@inproceedings{ChoudhuryTallaridaDasetal., author = {Choudhury, Sakeb Hasan and Tallarida, Massimo and Das, Chittaranjan and Schmeißer, Dieter}, title = {Atomic layer deposition of Ga2O3 using Tri-methyl-Gallium and H2O}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, abstract = {Considering numerous applications such as transparent conducting oxides, gas sensors, photovoltaic applications, deep UV photo detectors, field effect transistors and spintronics gallium oxide (Ga2O3) has earned quite a lot of focus recently. Various techniques have already been demonstrated to produce Ga2O3 naming evaporation, sputtering, pulsed laser deposition, chemical vapor deposition and atomic layer deposition (ALD). Among them, ALD gives the possibility of controlling the thickness at the atomic level, good step coverage and delivers dense and homogeneous films. In this contribution, we report on the growth of ALD Ga2O3 using trimethylgallium (TMG) and H2O as metal and oxygen precursors, respectively. We deposited thin Ga2O3 films on Si, TiO2, Al2O3 and RuO2 over a temperature range of 150-300°C and characterized them by X-ray photo emission spectroscopy and atomic force microscopy. From this study, we are able to discuss the influence of the temperature on the growth dynamics of Ga2O3 and its chemical composition.}, language = {en} } @inproceedings{DasTallaridaSkorupskaetal., author = {Das, Chittaranjan and Tallarida, Massimo and Skorupska, Katarzyna and Lewerenz, Hans-Joachim and Schmeißer, Dieter}, title = {An efficient Si photo cathode for a wide range of electrolyte pH values}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, abstract = {Hydrogen fuel cells, being environmental friendly to produce energy, are a technology of future. One of the efficient ways to produce hydrogen is solar driven photocatalysis using semiconducting materials as photo electrodes. The choice of electrodes is a crucial factor and is done on the basis of photo corrosion stability, light absorption efficiency, and photocarrier lifetime. P-type Si can be used as photo cathode to produce H2 by direct photocatalysis. Si cathodes can be used in acidic electrolytes to have efficient photo catalytic activity but they are unstable in alkaline electrolytes. Therefore, to use both Si electrodes in the same electrolyte, their chemical stability should be extended over a wide range of pH. To this purpose we modified the surface of a p-type Si photocathode with very thin films of TiO2 grown by atomic layer deposition (ALD). We found that the modified Si cathode shows an increased photoresponse and a lower onset potential with respect to the pristine surface and an increased stability at various pH values.}, language = {en} } @misc{SowinskaDasWojciechowskietal., author = {Sowinska, Małgorzata and Das, Chittaranjan and Wojciechowski, Konrad and Rouissi, Zied and Snaith, Henry J. and Schmeißer, Dieter}, title = {Atomic layer deposition of Al2O3 on CH3NH3PbI3 for enhancement of perovskite solar cells stability}, series = {Synchrotron Radiation in Natural Science : Bulletin of the Polish Synchrotron Radiation Society}, volume = {15}, journal = {Synchrotron Radiation in Natural Science : Bulletin of the Polish Synchrotron Radiation Society}, number = {1-2}, issn = {1644-7190}, pages = {S. 33}, language = {en} } @inproceedings{DasTallaridaSchmeisser, author = {Das, Chittaranjan and Tallarida, Massimo and Schmeißer, Dieter}, title = {TiO2 laminated Silicon microstructures based stable photocathode for water splitting}, series = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, booktitle = {Verhandlungen der Deutschen Physikalischen Gesellschaft}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, pages = {S. 213}, abstract = {The photoelectrochemical (PEC) water splitting is one of the most efficient ways to obtain hydrogen from water using solar power which can be used as carbon free fuel. The PEC