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In polymers, the equilibrium state is achieved when the chains have access to the maximum number of conformational states, which allows them to explore a larger conformational space, leading to an increase in the entropy of the system. Preparation of thin polymer films using the spin-coating technique results in polymer chains being locked in a nonequilibrium state with lower entropy due to possible stretching of chains during the process. Allowing enough time for recovery results in the relaxation of the spin-coating-induced molecular recoiling stress. Annealing such a film generates entropy due to its inherent irreversibility. We employed the dewetting technique to determine the molecular recoiling stress relaxation time in poly-(tertbutyl styrene) thin films. Furthermore, we qualitatively differentiated the metastable states achieved by the polymer film using entropy generation in a relaxing polymer film as an effect of thermal entropy and associated it with the conformational entropy of polymer chains utilizing the molecular recoiling stress relaxation time. This enabled us to explain molecular recoiling stress relaxation using a rather simplistic approach involving segmental level molecular rearrangements in polymer chains by attaining transient metastable states through an entropically activated process driving toward equilibrium. [ABSTRACT FROM AUTHOR]

Polymers when confined to a dimension comparable to the length scale of polymer chain coils such as thin films, often lead to molecular relaxation processes distinct from their bulk counterpart. Often observed as thermal and mechanical responses such relaxation has been frequently associated with the squeezing of polymer chains having conformations trapped far from thermodynamic equilibrium and subsequently generating processing‐induced molecular recoiling stress. Relaxation in polymer films can be modified by tuning the molecular recoiling stress, which is directly influenced by the preparation conditions of the polymer thin films. Hence a comprehensive understanding of the genesis and relaxation of molecular recoiling stress becomes necessary. Here, we provide insights into the nonequilibrium nature observed in polymer thin films, focusing majorly on the investigations into the molecular recoiling stress using the dewetting technique. The impact of various factors like temperature of dewetting, thickness of films, molecular weight of polymers, and physical aging affecting the relaxation of molecular recoiling stress is discussed. In addition, discussions on the possible mechanisms of relaxation and modification of molecular recoiling stress by varying the spin‐coating speed and addition of plasticizers are also provided. An alternate approach which gives a new perspective into the relaxation of molecular recoiling stress considering the entropy generated during the dewetting of polymer films is also included. The present work is expected to give the reader a comprehensive understanding of the characteristics of molecular recoiling stress relaxation occurring in polymer thin films. [ABSTRACT FROM AUTHOR]

Designing metal–organic framework (MOF)-based solid nanoparticles to stabilize Pickering emulsions by fine-tuning their hydrophobicity and lipophobicity is vital for essential applications and fundamental understanding. We demonstrate in situ grafting of palmitic acid in UiO-66 MOF through its linker defects. Our designed and activated nanoparticles (denoted as UP′) stabilized the Pickering emulsions of n-heptane-in-water. Furthermore, we showed how UP′ stabilized emulsion droplets disperse in media by covering each tiny droplet with a nanoscale layer made of UP′. To support our claim, we carried out the freeze-drying process to remove the liquid part from the emulsion, leaving behind the solid shell-like microstructures that we further characterized through several microscopic techniques. The stable n-heptane-in-water emulsion was confirmed by dilution (drop test), conductivity, zeta potential, and theoretical surface electrostatic potential measurements. Rheological studies indicate that the Pickering emulsions of n-heptane-in-water stabilized by UP′ are much more resistant to deformation and flow imparting higher (mechanical) stability and shelf-life. Pickering emulsions stabilized by UP′ emerged as a versatile way to design smart functional materials of UiO-66 through engineering linker defects that may have potential applications in interfacial catalysis, dye or contaminant separation, etc. [ABSTRACT FROM AUTHOR]

