu-Mn and a theory based on localized magnetic moments was proposed by Toyazawa [29]. Later, in an empirical model suggested by Khosla and Fischer [30], a negative component to magnetoresistance stemming from the localized magnetic moment model of Toyazawa and a positive component due to the eld dependence of Hall coefcient were combined to explain the data on CdS. In order to explain the observed magnetoresistance in SFCO, the empirical relation derived by Khosla and Fischer was employed. Thus, the isothermal MR was found to t to the following expression, B1 2 H n = A1 2 ln(1 + A2 2 H 2 ) + 1 + B2 2 H 2 (1)

where A1 , A2 , B1 , B2 and n are free parameters of tting and H is the applied magnetic eld. A1 and A2 are given by A1 2 = a2 J S (S + 1) + M 2 A2 2 = 1 + 4S 2 2 2JF g
4

(2) (3)

g 2 2 (kB T )2

where a is regarded as a measure of spin scattering. The positive component of MR is proportional to H n where n ranges from 0.77 to 2.19. A value less than 1.8 has been observed for systems showing a monotonic increase in negative MR [31]. The elddependent MR of SFCO at 14 K and 49 K are presented in Fig. 4 (c) and the data at 9

12 10 8
x 10 )
4

10
6 T 0 T (a) (b)

0 -10

6 4 2 0 0 50 100

log R

MR %

-20 -30 -40 -50

R (

log T

150
T (K)

200

250

300 0

50

100
T (K)

150

200 15

0 -10 -20
MR %

(c)

(d)

0 -15
MR %

-30 -40 -50 -60 -70 0 2 4 6

H (T) 14 K 49 K

-30 -45
14 K fit

-60 4 6
H (T)

10

12

10

12

Figure 4: (a) Temperature dependence of electrical resistance of Sr2 FeCoO6 in zero eld and an applied eld of 6 T. Inset shows the zero eld resistance in loglog scale. (b) Magnetoresistance of Sr2 FeCoO6 as a function of temperature. (c) Magnetoresistance as a function of applied magnetic eld at two temperatures, 14 K and 49 K. (d) Fit to the isothermal MR at 14 K using eqn. (1). The t parameters obtained are, A1 = 0.1086(4), A2 = 0.0013(4), B1 = 0.0159(3) and n =1.43(6). 14 K along with the t using equation (1) are presented in Fig. 4 (d). The value of n = 1.43(6) obtained from this t lies in the range consistent with negative MR.

3.3.1

Effect of disorder and spin glass nature in magnetoresistivity

Owing to crystal eld effects, the ve-fold degenerate 3d level of Co3+ splits into threefold degenerate t2g and two-fold degenerate eg states. The system may prefer further removal of degeneracy through Jahn-Teller distortion, if it can help in lowering the energy. It suits the system to undergo Jahn-Teller distortion of the Co3+ O6 octahedra. The distortion is manifested by changing the tilt angle and rotation angle from 180 and 90 respectively. However, the presence of a Jahn-Teller ion can lead to a local structural distortion thereby removing the degeneracy of the two-fold eg state. If, through such a degeneracy removal, the upper level of the two-fold eg states is available to an electron, it can strongly inuence the conduction mechanism of SFCO. From the structural studies it is evident that there is an increase in the bond length along the apical direction which means a descent in the symmetry to D4h . The lowering of the symmetry is treated as a perturbation to the cubic eld and in order to link the local structural distortion to 10

the energy level splitting, we note that the energy separation between the dx2 y2 and dz2 arises from the second order crystal eld coefcient of distorted octahedra. Hence the Jahn-Teller coupling EJT can be described as
g EJT = 4 Ds + 5 Dt 2g EJT = 3 Ds 4 Dt

(4) (5) (6) (7)

Ds =

5 A20 r2 e Dt = T r 4 14 e 14

3d 3d

where A20 is the second order crystal electric eld (CEF) coefcient, T = A40 A40 is the difference between fourth order CEF coefcients of distorted octahedra and perfect octahedra. rn is the expectation value of the nth power of the radial distance of a 3d orbital from the nucleus. Taking the radius of IS Co3+ (0.56 ), the value of Dt works out to be less than Ds . Hence the main contribution to energy arises from A20 and EJT can be written as
g 4 Ds = EJT

2e 7

5 A20 r2

3d

(8)

The radius of Co3+ in IS state is nearly equal to that of Fe3+ (0.55 ) and hence the second order CEF coefcient can be evaluated using the quadrupole splitting obtained from the Mssbauer data. The quadrupole splitting can be expressed as =
eQVzz 2 2 3 1/2

