Influence of a Photoconductive Polymer Matrix on the Photoluminescence of Cationic Polymethine Dyes

Using symmetric cationic indopolycarbocyanines HIC and HIDC as an example, the authors detected the enhancement of their photoluminescence in films of photoconductive polymers poly–N–epoxypropyl carbazole and poly–N–vinyl carbazole as compared to nonphotoconductive polymers, i.e., polyvinyl butyral, polystyrene, and polyethylene. The excitation was carried out on the shortwave edge of the absorption band of the dye and did not affect the absorption region of the polymer. It is shown that the effect of enhancement of the luminescence increases with decrease in the excitation wavelength and becomes weaker with increase in the molecular mass of carbazole–containing polymers. Its enhancement is interpreted as the recombination luminescence of electron–hole pairs formed in photogeneration of charge from the dye molecules.     

Sensitization of photoconductivity in ferrocene-containing oligomer by squarylium and merocyanine dyes

We have studied the photoconducting properties of films of ferrocene-containing oligomer with additives of squarylium and merocyanine dyes based on ferrocene and tetranitrofluorene in the dye absorption region. We have studied the characteristic features of the effect of an external magnetic field on the photocurrents. After the magnetic field is turned on, the photocurrent increases in the samples with squarylium dye and decreases in the samples with merocyanine dye. We discuss the hypothesis that in the first case, as a result of an internal photoelectric effect, predominantly triplet charge pairs are formed, while in the second case predominantly singlet charge pairs are formed. The latter may be one of the reasons for the higher photoconductivity of films with squarylium dye compared with merocyanine dye.     

Fast photoprocesses in a symmetric indotricarbocyanine dye (HITC) in solutions

Spectral-kinetic and photochemical properties of HITC dye with iodide and perchlorate counterions have been studied in environments where the dye molecules exist in different ionic forms. In ethanol, the dye molecules exist as free ions; in dichlorobenzene, as contact ion pairs. Superfast transformation of non-stationary spectra in an HITC dye bleaching band is found. The observed effects are interpreted within the framework of concepts on “burning out” a notch in the contour of a non-uniformly widened vibronic band of S ₀ → S ₁-absorption. Qualitative differences in recorded absorption spectra from the dye excited electronic states for weakly and highly polar solvents are found. It is shown that the observed differences are caused by superfast charge transfer in the contact ion pairs that results in the formation of free radicals.     

The effect of an electrostatic field on the photoluminescence and photoconductivity of polymer films doped by cationic polymethine dyes with end groups with different electron-donating properties

The effect of an external electrostatic field on the photoluminescence spectra and photoconductivity of symmetric and asymmetric cationic polymethine dyes with end groups possessing different electron-donating properties (basicity) in polymer films based on photoconductive poly-N-epoxypropylcarbazole and nonphotoconductive polyvinylethylal is studied. It is found that application of an electric field to films can both decrease and increase their luminescence intensity. The strongest decrease in the luminescence intensity is observed for symmetric dyes in poly-N-epoxypropylcarbazole films with either a decrease in the electron-donating ability of the end groups or with a decrease in the length of the polymethine chain. Colored polyvinylethylal films exhibit both a negative and a positive effect of the field on the photoluminescence intensity. The character of changes in the luminescence spectra does not depend on the electron-donating ability of the end groups. The spectral effects are explained by a change in the probability of vibronic transitions due to the redistribution of the electron density in the chromophore of the dye in the ground and excited states in an external electric field.     

Photogeneration of electrons and holes in amorphous molecular semiconductors

This paper reports on the results of investigations into the photoconducting properties of amorphous molecular semiconductors based on films of two types: (i) poly(styrene) films doped with epoxypropylcarbazole (EPC) and a cationic polymethine dye (PD1) and (ii) poly(styrene) films doped with tetranitrofluorenone (TNF) and an anionic polymethine dye (PD2). Films of the first type possess p-type conductivity, whereas films of the second type exhibit n-type conductivity. It is found that, for films with n-type conductivity, unlike films with p-type conductivity, the activation energy of photogeneration of mobile charge carriers decreases with a decrease in the optical wavelength in the absorption range of the dyes. The possible mechanisms of the influence of the photoexcitation energy on the initial distance between charge carriers in electron-hole pairs are analyzed. The inference is made that, when the excess thermal energy of excited dye molecules dissipates at a low rate, the distance between the photogenerated electrons and photogeneration centers increases as compared to the distance between the photogenerated holes and photogeneration centers due to the electron-nucleus interaction.     

