Synthesis,crystal growth,thermal studies and scaled quantum chemical studies of structural and vibrational spectra of the highly efficient organic NLO crystal: 1-(4-Aminophenyl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one

A new chalcone derivative, 1-(4-aminophenyl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one (DMAC) was synthesized and single crystals were grown by slow evaporation technique. The FT-Raman and FT-IR spectra of the sample were recorded in the region 3700–100 cm⁻¹ and 4000–400 cm⁻¹, respectively. The spectra were interpreted with the aid of normal coordinate analysis following structure optimizations and force field calculations based on density functional theory (DFT) at the B3LYP/6-311+G(d,p) level of theory. Normal coordinate calculations were performed using the DFT force field, corrected by a recommended set of scaling factors, yielding fairly good agreement between the observed and calculated wavenumbers. DMAC is thermally stable up to 220.0 °C and optically transparent in the visible region. Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). The SHG efficiency of DMAC is observed to be 10 times that of standard urea crystal of identical particle size.     

Nanoseed-assisted rapid formation of ultrathin ZnO nanorods for efficient room temperature NO2 detection

The influence of ZnO nanoseeds on the formation of ZnO nanorods from ε-Zn(OH)₂ in NaOH solution at 80 °C was investigated, using ZnO nanoparticles with a diameter of 4–10 nm as the seeds. The experimental results indicated that the presence of ZnO nanoseeds promoted the rapid heterogeneous formation of ultrathin ZnO nanorods. Compared with the ZnO submicron rods with a diameter of 0.5–1.0 µm, the ultrathin ZnO nanorods with a diameter of 10–15 nm were found to be more sensitive for detecting NO₂ at room temperature owing to their higher variation of channel conduction to the diameter.     

In situ chemical reduction and functionalization of graphene oxide for electrically conductive phenol formaldehyde composites

We report an efficient one-step approach to reduce and functionalize graphene oxide (GO) during the in situ polymerization of phenol and formaldehyde. The hydrophilic and electrically insulating GO is converted to hydrophobic and electrically conductive graphene with phenol as the main reducing agent. Simultaneously, functionalization of GO is realized by the nucleophilic substitution reaction of the epoxide groups of GO with the hydroxyl groups of phenol in an alkali condition. Different from the insulating GO and phenol formaldehyde resin (PF) components, PF composites are electrically conductive due to the incidental reduction of GO during the in situ polymerization. The electrical conductivity of PF composite with 0.85 vol.% of GO is 0.20 S/m, nearly nine orders of magnitude higher than that of neat PF. Moreover, the efficient reduction and functionalization of GO endows the PF composites with high thermal stability and flexural properties. A striking increase in decomposition temperature is achieved with 2.3 vol.% of GO. The flexural strength and modulus of the PF composite with 1.7 vol.% GO are increased by 316.8% and 56.7%, respectively.     

Temperature effect on polaron recombination in conjugated polymers

The microcosmic mechanism of electroluminescence in polymer light emitting diodes (PLEDs) is the recombination of the oppositely charged polarons. In previous studies, it has been demonstrated that the temperature-induced irregular lattice vibration may have non-negligible influence on polaron dynamics. Nevertheless, there are few reports about thermal effect on recombination process between polaron pair, although it is very important for the performance of PLEDs. In this paper, we adopt the modified one-dimensional tight-binding model, including to which the thermal random force, and explore the temperature effect on polaron collision driven by electric field with different strengths. The dynamical simulation is performed by using the non-adiabatic evolution method. The results show that under the influence of electric field, the oppositely charged polarons could recombine into either an exciton with one lattice distortion, or the mixed state of polaron pair and exciton with two lattice distortions. It depends on both field strength and temperature. Anyway, after including temperature effect, a significant improvement of exciton yield is obtained. In addition, the new-formed exciton could perform a random walk along the polymer chain driven by the thermal random force when its strength is large enough. If we further increase the temperature, the stability of exciton would become worse.     

Influence of oligothiophene-functionalized co-sensitizer on the electron injection efficiency for multiple dye-TiO2 interface

Co-sensitizer has been employed in dye-sensitized solar cells (DSSCs) to enhance light harvesting at organic/inorganic heterogeneous. Here, the multiple dyes@TiO₂ interface has been investigated by density functional theory simulations, to explore the role of varied oligothiophene-functionalized co-sensitizers on the electron injection efficiency. In presence of co-sensitizers, the simulated absorption spectra broaden with the increasing of the number of thiophene from 0, 1, to 2. Meanwhile, the co-sensitizer modifies the energy alignment of interface, and influences the electronic coupling between dye and TiO₂. Critically, the ratio of electron-hole recombination and electron injection rates k_rec/k_inj based on Marcus theory for both dye and co-sensitizer decrease significantly with increasing of the number of oligothiophene, resulting in the improved electron injection efficiency. Our result implies that the electron injection efficiency depends on the number of thiophene in co-sensitizer largely, and appropriate number plays an active role in tuning the electronic properties of hybrid heterostructure.     

