@misc{DasZiaMortanetal., author = {Das, Chittaranjan and Zia, Waqas and Mortan, Claudiu and Hussain, Navid and Saliba, Michael and Flege, Jan Ingo and Kot, Małgorzata}, title = {Top-Down Approach to Study Chemical and Electronic Properties of Perovskite Solar Cells: Sputtered Depth Profiling Versus Tapered Cross-Sectional Photoelectron Spectroscopies}, series = {Solar RRL}, volume = {5}, journal = {Solar RRL}, number = {10}, issn = {2367-198X}, doi = {10.1002/solr.202100298}, abstract = {A study of the chemical and electronic properties of various layers across perovskite solar cell (PSC) stacks is challenging. Depth-profiling photoemission spectroscopy can be used to study the surface, interface, and bulk properties of different layers in PSCs, which influence the overall performance of these devices. Herein, sputter depth profiling (SDP) and tapered cross-sectional (TCS) photoelectron spectroscopies (PESs) are used to study highly efficient mixed halide PSCs. It is found that the most used SDP-PES technique degrades the organic and deforms the inorganic materials during sputtering of the PSCs while the TCS-PES method is less destructive and can determine the chemical and electronic properties of all layers precisely. The SDP-PES dissociates the chemical bonding in the spiro-MeOTAD and perovskite layer and reduces the TiO2, which causes the chemical analysis to be unreliable. The TCS-PES revealed a band bending only at the spiro-MeOTAD/perovskite interface of about 0.7 eV. Both the TCS and SDP-PES show that the perovskite layer is inhomogeneous and has a higher amount of bromine at the perovskite/TiO2 interface.}, language = {en} } @misc{DasKediaZuoetal., author = {Das, Chittaranjan and Kedia, Mayank and Zuo, Weiwei and Mortan, Claudiu and Kot, Małgorzata and Flege, Jan Ingo and Saliba, Michael}, title = {Band Bending at Hole Transporting Layer-Perovskite Interfaces in n-i-p and in p-i-n Architecture}, series = {Solar RRL}, volume = {6}, journal = {Solar RRL}, number = {9}, issn = {2367-198X}, doi = {10.1002/solr.202200348}, abstract = {Interfaces between hybrid perovskite absorber and its adjacent charge-transporting layers are of high importance for solar cells performance. Understanding their chemical and electronic properties is a key step in designing efficient and stable perovskite solar cells. In this work, the tapered cross-section photoemission spectroscopy (TCS-PES) method is used to study the methylammonium lead iodide (CH3NH3PbI3) (MAPI)-based solar cells in two configurations, that is, in an inverted p-i-n and in a classical n-i-p architecture. It is revealed in the results that the MAPI film deposited once on the n-type TiO2 and once on the p-type NiOx substrates is neither an intrinsic semiconductor nor adapts to the dopant nature of the substrate underneath, but it is heavily n-type doped on both substrates. In addition to that, the TCS-PES results identify that the band bending between the MAPI film and the hole transporting layer (HTL) layer depends on the perovskite solar cells architecture. In particular, a band bending on the HTL side in the n-i-p and at the MAPI in the p-i-n architecture is found. The flat band of NiOx at the NiOx/MAPI interface can be explained by the Fermi level pinning of the NiOx at the interface.}, language = {en} } @misc{KotDasKegelmannetal., author = {Kot, Małgorzata and Das, Chittaranjan and Kegelmann, Lukas and K{\"o}bler, Hans and Vorokhta, Mykhailo and Escudero, Carlos and Albrecht, Steve and Abate, Antonio and Flege, Jan Ingo}, title = {Application of atomic layer deposition and x-ray photoelectron spectroscopy in perovskite solar cells}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {In this work we have utilized near-ambient pressure and ultra-high vacuum X-ray photoelectron spectroscopy as well as atomic layer deposition to investigate perovskite solar cells (PSCs). We have demonstrated that ultrathin room temperature atomic layer-deposited aluminium oxide on the perovskite surface very effectively suppresses iodine migration[1] and improves the long term stability and efficiency of PSCs [2,3]. Furthermore, exposure to light proves more detrimental to the perovskite film than exposure to water vapor.