Properties Of Thin Polymer Films Research Articles

Pattern Formation in Evaporating Polymer Solutions-Interplay between Dewetting and Decomposition.

Pattern formation during solution evaporation is common in several industrial settings and involves a complex interplay of multiple processes, including wetting/dewetting, diffusion, and rheological characteristics of the solution. Monitoring the emergence of patterns during evaporation under controlled conditions may allow deconvolution of different processes and, in turn, improve our understanding of this common yet complex phenomenon. Here, we probe the importance of initial conditions, defined by the solution concentration c 0, on the pattern formation in evaporating polymer solutions on the air-water interface. Intriguingly, the initial decrease in the lateral length scale (ξ), characterizing the patterns, takes an upturn at higher concentrations, revealing reentrant behavior. We employ a gradient dynamics model consisting of coupled evolution equations for the film height and the polymer fraction in the solution. Our simulations capture two different length scales revealing the reasons underlying the re-entrant behavior of ξ(c 0). While the long-range destabilizing interactions between suspension and water result in the dewetting of thin film solutions, the phase separation between the polymer and solvent occurs at shorter length scales. Our results demonstrate the importance of initial concentration on pattern formation and, thereby, on the resultant properties of thin polymer films.

Interfacial molecular structure and orientation evolution of the polystyrene under confinement during annealing revealed by sum frequency generation vibrational spectroscopy

The geometrical confinement directly affects many crucial properties of polymer thin films by interfacial interactions. A key to understanding the role of these interfacial interactions is to specifically probe the confined interface at the molecular level and in situ. However, the direct and nondestructive detection of interfacial polymer structures under confinement is very difficult. In this study, specific interface-sensitive sum frequency generation (SFG) spectroscopy was applied to study the deuterated PS (d8-PS) film confined between hydrogenated poly (methyl methacrylate) (PMMA) films at the molecular level and in situ. The results showed that the ordering/orientation of the PS chain (backbone and phenyl group) evolved at the buried d8-PS/PMMA interface during annealing. The tilt angle of the PS phenyl group increased while the twist angle decreased with elevated annealing temperature. Both overall SFG ssp and ppp intensities decreased after annealing at 433 K for 24 h, indicating that PS chains entangled with or penetrated the PMMA chains at the confined interface. This study qualitatively and quantitatively revealed the interfacial structure and structural evolution of the PS chain confined between PMMA films in situ during annealing, which is beneficial to the molecular-level understanding of the interfacial chain conformational relaxation of polymers under confinement.

From non‐doped to dopable: The impact of methoxy functionalization on doping and thermoelectric properties of conjugated polymers

AbstractThe introduction of alkoxy side chains into the backbone of conjugated polymers is an effective way to change their properties. While the impact on the structure and optoelectronic properties of polymer thin films was well‐studied in organic solar cells and transistors, limited research has been conducted on their effects on doping and thermoelectric properties. In this study, the effects of methoxy functionalization of conjugated backbones on the doping and thermoelectric properties are investigated through a comparative study of diketopyrrolopyrrole‐based conjugated polymers with and without methoxy groups (P29DPP‐BTOM and P29DPP‐BT, respectively). Methoxy‐functionalization significantly enhances doping efficiency, converting undopable pairs to dopable ones. This dramatic change is attributed to the structural changes in the polymer film caused by the methoxy groups, which increases the lamellar spacing and facilitates the incorporation of dopants within the polymer crystals. Moreover, methoxy‐functionalization is advantageous in improving the Seebeck coefficient and power factor of the doped polymers, because it induces a bimodal orientational distribution in the polymer, which contributes to the increased splitting of Fermi and charge transport levels. This study demonstrates the impact of methoxy‐functionalization of a conjugated polymer on doping behavior and thermoelectric properties, providing a guideline for designing high‐performance conjugated polymers for thermoelectric applications.image

Temperature Coefficient of Electronic Polarizability in Thin Polymer Films Deposited on Si and SiO2 Substrates Determined via Spectroscopic Ellipsometry

