Monolayer vs. multilayer self-assembled alkylphosphonate films: X-ray photoelectron spectroscopy studies

Irina Gouzman, Manish Dubey, Michael D. Carolus, Jeffrey Schwartz, Steven L. Bernasek

Research output: Contribution to journalArticlepeer-review

163 Scopus citations


Combining functional organic self-assembled monolayers (SAMs) with conventional semiconductor materials is a key step in the development of integrated electronics-based devices. T-BAG (Tethering by Aggregation and Growth) has been shown to be a simple and reliable method to grow SAMs of alkylphosphonates on oxide surfaces. However, distinguishing SAMs from ultra-thin multilayers is a challenge for most conventional surface characterization techniques. Self-assembled films of octadecylphosphonic acid (ODPA) were deposited on oxide-covered silicon coupons, converted to the corresponding phosphonates, and characterized by high resolution angularly resolved X-ray photoelectron spectroscopy (XPS). It was our goal to distinguish among different bonding configurations for phosphorous in the phosphonate head groups, namely, mono-dentate, bi-dentate or tri-dentate interactions with the oxide surface, as well as to assess quantitatively the near-surface layer composition. We also present an innovative method that allows us to distinguish between monolayer and multilayer films of ODPA on silicon oxide surfaces. This method is based on differential surface charging effects in XPS. It was found that variation in the ODPA film thickness causes differential responses of various spectral characteristics to an electrical bias applied to the sample during XPS measurements. Both positive and negative applied biases were found to affect the carbon core-level (C1s) line-shape and intensity in the case of the multilayer ODPA film, whereas line-shapes and intensities of all XPS lines measured for the monolayer film were unaffected by the application of a dc bias in the ±30 V range.

Original languageEnglish (US)
Pages (from-to)773-781
Number of pages9
JournalSurface Science
Issue number4
StatePublished - Feb 15 2006

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films
  • Materials Chemistry


  • Bias
  • Charging
  • Phosphonates
  • Phosphonic acid
  • Self-assembled monolayers
  • X-ray photoelectron spectroscopy


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