Light-emitting devices from the tris(2,2'-bipyridyl)ruthenium(II) complex [Ru(bpy)(3)(2+)] and new derivatives thereof were prepared. Due to the electrochemical nature of the device operation, single-layer devices in an ITO/ Ru(bpy)(3)(2+) complex + PMMA/Ag sandwich configuration achieved very high external quantum efficiencies. The derivatives of the Ru(bpy)(3)(2+) complex were designed and synthesized to inhibit self-quenching of the excited state by adding different alkyl substituents on the bipyridyl ligands. As a result, devices that contain these new Ru(bpy)(3)(2+) complexes show a higher photoluminescence and electroluminescence efficiency than devices made from the unmodified Ru(bpy)(3)(2+) complex. External quantum efficiencies up to 5.5% at brightnesses in the range of 10-50 cd/m(2) are reported. In addition, the response time of such devices (which is a result of the electrochemical operation) has been shortened dramatically. An "instantaneous" light emission is achieved for devices that employ smaller counterions such as BF(4)(-) to increase the ionic conductivity. Such a device shows a response time of less than 1 s to emit 10-20 cd/m(2) after the operating voltage of 2.4 V has been applied.
The solvation of the ruthenium(II) tris(bipyridine) ion ([Ru(bpy) 3 ] 2þ) is investigated with molecular dynamics simulations of lithium halide solutions in polar solvents. The anion distribution around the [Ru(bpy) 3 ] 2þ complex exhibits a strong solvent dependence. In aqueous solution, the iodide ion forms a solvent shared complex with [Ru(bpy) 3 ] 2þ , but not in the other solvents. Between Cland [Ru(bpy) 3 ] 2þ , the strong hydration of the chloride ion results in a solvent separated complex where more than one solvent molecule separates the anion from the metal center. Hence, tailored solvation properties in electrolytes is a route to influence ion-ion interactions and related electron transfer processes. V
In this work, the operational mechanism of single-layer light-emitting electrochemical cells (LECs) based on the small molecule tris(2,2’ bipyridyl) ruthenium(II) [Ru(II)] was investigated using capacitance and resistance measurements. The current–voltage and capacitance–voltage characteristics of such devices suggest that an electrochemical junction is formed during operation with a high electric field across the junction. A similar mechanism has been proposed for polymer LECs. In the case of Ru(II) devices, electrically conducting regions adjacent to the electrodes are the result of mixed-valent states that form due to oxidation and reduction of the complex. The junction thickness is a function of the type of counterions used and the operating voltage. Thinner junctions were observed for devices with high ionic conductivity and at higher operating voltages. Transient capacitance and resistance measurements show that the junction formation is faster in devices with higher ion mobility and during higher operating voltages. In addition, the capacitance and resistance exhibit a relaxation time after the device is turned off. This relaxation shows that the electrochemical junction stays present in a device for some time (several seconds to minutes) once a device is turned off. The electrochemical junction disappears as the counterions relax back. Furthermore, a theoretical model is presented, which shows that due to the concentration gradient of mixed-valent states during operation, an electric field has to be present in the device. The model also shows that there can be no local charge neutrality in the bulk of the device during operation.
Light emitting electrochemical cells based on the tris͑2,2Ј bipyridyl͒ ruthenium͑II͒ complex show improved performance if electrochemically stable materials such as Ag are used as the cathode material. In contrast, if Al is used as the cathode such devices undergo degradation when stored in the off-state in inert atmosphere. In this work, the mechanism of the aluminum-induced degradation is investigated. X-ray photoelectron spectroscopy shows that some of the Ru͑II͒ complexes are reduced in the presence of the Al cathode to Ru͑I͒. In addition, secondary ion mass spectrometry depth profiles indicate degradation of the indium tin oxide in devices with Al cathodes. Because of the mixed-valent Ru͑II͒/͑I͒ states, devices with Al cathodes exhibit unipolar charge injection at voltages below the turn-on voltages. The unipolar charge injection can be described by a theory of charge hopping in mixed-valent redox systems. In addition, impedance analysis data at 0 V bias of devices with Al or Ag cathodes can be fit using simple equivalent electric circuits. In the case of Al devices, the equivalent electric circuit was modified to account for the redox conduction at 0 V bias and an oxide layer at the cathode interface.
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