Competing interparticle interactions and surface anisotropy in NiO nanoparticles

C. T. Meneses, J. G. S. Duque, E. de Biasi, W. C. Nunes, S. K. Sharma et al. Citation: J. Appl. Phys. 108, 013909 (2010); doi: 10.1063/1.3459890 View online: http://dx.doi.org/10.1063/1.3459890 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v108/i1 Published by the American Institute of Physics.

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JOURNAL OF APPLIED PHYSICS 108, 013909 2010

Competing interparticle interactions and surface anisotropy in NiO nanoparticles

C. T. Meneses,1,a J. G. S. Duque,1 E. de Biasi,2 W. C. Nunes,3 S. K. Sharma,4 and M. Knobel4
1

Universidade Federal de Sergipe, Campus Prof. Alberto Carvalho, Ncleo de Fsica, 49500-000 Itabaiana, SE, Brazil 2 Centro Atmico Bariloche (CAB), Instituto Balseiro, CP 8400 S.C. de Bariloche, Rio Negro, Argentina 3 Instituto de Fsica, Universidade Federal Fluminense, 24210-340 Niteroi, RJ, Brazil 4 Instituto de Fisica Gleb Wataghin, Universidade Estadual de Campinas, 13083-859 Campinas, SP, Brazil

Received 26 January 2010; accepted 4 June 2010; published online 15 July 2010 We report unconventional magnetic properties on NiO nanoparticles of an average diameter 5.8 7 nm obtained by coprecipitation method. To investigate the effect of the intra and interparticles interactions in the magnetic properties nanoparticles were dispersed in a polyvinyl-pyrrodone matrix at two different concentrations. X-ray, ac, and dc magnetization and ferromagnetic resonance experiments were carried out on powder and dispersed NiO systems. Our results show that dispersed and concentrated samples exhibit following two different magnetic behaviors: i a high temperature peak related to the blocking of the particle core and ii a low temperature maximum likely related to the freezing of the frustrated spins on surface particle. Besides, we have observed that the low temperature maximum is not eld-dependent and depend strongly on the distance among particles. This result can be understood taking account the decreasing of the dipolar interaction to more dispersed samples. 2010 American Institute of Physics. doi:10.1063/1.3459890
I. INTRODUCTION

In the last few decades, studies on magnetic properties of ne particles with dimensions in the nanometer range have been the subject of intense theoretical and experimental investigations.16 In this sense, magnetic nanoparticles NPs have gained an increasing interest owing to their unique physical properties as compared to their bulk counterparts. It is well known that below a critical size, magnetic NPs behave as a single-domain, in contrast with the multidomain structure observed in their bulk form. In a rough approximation, the energy states of the magnetization vector of the particles can be modeled as a two level system separated by barriers that depend on their size and magnetic anisotropies.24,712 In the most general case the magnetic NPs can present following two different magnetic regimes as a function of temperature: i Below a critical temperature, so-called blocking temperature TB, T TB the energy barriers can trap the magnetization vector in two or more metastable orientations, giving rise to hysteresis and ii for T TB, the thermal energy kBT becomes large enough when compared to the energy barrier leading to the so-called superparamagnetic SPM regime. Additionally, unusual magnetic behavior has been observed in the low temperature regime, which can be interpreted as a result of their nite size, that is, the breaking of a large number of exchange bonds for surface atoms driving the spins to a strongly frustrated state on particle surface. For example, small core moment antiferromagnetic AFM and ferromagnetic FM amorphous NPs
a

Electronic mail: ctmeneses@gmail.com.

