Schmidt-Mende, Lukas
0000-0001-6867-443X Berufsbeschreibung
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Organic binary charge-transfer compounds of 2,2′ : 6′,2′′ : 6′′,6-trioxotriphenylamine and a pyrene-annulated azaacene as donors
Three binary charge-transfer (CT) compounds resulting from the donor 2,2′ : 6′,2′′ : 6′′,6-trioxotriphenylamine (TOTA) and the acceptors F4TCNQ and F4BQ and of a pyrene-annulated azaacene (PAA) with the acceptor F4TCNQ are reported. The identity of these CT compounds are confirmed by single-crystal X-ray diffraction as well as by IR, UV-vis-NIR and EPR spectroscopy. X-ray diffraction analysis reveals a 1 : 1 stoichiometry for TOTA·F4TCNQ, a 2 : 1 donor : acceptor ratio in (TOTA)2·F4BQ, and a rare 4 : 1 stoichiometry in (PAA)4·F4TCNQ, respectively. Metrical parameters of the donor (D) and acceptor (A) constituents as well as IR spectra indicate full CT in TOTA·F4TCNQ, partial CT in (TOTA)2·F4BQ and only a very modest one in (PAA)4·F4TCNQ. Intricate packing motifs are present in the crystal lattice with encaged, π-stacked (F4TCNQ-)2 dimers in TOTA·F4TCNQ or mixed D/A stacks in the other two compounds. Their solid-state UV-vis-NIR spectra feature CT transitions. The CT compounds with F4TCNQ are electrical insulators, while (TOTA)2·F4BQ is weakly conducting.
Ethylenediamine Vapors‐Assisted Surface Passivation of Perovskite Films for Efficient Inverted Solar Cells
Defects present at the surface or within the bulk of halide perovskites act as a barrier to charge transfer/transport, induce nonradiative recombination thereby limit open-circuit voltage (VOC), and accelerate degradation in the perovskite solar cells (PSCs). Passivation of these defects at surfaces, interfaces, and grain boundaries to suppress the charge recombination is therefore imperative to improving photovoltaic performance in the PSCs. Herein, a facile posttreatment of perovskite surface by ethylenediamine (EDA) via mixed solvent vapor annealing method is reported. The results show that only a trace amount of EDA causes significant suppression of nonradiative recombination leading to over 100 mV increased VOC and ≈22% improvement in power conversion efficiency (PCE) of the inverted PSCs. The key reasons for this improvement are an upward shift in the Fermi energy level, reduced lattice strain and Urbach energy, and reduction in nonradiative recombination upon EDA passivation. These lead to a PCE exceeding 20% up from 16% for a nonpassivated film. The unencapsulated EDA-modified PSCs also demonstrate an improved shelf-life and retain 87% of the initial PCE after 850 h.
Controlled Crystallinity of TiO2 Layers Grown by Atmospheric Pressure Spatial Atomic Layer Deposition and their Impact on Perovskite Solar Cell Efficiency
Atmospheric Pressure Spatial Atomic Layer Deposition (AP-SALD) is an upcoming deposition technique suitable for a variety of materials and combines the benefits of a regular atomic layer deposition with a significantly increased deposition rate at ambient conditions. In this work, amorphous and anatase TiO2 layers are fabricated by AP-SALD via systematic variation of process conditions such as temperature, reactant (H2O and O3), and posttreatment. The formed layers are characterized for their structural and optoelectronic properties and utilized as a hole-blocking layer in hybrid perovskite solar cells. It is found that TiO2 layers fabricated at elevated deposition temperatures possess strong anatase character but expose an unfavorable interface to the perovskite layer, promoting recombination and lowering the shunt resistance and open circuit voltage of the solar cells. Therefore, the interface is essential for efficient charge extraction, which can be significantly improved by controlling the process parameters.