[2] Absorbed photons create Frenkel defects in the perovskite crystal and their number strongly depends on the used illumination. The higher the photon flux, the higher the concentration of Frenkel defects, and thus the stronger the degradation of power conversion efficiency and the stronger the hysteresis in the J-V characteristics. [1] C. Das, M. Kot et al., Cell Reports Physical Science 2020, 1, 100112. [2] M. Kot et al., ChemSusChem 2020, 13, 5722. [3] M. Kot et al., ChemSusChem 2018, 11, 3640.}, language = {en} } @misc{ZiaMalekshahiByranvandRudolphetal., author = {Zia, Waqas and Malekshahi Byranvand, Mahdi and Rudolph, Toby and Rai, Monika and Kot, Małgorzata and Das, Chittaranjan and Kedia, Mayank and Zohdi, Mohammadreza and Zuo, Weiwei and Yeddu, Vishal and Saidaminov, Makhsud I. and Flege, Jan Ingo and Kirchartz, Thomas and Saliba, Michael}, title = {MAPbCl3 Light Absorber for Highest Voltage Perovskite Solar Cells}, series = {ACS Energy Letters}, volume = {9}, journal = {ACS Energy Letters}, issn = {2380-8195}, doi = {10.1021/acsenergylett.3c02777}, pages = {1017 -- 1024}, abstract = {Perovskite solar cells (PSCs) excel in achieving high open-circuit voltages (VOC) for narrow bandgaps (∼1.6 eV) but face challenges with wide-bandgap perovskites, like methylammonium lead trichloride (MAPbCl3) with a 3.03 eV bandgap. These materials are transparent in visible absorbing ultraviolet (UV) light. However, achieving uniform film crystallization remains a hurdle. Here, we enhance MAPbCl3 crystallization by manipulating annealing atmospheres (nitrogen, air, and MACl vapor). Excess MACl vapor improves surface coverage, which is crucial for film stability. We demonstrate that the microstructure of the perovskite film, including surface morphology, grain boundaries, and interfaces, can affect the photovoltaic properties. The subsequently obtained VOC of 1.78 V is the highest recorded for single-junction PSCs to the best of our knowledge. Surprisingly, the conventional hole-transport layer spiro-OMeTAD, optimized for narrow bandgaps, sustains such high voltages. Photoluminescence measurements reveal a trap-assisted recombination peak at 1.65 eV, indicating deep traps as significant to voltage loss in MAPbCl3.}, language = {en} } @misc{KodalleMalekshahiByranvandGoudreauetal., author = {Kodalle, Tim and Malekshahi Byranvand, Mahdi and Goudreau, Meredith and Das, Chittaranjan and Roy, Rajarshi and Kot, Małgorzata and Briesenick, Simon and Zohdi, Mohammadreza and Rai, Monika and Tamura, Nobumichi and Flege, Jan Ingo and Hempel, Wolfram and Sutter-Fella, Carolin M. and Saliba, Michael}, title = {An integrated deposition and passivation strategy for controlled crystallization of 2D/3D Halide Perovskite films}, series = {Advanced Materials}, volume = {36}, journal = {Advanced Materials}, number = {24}, publisher = {Wiley}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.202309154}, pages = {12}, abstract = {This work introduces a simplified deposition procedure for multidimensional (2D/3D) perovskite thin films, integrating a phenethylammonium chloride (PEACl)-treatment into the antisolvent step when forming the 3D perovskite. This simultaneous deposition and passivation strategy reduces the number of synthesis steps while simultaneously stabilizing the halide perovskite film and improving the photovoltaic performance of resulting solar cell devices to 20.8\%. Using a combination of multimodal in situ and additional ex situ characterizations, it is demonstrated that the introduction of PEACl during the perovskite film formation slows down the crystal growth process, which leads to a larger average grain size and narrower grain size distribution, thus reducing carrier recombination at grain boundaries and improving the device's performance and stability. The data suggests that during annealing of the wet film, the PEACl diffuses to the surface of the film, forming hydrophobic (quasi-)2D structures that protect the bulk of the perovskite film from humidity-induced degradation.