Publications

@article{nokey,

title = {Improvement of the thermoelectric properties of PEDOT:PSS films via DMSO addition and DMSO/salt post-treatment resolved from a fundamental view},

author = {S Tu and T Tian and A Lena Oechsle and S Yin and X Jiang and W Cao and N Li and M A Scheel and L K Reb and S Hou and A S Bandarenka and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S1385894721038742},

doi = {https://doi.org/10.1016/j.cej.2021.132295},

issn = {1385-8947},

year  = {2022},

date = {2022-09-06},

urldate = {2022-09-06},

journal = {Chemical Engineering Journal},

volume = {429},

pages = {132295},

abstract = {The combination of dimethyl sulfoxide (DMSO)-solvent doping and physical\textendashchemical DMSO/salt de-doping in a sequence has been used to improve the thermoelectric (TE) properties of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films. A high power factor of ca.105.2 µW m−1 K−2 has been achieved for the PEDOT:PSS film after post-treatment with 10 % sodium sulfite (Na2SO3) in the DMSO/salt mixture (v/v), outperforming sodium bicarbonate (NaHCO3). The initial DMSO-doping treatment induces a distinct phase separation by facilitating the aggregation of the PEDOT molecules. At the same time, the subsequent DMSO/salt de-doping post-treatment strengthens the selective removal of the surplus non-conductive PSS chains. Substantial alterations in the oxidation level, chain conformations, PEDOT crystallites and their preferential orientation are observed upon treatment on the molecular level. At the mesoscale level, the purification and densification of PEDOT-rich domains enable the realization of inter-grain coupling by the formation of the electronically well-percolated network. Thereby, both electrical conductivity and Seebeck coefficient are optimized.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Size and Coverage Effects of Ni and Pt Co-Catalysts in the Photocatalytic Hydrogen Evolution from Methanol on TiO2(110)},

author = {M Eder and C Courtois and P Petzoldt and S Mackewicz and M Tschurl and U Heiz},

url = {https://doi.org/10.1021/acscatal.2c02230},

doi = {10.1021/acscatal.2c02230},

year  = {2022},

date = {2022-07-21},

journal = {ACS Catalysis},

pages = {9579-9588},

abstract = {In the past decade, hydrogen evolution from photocatalytic alcohol oxidation on metal-loaded TiO2 has emerged as an active research field. While the presence of a metal cluster co-catalyst is crucial as a H2 recombination center, size and coverage effects on the catalyst performance are not yet comprehensively understood. To some extent, this is due to the fact that common deposition methods do not allow for an independent change in size and coverage, which can be overcome by the use of cluster sources and the deposition of size-selected clusters. This study compares size-selected Ni and Pt clusters as co-catalysts on a TiO2(110) single crystal and the resulting size- and coverage-dependent effects in the photocatalytic hydrogen evolution from alcohols in ultrahigh vacuum (UHV). Larger clusters and higher coverages of Ni enhance the product formation rate, although deactivation over time occurs. In contrast, Pt co-catalysts exhibit a stable and higher activity and size-specific effects have to be taken into account. While H2 evolution is improved by a higher concentration of Pt clusters, an increase in the metal content by the deposition of larger particles can even be detrimental to the performance of the photocatalyst. The acquired overall mechanistic picture is corroborated by H2 formation kinetics from mass spectrometric data. Consequently, for some metals, size effects are relevant for improving the catalytic performance, while for other co-catalyst materials, merely the coverage is decisive. The elucidation of different size and coverage dependencies represents an important step toward a rational catalyst design for photocatalytic hydrogen evolution.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Statistically optimal analysis of the extended-system adaptive biasing force (eABF) method},

author = {A Hulm and J C B Dietschreit and C Ochsenfeld},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0095554},

doi = {10.1063/5.0095554},

year  = {2022},

date = {2022-07-13},

journal = {The Journal of Chemical Physics},

volume = {157},

number = {2},

pages = {024110},

abstract = {The extended-system adaptive biasing force (eABF) method and its newer variants offer rapid exploration of the configuration space of chemical systems. Instead of directly applying the ABF bias to collective variables, they are harmonically coupled to fictitious particles, which separates the problem of enhanced sampling from that of free energy estimation. The prevalent analysis method to obtain the potential of mean force (PMF) from eABF is thermodynamic integration. However, besides the PMF, most information is lost as the unbiased probability of visited configurations is never recovered. In this contribution, we show how statistical weights of individual frames can be computed using the Multistate Bennett’s Acceptance Ratio (MBAR), putting the post-processing of eABF on one level with other frequently used sampling methods. In addition, we apply this formalism to the prediction of nuclear magnetic resonance shieldings, which are very sensitive to molecular geometries and often require extensive sampling. The results show that the combination of enhanced sampling by means of extended-system dynamics with the MBAR estimator is a highly useful tool for the calculation of ensemble properties. Furthermore, the extension of the presented scheme to the recently published Gaussian-accelerated molecular dynamics eABF hybrid is straightforward and approximation free.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Sr Surface Enrichment in Solid Oxide Cells - Approaching the Limits of EDX Analysis by Multivariate Statistical Analysis and Simulations},

author = {H T\"{u}rk and T G\"{o}tsch and F-P Schmidt and A Hammud and D Ivanov and L G J De Haart and I Vinke and R-A Eichel and R Schl\"{o}gl and K Reuter and A Knop-Gericke and T Lunkenbein and C Scheurer},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cctc.202200300},

doi = {https://doi.org/10.1002/cctc.202200300},

issn = {1867-3880},

year  = {2022},

date = {2022-07-08},

journal = {ChemCatChem},

volume = {n/a},

number = {n/a},

abstract = {In solid oxide cells, Sr segregation has been correlated with degradation. Yet, the atomistic mechanism remains unknown. Here we begin to localize the origin of Sr surface nucleation by combining force field based simulations, energy dispersive X-ray spectroscopy (EDX) and multi-variate statistical analysis. We find increased ion mobility in the complexion between yttria-stabilized zirconia and strontium-doped lanthanum manganite. Furthermore, we developed a robust and automated routine to detect localized nucleation seeds of Sr at the complexion/vacuum interface. This hints at a mechanism originating at the complexion and requires in-depths studies at the atomistic level, where the developed routine can be beneficial for analysing large hyperspectral EDX datasets.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Structure-Dependent Electrical Double-Layer Capacitances of the Basal Plane Pd(hkl) Electrodes in HClO4},

author = {E Gubanova and T O Schmidt and S Watzele and V Alexandrov and A S Bandarenka},