Electron-Rich Diruthenium Complexes with π-Extended Alkenyl Ligands and Their F4TCNQ Charge-Transfer Salts
The synthesis of dinuclear ruthenium alkenyl complexes with {Ru(CO)(Pi Pr3 )2 (L)} entities (L=Cl- in complexes Ru2 -3 and Ru2 -7; L=acetylacetonate (acac- ) in complexes Ru2 -4 and Ru2 -8) and with π-conjugated 2,7-divinylphenanthrenediyl (Ru2 -3, Ru2 -4) or 5,8-divinylquinoxalinediyl (Ru2 -7, Ru2 -8) as bridging ligands are reported. The bridging ligands are laterally π-extended by anellating a pyrene (Ru2 -7, Ru2 -8) or a 6,7-benzoquinoxaline (Ru2 -3, Ru2 -4) π-perimeter. This was done with the hope that the open π-faces of the electron-rich complexes will foster association with planar electron acceptors via π-stacking. The dinuclear complexes were subjected to cyclic and square-wave voltammetry and were characterized in all accessible redox states by IR, UV/Vis/NIR and, where applicable, by EPR spectroscopy. These studies signified the one-electron oxidized forms of divinylphenylene-bridged complexes Ru2 -7, Ru2 -8 as intrinsically delocalized mixed-valent species, and those of complexes Ru2 -3 and Ru2 -4 with the longer divinylphenanthrenediyl linker as partially localized on the IR, yet delocalized on the EPR timescale. The more electron-rich acac- congeners formed non-conductive 1 : 1 charge-transfer (CT) salts on treatment with the F4 TCNQ electron acceptor. All spectroscopic techniques confirmed the presence of pairs of complex radical cations and F4 TCNQ.- radical anions in these CT salts, but produced no firm evidence for the relevance of π-stacking to their formation and properties.
Solvent-Assisted Crystallization of an α-Fe2O3 Electron Transport Layer for Efficient and Stable Perovskite Solar Cells Featuring Negligible Hysteresis
Inorganic–organic metal halide perovskite solar cells (PSCs) show power conversion efficiency values approaching those of state-of-the-art silicon solar cells. In a quest to find suitable charge transport materials in PSCs, hematite (α-Fe2O3) has emerged as a potential electron transport layer (ETL) in n–i–p planar PSCs due to its low cost, UV light stability, and nontoxicity. Yet, the performance of α-Fe2O3-based PSCs is far lower than that of state-of-the-art PSCs owing to the poor quality of the α-Fe2O3 ETL. In this work, solvent-assisted crystallization of α-Fe2O3 ETLs was carried out to examine the impact of solvents on the optoelectronic properties of α-Fe2O3 thin films. Among the various solvents used in this study (deionized water, ethanol, iso-propanol, and iso-butanol), optimized ethanol-based α-Fe2O3 ETLs lead to champion device performance with a power conversion efficiency of 13% with a reduced hysteresis index of 0.04 in an n–i–p-configured PSC. The PSC also exhibited superior long-term inert and ambient stabilities compared to a reference device made using a SnO2 ETL. Through a series of experiments spanning structural, morphological, and optoelectronic properties of the various α-Fe2O3 thin films and their devices, we provide insights into the reasons for the improved photovoltaic performance. It is noted that the formation of a pinhole-free compact morphology of ETLs facilitates crack-free surface coverage of the perovskite film atop an α-Fe2O3 ETL, reduces interfacial recombination, and enhances charge transfer efficiency. This work opens up the route toward novel ETLs for the development of efficient and photo-stable PSCs.
Uncovering solvent-engineering mechanisms in Y6:PM6 solar cells
Additives, like 1-chloronaphtalene (CN), are commonly used in Y6:PM6 solar cells as they lead to an increased power conversion efficiency. In this work, we investigate the influence of CN during spin coating of Y6:PM6 dissolved in chloroform via an in situ transmission setup. We show that, in the presence of CN, the film formation of Y6:PM6 can be divided into two parts: one related to the evaporation of chloroform and one related to the evaporation of CN. This is mostly related to Y6 being dissolved in CN. We find that even for low CN concentration, the film formation is not completed for several minutes after the spin coating process. Furthermore, the removal of CN is needed to achieve a smooth film surface. We demonstrate that this fast removal can be achieved by spin coating the electron transport layer PDINN from methanol. The methanol is acting as an anti-solvent for the CN, leading to its removal from the film. Using this approach, solar cells fabricated with a high CN concentration of 5% feature a comparable performance to ones with more common concentrations between 0.5% and 1%.
