Appl. Phys. A 84, 459463 (2006) DOI: 10.

1007/s00339-006-3646-5

Applied Physics A
Materials Science & Processing

q. zhang1 g.h. rao1,u y.g. xiao1 g.y. liu1 y. zhang1 j.k. liang1,2

Hole doping effects in (Sr2xNax)FeMoO6 double perovskite

1

Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080, P.R. China 2 International Center for Materials Physics, Chinese Academy of Sciences, Shenyang 110016, P.R. China

Received: 2 June 2006/Accepted: 8 June 2006 Published online: 4 July 2006 Springer-Verlag 2006

Hole-doped double perovskite compounds (Sr, Na)2 FeMoO6 with the Na content of x = 0, 0.02, 0.03, 0.07 and 0.17 have been synthesized by solgel method. Effects of hole doping on the crystal structure and magnetic properties of Sr2 FeMoO6 have been investigated by means of X-ray powder diffraction (XRD) and magnetic measurements. The XRD pattern indicates that all the samples are of single phase and belong to the space group I4/m. Due to the smaller ionic radius of Na+ than that of Sr2+ ions, the lattice constants and unit cell volume of the compound decrease slightly with x. The degree of cation ordering in the Na-doped Sr2 FeMoO6 compounds shows a non-monotonic variation with the doping level, increasing from x = 0 to x = 0.03 and decreasing slightly with further increase of the doping. In contrast to the composition dependence of the degree of ordering, the Curie temperature of the compound decreases at low doping level and increases at high doping level. The saturation magnetization of the compound increases with x for x < 0.17. Similar to the electron-doped Sr2 FeMoO6 , provided that the doped hole enters selectively the spin-down band, the variation of the saturation magnetization can be explained in light of the ferrimagnetic model (FIM).
ABSTRACT PACS 61.72.Ww;

75.50.-y; 75.30.Cr; 75.50.Gg

Introduction

Ordered double perovsites with the general formula A2 BB O6 (A is an alkali-earth ion, B and B are the transitional metals) have been known for about 40 years [14]. In 1998, Kobayashi et al reported that the ordered double perovskite Sr2 FeMoO6 exhibited a large room-temperature loweld magnetoresistance (LFMR) [5]. Since then, Sr2 FeMoO6 (SFMO) and related oxides have been intensively studied. Owing to the highly polarization nature of the conduction electrons, the tunneling-type magnetoresistance (TMR) in SFMO can be interpreted as a spin-dependent electron tunneling through grain boundaries. The grain boundary resistivity is tuned by the relative angle between the magnetic moments of ferromagnetic domains, which is inuenced by the applied magnetic eld. This mechanism helps us to understand the LFMR observed in polycrystalline Sr2 FeMoO6 .
u Fax: +86-1082649531, E-mail: ghrao@aphy.iphy.ac.cn

Band structure calculation predicted that Sr2 FeMoO6 is a halfmetal, the occupied spin-up sub-band near the Fermi level essentially composed of Fe t2g and Fe eg states is separated by an insulating gap and these electrons are localized, while the spin-down sub-band mainly occupied by the Mo t2g and Fe t2g states crosses the Fermi level and these electrons are itinerant [57]. Therefore, the itinerancy of the spin-down electron results in the metallic conductivity and is responsible for the strong magnetic coupling between Fe and Mo via a sort of doubleexchangelike mechanism. Sr2 FeMoO6 crystallizes in a cubic [1] or tetragonal [8, 9] space group. Due to the large difference in charge and ionic radius, the cations Fe and Mo are alternately ordered in the rocksalt lattice. Its crystal structure can be visualized as a regular arrangement of corner-sharing FeO6 and MoO6 octahedra, alternating along cubic axes in all three directions, with the voluminous Sr cations occupying the voids between the octahedra. Within the framework of the simplest ferrimagneticarrangement model (the FIM model) and assuming a spinonly contribution, the moments of the Fe3+ and the Mo5+ sublattices are 5 B /f.u. and 1 B /f.u., respectively, for a perfectly ordered Sr2 FeMoO6 and these sublattices couple antiferromagnetically, resulting in a saturation magnetization ( MS ) of 4 B /f.u. [10]. However, the MS of bulk materials reported so far are systematically lower (3.1 B /f.u. [5], 3.5 B /f.u. [11]) than the prediction (4 B /f.u.), which could be due to the occurrence of anti-site defects (AS, the fraction of Mo on the Fe sites or that of Fe on the Mo sites) [10, 12]. The character of half-metallic ferromagnets with a high Curie temperature and a large LFMR make the compound Sr2 FeMoO6 promising for the development of spin electronics. Therefore, intensive efforts have been devoted to understanding its structural, magnetic and transport properties. It is well known that carrier doping in strongly correlated electron systems has been an effective way for disclosing some of the most exciting new phenomena and for discovering novel materials. This approach has been successfully used in the investigation of high-TC superconducting cuprates and colossal magnetoresistive (CMR) manganese perovskites. The ferrimagnetic state of SFMO is stabilized via an antiferromagnetically coupling between spin-up valence and spin-down conduction electrons, and therefore the strength of magnetic coupling is directly related to the density of electrons at the Fermi level [13]. In order to enhance the Curie temperature of

