Thermal effect on the dielectric function and small polaron hopping conduction in organic molecular crystals

A Green function formalism is applied to study the dielectric function spectra and the small polaron hopping conduction in organic molecular crystals. In the calculations, the electron-phonon interaction is considered within the Hartree-Fock approximation, and the temperature effect is taken into account. Our theoretical approach is based on the polar electron-phonon interaction (Fröhlich type) to characterize the non-degenerate polaron gas, with the assumption of the electronic hopping between the first-neighbor.     

Simulation study of the losses and influences of geminate and bimolecular recombination on the performances of bulk heterojunction organic solar cells

We use the method of device simulation to study the losses and influences of geminate and bimolecular recombinations on the performances and properties of the bulk heterojunction organic solar cells. We find that a fraction of electrons(holes)in the device are collected by anode(cathode). The direction of the corresponding current is opposite to the direction of photocurrent. And the current density increases with the bias increasing but decreases as bimolecular recombination(BR)or geminate recombination(GR) intensity increases. The maximum power, short circuit current, and fill factor display a stronger dependence on GR than on BR. While the influences of GR and BR on open circuit voltage are about the same.Our studies shed a new light on the loss mechanism and may provide a new way of improving the efficiency of bulk heterojunction organic solar cells.     

Femtosecond dynamics of geminate recombination of radicals upon photodissociation of aromatic disulfides

The dynamics of the geminate recombination of thiyl radicals formed upon photodissociation of aromatic disulfides and the effect of the intramolecular relaxation on this recombination are studied using pico-and femtosecond kinetic spectroscopy. It is shown that, in terms of a phenomenological model, the geminate recombination of phenylthiyl radicals in neutral solvents can be satisfactorily described by a biexponential dependence. The model suggests the occurrence of primary geminate recombination in a solvent cage formed around an original molecule and secondary recombination controlled by the diffusional motion of the radicals of a pair. The primary geminate recombination, whose characteristic time (9 ps) is close to the characteristic times of intermolecular vibrational relaxation of complex molecules in solvents at room temperatures, masks the manifestation of thermalization processes in the time kinetics. The direct geminate recombination of aminophenylthiyl radicals with the formation of original molecules virtually does not occur because of the intramolecular charge transfer. In connection with this, the intermolecular vibrational relaxation manifests itself in the kinetics of the induced optical density in the region of the absorption band maximum of radicals as a growing component with a characteristic time of 6 ps.     

A geminate recombination model for photoluminescence decay in plasma-deposited amorphous Si:H

We develop a model of geminate electron-hole recombination, including tunnelling and diffusion, to account for photoluminescence decay in amorphous semiconductors. The model correctly predicts the shape of the decay, the luminescence quantum efficiency, and the microscopic electron mobility.     

The CIDNP kinetics in recombination of successive radical pairs

A theory of chemically induced dynamic nuclear polarization (CIDNP) formed in recombination of successive radical pairs (PRs) is developed. The theory is based on that of RP recombination with the spin Hamiltonian instantaneously changing in time. With kinematics approximation it is shown that general relations for CIDNP are fully expressed via the quadratures of Green functions, which characterize the molecular motion of reagents. Analytical formulae for the time dependence of CIDNP both of primary and secondary RPs have been derived in the strong magnetic field approximation (S-T₀ approximation); field dependences of stationary CIDNP effect for some model cases have been analyzed. For long-lived systems the sensitivity of secondary RP CIDNP to the singlet-triplet evolution of primary RP has been demonstrated. It is shown that sometimes the correct analysis of the effect calls for taking into account the reactivity anisotropy.     

The effect of orientational disorder on hopping conductivity in disordered organic semiconductors

The model of variable range hopping is generalized to systems with extended sites. The calculation of the hopping conductivity of a disordered medium with chain structure is reduced to the percolation problem for a system of one-dimensional fragments with random distribution of lengths and orientations. The percolation problem is solved using the Monte Carlo method and the method based on the bonding criterion. The percolation threshold, which determines the dependence of the conductivity on the fragment lengths and degree of their orientational ordering (texture), is calculated. It is shown that the conductivity increases exponentially with fragment lengths and decreases with orientational ordering.     

