Richard Hahnkee Kim

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.

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.

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 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.

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.

Tailored Single Crystals of Triisopropylsilylethynyl Pentacene by Selective Contact Evaporation Printing

Organic semiconductors have great potential for application in numerous emerging low-cost and disposable electronic devices such as organic thin fi lm transistors (OTFTs), solar cells, memories, sensors, and fl exible displays. [ 1–3 ] One of the most urgent demands for the realization of such devices is the need to develop new organic semiconductors with a high carrier mobility as well as good and cost-effective processibility for highperformance devices. Chemically-modifi ed pentacene derivatives such as triisopropylsilylethynyl pentacene (TIPS-PEN) have received much attention, in particular in OTFTs. [ 4 , 5–14 ]

High throughput modification of chemically reduced graphene oxides by a conjugated block copolymer in non-polar medium

We present a simple, but robust route to efficiently disperse very high rGO concentrations of chemically reduced graphene oxides (rGOs) in various non-polar solvents and polymers. Our method is based on the noncovalent, nondestructive modification of rGOs with a conjugated block copolymer, poly(styrene-block-paraphenylene) (PS-b-PPP). The dispersion of rGOs occurred because PPP blocks strongly adhered to basal planes of rGOs by π–π interactions, while PS blocks provided good solubility in a variety of non-polar environments. The resulting PS-b-PPP modified rGOs (PMrGOs) showed excellent solubility and dispersion stability that was dependent on the quality of the solvent with respect to the PS blocks. In particular, extremely high solubility of the rGOs, as high as 1.5 mg mL−1, was achieved in THF. Our PMrGOs and their solution blends with other non-polymer polymers such as PS, poly(methylmethacrylate) and poly(isoprene-block-styrene) were conveniently spin-coated on various substrates, giving rise to ultra-thin nanohybrid films where the amount of rGO can be systematically controlled. The scalable and simple strategy employed for fabricating rGO nanohybrid films allowed us to assemble a high performance non-volatile resistive polymer memory device in which the bias-dependent trapping and de-trapping of injected charges were efficiently manipulated on the surface of highly dispersed rGO sheets in the nanohybrid.

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.

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.