url = {https://doi.org/10.1021/acs.jpcc.2c03117},

doi = {10.1021/acs.jpcc.2c03117},

issn = {1932-7447},

year  = {2022},

date = {2022-07-05},

journal = {The Journal of Physical Chemistry C},

volume = {126},

number = {27},

pages = {11414-11420},

abstract = {Electrical double-layer capacitance (CDL) measurements are among the key experiments in physical electrochemistry aimed to understand the properties of electrified solid/liquid interfaces. CDL serves as a critical parameter for developing physical models of electrochemical interfaces. Palladium (Pd) electrodes are among the most widely used functional materials in many applications, including (electro)catalysis. In this work, we report on double-layer capacitances of the basal plane Pd(111), Pd(100), and Pd(110) electrodes in aqueous HClO4 electrolytes measured using electrochemical impedance spectroscopy. Importantly, we find that the CDL values estimated at the minima of the capacitance vs electrode potential curves can be correlated with the density-functional-theory (DFT)-calculated adsorption energies for water molecules and the coordination of electrode surface atoms. Our results thus suggest that it might be possible to find simple descriptors of the electrical double layer (EDL) analogous to those used for functional electrode materials. Taken together, such descriptors could be employed for efficient high-throughput screening of various electrode/electrolyte interfaces, such as in supercapacitor and electrocatalytic systems.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Silver-Bismuth Based 2D Double Perovskites (4FPEA)4AgBiX8 (X = Cl, Br, I): Highly Oriented Thin Films with Large Domain Sizes and Ultrafast Charge-Carrier Localization},

author = {R Hooijer and A Weis and A Biewald and M T Sirtl and J Malburg and R Holfeuer and S Thamm and A Y Amin and M Righetto and A Hartschuh and L M Herz and T Bein},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202200354},

doi = {https://doi.org/10.1002/adom.202200354},

issn = {2195-1071},

year  = {2022},

date = {2022-07-03},

journal = {Advanced Optical Materials},

volume = {10},

number = {14},

pages = {2200354},

abstract = {Abstract Two-dimensional (2D) hybrid double perovskites are a promising emerging class of materials featuring superior intrinsic and extrinsic stability over their 3D parent structures, while enabling additional structural diversity and tunability. Here, we expand the Ag\textendashBi-based double perovskite system, comparing structures obtained with the halides chloride, bromide, and iodide and the organic spacer cation 4-fluorophenethylammonium (4FPEA) to form the n = 1 Ruddlesden\textendashPopper (RP) phases (4FPEA)4AgBiX8 (X = Cl, Br, I). We demonstrate access to the iodide RP-phase through a simple organic spacer, analyze the different properties as a result of halide substitution and incorporate the materials into photodetectors. Highly oriented thin films with very large domain sizes are fabricated and investigated with grazing incidence wide angle X-ray scattering, revealing a strong dependence of morphology on substrate choice and synthesis parameters. First-principles calculations confirm a direct band gap and show type Ib and IIb band alignment between organic and inorganic quantum wells. Optical characterization, temperature-dependent photoluminescence, and optical-pump terahertz-probe spectroscopy give insights into the absorption and emissive behavior of the materials as well as their charge-carrier dynamics. Overall, we further elucidate the possible reasons for the electronic and emissive properties of these intriguing materials, dominated by phonon-coupled and defect-mediated polaronic states.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Maximizing the Accessibility in DNA Origami Nanoantenna Plasmonic Hotspots},

author = {C Close and K Trofymchuk and L Grabenhorst and B Lalkens and V Glembockyte and P Tinnefeld},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/admi.202200255},

doi = {https://doi.org/10.1002/admi.202200255},

issn = {2196-7350},

year  = {2022},

date = {2022-07-01},

journal = {Advanced Materials Interfaces},

volume = {n/a},

number = {n/a},

pages = {2200255},

abstract = {Abstract DNA nanotechnology has conquered the challenge of positioning quantum emitters in the hotspot of optical antenna structures for fluorescence enhancement. Therefore, DNA origami serves as the scaffold to arrange nanoparticles and emitters, such as fluorescent dyes. For the next challenge of optimizing the applicability of plasmonic hotspots for molecular assays, a Trident DNA origami structure that increases the accessibility of the hotspot is introduced, thereby improving the kinetics of target molecule binding. This Trident NanoAntenna with Cleared HOtSpot (NACHOS) is compared with previous DNA origami nanoantennas and improved hotspot accessibility is demonstrated without compromising fluorescence enhancement. The approach taps into the potential of Trident NACHOS for single-molecule-based plasmonic biosensing.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Giant second-harmonic generation in ferroelectric NbOI2},

author = {I Abdelwahab and B Tilmann and Y Wu and D Giovanni and I Verzhbitskiy and M Zhu and R Bert\'{e} and F Xuan and L D S Menezes and G Eda and T C Sum and S Y Quek and S A Maier and K P Loh},

url = {https://doi.org/10.1038/s41566-022-01021-y},

doi = {10.1038/s41566-022-01021-y},

issn = {1749-4893},

year  = {2022},

date = {2022-06-30},

journal = {Nature Photonics},

abstract = {Implementing nonlinear optical components in nanoscale photonic devices is challenged by phase-matching conditions requiring thicknesses in the order of hundreds of wavelengths, and is disadvantaged by the short optical interaction depth of nanometre-scale materials and weak photon\textendashphoton interactions. Here we report that ferroelectric NbOI2 nanosheets exhibit giant second-harmonic generation with conversion efficiencies that are orders of magnitude higher than commonly reported nonlinear crystals. The nonlinear response scales with layer thickness and is strain- and electrical-tunable; a record >0.2% absolute SHG conversion efficiency and an effective nonlinear susceptibility $$chi _mathrmeff^(2)$$in the order of 10−9 m V−1 are demonstrated at an average pump intensity of 8 kW cm\textendash2. Due to the interplay between anisotropic polarization and excitonic resonance in NbOI2, the spatial profile of the polarized SHG response can be tuned by the excitation wavelength. Our results represent a new paradigm for ultrathin, efficient nonlinear optical components.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Elucidating the Role of Antisolvents on the Surface Chemistry and Optoelectronic Properties of CsPbBrxI3-x Perovskite Nanocrystals},

author = {J Ye and Z Li and D J Kubicki and Y Zhang and L Dai and C Otero-Mart\'{i}nez and M A Reus and R Arul and K R Dudipala and Z Andaji-Garmaroudi and Y-T Huang and Z Li and Z Chen and P M\"{u}ller-Buschbaum and H-L Yip and S D Stranks and C P Grey and J J Baumberg and N C Greenham and L Polavarapu and A Rao and R L Z Hoye},