Ellipsometry is widely used to determine the thermo-optical properties of thin polymer films. However, if the thermo-optic coefficient (TOC) and the linear thermal expansion coefficient (LTEC) are to be used to determine the temperature coefficient of electronic polarizability (TCEP) in thin polymer films, their values must be determined with the greatest possible accuracy, as both have the opposite effect. In this article, we analyze changes in ellipsometric parameters resulting from changes in the thin film temperature in order to develop a data analysis method for temperature-dependent spectroscopic ellipsometry that will facilitate the accurate determination of thermo-optical parameters, including the TCEP, in polymer thin films. As practical application examples, we identified optimal spectral windows to accurately determine the thermo-optical parameters of 50 to 150 nm-thick PMMA thin films deposited on Si and SiO2 substrates. The influence of thin-film thickness on the accuracy of TOC and LTEC determination is discussed.

Direct measurement and modeling of viscoelastic-viscoplastic properties of freely standing thin polystyrene films.

The demand for applications, such as coatings, separation filters, and electronic packaging, has greatly driven the research of polymer films. At nanometer scale, mechanical properties of thin polymer films can significantly deviate from bulk. Despite outstanding progresses, there still lack deep discussions on nonlinear viscoelastic-viscoplastic response and their interactions under nanoconfinement. In this work, by conducting measurements via the bubble inflation method and modelling using Schapery and Perzyna equations, we demonstrate nonlinear viscoelastic-viscoplastic properties of freely standing thin polystyrene (PS) films. The results show the unchanged glassy compliance and the rubbery stiffening phenomenon for thin PS films, where the lower rubbery plateau in rubbery stiffening may originate from the induced molecular orientation by plastic deformation. With decreasing film thickness, viscosity and yield stress in viscoplasticity increase in an exponential and a linear trend, respectively, indicating the significant role of nanoconfinement effect on viscoplastic properties. These findings may reveal that there are many properties from linear viscoelasticity to nonlinear viscoelasticity-viscoplasticity that need to be explored and unveiled for sufficient understanding of the nanoconfinement effect on altering mechanical behavior of polymers.

Dependence of Slippery and Elastic Properties of Thin Polymer Films on the Grafted Flexible Sidechain Amount

In modern life, people face a wide number of sticky problems when adhesion is highly undesirable: water and dirt stick to clothes, useful materials stick to the walls of their containers and cannot be fully used, water sticking and freezing on airplane wings affects handling and can be dangerous, biological liquids can stick and form clots inside medical devices threatening patients' lives, etc. Slippery liquid-infused porous surfaces (SLIPSs) with pressure stable omniphobicity could help to solve these issues. Lubricant depletion from porous surface and subsequent degradation of omniphobic properties is the major problem for SLIPS. It could be resolved by attaching flexible, liquid-like sidechains to the polymer matrix. Understanding the relationship between the structure of such polymer films and wetting effects is therefore of great importance. The present work is devoted to the study of droplet pinning on crosslinked polydimethylsiloxane (PDMS) polymer films with varied amounts of attached flexible PDMS sidechains and clarification of the relationship between slippery and viscoelastic properties of the films. An one-stage approach to the synthesis of such slippery coatings on smooth and porous substrates in "eco-friendly" pressurized CO2 solutions is proposed. Pinning force and Young's modulus (E) of the films on silicon substrates with variation of the grafted sidechains amount (x) are measured. The non-monotonic dependence of the pinning force on the amount of sidechains is obtained: the pinning force decreases at small x values (region I) and starts to increase at higher x (region II). The effects of the grafted sidechains amount, as well as matrix softening, are discussed for each case. It is demonstrated that the proposed method of film synthesis allows one to obtain thin, uniform coatings on fabrics without gluing the fibers. Such coatings with an optimal amount of PDMS sidechains demonstrate decreased sliding angles for droplets of water and aqueous alcohol solutions, as compared to PDMS coatings without grafted sidechains. The proposed technique may be of interest for deposition of coatings on porous surfaces having a complex morphology, such as textiles, aerogels, porous electrodes, etc.