An efficient and secure cipher scheme for images confidentiality preservation

In this paper, a novel image encryption scheme based on two rounds of substitution–diffusion is proposed. Two main objectives have guided the design of this scheme: (a) robustness against the most known type of attacks (statistical, chosen/known plaintext, ciphertext-only and brute force attacks) and (b) efficiency in terms of computational complexity (i.e., execution time reduction) in order to meet recent mobiles’ applications’ requirements. First, a dynamic key, changed for every input image is generated and used as the basis to construct the substitution and diffusion processes. Then, the encryption process is performed by the transmitter based on a non-linear S-box (substitution) and a matrix multiplication (diffusion), applied on each sub-matrix of the image. At the destination side, decryption is applied in the reverse order. We have conducted several series of experiments to evaluate the effectiveness of the proposed scheme. The obtained results validated the robustness of our scheme against all considered types of attacks and showed an improvement in terms of execution time reduction compared to the recent existed image-encryption schemes.     

Comparison of hot corrosion resistance of Sm2Zr2O7 and (Sm0.5Sc0.5)2Zr2O7 ceramics in Na2SO4+V2O5 molten salt

Sm₂Zr₂O₇ and (Sm_0.5Sc_0.5)₂Zr₂O₇ ceramics were fabricated by a chemical co-precipitation and calcination method, and their hot corrosion behaviors in Na₂SO₄+V₂O₅ molten salt were investigated. Hot corrosion tests were carried at 700 °C, 800 °C and 900 °C for 4 h, and corroded surfaces were investigated using X-ray diffractometer and scanning electron microscopy. The corrosion products of Sm₂Zr₂O₇ ceramics were composed of SmVO₄ and monoclinic-ZrO₂, while those of (Sm_0.5Sc_0.5)₂Zr₂O₇ ceramic consisted of SmVO₄ and Zr₅Sc₂O₁₃. Considering the fact that Zr₅Sc₂O₁₃ is more desirable than monoclinic-ZrO₂ for thermal barrier coating applications, (Sm_0.5Sc_0.5)₂Zr₂O₇ showed better corrosion resistance to Na₂SO₄+V₂O₅ salt than Sm₂Zr₂O₇. The hot corrosion mechanisms of Sm₂Zr₂O₇ and (Sm_0.5Sc_0.5)₂Zr₂O₇ in Na₂SO₄+ V₂O₅ salt were discussed in detail.     

A surface modification layer capable of tolerating substrate contamination on transparent electrodes of organic electronic devices

An organic molecule, hexaazatriphenylene hexacarbonitrile (HAT-CN), is found that it can be used not only as a hole-injecting material but also a surface modification material to clean contaminated substrate electrodes for the fabrication of organic electronic devices. As an example, HAT-CN can modify or “clean” indium-tin-oxide (ITO) anode surface in organic light-emitting diodes (OLEDs). Negative effect from ITO surface contamination on the electroluminescence performance of OLEDs can be dramatically reduced with this modification layer. As a result, the OLEDs with the same device architecture but with different ITO surface conditions, even with intentional contamination, can all exhibit substantially identical and superior electroluminescence performance. The surface modification function of this material is feasibly useful for the real fabrications of OLEDs as well as for advanced research on other organic electronic devices.     

Interplay of interfacial compounds,catalyst thickness and carbon precursor supply in the selectivity of single-walled carbon nanotube growth

This study is devoted to elucidate the interplay of catalyst thickness and growth conditions in the activation and selectivity of single-walled carbon nanotube growth using cobalt deposited on Si/SiO₂ as a model system. In situ Raman studies reveal that thin catalyst layers require a higher pressure of carbon precursor to initiate nanotube growth. However, if the catalysts are pre-reduced, all catalyst thicknesses display the same low threshold pressure and a higher yield of single-walled carbon nanotubes. To explain these results, catalysts formed from a gradient of cobalt thickness are studied. Surface analyses show that during the catalyst preparation, catalyst atoms at the interface with silica form small and hard-to-reduce silicate nanoparticles while the catalyst in excess leads to the formation of large oxide particles. Weakly-reducing conditions of pretreatment or synthesis are sufficient to reduce the large oxide particles and to lead to the growth of large-diameter multi-walled carbon nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled carbon nanotubes. These results show that reaction of the catalyst with the support to form more refractory compounds greatly impact the nucleation yield and the growth selectivity of single-walled carbon nanotubes.