Photonic crystallization of two-dimensional MoS2 for stretchable photodetectors.

Low temperature synthesis of high quality two-dimensional (2D) materials directly on flexible substrates remains a fundamental limitation towards scalable realization of robust flexible electronics possessing the unique physical properties of atomically thin structures. Herein, we describe room temperature sputtering of uniform, stoichiometric amorphous MoS2 and subsequent large area (>6.25 cm2) photonic crystallization of 5 nm 2H-MoS2 films in air to enable direct, scalable fabrication of ultrathin 2D photodetectors on stretchable polydimethylsiloxane (PDMS) substrates. The lateral photodetector devices demonstrate an average responsivity of 2.52 µW A-1 and a minimum response time of 120 ms under 515.6 nm illumination. Additionally, the surface wrinkled, or buckled, PDMS substrate with conformal MoS2 retained the photoconductive behavior at tensile strains as high as 5.72% and over 1000 stretching cycles. The results indicate that the photonic crystallization method provides a significant advancement in incorporating high quality semiconducting 2D materials applied directly on polymer substrates for wearable and flexible electronic systems.

Flexible Nonvolatile Transistor Memory with Solution-Processed Transition Metal Dichalcogenides.

Nonvolatile field-effect transistor (FET) memories containing transition metal dichalcogenide (TMD) nanosheets have been recently developed with great interest by utilizing some of the intriguing photoelectronic properties of TMDs. The TMD nanosheets are, however, employed as semiconducting channels in most of the memories, and only a few works address their function as floating gates. Here, a floating-gate organic-FET memory with an all-in-one floating-gate/tunneling layer of the solution-processed TMD nanosheets is demonstrated. Molybdenum disulfide (MoS2 ) is efficiently liquid-exfoliated by amine-terminated polystyrene with a controlled amount of MoS2 nanosheets in an all-in-one floating-gate/tunneling layer, allowing for systematic investigation of concentration-dependent charge-trapping and detrapping properties of MoS2 nanosheets. At an optimized condition, the nonvolatile memory exhibits memory performances with an ON/OFF ratio greater than 104 , a program/erase endurance cycle over 400 times, and data retention longer than 7 × 103 s. All-in-one floating-gate/tunneling layers containing molybdenum diselenide and tungsten disulfide are also developed. Furthermore, a mechanically-flexible TMD memory on a plastic substrate shows a performance comparable with that on a hard substrate, and the memory properties are rarely altered after outer-bending events over 500 times at the bending radius of 4.0 mm.

Organic light emitting board for dynamic interactive display.

Interactive displays involve the interfacing of a stimuli-responsive sensor with a visual human-readable response. Here, we describe a polymeric electroluminescence-based stimuli-responsive display method that simultaneously detects external stimuli and visualizes the stimulant object. This organic light-emitting board is capable of both sensing and direct visualization of a variety of conductive information. Simultaneous sensing and visualization of the conductive substance is achieved when the conductive object is coupled with the light emissive material layer on application of alternating current. A variety of conductive materials can be detected regardless of their work functions, and thus information written by a conductive pen is clearly visualized, as is a human fingerprint with natural conductivity. Furthermore, we demonstrate that integration of the organic light-emitting board with a fluidic channel readily allows for dynamic monitoring of metallic liquid flow through the channel, which may be suitable for biological detection and imaging applications.

Non-Volatile ReRAM Devices Based on Self-Assembled Multilayers of Modified Graphene Oxide 2D Nanosheets.