device can bedesigned using semiconducting material that will convert solar radiation to H2. Silicon can be one of the best choices for PEC due to its success in solar cells technology. There are certain issues with Si such as stability in electrochemical medium [1] and higher surface reflectance (25\%) which limits the Si as an ideal candidate for PEC technique [2]. In the present work we addressed these issues by surface structuring and laminating the surface with metal oxide. The microstructuring of Si was done by electrochemical method. The Si microstructure photocathode was stabilized by thin layer of ALD grown TiO2 film. The microstructuring and lamination of Si photocathode by ALD layer of TiO2 decreased the reflectance ofthe surface and shift the onset potential towards anodic direction by 350 mV with a prolonged stability over 60 hours[3]. [1] C. Levy-Clement, J. Electrochem. Soc 1991, 12, 69 [2] J. Oh, et al. Energy Environ. Sci., 2011, 4, 1690 [3] C. Das, et al. Nanoscale 2015,7, 7726}, language = {en} } @misc{GhoshBiswasSenetal., author = {Ghosh, Sujoy Kumar and Biswas, Anirban and Sen, Shrabanee and Das, Chittaranjan and Henkel, Karsten and Schmeißer, Dieter and Mandal, Dipankar}, title = {Yb3+ Assisted Self-Polarized PVDF Based Ferroelectretic Nanogenerator: A Facile Strategy of Highly Efficient Mechanical Energy Harvester Fabrication}, series = {Nano Energy}, volume = {2016}, journal = {Nano Energy}, number = {30}, issn = {2211-2855}, doi = {10.1016/j.nanoen.2016.10.042}, pages = {621 -- 629}, abstract = {Ytterbium (Yb3+) assisted porous poly(vinylidene fluoride) (PVDF) composite film comprising flexible ferroelectretic nanogenerator (FTNG) is highlighted where traditional poling treatment is completely avoided. The piezoelectric output of FTNG is realized by the co-operative activity of self-polarized -CH2/-CF2 dipoles with porous electret-like structure in the composite film. Owing to extraordinary ferroelectric and dielectric properties, FTNG is acting as a highly efficient mechanical energy harvester. It is capable to capture several forms of abundant mechanical energy arising from humanfinger movements, machine vibrations and sound waves. As a proof of concept, under compressive deformation, FTNG is enable to instantly powers up several consumer electronics and thus provides a promising strategy for achieving self-powered electronic devices.}, language = {en} } @misc{KotDasWangetal., author = {Kot, Małgorzata and Das, Chittaranjan and Wang, Zhiping and Henkel, Karsten and Rouissi, Zied and Wojciechowski, Konrad and Snaith, Henry J. and Schmeißer, Dieter}, title = {Room-Temperature Atomic Layer Deposition of Al₂O₃: Impact on Efficiency, Stability and Surface Properties in Perovskite Solar Cells}, series = {ChemSusChem}, volume = {9}, journal = {ChemSusChem}, number = {24}, issn = {1864-5631}, doi = {10.1002/cssc.201601186}, pages = {3401 -- 3406}, abstract = {In this work, solar cells with a freshly made CH₃NH₃PbI₃ perovskite film showed a power conversion efficiency (PCE) of 15.4 \% whereas the one with 50 days aged perovskite film only 6.1 \%. However, when the aged perovskite was covered with a layer of Al₂O₃ deposited by atomic layer deposition (ALD) at room temperature (RT), the PCE value was clearly enhanced. X-ray photoelectron spectroscopy study showed that the ALD precursors are chemically active only at the perovskite surface and passivate it. Moreover, the RT-ALD-Al2O3-covered perovskite films showed enhanced ambient air stability.