Authors: Giovanni Barcaro , Luca Sementa, Susanna Monti , Vincenzo Carravetta, Peter Broqvist, Jolla Kullgren, and Kersti Hermansson
The widespread use of ceria-based materials and the need to design suitable strategies to prepare eco-friendly CeO2 supports for effective catalytic screening induced us to extend our computational multiscale protocol to the modeling of the hybrid organic/oxide interface between prototypical fluorinated linear alkane chains (polyethylene-like oligomers) and low-index ceria surfaces. The combination of quantum chemistry calculations and classical reactive molecular dynamics simulations provides a comprehensive picture of the interface and discloses, at the atomic level, the main causes of typical adsorption modes. The data show that at room temperature a moderate percentage of fluorine atoms (around 25%) can enhance the interaction of the organic chains by anchoring strongly pivotal fluorines to the channels of the underneath ceria (100) surface, whereas an excessive content can remarkably reduce this interaction because of the repulsion between fluorine and the negatively charged oxygen of the surface.
J. Phys. Chem. C, Volume 41, 2018, Page 23405
Authors: Vanessa Quaranta, Matti Hellström, Jörg Behler, Jolla Kullgren, Pavlin D. Mitev, and Kersti Hermansson
Unraveling the atomistic details of solid/liquid interfaces, e.g., by means of vibrational spectroscopy, is of vital importance in numerous applications, from electrochemistry to heterogeneous catalysis. Water-oxide interfaces represent a formidable challenge because a large variety of molecular and dissociated water species are present at the surface. Here, we present a comprehensive theoretical analysis of the anharmonic OH stretching vibrations at the water/ZnO(10-10) interface as a prototypical case. Molecular dynamics simulations employing a reactive high-dimensional neural network potential based on density functional theory calculations have been used to sample the interfacial structures. In the second step, one-dimensional potential energy curves have been generated for a large number of configurations to solve the nuclear Schrödinger equation. We find that (i) the ZnO surface gives rise to OH frequency shifts up to a distance of about 4 Å from the surface; (ii) the spectrum contains a number of overlapping signals arising from different chemical species, with the frequencies decreasing in the order ν(adsorbed hydroxide) > ν(non-adsorbed water) > ν(surface hydroxide) > ν(adsorbed water); (iii) stretching frequencies are strongly influenced by the hydrogen bond pattern of these interfacial species. Finally, we have been able to identify substantial correlations between the stretching frequencies and hydrogen bond lengths for all species.
The Journal of Chemical Physics, 148, 241720 (2018);
Authors: Getachew G. Kebede , Pavlin D. Mitev, Peter Broqvist, Jolla Kullgren , and Kersti Hermansson
This paper concerns thin water films and their hydrogen-bond patterns on ionic surfaces. As far as we are aware, this is the first time H-bond correlations for surface water and hydroxide species are presented in the literature while hydrogen-bond relations in the solid state have been scrutinized for at least five decades. Our data set, which was derived using density functional theory, consists of 116 unique surface OH groups–intact water molecules as well as hydroxides–on MgO(001), CaO(001) and NaCl(001), covering the whole range from strong to weak to no H-bonds. The intact surface water molecules are found to always be redshifted with respect to the gas-phase water OH vibrational frequency, whereas the surface hydroxide groups are either redshifted (OsH) or blueshifted (OHf) compared to the gas-phase OH– frequency. The surface H-bond relations are compared with the traditional relations for bulk crystals. We find that the “ν(OH) vs R(H···O)” correlation curve for surface water does not coincide with the solid state curve: it is redshifted by about 200 cm–1 or more. The intact water molecules and hydroxide groups on the ionic surfaces essentially follow the same H-bond correlation curve.
