In situ ellipsometry studies on swelling of thin polymer films: A review

The properties of a thin polymer film can be significantly affected by the presence of a penetrant. This can have potential implications for many technological applications, such as protective and functional coatings, sensors, microelectronics, surface modification and membrane separations. In situ ellipsometry is a powerful technique for the characterization of a film in contact with a penetrant. The main advantages of ellipsometry include the very high precision and accuracy of this technique, combined with the fact that it is non-intrusive. Recent advances in the speed and automation of the technique have further expanded its application.This article provides an overview of the research that has been done with in situ UV–vis ellipsometry on penetrant-exposed polymeric films, in the last 15–20 years. The focus is predominantly on films that are not attached covalently to a substrate. Polymer brushes and grafts are therefore excluded. This review addresses a variety of topics, covering instrumental aspects of in situ studies, approaches to data analysis and optical models, reported precision and repeatability, the polymer-penetrant systems that have been studied, the kind of information that has been extracted, and other in situ techniques that have been combined with ellipsometry. Various examples are presented to illustrate different practical approaches, the consequences of the optical properties of the ambient, and the various ways that have been employed to bring polymer films in contact with a penetrant, ranging from simple ex situ-like configurations (i.e., drying studies) to complex high pressure cells. The versatility of in situ ellipsometry is demonstrated by examples of the distinctive phenomena studied, such as film dilation, penetrant diffusion mechanisms, film degradation, electrochemical processes, and the broad variety of polymer-penetrant systems studied (glassy and rubbery polymers, multilayer stacks, etc.). An outlook is given on possible future trends.     

Impact of polymer modulus/chain mobility on water accumulation at polymer/metal oxide interfaces

Moisture is known to accumulate at the interface between polymers and metal oxides, leading to detrimental effects on physical properties such as modulus and adhesion. Direct measurement of the interfacial moisture profile has been carried out with neutron reflectivity, while thickness dependent swelling of a thin film series has also been also utilized to indirectly assess the interfacial moisture content. In this work, the moisture adsorption on the clean surfaces is compared to that observed when the surface is coated with a series of polymer films. The mechanical properties of the polymer appear to impact the quantity of moisture adsorbed at the interface; surprisingly less moisture accumulates at the interface if the coating is rubbery (larger intrinsic mobility of polymer chains). For glassy polymers, the total accumulation at the interface is identical to the adsorption on the clean metal oxide surface. This result potentially provides an understanding of solvent distribution in glassy nanocomposites by measuring moisture adsorption onto the bare filler materials prior to incorporation into the polymer matrix.     

Carbon dioxide plasticization of thin glassy polymer films

We have demonstrated in previous studies that thin glassy polymer films exhibit complex responses to highly sorbing penetrants, such as CO₂, relative to their thick film counterparts. In this paper, we apply similar experiments to two new polymers, including a polysulfone made from bisphenol A (PSF), and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and compare their responses to Matrimid^® to understand better CO₂ plasticization behavior of these materials when in thin film form. As expected, the extent of plasticization response tracks with CO₂ solubility; CO₂ diffusivity may also be an important factor at shorter exposure times. Experiments at longer CO₂ exposure times revealed that each polymer experiences the permeability maximum observed in our previous work as well. However, polymers that are not as highly sorbing to CO₂, like polysulfone, may not at some conditions exhibit a distinct permeability maximum but will still decrease in permeability after a long period of CO₂ exposure owing to physical aging.     

Physical aging of thin glassy polymer films monitored by gas permeability

The physical aging at 35 °C of three glassy polymers, polysulfone, a polyimide and poly(2,6-dimethyl-1,4-phenylene oxide), has been tracked by measurement of the permeation of three gases, O₂, N₂, and CH₄, for over 200 days. Several techniques were used to accurately determine the thickness of films (∼400 nm-62 μm) in order to obtain absolute permeability coefficients and to study the effects of film thickness on the rate of physical aging. Each film was heated above the polymer T_g to set the aging clock to time zero; ellipsometry revealed that this procedure leads to isotropic films having initial characteristics independent of film thickness. A substantial pronounced aging response, attributed to a decrease in polymer free volume, was observed at temperatures more than 150 °C below T_g for thin films of each polymer compared to what is observed for the bulk polymers. The films with thicknesses of approximately 400 nm of the three polymers exhibit an oxygen permeability decrease by as much as two-fold or more and about 14-15% increase in O₂/N₂ selectivity at an aging time of 1000 h. The results obtained in this study were compared with prior work on thickness dependent aging. The effects of crystallinity on physical aging were examined briefly.     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Blocked crystallization in capped ultrathin polymer films studied by molecular simulations

