Paola Vivo

Enhanced performance and stability of inverted organic solar cells by using novel zinc-benzothiazole complexes as anode buffer layers

Performance of inverted bulk-heterojunction solar cells with widely used tris(8-quinolinolate)aluminium(III) (Alq3) is compared with a series of novel zinc-benzothiazole (Znb2) derivatives as buffer layer. The devices including a Znb2 thin layer between the poly(3-hexylthiophene) (P3HT):C61-butyric acid methyl ester (PCBM) blend and the Au anode show a significant improvement in the power conversion efficiency (η), which is enhanced by 30% compared to Alq3cells. Moreover, by combining both Alq3 and Znb2 in the device as a double buffer layer prior to the metal electrode deposition, the efficiency improves by 40%. The reasons for the enhanced performance of Znb2 cells are attributed to the efficient charge transport and electron/exciton blocking properties. Furthermore it is expected that the deposition of Znb2 modifies the Au work function to facilitate the hole transport and collection at the anode, and encapsulate the P3HT/PCBM blend during the electrode deposition. The presented photovoltaic cells also show high stability in ambient air conditions over a period of 245 days, which evidences the need of Znb2 buffer layers for long-term device durability.

Long term stability of air processed inkjet infiltrated carbon-based printed perovskite solar cells under intense ultra-violet light soaking

The long term stability of air processed inkjet infiltrated carbon based perovskite solar cells (CPSCs) is investigated under intense ultra-violet light soaking equivalent to 1.5 Sun UV light illumination. Two batches of the fabricated CPSCs were exposed systematically i.e. first without implementing any protective coating and then epoxying the CPSCs through a low cost commonly available epoxy which was applied to serve as a barrier against moisture and humidity intrusion. The CPSCs with no protective layer against moisture and humidity exhibited impressive preliminary stability for hundreds of hours during their exposure to intense UV light and provided great motivation to test the CPSCs further with more optimization. As a result, the CPSCs having commonly available epoxy as a protective barrier exhibited remarkable durability and showed no performance degradation for a period of 1002 hours under intense and continuous 1.5 Sun equivalent UV light illumination proving that the technology is clearly not inherently unstable and that future developments might lead to market breakthroughs.

Hole-Transporting Materials for Printable Perovskite Solar Cells

Perovskite solar cells (PSCs) represent undoubtedly the most significant breakthrough in photovoltaic technology since the 1970s, with an increase in their power conversion efficiency from less than 5% to over 22% in just a few years. Hole-transporting materials (HTMs) are an essential building block of PSC architectures. Currently, 2,2’,7,7’-tetrakis-(N,N’-di-p-methoxyphenylamine)-9,9’-spirobifluorene), better known as spiro-OMeTAD, is the most widely-used HTM to obtain high-efficiency devices. However, it is a tremendously expensive material with mediocre hole carrier mobility. To ensure wide-scale application of PSC-based technologies, alternative HTMs are being proposed. Solution-processable HTMs are crucial to develop inexpensive, high-throughput and printable large-area PSCs. In this review, we present the most recent advances in the design and development of different types of HTMs, with a particular focus on mesoscopic PSCs. Finally, we outline possible future research directions for further optimization of the HTMs to achieve low-cost, stable and large-area PSCs.

Synthesis of Benzothiadiazole Derivatives by Applying C–C Cross-Couplings

The benzothiadiazole moiety has been extensively exploited as a building block in the syntheses of efficient organic semiconducting materials during the past decade. In this paper, parallel synthetic routes to benzothiadiazole derivatives, inspired by previous computational findings, are reported. The results presented here show that various C-C cross-couplings of benzothiadiazole, thiophene, and thiazole derivatives can be efficiently performed by applying Xantphos as a ligand of the catalyst system. Moreover, improved and convenient methods to synthesize important chemical building blocks, e.g., 4,7-dibromo-2,1,3-benzothiadiazole, in good to quantitative yields are presented. Additionally, the feasibility of Suzuki-Miyaura and direct coupling methods are compared in the synthesis of target benzothiadiazole derivatives. The computational characterization of the prepared benzothiadiazole derivatives shows that these compounds have planar molecular backbones and the possibility of intramolecular charge transfer upon excitation. The experimental electrochemical and spectroscopic studies reveal that although the compounds have similar electronic and optical properties in solution, they behave differently in solid state due to the different alkyl side-group substitutions in the molecular backbone. These benzothiadiazole derivatives can be potentially used as building blocks in the construction of more advanced small molecule organic semiconductors with acceptor-donor-acceptor motifs.