Refs. 2, 4, 6, 9, and 1316 presents an additional maximum in the low temperature region of the magnetization curve. On the other hand, to best of our knowledge, there are not reports in literature about this unusual magnetic peak to FM crystalline NPs. Among a variety of such materials, nickel oxide NiO NPs have been a subject of avid research due their nite size effects, small moment core, and strong surface effects. Several models which consider different interparticle interactions4,9,1619 have been suggested to explain the experimental data. Recently, Winkler et al.9 have reported the complexity of the magnetic properties of NiO NPs with an average particle size of 4 nm. They explained their results as a consequence of the competition among size core effects, surface anisotropy and interface interaction. Additionally, theoretical calculations and experimental data have shown that NiO NPs ranging from 1 to 50 nm can present both AFM and FM couplings. This magnetic behavior appears to be linked with uncompensated surface moments.19 The main goal of this work is understand the role of the strengths of interparticle interactions in the magnetic properties of NiO NPs. In this sense, for using the same batch, we have prepared three NPs systems at following three different conditions: i concentrated powder form and ii two dispersed NPs systems. The results show to all samples a high temperature peak related with blocking effects of the NiO and a low temperature maximum likely related with the high degree of frustration of the spins on the particle surface. We also observed that the low temperature peak is strongly de 2010 American Institute of Physics

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108, 013909-1

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FIG. 1. Color online Observed cross and Rietveld rened line XRD pattern and difference between observed and calculated ones below line .

pendent on the distance among particles in contrast with the eld-dependent behavior generally presented for the blocking temperature.
II. EXPERIMENTAL PROCEDURES
FIG. 2. a TEM image of the as-prepared SP NiO NPs and b HRTEM image.

NiO NPs were prepared using coprecipitation method for mixing NiCl2 6H2O and gelatin aqueous solution with NaOH at temperature of 60 C. In order to control the size and minimize the coalescence effect of our particles system we have used gelatin as dispersant agent. The agglomeration is slowly reduced as can be visualized in the Fig. 1 if we compared with others works that NiO NPs only using coprecipitaiton method without addition of any organic precursor.20,21 The precipitated solution Ni OH 2 and disnatured gelatin were slowly cooled up to room temperature and then dried at a temperature of 80 C for 36 h. The precipitated material was annealed in air at 350 C for 3 h to obtain NiO NPs. The ne powder was washed several times with acetone in order to remove the chloride ions completely. Additional preparation details can be found elsewhere.22,23 NiO powder was taken as the most concentrated sample labeled as SP . The diluted NPs systems were obtained after centrifugation and dispersion of NiO NPs in polyvinyl-pyrrolidone PVP at following two concentrations: a 16% NiO/PVP in mass labeled as S1 and b 1.8% NiO/PVP in mass labeled as S2 . The powder x-ray diffraction XRD data were obtained with a Rigaku diffractometer using the BraggBrentano geometry in continuous mode with a scan speed of 1/4/min in the 2 range from 30 to 90 using Cu K radiation. Rietveld renements24 were performed using the software 25 DBWS9807, as described by Young et al. The full width at half maximum obtained from this renement was used to calculate the particle size and microstrain for 1 1 1 , 0 0 2 , 0 2 2 crystallographic families. The details of estimated particle size and strain can be found in Ref. 23. In order to analyze the structure and morphology of the samples transmission electron microscopy TEM images were taken in a high resolution 200 keV JEM 3010 microscope at the Laboratrio de Microscopia Eletrnica at Laboratorio Nacional de Luz Sincrotron LNLS, Brazil . Superconducting quantum interferometer device MPMS XL7 was used to characterize the magnetic properties as function of temperature 2300 K , time and applied mag-

netic eld up to 6 T . AC susceptibility measurements as a function of temperature 2300 K and frequency 102 104 Hz were performed in a commercial PPMS magnetometer Quantum Design . To study the thermal evolution of the anisotropy FM resonance FMR spectra were taken 10300 K using a Bruker ESP300 spectrometer.
III. RESULTS AND DISCUSSION A. Structural analysis

