Energy band and electron-vibration coupling in organic thin films: photoelectron spectroscopy as a powerful tool for studying the charge transport

This article describes the origins of the width of the highest occupied molecular orbital (HOMO) state observed in the ultraviolet photoemission spectra (UPS) of thin organic semiconductor films. Although much research has been performed on the electrical properties of organic devices, a lot of crucial problems still remain. Among these problems, the charge mobility in organic semiconductor systems is one the most important subjects to be elucidated. In order to discuss the mobility, it is essential to understand both the intermolecular interaction and the electron-molecular vibration coupling. Experimental measurements of the energy band dispersion give information about the intermolecular interaction, and experimental detection of the HOMO hole-vibration coupling is indispensable to comprehend impacts of the electron-vibration coupling on the hole transport. Since most of the information is hidden behind the finite bandwidth of the HOMO, only careful UPS measurements can provide information on these important phenomena related to charge carrier dynamics. In this article, we summarize our recent challenges on UPS measurements of organic thin films, which give the band dispersion of the HOMO and the HOMO hole-vibration coupling, and discuss the origins of the UPS bandwidth that relates to the charge carrier dynamics.     

Dynamic dc voltage band in vertical transport of superlattices

By the numerical method, we show a transition process from static to dynamic electric-field domain formation in semiconductor superlattices. During this transition, there can be noticed a sawtooth-like zone in which static and dynamic electric-field domain zones appear alternatively with increasing voltage. Therefore, a dynamic dc voltage band emerges from each sawtooth-like branch of the current－voltage characteristic. These results are qualitatively in agreement with experiment.     

Synthesis, characterization of the pentacene and fabrication of pentacene field-effect transistors

A comprehensive understanding of the organic semiconductor material pentacene is meaningful for organic fieldeffect transistors （OFETs）. Thin films of pentacene are the most mobile molecular films known to date. This paper reported that the pentacene sample was successfully synthesized. The purity of pentacene is up to 95%. The results of a joint experimental investigation based on a combination of infrared absorption spectra, mass spectra （MS）, element analysis, x-ray diffraction （XRD） and atom force microscopy （AFM）. The authors fabricated OFET with the synthesized pentacene. Its field effect mobility is about 1.23 cm^2/（V·s） and on-off ratio is above 10^6.     

Effect of illumination on the space charge limited current in organic bulk heterojunction diodes

Current–voltage (J–V) characteristics of organic bulk heterojunction diodes based on an interpenetrating network of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁-butyric acid methyl esters (PCBM) have been studied in the dark and under halogen lamp illumination. The diodes contained 1:1 and 1:0.6 weight ratios of P3HT and PCBM. For both diodes the currents measured in dark (J _d , commonly known as the dark current) in forward bias are found to agree with the space charge limited current (SCLC). The illuminated current consists of a current due to applied voltage (J _da ) and the light generated current (J _L ). J _da  extracted from the illuminated current agrees well with Shockley’s diffusion and recombination current. This observation shows that illumination changes the SCLC into Shockley’s diffusion and recombination current. The forward current under illumination has been observed to be greater than the dark current, which is contrary to the photo–voltaic (PV) theory. This result is well explained by the change of SCLC into Shockley’s diffusion and recombination current. Former address of S.C. Jain: IMEC, Kapeldreef 75, 3001 Leuven, Belgium.     

From polymer films to organic nanoparticles suspensions by means of excimer laser ablation in water

This study highlights the preparation of organic nanoparticles (NP) by laser ablation (LA) of polymeric materials in water. Experiments focused on poly(ethylene terephtalate) (PET) were carried out with the KrF laser pulse (248 nm). Size distribution and concentration of nanoparticles were deduced from suspensions turbidity measurements with the aid of Mie model, by Atomic Force Microscopy (AFM) on the basis of a statistical study and Scanning Electron Microscopy (SEM). The obtained results show that assemblies of spherical NP with a mean diameter 50 nm were synthesised. Composition and surface chemistry of NP were investigated using the Confocal Micro-Raman Spectroscopy (CMRS) and X-ray Photoelectron Spectroscopy (XPS). It indicates that NP are graphitic carbon rich and have a polymeric structure like polyacetylene. The possible mechanisms responsible of NP synthesis by under water LA of polymers was briefly discussed by investigating other polymers targets.     

