Anup Thomas

Photophysical, electrochemical and photovoltaic properties of dye sensitized solar cells using a series of pyridyl functionalized porphyrin dyes

Three porphyrin dyes, P1, P2 and P3, bearing one, two and four pyridyl groups, respectively, in the meso positions, acting as electron acceptor anchoring groups, were synthesized, characterized and investigated as sensitizers for the fabrication of dye sensitized solar cells (DSSCs). The overall power conversion efficiencies (PCEs) of DSSCs based on these dyes lay in the range 2.46–3.9% using a 12 μm thick TiO2 photoanode. Porphyrin P2 achieved the maximum performance, which can be rationalized by the high dye loading, efficient electron injection, dye regeneration process and longer electron lifetime, as demonstrated by the electrochemical impedance spectroscopy (EIS) measurements. The PCE of the DSSC based on the P2 sensitizer when the photoanode was treated with formic acid, showed an enhanced efficiency of 5.23%. This improvement, attributed to multifunctional properties such as higher dye uptake, reduced recombination process and enhanced charge collection efficiency. Deoxycholic acid (DCA) was also used as a coadsorbent in order to prevent dye aggregation and it was found that the PCE improved up to 6.12% for sensitizer P2 and the modified TiO2 photoanode, which can be attributed to further improvement in the electron injection efficiency and charge collection efficiency.

Synthesis and characterization of 9,10-bis(2-phenyl-1,3,4-oxadiazole) derivatives of anthracene: Efficient n-type emitter for organic light-emitting diodes

With a general aim to make anthracene derivatives multifunctional (n-type emitter) and also study their suitability as electron transport layers for organic light emitting diodes (OLED), and with a more specific interest to understand the charge transport and packing pattern in the solid state due to the rotating side rings, we report the synthesis and characterization of six novel molecules (5–10) in which the 9 and 10 positions of anthracene have been directly substituted by phenyloxadiazole groups. We have carried out detailed studies of these molecules including photophysical, electrochemical, electroluminescent studies and solid state structure determination through crystallographic techniques. The electron affinity is very high, around 3.1–3.2 eV, and the ionization potential is around 5.9–6.0 eV, comparable to the more commonly used electron transport electroluminescent layer Alq3. The studies reveal that the new molecules being reported by us, in addition to the high thermal stability, are quite efficient in a two layer unoptimized device with the device structure ITO/α-NPD/5–10/LiF/Al and have an emission in pure green. They also show very high efficiency as electron transport layer in device structure ITO(120nm)/α-NPD(30nm)/Ir(ppy)3 doped CBP(35nm)/BCP(6nm)/5(28nm)/Al(150nm). From these studies we conclude that the anthracene derivatives also have considerable potential as multifunctional layers and as electron transport layers in OLED.

Comparative Study of the Semiconducting Properties of Benzothiadiazole and Benzobis(thiadiazole) Derivatives Using Computational Techniques

Recent literature reports indicate that derivatives of benzothiadiazole (BT) and benzobis(thiadiazole) (BBT), which differs from BT by an extra thiadiazole ring, exhibit good semiconducting properties, such as high electron mobility and low-lying lowest unoccupied molecular-orbital (LUMO) levels. In this study herein, computational techniques like density functional theory (DFT), spin-flip DFT and valence-bond methods are used to analyze the semiconducting properties of these molecules. Calculations at the B3LYP/cc-pVTZ level reveal that all the BBT molecules, including the bare BBT ring, have lower lying LUMO energies (3.70-4.11 eV) compared to the BT derivatives (2.56-3.41 eV) with similar substitution. The reorganization energies (λ(+)/λ(-)) obtained at this level of theory of the BT derivatives are around (225-333)/(246-315) meV, while BBT derivatives have much smaller reorganization energies and these are in the range of (129-259)/(150-230) meV. We observe that the different behavior of BBT is due to the inherited biradicaloid character from the parent molecule tetramethylenebenzene (TMB), a disjoint non-Kekule biradical having non-bonding molecular orbitals (NBMOs) as the highest occupied molecular orbital (HOMO) and LUMO. Additionally, the perturbation of the orbitals of the biradical TMB to obtain BBT is the major cause for the BBT derivatives to have a larger electron affinity (EA) and a smaller HOMO-LUMO gap (HLG) compared to BT derivatives.