The photophysics of solution processable semiconductors for applications in optoelectronic devices

A large amount of the demand for energy worldwide is for electricity which in turn goes towards domestic uses, powering electronic devices, communication, lighting, et cetera. Solar energy has thus gained much attention over the past few decades as a clean, renewable and well-distributed source of energy globally. Although Silicon solar cells remain the most purchased solar cells these past few decades and currently have module-scale efficiencies exceeding 20%; emerging solar cell technologies (based on materials such as organic polymers, quantum dots and perovskites) have become increasingly popular and continuously challenge the dominance of Silicon. This is especially true for niche applications where their flexibility, semi-transparency, and range of colours give them advantages over Silicon. In particular, they can be cheaply synthesised and coated into ultrathin layers which makes them ideal for technologies such as disposable electronics, sensors, semi-transparent barriers, and wearables, among others. This thesis presents the results of experiments on these emerging solution-processable optoelectronic materials. The experiments described herein address methodologies such as the use of additives to improve the dielectric constant of organic photovoltaic blends, the related strategy of using the intrinsic dipolar alignment of a ferroelectric polymer to enhance the efficiency of polymer solar cells, as well as topics regarding hybrid organic-inorganic perovskites - such as the light-soaking effect in perovskite solar cells, and the photophysical properties of perovskite-shelled Lead Sulphide quantum dots. The final results improve our understanding of these classes of solution-processable semiconductors and point towards avenues for further material improvements

Synthesis, Optical and Electrochemical Properties of High-Quality Cross-Conjugated Aromatic Polyketones

This paper describes the synthesis and characterization of three new aromatic polyketones with repeating units based on 2,2′-(2,5-dihexyl-1,4-phenylene) dithiophene (PTK), 2,2′-(9,9-dihexyl-9H-fluorene-2,7-diyl)dithiophene (PFTK), and 4,7-bis(3-hexylthiophen-2-yl)benzo[c][1,2,5]thiadiazole (PBTK). These polymers were obtained with a one-pot Suzuki-Miyaura cross-coupling-promoted homopolymerization to afford high-quality, defect-free polymers. Experimental and theoretical studies were applied to investigate their optical and electrical properties. The cross-conjugated nature of aromatic polyketones imparts excellent thermal stability. Exposure to acid converts the cross-conjugation to linear-conjugation, enabling the dynamic tuning of optoelectronic properties

Photophysical and electronic properties of bismuth-perovskite shelled lead sulfide quantum dots

Metal halide perovskite shelled quantum dot solids have recently emerged as an interesting class of solution-processable materials that possess the desirable electronic properties of both quantum dots and perovskites. Recent reports have shown that lead sulfide quantum dots (PbS QDs) with perovskite ligand-shells can be successfully utilized in (opto)electronic devices such as solar cells, photoconductors, and field-effect transistors (FETs), a development attributed to the compatibility of lattice parameters between PbS and certain metal halide perovskites that results in the growth of the perovskite shell on the PbS QDs. Of several possible perovskite combinations used with PbS QDs, bismuth-based variants have been shown to have the lowest lattice mismatch and to display excellent performance in photoconductors. However, they also display photoluminescence (PL), which is highly sensitive to surface defects. In this work, we present an investigation of the transport and optical properties of two types of bismuth-based perovskite (MA(3)BiI(6) and MA(3)Bi(2)I(9)) shelled PbS QDs. Our photophysical study using temperature-dependent PL spectroscopy between 5 and 290 K indicates that the PL efficiency of the reference oleic acid (OA) capped samples is much higher than that of the Bi-shelled ones, which suffer from traps, most likely formed at their surfaces during the phase-transfer ligand exchange process. Nevertheless, the results from electrical measurements on FETs show the successful removal of the native-OA ligands, displaying electron dominated transport with modest mobilities of around 10(-3) cm(2) [V s](-1) - comparable to the reported values for epitaxial Pb-based shelled samples. These findings advance our understanding of perovskite shelled QD-solids and point to the utility of these Bi-based variants as contenders for photovoltaic and other optoelectronic applications. Published under license by AIP Publishing

Interfacial Morphology Addresses Performance of Perovskite Solar Cells Based on Composite Hole Transporting Materials of Functionalized Reduced Graphene Oxide and P3HT

