Stretchable OFET Memories: Tuning the Morphology and the Charge-Trapping Ability of Conjugated Block Copolymers through Soft Segment Branching.

The mechanical properties and structural design flexibility of charge-trapping polymer electrets have led to their widespread use in organic field-effect transistor (OFET) memories. For example, in the electrets of polyfluorene-based conjugated/insulating block copolymers (BCPs), the confined fiberlike polyfluorene nanostructures in the insulating polymer matrix act as effective hole-trapping sites, leading to controllable memory performance through the design of BCPs. However, few studies have reported intrinsically stretchable charge-trapping materials and their memory device applications, and a practical method to correlate the thin-film morphology of BCP electrets with their charge-trapping ability has not yet been developed. In this study, a series of new conjugated/insulating BCPs, poly(9,9-di-n-hexyl-2,7-fluorene)-block-poly(δ-decanolactone)s (PF-b-PDLx, x = 1-3), as stretchable hole-trapping materials are reported. The linear and branched PDL blocks with comparable molecular weights were used to investigate the effect of polymer architecture on morphology and device performance. Moreover, the coverage area of the polyfluorene nanofibers on the BCP films was extracted from atomic force microscopy images, which can be correlated with the trapping density of the polymer electrets. The branched PDL segments not only improve stretchability but also tailor crystallinity and phase separation of the BCPs, thus increasing their charge-trapping ability. The OFET memory device with PF-b-PDL3 as the electret layer exhibited the largest memory window (102 V) and could retain its performance at up to 100% strain. This research highlights the importance of the BCP design for developing stretchable charge-trapping materials.

Nanostructure- and Orientation-Controlled Resistive Memory Behaviors of Carbohydrate-block-Polystyrene with Different Molecular Weights via Solvent Annealing.

We report the resistive electrical memory characteristics controlled by the self-assembled nanostructures of maltoheptaose-block-polystyrene (MH-b-PS) block copolymers, where the MH and PS blocks provide the charge-trapping and the insulating tunneling layer, respectively. A simple solvent annealing process, with various annealing conditions, were introduced for MH-b-PS thin films to achieve disordered, orientated cylinders and ordered-packed spheres morphologies. More details about the self-assembled MH-b-PS nanostructures, coupled with different volume fractions between MH and PS blocks, were investigated using atomic force microscopy and grazing-incidence small-angle X-ray scattering analyses. Moreover, various electrical memory behaviors including nonvolatile write-once-read-many-times (WORM) and Flash, and volatile dynamic-random-access-memory (DRAM) could be obtained by the same material (MH-b-PS3k). This study establishes a detailed relationship between the nanostructure of the MH-b-PS-based block copolymers and their memory behavior of the resistive memory devices.

Multilevel Photonic Transistor Memory Devices Using Conjugated/Insulated Polymer Blend Electrets.

Photonic data storage has diverse optoelectronic applications such as optical sensing and recording, integrated image circuits, and multibit-storage flash memory. In this study, we employ conjugated/insulated polymer blends as the charge storage electret for photonic field-effect transistor memory devices by exploring the blend composition, energy level alignment, and morphology on the memory characteristics. The studied conjugated polymers included poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PF), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), poly[{2,5-di(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene}-co-{3-(4'-(3″,7″-dimethyloctyloxy)phenyl)-1,4-phenylenevinylene}-co-{3-(3'-(3',7'-dimethyloctyloxy)phenyl)-1,4-phenylenevinylene}] (SY-PPV), and poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT), and the insulated polymers were polystyrene (PS) and poly(methyl methacrylate) (PMMA). The photonic memory device using the PF/PS blend electret exhibited a dynamic switching behavior with light-writing and voltage-erasing processes both within only 1 s, along with a high contrast on the current on/off ratio between "Photo-On" and "Electrical-OFF" over 106 and the decent retention time for more than 3 months. In addition, the multilevel memory behavior could be observed using different light sources of 405, 450, and 520 nm or energy intensity, which was supported by surface potential analysis. The characteristics were superior to those of the devices using PF/PMMA blend due to the higher charge storage behavior of PS supported by fluorescence analysis. The PF/PS blend film prepared from the chlorobenzene solvent exhibited mesh-like and aggregated PF domains in the PS matrix and enhanced the contact surface area between the semiconductor and blend electret, leading to a higher memory window. The photonic memory behavior was also observed in the blend electrets of PS with the low band gap polymer, MEH-PPV, SY-PPV, or F8BT, by changing the photoresponsive light sources. Our study demonstrated a new electret system to apply on the multilevel photonic memory devices.

Stretchable Fluorescent Polyfluorene/Acrylonitrile Butadiene Rubber Blend Electrospun Fibers through Physical Interaction and Geometrical Confinement.

Stretchable light-emitting polymers are important for wearable electronics; however, the development of intrinsic stretchable light-emitting materials with great performance under large applied strain is the most critical challenge. Herein, this study demonstrates the fabrication of stretchable fluorescent poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene)]/acrylonitrile butadiene rubber (PFN/NBR) blend nanofibers using the uniaxial electrospinning technique. The physical interaction of PFN with NBR and the geometrical confinement of nanofibers are employed to reduce PFN aggregation, leading to the high photoluminescence quantum yield of 35.7%. Such fiber mat film shows stable blue emission at the 50% strain for 200 stretching/release cycles, which has potential applications in smart textiles.

Development of a titanium dioxide nanoparticle pipette-tip for the selective enrichment of phosphorylated peptides.

The selective enrichment of specific proteins or peptides on micropipette tips prior to mass spectrometry analysis, which can minimize non-specific interferences as well as sample loss, has been an important issue in current proteomics field. In this paper, we have developed an easy-to-use phosphopeptide-selective pipette tip in which titanium dioxide nanoparticles were embedded in monolithic structure photopolymerized from ethylene glycol dimethacrylate. The simple and convenient fabrication was feasible in a commercial polypropylene pipette tip. Phosphorylated peptides were isolated from non-phosphopeptides by TiO(2) nanoparticle and eluted by 100 mM ammonium phosphate (pH 8.5), which was compatible with 2,5-dihydroxybenzoic acid (DHB)/1% phosphoric acid matrix and allowed for direct analysis of the elution fraction by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) without the necessity of desalting pretreatment. Tryptic digested alpha-casein and beta-casein spiked into bovine serum albumin (BSA) nonphosphorylated peptides (molar ratio 1:1:10) were used to assess the selectivity of TiO(2) tips. The effect of 50 mM ammonium hydrogencarbonate, pH 8 in 50% acetonitrile used as a wash buffer in reduction of nonspecific bound peptide to TiO(2) tip was dramatic. Almost all non-phosphopeptides were not detected by MALDI-MS analysis. The lowest detectable amount of phosphopeptide was estimated at low femtomole level. The easy-to-use TiO(2)-embeded tips operated in combination with the modified wash and elution conditions enable an efficient phosphopeptide enrichment for mass spectrometric analysis.