Hard Magnetic FePt Nanoparticles within Nanostructured Silicon to Improve the Maximum Energy Product
Authors: Rumpf Klemens , Granitzer Petra , Gonzalez-Rodriguez Roberto , Coffer Jeffery 
Published: August 2024

In this work nanostructured silicon, silicon nanotubes (SiNTs) and porous silicon (PSi), with embedded hard magnetic FePt nanoparticles (NPs) is used as platform to create nanomagnet-arrays. The magnetic response of FePt-loaded composite materials is investigated, which have potential in high-performance magnets and as rare earth magnet alternatives. PSi/FePt demonstrates superior hard magnetic behavior with a higher coercivity and remanence compared to SiNTs/FePt. Varying the Fe molar ratio in deposits results in a small coercivity range. FePt-loaded samples consistently show increased coercivity and remanence compared to Co-loaded samples, with PSi exhibiting a stronger effect compared to SiNTs.
The fabrication of the PSi samples was performed by anodization of p+ silicon in a 5 wt% HF solution. A current density of 50 mAcm-2 was applied during the etching. The samples offer an average diameter of 50 nm. The SiNTs were produced by using arrays of ZnO nanowires (NWs) as template, followed by Si deposition and finally etching off the ZnO NWs which is described in (1). FePt nanocrystals were formed within the SiNTs by a multistep process, consisting of soaking previously APTES functionalized SiNTs in a solution containing 0.1 mM Citric acid, 0.5 mM of H2PtCl6 6H2O, and depending on the given ratio 0.5-1.5 mM of Fe(NO3)3 9H2O. The samples were dried in a vacuum oven, followed by a heat treatment at 500° C for 1 hr in Ar atmosphere, then the samples were washed several times with water and ethanol. In a similar way FePt NPs were formed in PSi samples, however PSi did not receive the APTES functionalization before the solution soaking.
For these samples, the average FePt particle size is 5 (± 2) nm in SiNTs samples and 9 (± 4) nm for the particles inside PSi, however it should be pointed out that the FePt ratios calculated from reactants was different than the ratios determined from EDX experimental data. The calculated stoichiometry of Pt:Fe (based on reactant concentrations) of 1:1, 1:3 and 1:6 was experimentally determined values via EDX to be 10:1, 1.6:1 and 0.5:1 for SiNTs; for the corresponding PSi samples of calculated 1:3 and 1:6 ratios was experimentally 40:1 and 10:1.
Magnetization measurements were carried out by VSM in recording the magnetic response dependent on the magnetic field. Samples with different Fe content (Pt:Fe = 1:1, 1:3, 1:6) offer a variation of the coercivity in the range of 5% for both types of matrices (SiNTs, PSi). Furthermore the investigations show that the coercivities of PSi loaded with FePt NPs is about twice the coecivities of SiNTs loaded with FePt NPs. SiNTs/FePt samples with a ratio Pt:Fe 1:6 offer a coercivity of about 240 Oe and PSi/FePt offers a coercivity more than twice as high of about 560 Oe.
Comparing the FePt loaded samples with samples loaded with Co NPs, in both sample types an increase of the coercivity is observed for FePt. Also in the case of Co-loading the utilization of PSi as template offers higher coercivities compared to SiNTs as template. From the investigated composite systems the ones consisting of PSi and FePt offer the highest energy product.
(1) Huang, X., Gonzalez-Rodriguez, R., Rich, R., Gryczynski, Z., Coffer, J.L., Chem. Comm. 2013, 49, 5760.