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6 Journal of Magnetism and Magnetic Materials 226}230 (2001) 794}796
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10 E!ects of Fe doping in La Ca MnO
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12 P. Levy*, L. Granja, E. Indelicato, D. Vega, G. Polla, F. Parisi
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14 Grupo Materia Condensada, Departamento de Fn& sica, Centro Ato& mico Constituyentes, Comisio& n Nacional de Energn& a Ato& mica,
15 Av. Gral Paz 1499 (1650) San Martn& n, Argentina
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18 Abstract
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20 The e!ect of Fe doping in the Mn site on the magnetic, transport and structural properties of polycrystalline
21 La Ca MnO was studied. Doping with low Fe concentration ((10%) strongly a!ects electrical transport and
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magnetization. Long range charge order is disrupted even for the lowest doping level studied (&2%). For Fe
23 concentration up to 5% a ferromagnetic state develops at low temperature with metallic-like conduction and thermal
24 hysteresis. In this range, the Curie temperature decreases monotonously as a function of Fe doping. Insulating behavior
25 and a sudden depression of the ferromagnetic state is observed by further Fe doping.  2001 Elsevier Science B.V.
26 All rights reserved.
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28 Keywords: Charge ordering; Phase transitions*antiferro-ferromagnetic; Phase transitions*metal insulator; Magnetoresistance
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33 Mixed valence manganates Ln D MnO (where have studied the e!ect of Fe substitution in the Mn site of
\V V >B
34 Ln is a lanthanide and D an alkaline earth ion) have been La Ca MnO . Low temperature long range CO is
  
35 the subject of broad research because of the variety of disrupted and a FM state is obtained for Fe concentra- 59
36 properties they exhibit [1}3]. Among them, those com- tion below 5%. By further Fe doping insulating behavior 60
37 pounds exhibiting charge order (CO) phenomena are and a sudden depression of the ferromagnetic state is 61
38 being the focus of intense studies because percolative observed. 62
39 paths of coexisting ferromagnetic (FM) metallic phases Polycrystalline samples of La Ca Fe Mn O 63
  W \W 
40 are suspected to be responsible of colossal magnetoresis- (0(y(0.1) were prepared by thermal decomposition of 64
41 tance [4]. The low temperature ordering of Mn> and the corresponding citrates at 7003C, followed by a heat 65
42 Mn> can be destroyed by substitutionally induced ca- treatment at 10003C for 10 h. Powders were pelletized 66
43 tion disorder, either in the Mn site [5,6] or in the Ln-D and sintered at the same temperature for 5 h. X}ray 67
44 site [7]. Also, application of magnetic "eld may lead to powder di!raction data was collected at room temper- 68
45 a charge melting [8] of the otherwise ordered lattice. ature using a Philips di!ractometer. Magnetization was 69
46 The La Ca MnO compound has antiferromag- measured using a commercial SQUID magnetometer. 70
  
47 netic (AFM) ground state with CO; upon warming, a "rst Resistivity was measured by the four-probe technique. 71
48 order phase transition to a FM state is observed. Ther- The obtained samples were single phase and all re#ec- 72
49 mal disorder inhibits charge localization and AFM coup- tions could be indexed on the basis of an orthorhombic 73
50 ling, and thereby the double exchange (DE) mechanism cell with space group Pnma and lattice parameters 74
51 leads to a FM state. The subtle competition between FM a"5.4148(5) As , b"7.6389(7) As , c"5.4260(5) As for the 75
52 and CO states gives rise to phase separation into undoped sample. A slight and smooth increase in lattice 76
53 nanodomains of FM and CO states below 150 K [9]. We parameters as a function of y was obtained, of the order 77
54 of 0.3% for y"0.1. MoK ssbauer spectra con"rmed the 78
55 presence of the dopant as Fe>. 79
56 The temperature dependence of the magnetization at 80
57 * Corresponding author. Fax: 54-11-4754-7121. H"1 T is shown in Fig. 1 for samples with di!erent Fe 81
58 E-mail address: levy@cnea.gov.ar (P. Levy). doping level. The undoped sample displays the typical 82
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0304-8853/01/$ - see front matter  2001 Elsevier Science B.V. All rights reserved. 84
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 P. Levy et al. / Journal of Magnetism and Magnetic Materials 226}230 (2001) 794}796 795