Characteristic features of charge transfer in the interaction between sensitizer molecules and AgCl(I) molecules

We have used flash luminescence stimulation and photoinduced emission methods to study deep impurity states of AgCl(I) microcrystals with adsorbed organic cationic and anionic dye molecules. We have observed that when these molecules interact with the crystal, charge transfer occurs simultaneously from different orbitals and the transfer occurs differently from each orbital: some orbitals of the molecule pick up a negative charge, others at the same time give up a negative charge. We hypothesize that the type of transfer is determined by the overall charge.     

Properties and the nature of electric-field-induced variations in optical absorption spectra of polymethine dyes in polymer matrices

The effect of a permanent electric field on the absorption spectra of ionic (cationic and anionic) and intraionic symmetric and asymmetric polymethine dyes in poly-N-epoxypropylcarbazole, polyvinylbutyral, and polystyrene polymer films is studied. It is found that the electric field causes an increase in absorption of symmetric dyes in the short-wavelength region and a decrease in their absorption in the long-wavelength region. Asymmetric dyes exhibit opposite properties. These properties are common for these groups of dyes irrespective of their chemical structure and ionic nature. They are retained both in photoconducting polymers and in polymers that are incapable of charge photogeneration. These effects also take place in liquid solutions, although in this case they are much weaker. Various mechanisms of the influence of an electric field on the spectra, such as the electron transfer, Stark and Kerr effects, intermolecular interactions, and dye isomerization, are discussed. It is shown that the spectral effects are caused by the redistribution of the electron density in a chromophore of the dye in the ground state resulting in a change in the probability of vibronic transitions.     

Charge transfer between ZnO crystals and dye layers

The interaction between crystal and adsorbed dye molecules has been studied under well defined conditions by measurements of field effect and spectrally sensitized photoconductivity. The (101̄0) surfaces of n-type ZnO crystals (band gap 3.3 eV) are cleaned in ultrahigh vacuum. A pretreatment with atomic hydrogen produces an accumulation layer. Merocyanine (polymethine) dye molecules are deposited by sublimation in the same vacuum (coverage (1–2000) × 10¹⁴ cm^?2. Optical excitation of the dye causes a sensitized photoconductivity in the ZnO crystal close to the surface. The spectra distribution resembles the absorption spectrum of the dye with a maximum at 2.3 eV. An electric field applied perpendicular to the dye covered surface induces charge carriers in the crystal and changes the surface conductivity (field effect). Additional excitation of the dye by light causes a slow relaxation of the field-induced change of surface conductivity. This relaxation is observed for both signs of the field. Furthermore a memory of the dye covered crystals has been found. It can be programmed by field and light, read out via the surface conductivity and quenched by light. A phenomenological model for relaxation and memory is refined by kinetic equations and by considerations about charge transport within the dye layer. The observations can only be explained by a charge transfer between crystal and dye operating in both directions. From these results the following conclusion is drawn for the mechanism of spectrally sensitized photoconductivity of the present system: An electron transfer between dye molecules and crystal represents the decisive step rather than an energy transfer.     

Characteristic features of the photoconductivity and spin conversion of electron-hole pairs in doped amorphous molecular semiconductors in the dye absorption region

The photoconductivity of doped poly-N-epoxypropylcarbazole films in the absorption region of a cationic polymethine dye is observed to increase when the BF ₄ ⁻ ion is replaced by Cl⁻ and I⁻. The effect of a magnetic field on the photoluminescence is investigated at room temperature. The photoconductivity is studied as a function of the electric field intensity and wavelength of light. The dependence of the photoconductivity on the nature of the anion can be explained by a change in the probability of intercombination conversion in ionic and electron-hole pairs. Fiz. Tverd. Tela (St. Petersburg) 41, 44–48 (January 1999)     

Dynamic photorefractivity in nematic liquid crystal cells with photoconductive orienting layers

A new mechanism of photorefractivity in nematic liquid crystal cells with photoconductive orienting layers, referred to as dynamic photorefractivity, is proposed. The essence of this mechanism is as follows: an external ac electric field excites quasi-periodic subgratings at the interface between a liquid crystal and a photoconductive orienting layer. The interference optical field, inducing a charge distribution on the surface of the orienting layers, modulates the surface anchoring force and the penetration depth of the external field into the liquid crystal layer. As a result, the surface charge grating azimuthally reorients subgratings according to its structure and stabilizes their period. Since the amplitude of the subgratings is determined by the strength of the applied electric field and the cell parameters, the wave mixing efficiency in the dynamic mode may significantly exceed that in the classical orientational effect.