460

Applied Physics A Materials Science & Processing

the compound, injection of electrons into the conduction band by appropriate electron doping was performed. As reported in [1418], partial substitution of divalent Sr2+ in SFMO with trivalent La3+ or Nd3+ did inuence its physical properties signicantly, e.g., the TC was increased, the degree of cation ordering and magnetoresistance were reduced. However, few results have been reported about the inuence of hole doping in SFMO on the structural, magnetic and transport properties of the compound. In this work, we synthesized and studied the structural and magnetic properties of hole-doped (Sr2x Nax )FeMoO6 compounds with x = 0, 0.05, 0.1, 0.15 and 0.2. It is found that all the samples are of single phase and belong to the I4/m space group. The degree of Fe/Mo ordering and the MS of the compound increase with x at low doping concentration and decrease at high doping concentration, while the Curie temperature of the compound exhibits an opposite response to the doping. Analysis of MS indicates that the doped holes seem to selectively enter the spin-down band, which is similar to the case of the electron-doped Sr2 FeMoO6 .
2 Experiment

XRD patterns of the Na-doped Sr2 FeMoO6 . From bottom to top, the Na concentration is x = 0, 0.02, 0.03, 0.07 and 0.17. The inset shows the composition dependence of the degree of ordering
FIGURE 1

Polycrystalline (Sr2x Nax )FeMoO6 (x = 0, 0.05, 0.1, 0.15 and 0.2) were prepared by solgel method followed by a heat treatment. Stoichiometric Sr(NO3 )2 , NaNO3 , Fe(NO3 )3 9H2 O and (NH4 )6 Mo7 O24 4H2 O were mixed with nitric acid until a gel was formed. The gel was dried at 60 , then it was powderized and preheated at 700 for 5 h. Finally, the pre-heated powders were nely ground, pressed into pellets and sintered at 1050 in a stream of 5% H2 /Ar gas for 12 h with intermediate grindings. Samples were heated and cooled at a rate of 5 C/min in the same atmosphere. Crystal structure and phase purity of the samples were examined by X-ray diffraction (XRD) using a Rigaku D/max 2500 diffractometer with Cu K radiation (50 kV 250 mA) and a graphite monochromator. The XRD data were collected in the 2 range of 15 140 by a step scan mode with a step width of 2 = 0.02 and a sampling time of 1 s per step. The XRD pattern showed that all the samples were single phase without detectable impurity. The XRD data were analysed by the Rietveld renement program FULLPROF [19, 20]. Field dependence of magnetization of the compounds was measured at 5 K on a superconducting quantum interference device (SQUID). Temperature dependence of magnetization was recorded by a vibrating sample magnetometer in a eld of 500 Oe. Considering possible vaporization of Na, we measured the chemical composition of the compounds by the standard addition method based on the ICP-AES (inductively coupled plasma-atomic emission spectroscopy). It was showed that Na did vaporize by different degree, while the concentration of Sr, Fe and Mo were almost equal to the nominal ones. The measured Na concentration for the x = 0, 0.05, 0.1, 0.15 and 0.2 samples are 0, 0.02, 0.03, 0.07 and 0.17 respectively. In the following discussion, we use the measured Na concentration as the doping level.
3 Results and discussion

