Fourier transform infrared external reflection and photoacoustic spectroscopy has been used for the vibrational characterization of a Prussian Blue (PB) film on Pt and a cupric hexacyanoferrate (CuHCF) film on glassy carbon (GC) irradiated at normal incidence. Since the optical response appeared to be substrate dependent, the mean-square electric fields as a function of the optical constants of the substrates (Pt, GC) and the films (PB, CuHCF) were calculated. The results of these calculations, used with the experimentally determined signal-to-noise ratios, were employed to predict film detection limits. It was found that the electric field intensity near the CuHCF/GC interface was much greater than that near the PB/Pt interface. For this reason, the film thicknesses detectable by these spectroscopic methods are lower at the interface of the GC substrate than at the Pt substrate.
ArmstrongN. R.LinA. W., and KuwanaT., Anal. Chem.48, 741 (1976).
2.
EvansJ. F. and KuwanaT., Anal. Chem.49, 1632 (1977).
3.
LinA. W.YehP.YacynychA. M., and KuwanaT., J. Electroanal. Chem.84, 411 (1977).
4.
DautartusM. F.EvansJ. F., and KuwanaT., Anal. Chem.51, 104 (1979).
5.
MillerC. W.KarweikD. H., and KuwanaT., Anal. Chem.53, 2319 (1981).
6.
MillerC. W.KarweikD. H., and KuwanaT., “Radio Frequency Plasma Introduction of Surface Functionalities onto Carbon and Surface Characterization by X-Ray Photoelectron Spectroscopy,” in Recent Advances in Analytical Spectroscopy, FuwaK., Ed. (Pergamon Press, New York, 1982), pp. 233–247.
7.
KarweikD. H.MillerC. W.PorterM. D., and KuwanaT., “Prospects in the Analysis of Chemically Modified Electrodes,” in Industrial Applications of Surface Analysis, CasperL. A. and PowellC. J., Eds. ACS Symposium Series, Vol. 199 (American Chemical Society, Washington, D.C., 1982), Chap. 6.
8.
FujihiraM.OsaT.HurshD., and KuwanaT., J. Electroanal. Chem.88, 285 (1978).
9.
FischerA. B.KinneyJ. B.StaleyR. H., and WrightonM. S., J. Am. Chem. Soc.101, 6501 (1979).
10.
MalpasR. E. and BardA. J., Anal. Chem.52, 109 (1980).
11.
See reference 7 and references therein.
12.
PolingG. W., Corros. Sci.10, 359 (1970).
13.
DuBoisJ. E.TourillonG., and LacazeP. C., J. Electrochem. Soc.125, 1257 (1978).
14.
TourillonG. T.DuBoisJ. E., and LacazeP. C., J. Electrochem. Soc.125, 1262 (1978).
15.
VolkovA.TourillonG.LacazeP. C., and DuBoisJ. E., J. Electroanal. Chem.115, 279 (1980).
16.
BewickA. and KunimatsuK., Surf. Sci.101, 131 (1980).
17.
BewickA.KunimatsuK.RobinsonJ., and RussellJ. W., J. Electroanal. Chem.119, 175 (1981).
18.
BedenB.LamyC.BewickA., and KunimatsuK., J. Electroanal. Chem.121, 343 (1981).
19.
DavidsonT.PonsB. S.BewickA., and SchmidtP. P., J. Electroanal. Chem.125, 237 (1981).
20.
BewickA. and RussellJ. W., J. Electroanal. Chem.132, 329 (1982).
21.
DebeM. K., J. Vac. Sci. Technol.21, 74 (1982).
22.
RosencwaigA., Photoacoustics and Photoacoustic Spectroscopy (Wiley-Interscience, New York1980).
23.
LowM. J. D. and ParodiG. A., Appl. Spectrosc.34, 76 (1980).
24.
LowM. J. D. and ParodiG. A., J. Mol. Struct.61, 119 (1980).
25.
KanstadS. O. and NordalP. E., Appl. Surf. Sci.5, 286 (1980).
26.
LloydL. B.YeatesR. C., and EyringE. E., Anal. Chem.54, 549 (1982).
27.
FrancisS. A. and EllisonA. H., J. Opt. Soc. Am.49, 131 (1959).
28.
TompkinsH. G. and GreenlerR. G., Surf. Sci.28, 194 (1971).
29.
TompkinsH. G., “Infrared Reflection-Absorption Spectroscopy,” in Methods of Surface Analysis, CzandernaA. W., Ed. (Elsevier Scientific Pub. Co., New York, 1975), Chap. 10.
30.
TompkinsH. G., Appl. Spectrosc.30, 377 (1976).
31.
AllaraD. L.BacaA., and PrydeC. A., Macromolecules11, 1215 (1978).
32.
HebardA. F.ArthurJ. R., and AllaraD. L., J. Appl. Phys.49, 6039 (1978).
33.
AllaraD. L., “Organic Monolayer Studies Using Fourier Transform Infrared Reflection Spectroscopy,” in Vibrational Spectroscopies for Adsorbed Species, BellA. T. and HairM. L., Eds. ACS Symp. Ser. Vol. 137 (American Chemical Society, Washington, D.C., 1980), Chap. 3.
34.
AllaraD. L., “Analysis of Surfaces and Thin Films by IR, Raman, and Optical Spectroscopy,” in Industrial Applications of Surface Analysis, CasperL. A. and PowellC. J., Eds. ACS Symp. Ser. Vol. 199 (American Chemical Society, Washington, D.C., 1982), Chap. 3.
35.
SiperkoL. M. and KuwanaT., J. Electrochem. Soc, 130, 396 (1983).
36.
RamamurthyA. C.KuwanaT., and MacDonaldD. D., unpublished results.
37.
TheisW. M.LittonC. W., and BajajK. K., Proc. Soc. Photo-Opt. Instrum. Eng.276, 109 (1981).
38.
PorterM. D.TheisW. M.KarweikD. H., and KuwanaT., unpublished.
39.
AyersJ. B. and WaggonerW. K., J. Inorg. Nucl. Chem.33, 722 (1971).
40.
GhoshS. N., J. Inorg. Nucl. Chem.36, 2465 (1974).
41.
EllisD.EckhoffM., and NeffV. D., J. Phys. Chem.85, 1225 (1981).
42.
GreenlerR. G., J. Chem. Phys.44, 310 (1966).
43.
HansenW. N., J. Opt. Soc. Am.58, 380 (1968).
44.
MaclntyreJ. D. E., “Specular Reflection Spectroscopy of the Electrode-Solution Interphase,” in Advances in Electrochemistry and Electrochemical Engineering, MüllerR. H., Ed. (Wiley and Sons, New York, 1973), Vol. 9, pp. 61–166.
45.
MullerR. H., Surf. Sci.16, 14 (1969).
46.
American Institute of Physics Handbook, GrayD. E., Ed. (McGraw-Hill, New York, 1972), pp. 6–144.
47.
WilliamsM. W. and ArakawaE. T., J. Appl. Phys.43, 3460 (1972).
48.
CRC Handbook of Chemistry and Physics, WeastR. C., Ed. (CRC Press, Cleveland, Ohio, 1973), pp. B-123.
49.
IshitaniA.IshidaH.SoedaF., and NagasawaY., Anal. Chem.54, 682 (1982).
50.
MartinC. R.RubinsteinI., and BardA. J., J. Am. Chem. Soc, 104, 4817 (1982).
51.
GreenlerR. G., J. Vac. Sci. Technol.12, 1410 (1975).
