Polystyrene Thin Films Research Articles

Diffusiophoretically Mediated Nanopatterning by Solvent Nanodroplets on Polystyrene Surfaces.

Dissolution is a ubiquitous process in nature and industry. However, due to technical difficulties, the detailed dissolution process at the nanoscale has seldom been captured experimentally. In this study, we investigated the dissolution dynamics in the confinement of toluene surface nanodroplets on polystyrene (PS) thin films in oversaturated toluene/water mixture solutions. This was achieved by adjusting the immersion durations from several minutes to 9 h. Dissolution takes place upon the deposition of nanodroplets on the PS surfaces, leading to the formation of surface nanostructures. Interestingly, we found that the induced nanostructures underwent complex morphological changes, from complex nanocraters with central bulges and/or multiple rims to simple nanocraters. We speculate that diffusiophoresis plays a key role in the formation of the complex nanocraters, as it facilitates the transportation of dissolved PS molecules inside the nanodroplets. We believe this finding not only enhances our understanding of dissolution dynamics at the nanoscale but also holds promise for applications in dissolution-based nanopatterning.

Surface modification and patterning of polymer thin films by plasma and adsorption behavior of proteins

The surface wettability property of hydrophobic polystyrene (PS) and hydrophilic polyethylene glycol (PEG) thin films subjected to modification by direct current plasma glow discharge is studied. The polymer films exhibited change of surface wettability on exposure to air, nitrogen, oxygen or argon plasmas. In PS films a swift modification to hydrophilic surface and subsequent steady recovery following first order kinetics are observed. The rate of modification and recovery are adjustable by adjusting the plasma ambient and parameters and additional wet-chemical treatment using ionic solutions. In PEG films the hydrophobic wettability evolve with ageing following the first order kinetics, and is stable for long period on exposure to air ambient. Moreover, a vapor deposition like process is possible using the PEG films as source to deposit self-assembled molecular layers with hydrophobic wettability on other surfaces. Using these surface modification or molecular deposition processes, the fabrication of wettability patterns in the surface of PS and PEG films and on other surfaces by vapor transport using PEG films, and also the possibility to produce gradient wettability patterns are demonstrated. Moreover, the adsorption behavior of immuno-specific system of proteins on surface modified hydrophilic PS films is studied.

Thickness-Dependent Segmental Dynamics in Supported Thin Films: Insights from a Dynamically Correlated Network Model.

A large body of experimental studies shows that the local dynamics in supercooled liquids are significantly altered by spatial nanoconfinement. In a previous study, we proposed a concept of a dynamically correlated network (DCN) model, which assumes that segments in a supercooled liquid undergo cooperative rearrangements within a network-like cluster. We further demonstrated that a model modified for freestanding thin films can predict for the glass transition dynamics in atactic polystyrene (PS) films consistent with experimental results. In this study, we adapted the model to apply it to supported thin films by introducing a layer of virtual vacant segments at the free surface and virtual anchoring segments at the liquid/substrate interface. The latter segments, carrying a finite number of virtual segments, reduce mobility at the interface. We evaluated the cooperative cluster size and distribution with respect to temperature and film thickness, along with the average relaxation time and glass transition temperature Tg for supported thin films of PS. The model predicted that the thickness dependence of Tg for PS becomes stronger with increasing time scale, and this result agreed well with experimental data across different timescales from pseudothermodynamic and dynamic measurements. The results provide insights into the origin of the dynamical decoupling between pseudothermodynamic and dynamic glass transition behaviors.

