Epitaxial growth of binary and ternary metallic strained superlattices and their magnetic properties

Since the structure at/near the interface of superlattices influences physical properties such as magnetic property, it is important to investigate details of the structure. The interface structure is characterized by the factors like atomic species, strain, mixing and roughness. The reflection high-energy electron diffraction (RHEED) system installed in our molecular-beam epitaxy (MBE) system enables us to observe, continuously, the change of the surface in-plane lattice constant, which is affected by atomic species, strain and/or mixing, on a real-time basis. Ternary superlattices consisting of three elements can clarify the effect of stacking sequence by comparison between the two types of superlattices with the reverse deposition sequences, since the effect caused by the combination of the same atomic species is cancelled out and the effect caused by the different stacking sequences remains. In the present paper, we review growth behaviors of binary and ternary metallic strained superlattices, especially magnetic ones, investigated mainly by our group, and summarize the discussion on their magnetic properties, mainly on the magnetic anisotropy, in terms of their structural characteristics. First, we introduce our RHEED system that works efficiently under a magnetic field arising from evaporation sources for low vapor-pressure materials. Then, MBE-grown binary strained superlattices, Co/Au, Co/Pt and Cu/Au, are discussed, with comparing to incoherent superlattices of Co/Ag and Cu/Ag having nearly the same lattice mismatch of constituents. Next, we review ternary strained superlattices with immiscible constituents with reverse deposition order, Au/Co/Ag and Ag/Co/Au superlattices, and Au/Co/Cu and Cu/Co/Au superlattices, in relation to the growth behaviors of binary superlattices. Finally, ternary strained superlattices containing both miscible and immiscible constituents, Pt/Co/Ag and Ag/Co/Pt superlattices, and Au/Ni/Ag and Ag/Ni/Au superlattices, are reviewed.     

Epitaxial growth and thermal-conductivity limit of single-crystalline Bi2Se3/In2Se3 superlattices on mica

Nano Research - Thermal transport in superlattices is governed by various phonon-scattering processes. For extracting the phonon-scattering contribution of hetero-interfaces in chalcogenide...     

Inhomogeneous nucleation and growth of palladium and alloyed cobalt during self-aligned capping of advanced copper interconnects

We investigate the nucleation and growth of two cobalt alloys (CoWB and Pd-CoWP) used to encapsulate copper interconnects. We demonstrate that very uniform deposits are obtained across 300 mm wafers, with accurate thickness control. However, large local thickness variations are observed, possibly compromising the continuity of thin deposits. The origin of this phenomenon is first investigated by electron back scatter diffraction. A clear correlation between areas of dense Pd nucleation and the (111) grains of the polycrystalline copper surface is demonstrated. Then, an epitaxial relationship between the cobalt alloys and the underlying copper substrate is evidenced by TEM characterization. Local nucleation density could thus be affected by the substrate orientation, accounting for thickness inhomogeneities after growth.     

Synthesis of metallic Zn microprisms, their growth mechanism and PL properties

Novel metallic Zn hexagonal hollow microprisms have been synthesized by a simple thermal evaporation technique using NH₃ as a carrier gas under atmospheric pressure. As-prepared hollow microprisms were characterized using X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy and transmission electron microscopy. The hollow microprisms collected on silicon substrate are found to be 3-7 μm long with diameter in the range 900-950 nm. A vapour-solid (VS) process based growth mechanism has been proposed for the formation of hexagonal Zn microprisms grown along (0001) basal plane in [0001] direction. Photoluminescence (PL) emission spectrum of zinc microprisms at room temperature exhibited a very prominent peak at 384 nm owing to the radiative recombination of electrons in s, p conduction band near Fermi surface and the holes in the d bands generated by optical excitation.     

Epitaxial growth of CoFe2O4 on SrTiO3 (100) and MgO (100) substrates without buffer layer by laser molecular beam epitaxy technique

Among the family of ferrite materials, cobalt ferrite (CoFe₂O₄) is unique in that it has the highest values of magneto-crystalline anisotropy and magnetostriction. Recently, much of the efforts have been focused on the fabrication of single crystalline cobalt ferrite films. For the epitaxial growth of cobalt ferrite, the issues of lattice parameter and crystal symmetry mismatch with the substrate are of considerable importance. The growth of thin films of CoFe₂O₄ on MgO and SrTiO₃ single crystal substrates is reported in this paper. The key parameters on the growth modes were investigated by changing oxygen pressure and substrate temperature. Results show that the two-dimensional layer-by-layer growth mode only occurs under high oxygen pressure for epitaxy of Co ferrite. The significant observation presents the controllable lattice constant of a highly strained thin film by modulation of the substrate temperature. In this light, to grow high quality Co ferrite thin films on SrTiO₃ is of a considerable importance to modulate intrinsic magnetic properties.     

Electronic and magnetic properties of ultra-thin epitaxial magnetite films on MgO(001)

The electronic and magnetic properties of epitaxial Fe₃O₄ (001) films on MgO(100) substrates were studied throughout the 2.5- to 30-nm thickness range using conversion electron Mössbauer spectroscopy. Despite the superparamagnetism that was observed for film thickness below 5 nm, the Verwey transition persisted even for the thinnest film. Temperature-dependent Mössbauer measurements between 80 K and 400 K revealed that the activation energy for the magnetic moment fluctuations in the 3-nm magnetite film is higher than the magnetic anisotropy energy by an order of magnitude.     

Effect of the preparation route,PEG and annealing on the phase stability of Fe3O4 nanoparticles and their magnetic properties

Fe₃O₄ nanoparticles are synthesised via two different methods: (1) co-precipitation of Fe²⁺ and Fe³⁺ ions and (2) oxidative alkaline hydrolysis of Fe²⁺ ions under atmospheric pressure using different protective agents (PEG 200 and PEG 3000) and urea as a base. The preparation method and the polyethylene glycol (PEG) used are concurrently affecting the phase stability of the formation of the iron oxides: the co-precipitation method using PEG 200 (E4a) or PEG 3000 (E4b) leads to the formation of different ratios of Fe₂O₃ and Fe₃O₄, whereas the oxidative hydrolysis of Fe²⁺ using PEG 200 gives Fe₃O₄ (E2) powder as a major product. The average crystallites size of E4a and E4b is almost identical, i.e. around 19?nm but the saturation magnetisation of E4b is three times larger than that of E4a. The sample E2 shows the highest saturation magnetisation value 74?emu/g, with an average crystallites size of 71?nm. Transmission electron microscopy analysis confirmed that the E2 sample shows the presence of needles crystals with typical sizes around 10 and 50?nm and its selected area diffraction (SAD) shows a typical diffraction of the spinel structure of magnetite. On the other hand, E4b sample shows elongated nanoparticles with typical sizes around 24?nm and its SAD confirmed the presence of a mixture of Fe₂O₃ and Fe₃O₄ as many dispersed spots were obtained.