EMR searching of quantum behavior of magnetic γ-Fe2O3 nanoparticles encapsulated into poly(propylene imine) dendrimer Текст научной статьи по специальности «Физика»

ISSN 2072-5981

aänetic Resonance in Solids

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Volume 18, Issue 2 Paper No 16208, 1-4 pages 2016

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EMR searching of quantum behavior of magnetic y-Fe2O3 nanoparticles encapsulated into poly(propylene imine) dendrimer

V.E. Vorobeva 1 2, N.E. Domracheva 1 *, M.S. Gruzdev3

1 Zavoisky Physical Technical Institute, Sibirsky tract 10/7, Kazan 420029, Russia

2 Kazan Federal University, Kremlevskaya 18, Kazan 420008, Russia

3 G.A. Krestov Institute of Solution Chemistry RAS, Akademicheskaja 1, Ivanovo 153045, Russia

*E-mail: ndomracheva@gmail.com

(Received December 10, 2016; accepted December 19, 2016)

The superparamagnetic y-Fe2O3 nanoparticles (average diameter of 2.5 nm) encapsulated in poly(propylene imine) dendrimer have been investigated by electron magnetic resonance (EMR). EMR measurements have been recorded in perpendicular and parallel configurations in the wide temperature range (4.2-300 K). It has been shown that the model based on the spin value S = 30, corresponding to the total magnetic moment of the nanoparticle, can be used to interpret the experimental results and the proof of the quantum behavior of y-Fe2O3 nanoparticles.

PACS: 76.30.-v, 75.10. Dg, 61.46.+w, 75.20.-g, 96.15.Gh

Keywords: ESR/EPR, iron oxide nanoparticles, magnetism, quantum behavior, dendrimers

1. Introduction

Recently, interest in the study of nanoscale magnetic systems has increased significantly, which is caused by both wide technological applications of such systems (catalysis [1], storage [2], spintronics [3], MRI [4], magnetic fluids [5], biotechnology and biomedicine [6, 7]), and fundamental scientific interest [8, 9]. In the world of nanoscale magnetic systems, two classes of such objects can be distinguished: magnetic nanoparticles (NPs) and molecular nanomagnets (MNMs). The behavior of MNMs is known to be described by quantum mechanics, where calculations begin by considering the behavior of a single ion, while NPs behavior is described in terms of classical physics on the basis of parameters obtained for bulk materials. It seems interesting to develop a common approach for the consideration of nanoscale magnetic systems, which could provide a better understanding of their properties. Electron magnetic resonance (EMR) is an excellent tool to demonstrate the similarities in the behavior of NPs and MNMs, and its use can provide experimental evidences of quantum behavior of single-domain NPs. Some evidences in favor of the discrete nature of spin levels of NPs are already known in the literature. For example, a small signal is observed in the half-field of EMR spectra [10, 11], which, according to some authors, is attributed to forbidden transitions between states with Am = ± 2. Its appearance is interpreted as a proof of the quantum nature of the system and in such approach a nanoparticle is considered to be a giant exchange-coupled cluster with a total spin S.

In this paper, we try to find new arguments in favor of the quantum nature of NPs, and for this purpose we offer a new approach - to record EMR spectra of NPs in both (parallel and perpendicular) configurations, that is, when the H field of the microwave radiation is parallel or perpendicular to the external magnetic H0 field. These alternative configurations have different selection rules for the allowed transitions between the total spin projections, and therefore, provide the opportunity to "feel" the quantum nature of the system.

2. Results and discussion

In our previous paper [12], we investigated by EMR spectroscopy the behavior of superparamagnetic single-domain y-Fe2O3 NPs (average diameter of 2.5 nm) encapsulated in poly(propylene imine) dendrimer of the second generation (Figure 1), using the classical theoretical approach [13].

f This paper material was selected at XIX International Youth Scientific School "Actual problems of magnetic resonance and its application", Kazan, 24 - 28 October 2016. The paper was recommended to publication in our journal and it is published after additional MRSej reviewing.

EMR searching of quantum behavior of magnetic y-Fe2Os nanoparticles...

The typical EMR spectra (for configuration H ± Ho) are shown in Figure 2. As we can see, one basic signal with g-factor 2 is observed, which becomes broader and its resonance position is shifted to lower magnetic fields with the temperature decrease. The temperature dependence of the shift of the resonance position of this signal, Hres - Ho, is described by the following expression: Hres - Ho = ha [1/L(£) - 3/£], where ha is the anisotropic field of NP, % = MVHolkBT, Vis the volume, M is the magnetization of NPs, £b is the Boltzmann constant, T is the absolute temperature, Ho = 3342 G and L(E) is the Langevin function. The best agreement between the experimental data and the theoretical dependence (Figure 3) [11] is obtained for the value of the anisotropic field ha = - 1375 G.

The magnetic measurements made using a SQUID magnetometer for this system (Figure 4) in the two cooling regimes of the sample - in the presence (FC) and in the absence of an external magnetic field (ZFC) have shown that there is a temperature-driven transition from superparamagnetic to ferrimagnetic state and the value of the effective magnetic moment of NPs is about ^fr ~ 60 ¡j.b.

Besides this basic signal (g ~ 2), EMR spectra demonstrate the presence of a small signal in the half-field around 1500 G (Figure 5), which has been attributed in the literature to 'partially' forbidden transitions between states with Am = ± 2, where m is the expectation value of SZ and S the total spin of the NP. If this interpretation is correct, then the intensity of this small signal should increase when the

Figure 1. Schematic model of localization y-Fe2O3 NPs into poly (propylene imine) dendrimer.

Magnetic field [G]

Figure 2. Temperature dependence of EMR spectra for y-Fe2O3 NPs in dendrimer recorded at X-band in perpendicular configuration (v = 9.64 GHz).

