Organic binary charge-transfer compounds of 2,2′ : 6′,2′′ : 6′′,6-trioxotriphenylamine and a pyrene-annulated azaacene as donors
2023-01-30, Das, Rajorshi, Linseis, Michael, Schupp, Stefan, Gogesch, Franciska S., Schmidt-Mende, Lukas, Winter, Rainer F.
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.
Uncovering solvent-engineering mechanisms in Y6:PM6 solar cells
2023, Raab, Timo, Seewald, Tobias, Kraner, Stefan, Schmidt-Mende, Lukas
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%.
Solvent-Assisted Crystallization of an α-Fe2O3 Electron Transport Layer for Efficient and Stable Perovskite Solar Cells Featuring Negligible Hysteresis
2023, Qureshi, Akbar Ali, Javed, Sofia, Akram, Muhammad Aftab, Schmidt-Mende, Lukas, Fakharuddin, Azhar
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.
Chemical Strain Engineering of MAPbI3 Perovskite Films
2022-10, Yalcinkaya, Yenal, Hermes, Ilka M., Seewald, Tobias, Amann‐Winkel, Katrin, Veith, Lothar, Schmidt-Mende, Lukas, Weber, Stefan A. L.
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.
A Triethyleneglycol C60 Mono-adduct Derivative for Efficient Electron Transport in Inverted Perovskite Solar Cells
2023, Fakharuddin, Azhar, Armadorou, Konstantina‐Kalliopi, Zorba, Leandros P., Tountas, Marinos, Seewald, Tobias, Schütz, Emilia R., Schmidt-Mende, Lukas, Vougioukalakis, Georgios C., Nazeeruddin, Mohammad Khaja, Vasilopoulou, Maria
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.
Low-temperature processed natural hematite as an electron extraction layer for efficient and stable perovskite solar cells
2023, Qureshi, Akbar Ali, Javed, Sofia, Fakharuddin, Azhar, Akram, Muhammad Aftab, Schmidt-Mende, Lukas
The mixed halide perovskite solar cells (PSC) have manifested as a contender to market-dominating silicon counterparts owing to their low-temperature solution processing and high efficiency. In PSCs, the electron extraction layer (EEL) plays a vital role as it controls charge transport/extraction from the perovskite absorber layer to the EEL and also determines interfacial recombination and charge accumulation at the EEL/perovskite interface. In this work, high-purity natural hematite (α-Fe2O3) is reported for the first time as the EEL in triple-cation perovskite (CsFAMA) solar cells. To show the cost-effectiveness of this novel EEL, the entire device fabrication process was carried out at a temperature below 150 °C. The optimal α-Fe2O3 EEL shows a mobility value of 9.5 × 10−4 cm−2 V−1 s−1 and trap densities of around 2.40 × 1016 cm−3; the latter is close to state-of-the-art SnO2 EEL (1.26 × 1016 cm−3). The PSCs employing optimal EEL concentration of 10 mg/mL demonstrated a power conversion efficiency (PCE) of 13.3 %, fill factor of 68 %, and VOC of 1.03 V. X-ray diffraction studies show a high crystallinity of natural hematite whereas the photoluminescence studies show a fast carrier extraction from the perovskite to the EEL. The natural α-Fe2O3-based PSCs exhibited superior shelf-life stability of over 30 days due to less charge recombination and smoother CsFAMA thin film deposited over α-Fe2O3 EEL. The low-temperature processed natural α-Fe2O3 EEL can therefore be a promising EEL material for low-cost efficient PSCs.
