Luminous Self-Assembled Fibers of Azopyridines and Quantum Dots Enabled by Synergy of Halogen Bond and Alkyl Chain Interactions.

Herein, a simple approach for the fabrication of luminous self-assembled fibers based on halogen-bonded azopyridine complexes and oleic acid-modified quantum dots (QDs) is reported. The QDs uniformly align on the edge of the self-assembled fibers through the formation of van der Waals force between the alkyl chain of oleic acid on the QD surface and the alkyl chain of the halogen-bonded complexes, 15Br or 15I. Furthermore, the intermolecular interaction mechanism was elucidated by using Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and density functional theory (DFT) calculations. This approach results in retention of the fluorescence properties of the QDs in the fibers. In addition, the bromine-bonded fibers can be assembled into tailored directional fibers upon evaporation of the solvent (tetrahydrofuran) when using capillaries via the capillary force. Interestingly, the mesogenic properties of the halogen-bonded complexes are preserved in the easily prepared halogen-bonded fluorescent fibers; this provides new insight into the design of functional self-assembly materials.

In-Situ Oxidative Polymerization of Pyrrole Composited with Cellulose Nanocrystal by Reactive Ink-Jet Printing on Fiber Substrates.

A simple and novel method for the deposition of polypyrrole (PPy) and cellulose nanocrystal (CNC) composites on different fiber substrates by reactive ink-jet printing was proposed. PPy/CNCs composites were successfully prepared, and the surface resistance of conductive layer deposited on different fiber substrates is the least when the monomer concentration is 0.6 M. PPy/CNCs were deposited on polyethylene terephthalate (PET) to form a conductive layer by adding polyvinyl alcohol (PVA), and the optimum sintering temperature is 100 °C (monomer/PVA ratio 4.0, conductivity 0.769 S cm-1). The PPy/CNCs conductive layer deposited on the paper has the lowest surface resistance and the best adhesion, and the surface resistance of PPy/CNCs conductive layer decreases first and then increases with the increase of sulfonate concentration. Moreover, the volume of anion in sulfonate will affect the arrangement and aggregation of PPy molecular chain in composite materials. Appropriate sulfonate doping can improve the conductivity and stability of conductive paper, and the maximum conductivity is 0.813 S cm-1. Three devices based on PPy/CNCs conductive paper were proposed and fabricated. Therefore, this ink-jet printing provides a new method for the preparation of conductive materials, sensors, energy storage and electromagnetic shielding, etc.

LBL assembly of Ag@Ti3C2TXand chitosan on PLLA substrate to enhance antibacterial and biocompatibility.

Poly L-lactic acid (PLLA) is a non-toxic, biocompatible degradable polymer material with excellent mechanical properties after moulding. However, it faces challenges in the use of biomedical materials because of its intolerance to bacteria. Here, we use an easy-to-operate method to prepare a composite multilayer membrane: PLLA membrane was used as substrates to assemble positively charged chitosan and negatively charged Ag@MXene on the surface using the layer-by-layer (LBL) method. The assembly process was detected by fluorescein isothiocyanate-labelled chitosan and the thickness of the coating multilayer was also detected as 210.0 ± 12.1 nm for P-M membrane and 460.5 ± 26.5 nm for P-Ag@M membrane. The surface self-assembled multilayers exhibited 91.27% and 96.11% growth inhibition ratio againstEscherichia coliandStaphylococcus aureusstrains under 808 nm near-infrared laser radiation with a synergistic photothermal antibacterial effect. Furthermore, best biocompatibility of P-M and P-Ag@M membranes compare to PLLA membrane motivated us to further explore its application in biomedical materials.

Printed and Flexible Capacitive Pressure Sensor with Carbon Nanotubes based Composite Dielectric Layer.

