Sum frequency generation spectroscopy of fluorinated organic material-based interfaces: a tutorial review.

Molecular interactions at interfaces have a significant effect on the wetting properties of surfaces on a macroscale. Sum frequency generation (SFG) spectroscopy, one of a few techniques capable of probing such interactions, generates a surface vibrational spectrum sensitive to molecular structures and has been used to determine the orientation of molecules at interfaces. The purpose of this review is to assess SFG spectroscopy's ability to determine the molecular orientations of interfaces composed of fluorinated organic molecules. We will explore three different types of fluorinated organic material-based interfaces, naming liquid-air, solid-air, and solid-liquid interfaces, to see how SFG spectroscopy can be used to gain valuable and unique information regarding the molecular orientation of each interface. We hope this review will help to broaden the understanding of how to employ SFG spectroscopy to obtain more complex structural information for various fluorinated organic material-based interfaces in the future.

Chemical Imaging of Surfaces with Sum Frequency Generation Vibrational Spectroscopy.

Surface chemistry is a key area of study in the chemical sciences, and many system properties are dominated by the chemistry at the interface between two bulk media. While the interface may have a large influence on the system behavior, there are relatively few molecules at the interface compared to the bulk; thus, probing their unique properties has become a specialized field in physical chemistry. In addition to the heterogeneous phase chemistry, surfaces also present spatial heterogeneity (Chemistry in Two Dimensions). This 2D chemistry affects the properties as much as the heterogeneous phases. If we consider the Cartesian z-axis as defining the dimension across the interface between the two bulk phases, then the x-y plane is the 2D region of the surface. We might even consider that the majority of surface chemistry has been concerned with this z-dimension, i.e., surface structure, partition excess, thermodynamics, etc. relative to the bulk, where the 2D distribution was only considered on average. This treatment is understandable since few techniques provide the spatial and chemical resolution needed to deduce the effects of 2D heterogeneity on the surface properties. It is desirable to use an all-optical technique for interface studies because the optical methods provide the chemical specificity through spectroscopy. Also, the use of second-order spectroscopy is typically surface-sensitive without background subtractions or enhancement mechanisms that could limit the range of systems to be investigated.In this Account, the development and selected results of sum frequency generation microscopy and its contributions to the surface chemistry are presented. Sum frequency generation (SFG) provides a unique probe for studying surface chemistry in ambient conditions with surface specificity. SFG provides image contrast based on multiple-chemically important-mechanisms such as chemical functional groups, molecular orientation, surface concentration, molecular conformation, local electric fields, among others. To understand the spatial distribution of heterogeneous chemistry, multiple microscopy methods have been developed which utilize the SFG process to yield spatial information with chemical sensitivity. These spectroscopic-microscopies come with unique advantages as well as challenges. Multiple solutions have been developed in this field to overcome the challenges and improve the advantages. In this Account, some of the leading SFG surface microscopies for surface studies are introduced. Initially, direct imaging of the SFG signal onto a CCD camera provided spatially and spectrally resolved imaging of monolayers on surfaces. However, to speed up the imaging process, the technique of compressive sensing was applied to SFG imaging. Most recently the use of machine learning methods and target factor analysis have improved the quality and acquisition speed of SFG images.

In situ quantitative study of the phase transition in surfactant adsorption layers at the silica-water interface using total internal reflection Raman spectroscopy.

Dimethyldodecylamine N-oxide (DDAO), a unique type of surfactant, shows high surface activity with two distinct energy states at the buried hydrophilic silica/aqueous solution interface studied by total internal reflection (TIR) Raman spectroscopy combined with ratiometric and kinetic analysis. Different from other types of surfactant, i.e., ionic and nonionic, the adsorption of DDAO demonstrates a specific critical surface aggregation concentration (csac) at 0.15 mM gives a complete surface coverage of 6.6 ± 0.3 µmol m-2, much lower than the bulk critical micellization concentration (cmc) at the same conditions (csac ≈ 0.072 cmc). A phase transition of adsorbed layers from liquid crystalline as the intermediate state to the disordered liquid phase is spectroscopically and energetically analyzed. The adsorption of DDAO on silica surfaces is described quantitatively in a potential energy curve.

