Growth and Magnetism of Nanostructures Investigated by STM, MOKE, and XMCD

This thesis presents our studies on nanostructures growth and magnetism, mainly based on scanning tunneling microscopy (STM), magneto-optical Kerr effect (MOKE), and x-ray magnetic circular dichroism (XMCD) measurements. In most of these experiments, nanostructures were grown by molecular beam epitaxy on single crystal substrates under ultra high vacuum conditions. Our combined morphological and magnetic investigations aim at an atomic-level description of the nanostructures magnetic properties. In particular, we are searching for strategies to design the smallest ferromagnet with stable magnetization at room temperature to be used in devices such as magnetic random access memories, storage media, and sensors. A critical factor in pursuing this aim is the determination and control of the magnetization reversal mechanism. Different reversal mechanisms may occur in the nanostructures we considered: either all the spins quasi-coherently rotate or a domain wall is nucleated and propagated along the particle. We prepared monolayer-high Co islands on Pt(111) with compact and ramified shape by adjusting the deposition temperatures and coverages for a sequence of deposition and annealing steps. Combining field-dependent magnetization curves and temperature dependent zero-field susceptibility measurements we identify a size- and shape-dependent transition from quasi-coherent to domain wall propagation reversal regimes. In a second study we investigated a system which according to a recent publication presents many of the characteristics desired in bit patterned magnetic media for ultra-high density storage devices. In particular, it was claimed that Co nanoclusters, growing in registry with the GdAu2/Au(111) moiré periodic substrate, and featuring a density of 52 Tera/in2, present out-of-plane remanent magnetization at T = 300 K. At odds with this claim, no perpendicular magnetic anisotropy was found in our combined MOKE and STM study, which shows an in-plane remanent signal appearing only for coalesced islands. A third study is devoted to FeRh, an alloy material which, thanks to its peculiar magnetic phase diagram, has been proposed coupled to FePt for advanced magnetic recording schemes. We present the first observation of low temperature stabilization of the ferromagnetic (FM) phase in FeRh chemically ordered crystals. Nanocrystals measuring 3.3 nm in diameter have B2 structure with alternating atomic Fe and Rh layers. XMCD demonstrates FM alignment of the Fe and Rh magnetic moments of 3 and 1 μB, respectively. In sharp contrast to FeRh bulk and thin films, which show antiferromagnetic iii Abstract (AFM) order below 300 K, the low-temperature FM 3.3 nm nanocrystals are the hallmark of a size-dependent AFM-FM transition temperature. Finally we present our results towards creation by chemical vapor deposition of a “mille-feuille” structure composed of graphene and magnetic nanoclusters. To realize this objective we optimized the cluster size, composition, and annealing temperature to obtain a compromise between graphene syntesis and cluster coalescence. We demonstrate by STM that annealing to T = 720 K in ethylene stabilizes Ir-seeded clusters against diffusion and coalescence, and by Auger Electron Spectroscopy (AES) that Ni-coated clusters can be covered with up to half of the Carbon contained in a graphene layer.