}, language = {en} } @misc{HenkelDasKotetal., author = {Henkel, Karsten and Das, Chittaranjan and Kot, Małgorzata and Schmeißer, Dieter and Naumann, Franziska and K{\"a}rkk{\"a}nen, Irina and Gargouri, Hassan}, title = {In-gap states in titanium dioxide and oxynitride atomic layer deposited films}, series = {Journal of Vacuum Science and Technology: A}, volume = {35}, journal = {Journal of Vacuum Science and Technology: A}, number = {1}, issn = {0734-2101}, doi = {10.1116/1.4972247}, pages = {01B135-1 -- 01B135-8}, abstract = {Valence band (VB) spectra of titanium dioxide (TiO2) and oxynitride (TiOxNy) films prepared by different atomic layer deposition (ALD) processes are compared and related to electrical characterization [current-voltage (JV) and capacitance-voltage (CV)] results. By increasing the nitrogen amount in the TiO2 film, band-gap narrowing is observed. The band-gap decrease is related to the contribution of the nitrogen density of states, which induces defects within the band-gap and thus reduces its optical band-gap. In-gap states are found in the VB spectra at 1 eV below the Fermi energy in all investigated ALD samples, i.e., in TiO2 as well as in TiOxNy films. An exponential correlation between leakage current density and in-gap state intensity is derived by the combination of JV measurements and VB spectra, whereas the in-gap states seem to have no influence on hysteresis and fixed oxide charges found in the CV data. It is argued that the in-gap states in TiO2 and TiOxNy have an excitonic or polaronic origin. Both, band-gap narrowing and in-gap state intensity can be tuned by the ALD process selection and the variation of its parameters.}, language = {en} } @misc{MenezesIndraDasetal., author = {Menezes, Prashanth W. and Indra, Arindam and Das, Chittaranjan and Walter, Carsten and G{\"o}bel, Caren and Gutkin, Vitaly and Schmeißer, Dieter and Driess, Matthias}, title = {Uncovering the Nature of Active Species of Nickel Phosphide Catalysts in High-Performance Electrochemical Overall Water Splitting}, series = {ACS Catalysis}, volume = {7}, journal = {ACS Catalysis}, number = {1}, issn = {2155-5435}, doi = {10.1021/acscatal.6b02666}, pages = {103 -- 109}, abstract = {A systematic structural elucidation of the near-surface active species of the two remarkably active nickel phosphides Ni12P5 and Ni2P on the basis of extensive analytical, microscopic, and spectroscopic investigations is reported. The latter can serve as complementary efficient electrocatalysts in the hydrogen (HER) versus oxygen evolution reaction (OER) in alkaline media. In the OER Ni12P5 shows enhanced performance over Ni2P due to the higher concentration of nickel in this phase, which enables the formation of an amorphous NiOOH/Ni(OH)2 shell on a modified multiphase with a disordered phosphide/phosphite core. The situation is completely reversed in the HER, where Ni2P displayed a significant improvement in electrocatalytic activity over Ni12P5 owing to a larger concentration of phosphide/phosphate species in the shell. Moreover, the efficiently combined use of the two nickel phosphide phases deposited on nickel foam in overall electrocatalytic water splitting is demonstrated by a strikingly low cell voltage and high stability with pronounced current density, and these catalysts could be an apt choice for applications in commercial alkaline water electrolysis.}, language = {en} } @misc{IndraMenezesDasetal., author = {Indra, Arindam and Menezes, Prashanth W. and Das, Chittaranjan and G{\"o}bel, Caren and Tallarida, Massimo and Schmeißer, Dieter and Driess, Matthias}, title = {A facile corrosion approach to the synthesis of highly active CoOxwater oxidation catalysts}, series = {Journal of Materials Chemistry A}, journal = {Journal of Materials Chemistry A}, number = {5}, issn = {2050-7488}, doi = {10.1039/c6ta10650a}, pages = {5171 -- 5177}, abstract = {Ultra-small rock salt cobalt monoxide (CoO) nanoparticles were synthesized and subjected to partial oxidation ('corrosion') with ceric ammonium nitrate (CAN) to form mixed-valence CoOx(1 < x< 2) water oxidation catalysts. Spectroscopic, microscopic and analytical methods evidenced a structural reformation of cubic CoO to active CoOx with a spinel structure. The superior water oxidation activity of CoOx has been established in electrochemical water oxidation under alkaline conditions. Electrochemical water oxidation with CoOx was recorded at a considerably low overpotential of merely 325 mV at a current density of 10 mA cm-2 in comparison to 370 mV for CoO. Transformation of both octahedral CoII and CoIII sites into amorphous Co(OH)2-CoOOH is the key to high electrochemical activity while the presence of a higher amount of octahedral CoIII sites in CoOx is imperative for an efficient oxygen evolution process.