Coherent X-ray Spectroscopy Elucidates Nanoscale Dynamics of Plasma-Enhanced Thin-Film Growth.

Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

de Gennes Narrowing and Relationship between Structure and Dynamics in Self-Organized Ion-Beam Nanopatterning.

Investigating the relationship between structure and dynamical processes is a central goal in condensed matter physics. Perhaps the most noted relationship between the two is the phenomenon of de Gennes narrowing, in which relaxation times in liquids are proportional to the scattering structure factor. Here, a similar relationship is discovered during the self-organized ion-beam nanopatterning of silicon using coherent x-ray scattering. However, in contrast to the exponential relaxation of fluctuations in classic de Gennes narrowing, the dynamic surface exhibits a wide range of behaviors as a function of the length scale, with a compressed exponential relaxation at lengths corresponding to the dominant structural motif-self-organized nanoscale ripples. These behaviors are reproduced in simulations of a nonlinear model describing the surface evolution. We suggest that the compressed exponential behavior observed here is due to the morphological persistence of the self-organized surface ripple patterns which form and evolve during ion-beam nanopatterning.

Coherent X-ray measurement of step-flow propagation during growth on polycrystalline thin film surfaces.

The properties of artificially grown thin films are strongly affected by surface processes during growth. Coherent X-rays provide an approach to better understand such processes and fluctuations far from equilibrium. Here we report results for vacuum deposition of C60 on a graphene-coated surface investigated with X-ray Photon Correlation Spectroscopy in surface-sensitive conditions. Step-flow is observed through measurement of the step-edge velocity in the late stages of growth after crystalline mounds have formed. We show that the step-edge velocity is coupled to the terrace length, and that there is a variation in the velocity from larger step spacing at the center of crystalline mounds to closely-spaced, more slowly propagating steps at their edges. The results extend theories of surface growth, since the behavior is consistent with surface evolution driven by processes that include surface diffusion, the motion of step-edges, and attachment at step edges with significant step-edge barriers.

Sawtooth structure formation under nonlinear-regime ion bombardment.

Linear-regime Ar+ bombardment of Si produces symmetrical ripple structures at ion incidence angles above 45° measured off-normal (Madi 2009 J. Phys.: Condens. Matter 21). In the nonlinear regime, new behaviors emerge. In this paper, we present experimental results of ion bombardment that continues into the nonlinear regime until pattern saturation at multiple ion incidence angles, showing the evolution of their grazing incidence small-angle x-ray scattering (GISAXS) spectra as well as atomic force microscopy topographs of the final, saturated structures. Asymmetric structures emerge parallel to the direction of the projected ion beam on the sample surface, constituting a height asymmetry not found in the linear regime. We then present simulations of surface height evolution under ion bombardment using a nonlinear partial differential equation developed by Pearson and Bradley (2015 J. Phys.: Condens. Matter 27 015010). We present simulated GISAXS spectra from these simulations, as well as simulated scattering from a sawtooth structure using the FitGISAXS software package (Babonneau 2010 J. Appl. Crystallogr. 43 929-36), and compare the simulated spectra to those observed experimentally. We find that these simulations reproduce many features of the sawtooth structures, as well as the nearly-flat final GISAXS spectra observed experimentally perpendicular to the sawtooth structures. However, the model fails to reproduce the final GISAXS spectra observed parallel to the sawtooth structures.

Simulations of Co-GISAXS during kinetic roughening of growth surfaces.

The recent development of surface growth studies using X-ray photon correlation spectroscopy in a grazing-incidence small-angle X-ray scattering (Co-GISAXS) geometry enables the investigation of dynamical processes during kinetic roughening in greater detail than was previously possible. In order to investigate the Co-GISAXS behavior expected from existing growth models, calculations and (2+1)-dimension simulations of linear Kuramoto-Sivashinsky and non-linear Kardar-Parisi-Zhang surface growth equations are presented which analyze the temporal correlation functions of the height-height structure factor. Calculations of the GISAXS intensity auto-correlation functions are also performed within the Born/distorted-wave Born approximation for comparison with the scaling behavior of the height-height structure factor and its correlation functions.

