Melding Vapor-Phase Organic Chemistry and Textile Manufacturing To Produce Wearable Electronics.

Body-mountable electronics and electronically active garments are the future of portable, interactive devices. However, wearable devices and electronic garments are demanding technology platforms because of the large, varied mechanical stresses to which they are routinely subjected, which can easily abrade or damage microelectronic components and electronic interconnects. Furthermore, aesthetics and tactile perception (or feel) can make or break a nascent wearable technology, irrespective of device metrics. The breathability and comfort of commercial fabrics is unmatched. There is strong motivation to use something that is already familiar, such as cotton/silk thread, fabrics, and clothes, and imperceptibly adapt it to a new technological application. (24) Especially for smart garments, the intrinsic breathability, comfort, and feel of familiar fabrics cannot be replicated by devices built on metalized synthetic fabrics or cladded, often-heavy designer fibers. We propose that the strongest strategy to create long-lasting and impactful electronic garments is to start with a mass-produced article of clothing, fabric, or thread/yarn and coat it with conjugated polymers to yield various textile circuit components. Commonly available, mass-produced fabrics, yarns/threads, and premade garments can in theory be transformed into a plethora of comfortably wearable electronic devices upon being coated with films of electronically active conjugated polymers. The definitive hurdle is that premade garments, threads, and fabrics have densely textured, three-dimensional surfaces that display roughness over a large range of length scales, from microns to millimeters. Tremendous variation in the surface morphology of conjugated-polymer-coated fibers and fabrics can be observed with different coating or processing conditions. In turn, the morphology of the conjugated polymer active layer determines the electrical performance and, most importantly, the device ruggedness and lifetime. Reactive vapor coating methods allow a conjugated polymer film to be directly formed on the surface of any premade garment, prewoven fabric, or fiber/yarn substrate without the need for specialized processing conditions, surface pretreatments, detergents, or fixing agents. This feature allows electronic coatings to be applied at the end of existing, high-throughput textile and garment manufacturing routines, irrespective of dye content or surface finish of the final textile. Furthermore, reactive vapor coating produces conductive materials without any insulating moieties and yields uniform and conformal films on fiber/fabric surfaces that are notably wash- and wear-stable and can withstand mechanically demanding textile manufacturing routines. These unique features mean that rugged and practical textile electronic devices can be created using sewing, weaving, or knitting procedures without compromising or otherwise affecting the surface electronic coating. In this Account, we highlight selected electronic fabrics and garments created by melding reactive vapor deposition with traditional textile manipulation processes, including electrically heated gloves that are lightweight, breathable, and sweat-resistant; surface-coated cotton, silk, and bast fiber threads capable of carrying large current densities and acting as sewable circuit interconnects; and surface-coated nylon threads woven together to form triboelectric textiles that can convert surface charge created during small body movements into usable and storable power.

Triplet exciton dissociation and electron extraction in graphene-templated pentacene observed with ultrafast spectroscopy.

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Preorganization Increases the Self-Assembling Ability and Antitumor Efficacy of Peptide Nanomedicine.

Inspired by the biological process of phosphorylation for which different sites of the same protein may have different activities and functions, we utilized phosphatase-based enzyme-instructed self-assembly (EISA) to construct self-assembled nanomedicine from the precursors with different phosphorylated sites. We found that, although the obtained self-assembling molecules after EISA were identical, the changes of EISA catalytic sites could determine the outcome of molecular self-assembly. The precursor with the phosphorylated site in the middle preorganized before EISA, while the ones with other phosphorylated sites could not preorganize before EISA. After EISA, the preorganized precursor then resulted in more stable and ordered assemblies than those of the others, which showed increased cellular uptake and up to 1.7-fold higher efficacy in an antitumor therapeutic compared to those assembled from unorganized precursors.

Using the Surface Features of Plant Matter to Create All-Polymer Pseudocapacitors with High Areal Capacitance.