Direct imaging of electric field behavior in 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene organic field-effect transistors by sum-frequency generation imaging microscopy.

Sum-frequency generation imaging microscopy combined with compressive-sensing (CS-SFG) is a powerful micro-spectroscopic technique for probing interfaces and surfaces with a spatial resolution where contrast is based on the chemical functional groups. We reported the use of the CS-SFG technique to probe the electric field due to charge accumulation and the internal electric field in operating organic field-effect transistors (OFETs) with the aluminum oxide and octadecylphosphonic acid (ODPA) self-assembled monolayer as the gate dielectric layer and 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DPh-BTBT) as the semiconductor layer. In addition, the electric field behavior was discussed by a difference in the electric field induced SFG intensity between the open-circuit and the voltage application conditions. The SFG peak of CH stretching mode derived from methyl groups of ODPA and phenyl groups of DPh-BTBT could be observed at each interface of ODPA/DPh-BTBT or DPh-BTBT/Au, respectively. Moreover, the electric field induced SFG coming from ODPA/DPh-BTBT shows the presence of intense electric field due to charge injection and accumulation near the drain and source electrode edges under the operation of OFETs. Our studies show that the electric field-induced SFG imaging technique is useful for probing the local electric field distribution or charge accumulation behavior in OFETs under operating conditions.

Distortion Correction for an Imaging Ellipsometer.

A simple imaging add-on utilizing the combination of a relay lens and an optical grating to a nulling ellipsometer for the purpose of imaging and correcting angular distortion is designed, built, and tested. Image contrast is achieved on a standardized silicon wafer, graphene transferred on silicon wafer, a self-assembled monolayer of 1-octadecanethiol on gold, and a 1:1 mixture of dilauroylphosphatidylcholine / distearoylphosphatidylcholine (DLPC/DSPC) on copper. The configuration used in this paper corrects the angular distortion and depth of focus with a spatial resolution of 4.38 µm in the laser's incident direction and 7.81 µm in the direction that is perpendicular to the incident plane together with 3 Å of normal resolution while still maintaining a large field of view of at least 720 µm × 550 µm in focus without executing any line scanning, post-image reconstruction, or specially customized objective method. Better resolution is possibly attained with higher NA optics.

Spectroscopic imaging of surfaces-Sum frequency generation microscopy (SFGM) combined with compressive sensing (CS) technique.

Surface chemistry is notoriously difficult to study, in part, due to the decreased number of molecules that contribute to the properties compared to the bulk phase but often has significant effects on the chemical activity of the material. This is especially true in topics such as corrosion, catalysis, wetting, and many others in nature and industry. Sum frequency generation (SFG) spectroscopy was developed for interface studies due to its high molecular selectivity and surface sensitivity, which is quite useful to study the effects of structural inhomogeneity in microscopy. Compressive sensing (CS) combined with SFG spectroscopy minimizes the imaging time while still producing quality images. Selected systems are presented here to demonstrate the capability of CS-SFG microscopy. CS-SFG microscopy successfully distinguished the static monolayer molecular mixtures, the orientations and adsorption of adsorbed molecules by the dip-coating technique, and the localized CO behaviors on polycrystalline Pt electrodes. Further discussion includes dynamic imaging as a future direction in CS-SFG microscopy. As materials and surfaces become more complex, imaging with chemical contrast becomes indispensable to understanding their performance and CS-SFG microscopy seems highly beneficial in this respect.

Sum Frequency Generation Imaging Microscopy of Self-Assembled Monolayers on Metal Surfaces: Factor Analysis of Mixed Monolayers.

