Combined ATR Infrared Microspectroscopy and SIL Raman Microspectroscopy

Sohn, Alex; Tisinger, Louis G.; Sommer, André J.

doi:10.1017/s1431927604884757

Cited by 7 publications

(8 citation statements)

References 2 publications

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“…Efforts to extend TIR Raman spectroscopy to microscopy have been quite limited. Tisinger and Sommer31–33 made the first significant progress in this area, reporting the acquisition of Raman spectra from micro‐domains using TIR illumination through a hemispherical ZnSe solid immersion lens (SIL) in 2004. Poweleit et al 34 also reported on the acquisition of Raman signals from silicon through a high‐index glass SIL in order to achieve enhanced spatial resolution.…”

Section: Introductionmentioning

confidence: 99%

“…Desmedt et al 35 also have recently reported on enhanced Raman sensitivity in cases where spectra are obtained through a so‐called nanolens, consisting of a polystyrene microsphere that is presumably acting as a microscopic immersion lens. However, with the noted exception of Tisinger and Sommer,31–33 the topic of Raman microscopy with TIR illumination has been largely unexplored.…”

Section: Introductionmentioning

confidence: 99%

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Surface‐sensitive Raman microscopy with total internal reflection illumination

Michaels

2010

J Raman Spectroscopy

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A Raman microscope using a total internal reflection (TIR) annular illumination geometry through a ZnSe solid immersion lens (SIL) is described. Spectra of a thin-film sample of the transparent organic conductor poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT : PSS) on a polyethylene terephthalate (PET) substrate are presented and compared with those from a conventional confocal Raman configuration. These spectra demonstrate a significant increase in surface selectivity upon the use of TIR illumination, as the decay length of the evanescent excitation field limits the depth of sample probed in this configuration. Spectral interference from the underlying PET substrate layer is thus greatly reduced. An increase in surface selectivity is also demonstrated for spectra acquired through the SIL with uniform illumination. Raman images of a micropatterned PEDOT : PSS film acquired with TIR illumination are also reported. Enhanced lateral resolution is realized in this configuration because of the immersion effect of the SIL, and the sampling depth is limited to 150 nm by the choice of illumination geometry. This results in analysis volumes on the order of tens of femtoliters, nearly two orders of magnitude smaller than typically achieved in conventional confocal Raman microscopes. This approach yields Raman spectra and images with surface selectivity significantly greater than can be achieved in confocal Raman, and provides a valuable tool for the microanalysis of thin surface films. Published in

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Surface‐sensitive Raman microscopy with total internal reflection illumination

Michaels

2010

J Raman Spectroscopy

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“…Common enhancement strategies for linear Raman spectroscopy are surface enhanced Raman spectroscopy (SERS), 17-18 resonance Raman spectroscopy (RRS), [19][20] or in combination surface enhanced resonance Raman spectroscopy (SERRS). 21 These enhancement techniques have limitations that reduce their broad applicability.…”

Section: Discussionmentioning

confidence: 99%

“…9-10 Since then, TIR Raman spectra have been collected from a variety of solid-solid, solid-liquid, and liquid-liquid interfaces with the majority of work utilizing visible excitation sources or fixed excitation angles. [10][11][12][13][14][15][16][17][18][19][20][21][22] The versatility of TIR-Raman spectroscopy is illustrated by the wide variety of samples that have been analyzed including polymer films, epicuticular wax layers on leaves, adsorbates from solution, and lubricants at frictional contacts. 5 A key advance in TIR Raman spectroscopy was the inclusion of high efficiency microscope optics as a means to collect the Raman scatter from the analyte.…”

Section: Tir Raman Spectroscopymentioning

confidence: 99%

“…This background proved to be too high for practical TIR Raman measurements with this instrument. ZnSe, which has been used previously as in internal reflection element for ATR Infrared and Solid Immersion Lens Raman Microspectroscopy,19 was found to produce the lowest background signal of the prisms tested, between 1.14 and 15.19 counts/sec, and was thus used for all subsequent Raman measurements. Additionally, the Raman spectrum of ZnSe only shows strong bands in the 200 to 500 cm -1 range, which do not interfere with the main Raman modes of benzonitrile or the commonly analyzed modes for most organic analytes.…”

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confidence: 99%

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Scanning angle total internal reflection Raman spectroscopy and plasmon enhancement techniques as a tool for interfacial analysis

McKee

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Plasmon Waveguide Resonance Raman Spectroscopy

2012

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Raman spectra were collected from a 1.25 M aqueous pyridine solution, 100-nm polystyrene film or a trimethyl(phenyl)silane monolayer at a plasmon waveguide interface under total internal reflection (TIR). The plasmon waveguide resonance (PWR) interface consisted of a sapphire prism/49 to 50 nm Au/548 to 630 nm SiO(2) and a monolayer, thin film or aqueous analyte. The Raman peak area as a function of incident angle was measured using a 785-nm excitation wavelength, and was compared to the Raman peak area obtained at a sapphire or sapphire/50 nm Au interface. In contrast to measurements at a bare sapphire prism, increased surface sensitivity and signal were obtained from the PWR interface. In contrast to measurements at a bare Au film where only p-polarized incident light generates an enhanced interfacial electric field, plasmon waveguide interfaces enable excitation with orthogonal polarizations using s- or p-polarized incident light. The Raman scatter from a monolayer was recorded at the PWR interface with a signal-to-noise ratio of 5.6 when averaging 3 accumulations with 3 min acquisition times using nonresonant excitation, whereas no signal was recorded from a monolayer at the sapphire interface. The reflected light from the interface enabled the identification of the incident angle where the maximum Raman scatter was produced, and the Raman signal generated at the plasmon waveguide interface was modeled by the enhanced interfacial mean square electric field relative to the incident field. In comparison to the techniques on which this work was based (i.e., PWR spectroscopy, TIR Raman spectroscopy at the prism interface, and surface plasmon resonance (SPR) Raman spectroscopy at the prism/Au interface), chemical specificity was added to PWR spectroscopy, a signal enhancement mechanism was introduced for TIR Raman spectroscopy, and polarization control of the interfacial electric field was added to SPR Raman spectroscopy.

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Combined ATR Infrared Microspectroscopy and SIL Raman Microspectroscopy

Abstract: Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Cited by 7 publications

References 2 publications

Surface‐sensitive Raman microscopy with total internal reflection illumination

Surface‐sensitive Raman microscopy with total internal reflection illumination

Scanning angle total internal reflection Raman spectroscopy and plasmon enhancement techniques as a tool for interfacial analysis

Plasmon Waveguide Resonance Raman Spectroscopy

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