Characterization of nanoporous low-k thin films by small-angle neutron scattering contrast variation

Small-angle neutron scattering contrast variation is applied to characterization of nanoporous low-dielectric constant (low-k) thin films. Films are exposed to saturated solvent vapor in air, whereby the pores fill with liquid by capillary condensation. The pores are filled with mixtures of hydrogen- and deuterium-containing solvents to vary the neutron contrast with the matrix (wall). The composition of the solvent mixture is systematically varied to identify a composition that minimizes the scattered intensity (contrast match point). From the contrast match point composition, film characteristics including matrix density and homogeneity are assessed. Four spin-on low-k materials including a methylsilsesquioxane, an organic polymer, a xerogel, and a hydrogensilsesquioxane are characterized by the new technique. Calculated matrix mass densities are compared to independent density measurements obtained by an established specular X-ray reflectivity technique. We find no evidence of "closed pores", defined here as pores inaccessible to the probe solvent, in any of the materials studied.     

Characterization of pore structure in metal-organic framework by small-angle X-ray scattering

MOF-5-like crystals were studied by small-angle X-ray scattering (SAXS) to reveal, both quantitatively and qualitatively, their real structural details, including pore surface characteristics, pore shape, size distribution, specific surface area (SSA), spatial distribution, and pore-network structure. A combined SAXS and wide-angle X-ray scattering (WAXS) experiment was conducted to investigate the variation of the pore structure with the MOF-5 crystalline phase produced at different cooling rates. The SSA of the MOF-5 crystals synthesized herein spanned a broad range from approximately 3100 to 800 m2/g. The real pore structures were divided into two regimes. In regime I the material consisted mainly of micropores of radius approximately 8 A as well as mesopores of radius 120 approximately 80 A. The structure in regime II was a fractal network of aggregated mesopores with radius >or=32 A as the monomer, reducing SSA and hydrogen uptake capacity at room temperature. The two regimes can be manipulated by controlling the synthesis parameters. The concurrent evolution of pore structure and crystalline phase during heating for solvent removal was also revealed by the in-situ SAXS/WAXS measurement. The understanding of the impact of the real pore structure on the properties is important to establish a favorable synthetic approach for markedly improving the hydrogen storage capacity of MOF-5.     

Characterization of highly porous polymeric materials with pore diameters larger than 100 nm by mercury porosimetry and X-ray scattering methods

Highly porous polymeric materials with pore sizes ranging from 100 nm to 1 microm are a very challenging class of materials not only to prepare synthetically (due to the high capillary pressures generated upon solvent removal) but also to characterize structurally. Through the examples of three different types of porous compounds synthesized in our laboratory (i) high-density melamine-based "MF-hd" with monomodal pore diameters around 500-900 nm, (ii) low-density melamine-based "MF-ld" with bimodal pore size distribution and average diameters around 2.3 microm and 350 nm, (iii) highly porous polyurethane "PU" with monomodal pore sizes around 150 nm, we confirm the limitations of mercury porosimetry as a means to investigate the architecture of materials with very high porosity (>80 vol %) and low compressive strength. Instead, a combination of high-resolution scanning electron microscopy and small-angle and ultrasmall-angle X-ray scattering (SAXS and USAXS, respectively) studies of these three types of materials helps in determining both the network and the pore structures. This work elucidates the need and applicability of the SAXS/USAXS techniques in characterizing such porous materials. For instance, the polyurethane specimens can only be quantitatively characterized by scattering techniques, the results of which are corroborated by high-resolution scanning electron microscopy observations.     

In situ monitoring of atomic layer deposition in nanoporous thin films using ellipsometric porosimetry

Ellipsometric porosimetry (EP) is a handy technique to characterize the porosity and pore size distribution of porous thin films with pore diameters in the range from below 1 nm up to 50 nm and for the characterization of porous low-k films especially. Atomic layer deposition (ALD) can be used to functionalize porous films and membranes, e.g., for the development of filtration and sensor devices and catalytic surfaces. In this work we report on the implementation of the EP technique onto an ALD reactor. This combination allowed us to employ EP for monitoring the modification of a porous thin film through ALD without removing the sample from the deposition setup. The potential of in situ EP for providing information about the effect of ALD coating on the accessible porosity, the pore radius distribution, the thickness, and mechanical properties of a porous film is demonstrated in the ALD of TiO(2) in a mesoporous silica film.     

