Tetradentate Schiff bases (H(2)L(i)), derivatives of salicylic aldehyde (H(2)L(1), H(2)L(2)) or o-vanillin (H(2)L(3), H(2)L(4)) with ethylenediamine or o-phenylenediamine as a bridge, and their zinc complexes were studied experimentally and theoretically in view of their possible application as emitters in organic light emitting diodes (OLEDs). The composition of thin films of the complexes was analyzed using a combination of different experimental and molecular modeling techniques taking into account changes in the Gibbs free energy of dehydration and dimerization reactions. The absorption spectra of the initial Schiff bases were investigated in methanol solutions, while the absorption spectra of their zinc complexes were investigated in thin films. Experimental results of elemental analysis, IR spectroscopy, laser desorption/ionization mass spectrometry (LDI MS), and X-ray diffraction as well as theoretical analysis of electronic absorption spectra by the quantum-chemical TD DFT method demonstrate that thin films of the zinc complexes contain binuclear anhydrous molecules. This conclusion should be taken into account when considering both transport and luminescence properties of these complexes in OLED heterostructures. A comparison of the results of CIS, TD DFT/PBE, and TD DFT/PBE0 calculations reveals the crucial importance of the inclusion of the exact exchange in the E(XC) functional for the further correct description of potential energy surfaces of excited states for the systems studied.

Mixed-ligand terbium carboxylates—Tb(Carb)3(TPPO)2 (HCarb=HSal (salicylic acid), Hpobz (2-phenoxybenzoic acid); TPPO=triphenylphosphine oxide) and zinc complexes with tetradentate Schiff bases—ZnSB (H2SB=H2SAL1, H2SAL2 (derivatives of salicylic aldehyde); H2MO1, H2MO2 (derivatives of o-vanillin)) were used as electroluminescent (EL) layers in organic light emitting diodes (OLEDs). These devices have undergone reversible and irreversible mechanisms of EL degradation. The reversible one is mainly associated with charge carrier trap filling. At the same time several mechanisms of irreversible degradation were observed under UV light irradiation, heating and ageing in ambient conditions. The degradation mechanisms of OLEDs under heating from 293K to 320K were related to the changes in the interface regions. The initial degradation was eliminated by (1) an application of alternating bias voltage; (2) a decrease of the substrate temperature and the velocity of the thermal evaporation of materials. The degradation of OLEDs was not observed under low UV irradiation that is promising for OLEDs operation under day light.

The novel tandem two-diode organic amplifier/converter of light based on successively connected photosensitive and light emission cells with spatial disjunction of processes of photocurrent multiplication (PM) and electroluminescence (EL) has been proposed and realized. The terbium complex Tb(Sal)3(TPPO)2 (HSal – salicylic acid, TPPO – triphenylphosphine oxide) or aluminum tris-(8-hydroxyquinoline (Alq3)) have been used as active layers in light emission cell of device as well as the perylene pigment Me-PTC (N,N″-dimethylperylene-3,4,9,10-bis(decarboximide)) in the photosensitive one. The suggested method of amplification/conversion has some advantages: (1) it avoids the necessity to adjust HOMO- and LUMO levels of photosensitive and electroluminescent layers and thus, extends the range of suitable light emissive materials including ones with high emission characteristics, (2) it also eliminates reabsorption of light by photosensitive part of the system and so, extends spectral band of amplification/conversion. A modernized model of field-activated structural traps has been suggested. Kinetics of PM during light- and voltage switching with time pauses is explained using this model. The peculiarities of PM and its kinetics at different light intensities, temperatures and applied voltages are analyzed too. Optimal values of temperatures, voltages and light excitation intensities providing high PM have been found. The PM gain up to 105-fold has been achieved. The conversion of long-wave (λ=600nm) light into narrow emission bands of Tb(Sal)3(TPPO)2 (λmax 545nm) and wide-band (from 490nm) emission of Alq3 has been obtained. Up- and down-conversion of light along with enhancement of emission have been observed in both devices. A computer simulation of the tandem-diode amplifier/converter has been performed and operation conditions providing transition from the up-conversion mode to the enhancement of light mode have been studied. It has been demonstrated that the processes of PM and the bias redistribution between the units of device exert strong influence to one another and only their unification leads to the tandem-diode operation.