Influence of laser annealing on defect-related luminescence of InGaN epilayers

InGaN epilayers exhibiting strong defect-related sub-bandgap emission, which is undesirable in epilayers and quantum well structures designed for light-emitting diodes and laser diodes, have been studied by confocal photoluminescence spectroscopy, Auger electron spectroscopy, and atomic force microscopy. Inhomogeneous spatial distribution of band-edge luminescence intensity and comparatively homogenous distribution of defect-related emission are demonstrated. It is shown that laser annealing at power densities causing the increase of the temperature at the epilayer surface high enough for indium atoms to move to the surface results in suppression of the defect-related emission.     

Synthesis of Linear and V-Shaped Carbazolyl-Substituted Pyridine-3,5-dicarbonitriles Exhibiting Efficient Bipolar Charge Transport and E-Type Fluorescence

With the aim of developing all-organic bipolar semiconductors with high charge mobility and efficient E-type fluorescence (so-called TADF) as environmentally friendly light-emitting materials for optoelectronic applications, four noble metals-free dyes with linear and V-shapes were designed using accepting pyridine-3,5-dicarbonitrile and donating carbazole units. By exploiting a donor-acceptor design strategy and using moieties with different donating and accepting abilities, TADF emitters with a wide variety of molecular weights were synthesized to achieve the optimum combination of charge-transporting and fluorescent properties in one TADF molecule. Depending on molecule structures, different TADF emitters capable of emitting in the range from 453 to 550 nm with photoluminescence quantum yields up to 98 % for the solutions in oxygen-free toluene were obtained. All compounds showed bipolar charge-transport. Hole mobility of 2.8×10⁻³ cm²/Vs at 7×10⁵ V cm⁻¹ was observed for the compound containing two di-tert-butyl-substituted carbazole moieties. The compounds were tested in both non-doped and doped organic light-emitting diodes using different hosts. It was shown that the developed TADF emitters are suitable for different color devices with electroluminescence ranging from blue to yellow and with brightness, maximum current and external quantum efficiencies exceeding 10 000 cd m⁻², 15 cd/A, and 7 %, respectively.     

Cationic ring-opening polymerization of carbazolyl-containing epoxy monomers by triphenyl carbenium salts as thermal- and photolatent initiators

Abstract  

Photoinitiated cationic polymerizations of various epoxy monomers bearing a carbazole moiety, 9-[3-(allyloxy)-2-(oxiran-2-ylmethoxy)propyl]-9H-carbazole, 9-[3-methoxy-2-(oxiran-2-ylmethoxy)propyl]-9H-carbazole, 9-[2-(oxiran-2-ylmethoxy)ethyl]-9H-carbazole, as well as a composition of 3,6-dibromo-9-(oxiran-2-ylmethyl)-9H-carbazole with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate were investigated in bulk using triphenyl carbenium salts having anions such as BF₄ ⁻, SnCl₅ ⁻, and SbCl₆ ⁻. Dark polymerizations of the carbazolyl monomers in the presence of the initiators are studied. These photoinduced polymerization reactions give oligomers of degree of polymerization 4-22. The effect of the anion of the photoinitiator and polymerization time on the polymerization reaction is discussed.     

Dynamics of Isomeric and Enantiomeric Fractions of Pinene in Essential Oil of Picea abies Annual Needles during Growing Season

Norway spruce (Picea abies (L.) H. Karst.) is one of the most important commercial tree species distributed naturally in the Boreal and subalpine forest zone of Europe. All parts of spruce trees, including needles, accumulate essential oils with a variety of chemical properties and ecological functions, such as modulating plant–insect communication. Annual needle samples from 15 trees (five from each of three habitats) of 15–17 years old were assayed for essential oils and their major compounds, including α-pinene, β-pinene, (1S)-(−)-α-pinene, and (1R)-(+)-α-pinene across a growing season. Results showed strong positive correlation between percentages of α- and β-pinene isomers (r = 0.69, p < 0.05) and between pinene isomers and essential oils: α-pinene correlated with essential oil stronger (r = 0.62, p < 0.05) than β-pinene (r = 0.33, p < 0.05). Correlation analyses performed with some weather conditions, including average monthly temperature, growing sum of effective temperatures over 5 °C, duration of sunshine, accumulated precipitation, relative humidity, and pressure, showed that temperature is the most important weather condition related to pinene dynamics: negative correlations of moderate strength were established between percentages of α- and β- pinenes and average monthly temperatures (r = −0.36, p < 0.01, n = 75 and r = −0.33, p < 0.01, n = 75, respectively). Out of pinene enantiomers, only (1S)-(−)-α-pinene showed some negative correlation with monthly temperature (r = −0.26, p < 0.05, n = 75). Different patterns of essential oil and pinene dynamics during growing season within separate habitats suggested that some genetic variables of Picea abies might be involved.     