}, language = {en} } @misc{KotDasAlonsoetal., author = {Kot, Małgorzata and Das, Chittaranjan and Alonso, Clara Patricia Aranda and Prochowicz, Daniel}, title = {Perovskites: from materials science to devices}, series = {Journal of Materials Chemistry C}, volume = {12}, journal = {Journal of Materials Chemistry C}, number = {28}, publisher = {Royal Society of Chemistry (RSC)}, address = {Cambridge}, issn = {2050-7526}, doi = {10.1039/d4tc90109f}, pages = {10244 -- 10245}, abstract = {An introduction to the Journal of Materials Chemistry C themed collection on perovskite materials.}, language = {en} } @misc{ZuoMalekshahiByranvandKodalleetal., author = {Zuo, Weiwei and Malekshahi Byranvand, Mahdi and Kodalle, Tim and Zohdi, Mohammadreza and Lim, Jaekeun and Carlsen, Brian and Friedlmeier, Theresa Magorian and Kot, Małgorzata and Das, Chittaranjan and Flege, Jan Ingo and Zong, Wansheng and Abate, Antonio and Sutter-Fella, Carolin M. and Li, Meng and Saliba, Michael}, title = {Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization}, series = {Advanced Materials}, volume = {35}, journal = {Advanced Materials}, number = {39}, issn = {0935-9648}, doi = {10.1002/adma.202302889}, abstract = {The most efficient and stable perovskite solar cells (PSCs) are made from a complex mixture of precursors. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g., by vacuum, an airstream, or a so-called antisolvent. Unfortunately, most oversaturation triggers do not expel the lingering (and highly coordinating) dimethyl sulfoxide (DMSO), which is used as a precursor solvent, from the thin films; this detrimentally affects long-term stability. In this work, (the green) dimethyl sulfide (DMS) is introduced as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, MAPbI3 PSCs are processed, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6\% efficiency, among the highest reported efficiencies for this system. To confirm the universality of the strategy, DMS is tested for FAPbI3 as another composition, which shows higher efficiency of 23.5\% compared to 20.9\% for a device fabricated with chlorobenzene. This work provides a universal strategy to control perovskite crystallization using coordination chemistry, heralding the revival of perovskite compositions with pure DMSO.}, language = {en} } @misc{KediaRaiPhirkeetal., author = {Kedia, Mayank and Rai, Monika and Phirke, Himanshu and Aranda, Clara A. and Das, Chittaranjan and Chirvony, Vladimir and Boehringer, Stephan and Kot, Małgorzata and Malekshahi Byranvand, Mahdi and Flege, Jan Ingo and Redinger, Alex and Saliba, Michael}, title = {Light Makes Right: Laser Polishing for Surface Modification of Perovskite Solar Cells}, series = {ACS Energy Letters}, volume = {8}, journal = {ACS Energy Letters}, issn = {2380-8195}, doi = {10.1021/acsenergylett.3c00469}, pages = {2603 -- 2610}, abstract = {Interface engineering is a common strategy for passivating surface defects to attain open circuit voltages (Voc) in perovskite solar cells (PSCs). In this work, we introduce the concept of polishing a perovskite thin-film surface using a nanosecond (ns) pulsed ultraviolet laser to reduce surface defects, such as dangling bonds, undesirable phases, and suboptimal stoichiometry. A careful control of laser energy and scanning speed improves the photophysical properties of the surface without compromising the thickness. Using laser polishing, a Voc of 1.21 V is achieved for planar PSCs with a triple cation composition, showing an improved perovskite/hole transport interface by mitigating surface recombination losses. We measure an efficiency boost from 18.0\% to 19.3\% with improved stability of up to 1000 h. The results open the door to a new class of surface modification using lasers for interface passivation in well-controllable, automated, scalable, and solvent-free surface treatments.