The composition dependence of XRD pattern of the compounds is shown in Fig. 1. All the peaks can be indexed based on the space group I4/m [2123]. Owing to the

ordered arrangement of Fe and Mo atoms on the B and B sites in the perovskite structure, all the XRD patterns exhibit the (101) superstructure reection. The degree of ordering is dened as = 1 AS, where AS is the anti-site defect concentration. It is well known that the degree of ordering in double perovskites is related to the charge difference between the cations on the Fe and Mo sites, the larger the difference, the more likely the ordered structure. Electron-doped Sr2 FeMoO6 is one of the examples. In this system, the selectively doping of electrons into the spin-down band reduces the charge difference between the cations on the Fe and Mo sites, therefore the degree of ordering of the compound decreases monotonically with the doping level [14, 18]. In the Na-doped Sr2 FeMoO6 system, the degree of ordering of all the doped compounds is larger than that of the parent compound, as evidenced by the variance of the intensity of superstructural reection. As shown in the inset of Fig. 1, Rietveld renements of the crystal structure manifest that the degree of ordering is 78.07% for the x = 0 parent compound. As x increases from x = 0 to x = 0.03, the degree of ordering increases to 86.59%, while with further increase of the doping concentration, the degree of ordering decreases slightly. Similar to the electron doping case, the increase of the Fe/Mo ordering due to the hole doping indicates that the charge difference between the cations on the Fe and Mo sites may be increased, since spin-down subband crossing the Fermi level is likely to be partially lled with hole carriers. Lattice constants and unit cell volume of the compounds as a function of the doping level are shown in Table 1. Due to the smaller ionic radius of Na+ than that of Sr2+ ions (Na+ : 1.39 , Sr2+ : 1.44 for CN = 12), the lattice constants and unit cell volume of the compounds decrease slightly with x . Based on the I4/m space group, we rened the structure of the compounds. During the renements, the Na concentration was xed at the measured value. In the preliminary renement, the thermal factors of Sr (Na), Fe, Mo and O atoms were given based on the values of Sr2 FeMoO6 derived from neutron diffraction [23], and the degree of ordering was re-

ZHANG et al.

Hole doping effects in (Sr2x Nax )FeMoO6 double perovskite

x =0 a () c() V(3 ) (%) O1 8h(xy0) x y O2 4e(00z) z BSr/Na (2 ) BFe (2 ) BMo (2 ) BO1 (2 ) BO2 (2 ) Rwp (%) Re (%) 5.5714(1) 7.8998(2) 245.21(1) 78.07 0.2601(8) 0.2445(7) 0.2512(6) 0.67(1) 0.39(1) 0.02(1) 0 2.09(11) 12.0 5.49 x = 0.02 5.5710(1) 7.8994(1) 245.16(1) 83.57 0.2755(5) 0.2318(4) 0.2521(5) 0.43(1) 0.21(1) 0.08(1) 0 1.57(11) 11.0 5.63 x = 0.03 5.5707(1) 7.8993(1) 245.13(1) 86.59 0.2785(5) 0.2299(4) 0.2544(5) 0.21(1) 0.39(1) 0.15(1) 0.01(4) 1.58(10) 11.6 5.66 x = 0.07 5.5702(1) 7.8991(1) 245.08(1) 85.18 0.2782(7) 0.2298(5) 0.2535(6) 0.21(1) 0.58(2) 0.27(1) 0.36(5) 1.19(11) 13.7 5.63

461
x = 0.17 5.5700(1) 7.8989(1) 245.06(1) 83.90 0.2786(7) 0.2299(4) 0.2543(5) 0.09(1) 0.69(2) 0.28(1) 0.58(5) 1.32(10) 12.0 5.65

