The objective of this paper is to demonstrate that Ag readily diffuses into Sb2S3 and that electric fields can control the diffusion. Ag diffusion influences the crystallization temperature and electrical properties of Sb2S3. We studied the interface between Ag and Sb2S3 using X-ray reflectivity and show that the Ag cations can be controlled by applying an electric field. We believe this effect has technological applications in data storage devices.

Aerogels are a promising material for aerospace applications and have recently been explored for biomedical applications also. In both environments, exposure to radiation is inevitable, such as from radiation in space or, radiation-based sterilization and tracking of implants. X-ray radiation, in particular, is of a concern. Here, polyurea-crosslinked silica aerogel (PCSA) samples were exposed to approximately 170- and 500-Gy X-irradiation at room temperature under varying environmental conditions and characterized using electron spin resonance (ESR) technique. Results obtained for PCSA were compared with those from polyether-ether ketone (PEEK) and ultra-high molecular weight polyethylene (UHMWPE) which served as benchmarks for this study. PEEK is known to be very radiation resistant, while UHMWPE is known to be less radiation resistant. All materials (PCSA, PEEK, and UHMWPE) were exposed to the same treatments and exposure conditions. Two exposure times were tested: 10 min and 30 min which corresponded to “low” and “high” conditions, as well as comparisons of nitrogen vs. air environments during exposure and post-exposure storage. Results showed significant quantities of free radicals produced in PCSA after exposure to X-irradiation which scaled with radiation dosage; quantities were in-between those produced in PEEK and UHMWPE. The storage conditions (air vs. nitrogen) also played an important role in the free radical levels detected and are reported in this study.

The solid–water interface is ubiquitous in natural and synthetic systems as the primary site for chemical reactions under near-ambient conditions. Examples include the interactions of contaminants with mineral–water interfaces in natural environments, electrochemical reactions at the electrode-electrolyte interface relevant to energy storage (e.g., ion adsorption/electrical double layer formation, ion insertion), and oxidation of structural materials (e.g., rust). Yet many of these phenomena remain largely mysterious at a mechanistic level. The x-ray reflectivity technique, using highly penetrating hard x-rays, directly probes the solid–water interfaces through in situ studies. This approach has provided new insights into the molecular-scale structures and processes that occur at these “wet” interfaces. In this article, we review recent advances in the understanding of these systems, focusing specifically on the organization of interfacial “hydration layers” and the important role of adsorbed ions at charged solid–liquid interfaces.

In the conventional X-ray reflectivity (XRR) analysis, the reflectivity is calculated based on the Parratt formalism, incorporating the effect of the interface roughness according to Nevot and Croce. However, the results of calculations of the XRR have shown strange outcomes, where interference effects increase at a rough surface because of a lack of consideration of diffuse scattering within the Parratt formalism. Therefore, we have developed a new improved formalism in which the effects of the surface and interface roughness are included correctly. In this study, for deriving a more accurate formalism of XRR, we tried to compare the measurements of surface roughness of the same sample by atomic force microscopy (AFM) and XRR. It is found that the AFM result could not be completely reproduced even with the improved XRR formalism. By careful study of the AFM results, we determined the need for an additional effective roughness term within the XRR simulation that depends on the angle of incidence of the beam.

X-ray reflectometry is a powerful tool for investigating rough surface and interface structures. Presently, X-ray reflectivity is based on Parratt formalism, accounting for the effect of roughness by the theory of Nevot–Croce. However, the calculated results showed a strange phenomenon in that the amplitude of the oscillation because of interference effects increases in the case of a specific roughness of the surface. We propose that the strange results originated from the currently used equation because of a serious error in which the Fresnel transmission coefficient in the reflectivity equation is increased at a rough interface, and the increase in the transmission coefficient completely overpowers any decrease in the value of the reflection coefficient because of lack of consideration in diffuse scattering. In the present study, we present a new improved formalism that corrects this error, and thereby derives an accurate analysis of X-ray reflectivity from a multilayer surface, taking into account the effect of roughness-induced diffuse scattering.

