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Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte

Jonathan B Gilbert¹, Michael F Rubner, Robert E Cohen

¹Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.

Proceedings of the National Academy of Sciences of the United States of America

|April 10, 2013

Summary

Controlling interlayer diffusion is key for organic thin films. A single layer of poly(allylamine hydrochloride) effectively blocks chitosan diffusion in polyelectrolyte multilayers, preserving nanostructure.

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Area of Science:

Materials Science
Polymer Science
Surface Science

Background:

Functional organic thin films require precise nanometer-level structural control.
Interlayer diffusion can disrupt this structure, necessitating methods to understand and control it.
Polyelectrolyte multilayers are susceptible to diffusion, component exchange, and competition between bonding interactions.

Purpose of the Study:

To investigate interlayer diffusion in polyelectrolyte multilayers.
To understand the factors controlling diffusion, such as hydrogen bonding and electrostatic interactions.
To determine methods for preventing unwanted diffusion and maintaining film integrity.

Main Methods:

Utilized X-ray photoelectron spectroscopy (XPS) combined with C60(+) cluster ion sputtering for high-resolution depth profiling.
Analyzed atomic composition and chemical states within organic thin films.
Quantified the diffusion coefficient of chitosan in specific multilayer systems.

Main Results:

Determined the diffusion coefficient of chitosan (M = ~100 kDa) in swollen poly(ethylene oxide)/poly(acrylic acid) multilayers to be 1.4*10(-12) cm(2)/s.
Observed displacement of poly(ethylene oxide) upon chitosan diffusion into hydrogen-bonded regions.
Demonstrated that a single layer of poly(allylamine hydrochloride) completely inhibited chitosan diffusion.

Conclusions:

High-resolution depth profiling is effective for studying diffusion in organic thin films.
Understanding diffusion mechanisms is crucial for controlling polyelectrolyte multilayer structure.
Specific barrier layers, like poly(allylamine hydrochloride), can effectively prevent polymer diffusion and maintain film integrity.