An Investigation of the Thermal Transitions and Physical Properties of Semiconducting PDPP4T:PDBPyBT Blend Films.

This work focuses on the study of thermal and physical properties of thin polymer films based on mixtures of semiconductor polymers. The materials selected for research were poly [2,5-bis(2-octyldodecyl)-pyrrolo [3,4-c]pyrrole-1,4(2H,5H)-dione-3,6-diyl)-alt-(2,2';5',2″;5″,2'''-quater-thiophen-5,5'''-diyl)]-PDPP4T, a p-type semiconducting polymer, and poly(2,5-bis(2-octyldodecyl)-3,6-di(pyridin-2-yl)-pyrrolo [3,4-c]pyrrole-1,4(2H,5H)-dione-alt-2,2'-bithiophene)-PDBPyBT, a high-mobility n-type polymer. The article describes the influence of the mutual participation of materials on the structure, physical properties and thermal transitions of PDPP4T:PDBPyBT blends. Here, for the first time, we demonstrate the phase diagram for PDPP4T:PDBPyBT blend films, constructed on the basis of variable-temperature spectroscopic ellipsometry and differential scanning calorimetry. Both techniques are complementary to each other, and the obtained results overlap to a large extent. Our research shows that these polymers can be mixed in various proportions to form single-phase mixtures with several thermal transitions, three of which with the lowest characteristic temperatures can be identified as glass transitions. In addition, the RMS roughness value of the PDPP4T:PDBPyBT blended films was lower than that of the pure materials.

Adsorption Kinetics of Polystyrene and Poly(9-anthracenyl methyl methacrylate) onto SiO2 Surface Measured by Chip Nano-Calorimetry.

The alternating current (AC) chip nano-calorimetry is a powerful tool to investigate the physical properties of polymer thin films. In this paper, we report on the adsorption kinetics of polymers in which an AC chip nano-calorimetry was used for the first time. This technique allows for the real-time measurement of the adsorption kinetics of polymer chains onto the SiO2 surface. We used polystyrene (PS) and poly(9-anthracenyl methyl methacrylate) (PAMMA), which have different chemical natures and side group sizes. It was confirmed that the observed adsorption kinetics for PS were consistent with previously reported results obtained by dielectric spectroscopy. For PAMMA, we found characteristic adsorption kinetics, which shows a clear kink at the crossover between the early and later stages, while PS exhibits a lesser tendency of showing the kink as demonstrated by previously reported results.

Effects of non-thermal plasma jet treatment of Pure/Doped Polystyrene thin films on UV-Vis optical properties

Non-thermal Cold Atmospheric Plasma (CAP) to improve optical property of pure and doped polystyrene (PS) thin films using He and Ar gas. These thin films were fabricated using the solution cast method. Surface treatment of PS thin films were performed by CAP. To analyze the effect of plasma treatment, the optical properties of the thin films were measured and derived by UV-Vis spectroscopy in wavelength range of 300-700 nm. Absorbance, transmittance, extinction coefficient, energy band gap, and optical conductivity before and after Cold jet plasma treatment (CJT) were compared. The results from Ar and He were similar in effectiveness. The treatment did have an impact on the optical properties of these PS thin films. This data will help to substantiate the use of CJT to enhance optical properties of polymer thin films.    