url = {https://doi.org/10.1021/jacs.2c02631},

doi = {10.1021/jacs.2c02631},

issn = {0002-7863},

year  = {2022},

date = {2022-06-27},

journal = {Journal of the American Chemical Society},

volume = {144},

number = {27},

pages = {12102-12115},

abstract = {Colloidal lead-halide perovskite nanocrystals (LHP NCs) have emerged over the past decade as leading candidates for efficient next-generation optoelectronic devices, but their properties and performance critically depend on how they are purified. While antisolvents are widely used for purification, a detailed understanding of how the polarity of the antisolvent influences the surface chemistry and composition of the NCs is missing in the field. Here, we fill this knowledge gap by studying the surface chemistry of purified CsPbBrxI3-x NCs as the model system, which in itself is considered a promising candidate for pure-red light-emitting diodes and top-cells for tandem photovoltaics. Interestingly, we find that as the polarity of the antisolvent increases (from methyl acetate to acetone to butanol), there is a blueshift in the photoluminescence (PL) peak of the NCs along with a decrease in PL quantum yield (PLQY). Through transmission electron microscopy and X-ray photoemission spectroscopy measurements, we find that these changes in PL properties arise from antisolvent-induced iodide removal, which leads to a change in halide composition and, thus, the bandgap. Using detailed nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR) measurements along with density functional theory calculations, we propose that more polar antisolvents favor the detachment of the oleic acid and oleylamine ligands, which undergo amide condensation reactions, leading to the removal of iodide anions from the NC surface bound to these ligands. This work shows that careful selection of low-polarity antisolvents is a critical part of designing the synthesis of NCs to achieve high PLQYs with minimal defect-mediated phase segregation.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Imaging elliptically polarized infrared near-fields on nanoparticles by strong-field dissociation of functional surface groups},

author = {P Rosenberger and R Dagar and W Zhang and A Sousa-Castillo and M Neuhaus and E Cortes and S A Maier and C Costa-Vera and M F Kling and B Bergues},

url = {https://doi.org/10.1140/epjd/s10053-022-00430-6},

doi = {10.1140/epjd/s10053-022-00430-6},

issn = {1434-6079},

year  = {2022},

date = {2022-06-27},

journal = {The European Physical Journal D},

volume = {76},

number = {6},

pages = {109},

abstract = {We investigate the strong-field ion emission from the surface of isolated silica nanoparticles aerosolized from an alcoholic solution, and demonstrate the applicability of the recently reported near-field imaging at 720 nm [Rupp et al., Nat. Comm., 10(1):4655, 2019] to longer wavelength (2 $$mu $$m) and polarizations with arbitrary ellipticity. Based on the experimental observations, we discuss the validity of a previously introduced semi-classical model, which is based on near-field driven charge generation by a Monte-Carlo approach and classical propagation. We furthermore clarify the role of the solvent in the surface composition of the nanoparticles in the interaction region. We find that upon injection of the nanoparticles into the vacuum, the alcoholic solvent evaporates on millisecond time scales, and that the generated ions originate predominantly from covalent bonds with the silica surface rather than from physisorbed solvent molecules. These findings have important implications for the development of future theoretical models of the strong-field ion emission from silica nanoparticles, and the application of near-field imaging and reaction dynamics of functional groups on isolated nanoparticles.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {In Situ Observation of Morphological and Oxidation Level Degradation Processes within Ionic Liquid Post-treated PEDOT:PSS Thin Films upon Operation at High Temperatures},

author = {A L Oechsle and J E Heger and N Li and S Yin and S Bernstorff and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.2c05745},

doi = {10.1021/acsami.2c05745},

issn = {1944-8244},

year  = {2022},

date = {2022-06-27},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

number = {27},

pages = {30802-30811},

abstract = {Organic thermoelectric thin films are investigated in terms of their stability at elevated operating temperatures. Therefore, the electrical conductivity of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) post-treated poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films is measured over 4.5 h of heating at 50 or 100 °C for different EMIM DCA concentrations. The changes in the electrical performance are correlated with changes in the film morphology, as evidenced with in situ grazing-incidence small-angle X-ray scattering (GISAXS). Due to the overall increased PEDOT domain distances, the resulting impairment of the interdomain charge carrier transport directly correlates with the observed electrical conductivity decay. With in situ ultraviolet−visible (UV\textendashVis) measurements, a simultaneously occurring reduction of the PEDOT oxidation level is found to have an additional electrical conductivity lowering contribution due to the decrease of the charge carrier density. Finally, the observed morphology and oxidation level degradation is associated with the deterioration of the thermoelectric properties and hence a favorable operating temperature range is suggested for EMIM DCA post-treated PEDOT:PSS-based thermoelectrics.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Designing Multifunctional Cobalt Oxide Layers for Efficient and Stable Electrochemical Oxygen Evolution},

author = {M Kuhl and A Henning and L Haller and L I Wagner and C-M Jiang and V Streibel and I D Sharp and J Eichhorn},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/admi.202200582},

doi = {https://doi.org/10.1002/admi.202200582},

issn = {2196-7350},

year  = {2022},

date = {2022-06-24},

journal = {Advanced Materials Interfaces},

volume = {9},

number = {21},

pages = {2200582},

abstract = {Abstract Disordered and porous metal oxides are promising earth-abundant and cost-effective alternatives to noble-metal electrocatalysts. Herein, nonsaturated oxidation in plasma-enhanced atomic layer deposition is leveraged to tune the structural, mechanical, and optical properties of biphasic cobalt hydroxide films, thereby tailoring their catalytic activities and chemical stabilities. Short oxygen plasma exposure times and low plasma powers incompletely oxidize the cobaltocene precursor to Co(OH)2 and result in carbon impurity incorporation. These Co(OH)2 films are highly porous and catalytically active, but their electrochemical stability is impacted by poor substrate adhesion. In contrast, long exposure times and high powers completely oxidize the precursor to Co3O4, reduce the carbon incorporation, and improve the crystallinity. While the Co3O4 films have high electrochemical stability, they are characterized by low oxygen evolution reaction activity. To overcome these competing properties, the established relation between deposition parameters and functional film properties is applied to design bilayer films exhibiting simultaneously improved electrochemical performance and chemical stability. The bilayer films combine a highly active Co(OH)2 surface with a stable Co3O4 interface layer. These coatings exhibit minimal light absorption, thus making them suitable as protective catalytic layers on semiconductor light absorbers for application in photoelectrochemical devices.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Macromolecular Rhenium\textendashRuthenium Complexes for Photocatalytic CO2 Conversion: From Catalytic Lewis Pair Polymerization to Well-Defined Poly(vinyl bipyridine)\textendashMetal Complexes},

author = {A S Maier and C Thomas and M Kr\"{a}nzlein and T M Pehl and B Rieger},

url = {https://doi.org/10.1021/acs.macromol.2c00440},

doi = {10.1021/acs.macromol.2c00440},

issn = {0024-9297},

year  = {2022},

date = {2022-06-23},

journal = {Macromolecules},

abstract = {Herein, the first catalytical polymerization of 4-vinyl-4′-methyl-2,2′-bipyridine (VBpy) via Lewis pair-mediated group-transfer polymerization using different combinations of Lewis acidic trialkyl aluminum compounds and Lewis basic phosphines is reported. In this context, a broad screening of different Lewis pairs is conducted, demonstrating the necessity of an adjustment of the steric and electronic properties of the Lewis pair to the demands of the monomer. Further, end-group analysis of short-chain oligomers via electrospray ionization mass spectrometry (ESI-MS) for the experimentally determined optimum combination Al(i-Bu)3/PMe3 ({D} = 1.31\textendash1.36},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Modeling of Space-Charge Layers in Solid-State Electrolytes: A Kinetic Monte Carlo Approach and Its Validation},