}, language = {en} } @misc{DasKotRouissietal., author = {Das, Chittaranjan and Kot, Małgorzata and Rouissi, Zied and Kędzierski, Kamil and Henkel, Karsten and Schmeißer, Dieter}, title = {Selective Deposition of an ultrathin Pt Layer on a Au-Nanoisland-Modified Si Photocathode for Hydrogen Generation}, series = {ACS Omega}, volume = {2}, journal = {ACS Omega}, number = {4}, issn = {2470-1343}, doi = {10.1021/acsomega.6b00374}, pages = {1360 -- 1366}, abstract = {Platinum, being the most efficient and stable catalyst, is used in photoelectrochemical (PEC) devices. However, a minimal amount of Pt with maximum catalytic activity is required to be used to minimize the cost of production. In this work, we use an environmentally friendly, ost-effective, and less Pt-consuming method to prepare PEC devices for the hydrogen evolution reaction (HER). The Pt monolayer catalyst is selectively deposited on a Au-nanoisland-supported boron-doped p-type Si (100) photocathode. The PEC device based on the Si photocathode with an ultralow loading of the Pt catalyst exhibits a comparable performance for the HER to that of devices with a thick Pt layer. In addition, we demonstrate that by using a thin TiO2 layer deposited by atomic layer deposition photo-oxidation of the Si photocathode can be blocked resulting in a stable PEC performance.}, language = {en} } @misc{KotHenkelDasetal., author = {Kot, Małgorzata and Henkel, Karsten and Das, Chittaranjan and Brizzi, Simone and K{\"a}rkk{\"a}nen, Irina and Schneidewind, Jessica and Naumann, Franziska and Gargouri, Hassan and Schmeißer, Dieter}, title = {Analysis of titanium species in titanium oxynitride films prepared by plasma enhanced atomic layer deposition}, series = {Surface and Coatings Technology}, volume = {324}, journal = {Surface and Coatings Technology}, issn = {0257-8972}, doi = {10.1016/j.surfcoat.2016.11.094}, pages = {586 -- 593}, abstract = {A comparative study of thin titanium oxynitride (TiOxNy) films prepared by plasma enhanced atomic layer deposition using tetrakis(dimethylamino)titanium (TDMAT) and N2 plasma as well as titanium(IV)isopropoxide and NH3 plasma is reported. The comparison is based on the combination of Ti2p core level and valence band spectroscopy and current-voltage measurements. The TDMAT/N2 process delivers generally higher fractions of TiN and TiON within the Ti2p spectra of the films and stronger photoemissions within the bandgap as resolved in detail by high energy resolution synchrotron-based spectroscopy. In particular, it is shown that higher TiN contributions and in-gap emission intensities correlate strongly with increased leakage currents within the films and might be modified by the process parameters and precursor selection.}, language = {en} } @misc{IndraMenezesDasetal., author = {Indra, Arindam and Menezes, Prashanth W. and Das, Chittaranjan and Schmeißer, Dieter and Driess, Matthias}, title = {Alkaline electrochemical water oxidation with multi-shelled cobalt manganese oxide hollow spheres}, series = {Chemical Communications}, volume = {53}, journal = {Chemical Communications}, number = {62}, issn = {1359-7345}, doi = {10.1039/C7CC03566G}, pages = {8641 -- 8644}, abstract = {Multi-shelled hollow spheres of cobalt manganese oxides (CMOs) deposited on Ni foam exhibited superior alkaline electrochemical water oxidation activity and surpassed those of bulk CMO and commercial noble metal-based catalysts. A higher amount of cobalt in the spinel structure resulted in the transformation of the tetragonal to the cubic phase with a decrease in the overpotential of oxygen evolution.