Tuning phase separation morphology in blend thin films using well-defined linear (multi)block copolymers

Tuning phase separation morphology in polymer blend thin films is a promising strategy to improve their properties. In this study, a series of poly(n-butyl methacrylate)-b-polystyrene linear copolymers with the same overall degree of polymerization but different number of blocks are synthesized by macroRAFT-mediated emulsion polymerization, and used as compatibilizers in poly(n-butyl methacrylate)/polystyrene blend thin films with thickness of ca. 20 nm. It is verified that multiblock copolymer is more effective to diminish the size of phase separation domains compared to diblock copolymer. Self-consistent field simulation agrees with the experimental results, and demonstrates that the compatibilization behaviors of diblock and multiblock copolymers are different. Diblock copolymer can compatibilize the blend well at a higher content, whereas multiblock copolymers tend to give a smaller domain size but less homogeneous morphology. In addition, simulation results show that copolymers with a longer block length would produce a narrower interface, which may weaken the penetration of block copolymers into their corresponding phases. This study provides a pioneering attempt in clarifying the effect of block copolymers on blend phase separation morphology, and it will be of practical value in obtaining desirable mechanical properties of polymer thin films.

Influence of Polymer Molecular Weight on Chain Conformation at the Polystyrene/Silver Interface.

The dependence between the conformation of polystyrene (PS) and its molecular weight (Mw) in the vicinity of a metal interface was investigated by sum frequency generation (SFG) spectroscopy. Tilt angles θ ≥ 50° (the angle between the C2 axis of the pendant phenyl ring and the surface normal) were observed for all samples because of the interaction between the aromatic rings and the metal surface. Furthermore, it was found that θ decreases with increasing Mw for PS samples ranging from 20 × 103 g/mol to 400 × 103 g/mol. The intensity of the backbone SFG signal was higher for high Mw PS, compared to low Mw PS, indicating a greater number of backbone interactions with the silver substrate surface for the high Mw sample. These structural differences are driven by different entropic and enthalpic contributions to the free energy of adsorption for different polymer molecular weights. Differences in the polymer free volume and in the relative amount of chain ends with higher mobility may also influence the chain conformation. These results suggest that important interfacial properties of polymeric thin films, such as adhesion and wettability, could be tailored by modifying the polymer Mw to achieve the desired interfacial conformation.

Micromorphology and microtexture evaluation of poly(o-ethoxyaniline) films using atomic force microscopy and fractal analysis

The morphology and microtexture of poly(o-ethoxyaniline) thin films deposited on the ITO substrate by electrodeposition were investigated. Cyclic voltammetry and FTIR were used to characterize the molecular structure, while Atomic Force Microscopy (AFM) technique was applied to obtain topographical images. The images were analyzed using commercial and free software. Moreover, three new parameters such as surface entropy, fractal succolarity, and fractal lacunarity were evaluated using recently developed theoretical models. The results showed that the morphology was affected according to the deposition cycles, while the analysis of the molecular structure indicated an increase in the polymer’s conjugation, mainly from 5 to 15 cycles. Structures related to the growth of poly(o-ethoxyaniline) were observed due to the increase in the number of deposition cycles. However, films did not grow completely. The microtexture was homogenized as the number of cycles increased. Furthermore, topographical uniformity was high for all films. Percolation remained low for all films, showing that although the formation of films was not completed, the microtexture of the material tended to homogenize as the film grew. These results revealed that the used tools can quantify the surface parameters, which are of great interest for the study of the corrosive properties of polymeric thin films.

Dielectric behavior of thin films of unsaturated polyester‐resin/carbon nanotube semiconductor composites

Since the discovery of carbon nanotubes (CNT), numerous studies have focused on the development of materials combining CNT with polymer composites to exploit both CNT's remarkable characteristics and the complimentary properties of polymer thin films. In particular, unsaturated polyester resin (UPR) and CNT composite materials have not been studied before. Here we develop and characterize a UPR/CNT‐based capacity resistor gas sensor and apply it on THF vapor. The CNT's high aspect ratio provides the composite with better electrical and mechanical performance than other realizations, such as carbon black. We identify and quantify THF in a wide range of operation frequencies, under SATP conditions, as functions of the vertical distance, sample volume and operation frequency. High sensitivity, reversibility and fast response to the dielectric vapor exposure in microliter volumes are achieved. The results are also analyzed in terms of the possible mechanisms relating to THF/sensor interactions, with good correspondence between the model and measured data.

