Han Sol Kang

Solvent-Assisted Gel Printing for Micropatterning Thin Organic–Inorganic Hybrid Perovskite Films

While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems.

Micropatterned Pyramidal Ionic Gels for Sensing Broad-Range Pressures with High Sensitivity

The development of pressure sensors that are effective over a broad range of pressures is crucial for the future development of electronic skin applicable to the detection of a wide pressure range from acoustic wave to dynamic human motion. Here, we present flexible capacitive pressure sensors that incorporate micropatterned pyramidal ionic gels to enable ultrasensitive pressure detection. Our devices show superior pressure-sensing performance, with a broad sensing range from a few pascals up to 50 kPa, with fast response times of <20 ms and a low operating voltage of 0.25 V. Since high-dielectric-constant ionic gels were employed as constituent sensing materials, an unprecedented sensitivity of 41 kPa-1 in the low-pressure regime of <400 Pa could be realized in the context of a metal-insulator-metal platform. This broad-range capacitive pressure sensor allows for the efficient detection of pressure from a variety of sources, including sound waves, a lightweight object, jugular venous pulses, radial artery pulses, and human finger touch. This platform offers a simple, robust approach to low-cost, scalable device design, enabling practical applications of electronic skin.

Electrically Tunable Soft-Solid Block Copolymer Structural Color.

One-dimensional photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid (IL) swollen block copolymer (BCP) films. Placement of a polymer/ionic liquid film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2-vinylpyridine) (PS-b-QP2VP) copolymer SC film allowed the development of red (R), green (G), and blue (B) full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3 to +6 V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

Printable and Rewritable Full Block Copolymer Structural Color

Structural colors (SCs) of photonic crystals (PCs) arise from selective constructive interference of incident light. Here, an ink-jet printable and rewritable block copolymer (BCP) SC display is demonstrated, which can be quickly written and erased over 50 times with resolution nearly equivalent to that obtained with a commercial office ink-jet printer. Moreover, the writing process employs an easily modified printer for position- and concentration-controlled deposition of a single, colorless, water-based ink containing a reversible crosslinking agent, ammonium persulfate. Deposition of the ink onto a self-assembled BCP PC film comprising a 1D stack of alternating layers enables differential swelling of the written BCP film and produces a full-colored SC display of characters and images. Furthermore, the information can be readily erased and the system can be reset by application of hydrogen bromide. Subsequently, new information can be rewritten, resulting in a chemically rewritable BCP SC display.

Epitaxially Grown Ferroelectric PVDF-TrFE Film on Shape-Tailored Semiconducting Rubrene Single Crystal

Epitaxial crystallization of thin poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) films is important for the full utilization of their ferroelectric properties. Epitaxy can offer a route for maximizing the degree of crystallinity with the effective orientation of the crystals with respect to the electric field. Despite various approaches for the epitaxial control of the crystalline structure of PVDF-TrFE, its epitaxy on a semiconductor is yet to be accomplished. Herein, the epitaxial growth of PVDF-TrFE crystals on a single-crystalline organic semiconductor rubrene grown via physical vapor deposition is presented. The epitaxy results in polymer crystals globally ordered with specific crystal orientations dictated by the epitaxial relation between the polymer and rubrene crystal. The lattice matching between the c-axis of PVDF-TrFE crystals and the (210) plane of orthorhombic rubrene crystals develops two degenerate crystal orientations of the PVDF-TrFE crystalline lamellae aligned nearly perpendicular to each other. Thin PVDF-TrFE films with epitaxially grown crystals are incorporated into metal/ferroelectric polymer/metal and metal/ferroelectric polymer/semiconductor/metal capacitors, which exhibit excellent nonvolatile polarization and capacitance behavior, respectively. Furthermore, combined with a printing technique for micropatterning rubrene single crystals, the epitaxy of a PVDF-TrFE film is formed selectively on the patterned rubrene with characteristic epitaxial crystal orientation over a large area.