Figure 1 shows the Rietveld renement XRD pattern for the as-prepared NiO NPs. The analysis of the positions and relative intensities of the diffracted lines conrms the presence of single phase cubic structure of NiO with a space group Fm3m and cell parameters a = 4.184 2 . The results obtained through Rietveld renement show a goodness of t 2 = 1.03. From the Rietveld renement, we are able to estimate the average particle size of NiO NPs around 5.8 7 nm and a strain of 0.5% for using WilliamsomHall plotting as discussed in Ref. 23. This value for strain is related to internal disconnections among the crystalline planes. According Rojas et al.26 and Nunes et al.27 this factor can strongly inuence the local magnetic ordering of these materials to TbAl2 alloys and Ni NPs. TEM images see Fig. 2 a for the SP sample show that our NPs system consist of homogeneous particles of nearly spherical shape with an average size of 6.4 8 nm and a log-normal distribution not shown here which is further veried using investigation of zero-eldcooled ZFC -eld-cooled FC curves presented below. Another noteworthy point is that our high resolution TEM HRTEM image shown in Fig. 2 b clearly demonstrates the highly crystalline nature of the NiO NPs.
B. Magnetic properties

Figure 3 shows the magnetization as a function of temperature for the as-prepared SP and dispersed NPs measured in ZFC and FC conditions in an external magnetic eld of 100 Oe. It is evident that as-prepared SP sample exhibits

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(a)

(b)

(c)
FIG. 4. Color online Imaginary components of the ac susceptibility as functions of temperature for samples a as prepared and b S2 sample. The inset is a close up to the behavior near maximum 40 K .

FIG. 3. Color online ZFC-FC magnetization curves to applied eld 100 Oe for samples a as prepared, b S1 sample, and c S2 sample.

a typical SPM behavior in the high temperature regime and a blocked state in the low temperature regime below around 75 K . In addition, the curve also indicates a wide distribution of energies barriers that can be associated to the particles sizes distribution. Therefore, for some case of interacting magnetic metallic NPs, it is almost impossible to see SPM behavior and estimate particles size distribution due to agglomeration of the particles doing that the set of particles behaviors as grain, and consequently, it present to be a multidomain system,28,29 differently of our system. But when these NPs are diluted in some matrix nonmagnetic, they begin appear SPM behavior.29 The M ZFC measurements show to all samples an increase in the magnetization in low temperatures region below 20 K , presenting a peak to SP and S1 samples. This kind of behavior was also observed previously for both crystalline as well as amorphous NPs systems.4,9 The origin of such maximum can be associated to the ordering of small magnetic clusters at the particle surface, inducing strong intraparticle interactions, which leads to a frustrated magnetic state.20 As it has been observed to various magnetic NPs systems the high temperature peak is eld-dependent, that is, it shifts to lower temperatures for increasing the magnetic external eld. However, a careful analysis of the position of the low temperature maxima reveals that the peaks shift to lower temperatures for decreasing the strength of the interparticle interactions, being 11 K for powder samples, 9 K for sample S1, and it is not observed for sample S2. The observation of the low temperature peaks to the SP and S1 samples, their shift into lower temperature region and the continuous increase in M ZFC around 2 K to S2 sample allow us to conclude that the dipolar interaction take an important role in determining the surface effects in the low temperature region. Winkler et al.9 2005 have observed similar effects to NiO noninteracting NPs. Their results indicate that the magnetic behavior dominated by an uncompensated AFM par-

ticle core moment contribution that thermally uctuates at high temperature and a low temperature behavior determined by surface cluster spins whose thermal uctuations freeze in a cluster-glass-like state. Here, we have observed that the surface effects become more and more pronounced as function of dilution, that is, when the particles are continuously diluted in the matrix, the surface effects become stronger and the low temperature maximum is decreased. Figure 4 shows the temperature dependence of the real T and imaginary T parts of the ac susceptibility, measured to SP sample at different frequencies in the range from 102 to 104 Hz using the same conditions of the ZFC magnetization curves measurements. It is clearly seen that increases as the temperature increases up to the proximity of 75 K and shows a frequency-dependent variation but TB decreases rapidly below 50 K and nally becomes frequency independent below 40 K. This suggests that the sample exhibits a blocking phenomenon at region high temperature. The weak dependence of the frequency at low temperatures around 11 K is a typical behavior of strong surface effects. The relaxation time calculated to both high and low temperature peak see insets of Fig. 4 is characteristic of a blocking phenomena and spin-or-cluster-glass-like state, respectively. It can be assumed that the reversal of the particles is due to thermal activation effects over a distribution of energy barriers E . The relaxation over a single barrier for noninteracting particles with uniaxial anisotropy is described by the NelArrhenius law given by 1 = f 0 exp E / KBT , where is the measurement time, f 0 is the attempt frequency to reversal, normally taken to be 109 s1, kB is the Boltzmann constant, and T is the measurement temperature. Assuming a grain volume dependence of the energy barriers to reversal of the form E = KAFV, where KAF is the magnetocrystalline anisotropy of the NiO particles and V is the median of the particles volume distribution, and a typical measurement time of 100 s, we obtain an expression of the form, KAFV = 25kBTB, where TB is the median blocking temperature. We can estimate the value of KAF TB using the approximation 3 that the AF moment mAF TN T 1/3 and KAF mAF for uniaxial anisotropy, i.e., KAF TB = KAF 0 TN TB / TN , with KAF 0 the bulk NiO value 4.96 106 erg/ cm3 Ref. 30