}, language = {en} } @misc{CibrevTallaridaDasetal., author = {Cibrev, Dejan and Tallarida, Massimo and Das, Chittaranjan and Lana-Villarreal, Teresa and Schmeißer, Dieter and Gómez, Roberto}, title = {New insights into water photooxidation on reductively pretreated hematite photoanodes}, series = {Physical Chemistry Chemical Physics}, volume = {19}, journal = {Physical Chemistry Chemical Physics}, number = {32}, issn = {1463-9076}, doi = {10.1039/C7CP03958A}, pages = {21807 -- 21817}, abstract = {It has been recently demonstrated that the photoactivity toward oxygen evolution of a number of n-type metal oxides can be substantially improved by a reductive electrochemical pretreatment. Such an enhancement has been primarily linked to the formation of low valent metal species that increase electrode conductivity. In this work, we report new insights into the electrochemical doping using highly ordered (110)-oriented hematite nanorods directly grown on FTO. The reductive pretreatment consists in applying negative potentials for a controlled period of time. Such a pretreatment was optimized in both potentiostatic and potentiodynamic regimes. We show that the optimized pretreatment enhances electrode conductivity due to an increase in charge carrier density. However, it additionally triggers changes in the morphologic, catalytic and electronic properties that facilitate the separation and collection of the photogenerated charge carriers causing an up to 8-fold enhancement in the photocurrent for water oxidation. The reductive pretreatment can be considered as a highly controllable electrochemical n-type doping with the amount of generated Fe2+/polaron species and the change in film morphology as the main factors determining the final efficiency for water photooxidation of the resulting electrodes.}, language = {en} } @misc{KotDasHenkeletal., author = {Kot, Małgorzata and Das, Chittaranjan and Henkel, Karsten and Wojciechowski, Konrad and Snaith, Henry J. and Schmeißer, Dieter}, title = {Room temperature atomic layer deposited Al₂O₃ on CH₃NH₃PbI₃ characterized by synchrotron-based X-ray photoelectron spectroscopy}, series = {Nuclear Instruments and Methods in Physics Research B}, volume = {411}, journal = {Nuclear Instruments and Methods in Physics Research B}, issn = {0168-583X}, doi = {10.1016/j.nimb.2017.01.082}, pages = {49 -- 52}, abstract = {An ultrathin Al₂O₃ film deposited on methylammonium lead triiodide (CH₃NH₃PbI₃) perovskite has the capability to suppress the carrier recombination process and improve the perovskite solar cells efficiency and stability. However, annealing at temperatures higher than 85°C degrades the CH₃NH₃PbI₃ perovskite film. The X-ray photoelectron spectroscopy study performed in this work indicates that it is possible to grow Al₂O₃ by atomic layer deposition on the perovskite at room temperature, however, besides pure Al₂O₃ some OH groups are found and the creation of lead and iodine oxides at the Al₂O₃/CH₃NH₃PbI₃ interface takes place.}, language = {en} } @incollection{SchmeisserKotCorreaetal., author = {Schmeißer, Dieter and Kot, Małgorzata and Corr{\^e}a, Silma Alberton and Das, Chittaranjan and Henkel, Karsten}, title = {Interface Potentials, Intrinsic Defects, and Passivation Mechanisms in Al₂O₃, HfO₂, and TiO₂ Ultrathin Films}, series = {Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry, vol. 3.1}, booktitle = {Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry, vol. 3.1}, editor = {Wandelt, Klaus}, publisher = {Elsevier}, address = {Oxford}, isbn = {978-0-12-809739-7}, doi = {10.1016/B978-0-12-409547-2.14119-8}, pages = {162 -- 171}, abstract = {We study the electronic structure of ultrathin Al₂O₃, HfO₂, and TiO₂ ALD films by resonant photoelectron spectroscopy. We identify intrinsic defects which are responsible for the active sites in interface reactions, for the incorporation of intrinsic charges, and for the formation of local dipole momenta. All of these features determine the surface potentials and the reactivity of the surface of the atomic layer deposition coated systems. We give examples of charges and dipoles in Al₂O₃, on a study of the surface potentials in HfO₂, and relate the intrinsic defects in TiO₂ to their electrochemical relevance.