Recently, a new experimental setup for quick X-ray reflectivity (q-XRR) measurements was proposed, which is based on simultaneous recording of an X-ray reflectivity curve over all angles of interest. This new setup for q-XRR allows measurements to be done within seconds, thus permitting studies of the time evolution of chemical, thermal, and mechanical changes at the surfaces and interfaces of different materials. Since the q-XRR measurement setup utilizes an extended X-ray source and detector, it is important to develop models and to account for the following two effects: (i) diffuse scattering associated with different points of the source and (ii) sample curvature. Models accounting for both effects are presented, and their influences on interpretation of the q-XRR measurement results are discussed.

In order to manufacture organic electronic devices with high performance, more detailed studies of the structure and the morphology of the organic materials as well as the underlying physical charge transport mechanisms are warranted. For instance, high efficiency organic thin film transistors (OTFTs) require materials with high charge carrier mobility [1, 2]. The parameters that determine the charge carrier mobility of the device include the structure of the first organic layer at the organic-dielectric interface as well as the morphology and the structural order of the other organic layers. Therefore, fundamental questions about structural properties of organic materials should be answered in order to optimize device performance [2-4].

In this work, several bilayer structures of LiF/PTCDI-C8 and LiF/pentacene were prepared and their morphology and molecular structure were characterized using X-ray reflectivity (XRR) technique. In order to study the effects of the films’ structures and dielectric/organic interfacial properties on the device performance, OTFTs based on these bilayers were fabricated and characterized. It has been observed that PTCDI-C8 thin films have higher molecular packing in the LiF/PTCDI-C8 bilayer structure, which results in superior electrical characteristics for OTFTs based on this organic material. Devices with LiF/PTCDI-C8 bilayer exhibit about one order of magnitude higher output current (Ids) at a constant drain-source voltage (Vds) compared to the devices with LiF/pentacene bilayer. The observed differences in the electrical characteristics of these devices can be attributed to the effects of the dielectric/organic interface and the molecular structure of the organic layers.

The thicknesses and oxygen concentration of tantalum oxide (TaO) and hafnium oxide (HfO) films, prepared by magnetron sputtering Ta and Hf in oxygen onto heated silicon (100) substrates, were measured by three different techniques. The first method uses X-ray reflectivity, which yields a thickness value independent of the film composition. The second method uses the simultaneous measurement of Ta and Hf fluorescence counts. For these <200-nm-thick films there is very little matrix effect so that the Ta and Hf fluorescence counts are expected to, and are observed to, increase linearly with the film thickness. The third method uses the attenuation of the Si Kα X-ray line from the underlying Si excited by a glancing incident X-ray beam for measurement. The TaO and HfO films were observed to grow for the sputtering conditions employed, in an initial mode characterized by a high mass absorption times density product and then grow as characterized by a lower mass absorption times density product. This change over occurred for the HfO films, at a film thickness of 13 nm. The change over occurred for the TaO films at a film thickness of 23 nm. Pure Ta and Hf films were also made by magnetron sputtering from Ta and Hf targets in argon. All X-ray measurements, including the reflectivity measurements, were made, with the addition of an X-ray fluorescence detector, using a Panalytical MRD system.

We present in this text a new experimental tool to study the mixing of atoms under irradiation. Based on physics of x ray diffraction, the specular reflectivy of x ray was used to estimate the Auto Correlation Function associated with the electron density gradient. The accuracy of the ACF is around 1 nanometer and does not evolve with the thickness of the probed layer. Thus, this point allows accurately measuring the broadening of the electron density gradient spreading induced by irradiation. Such an accurate profile extracted over a large range of fluences (about 3 decades) would lead to the determination of the functional dependence of this spreading with the fluence. This could allow pointing out the main mechanisms triggering the atomic mixing over large distances when atomic mixing occurring in thermal spikes is washed out.