Recently, inorganic perovskite materials have been attracting increasing attention owing to their exceptional structural, electronic, and optical characteristics in photovoltaic technology. Ca3AsI3 is a semiconductor material that shares similarities with the group of inorganic metal halide perovskites. Ca3AsI3 possesses a perovskite crystal structure that is cubic, which is classified under the space group Pm-3m (no. 221). Our research aims to analyze how the optical and electronic properties of Ca3AsI3 are influenced by spin–orbit coupling (SOC) and strain using the first-principles density-functional theory. The inorganic Ca3AsI3 perovskite has an electronic band structure that possesses a direct bandgap of roughly 1.58 eV at the Γ(gamma)-point. However, when the SOC relativistic effect is introduced, this value decreases to around 1.27 eV. As the level of compressive strain is increased, the bandgap becomes narrower, whereas with increasing tensile strain, the bandgap becomes wider. It has been observed through analysis of the dielectric functions, absorption coefficient, and electron loss function of these materials that the optical properties give Ca3AsI3 the ability to effectively absorb visible light. According to the study, the dielectric constant peaks of Ca3AsI3 shift toward a lower photon energy (redshift) as the level of compressive strain increases. On the other hand, when subjected to increased tensile strain, these peaks have a tendency to shift toward a higher photon energy (blueshift), as per the same study. Modifying the energy gap of Ca3AsI3 perovskites to suit optoelectronic and solar cell needs could be achieved by using techniques involving the SOC effect and by applying strain. These approaches have the potential to enable utilization of Ca3AsI3 in such applications in the future. [ABSTRACT FROM AUTHOR]

In organic photovoltaic blends, there is a trade-off between exciton harvesting and charge extraction because of the short exciton diffusion length. Developing a way of increasing exciton diffusion length would overcome this trade-off by enabling efficient light harvesting from large domains. In this work, we engineered (enhanced) both exciton diffusion length and domain size using solvent vapour annealing (SVA). We show that SVA can give a three-fold enhancement in exciton diffusion coefficient (D) and nearly a doubling of exciton diffusion length. It also increases the domain size, leading to enhancement of charge extraction efficiency from 63 to 89%. Usually larger domains would reduce exciton harvesting but this is overcome by the large increase in exciton diffusion, leading to a 20% enhancement in device efficiency. [ABSTRACT FROM AUTHOR]

Abstract: Characterization of polymers at the nanometer‐length scale has become increasingly important with the growth and expansion of nanotechnology. Due to limitations of sensitivity and specificity that persist with traditional materials characterization techniques, there is a growing need to develop new tools to measure the properties of confined polymer systems. Within the past 20 years, fluorescence characterization techniques have emerged to address this challenge. This review focuses on the employment of fluorescence techniques such as temperature‐ and time‐dependent steady‐state intensity, fluorescence recovery after photobleaching, and nonradiative energy transfer to study polymer behavior at the nanoscale. Properties discussed include glass transition temperature, physical aging, diffusion and mobility, and mechanical response. Particular attention is given to the unique insight gained through these techniques as well as opportunities for future studies. The ability of fluorescence to obtain location‐ and component‐specific measurements with nanometer resolution for a variety of polymer chemistries and geometries on a bench‐top instrument provides a valuable contribution to the characterization and understanding of polymers at the nanoscale. [ABSTRACT FROM AUTHOR]

The control of structure and thermal stability in semicrystalline polymer films remains an important challenge in applications ranging from solar energy devices to packaging films. Here, we demonstrate the ability to dramatically alter the morphology and melting temperature (Tm) of low-molecular-weight linear polyethylene (PE) by employing an innovative vapor-assisted deposition process termed matrix assisted pulsed laser evaporation (MAPLE). We report the ability to tune Tm of PE films by 20 °C by simply adjusting the deposition temperature during MAPLE processing. This unique capability stems from the ability of MAPLE to exploit confined crystallization during thin film growth. In addition, we demonstrate the ability to exploit MAPLE to design PE films that exhibit the same Tm as their melt-crystallized analogues but have an ~25% higher degree of crystallinity. Our investigation offers new insights into how confinement effects in polymer crystallization can be utilized in the emerging field of polymer film fabrication by MAPLE to control structure and key material properties of semicrystalline polymer films. [ABSTRACT FROM AUTHOR]

Using X-ray reflectivity, spectroscopic ellipsometry and Raman spectroscopy, we have studied the stratified structure and the two glass-like thermal transitions in sufficiently aged glassy polystyrene films. We find that favorable interaction between the solid substrate and the polymer film induces stratification within the film resulting in different densities across the film thickness. Existence of two glass-like thermal transitions (one at 70 °C and the other at 95 °C) is independently confirmed by temperature dependent spectroscopic ellipsometry and Raman spectroscopy measurements. Interestingly, the thermal coefficient of expansion of the polymer film displays anomalous behavior with temperature and is found to have the lowest value over the temperature range 70–95 °C, i.e. between the two observed glass-like thermal transition temperatures. [ABSTRACT FROM AUTHOR]