1+

where Q is the electric quadrupole moment of the 57 Fe nucleus, is

the asymmetry parameter, and Vzz is the principal component of the electric eld gradient at the nucleus which contains contributions from valence as well as the surrounding electrons. Vzz = Vzz (F e) + Vzz (lattice) Vzz (lattice) = qi (3cos2 1) = 3 Ri 5 A20
E , c

(9) (10) where c is the

e

Combining eqns (8) and (10) and converting Q to eV by a factor of

g = velocity of light and using Q = 0.281024 cm2 , = 0 for axial symmetry we get EJT

1.3 eV (note that this is the minimum energy and hence a contribution from Dt will only increase the energy). This value is high enough such that the electron in the eg level is not itinerant but localized, consistent with the experimentally observed resistivity. The large energy separation EJT , traps the electron leading to localization; consequently, 11

dx2 y2 b1g eg a1g b2g t2g e d orbital Co3+ Octahedral crystal field split Jahn-Teller split Spin split
g

dz2 dxy dxz, dyz

Figure 5: Schematic of Co3+ level scheme in IS state showing the removal of degeneracy. the ground state is insulating. Due to the tetragonal symmetry, the three-fold t2g state will further split into an b2g state and a doubly degenerate eg state while the eg state will split into a1g and b1g states as shown in Fig. 5. The insulating behaviour of SFCO suggests that the conducting carriers are holes that lie mainly in a1g state [32]. The holes are strongly coupled to lattice and leads to localization resulting in localized magnetic moments due to spin-phonon coupling. A small contribution of positive MR is also seen in the present case which is associated with the spin glass behaviour observed in this system. Strong competition occurs between spin clusters and ferromagnetic state below the spin glass transition temperature. As an external magnetic eld is applied the ferromagnetic coupling strength gets enhanced and hence we observe a large magnetoresistance. The mixed valence and disordered arrangement of Fe and Co leads to complex magnetic behaviour forming the spin glass state. From neutron diffraction and magnetization measurements it was conrmed that Fe and Co in SFCO have mixed valence states. While Co3+ is in an intermediate spin state the other valence states are in low spin states. Preferential stability of the IS state over HS due to strong ligand metal hybridization has also been reported already [33].Hence we infer that the positive contribution to MR, though small, is due to the coexistence of the FM and AFM interactions.

4 Conclusions
We conclude by listing the major results of the research reported in this thesis. The general objective of this thesis has been to look at the site disorder and its role in the magnetotransport properties of Sr2 FeCoO6 .

12

 From structural study, using X-ray and neutron diffraction measurements, we conrm that there is a site disorder which leads to a mixed valence state for Fe and Co. Co3+ is a Jahn-Teller ion and from structural studies we conrm that the presence of localized moments. The presence of site disorder and mixed valence results in frustration and a spin glass state in Sr2 FeCoO6 . A negative magnetoresistance of 63 % at 14 K in 12 T with a small positive contribution at low elds is observed. The observed magnetoresistance could be explained by applying a semi-empirical t consisting of a negative and a positive contribution and the negative magnetoresistance is due to spin scattering of carriers by localized magnetic moments in the spin glass phase.

REFERENCES
[1] uti c I. , Fabian J. and Sarma S. D. Spintronics: Fundamentals and applications. Rev. Mod. Phys. 76, 323 (2004). [2] Ramirez A. (1997). Colossal magnetoresistance. J. Phys.: Condens. Matter 9, 8171

[3] Lebon A. , Adler P. , Bernhard C. , Boris A. V. , Pimenov A. V. , Maljuk A. , Lin C. T. , Ulrich C. and Keimer B. Magnetism, Charge Order, and Giant Magnetoresistance in SrFeO3 Single Crystals. Phys. Rev. Lett. 92, 37202 (2004). [4] Kobayashi K. I. , Kimura T. , Sawada H. , Terakura K. and Tokura Y. Roomtemperature magnetoresistance in an oxide material with an ordered doubleperovskite structure. Nature 395, 677680 (1998). [5] Rogado N. S. , Li J. , Sleight A. W. and Subramanian M. A. Magnetocapacitance and magnetoresistance near room temperature in a ferromagnetic semiconductor: La2 NiMnO6 . Adv. Mater. 17, 22252227 (2005). [6] Sarma D. D. , Sampathkumaran E. V. , Ray S. , Nagarajan R. , Majumdar S. , Kumar A. , Nalini G. and Guru Row T. N. Magnetoresistance in ordered and disordered double perovskite oxide, Sr2 FeMoO6 . Solid State Commun. 114, 465468 (2000). [7] Munoz A. , Alonso J. A. , Martinez-Lope M. J. , de La Calle C. and Fernandez-Diaz M. T. High pressure synthesis, crystal, magnetic structure and magnetotransport of SrFe0.5 Co0.5 O3 , J. Solid State Chem. 179, 33653370 (2006). [8] Battle P. D. , Green M. A. , Rosseinsky M. J. , Spring L. E. , Vente J. F. , Mihut J. L. A. and Singleton J. Magnetoresistance in high oxidation state iron oxides. Chem. Commun. 9, 987988 (1998). 13