Transition metal multilayers are prime candidates for high reflectivity soft x-ray multilayer mirrors. In particular, Cr/Sc multilayers in the amorphous state have proven to give the highest reflectivity in the water window. We have investigated the influence of impurities N and O as residual gas elements on the growth, structure, and optical performance of Cr/Sc multilayers deposited in high vacuum conditions by a dual cathode direct current magnetron sputter deposition. Multilayer structures with the modulation periods in the range of 0.9–4.5 nm and Cr layer to bilayer thickness ratios in the range of 0.17–0.83 were deposited with an intentionally raised base pressure (pB), ranging from 2 × 10−7 to 2 × 10−5 Torr. Compositional depth profiles were obtained by elastic recoil detection analysis and Rutherford backscattering spectroscopy, while the structural investigations of the multilayers were carried out using hard x-ray reflectivity and transmission electron microscopy. By investigating stacked multilayers, i.e., several multilayers with different designs of the modulation periods, stacked on top of each other in the samples, we have been able to conclude that both N and O are incorporated preferentially in the interior of the Sc layers. At pB ≤ 2 × 10−6 Torr, typically <3 at.% of N and <1.5 at.% of O was found, which did not influence the amorphous nanostructure of the layers. Multilayers deposited with a high pB ∼2 × 10−5 Torr, a N content as high as ∼37 at.% was measured by elastic recoil detection analysis. These multilayers mainly consist of understoichiometric face-centered cubic CrNx/ScNy nanocrystalline layers, which could be grown as thin at 0.3 nm and is explained by a stabilizing effect on the ScNy layers during growth. It is also shown that by adding a background pressure of as little as 5 × 10−6 Torr of pure N2 the soft x-ray reflectivity (λ = 3.11 nm) can be enhanced by more than 100% by N incorporation into the multilayer structures, whereas pure O2 at the same background pressure had no effect.

Diatoms are unicellular eukaryotic algae found in fresh and marine water. Each cell is surrounded by an outer shell called a frustule that is composed of highly structured amorphous silica. Diatoms are able to transform silicic acid into these sturdy intricate structures at ambient temperatures and pressures, whereas the chemical synthesis of silica-based materials typically requires extremes of temperature and pH. Cationic polypeptides, termed silica affinity proteins (or silaffins) recently identified from dissolved frustules of specific species of diatoms are clearly involved and have been shown to initiate the formation of silica in solution. The relationship between the local environment of catalytic sites on these peptides, which can be influenced by the amino acid sequence and the extent of aggregation, and the observed structure of the silica is not understood. Moreover, the activity of these peptides in promoting silicification at lipid membranes has not yet been clarified. In this work we developed a model system to address some of these questions. We studied peptide adsorption to Langmuir monolayers and subsequent silicification using X-ray reflectivity and grazing incidence X-ray diffraction. The results demonstrate the lipid affinity of the parent sequences of several silaffin peptides. Further, the results show that the membrane-bound peptides promote the formation of interfacial nanoscale layers of amorphous silica at the lipid-water interface that vary in structure according to the peptide sequence.

We analyze properties of ultra-thin SiO2 + very thin SiOx double layer structure formed on high-doped n-type Si (100) wafers using FTIR, X-ray reflectivity and AFM methods. The observed absorption band around 1230 cm−1 is attributed to the longitudinal optical mode of SiOx precipitates incorporated in silicon matrix. In particular, the corresponding peak positions indicate that there are precipitates of SiOx with x >1.8. The absorption band around 1070 cm−1 is attributed to the Si–O–Si stretching bond. This position is characteristic for stoichiometric SiO2. From the results it can be concluded that differently shaped particles co-exist in the samples. This assumption is supported by the oxide density measurements performed by FTIR and X-ray reflectivity. We determined density of oxide layers, roughness of corresponding interfaces, and surface roughness by the X-ray reflectivity. The obtained values were compared with those determined by FTIR and AFM. Additionally, we present the results of multifractal analysis on a complete set of six samples.

Al2O3 films are grown by atomic layer deposition (ALD) using trimethylaluminum and water as precursors on HF-last and NH3 plasma pretreatment Si substrates. The thickness, surface roughness, and density of Al2O3 films as well as the nature of their interlayers with Si substrates are characterized by x-ray reflectivity and spectroscopic ellipsometry techniques. The growth rates of Al2O3 films are 1.1 Å/cycle and 1.3 Å/cycle, respectively, on HF-last and NH3-plasma-nitrided surfaces. Al2O3 layer densities are rather independent of the number of growth cycles in all cases. The interfacial film thickness increases with the number of ALD cycles when deposited on an HF-last Si substrate. However, because SiOxNy inhibits oxygen diffusion, the interfacial film thickness is independent of the number of ALD cycles on the nitrided Si substrate.