Augmenting stability and performance in perovskite solar cells : A critical review on perovskite-polymer synergy
2023, Ganesh, Gayathry, Yasin, Amina, Misnon, Izan Izwan, Fakharuddin, Azhar, Schmidt-Mende, Lukas, Ab Rahim, Mohd Hasbi, Thomas, Sabu, Jose, Rajan
Perovskite solar cells (PSCs) are intensively studied over the past decade to enhance the renewable contribution to the total energy mix; however, their market potential is hampered mostly by their poor operational stability. Polymers as encapsulants, UV-filters, charge transport layers, and interfacial layers are shown to be a potential remedy not only to improve stability but also to positively contribute to other figures of merits of solar cells. Highly efficient PSCs (>15 %) with prolonged operational stability (>3000 h) in various device architectures including fibres, yarns, and woven and knitted cloths are reported using perovskite embedded polymers. This article critically and comprehensively reviews the synergistic interactions between various polymers and the organic–inorganic lead halide perovskite material to establish a structure–property correlation and to examine the viability of the PSCs technology for practical deployment. Mechanistic details of polymers in the photoactive, charge transport and interfacial layers on the morphology, optical and photovoltaic properties, and stability are analysed and discussed. Particularly on stability, the role of polymers on defect tolerance, phase and structure evolution, and external stimuli (heat, moisture, light, electric field, and oxygen) are elaborated. The dielectric properties of polymers enable them to be superior encapsulants over their corresponding monomers or other organic molecules. Based on these broad considerations, adopting the polymeric approach is shown to be a more efficient and greener leap towards the sustainable commercialization of perovskites.
Ethylenediamine Vapors‐Assisted Surface Passivation of Perovskite Films for Efficient Inverted Solar Cells
2023, Haider, Muhammad Irfan, Hu, Hao, Seewald, Tobias, Ahmed, Safeer, Sultan, Muhammad, Schmidt-Mende, Lukas, Fakharuddin, Azhar
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.
Charge transfer in copper oxide thin films deposited at different electrodeposition potential
2023, Ali, Nazakat, Hussain, Sajad, Waqas, Muhammad, Faheem, M., Ahmad, Naveed, Ali, Adnan, Ali, Muhammad Yasir, Mahmood, Khalid, Schmidt-Mende, Lukas
The deposition potential affects the structural, morphological, optical, and electrochemical impedance spectroscopy properties of cuprous oxide (Cu2O) thin films formed on copper (Cu) substrates adopting a three-electrode electrochemical deposition procedure. XRD data revealed that the deposited films have a cubic structure established with desired (111) growth orientation. Scanning electron microscopy (SEM) images reveal that Cu2O film has very well three-sided pyramid-shaped grains which are equally spread over the surface of the Cu substrates and change substantially when the plating potential is changed. The photo-current density of prepared Cu2O thin films was increased from −1.41 × 10−4 to −3.01 × 10−4 A/cm2 with increasing the deposition potential of −0.3 to −0.6 V, respectively. Further, Cu2O thin films obtained at −0.6 V have the minimum charge transfer resistance (Rct) than Cu2O thin films synthesized at −0.3 to −0.5 V, suggesting that Cu2O thin films produced at −0.6 V have the highest electron transfer efficiency.
Hybrid supercapacitors, formation, and new advances with different electrochemical electrodes based on layered double hydroxides (LDHs), metal–organic framework (MOF) materials, smart supercapacitors
2023, Thirumurugan, Arun, Dhanabalan, Shanmuga Sundar, Shanavas, Shajahan, Udayabhaskar, R., Morel, Mauricio J., Dineshbabu, N., Ravichandran, K., Schmidt-Mende, Lukas, Ramadoss, Ananthakumar
Hybrid supercapacitors (HSCs) are made by the combination of electric double-layer capacitor (EDLC) materials, various types of pseudocapacitive, and battery-type materials. The progress made on the improvement of energy density without sacrificing the power density attracted the researchers to move toward HSC. The specific capacitance of the HSC showed a superior value than the EDLC or pseudocapacitance-based supercapacitors. Numerous advancements have been made on the HSCs with the development in preparation of electrode materials, electrolyte, formation of component, device structure, and the new mechanisms for the improvement of electrochemical characteristics. This chapter specifically emphasis the new development made on the HSCs based on the layered double hydroxides, metal–organic frameworks (MOFs), MOF-derived materials and their composites. The specific characteristics requirement of the electrode material, electrolyte, the substrate in support of electrode materials, and the progress made on them for smart supercapacitors are discussed.