Binghao Wang

Chitosan fibers enhanced gellan gum hydrogels with superior mechanical properties and water-holding capacity.

New hydrogels based on acetylated gellan gum (A-gellan) and chitosan fibers (F-chitosan) are prepared and coded as F-chitosan/A-gellan. Compared to A-gellan hydrogel, F-chitosan/A-gellan hydrogels show higher storage moduli and water-holding capacity. Specifically, the storage modulus of 2.0 F-chitosan/A-gellan (mass ratio of chitosan fibers and gellan gum is 2:1) hydrogels at regular frequency of 1 rad/s is 2.2 kPa, approximately 4.6 times more than that of the A-gellan hydrogel. In addition, the fractural morphology analysis of A-gellan and 2.0 F-chitosan/A-gellan hydrogels treated by different dry methods indicates that the 2.0 F-chitosan/A-gellan hydrogel has more stable macrostructure. Moreover, compared to A-gellan gel, 2.0 F-chitosan/A-gellan gel shows higher activation energy and water-holding capacity during dehydration and higher dielectric constant after dehydration. These results can be attributed to the special advantages of chitosan fibers, which are full of polar and hydrophilic amino group and can transfer the load applied on the hydrogels in fiber form.

New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH2)3)(CH3NH3)nPbnI3n+1: Structure, Properties, and Photovoltaic Performance

We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden-Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterparts with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH2)3)(CH3NH3)3Pb3I10 (n = 3) compound. Compact thin films from the (C(NH2)3)(CH3NH3)3Pb3I10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ∼1 V and a striking fill factor of ∼80%.

UV-Ozone Interfacial Modification in Organic Transistors for High-Sensitivity NO2 Detection

A new type of nitrogen dioxide (NO2 ) gas sensor based on copper phthalocyanine (CuPc) thin film transistors (TFTs) with a simple, low-cost UV-ozone (UVO)-treated polymeric gate dielectric is reported here. The NO2 sensitivity of these TFTs with the dielectric surface UVO treatment is ≈400× greater for [NO2 ] = 30 ppm than for those without UVO treatment. Importantly, the sensitivity is ≈50× greater for [NO2 ] = 1 ppm with the UVO-treated TFTs, and a limit of detection of ≈400 ppb is achieved with this sensing platform. The morphology, microstructure, and chemical composition of the gate dielectric and CuPc films are analyzed by atomic force microscopy, grazing incident X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, revealing that the enhanced sensing performance originates from UVO-derived hydroxylated species on the dielectric surface and not from chemical reactions between NO2 and the dielectric/semiconductor components. This work demonstrates that dielectric/semiconductor interface engineering is essential for readily manufacturable high-performance TFT-based gas sensors.

Boost up dielectric constant and push down dielectric loss of carbon nanotube/cyanate ester composites via gradient and layered structure design

How to develop high-k materials with extremely low dielectric loss based on commercially available conductors and polymers is still a big challenge. Here we present a general method that simultaneously increases the dielectric constant ten times and decreases the dielectric loss by five orders of magnitude. By adjusting the prepolymerization time of multi-walled carbon nanotube (MWCNT) and cyanate ester (CE) blends and using the layer-by-layer casting procedure, precisely controllable dispersion and distribution of MWCNTs in polymers were achieved. Consequently, a three-layer material (PE-[g-MWCNT0.5/CE-75%]2) with an optimized prepolymerization degree, consisting of two MWCNT/CE composite layers and one polyethylene (PE) thin film, exhibits a dielectric constant of 1027 and a dielectric loss of 0.02 at 1 Hz. This is one of the best results reported for polymer composites made up of nano-carbon or ceramics to date. The mechanism behind this was elucidated by analyzing the polarization of induced charges and transport of free charges. The formation of vastly interconnected networks of space charge regions, and the existence of a conductor fault and an insulating layer are the main factors that determine an extraordinarily high dielectric constant and extremely low dielectric loss simultaneously.

Low-Temperature Atomic Layer Deposition of MoS2 Films

Wet chemical screening reveals the very high reactivity of Mo(NMe2 )4 with H2 S for the low-temperature synthesis of MoS2 . This observation motivated an investigation of Mo(NMe2 )4 as a volatile precursor for the atomic layer deposition (ALD) of MoS2 thin films. Herein we report that Mo(NMe2 )4 enables MoS2 film growth at record low temperatures-as low as 60 °C. The as-deposited films are amorphous but can be readily crystallized by annealing. Importantly, the low ALD growth temperature is compatible with photolithographic and lift-off patterning for the straightforward fabrication of diverse device structures.

