Patterning of Organic Semiconductors Leads to Functional Integration: From Unit Device to Integrated Electronics.

The use of organic semiconductors in electronic devices, including transistors, sensors, and memories, unlocks innovative possibilities such as streamlined fabrication processes, enhanced mechanical flexibility, and potential new applications. Nevertheless, the increasing technical demand for patterning organic semiconductors requires greater integration and functional implementation. This paper overviews recent efforts to pattern organic semiconductors compatible with electronic devices. The review categorizes the contributions of organic semiconductor patterning approaches, such as surface-grafting polymers, capillary force lithography, wettability, evaporation, and diffusion in organic semiconductor-based transistors and sensors, offering a timely perspective on unconventional approaches to enable the patterning of organic semiconductors with a strong focus on the advantages of organic semiconductor utilization. In addition, this review explores the opportunities and challenges of organic semiconductor-based integration, emphasizing the issues related to patterning and interconnection.

Fabrication of nanomolded Nafion thin films with tunable mechanical and electrical properties using thermal evaporation-induced capillary force lithography.

In this paper, we report a simple and facile method to fabricate nanomolded Nafion thin films with tunable mechanical, and electrical properties. To achieve this, we combine a novel thermal evaporation-induced capillary force lithography method with swelling process to obtain enhanced pattern fidelity in nanomolded Nafion films. We demonstrate that structural fidelity and mechanical properties of patterned Nafion thin films can be modulated by changing fabrication parameters such as swelling time, Nafion polymer concentration, and curing temperature. Interestingly, we also find that impedance properties of nanomolded Nafion thin films are associated with the Nafion polymer concentration and curing temperature. In particular, 20% Nafion thin films exhibit greater impedance stability and lower impedance values than 5% Nafion thin films at lower frequencies. Moreover, curing temperature-specific impedance changes are observed. These results suggest that capillary lithography can be used to fabricate Nafion nanostructures with high pattern fidelity capable of modifying mechanical and electrical properties of Nafion thin films.

Orientation Control of Semiconducting Polymers Using Microchannel Molds.

The molecular orientation of organic semiconductors (OSCs) is of fundamental importance to anisotropic electrical behavior as well as superior properties in practical applications. Here, a simple and effective method is demonstrated to fabricate highly oriented semiconducting polymers, poly(3-hexylthiophene) (P3HT) and poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)), by mass transfer effect under microchannel molds by diffusion and convection. Furthermore, parallel or perpendicular molecular arrangements relative to the channel direction were achieved by varying the widths of the microchannels, which are directly observed using polarized optical microscopy and two-dimensional grazing-incidence X-ray diffraction experiments. The method could enable the fabrication of organic field-effect transistors that exhibit anisotropic electrical properties indicating inter- or intrachain charge transport. The resulting platform will provide a simple approach for multidirectional orientations of anisotropic OSCs.

Engineering Nano-to-Micron-Patterned Polymer Coatings on Bioresorbable Magnesium for Controlling Human Endothelial Cell Adhesion and Morphology.

Surface patterning is an attractive approach to modify the surface of biomaterials for modulating cell activities and enhancing the performance of medical implants without involving typical chemical changes to the implants such as adding growth factors, antibiotics, and drugs. In this study, nano-to-micron patterns were engineered on thermoplastic and thermoset polymer coatings on bioresorbable magnesium (Mg) substrates to control the cellular responses and material degradation for vascular applications. Capillary force lithography (CFL) was modified and integrated with spray coating to fabricate well-aligned nano-to-micron patterns on the thermoplastic poly(lactic-co-glycolic acid) (PLGA) and thermoset poly(glycerol sebacate) (PGS) coatings on Mg substrates. Specifically, a new process of molding-curing CFL was revised from the conventional CFL to successfully create nano-to-submicron patterns on thermoset PGS for the first time. The nano-to-micron-patterned polymer coatings of PLGA and PGS on Mg were carefully characterized, and their effects on cell adhesion and morphology were investigated through direct culture with human umbilical vein endothelial cells (HUVECs) in vitro. The results showed that the 3000 nm parallel grooves could effectively elongate the HUVECs, while the 740 nm parallel grooves tended to reduce the spreading of HUVECs. The PLGA coatings reduced the degradation of Mg substrates more than that of the PGS coatings in the direct culture with HUVECs in vitro. CFL-based methods coupled with spray coating should be further studied as a nonchemical approach for creating nano-to-micron-patterned polymer coatings on Mg-based substrates of various sizes and shapes, which may present a new direction for improving the performance of Mg-based bioresorbable vascular devices toward potential clinical translation.

Syndecan-1 in mechanosensing of nanotopological cues in engineered materials.