Growth and characterization of oriented CdSe nanobelts and nanorods

Oriented CdSe nanobelts and nanorods were grown successfully on GaAs and Si substrates by metal organic chemical vapor deposition. The thickness of Au film coated on the substrate plays an important role in determining the orientation, size, and density of these one-dimensional CdSe nanostructures. Preferred orientation was observed for nanostructures grown on the GaAs substrate coated with thick Au film, but not for the nanostructures grown on the Si substrate. Photoluminescence, transmission electron microscope, and X-ray diffraction measurements show that the CdSe nanostructures could have either wurtzite or zinc-blende structures, and there are more nanostructures with wurtzite structure than with zinc-blende structure.     

Preparation and characterization of PVAc–PMMA-based solid polymer blend electrolytes

In the present work, a novel blend polymer electrolyte membrane using poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), and lithium per chlorate (LiClO₄) in different compositions has been prepared by the solution-casting technique. Their chemical, structural characters, thermal behavior, surface morphology, and ionic conductivity were studied using Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric/differential thermal analyzer, scanning electron microscopy, and AC impedance analyzer, respectively. A maximum ionic conductivity value of 1.67 × 10⁻⁴ S/cm at 303 K is obtained for PVAc–PMMA–LiClO₄ complexes in the ratio of 25 × 75, keeping LiClO₄ constant as 10 wt.% among all the compositions studied.     

Ab?initio characterization of graphene nanoribbons and their polymer precursors

Bottom-up fabrication of graphene nanoribbons (GNRs) from halogen-terminated aromatic precursors is a promising method for achieving atomically precise nanoribbons at competitive yields. GNR fabrication proceeds via the polymerization of the precursors and successive dehydrogenation. By first principles density functional theory calculations, we perform a systematic characterization of the polymeric precursors and the corresponding graphene nanoribbons in terms of structural and electronic properties, and we compute the Raman and infrared spectra. The band structure properties are examined by considering the bonding features and the partial charge densities of the structures. The physical origin of the infrared and Raman peaks is investigated in terms of the morphology and vibrational properties of the precursors and products. We show that light spectroscopy provides a unique fingerprint for each type of GNR, which may be used to monitor the quality of the final products and the kinetics of the synthesis process.     

On the possible role of small polarons in the charge and energy transport in the α-helix proteins

We study the possibility of the small-polaron creation in α-helix proteins, accounting for the self-trapping of the intramolecular vibration energy quanta. The small-polaron concept of energy transfer in polypeptides has been revisited on the basis of these results. It was found that traditional small-polaron theories cannot be directly applied to the vibrational quanta transfer in these substances. In particular, true eigenstates of system should correspond to a partial dressed polarons rather than to the fully dressed small polaron states.     

Theoretical study of the optical and charge transport properties in non-peripherally octasubstituted phthalocyanine–tetrabenzoporphyrin hybrids

The charge transfer rate of seven non-peripherally phthalocyanine–tetrabenzoporphyrin hybrids was investigated theoretically at the level of B3LYP/6-31+G(d,p) using density functional theory. The results showed that the hybrids are semiconductor molecules, which have a certain absorption in the visible region. The hole or electron transport capability of a non-peripherally substituted octamethyl phthalocyanine molecule is obviously better than that of phthalocyanine or non-peripherally substituted octafluorine, octamethoxy phthalocyanine molecules at 300 K, whereas the holes or electron transport capabilities of four non-peripherally substituted octamethoxy phthalocyanine–tetrabenzoporphyrin hybrids are basically the same. Overall, the hole transport capability of hybrids is superior to their electron transport capability. The charge transfer rate constant and the carrier mobility rate of three representative molecules using three methods, that is the long range-corrected functionals CHB-B3LYP and WB97XD, the metahybrid GGA M06-2X functional, are consistent with the use of the density functional B3LYP method.     

Dynamic response of converse magnetoelectric effect in a PMN-PT-based multiferroic heterostructure

A multiferroic heterostructure, consisting of a 25 μm thick Metglas® ribbon affixed to a lead magnesium niobate–lead titanate (PMN-PT) crystal, was systemically studied to investigate the time response of converse magnetoelectric coupling under the application of electric fields at low frequencies (0.05<f<10 Hz). This multiferroic heterostructure exhibits a considerably strong converse magnetoelectric effect, CME=?80%, where CME=[M(E)?M(0)]/M(0), and a converse ME coupling constant, A=22.5 Oe-cm/kV, at frequencies below 1 Hz and near saturation electric polarization. A switching time (t _s), representing the response time of the CME coupling, is measured to be 0.6 seconds for this heterostructure under the application of instantaneous electric fields. The switching time results in significant influences on the magnetoelectric effect especially at frequencies higher than 2 Hz. The dynamic response of CME coupling is predominantly determined by ferroelectric relaxation within the PMN-PT crystal, as opposed to the magnetic relaxation of the Metglas® ribbon. A model was used to describe the dynamic behavior of CME coupling in disordered systems such as PMN-PT.     