The development of novel hole transporting materials (HTMs) for perovskite solar cells (PSCs) that can enhance device's reproducibility is a largely pursued goal, even to the detriment of a very high efficiency, since it paves the way to an effective industrialization of this technology. In this work, we study the covalent functionalization of reduced graphene oxide (RGO) flakes with different organic functional groups with the aim of increasing the stability and homogeneity of their dispersion within a poly(3-hexylthiophene) (P3HT) HTM. The selected functional groups are indeed those recalling the two characteristic moieties present in P3HT, i.e., the thienyl and alkyl residues. After preparation and characterization of a number of functionalized RGO@P3HT blends, we test the two containing the highest percentage of dispersed RGO as HTMs in PSCs and compare their performance with that of pristine P3HT and of the standard Spiro-OMeTAD HTM. Results reveal the big influence of the morphology adopted by the single RGO flakes contained in the composite HTM in driving the final device performance and allow to distinguish one of these blends as a promising material for the fabrication of highly reproducible PSCs

Can Ferroelectricity Improve Organic Solar Cells?

Blends of semiconducting (SC) and ferroelectric (FE) polymers have been proposed for applications in resistive memories and organic photovoltaics (OPV). For OPV, the rationale is that the local electric field associated with the dipoles in a blend could aid exciton dissociation, thus improving power conversion efficiency. However, FE polymers either require solvents or processing steps that are incompatible with those required for SC polymers. To overcome this limitation, SC (poly(3-hexylthiophene)) and FE (poly(vinylidene fluoride-trifluoroethylene)) components are incorporated into a block copolymer and thus a path to a facile fabrication of smooth thin films from suitably chosen solvents is achieved. In this work, the photophysical properties and device performance of organic solar cells containing the aforementioned block copolymer consisting of poly(vinylidene fluoride-trifluoroethylene): P(VDF-TrFE), poly(3-hexylthiophene): P3HT and the electron acceptor phenyl-C-61-butyric acid methyl ester: [60]PCBM are explored. A decrease in photovoltaic performance is observed in blends of the copolymer with P3HT:[60]PCBM, which is attributed to a less favorable nanomorphology upon addition of the copolymer. The role of lithium fluoride (the cathode modification layer) is also clarified in devices containing the copolymer, and it is demonstrated that ferroelectric compensation prevents the ferroelectricity of the copolymer from improving photovoltaic performance in SC-FE blends

Customizing the Polarity of Single-Walled Carbon-Nanotube Field-Effect Transistors Using Solution-Based Additives

Polarity control in semiconducting single-walled carbon-nanotube field-effect transistors (s-SWNT FETs) is important to promote their application in logic devices. The methods to turn the intrinsically ambipolar s-SWNT FETs into unipolar devices that have been proposed until now require extra fabrication steps that make preparation longer and more complex. It is demonstrated that by starting from a highly purified ink of semiconducting single-walled carbon nanotubes sorted by a conjugated polymer, and mixing them with additives, it is possible to achieve unipolar charge transport. The three additives used are benzyl viologen (BV), 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), which give rise to n-type field-effect transistors, and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F-4-TCNQ) which gives rise to p-type transistors. BV and N-DMBI transform the s-SWNTs transistors from ambipolar with mobility of the order of 0.7 cm(2) V-1 s(-1) to n-type with mobility up to 5 cm(2) V-1 s(-1). F-4-TCNQ transform the ambipolar transistors in p-type with mobility up to 16 cm(2) V-1 s(-1)

Conjugated Polyions Enable Organic Photovoltaics Processed from Green Solvents

This paper describes the design, synthesis, and optical and electronic properties of two conjugated polymers CPIZ-B and CPIZ-T that incorporate closed-shell cations into their conjugated backbones, balanced by anionic pendant groups. The zwitterionic nature of the polymers renders them soluble in and processable from polar, protic solvents to form semiconducting films that are not doped. These unique properties are confirmed by absorption and electron paramagnetic resonance spectroscopy. The energies of the unoccupied states respond to the tritylium moieties in the conjugated backbone, while the occupied states respond to the electron-donating ability of the uncharged, aromatic units in the backbone. Films cast from 80:20 HCOOH/H2O by volume show good electron mobilities, enabling a photovoltaic effect in proof-of-concept, bilayer solar cells

Elimination of the light soaking effect and performance enhancement in perovskite solar cells using a fullerene derivative

