Investigation on relationship between charge transfer position and dielectric definition of average energy gap in Eu3+-doped compounds

The dielectric definition of average energy gap E-g of the chemical bond has been calculated quantitatively in Eu3+-doped 30 lanthanide compounds based on the dielectric theory of chemical bond for complex structure crystals. The relationship between the experimental charge transfer (CT) energy of Eu3+ and the corresponding average energy gap E-g has been studied. The results show that the CT energy increases linearly with increasing of the average energy gap E-g. The linear model is obtained. It allows us to predict the CT position of Eu3+-doped lanthanide compounds with knowledge of the crystal structure and index of refraction. Applied to the Ca4GdO(BO3)(3):Eu and Li2Lu5O4(BO3)(3):Eu crystals, the predicted results of CT energies are in good agreement with the experimental values, and it can be concluded that the lowest CT energy in Li2Lu5O4(BO3)(3):Eu originates from the site of Lu1.

Effect of doped dye on the charge-carrier transport and electroluminescent performance in molecularly doped polymer light-emitting diodes

The effects of the concentration of 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H-(1)-benzopyropyrano(6, 78-i,j)quinolizin-11-one (C545T) as dopant in polyfluorene (PFO) on the charge-carrier transport and electroluminescence (EL) performance were investigated by steady-state and transient EL measurements. A fully green emission from C545T was observed and the EL performance depends strongly on the C545T concentration. The mobility in the C545T-doped PFO film was determined by transient EL. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the C545T molecules. The mobility in C545T:PFO changed significantly with the C545T concentration, and showed a nontrivial dependence on the doping level. The behavior may be understood in terms of the formation of an additional energy disorder due to potential fluctuation caused by the Coulomb interaction of the randomly distributed doping molecules.

Improved electron injection in organic light-emitting devices with a lithium acetylacetonate [Li(acac)]/aluminium bilayer cathode

Lithium acetylacetonate [Li(acac)] covered with aluminium was used as an efficient electron injection layer in organic light-emitting devices (OLEDs) consisting of NPB as the hole transport layer and Alq(3) as the electron transport and light emitting layer, resulting in lower turn- on voltage and increased current efficiency. The turn- on voltage (the voltage at a luminance of 1 cd m(-2)) was decreased from 5.5 V for the LiF/Al and 4.4 V for Ca/Al to 4.0 V for Li(acac)/Al, and the device current efficiency was enhanced from 4.71 and 5.2 to 7.0 cd A(-1). The performance tolerance to the layer thickness of Li(acac) is also better than that of the device with LiF. LiF can only be used when deposited as an ultra- thin layer because of its highly insulating nature, while the Li(acac) can be as thick as 5 nm without significantly affecting the EL performance. We suppose that the free lithium released from Li(acac) improves the electron injection when Li(acac) is covered with an Al cathode.

Charge carrier transporting, photoluminescent, and electroluminescent properties of zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex

Zinc(II)-2-(2-hydroxyphenyl)benzothiazolate complex is an excellent white-light-emitting material. Despite some studies devoted to this complex, no information on the real origin of the unusually broad electroluminescent (EL) emission is available. Therefore, we investigate photoluminescent and EL properties of the zinc complex. Orange phosphorescent emission at 580 nm was observed for the complex in thin film at 77 K, whereas only fluorescent emission was obtained at room temperature. Molecular orbitals, excitation energy, and emission energy of the complex were investigated using quantum chemical calculations. We fabricated the device with a structure of ITO/F16CuPc(5.5 nm)/Zn-complex/Al, where F16CuPc is hexadecafluoro copper phthalocyanine. The EL spectra varied strongly with the thickness of the emissive layer. We observed a significant change in the emission spectra with the viewing angles. Optical interference effects and light emission originating both from fluorescence and from phosphorescence can explain all of the observed phenomena, resulting in the broad light emission for the devices based on the Zn complex. We calculated the charge transfer integral and the reorganization energy to explain why the Zn complex is a better electron transporter than a hole transporter.