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(a)

(a)

(b)

(b)

(c)
FIG. 5. Color online Magnetization as a function of applied eld for three samples at different temperatures, a as prepared, b S1 sample, and c S2 sample.

(c)
FIG. 6. Color online Hysteresis loops at 2, 11, and 25 K for the samples a powder, b S1, and c S2.

and TN 520 K,31 hence KAF TB is 4.2 106 erg/ cm3. Therefore, the value of V obtained from this framework is 4.9 nm that is rather lower than the value obtained by x-ray and TEM analysis 5.8 nm . This nd should be associated to the disordered structure in the surface of the NPs. Figure 5 shows the M-H hysteresis curves taken at temperatures nearly above the irreversibility temperature for the as-prepared as well as for the dispersed NPs samples. One can clearly observe a linear dependence of magnetization even at high elds, whose slope increases with the decrease in strength of interactions. Interestingly, the curves for the as-prepared SP and S1 samples display following two different regimes: a one linear region, dependent on T , H that can be attributed to the partially oxidized surface and gives rise to a nonsaturating component of the magnetization4,9,32 and b one second component that shows a typical SPM trend, following a Langevin-like function, reaching a saturation. On the other hand, sample S2 exhibits only a linear region throughout. This fact reects a characteristic behavior of strongly frustrated systems in which there is a large number of uncompensated spins on the surface of the particles.

In order to get further insight into the nature of this anomalous behavior, hysteresis loops were measured in the ZFC condition at different temperatures around the low temperature peaks. Figure 6 shows the M-H curves recorded at temperatures 2, 11, and 25 K to as-prepared, S1, and S2 samples after subtracting the diamagnetic contribution from the PVP. It can be clearly seen that a large magnetic moment and coercivity are observed in the case of as-prepared sample see Fig. 6 a . These results conrm that these particles display a weak-FM-like33 behavior, which is reduced after the dispersion. It is also evident that, to as-prepared sample, the hysteresis curves measured close to low temperature maxima, the coercive eld HC and remanent magnetization M R are strongly narrowed. In fact, these results are well established and corroborated to the uncompensated spins systems either on the surface or in the core of the NiO NPs.2,9,13,14 However, due the decrease in the contribution from dipolar interactions, the surface effects turn out to become dominant when the particles are more disperse. In this scenario, the freezing of such uncompensated spins at the shell is more difcult, consequently it is necessary to de-

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FIG. 7. a Coercive eld and b remanent magnetization as function of the temperature after FC for three samples.

FIG. 8. FMR spectra at different temperatures for the powder sample.