author = {L Katzenmeier and M G\"{o}\sswein and A Gagliardi and A S Bandarenka},

url = {https://doi.org/10.1021/acs.jpcc.2c02481},

doi = {10.1021/acs.jpcc.2c02481},

issn = {1932-7447},

year  = {2022},

date = {2022-06-23},

journal = {The Journal of Physical Chemistry C},

volume = {126},

number = {26},

pages = {10900-10909},

abstract = {The space-charge layer (SCL) phenomenon in Li+-ion-conducting solid-state electrolytes (SSEs) is gaining much interest in different fields of solid-state ionics. Not only do SCLs influence charge-transfer resistance in all-solid-state batteries but also are analogous to their electronic counterpart in semiconductors; they could be used for Li+-ionic devices. However, the rather “elusive” nature of these layers, which occur on the nanometer scale and with only small changes in concentrations, makes them hard to fully characterize experimentally. Theoretical considerations based on either electrochemical or thermodynamic models are limited due to missing physical, chemical, and electrochemical parameters. In this work, we use kinetic Monte Carlo (kMC) simulations with a small set of input parameters to model the spatial extent of the SCLs. The predictive power of the kMC model is demonstrated by finding a critical range for each parameter in which the space-charge layer growth is significant and must be considered in electrochemical and ionic devices. The time evolution of the charge redistribution is investigated, showing that the SCLs form within 500 ms after applying a bias potential.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Low Band Gap Perovskite Concentrator Solar Cells: Physics, Device Simulation, and Experiment},

author = {T Ma and Y An and S Li and Y Zhao and H Wang and C Wang and S A Maier and X Li},

url = {https://doi.org/10.1021/acsami.2c06393},

doi = {10.1021/acsami.2c06393},

issn = {1944-8244},

year  = {2022},

date = {2022-06-22},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

number = {26},

pages = {29856-29866},

abstract = {Perovskite solar cells (PSCs) own rapidly increasing power conversion efficiencies (PCEs), but their concentrated counterparts (i.e., PCSCs) show a much lower performance. A deeper understanding of PCSCs relies on a thorough study of the intensive energy losses of the device along with increasing the illumination intensity. Taking the low band gap Sn\textendashPb PCSC as an example, we realize a device-level optoelectronic simulation to thoroughly disclose the internal photovoltaic physics and mechanisms by addressing the fundamental electromagnetic and carrier-transport processes within PCSCs under various concentration conditions. We find that the primary factor limiting the performance improvement of PCSCs is the significantly increased bulk recombination under the increased light concentration, which is attributed mostly to the inferior transport/collection ability of holes determined by the hole transport layer (HTL). We perform further electrical manipulation on the perovskite layer and the HTL so that the carrier-transport capability is significantly improved. Under the optoelectronic design, we fabricate low band gap PCSCs, which exhibit particularly high PCEs of up to 22.36% at 4.17 sun.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Elucidation of Structure\textendashActivity Relations in Proton Electroreduction at Pd Surfaces: Theoretical and Experimental Study},

author = {T O Schmidt and A Ngoipala and R L Arevalo and S A Watzele and R Lipin and R M Kluge and S Hou and R W Haid and A Senyshyn and E L Gubanova and A S Bandarenka and M Vandichel},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smll.202202410},

doi = {https://doi.org/10.1002/smll.202202410},

issn = {1613-6810},

year  = {2022},

date = {2022-06-20},

journal = {Small},

volume = {18},

number = {30},

pages = {2202410},

abstract = {Abstract The structure\textendashactivity relationship is a cornerstone topic in catalysis, which lays the foundation for the design and functionalization of catalytic materials. Of particular interest is the catalysis of the hydrogen evolution reaction (HER) by palladium (Pd), which is envisioned to play a major role in realizing a hydrogen-based economy. Interestingly, experimentalists observed excess heat generation in such systems, which became known as the debated “cold fusion” phenomenon. Despite the considerable attention on this report, more fundamental knowledge, such as the impact of the formation of bulk Pd hydrides on the nature of active sites and the HER activity, remains largely unexplored. In this work, classical electrochemical experiments performed on model Pd(hkl) surfaces, “noise” electrochemical scanning tunneling microscopy (n-EC-STM), and density functional theory are combined to elucidate the nature of active sites for the HER. Results reveal an activity trend following Pd(111) > Pd(110) > Pd(100) and that the formation of subsurface hydride layers causes morphological changes and strain, which affect the HER activity and the nature of active sites. These findings provide significant insights into the role of subsurface hydride formation on the structure\textendashactivity relations toward the design of efficient Pd-based nanocatalysts for the HER.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Strong Induced Circular Dichroism in a Hybrid Lead-Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization},

author = {M W Heindl and T Kodalle and N Fehn and L K Reb and S Liu and C Harder and M Abdelsamie and L Eyre and I D Sharp and S V Roth and P M\"{u}ller-Buschbaum and A Kartouzian and C M Sutter-Fella and F Deschler},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202200204},

doi = {https://doi.org/10.1002/adom.202200204},

issn = {2195-1071},

year  = {2022},

date = {2022-06-17},

journal = {Advanced Optical Materials},

volume = {n/a},

number = {n/a},

pages = {2200204},

abstract = {Abstract Chirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically-pure 3-aminobutyric acid (3-ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI3) is found to result in strong circular dichroism (CD) in the optical absorption. X-ray diffraction and grazing incidence small angle X-ray scattering (GISAXS) are applied to gain molecular-scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino-acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin-coating time, thereby achieving anisotropy factors (gabs) as high as 1.75 × 10\textendash2. Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Covalent Organic Framework Nanoplates Enable Solution-Processed Crystalline Nanofilms for Photoelectrochemical Hydrogen Evolution},

author = {L Yao and A Rodr\'{i}guez-Camargo and M Xia and D M\"{u}cke and R Guntermann and Y Liu and L Grunenberg and A Jim\'{e}nez-Solano and S T Emmerling and V Duppel and K Sivula and T Bein and H Qi and U Kaiser and M Gr\"{a}tzel and B V Lotsch},