[9] Golovanov V. , Mihaly L. and Moodenbaugh A. R. Magnetoresistance in La1x Srx CoO3 for 0.05< x< 0.25. Phys. Rev. B 53, 8207 (1996). [10] Wu J. and Leighton C. Glassy ferromagnetism and magnetic phase separation in La1x Srx CoO3 . Phys. Rev. B 67, 174408 (2003). [11] Motohashi T. , Raveau B. , Hervieu M. , Maignan A. , Pralong V. , Nguyen N. and Caignaert V. Enhancement of giant magnetoresistance effect in the RuddlesdenPopper phase Sr3 Fe2x Cox O7 : predominant role of oxygen nonstoichiometry and magnetic phase separation. J. Phys.: Condens. Matter 18, 2157 (2006). [12] Chang H. , Garca-Hernndez M. , Retuerto M. and Alonso J. A. Co-doped Sr2 F eM oO6 double perovskites: A plausible scenario for phase segregation. Phys. Rev. B 73, 104417 (Mar 2006). [13] Baidya S. and Saha-Dasgupta T. Electronic structure and phonons in La2 CoMnO6 : A ferromagnetic insulator driven by Coulomb-assisted spin-orbit coupling. Phys. Rev. B 84, 035131 (2011). [14] Maignan A. , Martin C. , Nguyen N. and Raveau B. Magnetoresistance in the ferromagnetic metallic perovskite SrFe1x Cox O3 . Solid State Sci. 3, 5763 (2001). [15] Bezdicka P. , Fourns L. , Wattiaux A. , Grenier J. C. and Pouchard M. Mssbauer characteristics of the Sr2 CoFeO6 perovskite obtained by electrochemical oxidation. Solid State Commun. 91, 501505 (1994). [16] Bannikov V. V. , Shein I. R. , Kozhevnikov V. L. and Ivanovskii A. L. Electronic structure and magnetic properties of double perovskites Sr2 FeMO6 (M= Sc, Ti,..., Ni, Cu) according to the data of FLAPW-GGA band structure calculations. J. Struc. Chem. 49, 781787 (2008). [17] Poddar A. and Mazumdar C. Magnetic frustration effect in Mn-rich Sr2 Mn1x Fex MoO6 system. J. Appl. Phys. 106, 093908093908 (2009). [18] Elad N. C. , Jorgensen J. D. , Lobanov M. V. and Greenblatt M. Structural disorder and magnetic frustration in ALaMnMoO6 (A= Ba, Sr) double perovskites. Phys. Rev. B 67, 134431 (2003). [19] Wallace D. C. . Thermodynamics of crystals. Dover New York 1998. [20] Martin L. O. , Chapman J. P. , Lezama L. , Garitaonandia J. J. S. , Marcos J. S. , Rodrguez-Fernndez J. , Arriortua M. I. and Rojo T. Spin-glass behaviour in the double perovskite Sr2 FeTeO6 due to mis-site disorder and cation vacancy formation J. Mater. Chem. 16, 66 (2006). [21] Lufaso M. W. , Woodward P. M. and Godberger J. Crystal structures of disordered A2 Mn3+ M5+ O6 (A= Sr, Ca; M= Sb, Nb, Ru) perovskites J. Solid State Chem. 177, 1651 (2004). [22] Satpathy S. , Popovi c Z. and Vukajlovi c F. Electronic Structure of the Perovskite Oxides: La1x Cax MnO3 . Phys. Rev. Lett. 76, 960963 (1996).