Flexible pressure sensors have attracted tremendous attention from researchers for their widely applications in tactile artificial intelligence, electric skin, disease diagnosis, and healthcare monitoring. Obtaining flexible pressure sensors with high sensitivity in a low cost and convenient way remains a huge challenge. In this paper, the composite dielectric layer based on the mixture of carbon nanotubes (CNTs) with different aspect ratios and polydimethylsiloxane (PDMS) was employed in flexible capacitive pressure sensor to increase its sensitivity. In addition, the screen printing instead of traditional etching based methods was used to prepare the electrodes array of the sensor. The results showed that the aspect ratio and weight fraction of the CNTs play an important role in improving the sensitivity of the printed capacitive pressure sensor. The prepared capacitive sensor with the CNTs/PDMS composite dielectric layer demonstrated a maximum sensitivity of 2.9 kPa-1 in the pressure range of 0-450 Pa, by using the CNTs with an aspect ratio of 1250-3750 and the weight fraction of 3.75%. The mechanism study revealed that the increase of the sensitivity of the pressure sensor should be attributed to the relative permittivity increase of the composite dielectric layer under pressure. Meanwhile, the printed 3 × 3 and 10 × 10 sensor arrays showed excellent spatial resolution and uniformity when they were applied to measure the pressure distribution. For further applications, the flexible pressure sensor was integrated on an adhesive bandage to detect the finger bending, as well as used to create Morse code by knocking the sensor to change their capacitance curves. The printed and flexible pressure sensor in this study might be a good candidate for the development of tactile artificial intelligence, intelligent medical diagnosis systems and wearable electronics.

Nano-Silver Ink of High Conductivity and Low Sintering Temperature for Paper Electronics.

Highly conductive ink with low sintering temperature is important for printed electronics on paper substrate. Silver nanoparticles (Ag NPs) of different average radii ranging from 48 to 176 nm were synthesized by adjusting the Ag+ concentration in the reaction process. The electric resistivity of the Ag NP-based ink film in relation to Ag NP size, sintering temperature, amount of PVP capping agent on Ag NP surface, and morphology evolution of the film during heating process was investigated. It was found that the resistivity of the films reduced very rapidly with increasing particle size due above all to reduced amount of protective agent capping on the Ag NPs. A semi-empirical relationship between the resistivity and the particle size was proposed. With the help of this mathematical expression, one gains both systematic and detailed insight to the resistivity evaluation with regard to the Ag particle size. The optimal electric resistivity of 4.6 µΩ cm was achieved at 140 °C for 10 min which was very close to the resistivity value of bulk Ag (1.58 µΩ cm). Mechanical flexibility of the printed electronics with the Ag NP-based ink on paper substrates was investigated. The prints on the art coated paper exhibited better flexibility compared to that on the photopaper. This might be attributed to the surface coating composition, surface morphology of the paper, and their corresponding ink absorption property.

Silver Nanoparticles Based Ink with Moderate Sintering in Flexible and Printed Electronics.

Printed electronics on flexible substrates has attracted tremendous research interest research thanks its low cost, large area production capability and environmentally friendly advantages. Optimal characteristics of silver nanoparticles (Ag NPs) based inks are crucial for ink rheology, printing, post-print treatment, and performance of the printed electronics devices. In this review, the methods and mechanisms for obtaining Ag NPs based inks that are highly conductive under moderate sintering conditions are summarized. These characteristics are particularly important when printed on temperature sensitive substrates that cannot withstand sintering of high temperature. Strategies to tailor the protective agents capping on the surface of Ag NPs, in order to optimize the sizes and shapes of Ag NPs as well as to modify the substrate surface, are presented. Different (emerging) sintering technologies are also discussed, including photonic sintering, electrical sintering, plasma sintering, microwave sintering, etc. Finally, applications of the Ag NPs based ink in transparent conductive film (TCF), thin film transistor (TFT), biosensor, radio frequency identification (RFID) antenna, stretchable electronics and their perspectives on flexible and printed electronics are presented.

Selective Conversion from p-Type to n-Type of Printed Bottom-Gate Carbon Nanotube Thin-Film Transistors and Application in Complementary Metal-Oxide-Semiconductor Inverters.

