Engineering of the interface between perovskite absorber thin films and charge transport layers has fueled the development of perovskite solar cells (PSCs) over the past decade. For p‐i‐n PSCs, the development and adoption of hole transport layers utilizing self‐assembled monolayers (SAM‐HTLs) based on carbazole functional groups with phosphonic acid anchoring groups has enabled almost lossless contacts, minimizing interfacial recombination to advance power conversion efficiency in single‐junction and tandem solar cells. However, so far these materials have been deposited exclusively via solution‐based methods. Here, for the first time, vacuum‐based evaporation of the most common carbazole‐based SAM‐HTLs (2PACz, MeO‐2PACz, and Me‐4PACz) is reported. X‐ray photoelectron spectroscopy and infrared spectroscopy demonstrate no observable chemical differences in the evaporated SAMs compared to solution‐processed counterparts. Consequently, the near lossless interfacial properties are either preserved or even slightly improved as demonstrated via photoluminescence measurements and an enhancement in open‐circuit voltage. Strikingly, applying evaporated SAM‐HTLs to complete PSCs demonstrates comparable performance to their solution‐processed counterparts. Furthermore, vacuum deposition is found to improve perovskite wetting and fabrication yield on previously non‐ideal materials (namely Me‐4PACz) and to display conformal and high‐quality coating of micrometer‐sized textured surfaces, improving the versatility of these materials without sacrificing their beneficial properties.

We demonstrate a simple and effective way to enhance the performance of perovskite light-emitting diodes (PeLEDs) by utilizing an alkali halide doped PEDOT:PSS as the hole transport layer (HTL). The...

Electrical doping is an important tool in the design of organic devices to modify charge carrier concentration in and Fermi level position of organic layers. The undesired diffusion of dopant molecules within common transport materials adversely affects both lifetime and device performance. To overcome this drawback, we developed a strategy to achieve immobilization of dopants through their covalent attachment to the semiconductor host molecules. Derivatization of the commonly employed n-type dopant 2-(2-methoxyphenyl)-1,3-dimethyl-2,3-dihydro-1H-benzoimidazole (o-MeO-DMBI) with a phenylazide enables the resulting o-AzBnO-DMBI to photochemically generate a reactive nitrene, which subsequently binds covalently to the host material, 6,6-phenyl-C 61 -butyric acid methyl ester (PCBM). Both the activation and addition reactions are monitored by mass spectrometry as well as optical and photoelectron spectroscopy. A suppression of desorption and a decrease in volatility of the DMBI derivative in ultrahigh vacuum were observed after activation of a bilayer structure of PCBM and o-AzBnO-DMBI. Electrical measurements demonstrate that the immobilized o-AzBnO-DMBI can (i) dope the PCBM at conductivities comparable to values reported for o-MeO-DMBI in the literature and (ii) yield improved electrical stability measured in a lateral two terminal device geometry. Our immobilization strategy is not limited to the specific system presented herein but should also be applicable to other organic semiconductor−dopant combinations.

The synthesis of unsubstituted, structurally perfect poly(para-phenylene) (PPP) has remained elusive for many decades. By modifying our previously reported precursor route towards PPP, we were able to simplify and optimize the precursor polymer synthesis and yields, the thermal conversion process to PPP, and the resulting material properties. We describe the synthesis of unprecedented anti-dialkoxycyclohexadienylenes, polymerized via Suzuki coupling to yield linear PPP precursor polymers. Changing the geometry and overall shape of the precursor viz upon going from syn-to anti-configuration of the monomer has two important consequences: (i) formation of the precursor polymer becomes more selective since cyclization of the monomer is no longer possible and (ii) the precursor polymer adopts a "stretched" geometry and becomes more similar to the rigid-rod of PPP, impacting the aromatization process and material properties. Films of the precursor polymers are thermally aromatized via dealkoxylation to yield structurally perfect and highly ordered, insoluble PPP. Long-range ordering within the thin films, not observed for its syn-analog, is induced as evidenced by atomic force microscopy, X-ray scattering, and IR and UV−vis/photoluminescence spectroscopy. The aromatization temperature, now feasible for fabrication of plastic devices, is significantly lowered from previously reported 300 °C to below 250 °C. The kinetics of the aromatization process were monitored via time-dependent IR measurements at different annealing temperatures, showing much faster quantitative aromatization for thin layers.