Atomic parameters, degree of Fe/Mo ordering ( = 1 AS), thermal factor (B) and reliability factors (RWP , Re ) of the Nadoped Sr2 FeMoO6 . The space group is I4/m with chemical formula per unit cell of Z = 2, Sr ion is located at 4d (1/2 0 1/4), Fe at 2a (0 0 0) and Mo at 2b (0 0 1/2)
TABLE 1

ned. Then, the thermal factors of atoms at different positions were rened on condition that the degree of ordering was not changed. After several separate renements of the thermal factors and the degree of ordering, all the parameters, including prole parameters, atomic parameters, thermal factors and the degree of ordering, were rened simultaneously. The nal renement results for the Na-doped Sr2 FeMoO6 are listed in Table 1. As an example, Fig. 2 shows the renement result of (Sr1.9 Na0.03 )FeMoO6 compound. The experimental and calculated XRD patterns, their difference and the expected peak positions are shown in the gure. Field dependence of magnetization of the Na-doped Sr2 FeMoO6 (0 x 0.17) compounds measured at 5 K is shown in Fig. 3. The magnetization increases rapidly with the applied eld and then saturates to a value of MS (derived by extrapolating 1/H to zero on the M-1/H curve), indicating

that all the compounds are ferromagnetic. Compared to the doped compounds, the magnetization of the parent compound increases slowly at low elds, revealing that due to the higher AS concentration, there are more pinning centers in the parent Sr2 FeMoO6 compound that prevent the magnetic domain from rotating. One of the most important parameters for magnetoresistive oxides is their saturation magnetization ( MS ), because a large MS favors a large LFMR. A large magnetic moment makes it easy for the applied magnetic eld to align the magnetization of the grains; therefore, the tunneling of the spin polarized carriers across the grains becomes easy, resulting in a large LFMR. For the Na-doped Sr2 FeMoO6 , as shown in Fig. 4, the observed MS (lled circle) increases from 2.28 B /f.u. for x = 0 to 3.21 B /f.u. for x = 0.07, while for the highest doping level compound (x = 0.17), its MS decreases slightly to 3.04 B /f.u. As reported by Ogale et al. [12], the saturation magnetization of the parent compound

FIGURE 2 Observed and calculated XRD patterns for (Sr1.9 Na0.03 )FeMoO6 compound. The vertical bars at the bottom indicate the Bragg reection positions, the lowest curve is the difference between the observed and the calculated XRD patterns

FIGURE 3

Magnetization curves of the Na-doped Sr2 FeMoO6 at 5 K, x is the measured Na concentration

462

Applied Physics A Materials Science & Processing

FIGURE 4 Dependence of saturation magnetization on doping content x. Filled circle is the experimental value, lled square represents the calculated value simply including AS, open circle represents the calculated value based on the FIM and the hole contribution

Sr2 FeMoO6 decreases with the increase of anti-site defects concentration. The saturation magnetization of Sr2 FeMoO6 is MS = m m , where m is the magnetization of the spin-up sub-band and m is the magnetization of the spin-down subbands. As the rst approximation, the hybridization between Fe, O and Mo is not considered in the simplest ferrimagnetization model (FIM) [10] and an antiferromagnetic coupling between the moments of the Fe and Mo sublatticces is assumed. If one takes into account the spin-only contribution of Fe3+ and Mo5+ ions, the FIM model gives MS = 4 8y B /f.u. for Sr2 FeMoO6 , where y is the AS defect concentration derived from the Rietveld renements. The FIM model elucidates satisfactorily the relationship between the measured MS of Sr2 FeMoO6 and AS [10]. If the effects of hole doping on the valence states of the cations on the Fe and Mo sites were not considered, the saturation magnetization of the doped compounds could also be expressed as MS = 4 8y B /f.u.. The calculated MS are shown in Fig. 4 as lled squares. The difference between the observed MS and the calculated one is large, especially for the high doping level compounds, indicating that the variation of MS can not be explained by simply considering the AS. In consistence with the analysis of the degree of ordering, the valence state of the cations on the Fe and Mo sites might be altered by the hole doping and the magnetization is changed accordingly. Contrary to the case of electron-doped Sr2 FeMoO6 , doping Na in Sr2 FeMoO6 introduces holes to the compound. Doping one Na atom would introduce one hole and vaporizing one Na atom would introduce two holes, so the total hole concentration () for Sr2 FeMoO6 , (Sr1.95 Na0.02 )FeMoO6 , (Sr1.9 Na0.03 )FeMoO6 , (Sr1.85 Na0.07 )FeMoO6 and (Sr1.8 Na0.17 )FeMoO6 compounds are 0, 0.08, 0.17, 0.23 and 0.23 respectively. Based on the analysis of the degree of ordering, if these holes were injected selectively into the spin-down subbands, the magnetization at the spin-down subbands will be reduced by (B /f.u.). Thus, the above formula should be modied as MS = 4 8y + B /f.u. The calculated MS is shown in Fig. 4 as open circles, which qualitatively reproduces the composition dependence of the observed MS , indicating that the assumed