Sum frequency generation (SFG) images of microcontact patterned self-assembled alkanethiol monolayers on metal surfaces were analyzed by factor analysis (FA) to determine the spatial distribution of the patterned monolayers over the images. Additionally, each significant abstract factor produced by FA was assessed to determine the information contained within it. These results indicate that FA of the SFG spectra is a promising method to determine the composition and identities of mixed alkanethiol systems that show different vibrational spectra and image contrast. Factor analysis has successfully been applied to SFG images obtained with low signals, which reduces the time required for full spectral SFG imaging.

From Micelles to Vesicle and Membrane Structures of Double-Strand Ionic Liquids in Water: Molecular Dynamics Simulation.

The structures of novel double-strand imidazolium iodide ionic liquids (ILs)-based lipid in the water phase have been studied in this research. We report the effect of alkyl chain length of 1,3-dimethyl-4,5-dialkyl-imidazolium iodide([2(Me)2(C n)im]I, n = 7, 11, 15) ILs on their structures in the aqueous solution by molecular dynamics simulation. The structure details of IL clusters lead to the various aggregation forms by increasing the alkyl chain length of ILs. The ILs with n = 7 and 11 can help develop micelle structures of different sizes, and the IL with n = 15, the benign IL, feasible to develop lipidlike vesicle. To obtain more details about bilayer properties, [2(Me)2(C15)im]I IL is investigated by different IL/water ratios in this study exclusively. The [2(Me)2(C15)im]I IL bilayer thickness and deuterium order parameters are compared with lipid membrane, and they reveal a small difference. The energies, radial distribution functions, spatial distribution function, cluster size, number density, and membrane properties all prove that the stable IL vesicle is formed in the dilute solution but the membrane is formed in the concentrated aqueous solution of [2(Me)2(C15)im]I.

Sum frequency generation spectroscopy of tetraalkylphosphonium ionic liquids at the air-liquid interface.

Sum frequency generation (SFG) spectroscopy is a nonlinear vibrational spectroscopic technique used in the study of interfaces, due to its unique ability to distinguish surface molecules that have preferential ordering compared to the isotropic bulk. Here, a series of alkyltrioctylphosphonium chloride ionic liquids, systematically varied by cation structure, were characterized at the air-liquid interface by SFG. The effect on surface structure resulting from molecular variation (i.e., addition of cyano- and methoxy-functional groups) of the cation alkyl chain was investigated. SFG spectra in the C-H stretching region (2750-3100 cm-1) for [P8 8 8 n ][Cl], where n = 4, 5, 8, 10, 12, or 14, showed characteristic changes as the alkyl chain length was increased. Spectral profiles for n = 4, 5, 8, or 10 appeared similar; however, when the fourth alkyl chain was sufficiently long (as in the case of n = 12 or n = 14), abrupt changes occurred in the spectra. Molecular dynamics (MD) simulation of a slab of each ionic liquid (with n = 8, 10, or 12) confirmed gauche defects, with enhancement for the long alkyl chain and an abrupt increase of gauche occurrence from n = 8 to n = 10. A comparison of the tilt angle distribution from the simulation and the SFG analysis show a broad distribution of angles. Using experimental SFG spectra in conjunction with MD simulations, a comprehensive molecular picture at the surface of this unique class of liquids is presented.

Distortion Correction for a Brewster Angle Microscope Using an Optical Grating.

A distortion-corrected Brewster angle microscope (DC-BAM) is designed, constructed, and tested based on the combination of an optical grating and a relay lens. Avoiding the drawbacks of most conventional BAM instruments, this configuration corrects the image propagation direction and consequently provides an image in focus over the entire field of view without any beam scanning or imaging reconstruction. This new BAM can be applied to both liquid and solid subphases with good spatial resolution in static and dynamic studies.

Quantitative orientation analysis by sum frequency generation in the presence of near-resonant background signal: acetonitrile on rutile TiO2 (110).

