Total internal reflection for precision small-angle measurement

A method for precision small-angle measurement is proposed. This method is based on the total-internal-reflection effect of a light beam at a pair of glass prisms. Angular displacement of the light beam is measured when the intensity change of the reflected beam is detected as a result of the relative phase shift between the s- and the p-polarized beams. An initial phase shift between the s- and the p-polarized components is introduced to increase measurement sensitivity. For increased measurement linearity and reduced effect of laser power fluctuation on the output, a differential method is used in which the light beam is split equally into two beams, each reflected at a prism and detected by a photodiode. The output is obtained as the difference of the two detected intensities divided by their sum. A prototype device was built, which demonstrated a nonlinearity error of 1.3% in a measurement range of ?0.6 degrees or 0.4% in ?0.3 degrees . The peak-to-peak noise level was found to be at approximately 0.5 arc sec. This noise level can be reduced further and resolution increased by a reduction of the measurement range.     

Total internal reflection ellipsometry: principles and applications

A concept for a measurement technique based on ellipsometry in conditions of total internal reflection is presented. When combined with surface plasmon resonance (SPR) effects, this technique becomes powerful for monitoring and analyzing adsorption and desorption on thin semitransparent metal films as well as for analyzing the semitransparent films themselves. We call this technique total internal reflection ellipsometry (TIRE). The theory of ellipsometry under total internal reflection combined with SPR is discussed for some simple cases. For more advanced cases and to prove the concept, simulations are performed with the Fresnel formalism. The use of TIRE is exemplified by applications in protein adsorption, corrosion monitoring, and adsorption from opaque liquids on metal surfaces. Simulations and experiments show greatly enhanced thin-film sensitivity compared with ordinary ellipsometry.     

Total internal reflection of pulsed light beam upon ideal non-absorbing plasma

Total internal reflection (TIR) of a pulsed light beam from vacuum incident upon an ideal non-absorbing plasma was investigated theoretically using the Fourier transform method. Because of the Goos–Hänchen effect, the reflected pulsed beam undergoes distortions such as carrier frequency shift and chirp. The distortions are magnified on condition that the pulsed beam is TM-polarized and illuminates the interface at large angle of incidence, which should be avoided for reflection of pulsed beam upon optical mirrors with metal film. Meanwhile, it is shown that the Goos–Hänchen shift and time delay of this TIR can be both positive and negative, which is consistent with the results obtained from stationary phase theory.     

Total internal reflection ellipsometry of metal-organic compound structures modified with gold nanoparticles

Total internal reflection ellipsometry (TIRE) technique was used to investigate the optical response of different hybrid multilayer systems. It was shown that the optical response was significantly changed by gold nanoparticles, which have been introduced for modification of functional properties of hybrid system. Nevertheless, the dispersion of optical parameters for gold nanoparticles was quite close in various hybrid systems in the case of adequate models used for interpretation of TIRE data.     

Total internal reflection microscopy: inspection of surfaces of high bulk scatter materials

The technique of total internal reflection microscopy (TIRM) introduced by P. Temple for inspection of the surface structure of transparent substrates is extended here for use with materials exhibiting high bulk scatter. A strong dependence of scratch illumination on the angle between scratches and the S polarization direction is observed and explained via a simple model.     

Total internal reflection fluorescence-correlation spectroscopy study of molecular transport in thin sol-gel films

Total internal reflection fluorescence correlation spectroscopy is used to measure mass transport rates through thin sol-gel films. Fluctuations in the fluorescence signal derive from molecular statistics due to the small number (approximately 1000) of rhodamine 6G dye molecules in the observation region. Autocorrelation of the fluctuating signal is fit to a model describing diffusion in the evanescent wave excitation. Silica sol-gel films were prepared by dip-coating 27-nm porous silica particles, which were synthesized by a base-catalyzed sol-gel method, onto microscope slides. The measured diffusivities ranged from 1 to 2 orders of magnitude slower than free diffusion and decreased with increasing number of dips used to prepare the film. Scanning electron microscopy (SEM) was used to examine the film structure and showed that increasing the number of dips produced more uniform and well-ordered films. To determine what role the dip-coating process plays in inducing order, deposited films were further dipped into ethanol containing no particles. These films were annealed by this process and become more ordered, as determined by SEM, and show a corresponding reduction in the molecular diffusivity.     

