Multiple-beam Interferometry Research Articles

Nanometer Resolved Real Time Visualization of Acidification and Material Breakdown in Confinement

AbstractLocalized surface reactions in confinement are inherently difficult to visualize in real‐time. Herein multiple‐beam‐interferometry (MBI) is extended as a real‐time monitoring tool for corrosion of nanometer confined bulk metallic surfaces. The capabilities of MBI are demonstrated, and the initial crevice corrosion mechanism on confined nickel and a Ni75Cr16Fe9 model material is compared. The initiation of crevice corrosion is visualized in real time during linear sweep polarization in a 1 × 10−3 m NaCl solution. Pre‐ and post‐experiment analysis is performed to complementarily characterize the degraded area with atomic force microscopy (AFM), optical microscopy, nano‐Laue diffraction (nano‐LD), scanning electron microscopy (SEM)/electron backscatter diffraction (EBSD), and X‐ray photoelectron spectroscopy (XPS). Overall, Ni75Cr16Fe9 displays a better corrosion resistance; however, MBI imaging reveals 200 nm deep severe localized corrosion of the alloy in the crevice opening. Chromium rich passive films formed on the alloy contribute to accelerated corrosion of the confined alloy by a strongly acidifying dissolution of the passive film in the crevice opening. Nano‐LD further reveals preferential crystallographic defect and corrosion migration planes during corrosion. MBI provides nanometer accurate characterization of topologies and degradation in confined spaces. The technique enables the understanding of the initial crevice corrosion mechanism and testing modeling approaches and machine‐learning algorithms.

Optimizing multiple beam interferometry in the surface forces apparatus: Novel optics, reflection mode modeling, metal layer thicknesses, birefringence, and rotation of anisotropic layers.

Multiple beam interferometry (MBI) evolved as a powerful tool for the simultaneous evaluation of thin film thicknesses and refractive indices in Surface Forces Apparatus (SFA) measurements. However, analysis has relied on simplifications for providing fast or simplified analysis of recorded interference spectra. Here, we describe the implementation of new optics and a generalized fitting approach to 4 × 4 transfer matrix method simulations for the SFA. Layers are described by dispersive complex refractive indices, thicknesses, and Euler angles that can be fitted, providing modeling for birefringent or colored layers. Normalization of data by incident light intensities is essential for the implementation of a fitting approach. Therefore, a modular optical system is described that can be retrofit to any existing SFA setup. Real-time normalization of spectra by white light is realized, alignment procedures are considerably simplified, and direct switching between transmission and reflection modes is possible. A numerical approach is introduced for constructing transfer matrices for birefringent materials. Full fitting of data to the simulation is implemented for arbitrary multilayered stacks used in SFA. This enables self-consistent fitting of mirror thicknesses, birefringence, and relative rotation of anisotropic layers (e.g., mica), evaluation of reflection and transmission mode spectra, and simultaneous fitting of thicknesses and refractive indices of media confined between two surfaces. In addition, a fast full spectral fitting method is implemented for providing a possible real-time analysis with up to 30 fps. We measure and analyze refractive indices of confined cyclohexane, the thickness of lipid bilayers, the thickness of metal layers, the relative rotation of birefringent materials, contact widths, as well as simultaneous fitting of both reflection and transmission mode spectra of typical interferometers. Our analyses suggest a number of best practices for conducting SFA and open MBI in an SFA for increasingly complex systems, including metamaterials, multilayered anisotropic layers, and chiral layers.

High-Resolution Studies of Crevice Corrosion of Nickel and Aluminum with Real Time Multiple Beam Interferometry and Microscopy