2D nanomaterials have been actively utilized in non-volatile resistive switching random access memory (ReRAM) devices due to their high flexibility, 3D-stacking capability, simple structure, transparency, easy fabrication, and low cost. Herein, it demonstrates re-writable, bistable, transparent, and flexible solution-processed crossbar ReRAM devices utilizing graphene oxide (GO) based multilayers as active dielectric layers. The devices employ single- or multi-component-based multilayers composed of positively charged GO (N-GO(+) or NS-GO(+)) with/without negatively charged GO(-) using layer-by-layer assembly method, sandwiched between Al bottom and Au top electrodes. The device based on the multi-component active layer Au/[N-GO(+)/GO(-)]n /Al/PES shows higher ON/OFF ratio of ≈105 with switching voltage of -1.9 V and higher retention stability (≈104 s), whereas the device based on single component (Au/[N-GO(+)]n /Al/PES) shows ≈103 ON/OFF ratio at ±3.5 V switching voltage. The superior ReRAM properties of the multi-component-based device are attributed to a higher coating surface roughness. The Au/[N-GO(+)/GO(-)]n /Al/PES device prepared from lower GO concentration (0.01%) exhibits higher ON/OFF ratio (≈109 ) at switching voltage of ±2.0 V. However, better stability is achieved by increasing the concentration from 0.01% to 0.05% of all GO-based solutions. It is found that the devices containing MnO2 in the dielectric layer do not improve the ReRAM performance.

Controlled Nanopores in Thin Films of Nonstoichiometrically Supramolecularly Assembled Graft Copolymers.

Herein, nanometer-scale morphologies of graft-copolymer-like supramolecular thin films, composed of sulfonic acid terminated polystyrene (SPS) and poly(2-vinylpyridine) (P2VP), and their application to antireflection coatings were investigated. The intermolecular complexes of SPS and P2VP, formed through nonstoichiometric multiple hydrogen bonding between the sulfonic acid group of SPS and the nitrogen atom in pyridine unit of P2VP, occurring in film deposition allowed for the formation of spherical micelles (with SPS and P2VP as the corona and core, respectively) in the thin film. Interestingly, the domain size of the micelles was tunable from approximately 20 to 90 nm on average by controlling either the blend ratio of components or the concentration of polymer solution. Furthermore, nanoporous thin films could be easily prepared by removing the core of micelle-based nanostructures by using a simple solvent etching process, leaving sulfonic acid groups on the surface of nanopores, which can be utilized as potential functional sites. Those resultant nanoporous thin films were conveniently employed as an antireflection layer on a glass substrate, giving a maximum 97.8 % transmittance in the visible wavelength range.

Flexible transition metal dichalcogenide nanosheets for band-selective photodetection.

The photocurrent conversions of transition metal dichalcogenide nanosheets are unprecedentedly impressive, making them great candidates for visible range photodetectors. Here we demonstrate a method for fabricating micron-thick, flexible films consisting of a variety of highly separated transition metal dichalcogenide nanosheets for excellent band-selective photodetection. Our method is based on the non-destructive modification of transition metal dichalcogenide sheets with amine-terminated polymers. The universal interaction between amine and transition metal resulted in scalable, stable and high concentration dispersions of a single to a few layers of numerous transition metal dichalcogenides. Our MoSe2 and MoS2 composites are highly photoconductive even at bending radii as low as 200 µm on illumination of near infrared and visible light, respectively. More interestingly, simple solution mixing of MoSe2 and MoS2 gives rise to blended composite films in which the photodetection properties were controllable. The MoS2/MoSe2 (5:5) film showed broad range photodetection suitable for both visible and near infrared spectra.

High through-plane thermal conduction of graphene nanoflake filled polymer composites melt-processed in an L-shape kinked tube.

Design of materials to be heat-conductive in a preferred direction is a crucial issue for efficient heat dissipation in systems using stacked devices. Here, we demonstrate a facile route to fabricate polymer composites with directional thermal conduction. Our method is based on control of the orientation of fillers with anisotropic heat conduction. Melt-compression of solution-cast poly(vinylidene fluoride) (PVDF) and graphene nanoflake (GNF) films in an L-shape kinked tube yielded a lightweight polymer composite with the surface normal of GNF preferentially aligned perpendicular to the melt-flow direction, giving rise to a directional thermal conductivity of approximately 10 W/mK at 25 vol % with an anisotropic thermal conduction ratio greater than six. The high directional thermal conduction was attributed to the two-dimensional planar shape of GNFs readily adaptable to the molten polymer flow, compared with highly entangled carbon nanotubes and three-dimensional graphite fillers. Furthermore, our composite with its density of approximately 1.5 g/cm(3) was mechanically stable, and its thermal performance was successfully preserved above 100 °C even after multiple heating and cooling cycles. The results indicate that the methodology using an L-shape kinked tube is a new way to achieve polymer composites with highly anisotropic thermal conduction.

