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Thin polymeric films are of great importance of high number of high-tech applications for instance in sensors and nanoelectronics. Form the scientific point of view thin films with thickness below 100 nm are ideal model systems to study confinement effects on its properties for instance on the molecular relaxation processes. In this contribution an overview is presented about the behavior of different systems as investigated by nanosized relaxation spectroscopy like broadband dielectric spectroscopy employing nano structured capacitors and AC chip calorimetry complimented by ellipsometry. The systems considered are PVME1, PVME/PS blends2,3 P2VP4, PBAC5 and polysulfone6. Besides the film also the adsorbed layer on the substrate prepared by a leaching approach and investigated by AFM is considered.1,4-7. For these investigationsss it is found that the adsorbed layer itself exhibits a relaxation dynamics which might be assigned either to molecular motions or to adsorptions desorption kinetics.
Carbon nanomembranes are synthetic two-dimensional sheets with nanometer thickness, macroscopic lateral dimensions, and high structural homogeneity. They have great application potential in various branches of nanotechnology. Because of their full carbon structure, it is not clear whether macromolecules like poly(methyl methacrylate) (PMMA) can be irreversibly adsorbed on their surface. Here, irreversible adsorption means that the polymer chains cannot be removed by a leaching process, which is assumed in technological transfer processes. However, if polar defects are present on the carbon nanomembranes (CNMs), it may occur that polymers can be irreversibly adsorbed. To address this question, PMMA was spin-coated on top of CNMs, annealed for a specific time at different temperatures, and then tried to be removed by a acetone treatment in a leaching approach. The samples were investigated in detail by atomic force microscopy, X-ray photoelectron spectroscopy, and broadband dielectric spectroscopy, where the latter method has been applied to CNMs for the first time. Unambiguously, it was shown that PMMA can be adsorbed on the surface of CNMs after annealing the sample above the glasstransition temperature of PMMA. The general occurrence of polar defects on the surface of CNMs and the adsorption of polymers open opportunities for advanced innovative hybrid materials combining the properties of the CNM with those of the polymer.
The thermodynamic behavior of thin PVME films including the irreversible adsorbed layer on the substrate is investigated. In a first step, the growth kinetics of the adsorbed layer was studied combining a leaching technique and atomic force microscopy. Further, it was shown that there is a critical initial film thickness for the formation of a surface-filling adsorbed layer. Additionally, spectroscopic ellipsometry measurements were carried out to investigate the influence of the adsorbed layer on the glass transition temperature of the thin films. For 30 nm films and below, the influence of the adsorbed layer percolates strongly to the bulk-like layer of the film. Finally, the molecular dynamics of the adsorbed layer was studied by broadband dielectric spectroscopy, employing nanostructured-electrode systems. One process was revealed, which was assigned either to molecular fluctuations taking place in a loosely-bounded the part of the adsorbed layer, or to the desorption/adsorption of segments at the substrate.
The composition of the surface layer in dependence from the distance of the polymer/air interface in thin films with thicknesses below 100 nm of miscible polymer blends in a spatial region of a few nanometers is not investigated completely. Here, thin films of the blend poly vinyl methyl ether) (PVME)/polystyrene (PS) with a composition of 25/75 wt% are investigated by Energy Resolved X-ray Photoelectron Spectroscopy (ER-XPS) at a synchrotron storage ring using excitation energies lower than 1 keV. By changing the energy of the photons the information depth is varied in the range from ca. 1 nm to 10 nm. Therefore, the PVME concentration could be estimated in dependence from the distance of the polymer/air interface for film thicknesses below 100 nm. Firstly, as expected for increasing information depth the PVME concentration decreases. Secondly, it was found that the PVME concentration at the surface has a complicated dependence on the film thickness. It increases with decreasing film thickness until 30 nm where a maximum is reached. For smaller film thicknesses the PVME concentration decreases. A simplified layer model is used to calculate the effective PVME concentration in the different spatial regions of the surface layer.
Copper has a strong bactericidal effect against multi-drug resistant pathogens and polyethers are known for their resistance to biofilm formation. Herein, we combined Cu nanoparticles (NPs) and a polyether Plasma polymer in the form of nanocomposite thin films and studied whether both effects can be coupled. Cu NPs were produced by magnetron sputtering via the aggregation in a cool buffer gas whereasolyether layers were synthesized by Plasma-Assisted Vapor Phase Deposition with poly(ethylene oxide) (PEO) used as a precursor. In situ specific heat spectroscopy and XPS analysis revealed the formation of a modified polymer layer around the NPs which propagates on the scale of a few nanometers from the Cu NP/polymer interface and then transforms into a bulk polymer phase. The chemical composition of the modified layer is found to be ether-deficient due to the catalytic influence of copper whereas the bulk polymer Phase exhibits the chemical composition close to the original PEO. Two cooperative glass transition phenomena are revealed that belong to the modified polymer layer and the bulk phase. The former is characterized by constrained mobility of polymer segments which manifests itself via a 30 K increase of dynamic glass transition temperature. Furthermore, the modified layer is characterized by the heterogeneous structure which results in higher fragility of this layer as compared to the bulk phase. The Cu NPs/polyether thin films exhibit reduced Protein adsorption; however, the constrained segmental dynamics leads to the Deterioration of the non-fouling properties for ultra-thin polyether coatings. The films are found to have a bactericidal effect against multi-drug resistant Gram-positive Methicillin-Resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa.
The molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding to the Kuhn segment length for the former relaxation and to the CRR for the latter one. The observed multiple glassy dynamics result from spatial local compositional heterogeneities on a microscopic level. Additionally, SHS investigations were performed for the first time for this system, proving an existence of a fourth relaxation process (α3-relaxation) due to the cooperative fluctuations of both PS and PVME segments. The separation between the thermal α3- and dielectric α2-relaxation increases dramatically with increasing polystyrene concentration, proving that the thermal response is dominated by PS.
A combination of nanosized dielectric relaxation (BDS) and thermal spectroscopy (SHS) was utilized to characterize the dynamics of thin films of Poly(vinyl methyl ether) (PVME) (thicknesses: 7 nm – 160 nm). For the BDS measurements, a recently designed nano-structured electrode system is employed. A thin film is spin-coated on an ultra-flat highly conductive silicon wafer serving as the bottom electrode. As top electrode, a highly conductive wafer with non-conducting nanostructured SiO2 nano-spacers with heights of 35 nm or 70 nm is assembled on the bottom electrode. This procedure results in thin supported films with a free polymer/air interface. The BDS measurements show two relaxation processes, which are analyzed unambiguously for thicknesses smaller than 50 nm. The relaxation rates of both processes have different temperature dependencies. One process coincidences in its position and temperature dependence with the glassy dynamics of bulk PVME and is ascribed to the dynamic glass transition of a bulk-like layer in the middle of the film. The relaxation rates were found to be thickness independent as confirmed by SHS. Unexpectedly, the relaxation rates of the second process obey an Arrhenius-like temperature dependence. This process was not observed by SHS and was related to the constrained fluctuations in a layer, which is irreversibly adsorbed at the substrate with a heterogeneous structure. Its molecular fluctuations undergo a confinement effect resulting in the localization of the segmental dynamics. To our knowledge, this is the first report on the molecular dynamics of an adsorbed layer in thin films.
The discussions on the nanoconfinement effect on the glass transition and glassy dynamics phenomena have yielded many open questions. Here, the thickness dependence of the thermal glass transition temperature of thin films of a PVME/PS blend is investigated by ellipsometry. Its thickness dependence was compared to that of the dynamic glass transition (measured by specific heat spectroscopy), and the deduced Vogel temperature (T0). While and T0 showed a monotonous increase, with decreasing the film thickness, the dynamic glass transition temperature () measured at a finite frequency showed a non-monotonous dependence that peaks at 30 nm. This was discussed by assuming different cooperativity length scales at these temperatures, which have different sensitivities to composition and thickness. This non-monotonous thickness dependence of disappears for frequencies characteristic for T0. Further analysis of the fragility parameter, showed a change in the glassy dynamics from strong to fragile, with decreasing film thickness.
Unraveling the Dynamics of Nanoscopically Confined PVME in Thin Films of a Miscible PVME/PS Blend
(2017)
Broadband dielectric spectroscopy (BDS) was employed to investigate the glassy dynamics of thin films (7−200 nm) of a poly(vinyl methyl ether) (PVME)/polystyrene (PS) blend (50:50 wt %). For BDS measurements, nanostructured capacitors (NSCs) were employed, where films are allowed a free surface. This method was applied for film thicknesses up to 36 nm. For thicker films, samples were prepared between crossed electrode capacitors (CECs). The relaxation spectra of the films showed multiple processes. The first process was assigned to the α-relaxation of a bulklike layer. For films measured by NSCs, the rates of α-relaxation were higher compared to those of the bulk blend. This behavior was related to the PVME-rich free surface layer at the polymer/air interface. The second process was observed for all films measured by CECs (process X) and the 36 nm film measured by NSCs (process X2). This process was assigned to fluctuations of constraint PVME segments by PS. Its activation energy was found to be thickness-dependent because of the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature dependence was observed for all films measured by NSCs (process X1). It resembled the molecular fluctuations in an adsorbed layer found for thin films of pure PVME, and thus, it is assigned accordingly. This process undergoes an extra confinement because of frozen adsorbed PS segments at the polymer/substrate interface. To our knowledge, this is the first example where confinement-induced changes were observed by BDS for blend thin films
In thin polymer films, little is known about the dynamics of the adsorbed layers, despite their importance in innovative applications. Here, Broadband Dielectric Spectroscopy (BDS) was utilized to investigate the glassy dynamics of thin films of a low MW Poly (vinyl methyl ether) (PVME) (thicknesses: 7 – 160 nm). A recently developed nano-structured capacitor arrangement was employed; where a silicon wafer with nanostructured SiO2 nano-spacers, with heights of 35 nm and 70 nm, is placed on top of a thin film spin coated on an ultra-flat highly conductive silicon wafer. Further, PVME/SiO2 interactions was confirmed by contact angle measurements, hence an adsorbed layer is allowed to form. For films with thicknesses smaller than 50 nm, BDS measurements showed two relaxation processes. The first process coincided, in its position and temperature dependence, with the -relaxation of bulk PVME, thus it was assigned to the -relaxation of a bulk-like layer. The second process showed a different temperature dependence and was ascribed to the relaxation of polymer segments adsorbed at the substrate. Both processes showed no thickness dependence. The results will be discussed in detail. To our knowledge, this is the first study of the segmental dynamics of an adsorbed layer in thin films.