Distinguishing physical mechanisms using GISAXS experiments and linear theory: the importance of high wavenumbers.

In this work we analyze GISAXS measurements of the structure factor of Si surfaces evolving during 1 keV Ar+ ion bombardment. Using newly-developed methods sensitive to the full range of experimentally-available wavenumbers q, we extract the linear amplification rate R(q) governing surface stability over a range of wavenumbers 4-5 times larger than has previously been obtained. Comparing with theoretical models also retaining full wavenumber-dependence, we find an excellent fit of the experimental data over the full range of irradiation angles and wavenumbers. Moreover, the fitted parameter values represent experimental evaluation of the magnitudes of most physical mechanisms currently believed to be important to the pattern-formation process. In all cases, the extracted values agree well with direct observations or atomistic simulations of the same quantities, suggesting that GISAXS analysis may allow more powerful comparison between experiment and theory than had previously been thought.

Effect of Sr Content and Strain on Sr Surface Segregation of La1-xSrxCo0.2Fe0.8O3-δ as Cathode Material for Solid Oxide Fuel Cells.

Strontium-doped lanthanum cobalt ferrite (LSCF) is a widely used cathode material due to its high electronic and ionic conductivity, and reasonable oxygen surface exchange coefficient. However, LSCF can have long-term stability issues such as surface segregation of Sr during solid oxide fuel cell (SOFC) operation, which can adversely affect the electrochemical performance. Thus, understanding the nature of the Sr surface segregation phenomenon and how it is affected by the composition of LSCF and strain are critical. In this research, heteroepitaxial thin films of La1-x SrxCo0.2Fe0.8O3-δ with varying Sr content (x = 0.4, 0.3, 0.2) were deposited by pulsed laser deposition (PLD) on single-crystal NdGaO3, SrTiO3, and GdScO3 substrates, leading to different levels of strain in the films. The extent of Sr segregation at the film surface was quantified using synchrotron-based total-reflection X-ray fluorescence (TXRF) and atomic force microscopy (AFM). The electronic structure of the Sr-rich phases formed on the surface was investigated by hard X-ray photoelectron spectroscopy (HAXPES). The extent of Sr segregation was found to be a function of the Sr content in bulk. Lowering the Sr content from 40% to 30% reduced the surface segregation, but further lowering the Sr content to 20% increased the segregation. The strain of LSCF thin films on various substrates was measured using high-resolution X-ray diffraction (HRXRD), and the Sr surface segregation was found to be reduced with compressive strain and enhanced with tensile strain present within the thin films. A model was developed correlating the Sr surface segregation with Sr content and strain effects to explain the experimental results.

Atomic layer deposition-based tuning of the pore size in mesoporous thin films studied by in situ grazing incidence small angle X-ray scattering.

Atomic layer deposition (ALD) enables the conformal coating of porous materials, making the technique suitable for pore size tuning at the atomic level, e.g., for applications in catalysis, gas separation and sensing. It is, however, not straightforward to obtain information about the conformality of ALD coatings deposited in pores with diameters in the low mesoporous regime (<10 nm). In this work, it is demonstrated that in situ synchrotron based grazing incidence small angle X-ray scattering (GISAXS) can provide valuable information on the change in density and internal surface area during ALD of TiO(2) in a porous titania film with small mesopores (3-8 nm). The results are shown to be in good agreement with in situ X-ray fluorescence data representing the evolution of the amount of Ti atoms deposited in the porous film. Analysis of both datasets indicates that the minimum pore diameter that can be achieved by ALD is determined by the size of the Ti-precursor molecule.

Atomic layer deposition of TiO2 on surface modified nanoporous low-k films.

