Efficient and stable air-processed ternary organic solar cells incorporating gallium-porphyrin as electron cascade material

Two gallium porphyrins, a tetraphenyl GaCl porphyrin, termed as (TPP)GaCl, and an octaethylporphyrin GaCl porphyrin, termed as (OEP)GaCl, were synthesized to use as an electron cascade in ternary organic bulk heterojunction films. A perfect matching of both gallium porphyrins’ energy levels with that of poly(3-hexylthiophene-2,5-diyl) (P3HT) or poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) polymer donor and the 6,6-phenyl C71 butyric acid methyl ester (PCBM) fullerene acceptor, forming an efficient cascade system that could facilitate electron transfer between donor and acceptor, was demonstrated. Therefore, ternary organic solar cells (OSCs) using the two porphyrins in various concentrations were fabricated where a performance enhancement was obtained. In particular, (TPP)GaCl-based ternary OSCs of low concentration (1:0.05 vv%) exhibited a ~17% increase in the power conversion efficiency (PCE) compared with the binary device due to improved exciton dissociation, electron transport and reduced recombination. On the other hand, ternary OSCs with a high concentration of (TPP)GaCl (1:0.1 vv%) and (OEP)GaCl (1:0.05 and 1:0.1 vv%) showed the poorest efficiencies due to very rough nanomorphology and suppressed crystallinity of ternary films when the GaCl porphyrin was introduced to the blend, as revealed from X-ray diffraction (XRD) and atomic force microscopy (AFM). The best performing devices also exhibited improved photostability when exposed to sunlight illumination for a period of 8 h than the binary OSCs, attributed to the suppressed photodegradation of the ternary (TPP)GaCl 1:0.05-based photoactive film

Energy transfer processes among emitters dispersed in a single polymer layer for colour tuning in OLEDs

The energy transfer processes taking place in a single polymeric layer that enable the definition of the three primary colours (red, green and blue) in selected areas via photochemically induced emission tuning are discussed. The polymers used as hosts are two wide band gap polymers, PVK and a polyfluorenyl derivative. In the polymer matrix are dispersed the green emitter, 1-(4'-dimethyl-aminophenyl)-6-phenyl-1,3,5-hexatriene (DMA-DPH), the red emitter, 4-dimethylamino-4'-nitrostilbene (DANS) and a photoacid generator (PAG). Upon irradiation, protons are released from the PAG and they react gradually with the two emitters, causing the blue shift of the green emitter fluorescence and the extinction of the red emitter fluorescence. Depending on the protonation extent, the relative concentrations of the emitters and the exposure dose the energy transfer processes occurring inside the matrix result in definition of different colour emitting areas. The understanding of the energy transfer processes with photoluminescence experiments is a necessary first step in order to rationalize the selection of suitable components enabling the definition of the three primary colours in OLEDs.</p

Passivation and process engineering approaches of halide perovskite films for high efficiency and stability perovskite solar cells

The surface, interfaces and grain boundaries of a halide perovskite film carry critical tasks in achieving as well as maintaining high solar cell performance due to the inherently defective nature across their regime. Passivating materials and felicitous process engineering approaches have significant ramifications in the resultant perovskite film, and the solar cell's overall macroscale properties as they dictate structural and optoelectronic properties. Herein, we exploit a vast number of defect engineering approaches aiming to increase the performance and the stability of perovskite solar cells, especially against humidity, continuous illumination, and heat. This review begins with the perovskite materials' fundamental structural properties followed by the advances made to induce higher stabilization in perovskite solar cells by fine-tuning materials chemistry design parameters. We continue by summarizing defect passivation strategies based on molecular entities' application, including suitable functional groups that enable sufficient surface, bulk and grain boundary passivation, morphology, and crystallinity control. We also present methods to control the density of defects through the variation of processing conditions, solvent annealing and solvent engineering approaches, gas-assisted deposition methods, and use of self-assembled monolayers, as well as colloidal engineering and coordination surface chemistry. Finally, we give our perspective on how a combined understanding of materials chemistry aspects and passivation mechanisms will further develop high-efficiency and stability perovskite solar cells

Hydrogenated under-stoichiometric tungsten oxide anode interlayers for efficient and stable organic photovoltaics

In this work a hydrogenated under-stoichiometric tungsten oxide is introduced as an efficient anode interlayer in organic photovoltaics (OPVs). The benefits of hydrogen incorporation into the oxide lattice for obtaining desirable properties of tungsten oxides are explored. These benefits include the occupation of gap states near the Fermi level, which may facilitate charge transport, and the maintenance of a high work function, nearly similar to that of the stoichiometric tungsten oxide, which contributes to the formation of a large interfacial dipole at the anode interface and enhances charge extraction. A large improvement was achieved in the operational characteristics-especially in the open-circuit voltage-of bulk heterojunction solar cells based on different polymeric donors, namely poly(3-hexylthiophene), P3HT, or poly[(9-(1-octylnonyl)-9H-carbazole-2,7-diyl)-2,5-thiophenediyl-2,1, 3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl], PCDTBT, and the fullerene acceptor [6,6]-phenyl-C71 butyric acid methyl ester, PC71BM, that incorporated a hydrogenated tungsten oxide as an anode interlayer. This improvement was correlated with the devices' incident photon-to-electron conversion efficiencies (IPCEs) and impedance measurements. Furthermore, an increase in both the device's flat-band voltage (Vfb) and the doping level of the organic semiconductor was measured in P3HT:PC71BM based devices by Mott-Schottky capacitance analysis. Additional benefits are the large process window established for the devices incorporating the hydrogenated tungsten oxide as an anode interlayer and the maintenance of a high PCE (&gt;80% of its initial efficiency) over 50 days, demonstrating good long-term stability, which is much better than that of the conventional devices based on PEDOT:PSS. The results suggest that the interface engineering with hydrogen-treated metal oxide interlayers is an important strategy to develop highly performing and stable organic photovoltaics.</p