Charge ordering induced metal-semiconductor transition in Ag2BiO3: A first-principles study

Accurate ab initio density-functional calculations are performed to investigate the relationship of the ground-state crystal structures and electronic properties of Ag2BiO3 compound. The results indicate that Ag2BiO3 in Pnna phase, in which the bismuth atoms occupy the same Wyckoff positions, exhibits metallic conductivity, while in Pnn2 and Pn phases, Ag2BiO3 exhibits semiconducting character, which is in agreement with the experimental results. Charge ordering is indeed induced by the crystal inversion twin in the Pnn2 phase compared with the Pnna phase. In the low temperature phase Pn, the charge ordering is similar to that of Pnn2 phase although it is more distorted in Pn phase. In addition, the calculation indicates that the charge ordering is caused in the 6s electron rearrangement.

Polyelectrolyte-functionalized ionic liquid for electrochemistry in supporting electrolyte-free aqueous solutions and application in amperometric flow injection analysis

As a green process, electrochemistry in aqueous solution without a supporting electrolyte has been described based on a simple polyelectrolyte-functionalized ionic liquid (PFIL)-modified electrode. The studied PFIL material combines features of ionic liquids and traditional polyelectrolytes. The ionic liquid part provides a high ionic conductivity and affinity to many different compounds. The polyelectrolyte part has a good stability in aqueous solution and a capability of being immobilized on different substrates. The electrochemical properties of such a PFIL-modified electrode assembly in a supporting electrolyte-free solution have been investigated by using an electrically neutral electroactive species, hydroquinone ( HQ) as the model compound. The partition coefficient and diffusion coefficient of HQ in the PFIL film were calculated to be 0.346 and 4.74 X 10(-6) cm(2) s(-1), respectively. Electrochemistry in PFIL is similar to electrochemistry in a solution of traditional supporting electrolytes, except that the electrochemical reaction takes place in a thin film on the surface of the electrode. PFILs are easily immobilized on solid substrates, are inexpensive and electrochemically stable. A PFIL-modified electrode assembly is successfully used in the flow analysis of HQ by amperometric detection in solution without a supporting electrolyte.

Surface charge influence on the surface plasmon absorbance of electroactive thiol-protected gold nanoparticles

Gold nanoparticles (3.1-5.0 nm in size) surface-derivatized with both electroactive and nonelectroactive self-assembled monolayers were synthesized. The surface-derivatized electroactive particles can be easily oxidized/reduced at an electrode surface based on the diffusion-controlled current-voltage curve observed in cyclic voltammetry measurements. Spectroelectrochemical investigation demonstrated that the maximum absorbance of the nanoparticles in their oxidized state red-shifted compared with their reduced state to a different extent according to their size distribution. In the case of the particles surface-derivatized with nonelectroactive monolayers, much less shift was observed. This study showed that surface plasmon absorbance of gold nanoparticles was not only related to core charge states but was also influenced by surface charge states as well.

Conducting probe atomic force microscopy investigation of anisotropic charge transport in solution cast PBD single crystals induced by an external field

2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxdiazole (PBD) is a good electron-transporting material and can form single crystals from solution. In this work, solution cast PBD single crystals with different crystallographic axes (b, c) perpendicular to the Au/S substrates in large area are achieved by controlling the rate of solvent evaporation in the presence and absence of external electrostatic field, respectively. The orientation of these single crystals on Au/S substrate was characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Conducting probe atomic force microscopy (CP-AFM) was used to measure the charge transport characteristics of PBD single crystals grown on Au/S substrates. Transport was measured perpendicular to the substrate between the CP-AFM tip and the Au/S substrate. The electron mobility of 3 x 10(-3) cm(2)/(V s) for PBD single crystal along crystallographic b-axis is determined. And the electron mobility of PBD single crystal along the c-axis is about 2 orders of magnitude higher than that along the b-axis due to the anisotropic charge transport at the low voltage region.