injection of the hole to the spin-down band may be close to the reality. Figure 5 shows the temperature dependence of magnetization of the Na-doped Sr2 FeMoO6 compound. For the sake of clarity, all curves were normalized at 300 K and shifted from each other. The transition temperature (TC ) is determined from the inection point of the M T curve. The strong magnetic coupling between Fe and Mo atoms can be explained in light of the double exchange mechanism via FeO-Mo-O-Fe charge transfer. Therefore, the strength of magnetic interaction should be closely related to the density of charge carriers. It is worth recalling that, in the electrondoped Sr2 FeMoO6 system, TC did increase monotonically with the doping level due to the band lling effect. In the Nadoped Sr2 FeMoO6 compounds; however, TC exhibits a nonmonotonic variation with x . As shown in the inset of Fig. 5, TC decreases rst with x from x = 0 to x = 0.03 and then increases for x beyond 0.03. Similar phenomenon has been reported in (La1x Cax )MnO3 system [24]. This composition dependence of TC may be explained based on the variation of n Mo /n Fe at Fermi level in the compound, where n denotes the density of states. Based on the density of states calculated by Kuepper et al. [25], when small amount of hole is introduced into the compound, both n Mo and n Fe decrease, but n Mo decreases faster than n Fe . Thus n Mo /n Fe is decreased, and TC of the compounds is decreased accordingly. With the increase of the hole concentration, n Mo and n Fe decrease further. If the increased hole concentration reaches some percolation threshold [26, 27], then n Fe will decrease substantially, while n Mo will decrease slowly. Consequently, n Mo /n Fe is increased and the TC of the compound increases. From the present work, the percolation threshold in hole concentration may be around = 0.23. When < 0.23 (corresponding to the compounds with x = 0, 0.02 and 0.03), n Mo /n Fe decreases with x , thus TC is decreased. When 0.23 (corresponding to the (Sr1.85 Na0.07 )FeMoO6 and the (Sr1.8 Na0.17 )FeMoO6 compounds), n Mo /n Fe increases with x and the TC of the compound is increased accordingly.

FIGURE 5 Temperature dependence of magnetization of the Na-doped Sr2 FeMoO6 compound. Inset is the variation of Curie temperature with the doping level, x

ZHANG et al.

Hole doping effects in (Sr2x Nax )FeMoO6 double perovskite

463

Conclusion

In summary, the structural and magnetic properties of the hole-doped Sr2 FeMoO6 compounds with the Na content x between 0 and 0.17 have been studied. Analysis of the XRD pattern indicates that all the compounds are of single phase and belong to the I4/m space group. Due to the smaller ionic radius of Na than that of Sr ions, the lattice constant and cell volume of the compound decrease slightly. The degree of the Fe/Mo ordering increases from 78.44% for the parent compound to 86.59% for the x = 0.03 compound, then decreases slightly to 83.90% for the x = 0.17 compound. The saturation magnetization of the Na-doped Sr2 FeMoO6 compound increases with x for x < 0.17. Assuming that the doped hole selectively enters the spin-down subbands, the moment on this subbands will be decreased accordingly. Taking into account the hole contribution, the calculated MS based on the FIM model reproduces qualitatively the composition dependence of the experimental MS , which is similar to the case of electron-doped Sr2 FeMoO6 system. Contrary to the composition dependence of the degree of ordering, the Curie temperature of the compound decreases rst with x from x = 0 to x = 0.03, then it increases for the high doping level (x = 0.07 and x = 0.17). The carrier concentration ratio n Mo /n Fe may account for this phenomenon.
REFERENCES
1 F.K. Patterson, C.W. Moeller, R. Ward, Inorg. Chem. 2, 196 (1963) 2 F.S. Galasso, F.C. Douglas, R.J. Kasper, J. Chem. Phys. 44, 1672 (1966) 3 J. Longo, R. Ward, J. Am. Chem. Soc. 83, 2816 (1961) 4 E.J. Fresia, L. Katz, R. Ward, J. Am. Chem. Soc. 81, 4783 (1959) 5 K.-I. Kobayashi, T. Kimura, H. Sawada, K. Terakura, Y. Tokura, Nature 395, 677 (1998) 6 D.D. Sarma, P. Mahadevan, T. Saha-Dasgupta, S. Ray, A. Kumar, Phys. Rev. Lett. 85, 2549 (2000)