J. Phys. Chem. C, 2018, 122 (9), pp 4849–4858
Authors: M.Pazoki, M. J. Wolf, T. Edvinsson and J.Kullgren
Ion migration has recently been suggested to play critical roles in the operation of lead halide perovskite solar cells. However, so far there has been no systematic investigation of how the monovalent cation affects the vacancy formation, ion migration and the associated hysteresis effect. Here, we present density functional theory calculations on all possible ion migration barriers in the perovskite materials with different cations i.e. CH3NH3PbI3, CH(NH2)2PbI3 and CsPbI3 in the tetragonal phase and investigate vacancy monovalent-cation interactions within the framework of the possible ion migrations. The most relevant ion movement (iodide) is investigated in greater detail and corresponding local structural changes, the relationships with the local ionic dielectric response, Stark effect and current-voltage hysteresis are discussed. We observe a correlation between the energy barrier for iodine migration and the magnitude of the dipole of the monovalent cation. From the data, we suggest a vacancy-dipole interaction mechanism by which the larger dipole of the monovalent cation can respond to and screen the local electric fields more effectively. The stronger response of the high dipolar monovalent cation to the vacancy electrostatic potential in turn leads to a lower local structural changes within the neighbouring octahedra. The presented data reveal a detailed picture of the ion movement, vacancy dipole interactions and the consequent local structural changes, which contain fundamental information about the photo-physics, and dielectric response of the material.
Nano Energy, 38, 2017, pp. 537-543
Authors: Jolla Kullgren, Matthew J. Wolf, Pavlin D. Mitev, Kersti Hermansson and Wim J. Briels
The interplay between energetics and entropy in determining defect distributions at ceria(111) is studied using a combination of DFT+U and lattice Monte Carlo simulations. Our main example is fluorine impurities, although we also present preliminary results for surface hydroxyl groups. A simple classical force-field model was constructed from a training set of DFT+U data for all symmetrically inequivalent (F−)n(Ce3+)n nearest-neighbor clusters with n = 2 or 3. Our fitted model reproduces the DFT energies well. We find that for an impurity concentration of 15% at 600 K, straight and hooked linear fluorine clusters are surprisingly abundant, with similarities to experimental STM images from the literature. We also find that with increasing temperature the fluorine cluster sizes show a transition from being governed by an attractive potential to being governed by a repulsive potential as a consequence of the increasing importance of the entropy of the Ce3+ ions. The distributions of surface hydroxyl groups are noticeably different.
J. Phys. Chem. C, 2017, 121 (28), pp 15127–15134
Authors: M. Pazoki, A. Röckert, M. J. Wolf, R. Imani, T. Edvinsson, and J. Kullgren.
The emergence of highly efficient lead halide perovskite solar cell materials makes the exploration and engineering of new lead free compounds very interesting both from a fundamental perspective as well as for potential use as new materials in solar cell devices. Herein we present the electronic structure of several lanthanide (La) based materials in the metalorganic halide perovskite family not explored before. Our estimated bandgaps for the lanthanide (Eu, Dy, Tm, Yb) perovskite compounds are in the range of 2.0–3.2 eV showing the possibility for implementation as photo-absorbers in tandem solar cell configurations or charge separating materials. We have estimated the typical effective masses of the electrons and holes for MALaI3 (La= Eu, Dy, Tm, Yb) to be in the range of 0.3–0.5 and 0.97–4.0 units of the free electron mass, respectively. We have shown that the localized f-electrons within our DFT+U approach, make the dominant electronic contribution to the states at the top of the valence band and thus have a strong impact on the photo-physical properties of the lanthanide perovskites. Therefore, the main valence to conduction band electronic transition for MAEuI3 is based on inner shell f-electron localized states within a periodic framework of perovskite crystal by which the optical absorption onset would be rather inert with respect to quantum confinement effects. The very similar crystal structure and lattice constant of the lanthanide perovskites to the widely studied CH3NH3PbI3 perovskite, are prominent advantages for implementation of these compounds in tandem or charge selective contacts in PV applications together with lead iodide perovskite devices.
J. Mater. Chem. A, 5, 2017, pp. 23131-23138
Authors: Meysam Pazoki, T. Jacobsson, Silver H. Jesper and Cruz, Malin Johansson, Roghayeh Imani, Jolla Kullgren, Anders Hagfeldt, Erik M. J. Johansson, Tomas Edvinsson and Gerrit Boschloo.