The fabrication of printed high-performance and environmentally stable n-type single-walled carbon nanotube (SWCNT) transistors and their integration into complementary (i.e., complementary metal-oxide-semiconductor, CMOS) circuits are widely recognized as key to achieving the full potential of carbon nanotube electronics. Here, we report a simple, efficient, and robust method to convert the polarity of SWCNT thin-film transistors (TFTs) using cheap and readily available ethanolamine as an electron doping agent. Printed p-type bottom-gate SWCNT TFTs can be selectively converted into n-type by deposition of ethanolamine inks on the transistor active region via aerosol jet printing. Resulted n-type TFTs show excellent electrical properties with an on/off ratio of 106, effective mobility up to 30 cm2 V-1 s-1, small hysteresis, and small subthreshold swing (90-140 mV dec-1), which are superior compared to the original p-type SWCNT devices. The n-type SWCNT TFTs also show good stability in air, and any deterioration of performance due to shelf storage can be fully recovered by a short low-temperature annealing. The easy polarity conversion process allows construction of CMOS circuitry. As an example, CMOS inverters were fabricated using printed p-type and n-type TFTs and exhibited a large noise margin (50 and 103% of 1/2 Vdd = 1 V) and a voltage gain as high as 30 (at Vdd = 1 V). Additionally, the CMOS inverters show full rail-to-rail output voltage swing and low power dissipation (0.1 µW at Vdd = 1 V). The new method paves the way to construct fully functional complex CMOS circuitry by printed TFTs.

The protonated 2-halogenated imidazolium cation as the noncovalent interaction donor: the σ-hole and π-hole interactions.

The σ-hole and π-hole of the protonated 2-halogenated imidazolium cation (XC3H4N2+; X = F, Cl, Br, I) were investigated and analyzed. The monomers of (CH3)3SiY(Y=F, Cl, Br, I), considered as the Lewis base, were combined with the σ-hole and π-hole of XC3H4N2+ to form the σ-hole and π-hole interactions in the bimolecular complexes (CH3)3SiY · · · XC3H4N2+ and (CH3)3SiY · · · C3(X)H4N2+(X/Y=F, Cl, Br, I), respectively. For both the σ-hole and π-hole interactions, the equilibrium geometries of complexes show regular changes according to the sequence of heavy sequence of the noncovalent interaction acceptors and donors. The electrostatic energy is the main contribution in the formation of both kinds of interactions, it has linear relations with the V S,max values of σ-hole and the V' S,max values of π-hole. Both the σ-hole and π-hole interactions belong to the closed-shell and noncovalent interactions. The π-hole interactions are stronger than the σ-hole interactions. For the π-hole interactions, the contribution percents of the dispersion energies are somewhat greater than those of the σ-hole interactions, while it is contrary for the polarization energy. Graphical Abstract The protonated 2-halogenated imidazolium cation as the noncovalent interaction donor: the σ-hole and π-hole interactionsᅟ.

Chalcogen- and halogen-bonds involving SX2 (X = F, Cl, and Br) with formaldehyde.

The capacity of SX2 (X = F, Cl, and Br) to engage in different kinds of noncovalent bonds was investigated by ab initio calculations. SCl2 (SBr2) has two σ-holes upon extension of Cl (Br)-S bonds, and two σ-holes upon extension of S-Cl (Br) bonds. SF2 contains only two σ-holes upon extension of the F-S bond. Consequently, SCl2 and SBr2 form chalcogen and halogen bonds with the electron donor H2CO while SF2 forms only a chalcogen bond, i.e., no F···O halogen bond was found in the SF2:H2CO complex. The S···O chalcogen bond between SF2 and H2CO is the strongest, while the strongest halogen bond is Br···O between SBr2 and H2CO. The nature of these two types of noncovalent interaction was probed by a variety of methods, including molecular electrostatic potentials, QTAIM, energy decomposition, and electron density shift maps. Termolecular complexes X2S···H2CO···SX'2 (X = F, Cl, Br, and X' = Cl, Br) were constructed to study the interplay between chalcogen bonds and halogen bonds. All these complexes contained S···O and Cl (Br)···O bonds, with longer intermolecular distances, smaller values of electron density, and more positive three-body interaction energies, indicating negative cooperativity between the chalcogen bond and the halogen bond. In addition, for all complexes studied, interactions involving chalcogen bonds were more favorable than those involving halogen bonds. Graphical Abstract Molecular electrostatic potential and contour map of the Laplacian of the electron density in Cl2S···H2CO···SCl2 complex.