Figure 3. Temperature dependence of Hres - Ho for y-Fe2O3 NPs incorporated into dendrimer. The solid line shows the theoretical dependence.

Figure 4. Variation of the effective magnetic moment of y-Fe2O3 NP with temperature.

V.E. Vorobeva, N.E. Domracheva, M.S. Gruzdev

EMR spectra are recorded in a parallel configuration (H1 || H0). EMR experiments carried out by us for this configuration, confirmed that it is indeed the case (Figure 6) and the intensity of the transitions in the half-field really increases. X-band EMR measurements were performed on a CW-EPR EMXplus Bruker spectrometer equipped with helium ER 4112HV cryostat, ER 4131VT temperature control system, and the ER 4116DM EPR- resonator (Bruker, Germany) was used. The spectra were recorded using the modulation frequency of 100 kHz and a microwave power for the perpendicular configuration was 25 juW and 20 mW for the parallel configuration. So, one can see that the proposed by us approach opens additional possibilities for the analysis of the properties of magnetic nanoparticles with using a model where each NP is treated as a quantum object with a large spin, similar to the approach that was successfully used to MNMs.

Thus, we can use the following spin Hamiltonian to calculate the EMR spectra:

H = S-g H + S D -S,

(1)

where the first term gives the splitting of energy levels in the external magnetic field H, and the second term determines the fine structure of the levels of NP with spin S.

Magnetic field (G) Figure 5. EMR spectrum of maghemite NPs in dendrimer at 270 K with a small signal at the half-field (~1500 G).

Magnetic field [G]

Figure 6. Temperature dependence of EMR spectra recorded at X-band in parallel configuration (v = 9.39 GHz) for y-Fe2Û3 NPs encapsulated in dendrimer.

Perpendicular configuration

T= 180 K -ex per.

D = 40 MHz ----simulated by

S = 30 fi Easyspin

- j i P I < J P I F I 1 I

-10

Parallel configuration T= 180 K D = 40 MHz S = 30 AH = 22 MT

ex per.

simulated by Easyspin

1000 2000 3000 4000 5000 6000 7000 8000

1000 2000 3000 4000 5000 6000 7000 8000

Magnetic field [G] Magnetic field [G]

Figure 7. Experimental EMR spectra (continuous lines) acquired in the perpendicular and parallel configurations at 180 K, and simulated (dashed lines) spectra.

EMR searching of quantum behavior of magnetic y-Fe2Os nanoparticles...

The value of spin S for NPs was estimated from magnetic measurements according to the expression S = i/giB [14], and in our case S ~ 3o.

Using the relation D = - yha/2S [14] together with the known values of the anisotropic field (ha), and spin S value, we can obtain the estimated value of the fine structure parameter D for the NP, which is equal to D ~ 64 MHz. The simulation of EMR spectra for both magnetic field configurations was performed using the Easyspin program. The experimental and the simulated spectra at T = 18o K are shown in Figure 7. The best agreement between the experimental and theoretical spectra was obtained for the following parameters: S = 3o, D = 4o MHz with individual Lorentzian line shape and line width AH = 22o G. It is seen, that a fairly good qualitative agreement between the spectra is observed.

3. Summary

Thus, we can conclude that the obtained results demonstrate the possibility to analyze the magnetic properties of NP using the large spin value S = 3o, and hence NP can be considered as a quantum object.

Acknowledgments

We gratefully acknowledge the financial support for this work by RAS Presidium program No. 24. We thank Yu. N. Shvachko and D. V. Starichenko for magnetic measurements.

References

1. Lu A.H., Schmidt W., Matoussevitch N., Bonnemann H., Spliethoff B., Tesche B, Bill E., Kiefer W., Schuth F. Angew. Chem., Int. Ed. 43, 43o3 (2oo4)

2. Hyeon T. Chem. Commun. 2003, 927 (2oo3)

3. Nanomagnetism and Spintronics, edited by T. Shinjo (Elsevier, Amsterdam, 2oo9)

4. Laurent S., Forge D., Port M., Roch A., Robic C, Elst L., Muller R. Chem. Rev. 108, 2o64 (2oo8)

5. Chikazumi S., Taketomi S., Ukita M., Mizukami M., Miyajima H., Setogawa M., Kurihara Y, J. Magn. Magn. Mater. 65, 245 (1987)

6. Gupta A.K., Gupta M. Biomaterials 26, 3995 (2oo5)

7. Magnetism in Medicine: A Handbook, edited by W. Andra and H. Nowak (Wiley-VCH, Weinheim, 2oo7)

8. Fittipaldi M., Sorace L., Barra A.L., Sangregorio C., Sessoli R., Gatteschi D., Phys. Chem. Chem. Phys. 11, 6555 (2oo9)

9. Wernsdorfer W. Adv. Chem. Phys. 118, 99 (2oo1)

10. Noginova N., Weaver T., Giannelis E.P., Bourlinos A.B., Atsarkin V.A., Demidov V.V. Phys. Rev. B 77, o144o3 (2oo8)

11. Fittipaldi M., Innocenti C., Ceci P., Sangregorio C., Castelli L., Sorace L., Gatteschi D. Phys. Rev. B83, 1o44o9 (2o11)

12. Domracheva N., Pyataev A., Manapov R., Gruzdev M. ChemPhysChem 12, 3oo9 (2o11)

13. Raikher Yu.L., Stepanov V.I. J. Magn. Magn. Mater. 316, 417 (2oo7)

14. Fittipaldi M., Mercatelli R., Sottini S., Ceci P., Falvo E., Gatteschi D. Phys. Chem. Chem. Phys. 18, 3591 (2o16)