Crevice corrosion (CC) of engineering metals remains a serious concern for structural materials. Yet combining both, a real-time and high-resolution in-situ visualization of corrosion within confined geometries remains very challenging. In this contribution, we will discuss how multiple-beam interferometry (MBI) and simultaneous microscopy can be utilized to directly visualize corrosion processes in real-time and with Ångstrom resolution within well-defined confinement geometries. Here we will directly compare results of accelerated corrosion tests of confined Aluminum and Nickel surfaces in a modified surface forces apparatus1. With MBI, we can detect and track active sites of aluminum corrosion in NaCl solution within confined geometries in real time. We find that CC of aluminum randomly initiates in the confined crevice mouth, where the distance between apposing surfaces is between 20-300 nm. We can directly track oxide dissolution/formation, and corrosion-rates as well as their retardation due to sodium vanadate inhibitors present in solution. Formation of a compacted oxide layer effectively inhibits CC in 5 mM NaCl solutions with 2.5 mM of added NaVO3, while inhibition rapidly breaks down at chloride concentrations above 50 mM. Breakdown of the inhibition-layers is initiated by rapid dissolution of the protective oxide within the confined zone. Interestingly, Nickel CC shows distinctly different and unexpected corrosion mechanism depending on the NaCl concentration. We find that low Chloride concentration lead to “preferential pitting corrosion” inside of confined zones, while high Chloride concentrations lead to “crevice corrosion in the crevice mouth”. We will discuss these surprising results and we will show real time high-resolution videos of CC in confined geometries that detail this behavior. Literature 1. Shrestha, B. R.; Hu, Q.; Baimpos, T.; Kristiansen, K.; Israelachvili, J. N.; Valtiner, M., Real-Time Monitoring of Aluminum Crevice Corrosion and Its Inhibition by Vanadates with Multiple Beam Interferometry in a Surface Forces Apparatus. Journal of the Electrochemical Society 162 2015, C327-C332

Structural and optical properties of vacuum evaporated V2O5 thin films

Thin films of vanadium pentoxide (V2O5) have been deposited on to well-cleaned glass substrates under a vacuum of 10−5torr using 12A4 Hind Hivac coating unit. The thickness of the films was measured by the multiple beam interferometry technique and cross checked by using capacitance method. The structural, morphological and optical properties of deposited V2O5 films were determined by XRD, SEM and UV – vis analysis. XRD pattern indicates the amorphous nature of the film. Absorption co-efficient (α), extinction co-efficient (Kf) and refractive index were calculated from the optical transmission spectrum. The transmittance is found to decrease with the increase in thickness. The band gap of the film is found to decrease with increasing film thickness.

Real-Time Multiple Beam Interferometry Reveals Complex Deformations of Metal–Organic-Framework Crystals upon Humidity Adsorption/Desorption

Gas adsorption in metal–organic-frameworks (MOFs) can dramatically affect the size of the crystals (expansion and/or shrinkage) or lead to distortion of their porous structure/framework. This can strongly affect mechanical properties of MOFs potentially leading to loss or improvement of the performance of applications such as membranes, filters, or sensors. Here, we utilize white light multiple-beam-interferometry (MBI) in a surface forces apparatus (SFA) to measure in real-time the deformations taking place in HKUST-1 crystals during humidity adsorption/desorption cycles. MBI provides a real-time measurement of crystal deformations during guest molecule uptake with msecs time and A distance resolution. We find unusual and unexpected dynamic and nonmonotonic deformation behavior upon humidity loading in HKUST-1 crystals, which we attributed to the gradual filling of the different adsorption sites in the MOF crystal framework. Also, the effect of the external mechanical pressure applied to hydrated/dehydra...

High Resolution in Situ Studies of Localized and Crevice Corrosion with Multiple Beam Interferometry and Atomic Force Microscopy

Crevice corrosion (CC) and localized corrosion of metals remains a serious concern for structural materials. Yet both, a real-time and in-situ visualization of (1) initiation of localized corrosion, and (2) corrosion within confined geometries, remains very challenging. In this contribution, we will discuss how multiple-beam interferometry (MBI) can be utilized to directly visualize corrosion processes in real-time and with Ångstrom resolution within well-defined confinement geometries[1]. Also, we will discuss how electrochemical AFM can be utilized to study localized phenomena such as dealloying on patterned surfaces[2]. We will particularly aim to discuss and describe techniques and electrochemical cells, that we recently developed and will discuss how they may become useful in the field of corrosion and localized corrosion. With MBI, we can detect and track active sites of aluminum corrosion in NaCl solution within confined geometries[3]. We find that CC of aluminum randomly initiates in the confined crevice mouth, where the distance between apposing surfaces is between 20-300 nm. We can directly track oxide dissolution/formation, and corrosion-rates as well as their retardation due to sodium vanadate inhibitors present in solution. Formation of a compacted oxide layer effectively inhibits CC in 5 mM NaCl solutions with 2.5 mM of added NaVO3, while inhibition rapidly breaks down at chloride concentrations above 50 mM. Breakdown of the inhibition-layers is initiated by rapid dissolution of the protective oxide within the confined zone. With our newly developed electrochemical AFM cell we can accurately track localized initiation sites of corrosion in model de-alloying experiments on patterned surfaces with nm resolution in x/y and atomic resolution in vertical directions[4]. The time resolution of our EC-AFM is currently limited to about 10 seconds per frame. In both parts of this contribution we will discuss experiments with model systems and we aim to specifically focus on technical hurdles and pros/cons of our techniques, including an outlook into what may be achieved in the future.

