In-situ ellipsometry studies of thin swollen films, a review
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1 In-situ ellipsometry studies of thin swollen films, a review Wojciech Ogiegło, Herbert Wormeester, Klaus-Jochen Eichhorn, Matthias Wessling, Nieck E. Benes 1
2 Thin polymer films Why are they important? Functional coatings Membranes Displays Solar cells Thin polymer films Sensors Barriers Biosensitive films
3 Thin polymer films Interactions with penetrants Swollen Dry
4 Spectroscopic ellipsometry in-situ
5 Spectroscopic ellipsometry Drawbacks? or opportunities?
6 In-situ configurations No cell Advantages: - No window effects - Multi-angle possibility a Richardson H., et al., Physical Review E, 2004, 70(51), p Richardson H., et al., The European Physical Journal E, 2003, 12(0), p Lopez Garcia I., et al., Surface and Interface Analysis, 2011, 43(11), p b Hennig A., et al., Langmuir, 2004, 20(16), p Disadvantages: - Less defined ambient Delivery of osmotic shocks Rehfeldt F., et al., Langmuir, 2003, 19(5), p
7 In-situ configurations Trapezoidal cell Advantages: - Controlled ambient - Static or flowing Disadvantages: - Window offsets - Angle offset cell geometry Typical angles of incidence: 65-75
8 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 Zudans I., et al., Chemistry of Materials, 2004, 16(17), p
9 In-situ configurations High pressure cells Advantages: - p max = 200 bar - Broader T range C - Liquids, vapors, gases, vacuum, Sirard S.M., et al., The Journal of Physical Chemistry B, 2001, 105(4), p Carla V., et al., Macromolecules, 2005, 38(24), p Chandler C.M., et al., Macromolecules, 2009, 42(13), p Disadvantages: - Window offsets - Ambient optical dispersion permeation Ogieglo W., et al., Journal of Membrane Science, 2013, 437(0), p
10 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 Sirard S.M., et al., The Journal of Physical Chemistry B, 2001, 105(4), p
11 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
12 Types of studied phenomena Good sensor! Bad sensor! Burkert S., et al., Radiation Physics and Chemistry, 2007, 76(8-9), p Inaccurate at very high swelling Spaeth K., et al., Frasenius Journal of Analytical Chemistry, 1997, 357(3), p Optical contrast - sensors Dry film Swollen film
13 Types of studied phenomena Drying processes (i) (ii) (iii) Lopez Garcia I., et al., Surface and Interface Analysis, 2011, 43(11), p
14 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 Thermodynamic parameters Glassy systems? Ogieglo W., et al., Polymer, 2014, in press
15 Ellipsometry combined with other techniques Quartz Crystal Microbalance (QCM) Mass Resonance condition Data quantification Viscosity Shear modulus Source: BiolinScientific, QCM-D Seminar,
16 Ellipsometry combined with other techniques Quartz Crystal Microbalance (QCM) Highly complementary to ellipsometry Ellipsometry Thickness ε 1, ε 2 QCM-D Mass (Viscoelastic properties)
17 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 Roughness increases
18 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
19 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
20 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
21 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
22 In more detail: Ogieglo W., PhD Thesis, Chapter 1
23 Thank you for your attention! Questions?
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