Anisotropy of the hopping conductivity in TlGaSe2 single crystals

The temperature dependences of the conductivities parallel and perpendicular to the layers in layered TlGaSe₂ single crystals are investigated in the temperature range from 10 K to 293 K. It is shown that hopping conduction with a variable hopping length among localized states near the Fermi level takes place in TlGaSe₂ single crystals in the low-temperature range, both along and across the layers. Hopping conduction along the layers begins to prevail over conduction in an allowed band only at very low temperatures (10–30 K), whereas hopping conduction across the layers is observed at fairly high temperatures (T?210 K) and spans a broader temperature range. The density of states near the Fermi level is determined, N _F=1.3×10¹⁹eV·cm³)^?1, along with the energy scatter of these states J=0.011 eV and the hopping lengths at various temperatures. The hopping length R along the layers of TlGaSe₂ single crystals increases from 130 Å to 170 Å as the temperature is lowered from 30 K to 10 K. The temperature dependence of the degree of anisotropy of the conductivity of TlGaSe₂ single crystals is investigated.     

The kinetics of radiation defect accumulation in oxide crystals

The problem of radiation defect accumulation modeling is considered. The analysis is carried out for models describing basic processes and phenomena taking place during crystal irradiation, namely the genetic defects of recharging and recombination, displacement defect formation and ionization, as well as the limitation of these processes by recombination and complex formation.     

The physical kinetics of magnetoplasticity of diamagnetic crystals

The kinetic equations describing the rate of magnetically induced release of dislocations entrapped by stoppers were solved. The magnetic field effect on the mobility of dislocations was calculated. Its comparison with experiment gave the ratio between the rate constants for two key processes governing magnetoplasticity, namely, singlet-triplet conversion in a spin nanoreactor and the release of a dislocation from it. The kinetic criterion of the existence of magnetoplasticity as a physical phenomenon was obtained.     

Stationary hopping photoconduction among multiply charged impurity atoms in crystals

A derivation of the equation for the hopping current of electrons and holes (electron vacancies) among impurities of a single species in three charge states [(−1), (0), and (+1)] is given in the continuum approximation. The screening length of an electrostatic field and the diffusion length of charge carriers are calculated. The dependence of the effective lifetime of electrons hopping among impurities relative to (−1)→(+1) transitions [and of holes relative to (+1)→(−1) transitions] on the degree of compensation and the rate of interimpurity photoexcitation, which stimulates the formation of ions, is obtained. The calculations of the dependence of the hopping photoconductivity on photoexcitation rate are consistent with known experimental data, which have not previously found a theoretical explanation. Fiz. Tverd. Tela (St. Petersburg) 40, 1805–1809 (October 1998)     

A model of hopping and band DC photoconduction in doped crystals

Expressions for the screening length and the ambipolar diffusion length are derived, for the first time, for the case where hopping conduction and band conduction coexist in semiconductors with hydrogen-like impurities. A method is proposed for calculating the diffusion coefficient of electrons (holes) hopping between impurity atoms from data on the Hall effect, in the case where the hopping and band conductivities are equal. An interpretation is given of available experimental data on hopping photoconduction between acceptors (Ga) and donors (As) in p-Ge at T=4.2 K doped by a transmutation method. It is shown that the relative magnitude of the mobilities of electrons hopping between donors and holes hopping between acceptors can be found from the hopping photoconductivity measured as a function of the intensity of band-to-band optical carrier excitation.     

The influence of the drift shift of electrons undergoing thermalization on the kinetic characteristics of geminate conductivity and recombination

A program for numerically solving the Smoluchowski equation with a modified initial condition taking into account the drift shift of electrons that experience thermalization in an external electric field was developed. The probability of survival and the polarization current of isolated ion pairs were calculated. Shift effects were shown to be especially strong in the region of medium electric fields on the order of 10⁷ V/m and noticeably weaker in both low and high fields. This was related to the proportional relation between the drift shift and electric field applied. The program was used to critically analyze the available experimental data on pulsed photoconductivity of polyacenes.     