Determination of X-ray compression efficiency of a thin film X-ray waveguide structure using marker layer fluorescence

We demonstrate that a thin marker layer, sandwiched in the guiding medium of a thin film planner X-ray waveguide structure, can be used to determine X-ray compression efficiency for a particular excitation mode. It can also be used in evaluating the transmission efficiency of waveguide structure and for the determination of X-ray intensities reaching the waveguide exit. This approach has been applied for determining X-ray compression and transmission efficiency of a Mo/B₄C/Mo based X-ray waveguide structure, by inserting a thin Fe marker layer.     

Adsorption porosimetry application in the study of a porous structure of thin layers

The method of adsorption porosimetry (AP) has been long known in physical chemistry of porous sorbents, but its practical application was limited to studies of massive samples of such materials as silica gels, zeolites, etc. We have developed a technique to study the porous structure of dielectric thin films (d ～ 100 nm). It is stated that it provides us with quite novel information which permits the prediction of properties of dielectric layers and makes it possible on this basis to solve optimization problems of technological processes. The use of ellipsometry has further extended the potential of this method, and currently it is a powerful nondestructive technique to measure porosity and the size distribution of pores in thin layers for the purposes of modern electronics.     

Silicon supported lipid-DNA thin film structures at varying temperature studied by energy dispersive X-ray diffraction and neutron reflectivity

Non-viral gene transfection by means of lipid-based nanosystems, such as solid supported lipid assemblies, is often limited due to their lack of stability and the consequent loss of efficiency. Therefore not only a detailed thermo-lyotropic study of these DNA-lipid complexes is necessary to understand their interaction mechanisms, but it can also be considered as a first step in conceiving and developing new transfection biosystems. The aim of our study is a structural characterization of 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC)-dimethyl-dioctadecyl-ammonium bromide (DDAB)-DNA complex at varying temperature using the energy dispersive X-ray diffraction (EDXD) and neutron reflectivity (NR) techniques. We have shown the formation of a novel thermo-lyotropic structure of DOPC/DDAB thin film self-organized in multi-lamellar planes on (100)-oriented silicon support by spin coating, thus enlightening its ability to include DNA strands. Our NR measurements indicate that the DOPC/DDAB/DNA complex forms temperature-dependent structures. At 65°C and relative humidity of 100% DNA fragments are buried between single lamellar leaflets constituting the hydrocarbon core of the lipid bilayers. This finding supports the consistency of the hydrophobic interaction model, which implies that the coupling between lipid tails and hypo-hydrated DNA single strands could be the driving force of DNA-lipid complexation. Upon cooling to 25°C, EDXD analysis points out that full-hydrated DOPC-DDAB-DNA can switch in a different metastable complex supposed to be driven by lipid heads-DNA electrostatic interaction. Thermotropic response analysis also clarifies that DOPC has a pivotal role in promoting the formation of our observed thermophylic silicon supported lipids-DNA assembly.     

Enhanced electrochromics of nanoporous cobalt oxide thin film prepared by a facile chemical bath deposition

A highly porous cobalt oxide thin film was prepared on ITO glass by a facile chemical bath deposition (CBD) method. The as-prepared cobalt oxide film has an intercrossing net-like morphology. The electrochromic performance of cobalt oxide film was investigated in 0.1 M KOH by means of transmittance, cyclic voltammetry (CV) and chronoamperometry (CA) measurements. The cobalt oxide thin film exhibits a noticeable electrochromism with reversible color changes from pale yellow to dark grey and presents a transmittance variation with 36% in the visible range. The porous cobalt oxide thin film also shows good reaction kinetics with fast switching speed, and the coloration and bleaching time are 2.5 and 2 s, respectively.     

Probing the pore wall structure of nanoporous carbons using adsorption

Hitherto, adsorption has been traditionally used to study only the porous structure in disordered materials, while the structure of the solid phase skeleton has been probed by crystallographic methods such as X-ray diffraction. Here we show that for carbons density functional theory, suitably adapted to consider heterogeneity of the pore walls, can be reliably used to probe features of the solid structure hitherto accessibly only approximately even by crystallographic methods. We investigate a range of carbons and determine pore wall thickness distributions using argon adsorption, with results corroborated by X-ray diffraction.     

