Using UV/Vis and IR light to Interrogate surfaces

• UV-Vis spectra can be obtained on quartz slides by

transmission or reflectance
• Spectroscopic ellipsometry can provide film thickness
• IR spectra of surfaces usually obtained by reflectance
• Raman scattering spectra can be “surface enhanced”
and/or “resonance enhanced”
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J. F. Rusling and A.-E. F. Nassar, "Enhanced Electron Transfer for Myoglobin in Surfactant Films
on Electrodes" J. Am. Chem. Soc., 1993, 115, 11891-11897.
Spectroscopic ellipsometry
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Ellipsometry is a sensitive optical technique for determining properties of surfaces and thin
films. If linearly polarized light of a known orientation is reflected at oblique incidence from a
surface then the reflected light is elliptically polarized. The shape and orientation of the ellipse
depend on the angle of incidence, the direction of the polarization of the incident light, and the
reflection properties of the surface. Modeling the data gives film thickness. (Source; see previous slide)
 LbL film of polycation and 45 nm silica

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Yur i M. Lvov, James F. Rusling, D. Laurence Thomsen, Fotios Papadimi trakopoulos, Takeshi
Kawakami and Toyoki Kunitake, ÒHigh-Speed Multilayer Film Assembly by Alternate Adsorption
of Sili ca Nanoparticles and Linear PolycationÓ, J. Chem. Soc., Chem. Commun. 1998, 1229-1230.
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 = measured elliptical angle;  = incidence angle of light on sample

d = 173 nm
 Film characterization - Quartz Crystal
Microbalance (QCM)

Oscillation freq. ~ (mass)-1

 Adsorbed layer mass and
thickness
M/A (g cm-2) = -ΔF (Hz) / (1.83 x 108)
d (nm) ≈ - (-0.016±0.002) ΔF (Hz)

Ru = RuPVP polymer
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Yur i M. Lvov, James F. Rusling, D. Laurence Thomsen, Fotios Papadimi trakopoulos, Takeshi
Kawakami and Toyoki Kunitake, ÒHigh-Speed Multilayer Film Assembly by Alternate Adsorption
of Sili ca Nanoparticles and Linear PolycationÓ, J. Chem. Soc., Chem. Commun. 1998, 1229-1230.
 Reflectance-absorbance IR spectroscopy

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 Amide I & II

RAIR of
Myoglobin-
DDAB films

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CH2 bending DDAB

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K. Suga and J. F. Rusling, "Structural Characterization of Surfactant and Clay-Surfactant Film s of

Micrometer Thickness by FT-IR Spectroscopy", Langmuir, 1993, 9, 3649-3655.
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From RAIR analysis of angular dependence

- HC chains oriented ~30o to normal

K. Suga and J. F. Rusling, "Structural Characterization of Surfactant and Clay-Surfactant Film s of

Micrometer Thickness by FT-IR Spectroscopy", Langmuir, 1993, 9, 3649-3655.
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Resonance Raman Spectroscopy

Up to 106 enhancement in signal

 Identification of micro-organisms by Resonance Raman

Resonance Raman excitation in the UV-range to obtain selectively enhanced signals of

DNA/RNA and aromatic amino acids (see Figure 1).
Juergen Popp. Biomedical Optics & Medical Imaging, Identification of micro-organisms by
Raman spectroscopy,5 September 2007, SPIE Newsroom. DOI: 10.1117/2.1200708.0856
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Carbon
Nanotubes

Mildred S. Dresselhaus; Ado JorioI; Marcos A. PimentaI, Anais da Academia Brasileira de

Ciências. vol.78 no.3 Rio de Janeiro Sept. 2006
doi: 10.1590/S0001-37652006000300004
Resonance Raman spectroscopy in one-dimensional carbon materials
Surface enhanced Raman spectroscopy

Rough Au surface

Au or Ag NPs
 Figure 1. Surface-enhanced Raman spectra
of 1-methyl adenine (10−5 mol L−1) in
presence of a silver hydrosol prepared by the
reduction of [Ag(NH3)2]+ with D(+)−xylose.
The average particle size is 55nm. Silver
hydrosols were activated by 0.002 (A), 0.01
(B), and 0.1 mol L−1 (C) of NaCl. The Raman
spectrum of 1−methyl adenine (10−2 mol L−1)
in deionised water (D) is included for
comparison purposes.

Jana Soukupová, Robert Prucek, Libor Kvítek, and Aleš Panáček

Improving the molecular specificity of surface-enhanced Raman spectroscopy
The synthesis of silver colloid particles with controlled size significantly increases the application
range of surface-enhanced Raman spectroscopy.
23 September 2007, SPIE Newsroom. DOI: 10.1117/2.1200709.0835
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 cancer imaging with Raman

Two different boosters were used - gold-based nanoparticles and carbon nanotubes - which
were attached to a tumour-seeking peptide and tracked as they moved around the body
S. Keren et al, Proc. Natl. Acad. Sci., 2008, DOI: 10.1073/pnas.0710575105
M Schipper et al, Nat. Nanotech., 2008, DOI:10.1038/nnano.2008.68
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