Sum frequency generation (SFG) spectroscopic techniques are used to investigate the molecular orientation of adsorbed acetonitrile on rutile TiO2 (110) at the solid-vapor interface. Generally, most molecular orientation analyses using SFG have been performed on dielectric substrates, to avoid the spectral interference between resonant and the near-resonant background signal. Although rutile crystal can be treated as a dielectric substrate, its electronic state contributes to the intensity and interferes with the resonant signal when the SFG frequency is close to its band gap energy. In addition, the rutile crystal is a uniaxial birefringent material, and the (110) surface is anisotropic, which further complicates the spectral analysis. In this study, various SFG measurement techniques were applied, and quantitative analytical methods were established to interpret the surface orientation of an adsorbed molecule. SFG vibrational spectra of acetonitrile on rutile TiO2 (110) surface have been measured using distinct polarization combinations, polarization mapping, and null angle method. By varying the polarization combinations of SFG, the magnitude and shape of the spectra undergo substantial change, which originate from the interference between the near-resonant signal from the rutile substrate and the resonance signal from the acetonitrile. Theory, simulation, and analytical methods for obtaining quantitative orientation information of a molecule on an anisotropic semiconductor substrate in the presence of a near-resonant signal are presented.

Evidence for Ion Association at the Gas-Liquid Interface of the Mixture of 1-Butyl-3-methylimidazolium Hexafluorophosphate and Benzonitrile: A Sum Frequency Generation Spectroscopy and Surface Tension Study.

The gas-liquid interface for the mixtures of [BMIM][PF6] and benzonitrile is studied by sum frequency generation (SFG) spectroscopy and surface tension measurements as an important solute to reduce the viscosity of ionic liquids. Solvation of ionic compounds in bulk solvent is not necessarily the same as that at the surface due to the lower dielectric medium at the air/liquid interface. The results from the temperature-dependent SFG spectroscopy and surface tension study suggest that the ionic liquid in a benzonitrile solvent is associated as ion pairs at the surface rather than as dissociated─solvated─ions in the bulk solution. The influence of ionic liquids on the surface structure of benzonitrile is investigated from 0 to 1.0 mole fraction of benzonitrile. The CH stretching mode of vibration of benzonitrile in the SFG spectrum begins from a 0.2 mole fraction (x) of benzonitrile, and the intensity of the peak constantly increases on increasing the concentration of benzonitrile. However, the addition of benzonitrile does not result in extra peaks or shifting of the peak frequency to the spectra of [BMIM][PF6]. The surface tension measurements further support the presence of benzonitrile at the gas-liquid interface. The surface tension data of the mixture smoothly decrease as the benzonitrile concentration increases. The apparent tilt angle of the terminal methyl group of the cation of [BMIM][PF6] is calculated from SFG polarization spectra and shows an apparent lowering with the addition of benzonitrile. The effect of temperature on the surface structure of the binary mixture is also reported at four different temperatures between -15 and 40 °C for both the SFG spectroscopy and surface tension study. Benzonitrile shows different behavior in the mixture at higher temperatures than pure benzonitrile, as observed in the SFG spectra. In contrast, it does not show any CN peak in the mixture below 0.9 mole fraction. The temperature dependence of the interfacial tension is used to evaluate thermodynamic functions such as surface entropy and surface enthalpy. Both were found to be lowered with the increasing concentration of benzonitrile. Both spectroscopic and thermodynamic analyses indicate that the ionic liquid is highly associated as ion pairs and the benzonitrile is more ordered at the surface at concentration <0.4×.

Structural study at the gas-liquid interface of 1-alkyl-3-methylimidazolium alkylsulfates using surface potential measurements.