Trap-assisted recombination in disordered organic semiconductors

The trap-assisted recombination of electrons and holes in organic semiconductors is investigated. The extracted capture coefficients of the trap-assisted recombination process are thermally activated with an identical activation energy as measured for the hole mobility μ(p). We demonstrate that the rate limiting step for this mechanism is the diffusion of free holes towards trapped electrons in their mutual Coulomb field, with the capture coefficient given by (q/ε)μ(p). As a result, both the bimolecular and trap-assisted recombination processes in organic semiconductors are governed by the charge carrier mobilities, allowing predictive modeling of organic light-emitting diodes.     

The influence of light intensity on surface recombination in GaS single crystals

Gallium sulphide (GaS) is a layer structure semiconductor with relatively wide energy gap (E_g (295 K) = 2.5 eV and E_g (80 K) = 2.62 eV). It has potential applications in some areas of optoelectronics. This paper presents the investigations of the influence of light intensity on surface recombination velocity of charge carriers in GaS single crystals. To attain this purpose spectral dependences (between 420 and 550 nm) of absorption coefficients, reflectivity coefficients and photoconductivity were measured in vacuum. The investigations were performed for various light intensities in several temperatures from 80 to 333 K. The least square method was applied to fit the theoretical dependences of photoconductivity on wavelength and intensity of illumination at these temperatures. From the fittings the temperature and light intensity dependences of surface recombination velocity and bulk lifetime of charge carriers were obtained.     

Excimer formation of pyrene as a probe to investigate the recombination of geminate pairs: the effect of charge hopping process on fluorescence and ODESR spectra in X-irradiated ethylene propylene rubber doped with pyrene

The fluorescence detected ESR (ODESR) spectrum and X-induced and UV-excited fluorescence spectra were successfully obtained for ethylene propylene rubber doped with pyrene under various conditions. From the analysis of the ODESR intensity and its line-width, it was found that charge hopping between the solute pyrenes is the main mechanism for geminate recombination at the pyrene content larger than 0.3 wt%. At elevated temperatures, the excimer fluorescence relative to the monomer fluorescence induced by X-ray excitation is considerably stronger than that by UV-excitation, especially at high concentrations. On the other hand, at lower temperatures below ca. 280 K this difference could not be observed even at high concentration of 3.0 wt%. These observations indicate that the dimer cation formation, from which the excimer fluorescence is efficiently emitted, is accelerated by the hopping of cation-radical center to the clustering pyrenes at high temperatures and high concentrations. While only the electron hopping takes place at low temperatures, thus whether a charge recombination results in excimer formation or not is determined by the cationic trapping site, i.e. if several pyrenes are clustering there, excimer may be formed regardless of the excitation source. Although rapid translational motion is restricted in ethylene propylene rubber, the effective formation of excimer or dimer cation at high temperatures indicates that rotational diffusion and small distance translational diffusion are allowed within the fluorescence lifetime at those temperatures.     

Spectral response of (CH)x-CdZnS heterojunction: Application of Onsager's theory of geminate recombination

The Onsager's theory of geminate recombination is used to fit experimental photoresponse of (CH)_x-CdZnS heterojunctions. This model, which depends upon three adjustable parameters, gives good agreement between experimental and calculated spectral response in zero bias conditions and lead to a simple interpretation of the change of spectral response under reverse bias.     

MeV-ion-induced defects in organic crystals

We present scanning force microscope images of crater-like defects induced by MeV atomic ions incident on single-crystal L-valine surfaces. For grazing incidence ions, the craters are elongated alongthe ion azimuth of incidence and are followed by raised tails in the surface above the ion track. Craters formed by off-normal ions are wider than craters formed by nrmally incident ions. The crater volume is highly nonlinear in (dE/dx)_e. We discuss our observations qualitatively in terms of thermal-spike and pressure-pulse/shock-wave models for the sputtering of organic solids.