Effect of dye concentration on the charge carrier transport in molecularly doped organic light-emitting diodes

The effect of the concentration of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) as dopant in tris(8-quinolinolato) aluminum (Alq(3)) on the charge carrier transport in Alq(3):DCJTB was investigated by measuring the steady current-voltage characteristics and the transient electroluminescence. The dopant concentration dependence of the current-voltage relationship clearly indicates the carrier trapping by the DCJTB molecule. The DCJTB concentration significantly affects the electron mobility in Alq(3):DCJTB. The mobility has a nontrivial dependence on the doping level. For relatively low doping levels, less than 1%, the electron mobility of Alq(3):DCJTB decreases with the doping level. An increasing mobility is then observed if the dopant concentration is further increased, followed by a decrease for doping levels larger than similar to2%. The change of the electron mobility with the DCJTB concentration in Alq(3) is attributed to the additional energetic disorder due to potential fluctuations caused by the dipole-dipole interaction of random distribution dopant at the relatively low doping concentration, and to the phase separation at the high doping concentration.

Modeling of organic light-emitting diodes with graded concentration in the emissive multilayer

We model the electrical behavior of organic light-emitting diodes whose emissive multilayer is formed by blends of an electron transporting material, tris-(8-hydroxyquinoline) aluminum (Alq(3)) and a hole transporting material, N,N-'-diphenyl-N,N-'-bis(1,1(')-biphenyl)-4,4-diamine. The multilayer is composed of layers of different concentration. The Alq(3) concentration gradually decreases from the cathode to the anode. We demonstrate that these graded devices have higher efficiency and operate at lower applied voltages than devices whose emissive layer is made of nominally homogeneous blends. Our results show an important advantage of graded devices, namely, the low values of the recombination rate distribution near the cathode and the anode, so that electrode quenching is expected to be significantly suppressed in these devices.

Electrooxidative polymerization of phenothiazine derivatives on screen-printed carbon electrode and its application to determine NADH in flow injection analysis system

The electrooxidation polymerization of phenothiazine derivatives, including azure A and toluidine blue 0, has been studied at screen-printed carbon electrodes in neutral phosphate buffer. Both compounds yield strongly adsorbed electroactive polymer with reversible behavior and formal potentials closed to 0.04 V at pH 6.9. The modified electrodes exhibited good stability and electrocatalysis for NADH oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 500 mV lower than that of the bare electrodes. Further, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5-100 muM.

Electropolymerization of azure B on a screen-printed carbon electrode and its application to the determination of NADH in a flow injection analysis system

The electrooxidation polymerization of azure B on screen-printed carbon electrodes in neutral phosphate buffer was studied. The poly(azure B) modified electrodes exhibited excellent electrocatalysis and stability for dihydronicotinamide adenine dinucleotide (NADH) oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 400 mV lower than that at the bare electrodes. Different techniques, including cyclic voltammetry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy have been employed to characterize the poly (azure B) film. Furthermore, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5 muM to 100 muM.

Dependence of charge transfer energy on crystal structure and composition in Eu3+-doped compounds

We report a method for estimating the positions of charge transfer (CT) bands in Eu3+-doped complex crystals. The environmental factor ( he) influencing the CT energy is presented. he consists of four chemical bond parameters: the covalency, the bond volume polarization, the presented charge of the ligand in the chemical bond, and the coordination number of the central ion. These parameters are calculated with the dielectric theory of complex crystals. The relationship between the experimental CT energies and calculated environmental factors was established by an empirical formula. The calculated values are in good agreement with the experimental results. Such a relationship was confirmed by detailed analysis. In addition, our method is also useful to predict the charge-transfer position of any other rare earth ion.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Performance improvement by charge trapping of doping fluorescent dyes in organic memory devices

We studied the memory effect in the devices consisting of dye-doped N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine sandwiched between indium-tin oxide and Ag electrodes. It was found that the on/off current ratio was greatly improved by the doped fluorescent dyes compared with nondoping devices. A mechanism of charge trapping was demonstrated to explain the improvement of the memory effect. For the off state, the conduction process is dominated by the trapping current, which is a characteristic of the space-charge limited current, whereas the on state is dominated by the detrapping current, and interpreted by Poole-Frenkel emission.