Block copolymer structural color strain sensor

AbstractThe development of electrically responsive sensors based on the capacitance, voltage, and resistance that can detect and simultaneou sly visualize the large strain involved with human motion is in great demand. Here, we demonstrate a highly stretchable, large strain capacitive sensor that can visualize strain based on the strain-responsive structural color (SC). Our device contains an elastomeric sensing film that produces a capacitance change under strain, in which a self-assembled block copolymer (BCP) photonic crystal (PC) film with 1D periodic in-plane lamellae aligned parallel to the film surface is embedded for the efficient visualization of strain. The capacitance change arises from changes in the dimensions of the elastomer film under strain. The mechanochromic BCP PC film responds to strain, giving rise to an SC change with strain. The initial red SC of the sensor blueshifts and turns blue when the sensor is stretched to 100%, resulting in a full-color SC alteration as a function of the strain. Our BCP SC strain sensor exhibits a fast strain response with multi-cycle reliability of both the capacitance and SC changes over 1000 cycles. This property allows for efficient visible recognition not only of the strained positions during finger bending and poking with a sharp object but also of the shapes of the strained objects.Sensors: Getting the blues under strainA strain sensor that changes color when stretched has been developed by a team in Korea. Flexible sensors that measure pressure or strain could find application as wearable health monitors. One route to achieve such sensors is to use dielectric films whose capacitance changes in response to mechanical stimulus. However, an easy way is needed for wearers to read the output. Cheolmin Park from Yonsei University and colleagues constructed a polymer-based material with a periodic structure that reflects light of different colors depending on the degree to which it is extended. Specifically, they created a block copolymer soft-solid film with one-dimensional periodic layers. The capacitance changes under strain as a result of the dimensional change of the elastomer film, causing the initially red sensor to turn blue when fully stretched.A novel block copolymer structural color strain sensor was developed, capable of electrically sensing a strain in capacitance change with simultaneous visualization of the strain. A thin mechanochromic bilayer of a block copolymer structural film with 1-D periodic lamellae placed on an ionic gel layer allowed for direct visualization of strain while sensing in capacitance when embedded in an elastomeric dielectric medium. Our block copolymer structural strain sensor was suitable for a reflective mode electronic skin which readily recognized human motion of the finger, elbow, and knee.

Surface functionalized nanostructures: Via position registered supramolecular polymer assembly

Versatile control of cylindrical nanostructures formed by supramolecular assembly of end-functionalized polymer blends is demonstrated not only in their orientation over large areas but also in their surface chemical functionalities. Two binary blends consisting of supramolecular analogues of diblock copolymers with complementary end-sulfonated and aminated groups are investigated, viz., mono-end-functionalized polymers of (i) one-end-sulfonated polystyrene (SPS) and one-end-aminated poly(butadiene) (APBD) and (ii) one end-aminated polystyrene (APS) and one end-sulfonated poly(butadiene) (SPBD). The orientation of the cylinders with respect to the substrate surface depends on the solvent annealing time; either hexagonally ordered vertical cylinders or in-plane ones are readily obtained by controlling the solvent annealing time. Selective chemical etching of one of the polymers provides four different chemically modified nanostructures, viz., hexagonally ordered cylindrical holes and cylindrical posts with either sulfonate or amine surface functional groups. Additional supramolecular assembly is successfully achieved by solution coating either polymers or organic dyes that complementarily interact with the functional groups on the nanostructures. Furthermore, the supramolecularly assembled nanostructures are controlled by confining them to topographically pre-patterned Si substrates with pattern geometries of various shapes and sizes to produce globally ordered vertical or in-plane cylinders with chemical functionalities on their surfaces.

Electroluminescent Pressure-Sensing Displays

Simultaneous sensing and visualization of pressure provides a useful platform to obtain information about a pressurizing object, but the fabrication of such interactive displays at the single-device level remains challenging. Here, we present a pressure responsive electroluminescent (EL) display that allows for both sensing and visualization of pressure. Our device is based on a two-terminal capacitor with six constituent layers: top electrode/insulator/hole injection layer/emissive layer/electron transport layer/bottom electrode. Light emission upon exposure to an alternating current field between two electrodes is controlled by the capacitance change of the insulator arising from the pressure applied on top. Besides capacitive pressure sensing, our EL display allows for direct visualization of the static and dynamic information of position, shape, and size of a pressurizing object on a single-device platform. Monitoring the pressurized area of an elastomeric hemisphere on a device by EL enables quantitative estimation of the Youngs modulus of the elastomer, offering a new and facile characterization method for the mechanical properties of soft materials.