Lead halide perovskites have a range of spectacular properties and interesting phenomena and are a serious candidate for the next generation of photovoltaics with high efficiencies and low fabrication costs. An interesting phenomenon is the anomalous hysteresis often seen in current–voltage scans, which complicates accurate performance measurements but has also been explored to obtain a more comprehensive understanding of the device physics. Herein, we demonstrate a wavelength and illumination intensity dependency of the hysteresis in state-of-the-art perovskite solar cells with 18\% power conversion efficiency (PCE), which gives new insights into ion migration. The perovskite devices show lower hysteresis under illumination with near band edge (red) wavelengths compared to more energetic (blue) excitation. This can be rationalized with thermalization-assisted ion movement or thermalization-assisted vacancy generation. These explanations are supported by the dependency of the photovoltage decay with illumination time and excitation wavelength, as well as by impedance spectroscopy. The suggested mechanism is that high-energy photons create hot charge carriers that either through thermalization can create additional vacancies or by release of more energetic phonons play a role in overcoming the activation energy for ion movement. The excitation wavelength dependency of the hysteresis presented here gives valuable insights into the photophysics of the lead halide perovskite solar cells.
J. Phys. Chem. C, 121, 2017, pp. 26180-26187
Authors: Jolla Per Kullgren, Matthew Jason Wolf, Kersti Hermansson, Christof Köhler, Bálint Aradi, Thomas Frauenheim, and Peter Broqvist
Reducible oxides such as CeO2 are challanging to describe
with standard density functional theory (DFT) due to the mixed valence states of the cations, and often require the use of additional correction schemes, an
d/or more computationally expen- sive methods. This adds a new layer of complexity when it comes to the generation of Slater-Koster tables and the corresponding repulsive potentials for self-consistent density functional based tight binding (SCC-DFTB) calculations of such materials. In this work, we provide guidelines for how to set up a parameterisation scheme for mixed valence oxides within the SCC-DFTB framework, with a focus on reproducing structural and electronic properties as well as redox reaction energies calculated using a reference DFT method. This parameterisation procedure has been used to generate parameters for Ce–O interactions, with Ce in its +III or +IV formal oxidation states. The generated parameter set is validated through comparison to DFT calculations for various ceria (CeO2) and reduced ceria (CeO2−x ) systems of different dimensionalities ranging from 0D (nano-particles) to 3D (bulk). As oxygen vacancy defects in ceria are of crucial importance to many technological applications, special focus is directed towards the capability of describing such defects accurately.
J. Phys. Chem. C, 2017, 121 (8), pp 4593–4607
Authors: Matthew J. Wolf, Jolla Kullgren, Peter Broqvist, and Kersti Hermansson
We investigate the effects of anion doping with fluorine impurities on the chemistry of the CeO2 (111) facet, using the results of DFT + U
calculations. We consider three prototypical processes: the formation of oxygen vacancies, the adsorption of O2 and H2O molecules, and the re-oxidation of the surface with fragments of the two molecules. We find that the first two of these processes are not strongly affected, but that the presence of F lowers the energy gained in the re-oxidation of the surface in comparison to the healing of an oxygen vacancy, by 1.47 eV in the case of O2 (provided that the F is part of a cluster) and by 0.92 eV in the case of H2O. Based on these results, we suggest that F could enhance the redox chemistry of ceria by toggling between being in the surfaceand on the surface, effectively facilitating the release of lattice O by acting as a “place holder” for it. Finally, we find that the desorption of F as either 1212
F2 or HF is energetically unfavourable, suggesting that F doped ceria should be stable in the presence of O2 and H2O.
J. Chem. Phys. 2017, 146, 044703
Authors: Peter Broqvist, Jolla Kullgren, Matthew J. Wolf, Adri C. T. van Duin, and Kersti Hermansson
We have developed a reactive force-field of the ReaxFF type for stoichiometric ceria (CeO2) and partially reduced ceria (CeO2–x). We describe the parametrization procedure and provide results validating the parameters in terms of their ability to accurately describe the oxygen chemistry of the bulk, extended surfaces, surface steps, and nanoparticles of the material. By comparison with our reference electronic structure method (PBE+U), we find that the stoichiometric bulk and surface systems are well reproduced in terms of bulk modulus, lattice parameters, and surface energies. For the surfaces, step energies on the (111) surface are also well described. Upon reduction, the force-field is able to capture the bulk and surface vacancy formation energies (Evac), and in particular, it reproduces the Evac variation with depth from the (110) and (111) surfaces. The force-field is also able to capture the energy hierarchy of differently shaped stoichiometric nanoparticles (tetrahedra, octahedra, and cubes), and of partially reduced octahedra. For these reasons, we believe that this force-field provides a significant addition to the method repertoire available for simulating redox properties at ceria surfaces.
J. Phys. Chem. C, 2015, 119 (24), pp 13598–13609