Inexpensive Hole‐Transporting Materials Derived from Tröger's Base Afford Efficient and Stable Perovskite Solar Cells

The synthesis of three enamine hole‐transporting materials (HTMs) based on Tröger's base scaffold are reported. These compounds are obtained in a three‐step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time‐consuming purification steps. The best performing material, HTM3, demonstrated 18.62 % PCE in PSCs, rivaling spiro‐OMeTAD in efficiency, and showing markedly superior long‐term stability in non‐encapsulated devices. In dopant‐free PSCs, HTM3 outperformed spiro‐OMeTAD by a factror of 1.6. The high glass‐transition temperature (T_g=176 °C) of HTM3 also suggests promising perspectives in device applications.     

Synthesis, characterization, and DFT/TD-DFT calculations of highly phosphorescent blue light-emitting anionic iridium complexes

Highly phosphorescent blue-light-emitting anionic iridium complexes (C4H9)4N[Ir(2-phenylpyridine)2(CN)2] (1), (C4H9)4N[Ir(2-phenyl-4-dimethylaminopyridine)2(CN)2] (2), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-pyridine)2(CN)2] (3), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (4), and (C4H9)4N[Ir(2-(3,5-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (5) were synthesized and characterized using NMR, UV-vis absorption, and emission spectroscopy and electrochemical methods. In these complexes color and quantum yield tuning aspects are demonstrated by modulating the ligands with substituting donor and acceptor groups on both the pyridine and phenyl moieties of 2-phenylpyridine. Complexes 1-5 display intense photoluminescence maxima in the blue region of the visible spectrum and exhibit very high phosphorescence quantum yields, in the range of 50-80%, with excited-state lifetimes of 1-4 micros in acetonitrile solution at 298 K. DFT and time dependent-DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems.     

Novel oxygen sensitive complexes for optical oxygen sensing

Novel optical sensing films for oxygen based on highly luminescent iridium (III) and ruthenium (II) complexes have been developed. These demonstrate excellent long-term photostability (several months) when incorporated into polystyrene membranes. The influence of different plasticizers on the specific luminescence quantum yield, the Stern-Volmer constant, the reversibility and the response time were evaluated. Additionally the sensing films can be sterilized by chemical cleaning and gamma-ray irradiation.     

Structure–Function Relationships in Unsymmetrical Zinc Phthalocyanines for Dye‐Sensitized Solar Cells

Let it shine! The impact of the anchoring group on photovoltaic performance by a series of phthalocyanine sensitisers (see figure) has been demonstrated.

     

Alkyl chain barriers for kinetic optimization in dye-sensitized solar cells

The optimization of interfacial charge transfer is crucial to the design of dye-sensitized solar cells. In this paper we address the dynamics of the charge separation and recombination in liquid-electrolyte and solid-state cells employing a series of amphiphilic ruthenium dyes with varying hydrocarbon chain lengths, acting as an insulating barrier for electron-hole recombination. Dynamics of electron injection, monitored by time-resolved emission spectroscopy, and of charge recombination and regeneration, monitored by transient optical absorption spectroscopy, are correlated with device performance. We find that increasing dye alkyl chain length results in slower charge recombination dynamics to both the dye cation and the redox electrolyte or solid-state hole conductor (spiro-OMeTAD). These slower recombination dynamics are however paralleled by reduced rates for both electron injection into the TiO2 electrode and dye regeneration by the I-/I3- redox couple or spiro-OMeTAD. Kinetic competition between electron recombination with dye cations and dye ground state regeneration by the iodide electrolyte is found to be a key factor for liquid electrolyte cells, with optimum device performance being obtained when the dye regeneration is just fast enough to compete with electron-hole recombination. These results are discussed in terms of the minimization of kinetic redundancy in solid-state and liquid-electrolyte dye-sensitized photovoltaic devices.     

Stable single-layer light-emitting electrochemical cell using 4,7-diphenyl-1,10-phenanthroline-bis(2-phenylpyridine)iridium(III) hexafluorophosphate

A significant improvement in the stability of a light emitting electrochemical cell was achieved by utilizing a novel iridium(III) complex: 4,7-diphenyl-1,10-phenanthroline-bis(2-phenylpyridine)iridium(III) hexafluorophosphate. The enhanced device stability is correlated by means of DFT studies to be related to a more efficient shielding of the reactive LUMO of the complex.