Some relevant parameters affecting the glass transition of supported ultra-thin polymer films

We have measured, the thickness dependence of the glass transition temperature T(g)( h), using ellipsometry at variable temperature, for poly(methyl-methacrylate) (PMMA) of various tacticity in confined geometry. We report that several factors significantly affect T(g)( h): i) polymer microstructure (stereoregularity of PMMA) related to local dynamics; ii) interfacial interactions; iii) conformation of the polymer chains. These results raise many fundamental questions on the origin of the thickness-dependent glass transition. Why and how do the interactions with the substrate significantly affect T(g)( h)? Does T(g)( h) depend on the modifications of conformational parameters of the chains (their entropy)? What is the correlation between local dynamics and T(g)( h) in thin films? The aim of this paper is to summarise these open questions, which should stimulate further investigations in the thin polymer film scientific community.     

Dielectric relaxations in ultrathin isotactic PMMA films and PS-PMMA-PS trilayer films

The local and cooperative dynamics of supported ultrathin films ( L = 6.4 - 120 nm) of isotactic poly(methyl methacrylate) (i-PMMA, Mn = 118 x 10(3) g/mol) was studied using dielectric relaxation spectroscopy for a wide range of frequencies (0.1 Hz to 10(6) Hz) and temperatures (250 - 423 K). To assess the influence of the PMMA film surfaces on the glass transition dynamics, two different sample geometries were employed: a single layer PMMA film with the film surfaces in direct contact with aluminum films which act as attractive, hard boundaries; and a stacked polystyrene-PMMA-polystyrene trilayer film which contains diffuse PMMA-PS interfaces. For single layer films of i-PMMA, a decrease of the glass transition temperature T(g) by up to 10 K was observed for a film thickness L < 25 nm (comparable to R(EE)), indicated by a decrease of the peak temperature T(alpha) in the loss epsilon(")(T) at low and high frequencies and by a decrease in the temperature corresponding to the maximum in the apparent activation energy E(a)(T) of the alpha-process. In contrast, measurements of i-PMMA sandwiched between PS-layers revealed a slight (up to 5 K) increase in T(g) for PMMA film thickness values less than 30 nm. The slowing down of the glass transition dynamics for the thinnest PMMA films is consistent with an increased contribution from the less mobile PMMA-PS interdiffusion regions.     

Pressure, temperature, and thickness dependence of CO2-induced devitrification of polymer films

The glass transition temperature is known to increase with decreasing film thickness h for sufficiently thin poly(methyl methacrylate) films supported by silicon oxide substrates. We show that this system undergoes a CO2 pressure-induced devitrification transition, P(g), which is film thickness dependent, P(g)(h)=DeltaP(g)+P(bulk)(g). P(bulk)(g) is the bulk glass transition and DeltaP(g) can be positive or negative depending on T and P. The phenomenon of retrograde vitrification, wherein the polymer exhibits a rubbery-to-glassy-to-rubbery transition upon changing temperature isobarically, is also shown to occur in this system and it is film thickness dependent.     

Glass transitions and dynamics in thin polymer films: dielectric relaxation of thin films of polystyrene

The glass transition temperature T(g) and the temperature T(alpha) corresponding to the peak in the dielectric loss due to the alpha process have been simultaneously determined as functions of film thickness d through dielectric measurements for polystyrene thin films supported on glass substrate. The dielectric loss peaks have also been investigated as functions of frequency for a given temperature. A decrease in T(g) was observed with decreasing film thickness, while T(alpha) was found to remain almost constant for d>d(c) and to decrease drastically with decreasing d for d相似文献   

Two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films as measured by transmission ellipsometry

We study the glass transition in confined polymer films and present the first experimental evidence indicating that two separate mechanisms can act simultaneously on the film to propagate enhanced mobility from the free surface into the material. Using transmission ellipsometry, we have measured the thermal expansion of ultrathin, high molecular-weight (MW), freestanding polystyrene films over an extended temperature range. For two different MWs, we observed two distinct reduced glass transition temperatures (T(g)'s), separated by up to 60 K, within single films with thicknesses h less than 70 nm. The lower transition follows the expected MW dependent, linear T(g)(h) behavior previously seen in high MW freestanding films. We also observe a much stronger upper transition with no MW dependence that exhibits the same T(g)(h) dependence as supported and low MW freestanding polymer films.     