url = {https://doi.org/10.1021/jacs.2c01433},

doi = {10.1021/jacs.2c01433},

issn = {0002-7863},

year  = {2022},

date = {2022-06-15},

journal = {Journal of the American Chemical Society},

volume = {144},

number = {23},

pages = {10291-10300},

abstract = {As covalent organic frameworks (COFs) are coming of age, the lack of effective approaches to achieve crystalline and centimeter-scale-homogeneous COF films remains a significant bottleneck toward advancing the application of COFs in optoelectronic devices. Here, we present the synthesis of colloidal COF nanoplates, with lateral sizes of ∼200 nm and average heights of 35 nm, and their utilization as photocathodes for solar hydrogen evolution. The resulting COF nanoplate colloid exhibits a unimodal particle-size distribution and an exceptional colloidal stability without showing agglomeration after storage for 10 months and enables smooth, homogeneous, and thickness-tunable COF nanofilms via spin coating. Photoelectrodes comprising COF nanofilms were fabricated for photoelectrochemical (PEC) solar-to-hydrogen conversion. By rationally designing multicomponent photoelectrode architectures including a polymer donor/COF heterojunction and a hole-transport layer, charge recombination in COFs is mitigated, resulting in a significantly increased photocurrent density and an extremely positive onset potential for PEC hydrogen evolution (over +1 V against the reversible hydrogen electrode), among the best of classical semiconductor-based photocathodes. This work thus paves the way toward fabricating solution-processed large-scale COF nanofilms and heterojunction architectures and their use in solar-energy-conversion devices.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Radial bound states in the continuum for polarization-invariant nanophotonics},

author = {L K\"{u}hner and L Sortino and R Bert\'{e} and J Wang and H Ren and S A Maier and Y S Kivshar and A Tittl},

url = {https://arxiv.org/abs/2206.05206},

doi = {https://doi.org/10.48550/arXiv.2206.05206},

year  = {2022},

date = {2022-06-10},

journal = {arXiv preprint arXiv:2206.05206},

abstract = {All-dielectric nanophotonics underpinned by bound states in the continuum (BICs) have demonstrated breakthrough applications in nanoscale light manipulation, frequency conversion and optical sensing. Leading BIC implementations range from isolated nanoantennas with localized electromagnetic fields to symmetry-protected metasurfaces with controllable resonance quality (Q) factors. However, they either require structured light illumination with complex beamshaping optics or large, fabrication-intense arrays of polarization-sensitive unit cells, hindering tailored nanophotonic applications and on-chip integration. Here, we introduce radial quasi bound states in the continuum (rBICs) as a new class of radially distributed electromagnetic modes controlled by structural asymmetry in a ring of dielectric rod pair resonators. The rBIC platform provides polarization-invariant and tunable high-Q resonances with strongly enhanced near-fields in an ultracompact footprint as low as 2 μm2. We demonstrate rBIC realizations in the visible for sensitive biomolecular detection and enhanced second-harmonic generation from monolayers of transition metal dichalcogenides, opening new perspectives for compact, spectrally selective, and polarization-invariant metadevices for multi-functional light-matter coupling, multiplexed sensing, and high-density on-chip photonics.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {From Free-Energy Profiles to Activation Free Energies},

author = {J C Dietschreit and D J Diestler and A Hulm and C Ochsenfeld and R G\'{o}mez-Bombarelli},

url = {https://arxiv.org/abs/2206.02893},

doi = {https://doi.org/10.48550/arXiv.2206.02893},

year  = {2022},

date = {2022-06-06},

journal = {arXiv preprint arXiv:2206.02893},

abstract = {Given a chemical reaction going from reactant (R) to the product (P) on a potential energy surface (PES) and a collective variable (CV) that discriminates between R and P, one can define a free-energy profile (FEP) as the logarithm of the marginal Boltzmann distribution of the CV. The FEP is not a true free energy, however, it is common to treat the FEP as the free-energy analog of the minimum energy path on the PES and to take the activation free energy, ΔF‡RP, as the difference between the maximum of the FEP at the transition state and the minimum at R. We show that this approximation can result in large errors. Since the FEP depends on the CV, it is therefore not unique, and different, discriminating CVs can yield different activation free energies for the same reaction. We derive an exact expression for the activation free energy that avoids this ambiguity with respect to the choice of CV. We find ΔF‡RP to be a combination of the probability of the system being in the reactant state, the probability density at the transition state surface, and the thermal de~Broglie wavelength associated with the transition from R to P. We then evaluate the activation free energies based on our formalism for simple analytic models and realistic chemical systems. The analytic models show that the widespread FEP-based approximation applies only at low temperatures for CVs for which the effective mass of the associated pseudo-particle is small. Most chemical reactions of practical interest involve polyatomic molecules with complex, high-dimensional PES that cannot be treated analytically and pose the added challenge of choosing a good CV, typically through heuristics. We study the influence of the choice of CV and find that, while the reaction free energy is largely unaffected, ΔF‡RP is quite sensitive.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Light-driven molecular motors embedded in covalent organic frameworks},

author = {C St\"{a}hler and L Grunenberg and M W Terban and W R Browne and D Doellerer and M Kathan and M Etter and B V Lotsch and B L Feringa and S Krause},

url = {http://dx.doi.org/10.1039/D2SC02282F},

doi = {10.1039/D2SC02282F},

issn = {2041-6520},

year  = {2022},

date = {2022-06-02},

journal = {Chemical Science},

abstract = {The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host\textendashguest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm3 g−1 and 604 m2 g−1, respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Operando Study of Structure Degradation in Solid-State Dye-Sensitized Solar Cells with a TiO2 Photoanode Having Ordered Mesopore Arrays},

author = {N Li and R Guo and A L Oechsle and M A Reus and S Liang and L Song and K Wang and D Yang and F Allegretti and A Kumar and M Nuber and J Berger and S Bernstorff and H Iglev and J Hauer and R A Fischer and J V Barth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202200373},

doi = {https://doi.org/10.1002/solr.202200373},

issn = {2367-198X},

year  = {2022},

date = {2022-05-31},

journal = {Solar RRL},

volume = {n/a},

number = {n/a},

pages = {2200373},

abstract = {Via operando grazing-incidence small-angle X-ray scattering, the degradation mechanisms of solid-state dye-sensitized solar cells (ssDSSCs) using two types of ordered mesoporous TiO2 scaffolds with different pore sizes, and an exemplary dye D205, are investigated. The temporal evolution of the inner morphology shows a strong impact on device performance. The photoinduced dye aggregation on the TiO2 surface leads to an increase in the domain radius but a decreased spatial order of the photoactive layer during the burn-in stage. This dye aggregation on the TiO2 surface causes the short-circuit current density loss, which plays a major role in the power conversion efficiency decay. Finally, it is found that a larger surface area in the small-pore sample yields a faster short-circuit current density decay as compared with the big-pore sample. Therefore, a control of dye aggregation and the pore size of TiO2 photoelectrodes is crucial for the stability of TiO2-based ssDSSCs.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Metasurface-Enhanced Infrared Spectroscopy: An Abundance of Materials and Functionalities},

author = {A John-Herpin and A Tittl and L K\"{u}hner and F Richter and S H Huang and G Shvets and S-H Oh and H Altug},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202110163},

