ABSTRACT
An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.
ABSTRACT
Ellipsometry is one of the standard methods for observation of glass transition in thin polymer films. This work proposes that sensitivity of the method to surface morphology can complicate manifestation of the transition in a few nm thick samples. Two possible mechanisms of free surface roughening in the vicinity of glass transition are discussed: roughening due to lateral heterogeneity and roughening associated with thermal capillary waves. Both mechanisms imply an onset of surface roughness in the glass transition temperature range, which affects the experimental data in a way that shifts apparent glass transition temperature. Effective medium approximation models are used to introduce surface roughness into optical calculations. The results of the optical modeling for a 5 nm thick polystyrene film on silicon are presented.
ABSTRACT
An internal reference method is used for the first time to clearly demonstrate the glass transition temperature (Tg) depression effect in 5 nm thick polystyrene films spin-cast on silicon wafers. Initially flat films exhibit depressed Tg at approximately 85 °C. Temperature-induced dewetting on hexamethyldisilazane-treated silicon substrates leads to formation of discontinuous films with average effective thickness of 15-30 nm. Dewetted films demonstrate Tg close to the bulk value (≈ 100 °C) and are used as internal references. Data both for continuous and discontinuous films are obtained in the same experimental run for the same sample, which allows direct comparison between datasets. Phase-modulated ellipsometry in vacuum is used to monitor glass transition. Both traditional linear temperature scan method and a novel temperature modulated technique have been employed in the measurements.
ABSTRACT
Glass transition in thin (1-200 nm thick) spin-cast polystyrene films on silicon surfaces is probed by ellipsometry in a controlled vacuum environment. A temperature-modulated modification of the method is used alongside a traditional linear temperature scan. A clear glass transition is detected in films with thicknesses as low as 1-2 nm. The glass transition temperature (T(g)) shows no substantial dependence on thickness for coatings greater than 20 nm. Thinner films demonstrate moderate T(g) depression achieving 18 K for thicknesses 4-7 nm. Less than 4 nm thick samples are excluded from the T(g) comparison due to significant thickness nonuniformity (surface roughness). The transition in 10-20 nm thick films demonstrates excessive broadening. For some samples, the broadened transition is clearly resolved into two separate transitions. The thickness dependence of the glass transition can be well described by a simple 2-layer model. It is also shown that T(g) depression in 5 nm thick films is not sensitive to a wide range of experimental factors including molecular weight characteristics of the polymer, specifications of solvent used for spin casting, substrate composition, and pretreatment of the substrate surface.
Subject(s)
Glass/chemistry , Phase Transition , Polystyrenes/chemistry , Temperature , Nitrogen/chemistry , Oxidation-Reduction , Surface Properties , VacuumABSTRACT
A vacuum ellipsometer has been designed for probing the glass transition in thin supported polymer films. The device is based on the optics of a commercial spectroscopic phase-modulated ellipsometer. A custom-made vacuum chamber evacuated by oil-free pumps, variable temperature optical table, and computer-based data acquisition system was described. The performance of the tool has been demonstrated using 20-200 nm thick poly(methyl methacrylate) and polystyrene films coated on silicon substrates at 10(-6)-10(-8) torr residual gas pressure. Both polymers show pronounced glass transitions. The difficulties in assigning in the glass transition temperature are discussed with respect to the experimental challenges of the measurements in thin polymer films. It is found that the experimental curves can be significantly affected by a residual gas. This effect manifests itself at lower temperatures as a decreased or even negative apparent thermal coefficient of expansion, and is related to the uptake and desorption of water by the samples during temperature scans. It is also found that an ionization gauge--the standard accessory of any high vacuum system--can cause a number of spurious phenomena including drift in the experimental data, roughening of the polymer surface, and film dewetting.
ABSTRACT
The ultrasensitive differential scanning calorimetry is used to observe the glass transition in thin (1-400 nm) spin-cast films of polystyrene, poly (2-vinyl pyridine) and poly (methyl methacrylate) on a platinum surface. A pronounced glass transition is observed even at a thickness as small as 1-3 nm. Using the high heating (20-200 K/ms) and cooling (1-2 K/ms in glass transition region) rates which are typical for this technique, we do not observe appreciable dependence of the glass transition temperature over the thickness range from hundreds of nanometers down to 3 nm thick films. The evolution of calorimetric data with film thickness is discussed in terms of broadening of transition dynamics and loss of transition contrast.