Total internal reflection fluorescence correlation spectroscopy for counting molecules at solid/liquid interfaces

Fluorescence correlation spectroscopy, using tota internal reflection excitation (TIRFCS), is developed as a method to allow quantitative determination of molecular populations at solid/liquid interfaces. Population fluctuations of fluorescent molecules at the interface are observed as excess low-frequency noise on a fluorescence signal. Since the noise arises from molecular origins, its magnitude can be evaluated by Poisson statistics to determine the number of molecules in the interface volume. This quantitative information is available without sensitivity calibration or the preparation of standards and without fitting the transients to a kinetic model. Unlike single-molecule counting measurements, TIRFCS can produce these quantitative results even when the number of photoelectrons detected per molecule is small. Surface populations of rhodamine 6G dye molecules were measured at C-18-derivatized, flat silica surfaces in contact with aqueous solutions and compared with predicted values derived from chromatographic retention data. In addition, electrostatic and nonpolar contributions to the free energy of adsorption of the dye to C-18-modified silica surfaces were examined.     

Development of a total internal reflection ultrafast transient lens method for studying molecular dynamics on an interface

We have developed the total internal reflection ultrafast transient lens (TIR-UTL) method to detect nonradiative chemical processes at interfaces and surfaces with subpicosecond time resolution. In the TIR-UTL measurements, the evanescent field of a pump beam irradiated under the TIR condition generates a refractive index change. The refractive index change is attributed to changes of the molecular electronic state, of density by molecular orientation/structure change, and of temperature by vibrational relaxation processes. The refractive index change is detected as a change of the power intensity of the probe beam adjusted coaxially with the pump beam. At first, we discuss a theoretical principle of a coaxial configuration in the TIR-UTL measurement. This configuration has an advantage of versatility over the established TIR configuration. Then, we evaluate time resolution of TIR-UTL and obtain a value of less than 400 fs. We measure the ultrafast molecular dynamics of the cationic chromophore Auramine O (AuO) at a silica/water interface. Two slow time constants originating from AuO adsorbed on the silica surface are detected by TIR-UTL. These are attributed to AuO, whose twisting motion is strongly hindered by adsorption on a silica surface.     

Interferometer based on total internal reflection

An interferometer is investigated in which the interacting beams undergo total internal reflection from a boundary surface with a variable relative refractive index. The high sensitivity of the change in the interference pattern with respect to small changes in the refractive index in the vicinity of the critical angle is theoretically proved and experimentally confirmed.     

Superresolution in total internal reflection tomography

We simulate a total internal reflection tomography experiment in which an unknown object is illuminated by evanescent waves and the scattered field is detected along several directions. We propose a full-vectorial three-dimensional nonlinear inversion scheme to retrieve the map of the permittivity of the object from the scattered far-field data. We study the role of the solid angle of illumination, the incident polarization, and the position of the prism interface on the resolution of the images. We compare our algorithm with a linear inversion scheme based on the renormalized Born approximation and stress the importance of multiple scattering in this particular configuration. We analyze the sensitivity to noise and point out that using incident propagative waves together with evanescent waves improves the robustness of the reconstruction.     

High-pressure total internal reflection fluorescence apparatus

Important interfacial processes in disciplines ranging from medicine to the separations sciences occur over a wide range of pressures, temperatures, and time scales. In this paper we report a new high-pressure total internal reflection fluorescence (HP-TIRF) apparatus that allows rapid fluorescence measurements of sub-monolayers in contact with liquids and supercritical fluids between 293 K and 353 K and up to 250 bar with picosecond time resolution. We use the HP-TIRF system to study the in-plane rotational reorientation dynamics of the fluorescent probe BODIPY 494/503 (C(2v) symmetry) covalently attached to silica surfaces that have been silanized with n-propyltrimethoxysilane (C(3)-TMOS) or 3,3,3-trifluoropropyltrimethoxysilane (CF(3)-TMOS) when the interface is subjected to pure supercritical carbon dioxide (scCO(2)). The in-plane BODIPY 494/503 rotational reorientation dynamics are assessed by using the Debye-Stokes-Einstein expression. As the scCO(2) density increases the local microviscosity surrounding the tethered BODIPY 494/503 molecule decreases. The terminal group (CH(3) versus CF(3)) within the silane monolayer governs the onset and absolute magnitude of the observed viscosity changes. The results are explained in terms of the wellknown solubility of fluorine-containing species in scCO(2).     

Attenuated partial internal reflection infrared spectroscopy

A new method for the spectroscopic study of absorbing films is proposed. In contrast to the well-established methods that take advantage of the attenuation of total internal reflection (ATR) to obtain spectra, we intentionally arrange the optics to permit partial internal reflection from the sampling prism face. Attenuated partial internal reflection (APR) spectroscopy is introduced through theoretical calculations and experimental demonstrations. The calculated APR spectra in the infrared region were generated from the Fresnel and Airy equations. Experimentally, APR spectra of water films on a NaCl prism were obtained. APR is more sensitive than ATR, and can easily distinguish water films at the monolayer level (310 pm). The determination of film thickness from interference fringes in APR spectra is also illustrated. It is shown that APR can be used for film thickness measurements that can span 6 orders of magnitude. The limitations of APR are also discussed.     