Tungsten oxides as interfacial layers for improved performance in hybrid optoelectronic devices

Tungsten oxide (WO3) films with thicknesses ranging from 30 to 100 nm were grown by Hot Filament Vapor Deposition (HFVD). Films were studied by X-Ray Photoemission Spectroscopy (XPS) and were found to be stoichiometric. The surface morphology of the films was characterized by Atomic Force Microscopy (AFM). Samples had a granular form with grains in the order of 100 nm. The surface roughness was found to increase with film thickness. HFVD WO3 films were used as conducting interfacial layers in advanced hybrid organic-inorganic optoelectronic devices. Hybrid-Organic Light Emitting Diodes (Hy-OLEDs) and Organic Photovoltaics (Hy-OPVs) were fabricated with these films as anode and/or as cathode interfacial conducting layers. The Hy-OLEDs showed significantly higher current density and a lower turn-on voltage when a thin WO3 layer was inserted at the anode/polymer interface, while when inserted at the cathode/polymer interface the device performance was found to deteriorate. The improvement was attributed to a more efficient hole injection and transport from the Fermi level of the anode to the Highest Occupied Molecular Orbital (HOMO) of a yellow emitting copolymer (YEP). On the other hand, the insertion of a thin WO3 layer at the cathode/polymer interface of Hy-OPV devices based on a polythiophene-fullerene bulk-heterojunction blend photoactive layer resulted in an increase of the produced photogenerated current, more likely due to improved electron extraction at the Al cathode.</p

Interfacial engineering for organic and perovskite solar cells using molecular materials

Organic and perovskite solar cells have recently emerged as promising candidates for next-generation solar energy technologies due to their low-cost solution-based fabrication over large areas even on flexible substrates, while offering the possibility of on-chip integration and patterning for custom-designed applications. A key concern over these emerging technologies is their poor operational stability. In a typical device architecture, the organic or perovskite absorber is usually inserted between an electron and a hole transport (extraction) layer in order to match the energetic differences present at the heterointerfaces with the respective contacts. As these layers considerably influence the device performance and operational stability, they have witnessed intense research efforts in recent years resulting in the development of novel materials. Conductive or insulating polymers, non-polymer molecular materials and transition metal oxides are among the most studied classes of interfacial materials. In this review article, we focus on the application of molecular materials, but excluding polymers, either organic or inorganic, to engineer the interfaces in these devices due to their ease of synthesis and facile functionalization of their structure to meet the requirements for successful device modification. We also include ionic compounds of well-defined stoichiometry such as CuSCN, ionic liquids and compounds of molecular anions as the polyoxometalates. We provide a comprehensive account of various molecular interlayers for organic and perovskite solar cell devices. We highlight the origin of enhanced performance and device lifetime and provide a detailed outlook for a focused future development of these materials. © 2020 IOP Publishing Ltd

Reduced transition metal oxides as electron injection layers in hybrid-PLEDs

Here we report on the improved performance of hybrid polymer light emitting diodes (HyPLEDs) upon inserting an ultra thin layer of partially reduced tungsten oxide (WO2.5) or molybdenum oxide (MoO2.7), deposited (by heating a W or Mo filament while hydrogen was flowing through the chamber) at the polymer/Al cathode interface. Improved current densities, luminances and efficiencies were achieved as a result of improved electron injection and transport at its interface with Al. The observed electron injection improvement is attributed to the lowering of the effective cathode interfacial barrier due to the occupation of gap states with electrons after partial reduction.</p

Porphyrin oriented self-assembled nanostructures for efficient exciton dissociation in high-performing organic photovoltaics

Herein we report on enhanced organic solar cell performance through the incorporation of cathode interfacial layers consisting of self-organized porphyrin nanostructures with a face-on configuration. In particular, a water/methanol-soluble porphyrin molecule, the free base meso-tetrakis(1- methylpyridinium-4-yl)porphyrin chloride, is employed as a novel cathode interlayer in bulk heterojunction organic photovoltaics. It is demonstrated that the self-organization of this porphyrin compound into aggregates in which molecules adopt a face-to-face orientation parallel to the organic semiconducting substrate induces a large local interfacial electric field that results in a significant enhancement of exciton dissociation. Consequently, enhanced photocurrent and open circuit voltage were obtained resulting in overall device efficiency improvement in organic photovoltaics based on bulk heterojunction mixtures of different polymeric donors and fullerene acceptors, regardless of the specific combination of donor-acceptor employed. To highlight the impact of molecular orientation a second porphyrin compound, the Zn-metallated meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride, was also studied and it was found that it forms aggregates with an edge-to-edge molecular configuration inducing a smaller increase in the device performance.</p