ABSTRACT We have studied the dewetting process of thin polystyrene films on nonwettable substrates in the viscoelastic regime slightly above the glass transition temperature. The evolution of the shape of the dewetting rim for varying film thickness, molecular weights and dewetting temperatures allowed us to determine the relaxation rates of residual stresses, which originated from nonequilibrated polymer chain conformations formed during film preparation by spin-coating. For long chain polymers, we found rates notably faster than the longest bulk relaxation processes, highly independent of molecular weight and temperature. Our study demonstrates that dewetting is a powerful tool for sensitive characterization of nonequilibrium properties of thin polymer films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 515-523 [ABSTRACT FROM AUTHOR]

Both spin-coating and thermal annealing of thin supported glassy polymer films generally cause stresses arising from rapid solvent evaporation and from a mismatch in expansivities of film and substrate, respectively. While films on adhesive surfaces are typically stable, on slippery substrates film stability is sensitively determined by the thermal protocol, revealing the presence of these stresses. There, contraction of the film upon cooling causes in-plane tensile stresses that can lead to film fracture. While this is a general effect, the details of the film's response to thermal cycling allow to disentangle the origin of stresses within the film. For high molecular weight polymers, we found that preparation-induced stresses cause substantially reduced thermal expansivities. This demonstrates that intrinsic out-of-equilibrium states in spin-coated glassy films of long polymers are long-lived and thus difficult to equilibrate. [ABSTRACT FROM AUTHOR]

We have investigated the consequences of physical aging in thin spin-coated glassy polystyrene films through detailed dewetting studies. A simultaneous and equally fast exponential decay of dewetting velocity, width, and height of the rim with aging time was observed, which is related to a reduction of residual stresses within such films. The temperature dependence of these decay times followed an Arrhenius behavior, yielding an activation energy of 70 ± 6 kJ/mol, on the same order of magnitude as values for the β-relaxation of polystyrene and for relaxations of surface topographical features. Our results suggest that rearrangements at the level of chain segments are sufficient to partially relax frozen-in out-of-equilibrium local chain conformations, i.e., the cause of residual stresses, and they might also be responsible for macroscopic relaxations at polymer surfaces. [ABSTRACT FROM AUTHOR]

Polymer confinement is realized in hybrid nanocomposites where individual polymer molecules are confined by a nanoporous matrix to dimensions less than the molecular size of the polymer. Here it is shown that by functionalizing the interior pore surfaces of a nanoporous organosilicate matrix, the pores can be filled with polystyrene molecules to achieve extreme levels of molecular confinement not previously possible. This provides opportunities for unique thermal and mechanical properties. It is shown that pore surface functionalization markedly impacts the polymer mobility during polymer infiltration by affecting the polymer–pore surface interaction, addressing the challenge of filling high‐molecular‐weight polymer molecules into nanoscale‐confined spaces. This allows for achieving extreme levels of molecular confinement with the loss of interchain entanglement and extensive polymer elongation along the pore axis. The glass transition temperature of the polymer is suppressed compared to bulk polymer melt, and is significantly affected by the polymer–surface interaction, which changes the polymer segmental mobility. The polymer–surface interaction also affects the interfacial polymer–pore sliding shear stress during polymer pullout from the nanopores, markedly affecting the fracture resistance of the nanocomposite. [ABSTRACT FROM AUTHOR]

Competing Interests: The authors have no conflicts of interest.