Wetting of Nano-Confined Electrodes By Lithium-Ion Battery Electrolytes Using Multiple Beam Interferometry

The interface with the electrolyte is a decisive feature in the design of composite battery electrodes, which typically contain active material particles, conductive material, and polymer binder. A detailed understanding of the electrolyte layering and wetting of materials such as graphene, graphites, metals such as aluminum or even gold, silicon, and metal oxides are ultimately important for improving crucial lithium-ion battery mechanisms. In particular the solid electrolyte interphase (SEI) and lithium-ion mobility at electrode interfaces are still not well understood. Here we use the (Electrochemical) Surface Forces Apparatus (SFA) (1) to address the wetting behavior of nano-scale-confined lithium-ion battery electrodes by battery electrolytes. After its introduction in the 1970s by Israelachvili and Adams (2), the SFA has been used to investigate interfacial phenomena in fields varying from geoscience to microbiology (3). Figure 1 shows a detail of the SFA-setup that was used for the experiments. White light is thereby guided through a flat contact area of two semi-transparent SFA disks, causing interference patterns which are analyzed using a spectrometer. Monitoring the pattern throughout the experiments allows to follow electrolyte wetting behavior in the confined contact area. Some of the investigated surfaces were mica, gold and graphene. For instance for graphene, a unique combination of rigid and mobile lithium-ion containing electrolyte layers was observed. Figure 2 shows a typical population mapping of a SFA-experiment which focused on the initial wetting behavior of a battery electrolyte (EC/DEC - LiPF6) on dry mica, gold and graphene surfaces. After an initial drop of about 1.8 Å in the inter-mirror distance, which is due to the excretion of a monolayer of adsorbed water from the initially dry interface, the wetting process of the electrolyte was only in the case of graphene able to overcome the contact force. Similar observations were made when nano-confined gaps were wetted with ionic liquids. Molecular beam interferometry is a versatile and powerful tool for studying such nanoscaled wetting processes using battery electrodes including ionic liquids or organic solvents. REFERENCES 1. M. Valtiner et al., Langmuir, 28, 13080 (2012) 2. J. N. Israelachvili and G. E. Adams, Nature, 262, 774 (1976) 3. S. Raman, M. Valtiner, et al., Nature Communications, 5, 5539 (2014) Figure 1

Real-Time Monitoring of Aluminum Crevice Corrosion and Its Inhibition by Vanadates with Multiple Beam Interferometry in a Surface Forces Apparatus

Crevice corrosion (CC) of metals remains a serious concern for structural materials. Yet a real-time in situ visualization of corrosion, and its inhibition within a confined geometry, remains challenging. Here, we present how multiple-beam interferometry in a Surface Forces Apparatus can be utilized to directly visualize corrosion processes in real-time and with Ångstrom resolution within well-defined confinement geometries. We use atomically smooth muscovite mica surfaces to form round-shaped ∼1000 μm2 crevices on aluminum. After exposure to NaCl solutions we can detect and track active sites of aluminum corrosion within this confined geometry. CC of aluminum randomly initiates in the confined crevice mouth, where the distance between apposing surfaces is between 20–300 nm. We can directly track oxide dissolution/formation, and corrosion-rates as well as their retardation due to sodium vanadate inhibitors present in solution. Formation of a compacted oxide layer effectively inhibits CC in 5 mM NaCl solutions with 2.5 mM of added NaVO3, while inhibition rapidly breaks down at chloride concentrations above 50 mM. Breakdown of the inhibition-layers is initiated by rapid dissolution of the protective oxide within the confined zone. Our technique may be adapted for monitoring CC, corrosion inside of crack-tips, and evaluation of inhibitor efficiencies in a variety of metals.

Thickness and refractive index of DPPC and DPPE monolayers by multiple-beam interferometry.