In this work, we investigate how electron extraction layers (EELs) with different dielectric constants affect the device performance and the light-soaking phenomenon in hybrid perovskite solar cells (HPSCs). Fulleropyrrolidine with a triethylene glycol monoethyl ether side chain (PTEG-1) having a dielectric constant of 5.9 is employed as an EEL in HPSCs. The commonly used fullerene derivative [60] PCBM, which has identical energy levels but a lower dielectric constant of 3.9, is used as a reference. The device using PTEG-1 as the EEL shows a negligible light soaking effect, with a power conversion efficiency (PCE) of 15.2% before light soaking and a minor increase to 15.7% after light soaking. In contrast, the device using [60] PCBM as the EEL shows severe light soaking, with the PCE improving from 3.8% to 11.7%. Photoluminescence spectroscopy and impedance spectroscopy measurements indicate that trap-assisted recombination at the interface between the hybrid perovskite and the EEL is the cause of the light soaking effect in HPSCs. The trap-assisted recombination is effectively suppressed at the perovskite/PTEG-1 interface, while severe trap assisted recombination takes place at the perovskite/[60] PCBM interface. We attributed these experimental findings to the fact that the higher dielectric constant of PTEG-1 helps to screen the recombination between the traps and free electrons. In addition, the electron donating side chains of PTEG-1 may also contribute to the passivation of the electron traps. As a consequence, the devices using PTEG-1 as the EEL display a considerable increase in the efficiency and a negligible light soaking effect

The use of plants in the traditional management of diabetes in Nigeria: Pharmacological and toxicological considerations

Ethnopharmacological relevance: The prevalence of diabetes is on a steady increase worldwide and it is now identified as one of the main threats to human health in the 21st century. In Nigeria, the use of herbal medicine alone or alongside prescription drugs for its management is quite common. We hereby carry out a review of medicinal plants traditionally used for diabetes management in Nigeria. Based on the available evidence on the species׳ pharmacology and safety, we highlight ways in which their therapeutic potential can be properly harnessed for possible integration into the country׳s healthcare system. Materials and methods: Ethnobotanical information was obtained from a literature search of electronic databases such as Google Scholar, Pubmed and Scopus up to 2013 for publications on medicinal plants used in diabetes management, in which the place of use and/or sample collection was identified as Nigeria. ‘Diabetes’ and ‘Nigeria’ were used as keywords for the primary searches; and then ‘Plant name – accepted or synonyms’, ‘Constituents’, ‘Drug interaction’ and/or ‘Toxicity’ for the secondary searches. Results: The hypoglycemic effect of over a hundred out of the 115 plants reviewed in this paper is backed by preclinical experimental evidence, either in vivo or in vitro. One-third of the plants have been studied for their mechanism of action, while isolation of the bioactive constituent(s) has been accomplished for twenty three plants. Some plants showed specific organ toxicity, mostly nephrotoxic or hepatotoxic, with direct effects on the levels of some liver function enzymes. Twenty eight plants have been identified as in vitro modulators of P-glycoprotein and/or one or more of the cytochrome P450 enzymes, while eleven plants altered the levels of phase 2 metabolic enzymes, chiefly glutathione, with the potential to alter the pharmacokinetics of co-administered drugs. Conclusion: This review, therefore, provides a useful resource to enable a thorough assessment of the profile of plants used in diabetes management so as to ensure a more rational use. By anticipating potential toxicities or possible herb–drug interactions, significant risks which would otherwise represent a burden on the country׳s healthcare system can be avoided

Effects of Storage Conditions on Pharmacokinetics of Paracetamol Table

The effects of storage condition on the pharmacokinetics of paracetamol tablets were studied under several storage conditions. Three storage sites which were considered suboptimal were selected. Freshly purchased 1000-tablets tins of paracetamol were bought and stored in each of these sites for not less than two months and were being dispensed. Prior to storage a few tablets from each tin were selected to serve as control. Kinetic studies were carried out with tablets obtained after two months of storage in these sites. A colorimetric method was used for plasma concentration determination and data analysed using student t test. p value less than 0.05 was considered significant. Blood level data obtained from the studies were used to determine the pharmacokinetics of the drug. Plasma concentrations showed no statistical differences from two storage sites (p>0.05). The time taken to attain peak plasma level (t) was not statiscally affected in all the sites (p>0.05), but area under the curve from zero to infinity (AuC-) was statistically affected in two sites (