4]Rhombene: Solution‐Phase Synthesis and Application in Distributed Feedback Lasers With Emission Beyond 830 nm

AbstractGraphene‐like molecules with multiple zigzag edges are emerging as promising gain materials for organic lasers. Their emission wavelengths can vary widely, ranging from visible to near‐infrared (NIR), as the molecular size increases. Specifically, rhombus‐shaped molecular graphenes with two pairs of parallel zigzag edges, known as [n]rhombenes, are excellent candidates for NIR lasers due to their small energy gaps. However, synthesizing large‐size rhombenes with emission beyond 800 nm in solution remains a significant challenge. In this study, we present a straightforward synthesis of an aryl‐substituted [4]rhombene derivative, [4]RB‐Ar, using a method that combines intramolecular radical‐radical coupling with Bi(OTf)3‐mediated cyclization of vinyl ethers. The structure of [4]RB‐Ar was confirmed through X‐ray crystallographic analysis. Bond length analysis and theoretical calculations indicate that aromatic sextets are predominantly localized along the molecule's long axis. Significantly, [4]RB‐Ar demonstrates narrow amplified spontaneous emission at around 834 nm when dispersed in polystyrene thin films. Moreover, solution‐processed distributed feedback lasers employing [4]RB‐Ar as the active gain material display tunable narrow emissions in the range of 830 to 844 nm.

4]Rhombene: Solution-Phase Synthesis and Application in Distributed Feedback Lasers With Emission Beyond 830 nm.

Graphene-like molecules with multiple zigzag edges are emerging as promising gain materials for organic lasers. Their emission wavelengths can vary widely, ranging from visible to near-infrared (NIR), as the molecular size increases. Specifically, rhombus-shaped molecular graphenes with two pairs of parallel zigzag edges, known as [n]rhombenes, are excellent candidates for NIR lasers due to their small energy gaps. However, synthesizing large-size rhombenes with emission beyond 800 nm in solution remains a significant challenge. In this study, we present a straightforward synthesis of an aryl-substituted [4]rhombene derivative, [4]RB-Ar, using a method that combines intramolecular radical-radical coupling with Bi(OTf)3-mediated cyclization of vinyl ethers. The structure of [4]RB-Ar was confirmed through X-ray crystallographic analysis. Bond length analysis and theoretical calculations indicate that aromatic sextets are predominantly localized along the molecule's long axis. Significantly, [4]RB-Ar demonstrates narrow amplified spontaneous emission at around 834 nm when dispersed in polystyrene thin films. Moreover, solution-processed distributed feedback lasers employing [4]RB-Ar as the active gain material display tunable narrow emissions in the range of 830 to 844 nm.

Investigation of the effect of mass percentage concentration of polystyrene–toluene solution on the surface properties of the plasma‐treated polystyrene thin films

AbstractPolystyrene (PS) finds diverse applications across various fields, often necessitating a hydrophilic PS surface. In this study, the PS films were prepared using PS–toluene solutions of 15, 20, and 25 mass percentage concentrations (% w/v). Here, the main focus is on the influence of concentration on the hydrophilization of the prepared PS thin films under atmospheric pressure air dielectric barrier discharge plasma treatment. The contact angle, surface energy measurements, atomic force microscopy, and Fourier‐transform infrared spectroscopy analysis were conducted to evaluate the PS surface properties. Our results demonstrate, for the first time, the significant role of concentration in altering surface properties; the lower concentration of PS films leads to the most hydrophilic surface. Fourier‐transform infrared spectroscopy analysis confirms an increase in the OH functional group on the PS surface. atomic force microscopy analysis reveals needle‐shaped surface morphology, increased roughness and an expanded effective surface area. Surface energy analysis confirms an increase in the polar sector of surface energy. Overall, the findings from this research underscore the increase in film hydrophilicity with a decrease in PS–toluene concentration.Highlights Polystyrene (PS)–toluene solutions with different concentrations were prepared. PS–toluene films were spin‐coated and were been treated with dielectric barrier discharge plasma. The contact angle, surface energy measurements, atomic force microscopy, and Fourier‐transform infrared spectroscopy analysis were conducted. PS films with lower concentration have more impact from plasma treatment. Concentration, impact the hydrophilicity and roughness of treated PS films.

Creating Diverse Patterns on Thin Polystyrene Film through Water-in-Oil Emulsion Coating and Utilizing the Derived Hydrophilic Holes as a Microreactor

Creating Diverse Patterns on Thin Polystyrene Film through Water-in-Oil Emulsion Coating and Utilizing the Derived Hydrophilic Holes as a Microreactor

Determining the Characteristics of Ultrathin Polymer Films: A Spectroscopic Ellipsometry Approach.

