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Materials Research

Print version ISSN 1516-1439

Mat. Res. vol.14 no.2 São Carlos  2011  Epub June 03, 2011 

Chemical deposition of La0.7Ca0.3MnOδ films on ceramic substrates



Cássio Morilla-SantosI,*; Wido Herwig SchreinerII; Paulo Noronha Lisboa-FilhoIII

IPrograma de Pós-Graduação em Ciência e Tecnologia de Materiais, Universidade Estadual Paulista - UNESP, Bauru, SP, Brazil
IILaboratório de Superfícies e Interfaces, Departamento de Física, Universidade Federal do Paraná - UFPR, CP 19044, CEP 81531-980, Curitiba, PR, Brazil
IIIDepartamento de Física, Universidade Estadual Paulista - UNESP, CP 473, CEP 17033-360, Bauru, SP, Brazil




In this paper, it is reported the growth of La0.7Ca0.3MnOδ films using a chemical solution deposition method (CSD) by the spin-coating technique. Such solution was prepared through a route based on modified polymeric precursor method. Spin-coating deposition on different ceramic substrates was performed and analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The magnetic response of the prepared specimens was studied using a SQUID magnetometer. The obtained results indicated uniform deposition on SrTiO3 and LaAlO3 substrates with similar characteristics. Furthermore, significant differences were detected in the Mn3+/Mn4+ valence ratio and a corresponding diverse magnetic response was observed. The sample prepared on SrTiO3 and LaAlO3 presented a critical temperature around 270 K as expected.

Keywords: chemical solution deposition, Pechini method, spin-coating, magnetic material.



1. Introduction

Thin films based on manganites receive considerable investments and efforts, due to the fact that this material has potential usage in magnetic devices1. Besides, properties such as the magnetoresistance effect, as well as a variety of fundamental physical properties have been systematically studied1,2. Phenomena such as ferromagnetism, antiferromagnetism, ferrimagnetism and paramagnetism, can be found in manganite oxides systems containing metallic elements and a rare-earth element. Thus, it is expected to understand the structural and magnetic properties of these compounds in both films and in bulk.3,4. Amongst several methods used for the growth of oxide thin films, it is pointed the methods based on techniques such as Magnetron Sputtering, Laser Molecular Beam Epitaxy and Pulsed Laser Deposition5,6,7. In the case of the synthesis of La0.7Ce0.3MnO3 and La0.7Ca0.3MnO3 films, both are commonly grown on SrTiO3 substrates through laser deposition techniques8,9.

Considering LaMnO3 compounds at low temperatures, the presence of Mn3+ provides the insulating behavior and with the antiferromagnetic coupling. The replacement of transition metals at the manganese sites generates valence fluctuation, allowing the coexistence of cations Mn3+ and Mn4+[8]. In such cases, the magnetic responses in zero-field-cooling (ZFC) and field-cooling (FC) curves show ferromagnetic response and Curie temperature (Tc) of about 260 K9. It is also found reports on film synthesis of La1-xCaxMnO3±δgrown on several ceramic substrates, studying mismatch between the substrate and the film and electrical resistivity10, as well as their electrical transport and magnetic responses11. Other studies describe the synthesis of La0.67Ce0.33MnO3 film deposited at identical conditions on substrates of SrTiO3, LaAlO3, MgO, NdGaO3 and Si, through DC-sputtering technique12. Furthermore, by the use of targets synthesized through the solid state reaction route, films with thickness of 200 nm, epitaxially oriented toward (001), showed that the magnetic properties are dependent on the used substrate12.

Compared to physical deposition techniques, the one based on chemical solution deposition (CSD) represents an effective alternative, considering that this one allows the achievement of good quality samples with relatively lower costs13. In these cases, the obtained solution can be deposited on the substrate through the deposition techniques such as spin-coating, dip-coating and spray-coating, ending with thermal treatments that support the phase formation on the substrate.

Considering the chemical deposition technique, recent works aim to understand the structural and optical properties in La0.7Ca0.3MnO3 films, deposited on substrates of LaAlO3, via chemical vapor deposition from the vapors of metalloorganic compounds (MODVD) technique14. Generally, the properties of films prepared by chemical methods and questions such as epitaxy, post-annealing treatment, as well as the final quality of the samples have been studied in recent years1,15,16,17. It is also necessary to comment that film formation and its properties can present differences according to the method for the deposition and the substrate used15,18.