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[23] Lufaso M. W. and Woodward P. M. Prediction of the crystal structures of perovskites using the software program SPuDS. Acta Cryst. B 57, 725738 (2001). [24] Tholence J. L. On the frequency dependence of the transition temperature in spin glasses. Solid State Commun. 88, 917921 (1993). [25] Mydosh J. A. . Spin Glasses: An experimental Introduction. London: Taylor and Francis 1993. [26] Gunnarsson K. , Svedlindh P. , Nordblad P. , Lundgren L. , Aruga H. and Ito A. Dynamics of an Ising spin-glass in the vicinity of the spin-glass temperature. Phys. Rev. Lett. 61, 754757 (1988). [27] Luo X. , Xing W. , Li Z. , Wu G. and Chen X. Impact of the Fe doping on magnetism in perovskite cobaltites. Phys. Rev. B 75, 054413 (2007). [28] Viswanathan M. and Anil Kumar P. S. Observation of reentrant spin glass behavior in LaCo0.5 Ni0.5 O3 . Phys. Rev. B 80, 012410 (2009). [29] Toyozawa Y. Theory of Localized Spins and Negative Magnetoresistance in the Metallic Impurity Conduction. J. Phys. Soc. Jpn. 17, 986 (1962). [30] Khosla R. P. and Fischer J. R. Magnetoresistance in Degenerate CdS: Localized Magnetic Moments. Phys. Rev. B 2, 4084 (1970). [31] Luo X. G. , Chen X. H. , Wang G. Y. , Wang C. H. , Li X. , Wu G. and Xiong Y. M. Anomalous magnetoresistance in Sr2 Bi2x Pbx O4 RS CoO2 y (x= 0, 0.3, and 0.4; y 1.85) single crystals. Eur. Phys. J. B 49, 3745 (2006). [32] Mizokawa T. , Tjeng L. H. , Steeneken P. G. , Brookes N. B. , Tsukada I. , Yamamoto T. and Uchinokura K. Photoemission and x-ray-absorption study of mist-layered (Bi,Pb)-Sr-Co-O compounds: Electronic structure of a hole-doped Co-O triangular lattice. Phys. Rev. B 64, 115104 (2001). [33] Saitoh T. , Mizokawa T. , Fujimori A. , Abbate M. , Takeda Y. and Takano M. Electronic structure and magnetic states in La1x Srx CoO3 studied by photoemission and x-ray-absorption spectroscopy. Phys. Rev. B 56, 12901295 (1997).

5 Proposed Contents of the Thesis

The outline of the thesis is as follows: 1. Introduction 2. Experimental Techniques 3. Structural Analysis 4. Magnetic properties 5. Spin glass behaviour and Magnteoresistive behaviour 6. Conclusion 15

6 Publications
6.1 Papers in Refereed Journals
1. Observation of a spin glass state in weakly ferromagnetic Sr2 FeCoO6 , Pradheesh R, Harikrishnan. S. Nair, C. M. N. Kumar, Jagat Lamsal, R. Nirmala, P. N. Santhosh, W. B. Yelon, S. K. Malik , V. Sankaranarayanan, and K. Sethupathi J. Appl. Phys. 111, 053905, (2012) 2. Large magnetoresistance and Jahn-Teller effect in Sr2 FeCoO6 , Pradheesh R, Harikrishnan. S. Nair, V. Sankaranarayanan, and K. Sethupathi communicated to Eur. J. Phys. B 3. Exchange bias and Memory effect in Sr2 FeCoO6 , Pradheesh R, Harikrishnan S. Nair, V. Sankaranarayanan, and K. Sethupathi to be communicated

6.2 Presentations in Conferences

1. Poster titled Spin scattering based magnetoresistance in Sr2x Lax FeCoO6 spin glass, at the 56th MMM conference, Pradheesh R, Harikrishnan. S. Nair, R. Nirmala, P. N. Santhosh, V. Sankaranarayanan, and K. Sethupathi Phoenix, U. S. A. 01 November, 2011. 2. Poster titled Structural, Magnetic, transport and magnetocaloric properties of metamagnetic DyMn0.5 Co0.5 O3 , at the 56th MMM conference, Phoenix, U. S. A. 01 November, 2011. 3. Poster titled Size effect on the structural, magnetic and magnetotransport properties of electron doped manganite La0.15 Ca0.85 MnO3 , at the 56th MMM conference, Phoenix, U. S. A. 01 November, 2011. 4. Poster titled Complex magnetism in the intermetallic compound Tb2 Mn3 Si5 , at the 56th MMM conference, Phoenix, U. S. A. 01 November, 2011.

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