Ellipsometry is a powerful and convenient technique that is widely used to determine the thickness and optical characteristics of polymer thin films. The determination is accomplished by modeling the measured change in the polarization of an electromagnetic wave upon interacting with the thin film. However, due to the strong statistical correlations between the fit parameters in the model, simultaneous determination of the thickness and the refractive indices of optically anisotropic ultrathin films using ellipsometry remains a challenge. Here, we propose an approach that can be used to obtain reliable values of both the thickness and the optical anisotropy of ultrathin polymer films. The approach was developed by performing spectroscopic ellipsometry measurements on thin films of hydrophobic polystyrene and hydrophilic chitosan of thickness between a few tens to a few hundred nm and whose absolute value of the birefringence differed by approximately an order of magnitude. Careful consideration of the characteristics of the root mean squared error of the fits obtained by modeling the ellipsometry data and the statistical correlations between the fit parameters formed the basis of the proposed approach.

Modulus alteration of thin polystyrene films by their neighboring PDMS: Soft and hard confinement.

It is highly demanded to understand the confinement effect on nanoconfined polymers. Recent studies reported a strong perturbation of local dynamics and substantial alteration of glass transition temperature Tg at nanoscale. However, how confinement affects the mechanical properties of polymers is not fully understood. Here, we show that the modulus of thin polymer films could be remarkedly altered through a polymer-polymer interface. The modulus of a thin polystyrene (PS) film next to a polydimethylsiloxane (PDMS) was determined from the PS-PDMS bilayer bulging test. A series of experiments show that the modulus of PS can be increased up to 37%, when the modulus of the neighboring PDMS varies from 1.04 to 4.88 MPa. The results demonstrate a strong sensitivity of mechanical properties of thin polymers to the hard/soft environment, which we attribute to the change of high-mobility layer by the polymer-polymer interface.

Evaluating Free Thermal Expansion and Glass Transition of Ultrathin Polymer Films on Heated Liquid.

Thermomechanical properties of ultrathin films are crucial for fabrication and use of reliable thin electronic devices. Due to the lack of precise measurement techniques, the thermal deformation behavior of ultrathin films has not yet been clarified. Here, we propose a film on heated liquid (FOHL) method to simultaneously measure the coefficient of thermal expansion (CTE) and glass transition temperature (Tg) of multiple ultrathin polymer films. Free thermal expansion of thin films without substrate interaction can be guaranteed when the thin films are afloat on a liquid surface. To investigate the thermal behavior in a wide temperature range, glycerol is adopted as a thermally stable heating platform owing to its high boiling point of 290 °C. The thin films are transferred onto the glycerol surface from the water surface using the hygroscopic properties of glycerol. Highly accurate and high-throughput thermal strain measurement is achieved using three-dimensional digital image correlation (3D-DIC). The thermomechanical properties of ultrathin polystyrene thin films of various thicknesses (25-400 nm) are precisely characterized utilizing the FOHL and 3D-DIC method.

Utilizing machine learning to model interdependency of bulk molecular weight, solution concentration, and thickness of spin coated polystyrene thin films

Utilizing machine learning to model interdependency of bulk molecular weight, solution concentration, and thickness of spin coated polystyrene thin films

A comparative study on the speed-up dynamics of drop spreading on floating and glass-supported polystyrene thin films

The enhanced spreading of a 2D drop on a stiff and free-standing elastic thin film theoretically investigated by Shanahan (Rev. Phys. Appl. 1988, 23, 1031–1037) has not been studied and verified experimentally. To shed a light on this interesting problem, herein, we perform comparison studies on the spreading behavior of a silicone oil drop on stiff polystyrene thin films supported by two different substrates: glass vs. water. Scaling analysis on the time evolution of the contact radius for the drop spreading on the films of varied thickness (∼40 nm to ∼600 nm) reveals the difference on the dynamics for the drop spreading on glass-supported and floating films. Upon fitting the spreading data by using the spreading model developed by de Ruijter et al. (Langmuir 1999, 15, 2209–2216), we are able to identify the speed-up effect for the drop spreading on water supported floating films, which progressively decreases with film thickness and diminishes when the thickness is greater than ∼200 nm. The elastic driving force that is responsible for the speed-up of the drop spreading on the floating film is evaluated empirically, which is found to decay exponentially with contact radius of the drop. The pre-factor and the decay length of the decay function are determined by film thickness and drop volume, resepctively. Our findings expect to facilitate developing new theories with practical relevance on the spreading dynamics of a liquid drop on elastic films.