The crystallization of capped ultrathin polymer films is closely dependent on film thickness and interfacial interaction. Using dynamic Monte Carlo simulations, the crystallization behaviors of polymer films confined between two substrates were investigated. The crystallization rate of confined polymers is reduced with high interfacial interactions. Above a critical strength of interfacial interaction, polymer crystallization in the thin film is inhibited within the simulation time scales. An increase in film thickness leads to a rise in critical interfacial interaction. In thicker films, the chains have more space to change conformation to form crystal stems. In addition, there are fewer absorbed segments in confined chains for the thicker films, and thus the chains have stronger ability to adjust their conformation. Therefore an increase in film thickness can cause a reduction in the entropic barrier required for the formation of crystals and thus an increase in the critical interfacial interaction. © 2018 Society of Chemical Industry     

Crystallization and morphology of ultrathin films of homopolymers and polymer blends

Ultrathin films of thicknesses below 100 nm are now considered in different areas of applications. Their behavior in term of kinetics of crystallization is very different from that of bulk samples due to the film confinement in two-dimensions, and their morphologies are unique. In this review, recent advances in the crystallization of ultrathin films of homopolymers and miscible polymer blends will be described, with an emphasis on morphologies and, in the case of blends, on mixtures made of two crystalline polymers.     

Carbon dioxide plasticization and conditioning effects in thick vs. thin glassy polymer films

Recent studies have shown that thin glassy polymer films undergo physical aging more rapidly than thick films. This suggests that thickness may also play a role in the plasticization and conditioning responses of thin glassy films in the presence of highly-sorbing penetrants such as CO₂. In this paper, a carefully designed systematic study explores the effect of thickness on the CO₂ plasticization and conditioning phenomena in Matrimid^®, a polyimide commonly used in commercial gas separation membranes. Thin films are found to be more sensitive than thick films to CO₂ exposure, undergoing more extensive and rapid plasticization at any pressure. The response of glassy polymers films to CO₂ is not only dependent on thickness, but also on aging time, CO₂ pressure, exposure time, and prior history. Finally, thin films experiencing constant CO₂ exposure for longer periods of time exhibit an initial large increase in CO₂ permeability, which eventually reaches a maximum, followed by a significant decrease in permeability for the duration of the experiment. Thick films, in contrast, do not seem to exhibit this trend for the range of conditions explored.     

Comparison of two approaches to grafting hydrophilic polymer chains onto polysulfone films

To reduce the surface protein adsorption of polysulfone (PSf) film, we improved the hydrophilicity of this film by photochemical grafting of methoxypoly (ethylene glycol) (MPEG) derivatives on its surface. Grafting was achieved with both the simultaneous method and the sequential method. Surface analysis of the grafted film by X‐ray photoelectron spectroscopy (XPS) revealed that the PEG chains had successfully grafted onto the surface of the film. The grafting efficiencies by simultaneous and sequential methods were 20.8% and 10.2%, respectively. With an atomic force microscope (AFM), the surface topography of PEG‐grafted films by these two methods was compared. Static water contact angle measurement indicated that the surface hydrophilicity of the film had been improved. Protein adsorption measurement showed that the surface protein adsorption of the modified film was significantly reduced compared with that of the unmodified PSf film. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3818–3826, 2007     

Nanoindentation behavior of ultrathin polymeric films

Measurement of the mechanical properties of nanoscale polymeric films is important for the fabrication and design of nanoscale layered materials. Nanoindentation was used to study the viscoelastic deformation of low modulus, ultrathin polymeric films with thicknesses of 47, 125 and 3000 nm on a high modulus substrate. The nominal reduced contact modulus increases with the indentation load and penetration depth due to the effect of substrate, which is quantitatively in agreement with an elastic contact model. The flow of the nanoscale films subjected to constant indentation loads is shear-thinning and can be described by a linear relation between the indentation depth and time with the stress exponent of 1/2.     