In this paper, it was studied the synthesis viability of La0.7Ca0.3MnO3±δ (LCMO) thin films deposited on ceramic substrates of SrTiO3 (STO), LaAlO3 (LAO) and MgO, via CSD. For chemical synthesis, it was used Pechini method18, conducted with oxides and carbonates, less complex to the traditional synthesis Sol-Gel realized from precursors such as alkoxides and acetates1. The deposition was accomplished by spin-coating technique and determined the formation of the desired phase, the morphology, the states of electronic configuration and magnetic responses from the synthesized samples. The comparation of the properties from synthesized films with results found in the literature allowed evaluating the quality of the final samples.


2. Experimental Details

Based on a modified polymeric precursor method to perform chemical synthesis of complex oxides19, solutions were prepared using high purity (Aldrich) La2O3, CaCO3 and MnCO3 as precursors. These compounds were dissolved in stoichiometric ratio into deionized water by adding HNO3 and mixed with citric acid at a metal/citric acid proportion of 1/3. After 30 minutes, ethyleneglycol was also added at a temperature of 60 ºC, at a carboxylic acid/ethylene glycol molar ratio of 60/40. Under constant stirring, NH4OH was added until the solution's pH was 7. Ethylenediaminetetraacetic acid (EDTA) was then added to the solution as a complexant agent at proportion EDTA/acid citric of 1/4. The temperature was increased to 90 ºC in order to evaporate the water excess and form a gel with a viscosity of up to 15 cp.

Three different types of (100) ceramic substrates STO, LAO and MgO were used in this study. Previous to deposition, substrates were cleaned ultrasonically in acetone at 80 ºC for 10 minutes and then washed with deionized water. The obtained gel was then deposited on the different substrates by spin-coating at 1500 rpm for 60 seconds, optimized values for viscosity were deposited. In this process two drops were deposited over the stationary substrate. This process was repeated four times for each sample, and between each deposition, the films were pyrolized on a hot plate at 300 ºC. Heat-treatment followed at 500 ºC/2 hours + 900 ºC/4 hours and post-annealing at 500 ºC for 30 minutes under O2. All heat-treatment was performed in step ratio of 5 ºC/min.

After deposition, crystallographic phases were analyzed by X-ray diffraction in a Rigaku DMAX 2100/PC diffractometer. Chemical elements, quantitative analysis and microstructure were determined using a scanning electron microscope, associated to an electron dispersive energy spectrometer (SEM/EDS) FEG/ Philips with a resolution of 2 nm. For surface analysis and manganese valence state analyses, X-ray photoelectron (XPS) spectra were taken using a VG ESCA 3000 system and using MgKα radiation with overall energy resolution of approximately 0.8 eV. The energy scale was calibrated using the Fermi level and C1s peak at 284.5 eV. The spectra were normalized to maximum intensity after a constant background subtraction. Magnetic measurements were performed using a Quantum Design SQUID Magnetometer.


3. Results and Discussion

The use of modified polymeric precursors methods with the addition of EDTA on the synthesis, showed effective in obtaining the solution to be deposited on the substrate. EDTA is generally used, since it can connect itself to the most of metallic elements, in addition to increasing the stability of some components through the complexation of the species, depending on the pH used20,21. There were no signs of precipitation in the solutions.

In Figures 1 to 3 the diffractograms of LCMO film are presented, deposited on the STO, LAO and MgO substrates, respectively. It is possible to observe the diffraction peaks of the substrates and the deposited polycrystalline phase. The diffraction peaks of the film are quite evident in the positions realized on the STO and LAO substrates. Therefore, for the case of MgO substrate, its intensity is relatively low. A good match of the layer deposited directly on the substrate requires that factors such as the proximity of lattice parameters of film and substrates are considered. In the case of perovskite-type substrates such as STO and LAO, this difference is around 1%, and in the case of MgO substrate, this difference increases to about 7%1. One can relate the result described above to the best or the worst adaptation of the film to the substrate, since the samples were synthesized in the same way, following the same procedures. The influence of the difference among the lattice parameters of film and substrate, as well as its influence on physical properties of LCMO films have been studied22 and they are critical for the samples based on chemical methods12,23.