The thickness and refractive index of 1,2-dipalmitoyl-sn-glycero-3-phosphatidyl choline (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) monolayers Langmuir--Blodgett (LB) deposited on mica were measured in dry air and bulk water using multiple-beam interferometry (MBI). Measurements of thickness using atomic force microscopy (AFM) of identical monolayers, and X-ray reflectivity (XRR) of the monolayers on quartz were taken for comparison. The measurement of the properties of solid-supported monolayers in dry air allows lipid optical properties to be determined free from solvent effects. The thickness and refractive index measured by MBI were 25.5 ± 0.6 Å and 1.485 ± 0.007 for DPPE monolayers, and 23.9 ± 0.5 Å and 1.478 ± 0.006 for DPPC monolayers in dry air. These thicknesses are consistent with the other techniques used in this work as well as other measurements in the literature. The refractive indices of solid-supported lipid monolayers have not been previously measured. The values are higher than previous measurements on black lipid films done by reflectometry, which is attributed to increased lipid packing density and the absence of hydrocarbon solvents. Applying water to the monolayers had no measurable effect on their properties, indicating that any change in hydration was below detection.

Interferometry of surfaces with well-defined topography in the surface force apparatus

We studied the multiple beam interferometry of surfaces with well-defined microscale features in the surface force apparatus (SFA). The structures investigated consist of hexagonal arrays of microscale cylindrical posts made out of the photoresist SU-8. The ability of the SFA to visualize the profile and topography of the interacting surfaces leads to the observation of discontinuities in primary fringes of equal chromatic order that are caused by the microscale structural features. The shift in wavelengths has been analyzed to extract the post height and compared to independent profilometry measurements. The analysis based on the shift in wavelength is shown to be viable only when the order of the fringe and the position of the discontinuity is precisely known and within the field of view. Analysis of the full profile of the interacting surface for two orthogonal 2-dimensional slices can be used to determine how the surface lattice is oriented within the point of closest approach. Finally, we discuss cases in which the structural features detrimentally affect the spatial resolution of the SFA.

Morphology, Structural and Dielectric Properties of Vacuum Evaporated V2O5 Thin Films

Vanadium pentoxide (V2O5) thin films were deposited on well cleaned glass substrate using evaporation technique under the pressure of 10-5 Torr. The thickness of the films was measured by the multiple beam interferometry technique and cross checked by using capacitance method. Metal-Insulator-Metal (MIM) structure was fabricated by using suitable masks to study dielectric properties. The dielectric properties were studied by employing LCR meter in the frequency range 12 Hz to 100 kHz for various temperatures. The temperature co- efficient of permittivity (TCP), temperature co-efficient of capacitance (TCC) and dielectric constant (ɛ) were calculated. The activation energy was calculated and found to be very low. The activation energy was found to be increasing with increase in frequency. The obtained low value of activation energy suggested that the hopping conduction may be due to electrons rather than ions.

Highly accurate film thickness measurement based on automatic fringe analysis

This paper describes an automated multiple-beam interferometry for measuring a calibrated step height of (27.00±3.00) nm nominally. The fringes captured from the multiple-beam Fizeau–Tolansky interferometer were thinned by using a written program to obtain accurate measurement. We claim that multiple-beam interferometry based on automatic fringe thinning process can provide a real time solution for calibrating step heights precisely and with high accuracy. The uncertainty budget of the multiple-beam interferometry method due to incomplete parallelism of the incident beam and the inhomogeneity of the reflecting layers was calculated automatically with a written ray tracing program. The uncertainty budget in multiple-beam interferometry was estimated to be of the order of 3.00nm.

Radius of curvature measurement of spherical smooth surfaces by multiple-beam interferometry in reflection

In this paper a method is presented to accurately measure the radius of curvature of different types of curved surfaces of different radii of curvatures of 38 000,18 000 and 8000 mm using multiple-beam interference fringes in reflection. The images captured by the digital detector were corrected by flat fielding method. The corrected images were analyzed and the form of the surfaces was obtained. A 3D profile for the three types of surfaces was obtained using Zernike polynomial fitting. Some sources of uncertainty in measurement were calculated by means of ray tracing simulations and the uncertainty budget was estimated within λ/40.