Self-assembled block copolymer micelles with silver-carbon nanotube hybrid fillers for high performance thermal conduction.

The development of polymer-filled composites with an extremely high thermal conductivity (TC) that is competitive with conventional metals is in great demand due to their cost-effective process, light weight, and easy shape-forming capability. A novel polymer composite with a large thermal conductivity of 153 W m(-1) K(-1) was prepared based on self-assembled block copolymer micelles containing two different fillers of micron-sized silver particles and multi-walled carbon nanotubes. Simple mechanical mixing of the components followed by conventional thermal compression at a low processing temperature of 160 °C produced a novel composite with both structural and thermal stability that is durable for high temperature operation up to 150 °C as well as multiple heating and cooling cycles of ΔT = 100 °C. The high performance in thermal conduction of our composite was mainly attributed to the facile deformation of Ag particles during the mixing in a viscous thermoplastic medium, combined with networked carbon nanotubes uniformly dispersed in the nanoscale structural matrix of block copolymer micelles responsible for its high temperature mechanical stability. Furthermore, micro-imprinting on the composite allowed for topographically periodic surface micropatterns, which offers broader suitability for numerous micro-opto-electronic systems.

Laser-induced nondestructive patterning of a thin ferroelectric polymer film with controlled crystals using Ge8Sb2Te11 alloy layer for nonvolatile memory.

We present a simple but robust nondestructive process for fabricating micropatterns of thin ferroelectric polymer films with controlled crystals. Our method is based on utilization of localized heat arising from thin Ge(8)Sb(2)Te(11) (GST) alloy layer upon exposure of 650 nm laser. The heat was generated on GST layer within a few hundred of nanosecond exposure and subsequently transferred to a thin poly(vinylidene fluoride-co-trifluoroethylene) film deposited on GST layer. By controlling exposure time and power of the scanned laser, ferroelectric patterns of one or two microns in size are fabricated with various shape. In the micropatterned regions, ferroelectric polymer crystals were efficiently controlled in both degree of the crystallinity and the molecular orientations. Nonvolatile memory devices with laser scanned ferroelectric polymer layers exhibited excellent device performance of large remnant polarization, ON/OFF current ratio and data retention. The results are comparable with devices containing ferroelectric films thermally annealed at least for 2 h, making our process extremely efficient for saving time. Furthermore, our approach can be conveniently combined with a number of other functional organic materials for the future electronic applications.

Non-volatile organic memory with sub-millimetre bending radius.

High-performance non-volatile memory that can operate under various mechanical deformations such as bending and folding is in great demand for the future smart wearable and foldable electronics. Here we demonstrate non-volatile solution-processed ferroelectric organic field-effect transistor memories operating in p- and n-type dual mode, with excellent mechanical flexibility. Our devices contain a ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) thin insulator layer and use a quinoidal oligothiophene derivative (QQT(CN)4) as organic semiconductor. Our dual-mode field-effect devices are highly reliable with data retention and endurance of >6,000 s and 100 cycles, respectively, even after 1,000 bending cycles at both extreme bending radii as low as 500 µm and with sharp folding involving inelastic deformation of the device. Nano-indentation and nano scratch studies are performed to characterize the mechanical properties of organic layers and understand the crucial role played by QQT(CN)4 on the mechanical flexibility of our devices.

Wafer-scale arrays of nonvolatile polymer memories with microprinted semiconducting small molecule/polymer blends.