Considering the three most intense diffraction peaks, the medium crystallite size calculated via Debye-Scherrer equation24 for LCMO/STO and LCMO/LAO was estimated at about 20 nm.

The microstructural characterization of LCMO/STO and LCMO/MgO samples can be observed in Figures 4 and 5, respectively. In both images, it can be noted the typical polycrystalline structure, in agreement with microstructures reported in the literature15,17. The atomic percentages obtained for LCMO/STO and LCMO/LAO samples showed values very close to the desired stoichiometry. Therefore, in the case of LCMO/MgO sample, the atomic percentages values for La, Ca and Mn elements showed much lower. Another important observed characteristic is the porosity. Being in the presented micrographs, it is a characteristic of films from Sol-Gel routes. The porosity arises due to the removal process of organic compounds, prior to the formation of the desired phase15. For the case of EDTA use, it is expected an increase in the porosity, since this propitiates a greater carbon chain, compared to the use of citric acid.

The XPS analysis for the determination of oxidation states of manganese can be observed in Figures 6 and 7. The spectra in binding energy region of Mn2p for LCMO/STO and LCMO/MgO samples are present respectively. The values of the ratio Mn3+/Mn4+ for lanthanum manganite films are highly dependent on the synthesis process, and they are still subjects of study25,26. The presence of oxidation states Mn3+ e Mn4+ is expected for LCMO phase, although Mn2+ state is also reported after thermal treatments in spatial conditions26. The deconvolution results performed in the binding energy spectra of Mn2p are showed in Table 1. It can be noted that for LCMO/MgO sample there is a smaller contribution of Mn4+, whereas for LCMO/STO and LCMO/LAO samples the ratio Mn3+/Mn4+ are similar. As any other oxides, lanthanum manganese perovskites are oxygen deficient materials, thus fluctuating valence in these materials is directly related to oxygen stoichiometry. Considering the XPS results, it can be stated that the charge balancing of the deposited samples on STO and LAO substrates are close, and that the oxygen stoichiometry has an estimated value between 2.91 e 3. Moreover, for LCMO/STO and LCMO/LAO samples, the values of atomic percentages are shown in agreement with the results obtained from microstructural analysis. It was not considered the presence of Mn2+, since it was not observed a contribution around 647 eV, typical of Mn2+ state25.







In Figure 8 are present the magnetization as a function of curves for films deposited on STO and LAO substrates. Under a field application of 100 Oe, the ZFC curves showed the ferromagnetic response, in which the value of magnetic transition temperature (Tc) for LCMO/STO sample was around 276 K and for LCMO/LAO was around 274 K. These are intermediate values to those reported in the literature1,17, which indicates that the Tc value moves to higher temperatures with increasing grain17. The FC curves showed in the transition temperature the ferromagnetic order considering double exchange interactions due to the presence of manganese in the oxidation states 3+ e 4+. Considering the LCMO/MgO sample, it was observed the paramagnetic response. This behavior can be justified by the non-optimized stoichiometry for this sample27, a result evidenced by the low atomic percentages observed in the microstructural analysis. Another important point is the oxygen content, since it has a key role in the magnetic response of films based on oxidase manganites. The values obtained in this study present magnetic critical temperature values close to those observed for in-situ annealed samples prepared by rf-magnetron sputtering28. Under a field application of 1 KOe, it is observed for LCMO/STO sample the magnetic order is kept, by reducing the Tc value to 250 K, as shown in Figure 9. The measurement of magnetization (M) by the applied magnetic field (H) for LCMO/STO film can be seen in Figure 10. In 10 K, it was noted in the hysteresis a low value for coercivity, as well as the saturation magnetization in 5 KOe. Both results indicate the existence of surface effects in this sample, consistent with results reported by other groups29,30.