crease the temperature enough to envisage better the surface, as observed in the ZFC-FC magnetizations and ac susceptibility measurements. These anomalies are further conrmed from the dependence of coercive eld HC and remanent magnetization M R as functions of temperature Figs. 7 a and 7 b , respectively . As the demagnetizing and remagnetizing curves see Fig. 6 change rapidly in low elds, both coercive eld HC and remanent magnetization M R in as-prepared sample SP decrease with increasing temperature. Therefore, if one reduces the strength of dipolar interactions among the particles a maximum is observed at around 20 K for the HC T . This trend has already been reported for the NiO NPs of an average particle size 3 nm Ref. 9 and single-domain particle systems.5 Also, another interesting behavior has been found in case of more diluted sample S2 . It is clear from Fig. 7 that the change in both HC and M R are more pronounced in the case of the more diluted sample S2. One can infer that the surface effects become dominating over the particle core and it is more difcult to align the uncompensated spins in the particle shell. Therefore, for decreasing the temperature, a strong contribution of the blocked particles increases the HC values and consequently the M R.5 Besides, it is not unreasonable to state that this increase the total magnetization can be related with the formation of the FM clusters of short-range.32 In order to further understand and visualize the effect of anisotropy, we have also performed FMR spectra for the asprepared and S2 samples in the temperature range 4.2300 K at a frequency of 9.45 GHz X-band . To measure the X-band spectra, the magnetic eld was applied both parallel and perpendicular to the plane of the PVP matrix. However, no angular dependence was observed, suggesting that the samples are magnetically isotropic. Figure 8 shows the spectra derivative of the resonant absorption signal as functions of applied magnetic eld for the as-prepared sample at different measuring temperatures. It can be clearly seen that the high temperature spectra exhibit a symmetric shape which gradually decreases with the reduction of sample temperature. Also, the line widths H PP become broader with the decrease in the sample temperature T 140 K , as shown by the thermal dependence of H PP and HR see Fig. 9 . This T-dependence can be attributed to the thermal uctuations of

the magnetic moment with respect to the magnetic anisotropy axes and has been also reported in other NP systems.4,9,11,34 The shift in HR with respect to g = 2.0023 as well as the increase in H PP with the decrease in temperature are clear signatures of the FM character of the signal. For decreasing the temperature, the magnetic moment of the particle experience with more intensity the effect of anisotropy. In fact, the presence of the large size distribution as observed in the ZFC curves as well as the random orientation of the easy axes is responsible for the increase in H PP. Indeed, this is behavior expected to a strongly interacting system powder sample , that is, the dipolar and exchange interactions generate an effective local eld over each resonance center that helps it to reach the resonance condition. Finally, within the accuracy of our experimental set-up, we can state that in the high temperature regime, we observe the FMR of the magnetic moment of the core, e.g., H PP increases once the surface spins are in a paramagnetic state. Also, the formation of surface spin clusters creates an additional effective eld on the core leading to both the shift in the resonant eld and the broadening of the FMR linewidth.
IV. CONCLUSIONS

We have studied the magnetic properties of coprecipitated NiO NPs with different strength of interparticle interactions. X-ray and electronic microscopy probes conrm the

FIG. 9. Dependence thermal of the HR and powder sample.