Flexible CMOS-Like Circuits Based on Printed P-Type and N-Type Carbon Nanotube Thin-Film Transistors.

P-type and n-type top-gate carbon nanotube thin-film transistors (TFTs) can be selectively and simultaneously fabricated on the same polyethylene terephthalate (PET) substrate by tuning the types of polymer-sorted semiconducting single-walled carbon nanotube (sc-SWCNT) inks, along with low temperature growth of HfO2 thin films as shared dielectric layers. Both the p-type and n-type TFTs show good electrical properties with on/off ratio of ≈105 , mobility of ≈15 cm2 V-1 s-1 , and small hysteresis. Complementary metal oxide semiconductor (CMOS)-like logic gates and circuits based on as-prepared p-type and n-type TFTs have been achieved. Flexible CMOS-like inverters exhibit large noise margin of 84% at low voltage (1/2 Vdd = 1.5 V) and maximum voltage gain of 30 at Vdd of 1.5 V and low power consumption of 0.1 µW. Both of the noise margin and voltage gain are one of the best values reported for flexible CMOS-like inverters at Vdd less than 2 V. The printed CMOS-like inverters work well at 10 kHz with 2% voltage loss and delay time of ≈15 µs. A 3-stage ring oscillator has also been demonstrated on PET substrates and the oscillation frequency of 3.3 kHz at Vdd of 1 V is achieved.

Flexible transparent conductive films combining flexographic printed silver grids with CNT coating.

A high-performance ITO-free transparent conductive film (TCF) has been made by combining high resolution Ag grids with a carbon nanotube (CNT) coating. Ag grids printed with flexography have a 20 µm line width at a grid interval of 400 µm. The Ag grid/CNT hybrid film exhibits excellent overall performance, with a typical sheet resistance of 14.8 Ω/□ and 82.6% light transmittance at room temperature. This means a 23.98% reduction in sheet resistance and only 2.52% loss in transmittance compared to a pure Ag grid film. Analysis indicates that filling areas between the Ag grids and interconnecting the silver nanoparticles with the CNT coating are the primary reasons for the significantly improved conductivity of the hybrid film that also exhibits excellent flexibility and mechanical strength compared to an ITO film. The hybrid film may fully satisfy the requirements of different applications, e.g. use as the anode of polymer solar cells (PSCs). The J-V curve shows that the power conversion efficiency (PCE) of the PSCs using the Ag grid/CNT hybrid anode is 0.61%, which is 24.5% higher than that of the pure Ag grids with a PCE of 0.49%. Further investigations to improve the performance of the solar cells based on the printed hybrid TCFs are ongoing.

[Preparation and study on the spectra of conductive nano-silver film].

The preparation and study on the spectra of conductive nano-silver film were done under mild conditions. The silver citrate emulsion coating on the surface of PET was reduced by ascorbic acid (Vc) aqueous solution to prepare a silver film. The morphology, crystal structure, surface roughness and conductivity of the silver film were measured by FTIR, UV-Vis spectrum, X-ray diffraction (XRD), scanning electron microscope, scanning probe microscope system and so on. It was found that the silver citrate emumsion has a homogenous particle distribution from 60 nm-150 nm. The UV-Vis spectrum of the silver film shows a peak at 430 nm, and the silver thin film was considered to have a typical nano-scale structure. By the comparison of the XRD patterns of the films treated and untreated with water, it was concluded that the further deoxidization of silver citrate could be accelerated by water. The crystal structure of the silver film was improved and the surface resistance of the silver film was decreased greatly. The effect of ethanol on the decrease in the resistance of the silver film is much less than that of water.