Carbohydrate-Assisted Combustion Synthesis to Realize High-Performance Oxide Transistors

Owing to high carrier mobilities, good environmental/thermal stability, excellent optical transparency, and compatibility with solution processing, thin-film transistors (TFTs) based on amorphous metal oxide semiconductors (AOSs) are promising alternatives to those based on amorphous silicon (a-Si:H) and low-temperature (<600 °C) poly-silicon (LTPS). However, solution-processed display-relevant indium-gallium-tin-oxide (IGZO) TFTs suffer from low carrier mobilities and/or inferior bias-stress stability versus their sputtered counterparts. Here we report that three types of environmentally benign carbohydrates (sorbitol, sucrose, and glucose) serve as especially efficient fuels for IGZO film combustion synthesis to yield high-performance TFTs. The results indicate that these carbohydrates assist the combustion process by lowering the ignition threshold temperature and, for optimal stoichiometries, enhancing the reaction enthalpy. IGZO TFT mobilities are increased to >8 cm(2) V(-1) s(-1) on SiO2/Si gate dielectrics with significantly improved bias-stress stability. The first correlations between precursor combustion enthalpy and a-MO densification/charge transport are established.

Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport

Significance Shear-printing of electroactive polymers using natural brushes is a promising film deposition technique for printed electronics capable of microstructure control and electrical properties enhancement over large areas. Nevertheless, the interplay between film printing parameters, microstructure development, and charge transport is not well-understood. We report that natural brush-printing greatly enhances charge transport by as much as 5.7× through control of polymer nanofibril aggregate growth and backbone alignment, attributable to the oriented squamae of the natural hair. However, while brush shear-induced aggregation enhances charge transport, we show that backbone alignment alone does not guarantee charge transport anisotropy. These results provide additional understanding of shear-induced enhanced charge transport and set processing guidelines for high-performance printed organic circuitry. Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization.

Growth of Highly Oriented Ultrathin Crystalline Organic Microstripes: Effect of Alkyl Chain Length.

The growth of organic semiconductor with controllable morphology is a crucial issue for achieving high-performance devices. Here we present the systematic study of the effect of the alkyl chain attached to the functional entity on controlling the growth of oriented microcrystals by dip-coating. Alkylated DTBDT-based molecules with variable chain lengths from n-butyl to n-dodecyl formed into one-dimensional micro- or nanostripe crystals at different pulling speeds. The alignment and ordering are significantly varied with alkyl chain length, as is the transistor performance. Highly uniform oriented and higher-molecular-order crystalline stripes with improved field-effect mobility can be achieved with an alkyl-chain length of around 6. We attribute this effect to the alkyl-chain-length-dependent packing, solubility, and self-assembly behavior.

High-k Gate Dielectrics for Emerging Flexible and Stretchable Electronics

Recent advances in flexible and stretchable electronics (FSE), a technology diverging from the conventional rigid silicon technology, have stimulated fundamental scientific and technological research efforts. FSE aims at enabling disruptive applications such as flexible displays, wearable sensors, printed RFID tags on packaging, electronics on skin/organs, and Internet-of-things as well as possibly reducing the cost of electronic device fabrication. Thus, the key materials components of electronics, the semiconductor, the dielectric, and the conductor as well as the passive (substrate, planarization, passivation, and encapsulation layers) must exhibit electrical performance and mechanical properties compatible with FSE components and products. In this review, we summarize and analyze recent advances in materials concepts as well as in thin-film fabrication techniques for high- k (or high-capacitance) gate dielectrics when integrated with FSE-compatible semiconductors such as organics, metal oxides, quantum dot arrays, carbon nanotubes, graphene, and other 2D semiconductors. Since thin-film transistors (TFTs) are the key enablers of FSE devices, we discuss TFT structures and operation mechanisms after a discussion on the needs and general requirements of gate dielectrics. Also, the advantages of high- k dielectrics over low- k ones in TFT applications were elaborated. Next, after presenting the design and properties of high- k polymers and inorganic, electrolyte, and hybrid dielectric families, we focus on the most important fabrication methodologies for their deposition as TFT gate dielectric thin films. Furthermore, we provide a detailed summary of recent progress in performance of FSE TFTs based on these high- k dielectrics, focusing primarily on emerging semiconductor types. Finally, we conclude with an outlook and challenges section.

Scandium-Catalyzed Self-Assisted Polar Co-monomer Enchainment in Ethylene Polymerization

Direct coordinative copolymerization of ethylene with functionalized co-monomers is a long-sought-after approach to introducing polyolefin functionality. However, functional-group Lewis basicity typically depresses catalytic activity and co-monomer incorporation. Finding alternatives to intensively studied group 4 d0 and late-transition-metal catalysts is crucial to addressing this long-standing challenge. Shown herein is that mono- and binuclear organoscandium complexes with a borate cocatalyst are active for ethylene + amino olefin [AO; H2 C=CH(CH2 )n NR2 ] copolymerizations in the absence of a Lewis-acidic masking reagent. Both activity (up to 4.2×102  kg mol-1 ⋅h-1>  atm-1> ) and AO incorporation (up to 12 % at 0.2 m [AO]) are appreciable. Linker-length-dependent (n) AO incorporation and mechanistic probes support an unusual functional-group-assisted enchainment mechanism. Furthermore, the binuclear catalysts exhibit enhanced AO tolerance and enhanced long chain AO incorporation.