Controlling mesoscale organization in thick films of electroactive polymers is crucial for studying and optimizing charge and ion transport in these disordered materials. Conventional approaches focus on directing long-range polymer aggregation and/or crystallization during film formation by using interfaces, flow and/or shear forces. Here, we describe an alternative method that takes advantage of naturally textured biological substrates and vapor-coating to structure thick-conjugated polymer films. Reactive vapor-coating is a technique that enables in situ synthesis of doped conjugated polymers inside a reduced-pressure reactor. Reactive vapor deposition conformally coats the surface of plant matter, such as leaves and flower petals, with conducting polymer films while leaving these living substrates undamaged. Importantly, the intricate surface features of plant matter are faultlessly reproduced in the coating, effectively creating thick, high-surface-area, electrochemically active conducting polymer electrodes on plant matter. A microstructured, 10 µm thick film of p-doped poly(3,4-ethylenedioxythiophene) on a pilea involucrata leaf acts as an all-polymer pseudocapacitor with a higher areal capacitance (142 mF/cm2) than an analogous film on a planar plastic substrate lacking microstructure (50 mF/cm2). Taken together, reactive vapor deposition and microstructured plant matter present a unique combination of processing technique and substrate than can yield a diverse library of controllably microstructured electronic polymer films.

High Energy Density, Super-Deformable, Garment-Integrated Microsupercapacitors for Powering Wearable Electronics.

Lightweight energy storage technologies are integral for powering emerging wearable health monitors and smart garments. In-plane, interdigitated microsupercapacitors (MSCs) hold the greatest promise to be integrated into wearable electronics because of their miniaturized footprint, as compared to conventional, multilayered supercapacitors and batteries. Constructing MSCs directly on textiles, while retaining the fabric's pliability and tactile quality, will provide uniquely wearable energy storage systems. However, relative to plastic-backed or paper-based MSCs, garment-integrated MSCs are underreported. The challenge lies in creating electrochemically active fiber electrodes that can be turned into MSCs. We report a facile vapor deposition and sewing sequence to create rugged textile MSCs. Conductive threads are vapor-coated with a stably p-doped conducting polymer film and then sewn onto a stretchy textile to form three-dimensional, compactly aligned electrodes with the electrode dimensions defined by the knit structure of the textile backing. The resulting solid-state device has an especially high areal capacitance and energy density of 80 mF/cm2 and 11 µW h/cm2 with a polymer gel electrolyte, and an energy density of 34 µW h/cm2 with an ionic liquid electrolyte, sufficient to power contemporary iterations of wearable biosensors. These textile MSCs are also super deformable, displaying unchanging electrochemical performance after fully rolling-up the device.

Supramolecular Nanofibers of Drug-Peptide Amphiphile and Affibody Suppress HER2+ Tumor Growth.

Antibody-based medicines and nanomedicines are very promising for cancer therapy due to the high specificity and efficacy of antibodies. However, antibody-drug conjugates and antibody-modified nanomaterials frequently suffer from low drug loading and loss of functions due to the covalent modification of the antibody. A novel and versatile strategy to prepare supramolecular nanomaterials by the coassembly of an affibody (antiHER2) and drug-peptide amphiphiles is reported here. During the enzyme-instructed self-assembly process, the drug-peptide amphiphile can coassemble with the affibody, resulting in supramolecular nanofibers in hydrogels. The drug loading in the supramolecular nanofibers is high (>30 wt%), and the stability of antiHER2 is significantly improved in the nanofibers at 37 °C (>15 d in vitro). The supramolecular nanofibers exhibit high affinity for HER2+ cancer cells and can be efficiently taken up by these cells. In a mouse tumor model, the supramolecular nanofibers abolish HER2+ NCI-N87 tumor growth due to the good accumulation and retention of nanofibers in tumor. This study provides a novel strategy to prepare nanomedicines with high drug loading and high specificity.

Transforming Commercial Textiles and Threads into Sewable and Weavable Electric Heaters.

We describe a process to transform commercial textiles and threads into electric heaters that can be cut/sewn or woven to fashion lightweight fabric heaters for local climate control and personal thermal management. Off-the-shelf fabrics are coated with a 1.5 µm thick film of a conducting polymer, poly(3,4-ethylenedioxythiophene), using an improved reactive vapor deposition method. Changes in the hand feel, weight, and breathability of the textiles after the coating process are imperceptible. The resulting fabric electrodes possess competitively low sheet resistances-44 Ω/□ measured for coated bast fiber textiles and 61 Ω/□ measured for coated cotton textiles-and act as low-power-consuming Joule heating elements. The electrothermal response of the textile electrodes remain unaffected after cutting and sewing due to the robustness of the conductive coating. Coated, conductive cotton yarns can also be plain-woven into a monolithic fabric heater. A demonstrative circuit design for a soft, lightweight, and breathable thermal glove is provided.