Polarization-insensitive high-dispersion total internal reflection diffraction gratings

We report the first experimental realization of total internal reflection (TIR) diffraction gratings. Performance of less than 0.7-dB insertion loss (IL) for both TE and TM polarizations and 0.5-dB polarization-dependent loss (PDL) are predicted over a 50-nm spectral bandwidth with simultaneous fabrication tolerances on the depth and the duty cycle of binary gratings of +/-5% and +/-14%, respectively. Nineteen gratings were fabricated that met these specifications, yielding IL and PDL values less than 0.6 and 0.2 dB, respectively, across the entire 50-nm bandwidth. Measurements made under the Littrow configuration resulted in high efficiency and low PDL across a 100-nm bandwidth, with up to 100% diffraction efficiency within the experimental measurement error.     

Attenuated total internal reflection infrared microspectroscopic imaging using a large-radius germanium internal reflection element and a linear array detector

The number of techniques and instruments available for Fourier transform infrared (FT-IR) microspectroscopic imaging has grown significantly over the past few years. Attenuated total internal reflectance (ATR) FT-IR microspectroscopy reduces sample preparation time and has simplified the analysis of many difficult samples. FT-IR imaging has become a powerful analytical tool using either a focal plane array or a linear array detector, especially when coupled with a chemometric analysis package. The field of view of the ATR-IR microspectroscopic imaging area can be greatly increased from 300 x 300 microm to 2500 x 2500 microm using a larger internal reflection element of 12.5 mm radius instead of the typical 1.5 mm radius. This gives an area increase of 70x before aberrant effects become too great. Parameters evaluated include the change in penetration depth as a function of beam displacement, measurements of the active area, magnification factor, and change in spatial resolution over the imaging area. Drawbacks such as large file size will also be discussed. This technique has been successfully applied to the FT-IR imaging of polydimethylsiloxane foam cross-sections, latent human fingerprints, and a model inorganic mixture, which demonstrates the usefulness of the method for pharmaceuticals.     

Planar reflection grating lens for compact spectroscopic imaging system

A compact spectroscopic imaging device consisting of a planar reflection grating lens, a probe fiber array, and a two-dimensional image sensor was proposed and discussed. Reflected or luminescent lights from a subject are coupled to the probe fibers, guided to fiber output ends, radiated into the air, diffracted by the grating lens with wavelength-dependent angle, and focused onto lines on the image sensor. Two-dimensional intensity distribution on the image sensor can give one-dimensional spectrum distribution along a specified direction. A grating lens was designed with a fiber array and a CCD image sensor for 100-nm wavelength range and 10-mm fiber array width. A spectral resolution of 5 nm and a spatial resolution of 0.25 mm were experimentally confirmed.     

Behavior of total internal reflection in optical crystals

It is shown that a crystal can be cut so that one incident beam undergoing reflected from an inclined face inside the crystal excites four beams, two ordinary and two extraordinary, propagating in different directions. Pis’ma Zh. Tekh. Fiz. 25, 46–51 (January 12, 1999)     

Two-dimensional thickness measurements based on internal reflection ellipsometry

An imaging ellipsometer technique on internal reflection geometry that can measure the thickness distribution of a thin film possessing an assumed refractive index is described. Because a prism is used for the internal reflection geometry, it was theoretically predicted that angular derivation from the normal incidence on the prism surface affects only the psi value by a factor of 0.97 at maximum. Measurements were carried out for an optical system of silica substrate-TiO2 layer-silica layer-protein film-air, with a thin-film array of dried protein as the sample film. Thickness of the protein films was two-dimensionally estimated only from the measured map of the delta value by use of the simulated relationship between the thickness and the delta value. The thickness map obtained was coincident on the whole with the results according to a mechanical scanning. The detection limit was approximately +/- 0.2 nm. These findings validate the optical effect of a high-index additional layer to improve the sensitivity and precision of thickness measurements of the sample film on transparent substrates.     

MUSIC imaging applied to total internal reflection tomography

This paper applies the multiple signal classification (MUSIC) imaging method to determine the locations of a collection of small anisotropic spherical scatterers in the framework of total internal reflection tomography. Multiple scattering between scatterers is considered, and the inverse scattering problem is nonlinear, which, however, is solved by the proposed fast analytical approach where no associated forward problem is iteratively evaluated. The paper also discusses the role of propagating and evanescent waves, the polarization of incidence waves, separation of scatterers from the surface of the substrate, and the level of noise on the resolution of imaging.