Nonvolatile ferroelectric-gate field-effect transistors (Fe-FETs) memories with solution-processed ferroelectric polymers are of great interest because of their potential for use in low-cost flexible devices. In particular, the development of a process for patterning high-performance semiconducting channel layers with mechanical flexibility is essential not only for proper cell-to-cell isolation but also for arrays of flexible nonvolatile memories. We demonstrate a robust route for printing large-scale micropatterns of solution-processed semiconducting small molecules/insulating polymer blends for high performance arrays of nonvolatile ferroelectric polymer memory. The nonvolatile memory devices are based on top-gate/bottom-contact Fe-FET with ferroelectric polymer insulator and micropatterned semiconducting blend channels. Printed micropatterns of a thin blended semiconducting film were achieved by our selective contact evaporation printing, with which semiconducting small molecules in contact with a micropatterned elastomeric poly(dimethylsiloxane) (PDMS) mold were preferentially evaporated and absorbed into the PDMS mold while insulating polymer remained intact. Well-defined micrometer-scale patterns with various shapes and dimensions were readily developed over a very large area on a 4 in. wafer, allowing for fabrication of large-scale printed arrays of Fe-FETs with highly uniform device performance. We statistically analyzed the memory properties of Fe-FETs, including ON/OFF ratio, operation voltage, retention, and endurance, as a function of the micropattern dimensions of the semiconducting films. Furthermore, roll-up memory arrays were produced by successfully detaching large-area Fe-FETs printed on a flexible substrate with a transient adhesive layer from a hard substrate and subsequently transferring them to a nonplanar surface.

Functionalized soft nanoporous materials through supramolecular assembly of end-functionalized polymer blends.

Supramolecular assembly through complementary interaction between molecular subgroups belonging to phase-separating polymer species offers a great opportunity, not only for constructing nanoscale soft templates reminiscent of conventional block copolymer morphologies, but also for tailoring surface properties by facile removal of one of the structure components by cleaving complementary interactions. Herein we report the fabrication of a novel, organic, nanoporous film through supramolecular assembly of two complementarily, end-interacting, mono-end-functionalized polymers under solvent annealing. The film of end-functionalized polymer blends under solvent annealing yielded phase-separated nanodomains that resemble nanoscopically ordered structures of block copolymers, but that are more advantageous due to easily cleavable and exchangeable links between the phase-separated domains. The removal of one of the components of the precursor structure formed from the end-functionalized polymers through cleavage of complementary interactions allowed us to fabricate mono- or multilayered nanoporous structures in which the chemically useful end-functionalities of the remnant polymers are rich on the surface of the pores. The resultant, organic, nanoporous films with tailored surface functionality offer a useful platform for various chemical and biological applications.

Flexible non-volatile ferroelectric polymer memory with gate-controlled multilevel operation.

A flexible field-effect transistor with a poly(3-hexylthiophene) (P3HT) active channel and a ferroelectric poly(vinlyidene fluoride-co-trifluoro ethylene) (PVDF-TrFE) insulator exhibits gate-voltage-controllable multilevel non-volatile memory characteristics with highly reliable data retention and endurance.

High performance AC electroluminescence from colloidal quantum dot hybrids.

High performance field-induced AC electroluminescence (EL) in a simple ITO/insulator/hybrid emitter/Au structure was demonstrated with efficient control of the brightness and colors based on solution-processed nanohybrids of CdSe-ZnS core-shell colloidal quantum dots and fluorescent polymers.

Compression of cross-linked poly(vinylidene fluoride-co-trifluoro ethylene) films for facile ferroelectric polarization.

In this study, we demonstrated a facile route for enhancing the ferroelectric polarization of a chemically cross-linked poly(vinylidene fluoride-co-trifluoro ethylene) (PVDF-TrFE) film. Our method is based on thermally induced cross-linking of a PVDF-TrFE film with a 2,2,4-trimethyl-1,6-hexanediamine (THDA) agent under compression. The remanent polarization (P(r)) of a metal/ferroelectric/metal capacitor containing a cross-linked PVDF-TrFE film increased with pressure up to a certain value, whereas no change in the P(r) value was observed in the absence of THDA. A film cross-linked with 10 wt % THDA with respect to PVDF-TrFE under a pressure of 100 kPa exhibited a P(r) of approximately 5.61 µC/cm(2), which is 1.6 times higher than that in the absence of pressure. The enhanced ferroelectric polarization was attributed to highly ordered 20-nm-thick edge-on crystalline lamellae whose c-axes are aligned parallel to the substrate. The lamellae were effective for ferroelectric switching of the PVDF-TrFE when a cross-linked film was recrystallized under pressure. Furthermore, compression of a PVDF-TrFE film with a topographically prepatterned poly(dimethyl siloxane) mold gave rise to a chemically cross-linked micropattern in which edge-on crystalline lamellae were globally oriented over a very large area.