Crystallisation-enhanced bulk hole mobility in phenothiazine-based organic semiconductors

A series of three novel donor-acceptor systems based on C(3)-malononitrile-substituted phenothiazines was synthesised in good overall yields and their thermal, spectroscopic, and electrochemical properties were characterised. The compounds were prepared through a sequence of Ullmann-coupling, Vilsmeier-Haack formylation and Knoevenagel-condensation, followed by Suzuki-coupling reactions for introduction of aryl substitutents at C(7) position of the phenothiazine. The introduction of a donor unit at the C(7) position exhibited a weak impact on the optical and electrochemical characteristics of the compounds and led to amorphous films with bulk hole mobilities in the typical range reported for phenothiazines, despite the higher charge delocalisation as attested by computational studies. In contrast, highly ordered films were formed when using the C(7)-unsubstituted 3-malononitrile phenothiazine, exhibiting an outstanding mobility of 1 × 10−3 cm2 V−1 s−1, the highest reported for this class of compounds. Computational conformational analysis of the new phenothizanes suggested that free rotation of the substitutents at the C(7) position suppresses the ordering of the system, thereby hampering suitable packing of the new materials needed for high charge carrier mobility.

Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces

Terpyridine-substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl-crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn(2+) ions allowed for layer-by-layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid-state dye-sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed.

Tailored Fabrication of Transferable and Hollow Weblike Titanium Dioxide Structures

The preparation of weblike titanium dioxide thin films by atomic layer deposition on cellulose biotemplates is reported. The method produces a TiO2 web, which is flexible and transferable from the deposition substrate to that of the end application. Removal of the cellulose template by calcination converts the amorphous titania to crystalline anatase and gives the structure a hollow morphology. The TiO2 webs are thoroughly characterized using electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy to give new insight into manufacturing of porous titanium dioxide structures by means of template-based methods. Functionality and integrity of the TiO2 hollow weblike thin films were successfully confirmed by applying them as electrodes in dye-sensitized solar cells.

Vectorial photoinduced electron transfer in multicomponent film systems of poly(3-hexylthiophene), porphyrin–fullerene dyad, and perylenetetracarboxidiimide

Multistage electron transfer in a film system consisting of a hole-transporting layer (HTL), donor-acceptor pair (D-A), and an electron-transporting layer (ETL) was studied by photovoltage and flash-photolysis techniques. Poly(3-hexylthiophene) (PHT) was used as the HTL, while a symmetric porphyrin-fullerene dyad (P-F) and perylenetetracarboxidiimide (PTCDI) layers were functioning as the D-A pair and ETL, respectively. The photoexcitation of this three-component film system causes charge separations in the monomolecular P-F film, followed by electron transfer from the PHT polymer film and the fullerene anions to the porphyrin cations and the PTCDI layer, respectively. The final transient state is a charged PHT(+)|P-F|PTCDI(-) system, with significantly increased amplitude and lifetime of the photoelectrical signals compared to previously studied P-F|PTCDI and PHT|P-F systems, due to the its increased charge-separation distance. The study promotes the knowledge on the charge transfer mechanism in multilayered film systems.

Halogen-Bond-Assisted Photoluminescence Modulation in Carbazole-Based Emitter

Halogen bonding between a carbazole-based, pyridine-substituted organic semiconductor and a common halogen-bond donor (pentafluoroiodobenzene) yields efficient halogen-bond-driven fluorescence modulation in solution. Steady-state, time-resolved emission and absorption spectroscopy as well as density functional theory studies demonstrate that the fluorescence modulation arises from halogen-bond-induced intramolecular charge transfer. Fluorescence modulation offers a range of possibilities both in solution and in the solid state, for instance providing a potential pathway for the design of tunable luminescent materials for light-emitting devices.