Sum frequency generation, surface potential, and surface tension measurements have been combined on the pure ionic-liquid-gas interface for 1-alkyl-3-methylimidazolium alkylsulfate ionic liquids. The results show that surface potential of the ionic liquid generally increases as the alkyl chain on the cation or anion increases in length. This is due to the increased ordering of the surface dipole, mostly coming from the terminal methyl group of the alkyl chain. Both sum frequency generation spectroscopy and surface potential measurements suggest that the charged components, that is, the aromatic ring and the sulfate, occupy nearly the same plane at the surface for all ionic liquids studied herein.

Surface characterization of imidazolium-based ionic liquids with cyano-functionalized anions at the gas-liquid interface using sum frequency generation spectroscopy.

Advancement in the field of ionic liquid technology requires a comprehensive understanding of their surface properties, as a wide range of chemical reactions occur mainly at interfaces. As essential media currently used in several technological applications, their accurate molecular level description at the gas-liquid interface is of utmost importance. Due to the high degree of chemical information provided in the vibrational spectrum, vibrational spectroscopy gives the most detailed model for molecular structure. The inherently surface-sensitive technique, sum frequency generation (SFG) spectroscopy, in combination with bulk-sensitive vibrational spectroscopic techniques such as FTIR and Raman, has been used in this report to characterize the surface of cyano-containing ionic liquids, such as [BMIM][SCN], [BMIM][DCA], [BMIM][TCM] and [EMIM][TCB] at the gas-liquid interface. By structural variation of the anion while keeping the cation constant, emphasis on the molecular arrangement of the anion at the gas-liquid interface is reported, and its subsequent role (if any) in determining the surface molecular orientation of the cation. Vibrational modes seen in the C-H stretching region revealed the presence of the cation at the gas-liquid interface. The cation orientation is independent of the type of cyano-containing anion, however, a similar arrangement at the surface as reported in previous studies was found, with the imidazolium ring lying flat at the surface, and the alkyl chains pointing towards the gas phase. SFG results show that all three anions of varying symmetry, namely, [DCA](-) (C(2v)), [TCM](-)(D(3h)) and [TCB](-) (T(d)) in ionic liquids [BMIM]DCA], [BMIM][TCM] and [EMIM][TCB] are significantly tilted from the surface plane, while the linear [SCN](-) in [BMIM][SCN] exhibited poor ordering, as seen in the absence of its C-N stretching mode in the SFG vibrational spectra.

Surface structure of a "non-amphiphilic" protic ionic liquid.

The nanostructure of the ethanolammonium nitrate (EtAN)-air surface has been investigated using X-ray reflectometry (XRR), vibrational sum frequency spectroscopy (VSFS) and neutral impact collision ion scattering spectroscopy (NICISS). The XRR data decays more rapidly than expected for a perfectly sharp interface, indicating a diffuse electron (scattering length) density profile. Modelling of the XRR data using three different fitting routines produced consistent interfacial profiles that suggest the formation of interfacial EtAN clusters. Consistent with this, VSFS reveals that the EtAN surface is predominantly covered by -CH(2)- moieties, with the -NH(3)(+) and -OH groups of the cation buried slightly deeper in the interface. The elemental profiles determined using NICISS also show enrichment of carbon relative to nitrogen and oxygen in the outermost surface layer, which is consistent with the surface cation orientation deduced from VSFS, and with the presence of EtAN aggregates at the liquid surface.

Chemical Imaging of Lipid Segregation: Determining Different Length Scales of Heterogeneity with Compressive-Sensing Sum Frequency Generation Microscopy and Brewster Angle Microscopy.