Hydrophobic switching nature of methylcellulose ultra-thin films: thickness and annealing effects

We have studied the thermosensitive property of methylcellulose (MC) thin films supported on Si substrate by static sessile drop contact angle measurements, and their surface properties and thin film structure by x-ray reflectivity (XRR) and atomic force microscopy (AFM) techniques. From the static sessile drop contact angle measurements, the MC thin films showed the characteristic hydrophilic-to-hydrophobic transition at ～70?°C, which is the lower critical solution temperature of the bulk solution volume phase separation transition. For films with thickness d ≤ R(g), the onset of such a transition is affected by the film thickness while very thick films, d ? R(g), yielded higher contact angles. Annealing the MC thin films with thicknesses ～200 ? (near the radius of gyration, R(g), of the polymer) below the bulk glass transition temperature (T(g) ～ 195?° C) would not change the hydrophobic switch nature of the film but annealing 'at' and above the bulk T(g) would change its surface property. From surface topography images by AFM, there were no significant changes in either the roughness or the film texture before and after annealing. With XRR data, we were able to determine that such changes in the surface properties are highly correlated to the film thickness changes after the annealing process. This study, we believe, is the first to examine the thermal annealing affects on the thermal response function of a thermoresponsive polymer and is important for researching how to tailor the hydrophobic switching property of MC thin films for future sensing applications.     

Glass transition temperature of freely-standing films of atactic poly(methyl methacrylate)

We have used ellipsometry to measure the glass transition temperature T(g) of high molecular weight (M(w)=790 x 10(3)), freely-standing films of atactic poly(methyl methacrylate) (a-PMMA), as well as films of the same polymer supported on two different substrates: the native oxide layer of silicon (Si) and gold-covered Si. We observe linear reductions in T(g) with decreasing film thickness h for the freely-standing PMMA films with 30 nm < h<100 nm, which is qualitatively similar to previous results obtained for freely-standing polystyrene (PS) films. However the magnitude of the T(g) reductions for PMMA is much less than for freely-standing films of PS of comparable molecular weight and thickness. We also find that for films supported on either substrate, with thicknesses as small as 30 nm, the T(g) values do not deviate substantially from the value measured for thick films.     

Molecular mobility in polymer thin films

Fluorescence recovery after photobleaching was used to measure in-plane dye-probe diffusion coefficients, D, in thin films of monodisperse polystyrene supported on fused quartz substrates. The substrates were prepared with a high density of surface hydroxyl groups which interact favorably with repeat units of the polymer. The effects of temperature and film thickness were investigated, at temperatures above the bulk glass transition of the polymer, T(g), and in the range of film thicknesses from 1-10(2) times the radius of gyration (R(g)) of individual polymer molecules. As the film thickness decreases towards R(g) the value of D increases above the bulk values, with significant effects first appearing in films approximately 20R(g). In the thinnest films studied, about 4R(g), the values of D lie as much as two orders over bulk values. At the same time, the temperature dependence of D becomes much weaker than in bulk. Analysis by free volume theory indicates that apparent values of both T(g) and the thermal expansion coefficient for liquid state, alpha(L), decrease as the film thickness decreases. The possible effects of surface segregation of the dye probe are discussed.     

Thickness dependence of the dynamics in thin films of isotactic poly (methylmethacrylate)

The film thickness dependence of both the glass transition temperature (T(g)) and the 1 kHz alpha relaxation were studied for thin films of isotactic Poly (methylmethacrylate) (i-PMMA) supported on aluminium substrates. Films in the thickness range 7-200 nm were studied. The ellipsometrically determined T(g) was found to show reductions for films thinner than 60 nm, with the largest observed reduction being 12 K for a 7 nm thick film. Measurements of the T(g) were also performed on i-PMMA films supported on silicon substrates. Dielectric studies of the temperature dependent 1 kHz alpha relaxation peak, showed that the position (T(alpha)) and shape of the peak have no film thickness dependence. This was shown to hold for films with one free surface and films with a 30 nm thermally evaporated capping layer. Capping the films was shown to have no effect on the thickness dependence of either T(g) or T(alpha). The implications of these results are discussed further and the different film thickness dependencies of T(g) and T(alpha) are discussed. This is done within the framework of the Vogel-Fulcher-Tamann (VFT) theory of glass forming materials and also in the context of the existence of a dynamic correlation length xi.     

Thickness dependence of the dynamics in thin films of isotactic poly (methylmethacrylate)

The European Physical Journal E - The film thickness dependence of both the glass transition temperature (T g ) and the 1 kHz alpha relaxation were studied for thin films of isotactic Poly...     