doi = {https://doi.org/10.1002/adma.202110163},

issn = {0935-9648},

year  = {2022},

date = {2022-05-31},

journal = {Advanced Materials},

volume = {n/a},

number = {n/a},

pages = {2110163},

abstract = {Abstract Infrared (IR) spectroscopy provides unique information on the composition and dynamics of biochemical systems by resolving the characteristic absorption fingerprints of their constituent molecules. Based on this inherent chemical specificity and the capability for label-free, non-invasive, and real-time detection, IR spectroscopy approaches have unlocked a plethora of breakthrough application perspectives for fields ranging from environmental monitoring and defense to chemical analysis and medical diagnostics. Nanophotonics has played a crucial role for pushing the sensitivity limits of traditional far-field spectroscopy by using resonant nanostructures to focus the incident light into nanoscale hot-spots of the electromagnetic field, greatly enhancing light-matter interaction. Metasurfaces composed of regular arrangements of such resonators further increase the design space for tailoring this nanoscale light control both spectrally and spatially, which has established them as an invaluable toolkit for surface-enhanced spectroscopy. Starting from the fundamental concepts of metasurface-enhanced IR spectroscopy, we showcase a broad palette of resonator geometries, materials and arrangements for realizing highly sensitive metadevices, with a special focus on emerging systems such as phononic and 2D van der Waals materials, and integration with waveguides for lab-on-a-chip devices. Furthermore, we will highlight some advanced sensor functionalities of metasurface-based IR spectroscopy, including multiresonance, tunability, dielectrophoresis, live cell sensing, and machine-learning-aided analysis. This article is protected by copyright. All rights reserved},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Understanding Carotenoid Dynamics via the Vibronic Energy Relaxation Approach},

author = {V \v{S}ebel\'{i}k and C D P Duffy and E Keil and T Pol\'{i}vka and J Hauer},

url = {https://doi.org/10.1021/acs.jpcb.2c00996},

doi = {10.1021/acs.jpcb.2c00996},

issn = {1520-6106},

year  = {2022},

date = {2022-05-24},

journal = {The Journal of Physical Chemistry B},

abstract = {Carotenoids are an integral part of natural photosynthetic complexes, with tasks ranging from light harvesting to photoprotection. Their underlying energy deactivation network of optically dark and bright excited states is extremely efficient: after excitation of light with up to 2.5 eV of photon energy, the system relaxes back to ground state on a time scale of a few picoseconds. In this article, we summarize how a model based on the vibrational energy relaxation approach (VERA) explains the main characteristics of relaxation dynamics after one-photon excitation with special emphasis on the so-called S* state. Lineshapes after two-photon excitation are beyond the current model of VERA. We outline this future line of research in our article. In terms of experimental method development, we discuss which techniques are needed to better describe energy dissipation effects in carotenoids and within the first solvation shell.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Advances in nano-and microscale NMR spectroscopy using diamond quantum sensors},

author = {R D Allert and K D Briegel and D B Bucher},

url = {https://arxiv.org/abs/2205.12178},

doi = {https://doi.org/10.48550/arXiv.2205.12178},

year  = {2022},

date = {2022-05-24},

journal = {arXiv preprint arXiv:2205.12178},

abstract = {Quantum technologies have seen a rapid developmental surge over the last couple of years. Though often overshadowed by quantum computation, quantum sensors show tremendous potential for widespread applications in chemistry and biology. One system stands out in particular: the nitrogen-vacancy (NV) center in diamond, an atomic-sized sensor allowing the detection of nuclear magnetic resonance (NMR) signals at unprecedented length scales down to a single proton. In this article, we review the fundamentals of NV center-based quantum sensing and its distinct impact on nano- to microscale NMR spectroscopy. Furthermore, we highlight and discuss possible future applications of this novel technology ranging from energy research, material science, or single-cell biology, but also associated challenges of these rapidly developing NMR sensors.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Capabilities and limitations of rotating disk electrodes versus membrane electrode assemblies in the investigation of electrocatalysts},

author = {T Lazaridis and B M St\"{u}hmeier and H A Gasteiger and H A El-Sayed},

url = {https://doi.org/10.1038/s41929-022-00776-5},

doi = {10.1038/s41929-022-00776-5},

issn = {2520-1158},

year  = {2022},

date = {2022-05-23},

journal = {Nature Catalysis},

volume = {5},

number = {5},

pages = {363-373},

abstract = {Cost-competitive fuel cells and water electrolysers require highly efficient electrocatalysts for the respective reactions of hydrogen oxidation and evolution, and oxygen evolution and reduction. Electrocatalyst activity and durability are commonly assessed using rotating disk electrodes (RDEs) or membrane electrode assemblies (MEAs). RDEs provide a quick and widely accessible testing tool, whereas MEA testing is more complex but closely resembles the actual application. Although both experimental set-ups allow investigation of the same reactions, there are scientific questions that cannot be answered by the RDE technique. In this Perspective, we scrutinize protocols widely used to determine the activity and durability of electrocatalysts, and highlight discrepancies in the results obtained using RDEs and MEAs. We discuss where the use of RDEs is appropriate and, conversely, where it leads to erroneous interpretations. Ultimately, we show that many of the current challenges for hydrogen and oxygen electrocatalysts require MEA testing and advocate for its greater adoption in the early stages of electrocatalyst development.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {All-optical nanoscopic spatial control of molecular reaction yields on nanoparticles},

author = {W Zhang and R Dagar and P Rosenberger and A Sousa-Castillo and M Neuhaus and W Li and S A Khan and A S Alnaser and E Cortes and S A Maier and C Costa-Vera and M F Kling and B Bergues},

url = {http://opg.optica.org/optica/abstract.cfm?URI=optica-9-5-551},

doi = {10.1364/OPTICA.453915},

year  = {2022},

date = {2022-05-20},

journal = {Optica},

volume = {9},

number = {5},

pages = {551-560},

abstract = {Molecular adsorbate reactions on nanoparticles play a fundamental role in areas such as nano-photocatalysis, atmospheric, and astrochemistry. They can be induced, enhanced, and controlled by field localization and enhancement on the nanoparticle surface. In particular, the ability to perform highly controlled near-field-mediated reactions is key to deepening our understanding of surface photoactivity on nanosystems. Here, using reaction nanoscopy, we experimentally demonstrate all-optical nanoscopic control of surface reaction yields by tailoring the near fields on nanoparticles with waveform-controlled linear and bicircular two-color laser pulses, respectively. We observe site-selective proton emission from the dissociative ionization of adsorbate molecules on SiO2 nanoparticles as a function of the polarization and relative phase of the two-color pulses. The angularly resolved close-to-uniform mapping between the surface reaction yields and the measured ion momentum enables the observation and spatial control of molecular reactions on the nanoparticle surface with nanoscopic resolution. The experimental results are modeled and reproduced qualitatively by classical trajectory Monte Carlo simulations. Our work paves the way toward reliable all-optical control of photocatalytic chemical reactions on nanoscale surfaces.},