7 H. Wu, Phys. Rev. B. 64, 125 126 (2001) 8 Y. Tomioka, T. Okuda, Y. Okimoto, R. Kumai, K.-I. Kobayashi, Y. Tokura, Phys. Rev. B 61, 422 (2000) 9 M.W. Lufaso, P.M. Woodward, Acta Cryst. B 60, 10 (2004) 10 L. Balcells, J. Navarro, M. Bibes, A. Roig, B. Maitnez, J. Fontcuberta, Appl. Phys. Lett. 78, 781 (2001) 11 R.P. Borges, R.M. Thomas, C. Cullinam, J.M.D. Coey, R. Ruryanarayanan, L. Ben-Dor, L. Pinsard-Gaudart, A. Revcolevschi, J. Phys.: Condens. Matter. 11, L445 (1999) 12 A.S. Ogale, S.B. Ogale, R. Ramesh, T. Venkatesan, Appl. Phys. Lett. 75, 537 (1999) 13 M. Tovar, M.T. Causa, A. Butera, J. Navarro, B. Martnez, J. Fontcuberta, M.C.G. Passeggi, Phys. Rev. B. 66, 024 409 (2002) 14 J. Navarro, C. Frontera, L. Balcells, B. Martnez, J. Fontcuberta, Phys. Rev. B 64, 092 411 (2001) 15 D. Serrate, J.M. De Teresa, J. Blasco, M.R. Ibarra, L. Morell n, C. Ritter, o Appl. Phys. Lett. 80, 4573 (2002) 16 D. Serrate, J.M. De Teresa, J. Blasco, M.R. Ibarra, L. Morell n, C. Ritter, o Eur. Phys. J. B 39, 35 (2004) 17 J. Navarro, J. Nogu s, J.S. Muoz, J. Fontcuberta, Phys. Rev. B. 67, e 174 416 (2003) 18 D. Rubi, C. Frontera, G. Herranz, J.L. Garca Muoz, J. Fontcuberta, C. Ritter, J. Appl. Phys. 95, 7082 (2004) 19 R.A. Young, D.B. Wiles, J. Appl. Cryst. 15, 430 (1982) 20 J. Rodroguez-Carvajal, Physica B 192, 55 (1993) 21 J. Blasco, C. Ritter, L. Morellon, P.A. Algarable, J.M. De Teresa, D. Serrate, J. Garca, M.R. Ibarra, Solid State Sci. 4, 651 (2002) 22 O. Chmaissem, R. Kruk, B. Dabrowski, D.E. Brown, X. Xiong, S. Kolesnik, J.D. Jorgensen, C.W. Kimball, Phys. Rev. B 62, 14 197 (2000) 23 D. S nchez, J.A. Alonso, M. Garca-Hern ndez, M.J. Martnez-Lope, a a J.L. Martnez, Phys. Rev. B 65, 104 426 (2002) 24 S.W. Cheong, H.Y. Hwang, Ferromagnetism vs. Charge/Orbital Ordering in Mixed-Valent Manganites, in Colossal Magnetoresistive Oxides, ed. by Y. Tokura (Gordan and Breach Science Publishers, Germany, 2000) 25 K. Kuepper, M. Kadiro lu, A.V. Postnikov, K.C. Prince, M. Matteucci, g V.R. Galakhov, H. Hesse, G. Borstel, M. Neumann, J. Phys.: Condens. Matter. 17, 4309 (2005) 26 C.L. Yuan, Y. Zhu, P.P. Ong, J. Appl. Phys. 91, 4421 (2002) 27 X.M. Feng, G.H. Rao, G.Y. Liu, H.F. Yang, W.F. Liu, Z.W. Ouyang, L.T. Yang, Z.X. Liu, R.C. Yu, C.Q. Jin, J.K. Liang, J. Phys.: Condens. Matter. 14, 12 503 (2002)