Rare Earth and Bimetallic Transition Metal Islands at Surfaces

Dimitrios Mousadakos

This thesis reports on the growth and on the magnetic characterization of nanostructures made of 3d-4d transition metals and rare earths. In all the experiments the nanostructures have been grown by atomic beam epitaxy (ABE) in ultra high vacuum conditions (UHV) by performing growth steps with the precise selection of external parameters as: the deposition flux F, the sample deposition temperature Tdep and the sample annealing temperature Tann . The morphological and magnetic properties of the nanostructures have been characterized by performing two in situ measurement techniques in our experimental setup, namely: scanning tunneling microscopy (STM) and magneto-optical Kerr effect (MOKE). The first aims of the thesis consisted in the formation of a supperlattice of rare earth on the graphene moiré pattern induced by the lattice mismatch of a single graphene layer grown on Ir(111) crystal surface. We report the first cluster supperlattice made of rare earths, namely Sm, where clusters nucleate in registry with the moiré pattern, forming a superlattice for deposition temperatures between 80 K and 110 K. Within this temperature range, the Sm supperlattice shows long-range order extending over several tens of nanometers and a cluster size distribution competing with the finest superlattices grown by ABE. Sm cluster spatial order is preserved, up to a coverage of 0.5 ML yielding a mean cluster size of 50 atoms, while for higher coverages coalescence starts. Moreover, Sm clusters with a mean size of 9 atoms are thermally stable up to Tann = 130 K from where on the order is lost and the density reduces progressively by cluster coalescence. Similar experiments carried out for Dy in the same deposition temperature range show the absence of cluster arrays. The second part focused on the enhancement of the MAE of bimetallic nanostructures, grown on Pt(111), having a Co-core by forming atomically sharp interlines and interfaces with three 4d elements, namely Ag, Pd and Rh. Our approach is based on the experimental measurement of the island magnetic susceptibility x(T) and morphology by means of MOKE and STM, respectively, combined with magnetic simulation analysis in order to quantify the different contributions to the island magnetic anisotropy. The monolayer capping for all studied elements contributes positively to the out-of-plane MAE of Co islands, with Pd giving the largest increase in the magnetic hardness. In addition, the capping with two Pd monolayers of pure Co islands maximizes the blocking temperature Tb . However, the lateral decoration of Co islands with all elements contributes negatively to MAE, with the Co/Pd shell giving the smallest effect and Rh the largest. Morphologically, Ag was found to produce a partial decoration of the Co island edges while Rh completely decorates laterally Co islands forming a rim of irregular shape without nucleating on top of Co islands for the used deposition parameters. Simulations of the magnetization reversal process by using coherent rotation (CR) and/or domain wall nucleation and propagation (DW) reversal models including different contributions to the MAE for atoms located at the interface (Ks) and at interline (Kp) and an exchange interaction between Co and 4d transition metals have reproduced the experimental x'(T) and x''(T) curves.

EPFL2017

Magnetism and Atomic Scale Structure of Bimetallic Nanostructures at Surfaces

Sergio Vlaic

his thesis reports on the magnetic properties of bi- and tri-metallic nanostructures at surfaces. The main goal is to build the smallest nanostructure ferromagnetic at room temperature and the assembly of those structures in high density arrays. To this purpose we have developed an approach consisting in a fine engineering of the nanostructure chemical structure at the atomic level. We grow core-shell nanostructures with atomically sharp interfaces between the different constituents and we investigate the effects produced by these interfaces as a function of their chemistry and structure. This approach is then used to grow organized arrays of bimetallic nanostructures that represent model systems for next generation high density magnetic storage media. The magnetic properties of the different experimental systems were investigated by magneto-optical Kerr effect (MOKE) and they were correlated to the morphology obtained by scanning tunneling microscopy (STM). The first part focuses on the understanding of the effects of atomically sharp interfaces among several elements. Two dimensional cobalt nanostructures have been grown on Pt(111) single crystal surface and subsequently their edges have been decorated by Fe, Pt or Pd. This one-dimensional decoration produces element dependent variations of the magnetic anisotropy energy with strong enhancement for Fe decoration and reduction for Pt and Pd. Furthermore we observe a crystallographic direction dependence on the effect of Pt and Pd decoration since Co/Pt or Co/Pd staking with {111}-orientation strongly enhances the magnetic hardness of the nanostructures. The effect of atomically sharp Co/Fe one-dimensional interface has been compared with direct alloying of the two elements finding the first one to give the highest effect for shell thicknesses smaller than 5 atoms. With the help of fully relativistic ab-initio we were able to reproduce the experimental results and unravel their pure electronic origin. The electronic hybridizations at the interface between the elements gives rise to "hot spots" in the electronic band structure responsible of a strong variation of the magnetocrystalline anisotropy resulting in the enhanced magnetic hardness. By growing Co-core Fe-shell Pd-capped nanostructures we were able to enhance the magnetization thermal stability of nanostructures by almost a factor of 3 with respect single-metal nanostructures of the same size. In the second part of this thesis, the first attempt of growing organized array of bimetallic nanostructures is presented. Taking advantage of the well-known self organized growth of Co nanodots on Au(111)-vicinal surfaces, we were able to grow Co-core Fe-shell nanodots on Au(11,12,12) single crystal. The thermal stability enhancement produced by the atomically sharp Co/Fe interface is higher than the direct alloying of the two elements as in the previous case. We argue that with this method, combined with three-dimensional growth of nanostructures arrays, it will be possible to produce multimetallic nanodots composed by ≈ 3000 atoms with magnetization thermal stability suitable for magnetic storage media. In the last part another model system for magnetic nanostructure superlattices is presented. Fe nanostructures have been grown on the Pd-seeded and unseeded alumina thin film formed by oxidation of a Ni3Al(111) single crystal surface at high temperature. We found that the sample stoichiometry near the surface evolves with the preparation cycles. This leads to the formation of a Ni-rich region, close to the alumina surface, ferromagnetic up to 250 K. By means of X-ray magnetic circular dichroism measurements we were able to estimate the amount of Ni in excess. Fe clusters deposited on the alumina surface are magnetically coupled to the Ni-rich region independently on the presence of Pd. Nevertheless, the system behavior cannot be explained by a simple ferromagnetic or antiferromagnetic coupling. We argue that the Fe nanostructures are coupled to the substrate by an interlayer exchange coupling across the alumina thin film. The coupling constant is expected to change sign depending on the distance between the Fe clusters and the Ni-rich region resulting in a peculiar magnetic behavior of the system.