Modulation of refractive index and thickness of poly(methyl methacrylate) thin films with UV irradiation and heat treatment

This paper reports changes in refractive index and thickness of spin-coated poly(methyl methacrylate) (PMMA) thin films upon irradiation by a conventional high-pressure mercury UV lamp. Significant increase in refractive index and reduction in thickness are detected. Index modulations of greater than 0.01 are achieved in the thin films after 4 min of irradiation. The thickness reduction of an irradiated PMMA film is consistent with its weight loss. This is caused by the escape of the volatile molecules generated during the irradiation process. A slight increase in the refractive index is also found in the film, heat-treated above its glass transition temperature (Tg). This thermal effect is detected in the UV irradiation process. We propose three possible aliphatic structures that are formed during the photochemical reaction and may exist in the main chain of irradiated PMMA after the irradiation. Their refractive indices in aggregate state are greater than that of PMMA based on an evaluation using the Lorentz-Lorenz equation. This is suggested to be an important reason for the refractive index increase in the UV-irradiated PMMA films. A UV-irradiated film, heat-treated above its Tg, has a rough surface with many tiny holes as illustrated by atomic force microscopy. These holes are attributed to the evaporation of the small molecules generated during the irradiation process.     

X-ray reflectivity studies on glass transition of free standing polystyrene thin films

We have studied thermal expansion of free standing polystyrene thin films using X-ray reflectivity to elucidate the glass transition temperature and the thermal expansivity. We found that the glass transition temperature T_g decreased with the film thickness, depending on molecular weight. The reduction in the free standing films is much larger than in the supported films on Si substrate, suggesting that some segmental motions are activated due to free surfaces on both sides in the free standing films. We also found that the thermal expansivity in the glass and the melt decreased with the film thickness. This decrease must be attributable to chain confinement effects.     

Stability of thermoresponsive methylcellulose thin film: x‐ray reflectivity study

Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Qualitative discrepancy between different measures of dynamics in thin polymer films<Superscript>⋆</Superscript>

We have used ellipsometry to measure the initial stages of interface healing in bilayer polystyrene films. We also used ellipsometry to measure the glass transition temperature T_g of the same or identically prepared samples. The results indicate that as the film thickness is decreased, the time constant for the interface healing process increases, while at the same time the measured glass transition temperature in the same samples decreases as the film thickness is decreased. This qualitative difference in the behavior indicates that it is not always possible to make inferences about one probe of polymer dynamics from measurements of another. We propose a reason for this discrepancy based on a previously discussed origin for reduction in the T_g value of thin films.     

Shear modulation force microscopy study of near surface glass transition temperatures

We report results of glass transition (T(g)) measurements for polymer thin films using atomic force microscopy (AFM). The AFM mode, shear modulation force microscopy (SMFM), involves measuring the temperature-dependent shear force on a tip modulated parallel to the sample surface. Using this method we have measured the surface T(g) of thin (17-500 nm) polymer films and found that T(g) is independent of film thickness (t>17 nm), strength of substrate interactions, or even presence of substrate.     

The effects of post-thermal annealing on the optical parameters of indium-doped ZnO thin films

Indium-doped ZnO thin films are deposited on quartz glass slides by RF magnetron sputtering at ambient temper- ature. The as-deposited films are annealed at different temperatures from 400 C to 800 C in air for 1 h. Transmittance spectra are used to determine the optical parameters and the thicknesses of the films before and after annealing using a nonlinear programming method, and the effects of the annealing temperatures on the optical parameters and the thickness are investigated. The optical band gap is determined from the absorption coefficient. The calculated results show that the film thickness and optical parameters both increase first and then decrease with increasing annealing temperature from 400 C to 800 C. The band gap of the as-deposited ZnO:In thin film is 3.28 eV, and it decreases to 3.17 eV after annealing at 400 C. Then the band gap increases from 3.17 eV to 3.23 eV with increasing annealing temperature from 400 C to 800 C.     

Free surfaces cause reductions in the glass transition temperature of thin polystyrene films

The effect of free surfaces on the glass transition temperature (T(g)) of thin polystyrene films was studied. Measurements were performed on films (8 nm相似文献   

Ion crater healing and variable temperature ellipsometry as complementary probes for the glass transition in thin polymer films

The European Physical Journal E - Poly(methyl methacrylate) (PMMA) thin films of various tacticity and thickness were bombarded at grazing angles by 20 MeV Au ions at different temperatures. The...     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Differential AC-chip calorimeter for glass transition measurements in ultra thin polymeric films

A differential AC-chip calorimeter capable to measure the glass transition in nanometer thin films is described. Due to the differential setup pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below one nanogram even above room temperature as needed for the study of the glass transition in nanometer thin polymeric films. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin films of polystyrene (PS) (100–4 nm) and polymethylmethacrylate (PMMA) (400–10 nm) was determined at well defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K) - neither at constant frequency nor for the traces in the activation diagrams (1 Hz–1 kHz).