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.

Combined X-ray Reflectivity and Infrared Study of the Effect of Hydrogen Bonding of the OH Group on the Relaxation Behavior in Ultrathin Polyvinylphenol Films on SiO2.

Utilizing X-ray reflectivity and infrared reflection absorption spectroscopy (IR-RAS), we have investigated the thermal expansion and contraction of ultrathin polyvinylphenol (PVPh) films supported on a silicon (100) substrate capped with an amorphous SiO2 layer. Despite being known to form strong interactions with the SiO2 surface, the thin PVPh films showed a reduction in the glass-transition point Tg, similar to the behavior of polystyrene thin films deposited on SiO2. We explored the relationship between thermal expansivity and film thickness using well-annealed films and found that it decreases with film thickness in the range below twice the radius of gyration of a polymer chain (2Rg) in the glassy state. Thickness expansion in the glassy state and contraction in thickness at temperatures higher than Tg bulk (melt state) showed the presence of two competing relaxation processes. The reported negative thermal expansion in PVPh thin films, which was discovered to be one of the inherent properties, may have been caused by the fast relaxations that take place at the free polymer surface. IR-RAS was utilized to investigate the effect of thickness on hydrogen bonding in PVPh, and it was confirmed that with decreasing thickness, hydrogen bonding becomes weak, and the number of free OH groups increases. Therefore, thinner PVPh samples exhibit lower Tgs as an effect of easier molecular motions.

Development of Nonclassical Photoprecursors for Rh2 Nitrenes.

Characterization of reactive intermediates in C-H functionalization is challenging due to the fleeting lifetimes of these species. Synthetic photochemistry provides a strategy to generate post-turnover-limiting-step intermediates in catalysis under cryogenic conditions that enable characterization. We have a long-standing interest in the structure and reactivity of Rh2 nitrene intermediates, which are implicated as transient intermediates in Rh2-catalyzed C-H amination. Previously, we demonstrated that Rh2 complexes bearing organic azide ligands can serve as solid-state and in crystallo photoprecursors in the synthesis of transient Rh2 nitrenoids. Complementary solution-phase experiments have not been available due to the weak binding of most organic azides to Rh2 complexes. Furthermore, the volatility of the N2 that is evolved during in crystallo nitrene synthesis from these precursors has prevented the in crystallo observation of C-H functionalization from lattice-confined nitrenes. Motivated by these challenges, here we describe the synthesis and photochemistry of nonclassical nitrene precursors based on sulfilimine ligands. Sulfilimines bind to Rh2 carboxylate complexes more tightly than the corresponding azides, which has enabled the full solid-state and solution-phase characterization of these new complexes. The higher binding affinity of sulfilimine ligands as compared with organic azides has enabled both solution-phase and solid-state nitrene photochemistry. Cryogenic photochemical studies of Rh2 sulfilimine complexes confined within polystyrene thin films demonstrate that sulfilimine photochemistry can be accomplished at low temperature but that C-H amination is rapid at temperatures compatible with N═S photoactivation. The potential of these structures to serve as platforms for multistep in crystallo cascades is discussed.

Fused Triangulene Dimers: Facile Synthesis by Intramolecular Radical‐Radical Coupling and Application for Near‐Infrared Lasers

AbstractLarge graphene‐like molecules with four zigzag edges are ideal gain medium materials for organic near‐infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical‐radical coupling approach and successfully synthesize two fused triangulene dimers (1 a/1 b) efficiently. X‐ray crystallographic analysis of 1 a indicates that there is no intermolecular π‐π stacking in the solid state. When the more soluble derivative 1 b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1 b as the active gain material, we fabricate solution‐processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790 nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics.