EPFL2013

Magnetic Properties of Surface Adsorbed Metal Adatoms and Dimers

Dante Philippe Sblendorio

This thesis investigates the magnetic properties of single atoms and dimers adsorbed on graphene and oxide decoupling layers supported by single crystal metal substrates, using scanning tunneling microscopy (STM) and spin-polarized scanning tunneling microscopy (SP-STM). The goal is twofold: to use SP-STM to further advance the understanding of the interactions that determine the magnetic stability of Dy adatoms on graphene/Ir(111) and Ho adatoms on MgO/Ag(100), and to use insights from these systems to motivate the study of new systems-- mainly, IrCo heterodimers on graphene/Ir(111).For Dy adatoms on graphene/Ir(111), the characteristic lifetime of the spin system is measured as a function of temperature and tunnel bias, probing the available magnetization reversal pathways in the energy level diagram. The necessity of including the intra-atomic exchange to correctly describe spin lifetimes is demonstrated. In addition, naturally abundant Dy isotopes possess two possible nuclear spin values. Models of both nuclear spin cases of Dy are compared, and shown to produce similar behavior in the temperature and bias ranges probed by SP-STM. Furthermore, accounting for both nuclear spin cases allows for modeling of X-ray magnetic circular dichroism (XMCD) magnetization sweeps. For Ho adatoms on MgO/Ag(100), novel measurement protocols are used to determine the zero-field stability, and the correct ground state model. These protocols are also used to induce magnetic state reversal via Landau-Zener tunneling at avoided level crossings due to the hyperfine interaction. Finally, the study of the IrCo heterodimer adsorbed on graphene is motivated with stability considerations derived from the studies of Dy adatoms on graphene/Ir(111) and Ho adatoms on MgO/Ag(100), in addition to calculations based on density function theory (DFT). Strategies of engineering these heterodimers using statistical growth and atomic manipulation are successfully implemented. The heterodimer is highly mobile on graphene/Ir(111) and displays geometric instability, consistent with its predicted upstanding geometry. Despite this, measurement via STM and SP-STM is demonstrated. Observations are consistent with the robust magnetic stability expected from DFT studies, but additional investigation is needed to disentangle the measurements made thus far.

EPFL2022