Charge transport in monolayer poly（3-hexylthiophene） thin-film transistors

It is found that ultrathin poly（3-hexylthiophene） （P3HT） film with a 2.5 nm-thick layer exhibits a higher mobility of 5.0× 10-2 cm2/V-s than its bulk counterpart. The crystalline structure of the as-fabricated ultrathin P3HT layer is verified by atomic force microscopy as well as grazing incidence X-ray diffraction. Transient measurements of the as-fabricated transistors reveal the influence of the interface traps on charge transport. These results are explained by the trap energy level distribution at the interface manipulated by layers of polymer film.     

Numerical analysis of the mechanism of carrier transport in organic light—emitting devces

The mechanism of carrier transport in organic light-emitting devices is numerically studied,on the basis of trappedcharge-limited conduction with an exponential trap distribution.The spatial distributions of the electrical potential,field and carrier density in the organic layer are calculated and analysed.Most carriers are distributed near the two electrodes,only a few of them are distributed over the remaining part of the orgaic layer,The carriers are accumulated near the electrodes,and the remaining region is almost exhausted of carriers.When the characteristic energy of trap distribution is greater than 0.3eV.it leads to a reduction of current density.In order to improve the device efficiency,organic materials with minor traps and low characteristic energy should be chosen.The diffusion current is the dominant component near the injection electrode.whereas the drift current dominates the remaining region of the organic layer.     

Solid solutions of bismuth-based Aurivillius oxides: structural and dielectric characterization

Bismuth layered perovskite structures show interesting physical properties varying as a function of external parameters (temperature, frequency, electric and magnetic fields). When a magnetic ion is incorporated in some of these materials, some of the structures show simultaneous ferroelectricity and ferro/antiferromagnetism. Thus, they exhibit magnetoelectric properties under the influence of an external magnetic field. This paper compares the structural (XRD and SEM) and electrical properties of two eight-layered Aurivillius oxides.     

Application of abrupt cut-off models in the analysis of the capacitance spectra of conjugated polymer devices

In this paper, a detailed study of the capacitance spectra obtained from Au/doped-polyaniline/Al structures in the frequency domain (0.05 Hz–10 MHz), and at different temperatures (150–340 K) is carried out. The capacitance spectra behavior in semiconductors can be appropriately described by using abrupt cut-off models, since they assume that the electronic gap states that can follow the ac modulation have response times varying rapidly with a certain abscissa, which is dependent on both temperature and frequency. Two models based on the abrupt cut-off concept, formerly developed to describe inorganic semiconductor devices, have been used to analyze the capacitance spectra of devices based on doped polyaniline (PANI), which is a well-known polymeric semiconductor with innumerous potential technological applications. The application of these models allowed the determination of significant parameters, such as Debye length (≈20 nm), position of bulk Fermi level (≈320 meV) and associated density of states (≈2×10¹⁸ eV⁻¹ cm⁻³), width of the space charge region (≈70 nm), built-in potential (≈780 meV), and the gap states’ distribution.     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

TEM characterization of organic nanocrystals grown in sol–gel thin films

The tetracene molecule (2,3-benzanthracene, C₈H₁₂) was used to synthesize nanocrystals grown in sol–gel thin films, ranging from 10 to 100 nm of diameter. This confined nucleation and growth was compared to microcrystallizations of the same molecule in free solution. Transmission electron microscopy (TEM) was used to characterize these two kinds of tetracene crystals. The observation was performed under low-dose illumination to avoid amorphization of the samples during electron irradiation. Spatial confinement and size distribution of micro- and nanocrystals were compared. Using electron microdiffraction and diffraction patterns simulations, we showed that free microcrystals and nanocrystals confined in gel glasses exhibit the same triclinic structure. In addition, time-resolved spectroscopy was used to record fluorescence decays, showing a monoexponential fluorescence decay for nanocrystals while microcrystals exhibit a multiexponential decay. The simple signature of nanocrystals luminescence is promising for the future development of chemical or biological sensors.