Arun D. Rao

Self-assembled, aligned ZnO nanorod buffer layers for high-current-density, inverted organic photovoltaics.

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of ∼3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.

Layer-by-layer assembly of Nafion on Surlyn with ultrahigh water vapor barrier.

A layer-by-layer approach was used for the fabrication of multilayer films for ultra high gas barrier applications. The ultra high gas barrier material was designed by incorporating Nafion layer in between bilayers of poly(ethylene imine) and poly(acrylic acid) on a Surlyn substrate. When the barrier film with self-assembled Nafion is exposed to the moist environment, Nafion absorbs and desorbs water molecules simultaneously, thereby reducing the ingress of moisture in to the film. In order to study the effect of Nafion, the fabricated barrier materials with and without the presence of Nafion were tested for water vapor barrier properties. The barrier films were further used for encapsulating organic photovoltaic devices and were evaluated for their potential use in barrier applications. The devices encapsulated with the films containing Nafion exhibited better performance when subjected to accelerated aging conditions. Therefore, this study demonstrates the effectiveness of self-assembled Nafion in reducing the water vapor permeability by nearly five orders of magnitude and in increasing the lifetimes of organic devices by ∼22 times under accelerated weathering conditions.

New low band gap 2-(4-(trifluoromethyl)phenyl)-1H-benzo[d]imidazole and benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole based conjugated polymers for organic photovoltaics

Two new low band gap D–A structured conjugated polymers, PBDTTBI and PBDTBBT, based on 2-(4-(trifluoromethyl)phenyl)-1H-benzo[d]imidazole and benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole acceptor units with benzo[1,2-b;3,4-b′]dithiophene as a donor unit have been designed and synthesized via a Stille coupling reaction. The incorporation of the benzo[1,2-c;4,5-c′]bis[1,2,5]thiadiazole unit into PBDTBBT has significantly altered the optical and electrochemical properties of the polymer. The optical band gap estimated from the onset absorption edge is ∼1.88 eV and ∼1.1 eV, respectively for PBDTTBI and PBDTBBT. It is observed that PBDTBBT exhibited a deeper HOMO energy level (−4.06 eV) with strong intramolecular charge transfer interactions. Bulk heterojunction solar cells fabricated with a configuration of ITO/PEDOT:PSS/PBDTBBT:PC71BM/Al exhibited a best power conversion efficiency of 0.67%, with a short circuit current density of 4.9 mA cm−2, an open-circuit voltage of 0.54 V and a fill factor of 25%.

Solvent polarity and nanoscale morphology in bulk heterojunction organic solar cells: A case study

Organic bulk heterojunction solar cells were fabricated under identical experimental conditions, except by varying the solvent polarity used for spin coating the active layer components and their performance was evaluated systematically. Results showed that presence of nitrobenzene-chlorobenzene composition governs the morphology of active layer formed, which is due to the tuning of solvent polarity as well as the resulting solubility of the P3HT:PCBM blend. Trace amount of nitrobenzene favoured the formation of better organised P3HT domains, as evident from conductive AFM, tapping mode AFM and surface, and cross-sectional SEM analysis. The higher interfacial surface area thus generated produced cells with high efficiency. But, an increase in the nitrobenzene composition leads to a decrease in cell performance, which is due to the formation of an active layer with larger size polymer domain networks with poor charge separation possibility.

Organic solar cell by using vertically aligned nanostructured ZnO nanorods

A low temperature solution approach was employed to grow zinc oxide (ZnO) nanorods with various aspect ratios. Va r i o u s sizes (diameter-10-25nm) of the nanorods were grown by changing the concentrations of the growth solution. The length (50nm-500nm) of nanorods was controlled using growth times. These one-dimensional (1D) nanostructures with direct paths for a charge transport with high surface area for light harvesting, are promising candidates for organic photovoltaics (OPV). The structural and optical properties of the prepared ZnO nanorods have been studied using SEM, XRD and UV-Vis absorption spectroscopy. Using as-grown ZnO inverted OPV was fabricated. ZnO nanorods were subjected to various doses of UV-ozone irradiation which led to improvement in transmission and hence enhanced device performance.

Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

A series of low band gap, planar conjugated polymers, P1 (PFDTBT), P2 (PFDTDFBT) and P3 (PFDTTBT), based on fluorene and benzothiadiazole, was synthesized. The effect of fluorine substitution and fused aromatic spacers on the optoelectronic and photovoltaic performance was studied. The polymer, derived from dithienylated benzothiodiazole and fluorene, P1, exhibited a highest occupied molecular orbital (HOMO) energy level at −5.48 eV. Density functional theory (DFT) studies as well as experimental measurements suggested that upon substitution of the acceptor with fluorine, both the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels of the resulting polymer, P2, were lowered, leading to a higher open circuit voltage and short circuit current with an overall improvement of more than 110% for the photovoltaic devices. Moreover, a decrease in the torsion angle between the units was also observed for the fluorinated polymer P2 due to the enhanced electrostatic interaction between the fluorine substituents and sulfur atoms, leading to a high hole mobility. The use of a fused π-bridge in polymer P3 for the enhancement of the planarity as compared to the P1 backbone was also studied. This enhanced planarity led to the highest observed mobility among the reported three polymers as well as to an improvement in the device efficiency by more than 40% for P3.

Device fabrication of insoluble donor–acceptor–donor structured molecule by pulsed laser deposition: a comparative study using different laser source

Many of the conducting polymers though having good material property are not solution processable. Hence an alternate method of fabrication of film by pulsed laser deposition, was explored in this work. PDTCPA, a donor- acceptor- donor type of polymer having absorption from 900 nm to 300 nm was deposited by both UV and IR laser to understand the effect of deposition parameters on the film quality. It was observed that the laser ablation of PDTCPA doesn’t alter its chemical structure hence retaining the chemical integrity of the polymer. Microscopic studies of the ablated film shows that the IR laser ablated films were particulate in nature while UV laser ablated films are deposited as smooth continuous layer. The morphology of the film influences its electrical characteristics as current- voltage characteristic of these films shows that films deposited by UV laser are p rectifying while those by IR laser are more of resistor in nature.