Temperature dependence of CO2 concentration gradient within polymer films as determined by reactive templating

The swelling of thin polymer films by supercritical carbon dioxide has been shown to exhibit an anomalous maximum in the sorption isotherms. This swelling maximum occurs when the activity of the fluid phase approaches unity and the extent of the swelling increases as the critical temperature is approached. Using an in situ selective reactive templating approach based upon silica condensation within hydrophilic domains of an amphiphilic polymer film, the CO₂ distribution within the polymer film is elucidated from the pore sizes generated by hydrophobic domains upon removal of the amphiphile. The origin of the maximum in the swelling of the thin films is demonstrated to be concentration gradients that extend from both interfaces of the film; as the temperature approaches the critical temperature, the local swelling at both interfaces increases progressively. However, the pressure range over which gradients in CO₂ concentration occurs decreases as the critical temperature for CO₂ is approached.     

Relationship between thickness of polymer films and their oxidation on copper substrate

This research was undertaken to understand how the thickness of polyethylene films oxidized on a copper substrate influences the accumulation of carbonyl groups (measured by an IR‐spectroscopy technique) and of metal from the substrate (determined by polarography analysis). It was found that the whole polymer became inhibited by the time the copper stopped transferring into the specimen. Plots of copper concentration versus film thickness have two thickness sections: section I is found between 0 and 70 μm and section II between 80 and 170 μm. Between these two sections the metal concentration varies drastically. This situation can be explained by two schemes by which PE changes to inhibited condition. According to Scheme I (for section I, short oxidation time) this change has only one step: the inhibited layer gradually becomes thicker beginning from the interface and moving toward the outer surface. The second scheme (for section II) shows that the polymer becomes inhibited in two steps. It is typical of thicker films. In this case the oxidation process shifts and localizes in the outer surface because of longer treatment. As a result, transfer of metal and formation of an inhibited layer are interrupted for some time. The metal accumulation in the film only resumes when low‐molecular‐weight products of thermooxidative degradation—formed in the specimen outer surface—enter the region of adhesional contact. A so‐called second transfer stage for metal is realized during which the whole polymer becomes inhibited. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 671–675, 2003     

Construction of the state diagram of polymer blend thin films using differential AC chip calorimetry

The phase separation behavior of polymer blend thin films of 100-150 nm was studied using differential AC Chip calorimetry. By taking advantage of the low sensor and sample mass inherent to chip calorimetry, a new methodology based on temperature jumps was developed. This methodology allowed the construction of the state diagram of polymer blend thin films as evidenced for two model systems (PVME/PS and PVME/Phenoxy) displaying a lower critical solution temperature behavior.The state diagram in thin films was compared to the one obtained in bulk using Modulated Temperature DSC. In comparison with bulk, a lower phase separation temperature and a broadening of the homogeneous glass transition temperatures is observed for both model systems. This might be an indication of a surface induced ‘destabilization’ by composition gradients which are not present in bulk.     

Si diffusion induced adhesion and corrosion resistance in annealed RF sputtered SiC films on graphite substrate

Silicon carbide (SiC) is one of the promising candidates for graphite protection in different applications involving high temperatures and a highly corrosive environment. An ideal Silicon carbide coating should withstand a corrosive environment without compromising its adhesion. Herein, RF magnetron sputtered silicon-rich SiC thin films were deposited on a graphite substrate followed by annealing at 1000 °C, 1200 °C, and 1400 °C in an inert atmosphere. The impact of annealing temperature on microstructure, adhesion and chemical stability of SiC thin films was demonstrated. Different analytical techniques like Scanning electron microscopy (SEM), X-Ray Diffraction (XRD), Fourier's Transform Infrared (FTIR) spectroscopy and nano-indentation were used to study microstructural evaluation and mechanical characteristics. Moreover, the electrochemical analysis (Tafel and Electrochemical impedance spectroscopy) was performed in 3.5% NaCl solution. The microstructural analysis revealed that the amorphous SiC thin film turned into a crystalline and dense film upon annealing. Scanning electron micrographs showed that silicon-rich regions at SiC film surface started to disappear as Si diffuses into graphite matrix at elevated temperatures. Both these factors contributed to improvement in the adhesion of SiC coating with graphite substrate as annealing temperature increased. In addition, the nano-indentation hardness of 5.2 GPa was obtained for as grown sample, which decreased at 1000 °C, and then increased at 1200 °C and 1400 °C. Furthermore, the electrochemical analysis confirmed the enhancement in corrosion resistance upon annealing at a temperature of 1200 °C and 1400 °C due to Si diffusion and film compactness in these samples.     