H PP correspondent to the

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J. Appl. Phys. 108, 013909 2010 E. Winkler, R. D. Zysler, M. Vasquez Mansilla, and D. Fiorani, Phys. Rev. B 72, 132409 2005 . 10 R. D. Zysler, C. A. Ramos, E. De Biasi, H. Romero, A. Ortega, and D. Fiorani, J. Magn. Magn. Mater. 221, 37 2000 . 11 E. de Biasi, C. A. Ramos, and R. D. Zysler, J. Magn. Magn. Mater. 262, 235 2003 . 12 E. Tronc, D. Fiorani, M. Nogus, A. M. Testa, F. Lucari, F. Drazio, J. M. Grenche, W. Wernsdorfer, N. Galvez, C. Chanac, D. Mailly, and J. P. Lolivet, J. Magn. Magn. Mater. 262, 6 2003 . 13 A. E. Berkowitz, R. H. Kodama, S. A. Makhlouf, F. T. Parker, F. E. Spada, E. J. McNiff, Jr., and S. Foner, J. Magn. Magn. Mater. 196197, 591 1999 . 14 S. A. Makhlouf, F. T. Parker, F. E. Spada, and A. E. Berkowitz, J. Appl. Phys. 81, 5561 1997 . 15 R. D. Zysler, E. Winkler, M. Vasquez Mansilla, and D. Fiorani, Physica B 384, 277 2006 . 16 J. M. Vargas, W. C. Nunes, L. M. Socolovsky, M. Knobel, and D. Zanchet, Phys. Rev. B 72, 184428 2005 . 17 W. C. Nunes, L. M. Socolovsky, J. C. Denardin, F. Cebollada, A. L. Brandl, and M. Knobel, Phys. Rev. B 72, 212413 2005 . 18 M. F. Hansen, C. B. Koch, and S. Mrup, Phys. Rev. B 62, 1124 2000 . 19 J. B. Yi, J. Ding, Y. P. Feng, G. W. Peng, G. M. Chow, Y. Kawazoe, B. H. Liu, J. H. Yin, and S. Thongmee, Phys. Rev. B 76, 224402 2007 . 20 H. Bi, S. Li, Y. Zhang, and Y. Du, J. Magn. Magn. Mater. 277, 363 2004 . 21 L. Xiang, X. Y. Deng, and Y. Jin, Scr. Mater. 47, 219 2002 . 22 C. T. Meneses, W. H. Flores, F. Garcia, and J. M. Sasaki, J. Nanopart. Res. 9, 501 2007 . 23 A. O. G. Maia, C. T. Meneses, A. S. Menezes, W. H. Flores, D. M. A. Melo, and J. M. Sasaki, J. Non-Cryst. Solids 352, 3729 2006 . 24 H. M. Rietveld, Acta Crystallogr. 22, 151 1967 . 25 R. A. Young, A. Sakthivel, T. S. Moss, and C. O. Paiva-Santos, J. Appl. Crystallogr. 28, 366 1995 . 26 D. P. Rojas, L. F. Barquin, J. R. Fernandez, J. I. Espeso, and J. C. G. Sal, J. Phys.: Condens. Matter 19, 186214 2007 . 27 W. C. Nunes, E. De Biasi, C. T. Meneses, M. Knobel, H. Winnischofer, T. C. R. Rocha, and D. Zanchet, Appl. Phys. Lett. 92, 183113 2008 . 28 J. Jiao, S. Seraphin, X. Wang, and J. C. Withers, J. Appl. Phys. 80, 103 1996 . 29 A. F. Gross, M. R. Diehl, K. C. Beverly, E. K. Richman, and S. H. Tolbert, J. Phys. Chem. B 107, 5475 2003 . 30 H. Kondoh, J. Phys. Soc. Jpn. 15, 1970 1960 . 31 F. B. Lewis and N. H. Saunders, J. Phys. C 6, 2525 1973 . 32 R. D. Zysler, H. Romero, C. A. Ramos, E. De Biasi, and D. Fiorani, J. Magn. Magn. Mater. 266, 233 2003 . 33 R. N. Bhowmik, R. Nagarajan, and R. Ranganathan, Phys. Rev. B 69, 054430 2004 . 34 R. Berger, J. C. Bissey, J. Kliava, H. Daubric, and C. Estournes, J. Magn. Magn. Mater. 234, 535 2001 .

presence of single crystalline phase and a strain of 0.5% obtained through WilliamsomHall plotting, which can strongly inuence the local magnetic ordering of these materials. Magnetization as function of the temperature, magnetic eld and time and FMR measurements show that for decreasing the temperature one can see rst a progressive blocking process of the core particle moments and then, a strong surface effects likely relate with formation of spin clusters at the particle surface which is sensitive to the distance among particles. We argue that this fact is sufcient to explain the anomalies in the hysteresis loop shape and the behavior observed to M r and HC at low temperature. Our results also allow us to conclude that the NPs possess a high degree of spins surface disorder even with the decrease in the strength of interparticle interactions once we have observed that our systems turned out to be highly frustrated ones, displaying a spin-glass disorder to temperatures below 2.0 K for the sample with almost negligible interactions.
ACKNOWLEDGMENTS

The authors are grateful for access to the facilities of Laboratrio Nacional de Luz Sincrotron LNLS for the use of Laboratrio de Microscopia Eletrnica TEM micrographs on proposal TEM-4043/7362 . The authors thank Brazilian agency CNPq and FAPESP for nancial support.
1

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2

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