Development of lead iodide perovskite solar cells using three-dimensional titanium dioxide nanowire architectures.

Three-dimensional (3D) nanowire (NW) architectures are considered as superior electrode design for photovoltaic devices compared to NWs or nanoparticle systems in terms of improved large surface area and charge transport properties. In this paper, we report development of lead iodide perovskite solar cells based on a novel 3D TiO2 NW architectures. The 3D TiO2 nanostructure was synthesized via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) technique that also implemented the Kirkendall effect for complete ZnO NW template conversion. It was found that the film thickness of 3D TiO2 can significantly influence the photovoltaic performance. Short-circuit current increased with the TiO2 length, while open-circuit voltage and fill factor decreased with the length. The highest power conversion efficiency (PCE) of 9.0% was achieved with ∼ 600 nm long 3D TiO2 NW structures. Compared to other 1D nanostructure arrays (TiO2 nanotubes, TiO2-coated ZnO NWs and ZnO NWs), 3D TiO2 NW architecture was able to achieve larger amounts of perovskite loading, enhanced light harvesting efficiency, and increased electron-transport property. Therefore, its PCE is 1.5, 2.3, and 2.8 times higher than those of TiO2 nanotubes, TiO2-coated ZnO NWs, and ZnO NWs, respectively. The unique morphological advantages, together with the largely suppressed hysteresis effect, make 3D hierarchical TiO2 a promising electrode selection in designing high-performance perovskite solar cells.

Observing electron extraction by monolayer graphene using time-resolved surface photoresponse measurements.

Graphene is considered a next-generation electrode for indium tin oxide (ITO)-free organic photovoltaic devices (OPVs). However, to date, limited numbers of OPVs containing surface-modified graphene electrodes perform as well as ITO-based counterparts, and no devices containing a bare graphene electrode have been reported to yield satisfactory rectification characteristics. In this report, we provide experimental data to learn why. Time-resolved surface photoresponse measurements on templated pentacene-on-graphene films directly reveal that p-doped monolayer graphene efficiently extracts electrons, not holes, from photoexcited pentacene. Accordingly, a graphene/pentacene/MoO3 heterojunction displays a large surface photoresponse and, by inference, efficient dissociation of photogenerated excitons, with graphene serving as an electron extraction layer and MoO3 as a hole extraction layer. In contrast, a graphene/pentacene/C60 heterojunction yields a comparatively insignificant surface photoresponse because both graphene and C60 act as competing electron extraction layers. The data presented herein provide experimental insight for future endeavors involving bare graphene as an electrode for organic photovoltaic devices and strongly suggest that p-doped graphene is best considered a cathode for OPVs.

Tellurium thin films in hybrid organic electronics: morphology and mobility.

Elemental Te displays a wide variety of nanoscale morphologies of vapor-deposited films, depending on the substrate surface and temperature. These morphologies are correlated to field-effect mobilities in transistors made with Te as the lone semiconductor or from Te-organic multilayer semiconductors. Two examples of morphologies and transistor output characteristics, i.e., on a room temperature oxide and heated organic, are shown in the figure.

Effects of pulsing and interfacial potentials on tellurium-organic heterostructured films.

Polycrystalline thin films of tellurium and organic semiconductor molecules are paired in heterostructured field-effect transistors built on Si/SiO2 substrates. While charge carrier mobilities can exceed 1 cm(2)/(V s), there is only a limited gate voltage range over which the current is modulated. We employ continuous and pulsed measurements on transistors to explore the influence of charge equilibration time on device behavior, finding that pulsed gating improves output characteristics. We also use surface potential measurements to investigate the interfacial vacuum level offset between materials, and we modify the interlayer potential profile by interposing statically charged dielectric layers on the silicon dioxide. We show that interfacial fields determine the gate voltage range over which Te shows a field effect in heterostructures with organic semiconductors and that modification of these fields can extend this range.