4. Conclusions

In this work, it was studied the synthesis, structural and magnetic characterization of LCMO films obtained via CSD, grown on substrates of STO, LAO and MgO. The analyses showed a similar formation of the film on the substrates of STO and LAO. For these samples, the results obtained by XRD, XPS and SEM, indicated the film formation with stoichiometry very close to the required (2.91 < 3 ± δ < 3) and obtained through physical methods of deposition. It was also observed the attainment of porous films, characteristic of films obtained via Sol-Gel methods. For LCMO/STO and LCMO/LAO samples were found similar values for the Mn+3/Mn+4 ratio, without the presence of Mn2+ oxidation state. The magnetic responses of LCMO/STO and LCMO/LAO samples indicated a critical temperature around 270 K, as expected for high-quality samples. This work indicates that the procedures used in this contribution can be considered suitable for the synthesis of manganite-based films.



The authors wish to thank the Brazilian agencies FAPESP and CAPES for their financial support. Wilson A. Ortiz is also acknowledged for the use of the SQUID magnetometer.



1. Bae S-Y and Wang SX. Sol-gel epitaxial growth of La1-XCaXMnO3 with colossal magnetoresistance effect. Applied Physics Letters. 1996; 69:121-123.        [ Links ]

2. Salamon MB and Jaime M. The physics of manganites: Structure and transport. Review of Modern Physics. 2001; 73(3):583-628.        [ Links ]

3. Ma Y, Guilloux-Viry M, Barahona P, Peña O and Moure C. Observation of magnetization reversal in epitaxial Gd0.67Ca0.33MnO3 thin films. Applied Physics Letters. 2005; 86(6):062506.        [ Links ]

4. Barahona P, Peña O, Antunes AB, Campos C, Pecchi G, Moreno Y et al. Magnetic properties of Mn-substituted GdCoXMn1-XO3 and LaCoXMn1-XO3. Journal of Magnetism and Magnetic Materials. 2008; 320:e61-e64.        [ Links ]

5. Ray S, Banerjee R, Basu N, Batabyal AK and Barua AK. Properties of tin doped indium oxide thin films prepared by magnetron sputtering. Journal of Applied Physics. 1983; 54:3497-3501.        [ Links ]

6. Yoshimoto M, Sasaki A and Akiba S. Nanoscale epitaxial growth control of oxide thin films by laser molecular beam epitaxy - towards oxide nanoelectronics. Science and Technology of Advanced Materials. 2004; 5:527-532.        [ Links ]

7. Souza-Neto NM, Ramos AY, Tolentino HCN, Favre-Nicolin E and Ranno L. Local Structure in Strained Manganite Thin Films. Physica Scripta. 2005; T115:589-590.        [ Links ]

8. Wang DJ, Sun JR, Zhang SY, Liu GJ and Shen BG. Hall effect in La0.7Ce0.3MnO3±δ films with variable oxygen content. Physical Review B. 2006; 73(14).         [ Links ]

9. Gao G, Jin S and Wu W. Lattice-mismatch-strain induced inhomogeneities in epitaxial La0.7Ca0.3MnO3 films. Applied Physics Letters. 2007; 90(1).         [ Links ]

10. Boikov YA and Danilov VA. Effect of lateral tensile stresses on the low-temperature electrical resisitivity and magentoresistance of La0.67Ca0.33MnO3 nanofilms. Technical Physics. 2010; 55(8):1183-1188.        [ Links ]

11. Vlakhov ES, Nenkov KA, Donchev TI, Mateev ES, Chakalov RA, Szewczyk A et al. Coexistence and competition of ferromagnetic and charge orderer phases in strained La1-XCaXMnO3. Journal of Magnetism and Magnetic Materials. 2005; 290-291:955-958.        [ Links ]

12. Campillo G, Berger A, Osorio J, Pearson JE, Bader SD, Baca E et al. Substrate dependence of magnetic properties of La0.67Ca0.33MnO3 films. Journal of Magnetism and Magnetic Materials. 2001; 237:61-68.        [ Links ]

13. Schwartz RW, Schneller T and Waser R. Chemical solution deposition of electronic oxide filmes. Comptes Rendes Chimie. 2004; 7:433-461.        [ Links ]