Characterization of AlN thin film prepared by reactive sputtering

AlN films with a preferred orientation <002> have been prepared on Si(100) substrates via DC reactive magnetron sputtering. X‐ray diffraction, atomic force microscopy, scanning electron microscopy, ellipsometer, and ultraviolet–visible–near infrared (UV–VIS–NIR) spectrophotometer were used to investigate the structural and optical properties of the AlN thin films. When the sputtering pressure is about 0.4 Pa, the flow ratio between nitrogen and argon is 1 : 3, and the growth temperature is 400 °C, the transmissivity of the AlN film is about 90% in the visible and near‐infrared region, and its optical band gap is ~5.84 eV. The refractive index of the thin films is about 2.05, which is lower than the bulk AlN refractive index. Copyright © 2016 John Wiley & Sons, Ltd.     

Cavitation and pore blocking in nanoporous glasses

In gas adsorption studies, porous glasses are frequently referred to as model materials for highly disordered mesopore systems. Numerous works suggest that an accurate interpretation of physisorption isotherms requires a complete understanding of network effects upon adsorption and desorption, respectively. The present article deals with nitrogen and argon adsorption at different temperatures (77 and 87 K) performed on a series of novel nanoporous glasses (NPG) with different mean pore widths. NPG samples contain smaller mesopores and significantly higher microporosity than porous Vycor glass or controlled pore glass. Since the mean pore width of NPG can be tuned sensitively, the evolution of adsorption characteristics with respect to a broadening pore network can be investigated starting from the narrowest nanopore width. With an increasing mean pore width, a H2-type hysteresis develops gradually which finally transforms into a H1-type. In this connection, a transition from a cavitation-induced desorption toward desorption controlled by pore blocking can be observed. Furthermore, we find concrete hints for a pore size dependence of the relative pressure of cavitation in highly disordered pore systems. By comparing nitrogen and argon adsorption, a comprehensive insight into adsorption mechanisms in novel disordered materials is provided.     

Are pore size distributions in microfiltration membranes measurable by two-phase flow porosimetry?

The issue of evaluating equivalent pore diameter distributions in membrane microfilters from gas-liquid (g-l) porosimetry data has been critically examined. Experiments performed with one isotropic and one composite anisotropic membrane in both possible orientations revealed conspicous dependence of the obtained (g-l) porosimetry peaks on imposed pressure ramp rates, p. Interference of this kinetic effect can be eliminated from the measured data by extrapolation to p = 0. The ramp rate effect is most likely caused by tortuous pore length distribution, and relatively long times required for liquid expulsion. For two experiments, the observed effects of p could be reconciled with predictions of the Schlesinger-Bechhold theory [Bechold et al., Kolloid Z., 55 (1931) 172–198]. The data obtained with the thin top layer of the composite membrane facing intruding air directly did deviate somewhat from the theory. Pores characterized by (g-l) porosimetry are likely of the “throat type”, and their size distribution is considerably more narrow than that obtained for the “node-type” pores by SEM-image analysis [Zeman and Denault, J. Membrane Sci., 71 (1992) 221–231]. A single bivariate distribution function was constructed for these two distinct pore populations. Flow-weighted or number fraction distributions can be calculated from the extrapolated porosimetry data. For narrow ranges of “throat” diameters, these distributions are fairly similar.     

Electronic structure of a vapor-deposited metal-free phthalocyanine thin film

The electronic structure of a vapor-sublimated thin film of metal-free phthalocyanine (H2Pc) is studied experimentally and theoretically. An atom-specific picture of the occupied and unoccupied electronic states is obtained using x-ray-absorption spectroscopy (XAS), core- and valence-level x-ray photoelectron spectroscopy (XPS), and density-functional theory (DFT) calculations. The DFT calculations allow for an identification of the contributions from individual nitrogen atoms to the experimental N1s XAS and valence XPS spectra. This comprehensive study of metal-free phthalocyanine is relevant for the application of such molecules in molecular electronics and provides a solid foundation for identifying modifications in the electronic structure induced by various substituent groups.     

Integration of a nanoporous platinum thin film into a microfluidic system for non-enzymatic electrochemical glucose sensing.

In this paper, we describe an amperometric-type enzymeless glucose sensing system based on a nanoporous platinum (Pt) electrode embedded in a microfluidic chip. This microchip system is comprised of a microfluidic transport channel network and a miniaturized electrochemical cell for nonenzymatic glucose sensing. Sample and buffer solutions were transferred to the cell by programmed electroosmotic flow (EOF). A nanoporous Pt electrode with the roughness factor of 200.6 was utilized to determine glucose concentrations in phosphate buffered saline (PBS) by the direct oxidation of glucose, without any separation process. The sensitivity of the developed system is 1.65 microA cm-2 mM-1 in the glucose concentration range from 1-10 mM in PBS.     

