Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers
Functional organic thin films often demand precise control over the nanometer-level structure. Interlayer diffusion of materials may destroy this precise structure; therefore, a better understanding of when interlayer diffusion occurs and how to control it is needed. X-ray photoelectron spectroscopy...
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| Format: | Article |
| Language: | en_US |
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National Academy of Sciences (U.S.)
2013
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| Online Access: | http://hdl.handle.net/1721.1/83366 https://orcid.org/0000-0003-3570-8917 https://orcid.org/0000-0003-1085-7692 |
| _version_ | 1811085246937956352 |
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| author | Rubner, Michael F. Cohen, Robert E. Gilbert, Jonathan Brian |
| author2 | MIT Materials Research Laboratory |
| author_facet | MIT Materials Research Laboratory Rubner, Michael F. Cohen, Robert E. Gilbert, Jonathan Brian |
| author_sort | Rubner, Michael F. |
| collection | MIT |
| description | Functional organic thin films often demand precise control over the nanometer-level structure. Interlayer diffusion of materials may destroy this precise structure; therefore, a better understanding of when interlayer diffusion occurs and how to control it is needed. X-ray photoelectron spectroscopy paired with C[+ over 60] cluster ion sputtering enables high-resolution analysis of the atomic composition and chemical state of organic thin films with depth. Using this technique, we explore issues common to the polyelectrolyte multilayer field, such as the competition between hydrogen bonding and electrostatic interactions in multilayers, blocking interlayer diffusion of polymers, the exchange of film components with a surrounding solution, and the extent and kinetics of interlayer diffusion. The diffusion coefficient of chitosan (M = ∼100 kDa) in swollen hydrogen-bonded poly(ethylene oxide)/poly(acrylic acid) multilayer films was examined and determined to be 1.4*10[superscript −12] cm[superscript 2]/s. Using the high-resolution data, we show that upon chitosan diffusion into the hydrogen-bonded region, poly(ethylene oxide) is displaced from the film. Under the conditions tested, a single layer of poly(allylamine hydrochloride) completely stops chitosan diffusion. We expect our results to enhance the understanding of how to control polyelectrolyte multilayer structure, what chemical compositional changes occur with diffusion, and under what conditions polymers in the film exchange with the solution. |
| first_indexed | 2024-09-23T13:05:55Z |
| format | Article |
| id | mit-1721.1/83366 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:05:55Z |
| publishDate | 2013 |
| publisher | National Academy of Sciences (U.S.) |
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| spelling | mit-1721.1/833662022-09-28T11:59:32Z Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers Rubner, Michael F. Cohen, Robert E. Gilbert, Jonathan Brian MIT Materials Research Laboratory Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Materials Science and Engineering Gilbert, Jonathan Brian Rubner, Michael F. Cohen, Robert E. Functional organic thin films often demand precise control over the nanometer-level structure. Interlayer diffusion of materials may destroy this precise structure; therefore, a better understanding of when interlayer diffusion occurs and how to control it is needed. X-ray photoelectron spectroscopy paired with C[+ over 60] cluster ion sputtering enables high-resolution analysis of the atomic composition and chemical state of organic thin films with depth. Using this technique, we explore issues common to the polyelectrolyte multilayer field, such as the competition between hydrogen bonding and electrostatic interactions in multilayers, blocking interlayer diffusion of polymers, the exchange of film components with a surrounding solution, and the extent and kinetics of interlayer diffusion. The diffusion coefficient of chitosan (M = ∼100 kDa) in swollen hydrogen-bonded poly(ethylene oxide)/poly(acrylic acid) multilayer films was examined and determined to be 1.4*10[superscript −12] cm[superscript 2]/s. Using the high-resolution data, we show that upon chitosan diffusion into the hydrogen-bonded region, poly(ethylene oxide) is displaced from the film. Under the conditions tested, a single layer of poly(allylamine hydrochloride) completely stops chitosan diffusion. We expect our results to enhance the understanding of how to control polyelectrolyte multilayer structure, what chemical compositional changes occur with diffusion, and under what conditions polymers in the film exchange with the solution. National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762) American Society for Engineering Education. National Defense Science and Engineering Graduate Fellowship National Science Foundation (U.S.). Graduate Research Fellowship Program 2013-12-30T17:03:15Z 2013-12-30T17:03:15Z 2013-04 2012-12 Article http://purl.org/eprint/type/JournalArticle 0027-8424 1091-6490 http://hdl.handle.net/1721.1/83366 Gilbert, J. B., M. F. Rubner, and R. E. Cohen. “Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers.” Proceedings of the National Academy of Sciences 110, no. 17 (April 23, 2013): 6651-6656. https://orcid.org/0000-0003-3570-8917 https://orcid.org/0000-0003-1085-7692 en_US http://dx.doi.org/10.1073/pnas.1222325110 Proceedings of the National Academy of Sciences Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf National Academy of Sciences (U.S.) PNAS |
| spellingShingle | Rubner, Michael F. Cohen, Robert E. Gilbert, Jonathan Brian Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title | Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title_full | Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title_fullStr | Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title_full_unstemmed | Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title_short | Depth-profiling X-ray photoelectron spectroscopy (XPS) analysis of interlayer diffusion in polyelectrolyte multilayers |
| title_sort | depth profiling x ray photoelectron spectroscopy xps analysis of interlayer diffusion in polyelectrolyte multilayers |
| url | http://hdl.handle.net/1721.1/83366 https://orcid.org/0000-0003-3570-8917 https://orcid.org/0000-0003-1085-7692 |
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