14. Granovskii AB, Sukhorukov YP, Telegin AV, Bessonov VD, Gan'shina EA, Kaul AR et al. Giant magnetorefrative Effect in la0,67Ca0.3MnO3 films. Journal of Experimental and Theoretical Physics. 2011; 112(1):77-86.        [ Links ]

15. Fors R, Khartsev S, Grishin A, Pohl A and Westin G. Sol-gel derived versus pulsed laser deposited epitaxial La0.67Ca0.33MnO3 films: structure, transport and effects of post-annealing. Thin Solid Films. 2004; 467:112-116.        [ Links ]

16. Gorbenko OY, Kaul AR, Mel'nikov OV, Gan'shina EA, Ganin AY, Sukhorukov YP et al. Synthetic routes to colossal magnetoresistance manganitas thin films containing unstable or highly volatile metal oxides. Thin Solid Films. 2007; 515:6395-6401.        [ Links ]

17. Ravi V, Kulkarni SD, Samuel V, Kale SN, Mona J, Rajgopal R et al. Synthesis of La0.7Sr0.3MnO3 at 800ºC using citrate gel method. Ceramic International. 2007; 33:1129-1132.        [ Links ]

18. Pechini MP. Method of Preparing Lead and Alkaline Earth Titanates and Niobates and Coating Method Using the Same to Form a Capacitor. US 3330697. 1967 jul 11.         [ Links ]

19. Lisboa-Filho PN, Mombrú AW, Pardo H, Ortiz WA and Leite ER. Influence of processing conditions on the crystal structure and magnetic behavior of La0.7Ca0.3MnO3±δ. Journal of Physics and Chemistry os Solid. 2003; 64:583-591.         [ Links ]

20. Kakihana M. Sol-Gel preparation of high temperature superconducting oxides. Journal of Sol-Gel Science and Technology. 1996; 6:7-55.        [ Links ]

21. Baccan N, Andrade JC and Godinho OES. Química Analítica Quantitativa Elementar. 3th ed. São Paulo: Editora Edgard Blücher LTDA.; 2001.         [ Links ]

22. Liang Y-C and Liang Y-C. Correlation between lattice modulation and physical properties of La0.72Ca0.28MnO3 films grown on LaAlO3 substrates. Journal of Crystal Growth. 2007; 303(2):638-644.        [ Links ]

23. Tao R, Fang X, Dong W, Deng Z and Zhu TPX. Processing effects on the chemical solution deposition-derived La2/3Ca1/3MnO3 films on SrTiO3 (001) substrates. Journal of Crystal Growth. 2007; 306(2):356-360.        [ Links ]

24. Cullity BD and Stock SR. Elements of X-Ray Diffraction. 3th ed. New Jersey: Prentice Hall; 2001.         [ Links ]

25. Beyreuther E, Grafström S, Eng LM, Thiele C and Dörr K. XPS investigation of Mn valence in lanthanum manganite thin films under variation of oxygen content. Physical Review B. 2006; 73(15).         [ Links ]

26. Valencia S, Gaupp A, Gudat W, Abad Ll, Balcells Ll and Martínez B. Impact of microstructure on the Mn valence of La2∕3Ca1∕3MnO3 thin films. Physical Review B. 2007; 75(18).         [ Links ]

27. Raveau B. The crucial role of mixed valence in the magnetoresistance properties of manganites and cobaltites. Philosophical Transactions of The Royal Society A. 2008; 366:83-92. PMid:17827124.        [ Links ]

28. Valencia S, Gaupp A, Gudat W, Abad Ll, Balcells Ll, Cavallaro A et al. Mn valence instability in La2/3Ca1/3MnO3 thin films. Physical Review B. 2006; 73(10).         [ Links ]

29. Zhu X, Birringer R, Herr U and Gleiter H. X-ray diffraction studies of the structure of nanometer-sized crystalline materials. Physical Review B. 1987; 35(9).         [ Links ]

30. Zhang N, Ding W, Zhong W, Xing D and Du Y. Tunnel-type giant magnetoresistance in the granular perovskite La0.85Sr0.15MnO3. Physical Review B. 1997; 56(8).         [ Links ]



Received: January 5, 2011; Revised: April 29, 2011



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