This work demonstrates the application of a Markov Chain Monte Carlo (MCMC) approach to modeling X-ray reflectometry (XRR) data taken from a sub 10 nm Hafnium oxide film. We present here a comparison of two structural models for a 6 nm HfxOy atomic layer deposition (ALD) film on Si. Using the MCMC method and two distinct structural models, we show evidence of a thin interface between the HfxOy and Si layers with a density much higherthan native SiO2. Results from genetic algorithm XRR analysis and thickness measurements using cross-sectional transmission electron microscopy are included for comparison. We also demonstrate that our interpretation of HfxOy thickness differs between the two structural models (i.e., total film thicknesses may be partially additive within each model).

Fe-doped SrRuO3 thin films were grown on SrTiO3 (STO) substrates by using the Pulse Laser Deposition (PLD) method. Fe concentrations in the SrRuO3 thin films ranged from 0 % to 11 % to manifest the effect of Fe doping on their microstructure. Lattice constants of the films did not show obvious changes with the Fe doping whereas surface morphologies drastically changed from stepped to island structure with increasing Fe. X-ray reflectivity revealed that the surface and interfacial roughness decreased with increasing concentration of Fe. Surface roughness of the films was confirmed by atomic force microscopy. Therefore, a precise determination of film roughness as well as its growth mechanism using X-ray and AFM is exploited to correlate the Fe doping with structural disorder.

The electrical and mechanical properties of low-k dielectric materials have received a great deal of attention in recent years; however, measurements of thermal properties such as the coefficient of thermal expansion remain minimal. This absence of data is due in part to the limited number of experimental techniques capable of measuring this parameter. Even when data does exist, it has generally not been collected on samples of a thickness relevant to current and future integrated processes. We present a procedure for using x-ray reflectivity to measure the coefficient of thermal expansion of sub-micron dielectric thin films. In particular, we elucidate the thin film mechanics required to extract this parameter for a supported film as opposed to a free-standing film. Results of measurements for a series of plasma-enhanced chemical vapor deposited and spin-on low-k dielectric thin films will be provided and compared.

A recently developed bidirectional thermal expansion measurement (BTEM) method was applied to different types of low-k films to substantiate the reliability of the Poisson's ratio found with this technique and thereby to corroborate its practical utility. In this work, the Poisson's ratio was determined by obtaining the temperature gradient of the biaxial thermal stress from substrate curvature measurements, the temperature gradient of the whole thermal expansion strain along the film thickness from x-ray reflectivity (XRR) measurements, and reduced modulus of the film from nanoindentation measurements. For silicon oxide-based SiOC film having a thickness of 382.5 nm, the Poisson's ratio, Young's modulus and thermal extension coefficient (TEC) were determined to be Vf = 0.26, αf =21 ppm/K and Ef =9,7 GPa. These data are close to the levels of metals and polymers rather than the levels of fused silicon oxide, which is characterized by Vf = 0.17 and Er = 69.6 GPa. The alkyl component in the silicon oxide-based framework is thought to act as an agent in reducing the modulus and elevating the Poisson's ratio in SiOC low-k materials. In the case of an organic polymer SiLK film with a thickness of 501.5 nm, the Poisson's ratio, Young's modulus and TEC were determined to be Vf = 0.39, αf =74 ppm/K and Er =3.1 GPa, which are in the typical range of V= 0.34~0.47 with E =1.0~10 GPa for polymer materials. From the viewpoint of the relationship between the Poisson's ratio and Young's modulus as classified by different material types, the Poisson's ratios found for the silicon oxide-based SiOC and organic SiLK films are reasonable values, thereby confirming that BTEM is a reliable and effective method for evaluating the Poisson's ratio of thin films.