Fused Triangulene Dimers: Facile Synthesis by Intramolecular Radical-Radical Coupling and Application for Near-Infrared Lasers.

Large graphene-like molecules with four zigzag edges are ideal gain medium materials for organic near-infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical-radical coupling approach and successfully synthesize two fused triangulene dimers (1 a/1 b) efficiently. X-ray crystallographic analysis of 1 a indicates that there is no intermolecular π-π stacking in the solid state. When the more soluble derivative 1 b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1 b as the active gain material, we fabricate solution-processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790 nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics.

Lamellar orientation at the surface of isotactic polystyrene thin films analyzed by sum frequency generation spectroscopy.

Analyzing the orientation of polymeric crystalline lamella at the surface of thin films can be challenging. Even though atomic force microscopy (AFM) is often sufficient for this analysis, there are cases when imaging is not sufficient to confidently determine lamellar orientation. Here, we used sum frequency generation (SFG) spectroscopy to analyze the lamellar orientation at the surface of semi-crystalline isotactic polystyrene (iPS) thin films. The SFG orientation analysis indicated that the iPS chains are oriented perpendicular to the substrate (flat-on lamellar orientation), which was confirmed by AFM. By analyzing the evolution of the SFG spectral features with the progress of crystallization, we demonstrated that the ratios of the SFG intensities of the phenyl ring resonances are a good indication of the surface crystallinity. Furthermore, we explored the challenges associated with SFG measurements of heterogeneous surfaces, which is commonly present in many semi-crystalline polymeric films. To the best of our knowledge, this is the first time that the surface lamellar orientation of semi-crystalline polymeric thin films was determined by SFG. Also, this work pioneers in reporting the surface conformation of semi-crystalline and amorphous iPS thin films by SFG and in linking the SFG intensity ratios to the progress of the crystallization and the surface crystallinity. This study demonstrates the potential applicability of SFG spectroscopy in the conformational analysis of polymeric crystalline structures at interfaces and opens the way to the investigation of more complex polymeric structures and crystalline arrangements, especially for the case of buried interfaces, where AFM imaging is not an option.

Copper coated PEEK hollow waveguide and durability investigations for low-loss and bendable transmission of low-frequency terahertz wave

This work aims to develop a low-loss, bendable and durable terahertz (THz) hollow waveguide (HWG) based on cost-effective copper (Cu) and polyether-ether-ketone (PEEK) tubing. The as-prepared PEEK/Cu-coated HWG exhibited low transmission losses of 1.37–2.31 dB/m at 0.3 THz and 1.77–4.42 dB/m at 0.1 THz under bending conditions (0°-180°, radius 15 cm). The waveguide was found to be vulnerable to damage from the copper oxidation, especially in hot and humid environment, which could cause the transmission loss increasing up to 17.11 dB/m after 80 h of accelerated aging treatment (85 °C,85 RH%). In addition, the transmission loss reached 7.01 dB/m after six times temperature cycling tests (-40 °C-85 °C). A thin (∼300 nm) uniform polystyrene (PS) film was deposited on the copper reflective layer to improve its oxidation-resistant performances. The Cu/PS HWG achieved low transmission losses of 1.41–2.47 dB/m at 0.3 THz and 1.80–4.63 dB/m at 0.1 THz (0°–180°) and little deterioration in transmission loss (<0.11 dB/m) after even 200 h of aging treatment and ten times temperature cycling tests. The dispersion |β2| of this waveguide sample is less than 1.59 ps/THz/m within 0.3–1.5 THz range. The results show that the Cu/PS PEEK HWG could enable low-loss, bendable and durable transmission of low-frequency THz wave and can be potentially used in some practical applications such as THz sensing and 6G communication.

Tuning the Plasticization to Decouple the Effect of Molecular Recoiling Stress from Modulus and Viscosity in Dewetting Thin Polystyrene Films

Tuning the Plasticization to Decouple the Effect of Molecular Recoiling Stress from Modulus and Viscosity in Dewetting Thin Polystyrene Films