Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square

Joseph A. Libera, Richard W. Gurney, Craig Schwartz, Hua Jin, Tien Lin Lee, Sonbinh T. Nguyen, Joseph T Hupp, Michael J. Bedzyk

Research output: Contribution to journalArticle

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Abstract

The nanoscale structures of multilayer metal-phosphonate thin films prepared via a layer-by-layer assembly process using Zr 4+ and 1,12-dodecanediylbis(phosphonic acid) (DDBPA) or porphyrin square bis(phosphonic acid) (PSBPA) were studied using specular X-ray reflectivity (XRR), X-ray fluorescence, and long-period X-ray standing wave (XSW) analysis. The films were prepared in 1, 2, 3, 4, 6, and 8 layer series on both Si(001) substrates for XRR and on 18.6 nm period Si/Mo layered-synthetic microstructure X-ray mirrors for XSW. After functionalizing the SiO 2 substrate surfaces with a monolayer film terminated with phosphonate groups, the organic multilayer films were assembled by alternating immersions in (a) aqueous solutions containing Zr 4+or Hf 4+ (final metal layer only) cations and then (b) organic solvent solutions of PO 3-R-PO 3 4-, where R was DDBPA or PSBPA spacer molecule. The Hf 4+ cation served as the marker for the top surface of the films, whereas the Zf 4+ cation was present in all other layers. The PSBPA also contained Zn and Re atoms at its midline which served as heavy-atom markers for each layer. The long-period XSW generated by the 0th- (total external reflection) through 4th-order Bragg diffraction conditions made it possible to examine the Fourier transforms of the fluorescent atom distributions over a much larger q z range in reciprocal space which permitted simultaneous analysis of Hf, Zn/Re, and Zr atomic distributions.

Original languageEnglish
Pages (from-to)1441-1450
Number of pages10
JournalJournal of Physical Chemistry B
Volume109
Issue number4
DOIs
Publication statusPublished - Feb 3 2005

Fingerprint

Organophosphonates
Multilayer films
Porphyrins
standing waves
porphyrins
Metals
X rays
metals
acids
Acids
x rays
Cations
Positive ions
cations
Atoms
markers
reflectance
atoms
Substrates
n-dodecane

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Libera, J. A., Gurney, R. W., Schwartz, C., Jin, H., Lee, T. L., Nguyen, S. T., ... Bedzyk, M. J. (2005). Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square. Journal of Physical Chemistry B, 109(4), 1441-1450. https://doi.org/10.1021/jp0457038

Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square. / Libera, Joseph A.; Gurney, Richard W.; Schwartz, Craig; Jin, Hua; Lee, Tien Lin; Nguyen, Sonbinh T.; Hupp, Joseph T; Bedzyk, Michael J.

In: Journal of Physical Chemistry B, Vol. 109, No. 4, 03.02.2005, p. 1441-1450.

Research output: Contribution to journalArticle

Libera, Joseph A. ; Gurney, Richard W. ; Schwartz, Craig ; Jin, Hua ; Lee, Tien Lin ; Nguyen, Sonbinh T. ; Hupp, Joseph T ; Bedzyk, Michael J. / Comparative X-ray standing wave analysis of metal-phosphonate multilayer films of dodecane and porphyrin molecular square. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 4. pp. 1441-1450.
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