Homoleptic gadolinium amidinates as precursors for MOCVD of oriented gadolinium nitride (GdN) thin films.

Five new homoleptic gadolinium tris-amidinate complexes are reported, which were synthesized via the salt-elimination reaction of GdCl(3) with 3 equiv of lithiated symmetric and asymmetric amidinates at ambient temperature. The Gd-tris-amidinates [Gd{(N(i)Pr)(2)CR}(3)] [R = Me (1), Et (2), (t)Bu (3), (n)Bu (4)] and [Gd{(NEt)(N(t)Bu)CMe}(3)] (5) are solids at room temperature and sublime at temperatures of about 125 °C (6 × 10(-2) mbar) with the exception of compound 4, which is a viscous liquid at room temperature. According to X-ray diffraction analysis of 3 and 5 as representative examples of the series, the complexes adopt a distorted octahedral structure in the solid state. Mass spectrometric (MS) data confirmed the monomeric structure in the gas phase, and high-resolution MS allowed the identification of characteristic fragments, such as [{(N(i)Pr)(2)CR}GdCH(3)](+) and [{(N(i)Pr)(2)CR}GdNH](+). The alkyl substitution patterns of the amidinate ligands clearly show an influence on the thermal properties, and specifically, the introduction of the asymmetric carbodiimide leads to a lowering of the onset of volatilization and decomposition. Compound 5, which is the first Gd complex with an asymmetric amidinate ligand system to be reported, was, therefore, tested for the MOCVD of GdN thin films. The as-deposited GdN films were capped with Cu in a subsequent MOCVD process to prevent postdeposition oxidation of the films. Cubic GdN on Si(100) substrates with a preferred orientation in the (200) direction were grown at 750 °C under an ammonia atmosphere and exhibited a columnar morphology and low levels of C or O impurities according to scanning electron microscopy, Rutherford backscattering, and nuclear reaction analysis.

Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: importance of deposition sequence on the oriented growth.

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars.

Integrating AlN with GdN Thin Films in an in Situ CVD Process: Influence on the Oxidation and Crystallinity of GdN.

The application potential of rare earth nitride (REN) materials has been limited due to their high sensitivity to air and moisture leading to facile oxidation upon exposure to ambient conditions. For the growth of device quality films, physical vapor deposition methods, such as molecular beam epitaxy, have been established in the past. In this regard, aluminum nitride (AlN) has been employed as a capping layer to protect the functional gadolinium nitride (GdN) from interaction with the atmosphere. In addition, an AlN buffer was employed between a silicon substrate and GdN serving as a seeding layer for epitaxial growth. In pursuit to grow high-quality GdN thin films by chemical vapor deposition (CVD), this successful concept is transferred to an in situ CVD process. Thereby, AlN thin films are included step-wise in the stack starting with Si/GdN/AlN structures to realize long-term stability of the oxophilic GdN layer. As a second strategy, a Si/AlN/GdN/AlN stacked structure was grown, where the additional buffer layer serves as the seeding layer to promote crystalline GdN growth. In addition, chemical interaction between GdN and the Si substrate can be prevented by spatial segregation. The stacked structures grown for the first time with a continuous CVD process were subjected to a detailed investigation in terms of structure, morphology, and composition, revealing an improved GdN purity with respect to earlier grown CVD thin films. Employing thin AlN buffer layers, the crystallinity of the GdN films on Si(100) could additionally be significantly enhanced. Finally, the magnetic properties of the fabricated stacks were evaluated by performing superconducting quantum interference device measurements, both of the as-deposited films and after exposure to ambient conditions, suggesting superparamagnetism of ferromagnetic GdN grains. The consistency of the magnetic properties precludes oxidation of the REN material due to the amorphous AlN capping layer.