Relaxation pathways of excited N-(triphenylmethyl)salicylidenimine in solutions

Excited state relaxation of N-(triphenylmethyl)-salicylidenimine (MS1) in protic and aprotic solvents has been investigated by means of absorption pump-probe spectroscopy with femtosecond time resolution and fluorescence spectroscopy with picosecond time resolution. Short-lived excited states and long-lived photoproducts have been identified from the differential absorption spectra. Excited states and photoproducts were different under excitation of enol-closed and cis-keto tautomers. As a result, the commonly accepted excited state relaxation model of aromatic anils, which assumes an ultrafast transformation of excited enol-closed tautomers into cis-keto tautomers, has been modified. Performed quantum chemical calculations suggest that hydrogen-bonded ethanol molecules facilitate formation of cis-keto tautomers and are responsible for their different relaxation pathways in comparison with relaxation of excited enol-closed tauromers. Fluorescence decay on a nanosecond time scale was attributed to aggregated MS1 molecules.     

Stable All‐Organic Radicals with Ambipolar Charge Transport

A series of neutral long‐lived purely organic radicals based on the stable [4‐(N‐carbazolyl)‐2,6‐dichlorophenyl]bis(2,4,6‐trichlorophenyl)methyl radical adduct (Cbz‐TTM) is reported herein. All compounds exhibit ambipolar charge‐transport properties under ambient conditions owing to their radical character. High electron and hole mobilities up to 10^?2 and 10^?3 cm² V^?1 s^?1, respectively, were achieved. Xerographic single‐layered photoreceptors were fabricated from the radicals studied herein, exhibiting good xerographic photosensitivity across the visible spectrum.     

Glucose Dehydrogenase Based Bioelectrode Utilizing a Synergistic Scheme of Substrate Conversion

A Bioelectrode utilizing a synergistic scheme of substrate conversion was built using glucose dehydrogenase from Acinetobacter calcoaceticus immobilized on the surface of a graphite electrode. At saturated glucose concentration the bioelectrode responded to the low reactive substrate hexacyanoferrate(III) with a sensitivity of 0.0035 µA/µM cm². The response of the bioelectrode increased up to the 3.4×10⁴ fold in the presence of high reactive organic electron acceptors (mediators). The increase of the response depended on the concentration of the mediators and their chemical nature. The sensitivity of the bioelectrode to mediators reached 7.3–77 µA/µM cm². The comparison of the bioelectrode sensitivity with kinetic parameters of enzyme action in homogeneous solution revealed good correlation between the sensitivity of the bioelectrode and the predicted value from the kinetic scheme of the reactivity of mediators. This confirms a synergistic scheme of bioelectrode action.     

THE NATURE OF INTERMEDIATES OF ISOMERISATION AND OF NUCLEOPHILIC SUBSTITUTION OF β-CHLOROALKYLTHIOCARBOXYLIC ACID DERIVATIVES

Abstract

The addition of sulfenchlorides to the derivatives of unsaturated carboxylic acids results in the formation of kinetically controllable adducts, which in solution and even in a solid state isomerize into thermodinamically stable ones. The derivatives of β-chloroalkyl tiocarboxylic acids readily enter nucleophilic substitution reactions, particularly the reaction of hydrolytic splitting of C-C1 bonding. There still remains a problem to be solved concerning the nature of the intermediates which appear in the process of isomerisation and hydrolysis of these compounds. To solve the problem the research was carried out on the effect of chlorine and perchlorate ions concerning the rate of hydrolysis and isomerisation of the derivatives 2(3)-chloro-3(2)-alkylthio-2-methylpropanoic acids.     

Electrochemical Peroxidase‐Catalase Clark‐Type Biosensor: Computed and Experimental Response

A bioelectrode containing immobilized catalase and peroxidase was built using a Clark‐type oxygen electrode. The bioelectrode responded to hydrogen peroxide (H₂O₂) as well as to acetaminophen (Ac). The sensitivity of the bioelectrode for H₂O₂ was 0.35 mM O₂/mM H₂O₂ and for Ac it was 0.23–1.05 µM O₂/µM Ac at pH 6.6 and 25 °C. The limit of detection of Ac varied from 12 to 44 µM. The half‐time of the bioelectrode response to hydrogen peroxide was 36 s. The modeling of the bioelectrode action was performed digitally at transition and steady‐state conditions using finite difference technique. The calculated half‐time of the bioelectrode response to hydrogen peroxide was 53 % larger and the steady‐state response 11 % less than experimentally determined. The response to Ac was 2–3 times smaller in comparison to the experimental values. The calculated response change correlated with the experimentally determined when the catalase and peroxidase concentrations in the biocatalytical membrane changed 3–4 orders of magnitude. The simulations of the bioelectrode response revealed that the bioelectrode acts in diffusion limiting conditions at almost all enzymes concentrations. The model appears to be promising for optimization of the bioelectrode response.