No Arabic abstract
Atomic layer deposition (ALD) provides uniform and conformal thin films that are of interest for a range of applications. To better understand the properties of amorphous ALD films, we need improved understanding of their local atomic structure. Previous work demonstrated measurement of how the local atomic structure of ALD-grown aluminum oxide (AlOx) evolves in operando during growth by employing synchrotron high energy X-ray diffraction (HE-XRD). In this work, we report on efforts to employ electron diffraction pair distribution function (ePDF) measurements using more broadly available transmission electron microscope (TEM) instrumentation to study the atomic structure of amorphous ALD-AlOx. We observe electron beam damage in the ALD-coated samples during ePDF at ambient temperature and successfully mitigate this beam damage using ePDF at cryogenic temperatures (cryo-ePDF). We employ cryo-ePDF and Reverse Monte Carlo (RMC) modeling to obtain structural models of ALD-AlOx coatings formed at a range of deposition temperatures from 150-332{deg}C. From these model structures, we derive structural metrics including stoichiometry, pair distances, and coordination environments in the ALD-AlOx films as a function of deposition temperature. The structural variations we observe with growth temperature are consistent with temperature-dependent changes in the surface hydroxyl density on the growth surface. The sample preparation and cryo-ePDF procedures we report here can be used for routine measurement of ALD-grown amorphous thin films to improve our understanding of the atomic structure of these materials, establish structure-property relationships, and help accelerate the timescale for the application of ALD to address technological needs.
The availability of large-area substrates imposes an important constraint on the technological and commercial realization of devices made of layered materials. Aluminum nitride films on silicon are shown to be promising candidate materials as large-area substrates for such devices. Herein, the optical contrast of exemplar 2D layers - MoS2and graphene - on AlN films has been investigated as a necessary first step to realize devices on these substrates. Significant contrast enhancements are predicted and observed on AlN films compared to conventional SiO2films. Quantitative estimates of experimental contrast using reflectance spectroscopy show very good agreement with predicted values.
While a linear growth behavior is one of the fingerprints of textbook atomic layer deposition processes, the growth often deviates from that behavior in the initial regime, i.e. the first few cycles of a process. To properly understand the growth behavior in the initial regime is particularly important for applications that rely on the exact thickness of very thin films. The determination of the thicknesses of the initial regime, however, often requires special equipment and techniques that are not always available. We propose a thickness determination method that is based on X-ray reflectivity (XRR) measurements on double layer structures, i.e. substrate/base layer/top layer. XRR is a standard thin film characterization method. Utilizing the inherent properties of fast Fourier transformation in combination with a multi-Gaussian fitting routine permits the determination of thicknesses down to $t approx 2$ nm. We evaluate the boundaries of our model, which are given by the separation and full width at half maximum of the individual Gaussians. Finally, we compare our results from two layer stacks with data from X-ray fluorescence spectroscopy, which is a standard method for measuring ultra thin films.
We report on the delithiation of LiCoO2 thin films using oxalic acid (C2H2O4) with the goal of understanding the structural degradation of an insertion oxide associated with Li chemical extraction. Using a multi-technique approach that includes synchrotron radiation x-ray diffraction, scanning electron microscopy, micro Raman spectroscopy, photoelectron spectroscopy and conductive atomic force microscopy we reveal the balance between selective Li extraction and structural damage. We identify three different delithiation regimes, related to surface processes, bulk delithiation and damage generation. We find that only a fraction of the grains is affected by the delithiation process, which may create local inhomogeneities. The chemical route to Li extraction provides additional opportunities to investigate delithiation while avoiding the complications associated with electrolyte breakdown and could simplify in situ measurements.
The properties of a ferroelectric, (001)-oriented, thin film clamped to a substrate are investigated analytically and numerically. The emphasis is on the tetragonal, polydomain, ferroelectric phase, using a three domain structure, as is observed experimentally. The previously used, very restrictive set of boundary conditions, arising from the domain walls, is relaxed, creating more modes for energy relaxation. It is argued that this approach gives a more realistic description of the clamped ferroelectric film. It is shown that for the ferroelectric oxides PbZr_(1-x)Ti_xO_3} the tetragonal, polydomain phase is present over a wide range of substrate induced strains for x_Ti>0.5, corresponding to the tetragonal side of the bulk phase diagram. A polydomain, rhombohedral phase is present for x_Ti<0.5, at the bulk rhombohedral side. Phase-temperature diagrams, and ferroelectric, dielectric and piezoelectric properties, as well as lattice parameters, are calculated as function of substrate induced strain and applied field. The analytical formulation allows the decomposition of these properties into three different causes: domain wall motion, field induced elastic effects and piezoelectric effects. It is found that domain wall motion and polarization rotation of the in-plane oriented domains under an applied field contribute most to the properties, while the out-of-plane oriented domains hardly contribute.
In this work, we studied amorphous carbon ($a$-C) thin films deposited using direct current (dc) and high power impulse magnetron sputtering (HiPIMS) techniques. The microstructure and electronic properties reveal subtle differences in $a$-C thin films deposited by two techniques. While, films deposited with dcMS have a smooth texture typically found in $a$-C thin films, those deposited with HiPIMS consist of dense hillocks surrounded by a porous microstructure. The density of $a$-C thin films is a decisive parameter to judge their quality. Often, x-ray reflectivity (XRR) has been used to measure the density of carbon thin films. From the present work, we find that determination of density of carbon thin films, specially those with a thickness of few tens of nm, may not be accurate with XRR due to a poor scattering contrast between the film and substrate. By utilizing neutron reflectivity (NR) in the time of flight mode, a technique not commonly used for carbon thin films, we could accurately measure differences in the densities of $a$-C thin films deposited using dcMS and HiPIMS.