keywords = {Molecularly-Functionalized, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Effect of Solvent Vapor Annealing on Diblock Copolymer-Templated Mesoporous Si/Ge/C Thin Films: Implications for Li-Ion Batteries},

author = {C L Weindl and C E Fajman and M A Giebel and K S Wienhold and S Yin and T Tian and C Geiger and L P Kreuzer and M Schwartzkopf and S V Roth and T F F\"{a}ssler and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsanm.2c01191},

doi = {10.1021/acsanm.2c01191},

year  = {2022},

date = {2022-05-17},

journal = {ACS Applied Nano Materials},

volume = {5},

number = {5},

pages = {7278-7287},

abstract = {Although amphiphilic diblock copolymer templating of inorganic materials such as TiO2 is already well investigated, sol\textendashgel synthesis routines for porous silicon and germanium are relatively rare. Therefore, especially in the field of Li-ion batteries, novel synthesis routines with the possibility to tune the silicon and germanium ratio and the morphology in the nanometer regime are of high interest. Here, we demonstrate a synthesis method that allows a change of morphology and elemental composition with minimal effort. We evidence a morphological transformation in the nanometer regime with real space (scanning electron microscopy) and complementary reciprocal space analysis methods (grazing-incidence small-angle X-ray scattering). Although energy-dispersive X-ray spectroscopy (EDS) reveals a considerable amount of oxygen in the thin film, crystalline Ge in the bulk is detected with powder X-ray diffraction (PXRD) and Raman spectroscopy. Due to the system’s simplicity, chemical mass production options such as roll-to-roll or slot-die printing can also be considered high-yield methods compared to standard synthesis routines.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Gold\textendashrhodium nanoflowers for the plasmon enhanced ethanol electrooxidation under visible light for tuning the activity and selectivity},

author = {M P S Rodrigues and A H B Dourado and K Krischer and S I C Torresi},

url = {https://www.sciencedirect.com/science/article/pii/S0013468622006016},

doi = {https://doi.org/10.1016/j.electacta.2022.140439},

issn = {0013-4686},

year  = {2022},

date = {2022-05-12},

journal = {Electrochimica Acta},

volume = {420},

pages = {140439},

abstract = {Direct ethanol fuel cells (DEFCs) are a promising power source, but the low selectivity to ethanol complete oxidation is still challenging. The localized surface plasmon resonance (LSPR) excitation has been reported to accelerate and drive several chemical reactions, including the ethanol oxidation reaction (EOR), coming as a strategy to improve catalysts performance. Nonetheless, metallic nanoparticles (NPs) that present the LSPR excitation in the visible range are known for leading to the incomplete oxidation of ethanol. Thus, we report here the application of gold-rhodium nanoflowers (Au@Rh NFs) towards the plasmon-enhanced EOR. These hybrid materials consist of a Au spherical nucleus covered by Rh branches shell, combining plasmonic and catalytic properties. Firstly, the Au@Rh NFs metallic ratio was investigated in dark conditions to obtain an optimal catalyst. Experiments were also performed under light irradiation. Our data demonstrated an improvement of 352% in current density and 36% in selectivity to complete ethanol oxidation under 533 nm laser incidence. Moreover, the current density showed a linear increase with the laser power density, indicating a photochemical effect and thus enhancement due to the LSPR properties.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Controlling Plasmonic Chemistry Pathways through Specific Ion Effects},

author = {A Stefancu and L Nan and L Zhu and V Chiș and I Bald and M Liu and N Leopold and S A Maier and E Cortes},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202200397},

doi = {https://doi.org/10.1002/adom.202200397},

issn = {2195-1071},

year  = {2022},

date = {2022-05-11},

journal = {Advanced Optical Materials},

volume = {n/a},

number = {n/a},

pages = {2200397},

abstract = {Abstract Plasmon-driven dehalogenation of brominated purines has been recently explored as a model system to understand fundamental aspects of plasmon-assisted chemical reactions. Here, it is shown that divalent Ca2+ ions strongly bridge the adsorption of bromoadenine (Br-Ade) to Ag surfaces. Such ion-mediated binding increases the molecule's adsorption energy leading to an overlap of the metal energy states and the molecular states, enabling the chemical interface damping (CID) of the plasmon modes of the Ag nanostructures (i.e., direct electron transfer from the metal to Br-Ade). Consequently, the conversion of Br-Ade to adenine almost doubles following the addition of Ca2+. These experimental results, supported by theoretical calculations of the local density of states of the Ag/Br-Ade complex, indicate a change of the charge transfer pathway driving the dehalogenation reaction, from Landau damping (in the lack of Ca2+ ions) to CID (after the addition of Ca2+). The results show that the surface dynamics of chemical species (including water molecules) play an essential role in charge transfer at plasmonic interfaces and cannot be ignored. It is envisioned that these results will help in designing more efficient nanoreactors, harnessing the full potential of plasmon-assisted chemistry.},

keywords = {Molecularly-Functionalized, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Inverse Multislice Ptychography by Layer-wise Optimisation and Sparse Matrix Decomposition},

author = {A Bangun and O Melnyk and B M\"{a}rz and B Diederichs and A Clausen and D Weber and F Filbir and K M\"{u}ller-Caspary},

url = {https://arxiv.org/abs/2205.03902},

doi = {https://doi.org/10.48550/arXiv.2205.03902},

year  = {2022},

date = {2022-05-08},

journal = {arXiv preprint arXiv:2205.03902},

abstract = {We propose algorithms based on an optimisation method for inverse multislice ptychography in, e.g. electron microscopy. The multislice method is widely used to model the interaction between relativistic electrons and thick specimens. Since only the intensity of diffraction patterns can be recorded, the challenge in applying inverse multislice ptychography is to uniquely reconstruct the electrostatic potential in each slice up to some ambiguities. In this conceptual study, we show that a unique separation of atomic layers for simulated data is possible when considering a low acceleration voltage. We also introduce an adaptation for estimating the illuminating probe. For the sake of practical application, we finally present slice reconstructions using experimental 4D scanning transmission electron microscopy (STEM) data.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electronic and Optical Properties of Eu2+-Activated Narrow-Band Phosphors for Phosphor-Converted Light-Emitting Diode Applications: Insights from a Theoretical Spectroscopy Perspective},

author = {R Shafei and D Maganas and P J Strobel and P J Schmidt and W Schnick and F Neese},

