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Utilizing colloidal probe, lateral force microscopy and simultaneous confocal microscopy, combined with finite element analysis, we investigate how a microparticle starts moving laterally on a soft, adhesive surface. We find that the surface can form a self-contacting crease at the leading front, which results from a buildup of compressive stress. Experimentally, creases are observed on substrates that exhibit either high or low adhesion when measured in the normal direction, motivating the use of simulations to consider the role of adhesion energy and interfacial strength. Our simulations illustrate that the interfacial strength plays a dominating role in the nucleation of a crease. After the crease forms, it progresses through the contact zone in a Schallamach wave-like fashion. Interestingly, our results suggest that this Schallamach wave-like motion is facilitated by free slip at the adhesive, self-contacting interface within the crease.

 

Variable-pressure electron-beam lithography (VP-EBL) employs an ambient gas at subatmospheric pressures to reduce charging during electron-beam lithography. VP-EBL has been previously shown to eliminate pattern distortion and provide improved resolution when patterning poly(methyl methacrylate) (PMMA) on insulating substrates. However, it remains unknown how water vapor affects the contrast and clearing dose nor has the effect of water vapor on the negative-tone behavior of PMMA been studied. In addition, water vapor has recently been shown to alter the radiation chemistry of the VP-EBL process for Teflon AF. Such changes in radiation chemistry have not been explored for PMMA. In this work, VP-EBL was conducted on conductive substrates to study the effect of water vapor on PMMA patterning separately from the effects of charge dissipation. In addition, both positive and negative-tone processes were studied to determine the effect of water vapor on both chain scission and cross-linking. The contrast of PMMA was found to improve significantly with increasing water vapor pressure for both positive and negative-tone patterning. The clearing dose for positive-tone patterning increases moderately with vapor pressure as would be expected for electron scattering in a gas. However, the onset set dose for negative-tone patterning increased dramatically with pressure revealing a more significant change in the exposure mechanism. X-ray photoelectron spectra and infrared transmission spectra indicate that water vapor only slightly alters the composition of exposed PMMA. Also, electron scattering in water vapor yielded a much larger clear region around negative-tone patterns. This effect could be useful for increasing the range of the developed region around cross-linked PMMA beyond the backscattered electron range. Thus, VP-EBL for PMMA introduces a new means of tuning clearing/onset dose and contrast, while allowing additional control over the size of the cleared region around negative-tone patterns.

 

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi–steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hourT₈₅at maximum power point under 1-sun illumination. 

Metal‐coordinated hydrogels can form a percolated network with transient bonds due to metal ions‐functional group coordination. Each metal ion can link with more than one ligand, leading to intricate speciation of bonding modes. While the mechanics of transient gels made with four‐arm polymers are often studied, less is known about how increasing the number of arms affects the modulus. Using shear rheology, the modulus of hydrogels prepared from four‐, six‐, and eight‐armed poly(ethylene glycols), functionalized with histidine ligands that complex with nickel (II) ions is measured. These gels have matched polymer wt.% and varied pH to compare their moduli. It is considered whether the modulus can be described by established polymer network models by calculating the speciation of metal‐coordinated cross‐links and then incorporating it into a phantom network prediction. This study finds that 1) increasing the number of polymer arms increases the modulus, 2) the phantom network allows reasonable modulus approximation for four‐arm and six‐arm gels, and 3) the modulus of eight‐arm gels exceeds the phantom network prediction. Since polymer cores act as chemical cross‐links and metal‐coordinated cross‐links form network strands, it is possible that increasing the number of metal‐coordinated linkages per molecule reinforces the chemical cross‐link at the polymer core.

 

When a water drop is placed onto a soft polymer network, a wetting ridge develops at the drop periphery. The height of this wetting ridge is typically governed by the drop surface tension balanced by elastic restoring forces of the polymer network. However, the situation is more complex when the network is swollen with fluid, because the fluid may separate from the network at the contact line. Here we study the fluid separation and network deformation at the contact line of a soft polydimethylsiloxane (PDMS) network, swollen with silicone oil. By controlling both the degrees of crosslinking and swelling, we find that more fluid separates from the network with increasing swelling. Above a certain swelling, network deformation decreases while fluid separation increases, demonstrating synergy between network deformation and fluid separation. When the PDMS network is swollen with a fluid having a negative spreading parameter, such as hexadecane, no fluid separation is observed. A simple balance of interfacial, elastic, and mixing energies can describe this fluid separation behavior. Our results reveal that a swelling fluid, commonly found in soft networks, plays a critical role in a wetting ridge.

 

Small scale contact between a soft, liquid-coated layer and a stiff surface is common in many situations, from synovial fluid on articular cartilage to adhesives in humid environments. Moreover, many model studies on soft adhesive contacts are conducted with soft silicone elastomers, which possess uncrosslinked liquid molecules ( i.e. silicone oil) when the modulus is low. We investigate how the thickness of a silicone oil layer on a soft substrate relates to the indentation depth of glass microspheres in contact with crosslinked PDMS, which have a modulus of <10 kPa. The particles indent into the underlying substrate more as a function of decreasing oil layer thickness. This is due to the presence of the liquid layer at the surface that causes capillary forces to pull down on the particle. A simple model that balances the capillary force of the oil layer and the minimal particle–substrate adhesion with the elastic and surface tension forces from the substrate is proposed to predict the particle indentation depth.