Unusual enhancement of effective magnetic anisotropy with decreasing particle size in maghemite nanoparticles

TL;DR

This study investigates the counterintuitive increase in magnetic anisotropy in maghemite nanoparticles as their size decreases, using experimental data and a new core-shell model to explain the phenomenon.

Contribution

A novel core-shell-based model is proposed to explain the enhancement of magnetic anisotropy with decreasing nanoparticle size, extending previous simpler equations.

Findings

Keff increases as particle size decreases from 15 nm to 2.5 nm.

The new model fits experimental data better than previous models.

Shell spins significantly contribute to the anisotropy at small sizes.

Abstract

Experimental results and a model are presented to explain the observed unusual enhancement of the effective magnetic anisotropy Keff with decreasing particle size D from 15 nm to 2.5 nm in {\gamma}-Fe2O3 nanoparticles (NPs). The samples include oleic acid-coated NPs with D = 2.5, 3.4, 6.3 and 7.0 nm investigated here, with the results on other sizes taken from literature. Keff is determined from the analysis of the frequency dependence of the blocking temperature TB after considering the effects of interparticle interactions on TB. The data of Keff vs. D is fit to the derived core-shell-based relation: Keff = Kb + (6KS/D) +Ksh{[1-(2d/D)]^(-3) -1}, with Kb = 1.9 x10^5 ergs/cm^3 as the bulk-like contribution of the core, KS = 0.035 ergs/cm^2 as the contribution of the surface layer, and Ksh = 1.057 x10^4 ergs/cm^3 as the contributions of spins in the shell of thickness d = 1.1 nm. This equation represents an extension of the often-used Eq.: Keff = Kb + (6KS/D). Significance of this new result is discussed.