The nanoconfinement effects of glassy polymer thin films on their thermal and mechanical properties have been investigated thoroughly, especially with an emphasis on its altered glass transition behavior compared to bulk polymer, which has been known for almost three decades. While research in this direction is still evolving, reaching new heights to unravel the underlying physics of phenomena observed in confined thin polymer films, we have a much clearer picture now. This, in turn, has promoted their application in miniaturized and functional applications. To extract the full potential of such confined films, starting from their fabrication, function, and various applications, we must realize the necessity to have an understanding and availability of robust characterization protocols that specifically target thin film thermo-mechanical stability. Being nanometer-sized in thickness, often atop a solid substrate, direct mechanical testing on such films becomes extremely challenging and often encounters serious complexity from the dominating effect of the substrate. In this review, we have compiled together a few important novel and promising techniques for mechano-rheological characterization of glassy polymer thin films. The conceptual background involved in each technique, constitutive equations, methodology, and current status of research are touched upon following a pedagogical tutorial approach. Further, we discussed each technique's success and limitations, carefully covering the puzzling or contradicting observations reported within the broad nexus of glass transition temperature-viscosity-modulus-molecular mobility (including diffusion and relaxation)., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The remarkable performance of copper indium gallium selenide (CIGS)-based double heterojunction (DH) photovoltaic cells is presented in this work. To increase all photovoltaic performance parameters, in this investigation, a novel solar cell structure (FTO/SnS 2 /CIGS/Sb 2 S 3 /Ni) is explored by utilizing the SCAPS-1D simulation software. Thicknesses of the buffer, absorber and back surface field (BSF) layers, acceptor density, defect density, capacitance-voltage ( C - V ), interface defect density, rates of generation and recombination, operating temperature, current density, and quantum efficiency have been investigated for the proposed solar devices with and without BSF. The presence of the BSF layer significantly influences the device's performance parameters including short-circuit current ( J sc ), open-circuit voltage ( V oc ), fill factor (FF), and power conversion efficiency (PCE). After optimization, the simulation results of a conventional CIGS cell (FTO/SnS 2 /CIGS/Ni) have shown a PCE of 22.14% with V oc of 0.91 V, J sc of 28.21 mA cm -2 , and FF of 86.31. Conversely, the PCE is improved to 31.15% with V oc of 1.08 V, J sc of 33.75 mA cm -2 , and FF of 88.50 by introducing the Sb 2 S 3 BSF in the structure of FTO/SnS 2 /CIGS/Sb 2 S 3 /Ni. These findings of the proposed CIGS-based double heterojunction (DH) solar cells offer an innovative method for realization of high-efficiency solar cells that are more promising than the previously reported traditional designs., Competing Interests: The authors have no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Designing metal-organic framework (MOF)-based solid nanoparticles to stabilize Pickering emulsions by fine-tuning their hydrophobicity and lipophobicity is vital for essential applications and fundamental understanding. We demonstrate in situ grafting of palmitic acid in UiO-66 MOF through its linker defects. Our designed and activated nanoparticles (denoted as UP') stabilized the Pickering emulsions of n -heptane-in-water. Furthermore, we showed how UP' stabilized emulsion droplets disperse in media by covering each tiny droplet with a nanoscale layer made of UP'. To support our claim, we carried out the freeze-drying process to remove the liquid part from the emulsion, leaving behind the solid shell-like microstructures that we further characterized through several microscopic techniques. The stable n -heptane-in-water emulsion was confirmed by dilution (drop test), conductivity, zeta potential, and theoretical surface electrostatic potential measurements. Rheological studies indicate that the Pickering emulsions of n -heptane-in-water stabilized by UP' are much more resistant to deformation and flow imparting higher (mechanical) stability and shelf-life. Pickering emulsions stabilized by UP' emerged as a versatile way to design smart functional materials of UiO-66 through engineering linker defects that may have potential applications in interfacial catalysis, dye or contaminant separation, etc .

We utilized fast scanning calorimetry to characterize the glass transition temperature ( T g ) and intrinsic molecular mobility of low-molecular-weight poly( n -butyl methacrylate) thin films of varying thicknesses. We found that the T g and intrinsic molecular mobility were coupled, showing no film thickness-dependent variation. We further employed a unique noncontact capillary nanoshearing technique to directly probe layer-resolved gradients in the rheological response of these films. We found that layer-resolved shear mobility was enhanced with a reduction in film thickness, whereas the effective viscosity decreased. Our results highlight the importance of polymer-substrate attractive interactions and free surface-promoted enhanced mobility, establishing a competitive nanoconfinement effect in poly( n -butyl methacrylate) thin films. Moreover, the findings indicate a decoupling in the thickness-dependent variation of T g and intrinsic molecular mobility with the mechanical responses (shear mobility and effective viscosity)., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