1 undoped sample is inhibited for y"0.02, forcing a more 57

2 than seven orders of magnitude change in the resistivity 58
3 value. Metallic-like behavior is observed below 120 K on 59
4 cooling, with a resistivity peak at 140 K. Above 200 K 60
5
(¹) follows activated behavior. Thermal hysteresis is 61
6 observed:
(¹) around the peak is higher for cooling 62
7 curves than for those obtained upon warming the sample 63
8 from 30 K. The temperature range where hysteresis oc- 64
9 curs is about 80 K. Interestingly, the nature of the irre- 65
10 versibility is qualitatively di!erent to that depicted by the 66
11 undoped sample, re#ecting a change in the ground state. 67
12 Samples with doping levels y"0.03 and 0.05 display 68
13 a similar features to the y"0.02 sample described above, 69
14 with increased resistivity values and decreased peak resis- 70
15 tivity temperatures. For y"0.07 insulating reversible 71
16 behavior is obtained down to 30 K, although low mag- 72
17 Fig. 1. Field cool cooling magnetization as a function of temper- netization and depressed ¹ can still be observed in 73
ature at H"1 T for La Ca Fe Mn O (0(y(0.07) !
18   W \W  magnetization data. 74
samples.
19 The e!ect of Fe on the La Ca Fe Mn O com- 75
  W \W 
20 pound can be analyzed from two di!erent points of view, 76
21 namely the e!ects on the CO phase and on the DE 77
22 coupling. The undoped compound is now known to 78
23 exhibit phase separation into nanodomains [6] of FM 79
24 and CO states below 150 K. In our case, the low temper- 80
25 ature magnetization of 0.3
at H"1 T calls for about 81
26 a 10 % volume fraction of FM phase imbedded in a CO 82
27 insulating phase with no metallic percolation through the 83
28 sample. As low Fe doping levels are introduced, low 84
29 temperature long range CO is inhibited and metallic 85
30 percolation is induced through the whole sample. Mag- 86
31 netic measurements show that concomitantly a robust 87
32 low temperature FM phase develops. Thus it is suspected 88
33 that low Fe doping stabilizes enough FM metallic clus- 89
34 ters to account for both experimental facts. 90
35 As Fe does not participate in the DE mechanism, 91
36 it weakens the FM phase when it is introduced in the 92
37 Fig. 2. Temperature dependence of resistivity for Mn site. Quantitative considerations suggest a non-local 93
38 La Ca Fe Mn O (0(y(0.07) samples. Arrows indi- e!ect, instead of a single Mn}O}Mn bond interruption 94
  W \W 
39 cate the directions of the temperature change. produced by each Fe ion introduced. In the related 95
40 compound with pure FM metallic ground state 96
41 (La Ca MnO ) a decrease in ¹ and low "eld 97
   !
42 magnetization is obtained [10,11] when Fe is doping the 98
43 behavior already reported in the literature: paramagnetic Mn site. The increase in resistivity values in the FM 99
44 above 250 K, FM between ¹ "225 and 150 K on cool- phase of lightly doped compounds and the monotonous 100
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45 ing, and AFM below 150 K. Low doping level produces decrease in ¹ as Fe doping increases can then be related 101
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46 a gradual decrease in the Curie temperature, and an to the weakening of the DE mechanism within FM 102
47 abrupt increase of the low temperature magnetization up clusters. 103
48 to 3
for y"0.05. Beyond 5% Fe doping a sudden Summarizing, we have observed suppression of long 104
49 decrease in the low temperature magnetization is ob- range CO in La Ca MnO by low level doping with 105
  
50 served, obtaining 0.3
for y"0.07. Fe the Mn site. At low temperature a FM state develops, 106
51 The e!ect of Fe doping on
(¹) at H"0 is shown in which is further depressed by the increase of the impurity 107
52 Fig. 2. The undoped sample displays thermally activated concentration. Phase separation into FM and CO states 108
53 resistivity behavior above and close below ¹ "225 K. in the undoped compound, the presence of thermal hys- 109
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54 At ¹"150 K on cooling (200 K on warming) the resis- teresis and enhanced magnetoresistance on Fe doped 110
55 tivity increases (decreases) abruptly due to the CO samples suggest that CO regions coexist with percolative 111
56 transition. This low temperature CO phase present in the FM regions. 112
 796 P. Levy et al. / Journal of Magnetism and Magnetic Materials 226}230 (2001) 794}796

1 We thank L. Civale for help during magnetization [4] M. Uehara, S. Mori, C.H. Chen, S.W. Cheong, Nature 399 11
2 measurements. Part of this work was supported by (1999) 560. 12
3 CONICET PEI 98 C125. [5] A. BarnabeH et al., J. Appl. Phys. 71 (1997) 3907. 13
4 [6] F. Damay et al., J. Appl. Phys. 82 (1997) 1485. 14
[7] F. Damay, C. Martin, A. Maignan, B. Raveau, J. Appl.
5 15
Phys. 82 (12) (1997) 6181.
6 References [8] G. Xiao et al., Phys. Rev. B 54 (1996) 6073.
16
7 [9] S. Mori, C.H. Chen, S.-W. Cheong, Phys. Rev. Lett. 81 17
8 [1] P. Schi!er et al., Phys. Rev. Lett. 75 (1995) 3336. (1998) 3972. 18
9 [2] A. Ramirez et al., Phys. Rev. Lett. 76 (1996) 3188. [10] K.H. Ahn et al., J. Appl. Phys. 81 (1997) 5505. 19
10 [3] C.H. Chen et al., Phys. Rev. Lett. 76 (1996) 4042. [11] S.B. Ogale et al., Phys. Rev. B 57 (1998) 7841. 20
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