Molecular design for all-in-one self-assembled donor–acceptor organic solar cells
The stability of organic solar cells still remains one of the main challenges to make this technology suitable for large scale mass production. The stability of the morphology is one main degradation channel in currently used bulk heterojunction systems. We introduce three different all-in-one donor–acceptor amphiphilic triads and perform molecular dynamics simulations in order investigate the stacking of the donor and acceptor sub-molecules after performing a simulated annealing step. We show that the molecular volume of each sub-molecule of the triad plays an important role for the stability of the π -stacking within the bilayer sheet. Further, we found that TIPS-pentacene and TIPS-tetraazapentacene sub-molecules serving as donor and acceptor, respectively, keep their crystalline nature in the bilayer sheet. Thus, by such a system, charge carrier mobilities in the range of 1 cm 2 /Vs should be possible, which is three orders of magnitude higher compared to measured mobilities in existing highly efficient organic solar cells. Therefore, by this approach not only the stability can be increased, but also the fill factor and therefore the power conversion efficiency can be improved.
A Triethyleneglycol C60 Mono-adduct Derivative for Efficient Electron Transport in Inverted Perovskite Solar Cells
Inverted perovskite solar cells (PSCs) have attracted increasing attention in recent years owing to their low-temperature fabrication proces s. However, they suffer from a limited number of electron transport materials available with [6,6]-phenyl C61 butyric acid methyl ester (PCBM) to be the most widely studied based on its appropriate energy levels and high electron mobility. The low relative permittivity and aggregation tendency upon illumination of PCBM, however, compromises the solar cell efficiency whereas its modest hydrophobicity negatively impacts on the device stability. Alternative electron transport materials with desired properties and appropriate degree of hydrophobicity are thus desirable for further developments in inverted PSCs. Herein, we synthesize a triethyleneglycol C60 mono-adduct derivative (termed as EPF03) and test it as a novel electron transport material to replace PCBM in inverted PSCs based on a quadruple cation (RbCsMAFA) perovskite. We also compare this derivative with two novel fullerenes decorated with two (EPF01) or one dodecyl (EPF02) long side chains. The latter two fail to perform efficiently in inverted PSCs whereas the former enabled a power conversion efficiency of 18.43%, which represents a 9% improvement compared to the reference device using PCBM (17.21%). The enhanced performance mainly stems from improved electron extraction and reduced recombination enabled by the insertion of the large relative permittivity amongst other properties of EPF03. Furthermore, our results indicate that triethylene glycol side chains can also passivate perovskite trap states, suppress ion migration and enhance photostability and long-term stability of EPF03 based perovskite solar cells.
Chemical Strain Engineering of MAPbI3 Perovskite Films
This study introduces a new chemical method for controlling the strain in methylammonium lead iodide (MAPbI3) perovskite crystals by varying the ratio of Pb(Ac)2 and PbCl2 in the precursor solution. To observe the effect on crystal strain, a combination of piezoresponse force microscopy (PFM) and X-ray diffraction (XRD) is used. The PFM images show an increase in the average size of ferroelastic twin domains upon increasing the PbCl2 content, indicating an increase in crystal strain. The XRD spectra support this observation with strong crystal twinning features that appear in the spectra. This behavior is caused by a strain gradient during the crystallization due to different evaporation rates of methylammonium acetate and methylammonium chloride as revealed by time-of-flight secondary ion mass spectroscopy and grazing incidince X-ray diffraction measurements. Additional time-resolved photoluminescence shows an increased carrier lifetime in the MAPbI3 films prepared with higher PbCl2 content, suggesting a decreased trap density in films with larger twin domain structures. The results demonstrate the potential of chemical strain engineering as a simple method for controlling strain-related effects in lead halide perovskites.
Tuning the Electronic Properties of Mesocrystals
Colloidal crystals are arguably one of the most promising candidates when it comes to the fabrication of nanostructured metamaterials. Especially mesocrystals show exciting new properties that emerge from their inherent directional oriented assembly. With this work, the electrical conductivity of well-defined micrometer-sized platinum nanocube-based mesocrystals is demonstrated and tuned through the variation of different capping agents. Herein, a method is presented to reproducibly quantify the intrinsic resistance of individual mesocrystals through electrical nanoprobing and focused ion beam deposition contacting. A thermally activated tunneling mechanism is identified as the main effect for electron propagation. In addition, the mesocrystals are altered through organically linking and mineral bridging the individual nanoparticles. This results in an increase in mesocrystal rigidity and, more importantly, conductivity by seven orders of magnitude while retaining shape, structure, and composition. In addition, these observations are transferred onto multicomponent superstructures in the form of binary mesocrystals. There, it is demonstrated that the electrical properties could be tuned through the ratio of nanoparticles incorporated into a mesocrystalline host system while simultaneously maintaining potential catalytic or superparamagnetic features of the guest particles.