Quantifying Strain via Buckling Instabilities in Surface-Modified Polymer Brushes

A compressive strain applied to bilayer films (e.g. thin film adhered to a thick substrate) can lead to buckled or wrinkled morphologies, which has many important applications in stretchable electronics, anti-counterfeit technology, and high-precision micro and nano-metrology. A number of buckling-based metrology methods have been developed to quantify the residual stress and viscoelastic properties of polymer thin films. However, in some systems (e.g. solvent-induced swelling or thermal strain), the compressive strain is unknown or difficult to measure. We present a quantitative method of measuring the compressive strain of wrinkled polymer films and coatings with knowledge of the "skin" thickness, wrinkle wavelength, and wrinkle amplitude. The derived analytical expression is validated with a well-studied model system, e.g., stiff, thin film (PS) bonded to a thick, compliant substrate (PDMS). After validation, we use our expression to quantify the applied swelling strain of previously reported wrinkled poly(styrene-alt-maleic anhydride) brush surfaces. Finally, the applied strain is used to rationalize the observed persistence length of aligned wrinkles created during atomic force microscopy (AFM) lithography and subsequent solvent exposure.

Temperature-Dependent Spectroscopic Ellipsometry of Thin Polymer Films.

Thin polymer films have found many important applications in organic electronics, such as active layers, protective layers, or antistatic layers. Among the various experimental methods suitable for studying the thermo-optical properties of thin polymer films, temperature-dependent spectroscopic ellipsometry plays a special role as a nondestructive and very sensitive optical technique. In this Review Article, issues related to the physical origin of the dependence of ellipsometric angles on temperature are surveyed. In addition, the Review Article discusses the use of temperature-dependent spectroscopic ellipsometry for studying phase transitions in thin polymer films. The benefits of studying thermal transitions using different cooling/heating speeds are also discussed. Furthermore, it is shown how the analysis and modeling of raw ellipsometric data can be used to determine the thermal properties of thin polymer films.

The evolution of total internal reflection Raman spectroscopy for the chemical characterization of thin films and interfaces.

Total internal reflection (TIR) optical spectroscopies have been widely used for decades as non-destructive and surface-sensitive measurements of thin films and interfaces. Under TIR conditions, an evanescent wave propagates into the sample layer within a region approximately 50nm to 2μm from the interface, which limits the spatial extent of the optical signal. The most common TIR optical spectroscopies are fluorescence (i.e., TIRF) and infrared spectroscopy (i.e., attenuated total reflection infrared). Despite the first report of TIR Raman spectroscopy appearing in 1973, this method has not received the same attention to date. While TIR Raman methods can provide chemical specific information, it has been outshined in many respects by surface-enhanced Raman spectroscopy (SERS). TIR Raman spectroscopy, however, is garnering more interest for analyzing the chemical and physical properties of thin polymer films, self-assembled monolayers (SAMs), multilayered systems, and adsorption at an interface. Herein, we discuss the early experimental and computational work that laid the foundation for recent developments in the use of TIR Raman techniques. Recent applications of TIR Raman spectroscopy as well as modern TIR Raman instruments capable of measuring monolayer-sensitive vibrational modes on smooth metallic surfaces are also discussed. The use of TIR Raman spectroscopy has been on a rise and will continue to push the limits for chemical specific interfacial and thin film measurements. Graphical abstract Total internal reflection (TIR) Raman spectroscopy can extract the chemical and physical information from thin films and adsorbates.

Revealing Interfacial Interactions in Random Copolymer Adsorbed Layers by Solvent Leaching.