High-performance (Na0.5Bi0.5)(Ti0.97Fe0.03)O3-based heterostructure thin films for energy storage capacitors

This work presents a simple process to fabricate Na_0.5Bi_0.5(Ti_0.97Fe_0.03)O₃/Ba_(1–x)Sr_xTiO₃–based heterostructure thin films with a compositional graded sequence, and their energy storage properties are investigated systematically. A simulation technique is used to predict the experimental results. Interestingly, improved energy storage properties are obtained in the “up–graded” film, which is associated with the stress/strain. Furthermore, the “up–graded” film after aging with treating exhibits a higher breakdown strength (E_BD = 3176.4 kV/cm), recoverable energy storage density (W_rec = 67.18 J/cm³) and efficiency (η = 75.65%). This can be attributed to the ordered defect dipoles induced by aging with treating driving domain switching, which is favorable for high (P_m–P_r) and large W_rec. These results provide an approach and guidance to design thin film-based devices with optimal energy storage performance.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Measuring water diffusion in polymer films on the substrate by internal reflection fourier transform infrared spectroscopy

Among the various analysis modes which can be used in FTIR spectroscopy, the internal reflection mode enables us to gain near-surface information on solids or liquids. The interaction between the evanescent field created upon internal reflection of the infrared beam and a sample can be used to monitor the uptake of water molecules by a polymeric film. In this technique, a polymer film of sufficient thickness is applied to a substrate and a special cell is used to study the water diffusion in the polymer films. Spectra were taken automatically at specified time intervals without disturbing either the specimen or the instrument. Results for polystyrene and poly(methyl methacrylate) films applied to a ZnS substrate are presented to demonstrate the method. The diffusion coefficients of water in these polymers are calculated using the sorption kinetics approach, and the diffusion process in each type of polymer is discussed. The effects of the molecular weight and defects in the films on water transport in the polymers are illustrated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2465–2473, 1997     

Simulation of polyethylene thin films composed of various chain lengths

Polyethylene thin films are simulated using a coarse-grained on-lattice Monte Carlo technique. Properties of free-standing films, which are made up of either C₅₀, C₁₀₀ or C₃₁₆ chains, are analyzed in the melt phase at 509 K. As a result of increasing molecular weight, the following observations are made: (i) bulk density of the films increases; (ii) there is a higher degree of parallel orientation of bonds at the surface and a broader region over which this orientation survives; (iii) the decrease in the radius of gyration of the chains at the surface becomes more significant and (iv) parallel orientation of the chains at the surface is enhanced. Moreover, mixed films that contain both C₅₀ and C₁₀₀ chains are simulated. In these mixed films, the properties of C₁₀₀ chains do not change, whereas the orientation of C₅₀ chains and bonds is higher in the presence of longer chains.     

Creep and shrinkage behavior of improved ultrathin polymeric films

Long‐term creep‐deformation and shrinkage characteristics of improved ultrathin polymeric films for magnetic tapes are presented. These films include poly(ethylene terephthalate) (PET), poly(ethylene naphthalate) (PEN), and aromatic polyamide (ARAMID). PET film is currently the standard substrate used for magnetic tapes, and thinner tensilized‐type PET, PEN, and ARAMID have recently been used as alternate substrates with improved material properties. The thickness of the films ranges from 6.2 to 4.8 μm. More dimensional stability is required for advanced magnetic tapes, and the study of creep and shrinkage behavior is important for estimating the dimensional stability. Creep measurements were performed on all available substrates at 25, 40, and 55°C for 100 h. Based on these data, master curves were generated using time–temperature superposition to predict dimensional stability after several years. The amount of creep deformation is considerably smaller for ARAMID and tensilized‐type PET than for PEN, although Standard PET shows the largest amount of creep. In addition, creep measurements under high humidity also show similar trends. Shrinkage measurements at 55°C for 100 h show that the shrinkage of ARAMID is lower than that of PET and PEN. The relationship between the polymeric structure and dimensional stability are also discussed. Based on the creep and shrinkage behavior, ARAMID and tensilized‐type PET seem to be suitable for advanced magnetic tapes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1477–1498, 2002; DOI 10.1002/app.10012