Surface microtopography measurement of a standard flat surface by multiple-beam interference fringes at reflection

This paper describes a multiple-beam interferometry technique at reflection for measuring the microtopography of an optical flat nominally of λ/20. The measured value is the result of a piezoelectric phase shifting that made it possible to cover the area between the orders. The exposure area of the tested optical flat covered by the collimated laser beam is about 2 cm. The images captured by the digital detector were corrected using dark/flat field method. The uncertainty in the measurement due to incomplete parallelism of the incident beam and the inhomogeneity of the reflecting layers were calculated from the departure of the fringe position produced with a written ray tracing program. The uncertainty budget was estimated to be of the order of λ/40.

Measurement of friction force between two mica surfaces with multiple beam interferometry

Surface forces play a crucial role in the contact behavior of micro-components as well as the application of MEMS products. In this study, a microscopic measurement system based on multiple beam interferometry is developed to measure the adhesive force between two mica thin films. The contact area on the mica can be determined from the FECO fringes. A double cantilever spring is used to measure the adhesive (pull-off) forces between the two mica thin films. The usefulness of the adhesive force measurement system is validated by comparing with the result from JKR contact theory.

Passively Q-switched laser with single longitudinal mode based on the frequency selection of grating and F-P etalon in twisted-mode folded cavity

A passively Q-switched side-pumped laser with folded resonator is specially constructed for singlelongitudinal-mode smooth pulse output. Nd:YAG is chosen as the laser active medium and Crlsupg4+l/supg:YAG as the saturable absorber medium. Additionally, the method of frequency selection by grating with 1200 line/mm and Fabry-Perot (F-P) etalon is used in the twisted-mode cavity. The single-frequency smooth pulses are produced with 10-Hz repetition rate, 20-ns pulse width, and 1.064-\mu m wavelength. The probability of single-frequency laser output measured is over 99% by using the methods of Fourier analysis and F-P etalon multiple-beam interferometry at the threshold voltage. The measured near-field and far-field angles of divergence are 1.442 and 1.315 mrad, respectively. The values of Mlsupg2l/supg are 1.32 and 1.31 separately with the knife-edge method. Single pulse at 1.064 \mu m with the energy of 8.8 mJ is achieved in TEMlsubg00l/subg mode.

Solutions of Negatively Charged Graphene Sheets and Ribbons

Negatively charged graphene layers from a graphite intercalation compound spontaneously dissolve in N-methylpyrrolidone, without the need for any sonication, yielding stable, air-sensitive, solutions of laterally extended atom-thick graphene sheets and ribbons with dimensions over tens of micrometers. These can be deposited on a variety of substrates. Height measurements showing single-atom thickness were performed by STM, AFM, multiple beam interferometry, and optical imaging on Sarfus wafers, demonstrating deposits of graphene flakes and ribbons. AFM height measurements on mica give the actual height of graphene (ca. 0.4 nm).

Micromachined Fabry−Pérot Interferometer with Embedded Nanochannels for Nanoscale Fluid Dynamics

We describe a microfabricated Fabry-Pérot interferometer with nanochannels of various heights between 6 and 20 nm embedded in its cavity. By multiple beam interferometry, the device enables the study of liquid behavior in the nanochannels without using fluorescent substances. During filling studies of ethanol and water, an intriguing filling mode for partially wetting water was observed, tentatively attributed to the entrapment of a large amount of gas inside the channels.

Properties of Confined and Sheared Rhodamine B Films Studied by SFA−FECO Spectroscopy

We have used a surface forces apparatus and multiple beam interferometry to measure the absorbance of thin films of rhodamine B in water/ethylene glycol solutions while applying and measuring normal and lateral (shear) forces. Both normal and shear forces induced changes in the absorption spectra indicating a change in molecular alignment, and rhodamine-rhodamine and rhodamine-surface interactions. We also measured differences in the absorbance spectra in different regions of the contact indicating, as expected, that the stresses are not uniform throughout the contact area. We also observed crystallization (solidification) parallel to the shearing direction.

Two-dimensional periodic potential via multiple-beam interferometry for atom lithography

We propose the use of square arrays of multiple atomic lenses, produced by interference of four nearly collinear optical beams in atom lithography using dipole force. Simulated lithographic patterns are reported for collimated as well as divergent rubidium atomic beam traveling in such square arrays of optical channels. The proposed configuration has the ability to write large numbers of periodic structures in square arrays in a single step.