}, language = {en} } @misc{KotKegelmannDasetal., author = {Kot, Małgorzata and Kegelmann, Lukas and Das, Chittaranjan and Kus, Peter and Tsud, Nataliya and Matol{\´i}nov{\´a}, Iva and Albrecht, Steve and Matolin, Vladimir and Schmeißer, Dieter}, title = {Room temperature atomic layer deposited Al₂O₃ improves perovskite solar cells efficiency over time}, series = {ChemSusChem}, volume = {11}, journal = {ChemSusChem}, number = {20}, issn = {1864-5631}, doi = {10.1002/cssc.201801434}, pages = {3640 -- 3648}, abstract = {Electrical characterisation of perovskite solar cells consisting of room-temperature atomic-layer-deposited aluminium oxide (RT-ALD-Al₂O₃) film on top of a methyl ammonium lead triiodide (CH₃NH₃PbI₃) absorber showed excellent stability of the power conversion efficiency (PCE) over along time. Under the same environmental conditions (for 355 d), the average PCE of solar cells without the ALD layer decreased from 13.6 to 9.6 \%, whereas that of solar cells containing 9 ALD cycles of depositing RT-ALD-Al₂O₃on top of CH₃NH₃PbI₃ increased from 9.4 to 10.8 \%. Spectromicroscopic investigations of the ALD/perovskite interface revealed that the maximum PCE with the ALD layer is obtained when the so-called perovskite cleaning process induced by ALD precursors is complete. The PCE enhancement over time is probably related to a self-healing process induced by the RT-ALD-Al₂O₃ film. This work may provide a new direction for further improving the long-term stability and performance of perovskite solar cells.}, language = {en} } @misc{KotDasBaranetal., author = {Kot, Małgorzata and Das, Chittaranjan and Baran, Derya and Saliba, Michael}, title = {Themed issue on electronic properties and characterisation of perovskites}, series = {Journal of Materials Chemistry C}, volume = {7}, journal = {Journal of Materials Chemistry C}, issn = {2050-7526}, doi = {10.1039/c9tc90085c}, pages = {5224 -- 5225}, language = {en} } @misc{DasKotHellmannetal., author = {Das, Chittaranjan and Kot, Małgorzata and Hellmann, Tim and Wittich, Carolin and Mankel, Eric and Zimmermann, Iwan and Schmeißer, Dieter and Nazeeruddin, Mohammad Khaja and Jaegermann, Wolfram}, title = {Atomic Layer-Deposited Aluminum Oxide Hinders Iodide Migration and Stabilizes Perovskite Solar Cells}, series = {Cell Reports Physical Science}, volume = {1}, journal = {Cell Reports Physical Science}, number = {7}, issn = {2666-3864}, doi = {10.1016/j.xcrp.2020.100112}, pages = {18}, abstract = {Iodide migration causes degradation of the perovskite solar cells. Here,we observe the direct migration of iodide into the hole-transport layer in a device. We demonstrate that ultrathin room temperature atomic layer-deposited Al2O3 on the perovskite surface very effectively hinders the migration. The perovskite-Al2O3 interface enables charge transfer across the Al2O3 layer in the solar cells, without causing any drastic changes in the properties of the perovskite absorber. Furthermore, it helps to preserve the initial properties of the perovskite film during exposure to light and air under real operating conditions, and thus, improves the stability of the solar cells. The ultrathin Al2O3 layer deposited at room temperature significantly increases the lifetime of the perovskite solar cells, and we hope this may be a step toward the mass production of stable devices.}, language = {en} } @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} }