This paper explores the effects of different plasma treatments on low dielectric constant (low-k) materials and the consequences for the growth behavior of atomic layer deposition (ALD) on these modified substrates. An O2 and a He/H2 plasma treatment were performed on SiCOH low-k films to modify their chemical surface groups. Transmission FTIR and water contact angle (WCA) analysis showed that the O2 plasma changed the hydrophobic surface completely into a hydrophilic surface, while the He/H2 plasma changed it only partially. In a next step, in situ X-ray fluorescence (XRF), ellipsometric porosimetry (EP), and Rutherford backscattering spectroscopy (RBS) were used to characterize ALD growth of TiO2 on these substrates. The initial growth of TiO2 was found to be inhibited in the original low-k film containing only Si-CH3 surface groups, while immediate growth was observed in the hydrophilic O2 plasma treated film. The latter film was uniformly filled with TiO2 after 8 ALD cycles, while pore filling was delayed to 17 ALD cycles in the hydrophobic film. For the He/H2 plasma treated film, containing both Si-OH and Si-CH3 groups, the in situ XRF data showed that TiO2 could no longer be deposited in the He/H2 plasma treated film after 8 ALD cycles, while EP measurements revealed a remaining porosity. This can be explained by the faster deposition of TiO2 in the hydrophilic top part of the film than in the hydrophobic bulk which leaves the bulk porous, as confirmed by RBS depth profiling. The outcome of this research is not only of interest for the development of advanced interconnects in ULSI technology, but also demonstrates that ALD combined with RBS analysis is a handy approach to analyze the modifications induced by a plasma treatment on a nanoporous thin film.

Evidence for Family-Meakin dynamical scaling in island growth and coalescence during vapor phase deposition.

Using real-time grazing-incidence small-angle x-ray scattering, we find that the processes of island formation and coalescence during the room-temperature vapor phase deposition of aluminum lead to dynamical scaling of the evolving surface morphology. The scaling is quantitatively consistent with the self-similarity predicted by the Family-Meakin model, which was developed to describe liquid droplet deposition, growth, and coalescence. The Family-Meakin model assumes only that atomic diffusion over the substrate between islands or droplets is negligible and that diffusion between impinging islands or droplets is sufficient to give complete coalescence. Therefore the dynamical scaling morphology evolution identified here may be common in the initial stages of those solid film growth processes which proceed by island formation and growth.

Direct measurement of microstructural avalanches during the martensitic transition of cobalt using coherent x-ray scattering.

Heterogeneous microscale dynamics in the martensitic phase transition of cobalt is investigated with real-time x-ray scattering. During the transformation of the high-temperature face-centered cubic phase to the low-temperature hexagonal close-packed phase, the structure factor evolution suggests that an initial rapid local transformation is followed by a slower period during which strain relaxes. Coherent x-ray scattering measurements performed during the latter part of the transformation show that the kinetics is dominated by discontinuous sudden changes-avalanches. The spatial size of observed avalanches varies widely, from 100 nm to 10 µm, the size of the x-ray beam. An empirical avalanche amplitude quantifies this behavior, exhibiting a power-law distribution. The avalanche rate decreases with inverse time since the onset of the transformation.

Tailoring nanoporous materials by atomic layer deposition.

Atomic layer deposition (ALD) is a cyclic process which relies on sequential self-terminating reactions between gas phase precursor molecules and a solid surface. The self-limiting nature of the chemical reactions ensures precise film thickness control and excellent step coverage, even on 3D structures with large aspect ratios. At present, ALD is mainly used in the microelectronics industry, e.g. for growing gate oxides. The excellent conformality that can be achieved with ALD also renders it a promising candidate for coating porous structures, e.g. for functionalization of large surface area substrates for catalysis, fuel cells, batteries, supercapacitors, filtration devices, sensors, membranes etc. This tutorial review focuses on the application of ALD for catalyst design. Examples are discussed where ALD of TiO(2) is used for tailoring the interior surface of nanoporous films with pore sizes of 4-6 nm, resulting in photocatalytic activity. In still narrower pores, the ability to deposit chemical elements can be exploited to generate catalytic sites. In zeolites, ALD of aluminium species enables the generation of acid catalytic activity.

Mass redistribution causes the structural richness of ion-irradiated surfaces.

We show that the "sputter patterning" topographical instability is determined by the effects of ion impact-induced prompt atomic redistribution and that erosion--the consensus predominant cause--is essentially irrelevant. We use grazing incidence small angle x-ray scattering to measure in situ the damping of noise or its amplification into patterns via the linear dispersion relation. A model based on the effects of impact-induced redistribution of those atoms that are not sputtered away explains both the observed ultrasmoothening at low angles from normal incidence and the instability at higher angles.