}, language = {en} } @misc{DasRoyKediaetal., author = {Das, Chittaranjan and Roy, Rajarshi and Kedia, Mayank and Kot, Małgorzata and Zuo, Weiwei and F{\´e}lix, Roberto and Sobol, Tomasz and Flege, Jan Ingo and Saliba, Michael}, title = {Unraveling the Role of Perovskite in Buried Interface Passivation}, series = {ACS Applied Materials \& Interfaces}, volume = {15}, journal = {ACS Applied Materials \& Interfaces}, number = {48}, issn = {1944-8244}, doi = {10.1021/acsami.3c13085}, pages = {56500 -- 56510}, abstract = {Interfaces in perovskite solar cells play a crucial role in their overall performance, and therefore, detailed fundamental studies are needed for a better understanding. In the case of the classical n-i-p architecture, TiO2 is one of the most used electron-selective layers and can induce chemical reactions that influence the performance of the overall device stack. The interfacial properties at the TiO2/perovskite interface are often neglected, owing to the difficulty in accessing this interface. Here, we use X-rays of variable energies to study the interface of (compact and mesoporous) TiO2/perovskite in such a n-i-p architecture. The X-ray photoelectron spectroscopy and X-ray absorption spectroscopy methods show that the defect states present in the TiO2 layer are passivated by a chemical interaction of the perovskite precursor solution during the formation of the perovskite layer and form an organic layer at the interface. Such passivation of intrinsic defects in TiO2 removes charge recombination centers and shifts the bands upward. Therefore, interface defect passivation by oxidation of Ti3+ states, the organic cation layer, and an upward band bending at the TiO2/perovskite interface explain the origin of an improved electron extraction and hole-blocking nature of TiO2 in the n-i-p perovskite solar cells.}, language = {en} } @misc{KediaDasKotetal., author = {Kedia, Mayank and Das, Chittaranjan and Kot, Malgorzata and Yalcinkaya, Yenal and Zuo, Weiwei and Tabah Tanko, Kenedy and Matvija, Peter and Ezquer, Mikel and Cornago, I{\~n}aki and Hempel, Wolfram and Kauffmann, Florian and Plate, Paul and Lira-Cantu, Monica and Weber, Stefan A.L. and Saliba, Michael}, title = {Mitigating the amorphization of perovskite layers by using atomic layer deposition of alumina}, series = {Energy \& environmental science}, volume = {18}, journal = {Energy \& environmental science}, number = {11}, publisher = {Royal Society of Chemistry (RSC)}, address = {London}, issn = {1754-5692}, doi = {10.1039/D4EE05703A}, pages = {5250 -- 5263}, abstract = {Atomic layer deposition of aluminum oxide (ALD-Al2O3) layers has recently been studied for stabilizing perovskite solar cells (PSCs) against environmental stressors, such as humidity and oxygen. In addition, the ALD-Al2O3 layer acts as a protective barrier, mitigating pernicious halide ion migration from the perovskite towards the hole transport interface. However, its effectiveness in preventing the infiltration of ions and additives from the hole-transport layer into perovskites remains insufficiently understood. Herein, we demonstrate the deposition of a compact ultrathin (∼0.75 nm) ALD-Al2O3 layer that conformally coats the morphology of a triple-cation perovskite layer. This promotes an effective contact of the hole transporter layer on top of the perovskite, thereby improving the charge carrier collection between these two layers. Upon systematically investigating the layer-by-layer structure of the PSC, we discovered that ALD-Al2O3 also acts as a diffusion barrier for the degraded species from the adjacent transport layer into the perovskite. In addition to these protective considerations, ALD-Al2O3 impedes the transition of crystalline perovskites to an undesired amorphous phase. Consequently, the dual functionality (i.e., enhanced contact and diffusion barrier) of the ALD-Al2O3 protection enhanced the device performance from 19.1\% to 20.5\%, while retaining 98\% of its initial performance compared to <10\% for pristine devices after 1500 h of outdoor testing under ambient conditions. Finally, this study deepens our understanding of the mechanism of ALD-Al2O3 as a two-way diffusion barrier, highlighting the multifaceted role of buffer layers in interfacial engineering for the long-term stability of PSCs.}, language = {en} }