Single-crystal-like organic heterojunction with 40 nm thick charge accumulation layers

Single-crystal-like organic heterojunction films of copper phthalocyanine (CuPc) and copper-hexadecafluoro-phthalocyanine (F16CuPc) were fabricated by weak-epitaxy-growth method. The intrinsic properties of organic heterojunction were revealed through threshold voltage shift of field-effect transistors and measurement of single-crystal-like diodes. At both sides of the heterojunction interface 40 nm thick charge accumulation layers formed, which showed that the long carriers' diffusion length is due to the high crystallinity and low density of deep bulk traps of single-crystal-like films.

Theoretical studies on electronic structures, spectra and charge transporting properties of a series of Pt((CN)-N-Lambda)(2) complexes

We report a quantum-chemical study of electronic, optical and charge transporting properties of four platinum (II) complexes, pt((CN)-N-Lambda)(2) ((CN)-N-Lambda=phenylpyridine or thiophenepyridine). The lowest-lying absorptions at 442, 440, 447 and 429 nm are all attributed to the mixed transition characters of metal-to-ligand charge transfer (MLCT) and ligand-centered (LC) pi - pi(*) transition. While, unexpectedly, the lowest-lying phosphorescent emissions at 663, 660, 675 and 742 nm are mainly from metal-to-ligand charge transfer ((MLCT)-M-3) ligand-centered (LC) pi ->pi* transition. Ionization potential (IP), electron affinities (EA) and reorganization energy P (lambda(hole/electron)) were obtained to evaluate the charge transfer and balance properties between hole and electron.

Relationship between charge transfer energies of Yb3+ and Sm3+ and crystal environmental factor

Relationship between charge transfer energies E-CT of Yb3+ and Sm3+ and environmental factors h(e) in various crystals was investigated using a dielectric chemical bond method. Both results show that they have an exponential relation E-CT = A+B exp(-kh(e)), but the exponential factors are different, which indicates that the interaction between the rare earth ions and environment is connected with the kind of rare earth ion. This result provides a method of determining charge transfer energies of Yb3+ and Sm3+ from a crystal structure.

Charge Transport Processes of Immobilized Heteropolyanions at Self-assembled Monolayer Modified Gold Electrode by Electrochemical Quartz Crystal Microbalance Measurement

The in situ electrochemical quartz crystal microbalance(EQCM) technique was used to investigate the ion transport of immobilized heteropolyanions at a self-assembled monolayer(SAM) modified gold electrode during electrochemical redox process. A mixed transfer method was presented to analyse the abnormal change of resonant frequency based on the simultaneous insertion/extraction of different ions. The results indicate that the migration of HSO4- anions was indispensable in the redox process of the heteropolyan ions in a I mol/L H2SO4 solution and played a key role in the abnormal change of the resonant frequency. Such a change was attributed to different packing densities derived by means of differently immobilized methods.

Enhanced charge collection in polymer photovoltaic cells by using an ethanol-soluble conjugated polyfluorene as cathode buffer layer

We report enhanced polymer photovoltaic (PV) cells by utilizing ethanol-soluble conjugated poly (9, 9-bis (6'-diethoxylphosphorylhexyl) fluorene) (PF-EP) as a buffer layer between the active layer consisting of poly(3-hexylthiophene)/[6, 6]-phenyl C61-butyric acid methyl ester blend and the Al cathode. Compared to the control PV cell with Al cathode, the introduction of PF-EP effectively increases the shunt resistance and improves the photo-generated charge collection since the slightly thicker semi-conducting PF-EP layer may restrain the penetration of Al atoms into the active layer that may result in increased leakage current and quench photo-generated excitons. The power conversion efficiency is increased ca. 8% compared to the post-annealed cell with Al cathode.

Effect of Poly (3-hexylthiophene) Nanofibrils on Charge Separation and Transport in Polymer Bulk Heterojunction Photovoltaic Cells

Crystalline poly (3-hexylthiophene) (P3HT) nanofibrils are introduced into the P3HT: [6, 6]-phenyl C61-butyric acid methyl ester (PCBM) composite films via P3HT preaggregation in solution by adding a small amount of acetone, and the correlation of P3HT nanofibrils and the optoelectronic properties of P3HT:PCBM bulk heterojunction photovoltaic cells is investigated. It is found that the optical absorption and the hole transport or the resulted P3HT:PCBM composite films increase with the increase of the amount of P3HT nanofibrils due to the increased P3HT crystallinity and highly interconnected nanofibrillar P3HT networks. However, it is also found that high contents of crystalline P3HT nanofibrils may restrain PCBM molecules from demixing with the P3HT component that forms electron traps in the active layer. and hence reduce the charge collection efficiency. Small contents of P3HT nanofibrils not only improve the demixing between P3HT and PCBM components, but also enhance the hole transport via crystalline P3HT nanofibrillar networks, resulting in efficient charge collection.

A versatile color tuning strategy for iridium(III) and platinum(II) electrophosphors by shifting the charge-transfer states with an electron-deficient core

By fusing an electron-deficient ring system with the phenyl ring of a 2-phenylpyridine (ppy)-type ligand, a new and synthetically versatile strategy for the phosphorescence color tuning of cyclometalated iridium(III) and platinum(II) metallophosphors has been established. Two robust red electrophosphors with enhanced electron-injection/electron-transporting features were prepared by using an electron-trapping fluoren-9-one chromophore in the ligand design. The thermal, photophysical, redox and electrophosphorescent properties of these complexes are reported. These exciting results can be attributed to a switch of the metal-to-ligand charge-transfer (MLCT) character of the transition from the pyridyl groups in the traditional Ir-III or Pt-II ppy-type complexes to the electron-deficient ring core, and the spectral assignments corroborate well with the electrochemical data as well as the timedependent density functional theory (TD-DFT) calculations. The electron-withdrawing character of the fused ring results in much more stable MLCT states, inducing a substantial red-shift of the triplet emission energy from yellow to red for the Ir-III complex and even green to red for the PtII counterpart.

