@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{CuypersFleischmannDorpetal., author = {Cuypers, Daniel and Fleischmann, Claudia and Dorp, Dennis H. von and Brizzi, Simone and Tallarida, Massimo and M{\"u}ller, Matthias and H{\"o}nicke, Philipp and Billen, Arne and Chintala, Ravi and Conard, Thierry and Schmeißer, Dieter and Vandervorst, Wilfried and Elshocht, Sven van and Armini, Silvia and De Gendt, Stefan and Adelmann, Christoph}, title = {Sacrificial Self-Assembled Monolayers for the Passivation of GaAs(100) Surfaces and Interfaces}, series = {Chemistry of Materials}, volume = {28}, journal = {Chemistry of Materials}, number = {16}, issn = {0897-4756}, doi = {10.1021/acs.chemmater.6b01732}, pages = {5689 -- 5701}, abstract = {The use of sacrificial self-assembled monolayers (SAMs) to prepare clean n-type GaAs (100) surfaces without band bending in vacuo is demonstrated. GaAs surface passivation using octadecanethiol SAMs after HCl cleaning is shown to lead to an enhancement of the room-temperature photoluminescence intensity. Synchrotron-radiation photoelectron spectroscopy (SRPES) finds that the interfacial oxide between GaAs and the SAM remains below the detection limit. Evidence for both Ga-S and As-S bonds at the GaAs-thiolate interface is found. The limited thermal stability of the SAM allows the desorption of the alkyl chains by in situ thermal annealing at temperatures above 180 °C, leaving S bonded to Ga behind. The resulting surface contains only a very small amount of O (0.05 ML coverage) and C (about 3\% of the SAM remaining) and shows no band bending with the surface Fermi level close to the conduction band. Atomic layer deposition of Al₂O₃ on this surface occurs via the formation of Al-S bonds without introducing any additional band bending. This indicates that the surface preparation of n-type GaAs (100) using sacrificial octadecanethiol SAMs followed by in situ thermal removal provides a route toward GaAs/oxide interfaces without interfacial oxides and without band bending.}, 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{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} } @incollection{HenkelKotRichteretal., author = {Henkel, Karsten and Kot, Małgorzata and Richter, Matthias and Tallarida, Massimo and Schmeißer, Dieter}, title = {An (In Situ)² Approach: ALD and resPES Applied to 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/B978-0-12-409547-2.13852-1}, pages = {18 -- 26}, abstract = {Oxide surface coatings are of importance in tailoring interface properties with respect to surface passivation, adjustment of surface potentials, or providing active centers for surface reactions. In this contribution, we report about surface coatings prepared by the atomic layer deposition (ALD) method. ALD is known for its conformal growth of ultrathin, dense films which exhibit a low concentration of pinholes.}, language = {en} } @misc{DorpNynsCuypersetal., author = {Dorp, Dennis H. von and Nyns, Laura and Cuypers, Daniel and Ivanov, Tsvetan and Brizzi, Simone and Tallarida, Massimo and Fleischmann, Claudia and H{\"o}nicke, Philipp and M{\"u}ller, Matthias and Richard, Olivier and Schmeißer, Dieter and De Gendt, Stefan and Lin, Dennis H. C. and Adelmann, Christoph}, title = {Amorphous Gadolinium Aluminate as a Dielectric and Sulfur for Indium Phosphide Passivation}, series = {ACS Applied Electronic Materials}, volume = {1}, journal = {ACS Applied Electronic Materials}, number = {11}, issn = {2637-6113}, doi = {10.1021/acsaelm.9b00388}, pages = {2190 -- 2201}, abstract = {The passivation of n-type InP (100) using sulfur in combination with a gadolinium aluminate (GAO) dielectric layer has been studied. Photoluminescence, minority-carrier lifetime, and capacitance-voltage measurements indicate that a (NH4)2S vapor passivation step prior to atomic layer deposition of the oxide effectively lowers the interface state density. Surface and interface chemistry were studied by synchrotron radiation photoemission spectroscopy (SRPES). The effect of ex situ surface passivation after native oxide removal in HCl solution was examined. It was observed that surface reoxidation occurred during (NH4)2S vapor exposure, leading to the formation of Inx(HPO4)y. S was present on the surface as a sulfide in both surface and subsurface sites. After atomic layer deposition of GAO, sulfates were detected in addition to Inx(HPO4)y, which was confirmed by near-edge X-ray absorptionfine structure analysis. The S in the stack was quantified using reference-free grazing incidence X-rayfluorescence analysis. X-ray absorption spectroscopy showed that Gd was oxidized and present in the 3+ oxidation state, most likely as a phosphate close to the InP interface and possibly mixed with sulfates. Energy-dependent SRPES measurements of Al 2p and Gd 4d core levels, complemented by transmission electron microscopy, further suggest that the dielectric layer was segregated. Valence band measurements confirm the effective passivation of InP, indicating unpinning of the surface Fermi level.}, language = {en} } @misc{KotKegelmannKoebleretal., author = {Kot, Małgorzata and Kegelmann, Lukas and K{\"o}bler, Hans and Vorokhta, Mykhailo and Escudero, Carlos and K{\´u}š, Peter and Šm{\´i}d, Břetislav and Tallarida, Massimo and Albrecht, Steve and Abate, Antonio and Matol{\´i}nov{\´a}, Iva and Schmeißer, Dieter and Flege, Jan Ingo}, title = {In situ Near-Ambient Pressure X-ray Photoelectron Spectroscopy Reveals the Influence of Photon Flux and Water on the Stability of Halide Perovskite}, series = {ChemSusChem}, volume = {13}, journal = {ChemSusChem}, number = {21}, issn = {1864-5631}, doi = {10.1002/cssc.202001527}, pages = {5722 -- 5730}, abstract = {For several years, scientists have been trying to understand the mechanisms that reduce the long-term stability of perovskite solar cells. In this work, we examined the effect of water and photon flux on the stability of CH3NH3PbI3 perovskite films and solar cells using in situ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), field emission scanning electron microscopy (FESEM), and current density-voltage (J-V) characterization. The used amount of water vapor (up to 1 mbar) had a negligible impact on the perovskite film. The higher the photon flux, the more prominent were the changes in the NAP-XPS and FESEM data; also, a faster decline in power conversion efficiency (PCE) and a more substantial hysteresis in the J-V characteristics were observed. Based on our results, it can be concluded that the PCE decrease originates from the creation of Frenkel pair defects in the perovskite film under illumination. The stronger the illumination, the higher the number of Frenkel defects, leading to a faster PCE decline and more substantial hysteresis in the J-V sweeps.}, language = {en} }