Internal structure of nanoporous TiO2/polyion thin films prepared by layer-by-layer deposition

The internal structure of porous TiO2 films prepared by electrostatic layer-by-layer deposition was investigated. The films were prepared by alternate dipping of solid substrates into dispersions of TiO2 nanoparticles and polycations, polyanions, or pure buffer solution, respectively. The surface charge of the amphoteric TiO2 particles was controlled by the pH of the aqueous dispersions. The morphology of the film surface was investigated by means of scanning electron microscopy. It was found that the surface roughness strongly depends on the polymeric material used for the deposition process but is independent of the ionic strength of the solution or the molecular weight of the polyions. The samples with rough surfaces feature strong light scattering. The porosity and internal structure of the TiO2/polyelectrolyte films were investigated by adsorption/desorption of dye molecules. A crude estimate yields an internal surface that is up to 160 times the plane surface of the substrate for a film thickness of 1 microm. The composition of the films was investigated by X-ray photoelectron spectroscopy (XPS). Detection of the XPS signal after each deposition step of the first three dipping cycles shows a significant increase of the relative surface coverage of Ti after the TiO2 deposition step and of PSS after the PSS deposition step. For later dipping cycles, such an increase was also detectable but less prominent.     

Characterization of a molecular sieve coating using ellipsometric porosimetry

Ellipsometric porosimetry was used to determine the adsorption isotherms of toluene, methanol, and water on b-oriented Silicalite-1 coatings with a thickness of less than ca. 250 nm and to obtain adsorption kinetics. The adsorption isotherms are of sufficient quality to reveal several aspects of the pore structure such as the adsorbate capacity and the adsorbate/framework affinity. The use of a combination of different molecular probes in ellipsometric porosimetry to elucidate the molecular accessibility of Silicalite-1 pores is demonstrated. It is shown that ellipsometric porosimetry is an appropriate technique for probing the influence of aging of the Silicalite-1 coating and of planarization polishing on the porosity, pore accessibility, and adsorbate/framework affinity.     

The atomic structure of a metal-supported vitreous thin silica film

Clear as glass: The atomic structure of a metal-supported vitreous thin silica film was resolved using low-temperature scanning tunneling microscopy (STM). Based on the STM image, a model was constructed and the atomic arrangement of the thin silica glass determined (see picture). The total pair correlation function of the structural model shows good agreement with diffraction experiments performed on vitreous silica.     

Preparation, structure, and optical properties of nanoporous gold thin films

Thin nanoporous gold (np-Au) films, ranging in thickness from approximately 40 to 1600 nm, have been prepared by selective chemical etching of Ag from Ag/Au alloy films supported on planar substrates. A combination of scanning electron microscopy (SEM) imaging, synchrotron grazing incidence small angle X-ray scattering, and N2 adsorption surface area measurements shows the films to exhibit a porous structure with intertwined gold fibrils exhibiting a spectrum of feature sizes and spacings ranging from several to hundreds of nanometers. Spectroscopic ellipsometry measurements (300-800 nm) reveal the onset of surface plasmon types of features with increase of film thicknesses into the approximately 200 nm film thickness range. Raman scattering measurements for films functionalized with a self-assembled monolayer formed from 4-fluorobenzenethiol show significant enhancements which vary sharply with film thickness and etching times. The maximum enhancement factors reach approximately 10(4) for 632.8 nm excitation, peak sharply in the approximately 200 nm thickness range for films prepared at optimum etching times, and show high spot to spot reproducibility with approximately 1 microm laser spot sizes, an indication that these films could be useful as durable, highly reproducible surface-enhanced Raman substrates.     

Characterization of iron-silicon thin films by means of electron diffraction and X-ray spectroscopy

Iron-silicon thin films have been characterized by means of analytical transmission electron microscopic methods. Under certain conditions — composition and annealing temperature — these films exhibit thermoelectric behavior. In particular, the morphology and phase formation which results from annealing of these films, and doping with oxygen and nitrogen, are of interest. The thermoelectric phase -FeSi₂ is formed at temperatures above 500°C. This phase is transformed into electrically conducting phases at about 1000°C. A small oxygen content does not influence this crystallization process. If the oxygen content is higher than 15 atom-% the electrically conducting phases exist even at 500°C. The presence of a small nitrogen content inhibits the formation of the -FeSi₂ phase. The development of silicon and iron nitrides is possible.