From Tunneling to Hopping: A Comprehensive Investigation of Charge Transport Mechanism in Molecular Junctions Based on Oligo(p-phenylene ethynylene)s

The charge transport mechanism of oligo(p-phenylene ethynylene)s with lengths ranging from 0.98 to 5.11 nm was investigated using modified scanning tunneling microscopy break junction and conducting probe atomic force microscopy methods. The methods were based on observing the length dependence of molecular resistance at single molecule level and the current-voltage characteristics in a wide length distribution. An intrinsic transition from tunneling to hopping charge transport mechanism was observed near 2.75 nm. A new transitional zone was observed in the long length molecular wires compared to short ones. This was not a simple transition between direct tunneling and field emission, which may provide new insights into transport mechanism investigations. Theoretical calculations provided an essential explanation for these phenomena in terms of molecular electronic structures.

Particle Size-Dependent Charge Ordering and Magnetic Properties in Pr0.55Ca0.45MnO3

A series of Pr0.55Ca0.45MnO3 compounds with average particle size ranging from 2000 to 30 nm have been synthesized by the sol-gel method and their charge ordering (CO) and magnetic properties are investigated. It is observed that with particle size decreasing, the CO transition is gradually suppressed and finally disappears upon particle size down to 35 nm, while the ferromagnetism (FM) emerges and exhibits a nonmonotonous variation with a maximum at 45 nm samples. The FM components in all samples never reach long-range ordering but rather only show short-range clusters. A new explanation considering the coupling between lattice, charge, and spin in the system is raised to understand the suppression of the CO state, Both the competition between the CO/AFM and FM states and the core-shell model are employed to explain the variation of the FM phase. These results may provide a deeper insight into the physics of particle size effect on the charge ordering manganite.

Charge disproportionation in CaCu3Fe4O12

First-principles calculations using the APW+lo method, as implemented in the WIEN2K code, have been used to investigate the structural, electronic, and magnetic properties of the perovskite CaCu3Fe4O12, including the high-temperature Im-3 and low-temperature Pn-3 phase. The high-temperature phase presents a homogeneous valence and an orbital degenerate half-metallic behavior, which is consistent with the previous theoretical result. Instead orbital ordering, charge ordering, or disproportionation on Fe sites occur in the low-temperature phase, leading to the insulating character. More importantly, the charge disproportionation is of 2d(5)L -> d(5)L(2) + d(5) type (where L denotes an oxygen hole or a ligand hole), and the origin for the phenomenon is discussed in detail.

Improved optical photoluminescence by charge compensation in the phosphor system CaMoO4: Eu3+

It has been found that charge compensated CaMoO4:Eu3+ phosphors show greatly enhanced red emission under 393 and 467 nm-excitation, compared with CaMoO4:Eu3+ without charge compensation. Two approaches to charge compensation, (a) 2Ca(2+) -> EU3+ + M+, where M+ is a monovalent cation like Li+, Na+ and K+ acting as a charge compensator; (b) 3Ca(2+) -> 2EU(3+) + vacancy, are investigated. The influence of sintering temperature and Eu3+ concentration on the luminescent property of phosphor samples is also discussed.

Spectroscopic studies on charge transfer from Ce3+, to Yb3+ in KMgF3 : Ce, Yb nanocrystals

Nanocrystals of KMgF3 single-doped and codoped with Ce3+ or/and Yb3+ were synthesized separately by the microemulsion method. The X-ray diffraction(XRD) patterns were indexed to show that the KMgF, crystal system was unchanged. The fluorescent spectra of KMgF3:Ce, Yb polycrystal powders were studied and compared with those of the Ce, Yb doped KMgF3 crystals produced using the high-temperature solid phase method. The diffuse reflection spectra and infrared. emission of KMgF3:Ce, Yb were investigated. From the results, the authors could confirm that there were charge transfer processes from Ce3+ to Yb3+ in both KMgF3: Ce,Yb nanocrystals and polycrystal powders.

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.

Effects of doped dye on the charge carrier injection, transport, and electroluminescent performance in polymeric light-emitting diodes

The effects of doped fluorescent dye 4-(dicyanomethylene)-2-i-propyl-6-(1, 1, 7, 7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTI) on the charge carrier injection, transport and electroluminescence (EL) performance in polyfluorene (PFO)-based polymer light-emitting diodes (PLEDs) were investigated by steady-state current-voltage (I-V) characteristics and transient EL measurements. A red EL from DCJTI was observed and the EL performance depended strongly on the DCJTI concentration. The analysis of the steady-state I-V characteristics at different DCJTI concentrations found that three regions was shown in the I-V characteristics, and each region was controlled by different processes depending on the applied electric field. The effect of the dopant concentration on the potential-barrier height of the interface is estimated using the Fowler-Nordheim model. The dopant concentration dependence of the current-voltage relationship indicated clearly the carrier trapping by the DCJTI molecules. The mobility in DCJTI: PFO changed significantly with the DCJTI 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.