The cells of the vascular system are highly sensitive to biophysical cues from their local cellular microenvironment. To engineer improved materials for vascular devices and delivery of cell therapies, a key challenge is to understand the mechanisms that cells use to sense biophysical cues from their environment. Syndecans are heparan sulfate proteoglycans (HSPGs) that consist of a protein core modified with heparan sulfate glycosaminoglycan chains. Due to their presence on the cell surface and their interaction with cytoskeletal and focal adhesion associated molecules, cell surface proteoglycans are well poised to serve as mechanosensors of the cellular microenvironment. Nanotopological cues have become recognized as major regulators of cell growth, migration and phenotype. We hypothesized that syndecan-1 could serve as a mechanosensor for nanotopological cues and can mediate the responsiveness of vascular smooth muscle cells to nanoengineered materials. We created engineered substrates made of polyurethane acrylate with nanogrooves using ultraviolet-assisted capillary force lithography. We cultured vascular smooth muscle cells with knockout of syndecan-1 on engineered substrates with varying compliance and nanotopology. We found that knockout of syndecan-1 reduced alignment of vascular smooth muscle cells to the nanogrooves under inflammatory treatments. In addition, we found that loss of syndecan-1 increased nuclear localization of Yap/Taz and phospho-Smad2/3 in response to nanogrooves. Syndecan-1 knockout vascular smooth muscle cells also had elevated levels of Rho-associated protein kinase-1 (Rock1), leading to increased cell stiffness and an enhanced contractile state in the cells. Together, our findings support that syndecan-1 knockout leads to alterations in mechanosensing of nanotopographical cues through alterations of in rho-associated signaling pathways, cell mechanics and mediators of the Hippo and TGF-ß signaling pathways.

Wearable and Transparent Capacitive Strain Sensor with High Sensitivity Based on Patterned Ag Nanowire Networks.

In this study, a transparent and stretchable thin-film capacitive strain sensor based on patterned Ag nanowire networks (AgNWs) was successfully fabricated. The AgNWs were patterned using a capillary force lithography (CFL) method and were embedded onto the surface of the polydimethylsiloxane substrate. The strain (ε) sensitivity of the capacitive strain sensor was controlled and enhanced by patterning the AgNWs into electrodes with an interdigitated shape. The interdigitated capacitive strain sensor (ICSS) is expected to have -1.57 gauge factor (GF) at 30% ε by calculation, which is much higher than the sensitivity of typical parallel-plate-type capacitive strain sensors. Because of the interdigitated pattern of the electrodes, the GF of the ICSS was increased up to -2.0. The ICSS had no hysteresis behavior up to ε values of 15% and showed stable ε sensing performance during the repeated stretching test at ε values of 10% for 1000 cycles. Furthermore, there was no cross talk between ε and pressure sensing in the AgNW-based ICSS, which was found to be insensitive to externally applied pressure. The ICSS was then used to detect the finger and wrist muscle motions of the human body to simulate its application to large and small ε sensing.

Hierarchical patterning of multifunctional conducting polymer nanoparticles as a bionic platform for topographic contact guidance.

The use of programmed electrical signals to influence biological events has been a widely accepted clinical methodology for neurostimulation. An optimal biocompatible platform for neural activation efficiently transfers electrical signals across the electrode-cell interface and also incorporates large-area neural guidance conduits. Inherently conducting polymers (ICPs) have emerged as frontrunners as soft biocompatible alternatives to traditionally used metal electrodes, which are highly invasive and elicit tissue damage over long-term implantation. However, fabrication techniques for the ICPs suffer a major bottleneck, which limits their usability and medical translation. Herein, we report that these limitations can be overcome using colloidal chemistry to fabricate multimodal conducting polymer nanoparticles. Furthermore, we demonstrate that these polymer nanoparticles can be precisely assembled into large-area linear conduits using surface chemistry. Finally, we validate that this platform can act as guidance conduits for neurostimulation, whereby the presence of electrical current induces remarkable dendritic axonal sprouting of cells.

Permeability- and Surface-Energy-Tunable Polyurethane Acrylate Molds for Capillary Force Lithography.

A permeability- and surface-energy-controllable polyurethane acrylate (PUA) mold, a "capillary-force material (CFM)" mold, is introduced for capillary-force lithography (CFL). In CFL, the surface energy and gas permeability of the mold are crucial. However, the modulation of these two main factors at a time is difficult. Here, we introduce new CFM molds in which the surface energy and permeability can be modified by controlling the degree of cross-linking of the CFM. As the degree of cross-linking of the CFM mold increases, the surface energy and air permeability decrease. The high average functionality of the mold material makes it possible to produce patterns relatively finely and rapidly due to the high rate of capillary rise and stiffness, and the low functionality allows for patterns to form on a curved surface with conformal contact. CFMs with different functionality and controllable-interfacial properties will extend the capabilities of capillary force lithography to overcome the geometric limitations of patterning on a scale below 100 nm and micro- and nanopatterning on the curved region.

Spatial control of adult stem cell fate using nanotopographic cues.

Adult stem cells hold great promise as a source of diverse terminally differentiated cell types for tissue engineering applications. However, due to the complexity of chemical and mechanical cues specifying differentiation outcomes, development of arbitrarily complex geometric and structural arrangements of cells, adopting multiple fates from the same initial stem cell population, has been difficult. Here, we show that the topography of the cell adhesion substratum can be an instructive cue to adult stem cells and topographical variations can strongly bias the differentiation outcome of the cells towards adipocyte or osteocyte fates. Switches in cell fate decision from adipogenic to osteogenic lineages were accompanied by changes in cytoskeletal stiffness, spanning a considerable range in the cell softness/rigidity spectrum. Our findings suggest that human mesenchymal stem cells (hMSC) can respond to the varying density of nanotopographical cues by regulating their internal cytoskeletal network and use these mechanical changes to guide them toward making cell fate decisions. We used this finding to design a complex two-dimensional pattern of co-localized cells preferentially adopting two alternative fates, thus paving the road for designing and building more complex tissue constructs with diverse biomedical applications.