We report morphological regulation of NaCl (sodium chloride) crystals through the evaporative crystallisation process of microdroplets containing a cationic surfactant CTAB (cetyltrimethylammonium bromide). Various fascinating evaporative salt morphologies are observed using different combinations of salt ( C NaCl ) and surfactant ( C CTAB ) concentrations. Each observed morphology is carefully explained by the interplaying physical phenomena, such as crystallisation, micellisation, evaporative dewetting, and surface adsorption of anionic couneterions. Salt morphologies are investigated for low ( C NaCl = 0.1 (M)), intermediate ( C NaCl = 0.5 (M)) and high ( C NaCl = 2 (M)) concentrations, whereas surfactant concentrations are varied four orders of magnitudes (from 0.0001 (M) to 0.1 (M)). Interestingly, we observe a threshold in C CTAB at 0.001 (M), beyond which the peripheral rings of dried deposits are found to be composed of CTAB for C NaCl = 0.1 (M), while the same is seen to be made up of NaCl for C NaCl = 2 (M). We have explained the morphological evolution by the process of competitive surface adsorption phenomenon between Cl - and Br - counter ions. Such a detailed study of saline droplet crystallisation in the presence of a cationic surfactant underpins the fundamental understanding of the crystallisation process. In addition, it may further impact application sectors where crystallisation of saline solution plays an important role, especially in the presence of additives.

The influence of various processing conditions on the singlet exciton diffusion is explored in films of a conjugated random copolymer poly-(3-hexylthiophene-co-3-dodecylthiophene) (P3HT-co-P3DDT) and correlated with the degree of crystallinity probed by grazing incidence X-ray scattering and with exciton bandwidth determined from absorption spectra. The exciton diffusion coefficient is deduced from exciton-exciton annihilation measurements and is found to increase by more than a factor of three when thin films are annealed using CS 2 solvent vapour. A doubling of exciton diffusion coefficient is observed upon melt annealing at 200 °C and the corresponding films show about 50% enhancement in the degree of crystallinity. In contrast, films fabricated from polymer solutions containing a small amount of either solvent additive or nucleating agent show a decrease in exciton diffusion coefficient possibly due to formation of traps for excitons. Our results suggest that the enhancement of exciton diffusivity occurs because of increased crystallinity of alkyl-stacking and longer conjugation of aggregated chains which reduces the exciton bandwidth.

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh 2 ) 2 . Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton-exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10 -3 to 3.6 × 10 -3 cm 2 s -1 , resulting in an enhancement of the mean two-dimensional exciton diffusion length (L D = (4Dτ) 1/2 ) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions.

When geometrically confined to the nanometer length scale, a condition in which a large portion of the material is in the nanoscale vicinity of interfaces, polymers can show astonishing changes in physical properties. In this investigation, we employ a unique noncontact capillary nanoshearing method to directly probe nanoresolved gradients in the rheological response of ultrathin polymer films as a function of temperature and stress. Results show that ultrathin polymer films, in response to an applied shear stress, exhibit a gradient in molecular mobility and viscosity that originates at the interfaces. We demonstrate, via molecular dynamics simulations, that these gradients in molecular mobility reflect gradients in the average segmental relaxation time and the glass-transition temperature.

Phthalocyanines and their main group and metal complexes are important classes of organic semiconductor materials but are usually highly insoluble and so frequently need to be processed by vacuum deposition in devices. We report two highly soluble silicon phthalocyanine (SiPc) diester compounds and demonstrate their potential as organic semiconductor materials. Near-infrared (λ(EL) = 698-709 nm) solution-processed organic light-emitting diodes (OLEDs) were fabricated and exhibited external quantum efficiencies (EQEs) of up to 1.4%. Binary bulk heterojunction solar cells employing P3HT or PTB7 as the donor and the SiPc as the acceptor provided power conversion efficiencies (PCE) of up to 2.7% under simulated solar illumination. Our results show that soluble SiPcs are promising materials for organic electronics.

We have examined the aging behavior of spin-cast thin polymer films as a function of their processing history. Films prepared from solutions close to the Θ temperature were aged for varying times at room temperature, followed by a dewetting experiment above the glass transition temperature of the polymer. The characteristic aging time varied strongly with the quality of the solvent, which is attributed to distorted chain conformations in the as-cast films. This is an indication for the nonequilibrium nature of thin polymer films, possibly causing some of their unexplained properties.