Membranes of various phospholipids may separate into different domains at micrometer length scales at the air-water interface. A significant challenge is to visualize the molecular organization and obtain chemical information on this surface. Langmuir-Blodgett monolayers of 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) on fused silica were investigated with compressive sensing sum frequency generation (SFG) microscopy. Before and after mixing, SFG spectra for DSPC and DLPC revealed significant differences, indicating a structural change. Brewster angle microscopy images show phase separations that directly correlate the morphology of phospholipid mixtures with SFG images. Exploiting vibrational contrast in SFG images, exchange between the two phases was discovered, and quantitative thermodynamic analysis of lipid compositions in liquid-condensed and liquid-expanded (LE) phases was provided. Local SFG spectra reveal significant differences from one another, indicating the heterogeneity resulting from domain areas with distinct molecular orientation and conformation. Further heterogeneity across the domain boundary was presented on a finer scale, revealing an effect on DLPC due to the condensed phase DSPC, and the terminal methyl of DLPC perturbs the ordering of DSPC in the LE phase. This work demonstrates the heterogeneity of a two-dimensional binary lipid system mainly due to the aliphatic chain length and transition temperature difference.

Sum frequency generation-compressive sensing microscope.

A new sum frequency generation imaging microscope using a novel sampling theory, compressive sensing (CS), has been developed for surface studies. CS differentiates itself from the conventional sampling methods by collecting fewer measurements than the traditional methods to reconstruct a high quality image. Pseudorandom patterns were applied to a light modulator and reflected the sum frequency (SF) signal generated from the sample into a photomultiplier tube detector. The image of the sample was reconstructed using sparsity preserving algorithms from the SF signal. The influences of the number of CS testing patterns applied and the number of SF pulses acquired for each pattern on the quality of the images was investigated and a comparison of the image quality with the traditional raster scan was made at varying resolutions for a gold patterned Si surface. Our results demonstrate the CS technique achieved 16 times the pixel density beyond the resolution where the raster scan strategy lost its ability to image the sample due to the dilution of the SF signal below the detection limit of the detector.

Gas-liquid interface of room-temperature ionic liquids.

The organization of ions at the interface of ionic liquids and the vacuum is an ideal system to test new ideas and concepts on the interfacial chemistry of electrolyte systems in the limit of no solvent medium. Whilst electrolyte systems have numerous theoretical and experimental methods used to investigate their properties, the ionic liquids are relatively new and our understanding of the interfacial properties is just beginning to be explored. In this critical review, the gas-liquid interface is reviewed, as this interface does not depend on the preparation of another medium and thus produces a natural interface. The interface has been investigated by sum frequency generation vibrational spectroscopy and ultra-high vacuum techniques. The results provide a detailed molecular-level view of the surface composition and structure. These have been complemented by theoretical studies. The combinations of treatments on this interface are starting to provide a somewhat convergent description of how the ions are organized at this neat interface (108 references).

Cooperative Adsorption of Nonionic Triton X-100 and Dodecyldimethylamine Oxide Surfactant Mixtures at the Hydrophilic Silica-Water Interface Studied by Total Internal Reflection Raman Spectroscopy and Multivariate Curve Resolution.

The adsorption of dimethyldodecylamine oxide (DDAO) and Triton X-100 (TX) as single components and mixed systems at the silica-water interface has been studied using total internal reflection (TIR) Raman spectroscopy combined with multivariate curve resolution (MCR). In this study, the mixtures of DDAO and TX indicate minimal synergism in the bulk solution; however, the cooperative adsorption behavior on the silica surface is shown with various mixtures of DDAO (up to 1.3 mM) and TX (up to 1.1 mM). Adding the DDAO (up to 0.3 mM) to TX solution, the surface excess of TX shows 30% enhancement, from 1.2 to 1.8 µmol m-2. Adding the DDAO also shifts the TX adsorption isotherms, resulting in the Gibbs free energy change of -2.87 ± 0.73 kJ mol-1. This free energy change is interpreted as the decrease in surface energy when the silica surface charged sites are screened by the DDAO adsorbed layer. Alternatively, when a DDAO solution contains a small amount of TX molecules, i.e., < 30 µM, its adsorption on the silica surface quickly equilibrates. In addition, the formation of a more ordered liquid-crystalline adsorbed layer, as in the case of single-component DDAO adsorption, is not observed.