Effect of particle size on the magnetic and transport properties of La 0.875 Sr 0.125 MnO 3 Anulekha Dutta,* N. Gayathri, ² and R. Ranganathan ECMP Division, Saha Institute of Nuclear Physics, 1/AF Bidhan Nagar, Kolkata-700064, India Received 27 January 2003; published 29 August 2003 The magnetic and transport properties of nanocrystalline La 0.875 Sr 0.125 MnO 3 have been studied. Raw samples, prepared by the sol-gel method, were annealed at different temperatures to produce samples of particle sizes 18 nm, 36 nm, and 50 nm. Unlike bulk and single-crystalline samples of the same composition, magnetization data of the nanoparticle samples show no signature of structural transitions. The effects of particle size on the magnetic and transport properties have been attributed to the domain status, changes in the Mn-O-Mn bond angle, and Mn-O bond length in comparison with bulk samples. Field-cooled hysteresis measurements suggest a cluster glasslike behavior in the nanoparticle samples. DOI: 10.1103/PhysRevB.68.054432 PACS numbers: 75.47.Lx, 73.63.Bd I. INTRODUCTION Manganites having colossal magnetoresistive properties have been the subject of various research activities because of the close interplay between the magnetism and the trans- port exhibited by these manganites. 1 A number of structural and magnetotransport studies of the polycrystalline, single- crystal, and thin films of the doped manganites show that the ferromagnetic Curie temperature and the metal- semiconductor transition temperature are strongly dependent on the preparation method. Of the various manganese per- ovskites, the La 1 -x Sr x MnO 3 system has received a lot of interest because it exhibits the highest T c among all the doped manganite samples. Over the entire composition range, the system exhibits rich magnetic and electrical phases. 1 At low doping levels ( x 0.2) the system is a canted antiferromagnetic insulator for x 0.1, a ferromagnetic insu- lator for 0.1x 0.15, and a ferromagnetic metal for x 0.15. In the low doped regime of the La 1 -x Sr x MnO 3 sys- tem single crystals and bulk polycrystalline samples have been extensively studied because of the series of structural, magnetic, and electronic phase transitions they undergo as a function of temperature which is also a paradigmatic ex- ample of the interplay between carrier, lattice, spin, and or- bital degrees of freedom. 2–4 The composition of La 0.875 Sr 0.125 MnO 3 is in the region of ferromagnetic insula- tor. Exhaustive studies using single-crystal and bulk poly- crystalline samples have been performed on this composi- tion. The La 0.875 Sr 0.125 MnO 3 single crystal shows a series of structural transitions as a function of temperature. 3–13 The first transition is from the high-temperature rhombohedral phase to an orthorhombic Ophase at 450 K. The second transition occurs at around 270 K ( T OO ' ) which is associated with the O to O' the Jahn-Teller distorted orthorhombic phasetransition. This O' phase distorts to the orthorhombic Ophase at T 140 K ( T O ' O ). At T 180 K ( T C ) La 0.875 Sr 0.125 MnO 3 shows a paramagnetic to a ferromagnetic metal FMMtransition which is associated with a decrease in the resistivity with temperature (d/dT 0). As the tem- perature is lowered the FMM state gives way to a ferromag- netic insulator FMIat T 140 K, which coincides with the T O ' O structural transition. The magnetization shows a sud- den increase at this temperature. Detailed neutron-diffraction and high-energy x-ray-diffraction studies have given evi- dence of charge ordering at this temperature. 3,10–12 Though there were contradictory reports suggesting that the low- temperature phase be called an orbital ordered phase and not a charge ordered phase, 8,9,13,14 now a consensus has been reached that the phase is a charge ordered COone. Dab- rowski et al. have done a detailed magnetic, structural, and electronic properties study of La 1 -x Sr x MnO 3 around the composition x =0.125. 15 They have observed for x =0.125 that T C 190 K and there exists a small anomaly at T 135 K where magnetization decreases. The resistivity also shows a decrease at T C and then again an increase below 140 K which coincides with the T CO observed in single crystals. The transition is rather broad because of the polycrystalline nature of the sample. An earlier report on a similar compo- sition but with a varying oxygen content 16 shows an insulat- ing behavior throughout the temperature range and also a very broad ferromagnetic transition with no particular anomalies in the magnetization. In this study we examine the influence of particle size on this particular composition of the Sr-doped system. It is well known that reduction in particle size has a direct conse- quence on the electronic and magnetic properties of a sys- tem. Some salient features observed as we reduce the particle size of magnetic systems are ia decrease and broadening of the ferromagnetic transition temperature T C , iia decrease in the magnetization in comparison with single-crystal and bulk polycrystalline samples, showing superparamagnetic behavior at very low particle size, iiian increase in resis- tivity, showing insulating properties at very low particle size, and iva higher value of magnetoresistance compared to the bulk samples especially at low temperatures which is attrib- uted to a spin-polarized intergrain tunneling mechanism. 17 These observations can be logically explained by assuming the increase of an insulating grain-boundary contribution as the particle size decreases. 18–20 Formation of grain bound- aries causes broken bonds at the surface, which causes a decrease in the magnetization value. The increase in resistiv- ity is a consequence of the broken bonds as well. This is the most general observation in the case of nanoparticles of the manganite system. 18,21 There are a few exceptions to this general rule. A recent report by Fu 22 on the La 0.8 Ca 0.2 MnO 3 PHYSICAL REVIEW B 68, 054432 2003 0163-1829/2003/685/0544328/$20.00 ©2003 The American Physical Society 68 054432-1