In-situ ellipsometry studies of thin swollen films, a review Wojciech Ogiegło, Herbert Wormeester, Klaus-Jochen Eichhorn, Matthias Wessling, Nieck E. Benes 1
Thin polymer films Why are they important? Functional coatings Membranes Displays Solar cells Thin polymer films Sensors Barriers Biosensitive films
Thin polymer films Interactions with penetrants Swollen Dry
Spectroscopic ellipsometry in-situ
Spectroscopic ellipsometry Drawbacks? or opportunities?
In-situ configurations No cell Advantages: - No window effects - Multi-angle possibility a Richardson H., et al., Physical Review E, 2004, 70(51), p. 051805-1-051805-8 Richardson H., et al., The European Physical Journal E, 2003, 12(0), p. 87-91 Lopez Garcia I., et al., Surface and Interface Analysis, 2011, 43(11), p. 1448-1452 b Hennig A., et al., Langmuir, 2004, 20(16), p. 6685-6691 Disadvantages: - Less defined ambient Delivery of osmotic shocks Rehfeldt F., et al., Langmuir, 2003, 19(5), p. 1467-1473
In-situ configurations Trapezoidal cell Advantages: - Controlled ambient - Static or flowing Disadvantages: - Window offsets - Angle offset cell geometry Typical angles of incidence: 65-75
In-situ configurations Backside configuration Advantages: - Multiple angles of incidence - Relative simplicity (no windows) Disadvantages: - Bubble formation Pantelic N., et al., The Journal of Physical Chemistry B, 2005, 109(29), p. 13971-13979 Zudans I., et al., Chemistry of Materials, 2004, 16(17), p. 3339-3347
In-situ configurations High pressure cells Advantages: - p max = 200 bar - Broader T range 0-220 C - Liquids, vapors, gases, vacuum, Sirard S.M., et al., The Journal of Physical Chemistry B, 2001, 105(4), p. 766-772 Carla V., et al., Macromolecules, 2005, 38(24), p. 10299-10313 Chandler C.M., et al., Macromolecules, 2009, 42(13), p. 4867-4873 Disadvantages: - Window offsets - Ambient optical dispersion permeation Ogieglo W., et al., Journal of Membrane Science, 2013, 437(0), p. 313-323
Types of polymeric materials V polym Glassy state: - Frozen macromolecule - Non-equilibrium - History dependence T T g Rubbery state: - Fast macromolecule - Equilibrium Horn N.R., et al., Macromolecules, 2012, 45(6), p. 2820-2834 Sirard S.M., et al., The Journal of Physical Chemistry B, 2001, 105(4), p. 766-772
Types of polymeric materials Block co-polymers Multilayer films Zwitterionic films Cyclic oligomers Hydrogels Particle films Conducting polymers Composite films Metal Organic Frameworks Saccharides Schmidt D.J., et al., ACS Nano, 2009, 3(8), p. 2207-2216
Types of studied phenomena Good sensor! Bad sensor! Burkert S., et al., Radiation Physics and Chemistry, 2007, 76(8-9), p. 1324-1328 Inaccurate at very high swelling Spaeth K., et al., Frasenius Journal of Analytical Chemistry, 1997, 357(3), p. 292-296 Optical contrast - sensors Dry film Swollen film
Types of studied phenomena Drying processes (i) (ii) (iii) Lopez Garcia I., et al., Surface and Interface Analysis, 2011, 43(11), p. 1448-1452
Types of information extracted Penetrant volume fractions 1. Film dilation 2. Effective medium approximations 3. Clausius - Mossotti Chan K., et al., Langmuir, 2005, 21(19), p. 8930-8939 Thermodynamic parameters Glassy systems? Ogieglo W., et al., Polymer, 2014, in press
Ellipsometry combined with other techniques Quartz Crystal Microbalance (QCM) Mass Resonance condition Data quantification Viscosity Shear modulus Source: BiolinScientific, QCM-D Seminar, www.biolinscientific.com
Ellipsometry combined with other techniques Quartz Crystal Microbalance (QCM) Highly complementary to ellipsometry Ellipsometry Thickness ε 1, ε 2 QCM-D Mass (Viscoelastic properties)
Ellipsometry combined with other techniques Atomic Force Microscopy (AFM) Source: Aalto University, School of Science, Department of Applied Physics Blacklock J., Journal of Physical Chemistry B, 2010, 114(16), p. 5283-5291 Roughness increases
Ellipsometry combined with other techniques Neutron and X-ray reflectivity Electrochemical methods Gravimetric methods Contact angle measurements Spectroscopy (IR, UV-VIS) Surface plasmon resonance Methods to determine mechanical properties
Ellipsometry combined with other techniques Neutron and X-ray reflectivity Electrochemical methods Gravimetric methods Contact angle measurements Spectroscopy (IR, UV-VIS) Surface plasmon resonance Methods to determine mechanical properties Horn N.R., et. al., Macromolecules, 2012, 45(6), p. 2820-2834
Ellipsometry combined with other techniques Neutron and X-ray reflectivity Electrochemical methods Gravimetric methods Contact angle measurements Spectroscopy (IR, UV-VIS) Surface plasmon resonance Methods to determine mechanical properties Crossland E.J.W., Advanced Functional Materials, 2011, 21(3), p. 518-524
Ellipsometry combined with other techniques Neutron and X-ray reflectivity Electrochemical methods Gravimetric methods Contact angle measurements Spectroscopy (IR, UV-VIS) Surface plasmon resonance Methods to determine mechanical properties Nolte A.J., et. al., Macromolecules, 2008, 41(15), p. 5793-5798
In more detail: Ogieglo W., PhD Thesis, Chapter 1
Thank you for your attention! Questions?