Annealing a supported polymer film in the melt state results in the growth of an irreversibly adsorbed layer, which has been shown to influence thin film properties such as diffusion and glass transition temperature. Adsorbed layer growth is attributed to many simultaneous interactions between individual monomer units and the substrate, stabilizing chains against desorption. In this study, adsorbed layers of polystyrene (PS), poly(methyl methacrylate) (PMMA), and their random copolymers are isolated by select solvents. While PS adsorbed layer thickness is largely unaffected by the choice of washing solvent, the PMMA adsorbed layer completely desorbs when washed with tetrahydrofuran and chloroform, as opposed to toluene. Scaling relationships between adsorbed layer thickness and degree of chain adsorption at the substrate enable the use of adsorbed layer thickness to probe specific polymer-substrate interactions. Composition-dependent desorption trends indicate non-preferential adsorption between styrene and methyl methacrylate repeat units at the substrate, despite differences in substrate interaction strength. This insight contributes to the developing mechanism for the adsorption of random copolymers during melt-state annealing, further extending the ability to predict processing-inducted changes to the properties of polymer thin films to heterogeneous systems.

Molecular Doping of a Water‐Soluble Polythiophene Derivative

Intrinsic conducting polymers are promising candidates for bioelectronic devices due to their structural kinship to biological matter combined with electronic functionality. For sophisticated nano‐scaled bioelectronic devices, P3RT‐type polythiophene derivatives bearing water‐soluble, biocompatible sidechains are particularly appealing due to their well‐defined molecular structure and controllable end‐group composition. However, their employment in bioelectronic devices is not as straightforward as expected. Challenging is their poor performance due to, e.g., the low charge carrier concentration in the native state. Partial oxidation of these polymers by strong electron acceptors, so‐called p‐type doping, can increase the charge carrier concentration, and thus, the conductivity. The solution‐based molecular p‐type doping of such a water‐soluble polythiophene derivative by the dopant tetrafluoro‐tetracyano‐quinodimethane is reported. The mechanism of the doping process is thoroughly investigated by a combination of spectroscopic techniques covering the UV‐VIS and IR regions. Furthermore, the morphological and electronic properties of polymer thin films are examined as a dependence on the dopant concentration.

Investigating the mechanical and optical properties of thin PDMS film by flat-punched indentation

We investigated mechanical and optical properties of a thin polydimethylsiloxane (PDMS) film through a flat-punched indentation experiment and a finite element simulation. A microscopic imaging method was used to measure the compressive strain of thin PDMS films, and its corresponding bulk refractive index (RI) was estimated using the relation between density and refractive index. A total internal reflection (TIR) experiment was conducted to estimate the local RI values near the bottom surface of PDMS film. We obtained the correlations between force and indentation displacement in thin PDMS films (10–70 micron). Stress-strain curves present the non-linear deformation of PDMS film with the instantaneous modulus depending on the load and the thickness. Poisson's ratio of PDMS film is estimated by fitting with Yang's asymptotic solution and is inversely proportional to the aspect ratio between the radius of the flat punch probe and the film thickness. RI of PDMS film increases with the decreasing film thickness as well as the increasing load. The bulk RI was increased up to 1.476 by the compressing load while the bottom-surface RI was increased only up to 1.435. This difference is explained qualitatively through the localized stress-strain distribution from finite element analysis. An inhomogeneous stress-strain distribution is observed in the simulation with lower strain at the bottom of the film, corresponding to experiment. A lower strain leads to lower local density resulting in a lower refractive index. Our research provides fundamental insights into the correlation between mechanical and optical properties of thin polymer films.

Tuning relaxation dynamics and mechanical properties of polymer films of identical thickness.

Using dewetting as a characterization tool, we demonstrate that physical properties of thin polymer films can be regulated and tuned by employing variable processing conditions. For different molecular weights, the variable behavior of polystyrene films of identical thickness, prepared along systematically altered pathways, became predictable through a single parameter P, defined as the ratio of time required over time available for the equilibration of polymers. In particular, preparation-induced residual stresses, the corresponding relaxation times as well as the rupture probability of such films (of identical thickness) varied by orders of magnitude following scaling relations with P. Our experimental findings suggest that we can predictably enhance properties and hence maximize the performance of thin polymer films via appropriately chosen processing conditions.