url = {https://doi.org/10.1021/jacs.2c00218},

doi = {10.1021/jacs.2c00218},

issn = {0002-7863},

year  = {2022},

date = {2022-04-26},

journal = {Journal of the American Chemical Society},

volume = {144},

number = {18},

pages = {8038-8053},

abstract = {In this work, we present a computational protocol that is able to predict the experimental absorption and emission spectral shapes of Eu2+-doped phosphors. The protocol is based on time-dependent density functional theory and operates in conjunction with an excited-state dynamics approach. It is demonstrated that across the study set consisting of representative examples of nitride, oxo-nitride, and oxide Eu2+-doped phosphors, the energy distribution and the band shape of the emission spectrum are related to the nature of the 4f\textendash5d transitions that are probed in the absorption process. Since the 4f orbitals are very nearly nonbonding, the decisive quantity is the covalency of the 5d acceptor orbitals that become populated in the electronically excited state that leads to emission. The stronger the (anti) bonding interaction between the lanthanide and the ligands is in the excited state, the larger will be the excited state distortion. Consequently, the corresponding emission will get broader due to the vibronic progression that is induced by the structural distortion. In addition, the energy separation of the absorption bands that are dominated by states with valence 4f\textendash5d and a metal to ligand charge transfer character defines a measure for the thermal quenching of the studied Eu2+-doped phosphors. Based on this analysis, simple descriptors are identified that show a strong correlation with the energy position and bandwidth of the experimental emission bands without the need for elaborate calculations. Overall, we believe that this study serves as an important reference for designing new Eu2+-doped phosphors with desired photoluminescence properties.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Solution-based synthesis of wafer-scale epitaxial BiVO4 thin films exhibiting high structural and optoelectronic quality},

author = {V F Kunzelmann and C-M Jiang and I Ihrke and E Sirotti and T Rieth and A Henning and J Eichhorn and I D Sharp},

url = {http://dx.doi.org/10.1039/D1TA10732A},

doi = {10.1039/D1TA10732A},

issn = {2050-7488},

year  = {2022},

date = {2022-04-22},

journal = {Journal of Materials Chemistry A},

abstract = {We demonstrate a facile approach to solution-based synthesis of wafer-scale epitaxial bismuth vanadate (BiVO4) thin films by spin-coating on yttria-stabilized zirconia. Epitaxial growth proceeds via solid-state transformation of initially formed polycrystalline films, driven by interface energy minimization. The (010)-oriented BiVO4 films are smooth and compact, possessing remarkably high structural quality across complete 2′′ wafers. Optical absorption is characterized by a sharp onset with a low sub-band gap response, confirming that the structural order of the films results in correspondingly high optoelectronic quality. This combination of structural and optoelectronic quality enables measurements that reveal a strong optical anisotropy of BiVO4, which leads to significantly increased in-plane optical constants near the fundamental band edge that are of particular importance for maximizing light harvesting in semiconductor photoanodes. Temperature-dependent transport measurements confirm a thermally activated hopping barrier of ∼570 meV, consistent with small electron polaron conduction. This simple approach for synthesis of high-quality epitaxial BiVO4, without the need for complex deposition equipment, enables a broadly accessible materials base to accelerate research aimed at understanding and optimizing photoelectrochemical energy conversion mechanisms.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Revealing the Nature of Active Sites on Pt\textendashGd and Pt\textendashPr Alloys during the Oxygen Reduction Reaction},

author = {R M Kluge and E Psaltis and R W Haid and S Hou and T O Schmidt and O Schneider and B Garlyyev and F Calle-Vallejo and A S Bandarenka},

url = {https://doi.org/10.1021/acsami.2c03604},

doi = {10.1021/acsami.2c03604},

issn = {1944-8244},

year  = {2022},

date = {2022-04-20},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

number = {17},

pages = {19604-19613},

abstract = {For large-scale applications of hydrogen fuel cells, the sluggish kinetics of the oxygen reduction reaction (ORR) have to be overcome. So far, only platinum (Pt)-group catalysts have shown adequate performance and stability. A well-known approach to increase the efficiency and decrease the Pt loading is to alloy Pt with other metals. Still, for catalyst optimization, the nature of the active sites is crucial. In this work, electrochemical scanning tunneling microscopy (EC-STM) is used to probe the ORR active areas on Pt5Gd and Pt5Pr in acidic media under reaction conditions. The technique detects localized fluctuations in the EC-STM signal, which indicates differences in the local activity. The in situ experiments, supported by coordination\textendashactivity plots based on density functional theory calculations, show that the compressed Pt\textendashlanthanide (111) terraces contribute the most to the overall activity. Sites with higher coordination, as found at the bottom of step edges or concavities, remain relatively inactive. Sites of lower coordination, as found near the top of step edges, show higher activity, presumably due to an interplay of strain and steric hindrance effects. These findings should be vital in designing nanostructured Pt\textendashlanthanide electrocatalysts.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Introducing a Symmetry-Breaking Coupler into a Dielectric Metasurface Enables Robust High-Q Quasibound States in the Continuum and Efficient Nonlinear Frequency Conversion},

author = {G Q Moretti and A Tittl and E Cort\'{e}s and S A Maier and A V Bragas and G Grinblat},

url = {https://doi.org/10.48550/arXiv.2204.07097},

doi = {https://doi.org/10.48550/arXiv.2204.07097},

year  = {2022},

date = {2022-04-14},

journal = {arXiv preprint arXiv:2204.07097},

abstract = {Dielectric metasurfaces supporting quasi-bound states in the continuum (quasi-BICs) exhibit very high quality factor resonances and electric field confinement. However, accessing the high-Q end of the quasi-BIC regime usually requires marginally distorting the metasurface design from a BIC condition, pushing the needed nanoscale fabrication precision to the limit. This work introduces a novel concept for generating high-Q quasi-BICs, which strongly relaxes this requirement by incorporating a relatively large perturbative element close to high-symmetry points of an undistorted BIC metasurface, acting as a coupler to the radiation continuum. We validate this approach by adding a ∼100 nm diameter cylinder between two reflection-symmetry points separated by a 300 nm gap in an elliptical disk metasurface unit cell, using gallium phosphide as the dielectric. We find that high-Q resonances emerge when the cylindrical coupler is placed at any position between such symmetry points. We further explore this metasurface's second harmonic generation capability in the optical range. Displacing the coupler as much as a full diameter from a BIC condition produces record-breaking normalized conversion efficiencies >102 W−1. The strategy of enclosing a disruptive element between multiple high-symmetry points in a BIC metasurface could be applied to construct robust high-Q quasi-BICs in many geometrical designs.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Spatially Resolved Electrochemical Impedance Spectroscopy of Automotive PEM Fuel Cells},

author = {A S Bandarenka and F Haimerl and J P Sabawa and T A Dao},

url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/celc.202200069},

doi = {https://doi.org/10.1002/celc.202200069},

issn = {2196-0216},

year  = {2022},

date = {2022-04-13},

urldate = {2022-04-13},

journal = {ChemElectroChem},

volume = {n/a},

number = {n/a},

abstract = {Fuel cell electric vehicles (FCEVs), which use polymer electrolyte membrane fuel cells (PEMFCs), provide a prospect to add to a future mobility. However, an in-depth understanding of degradation mechanisms and contributions to performance losses is needed to commercialize FCEVs further. Previous PEMFC degradation research has focused on global indicators of the cell condition. Failure occurs typically due to inhomogeneities in operation, leading to localized regions of high degradation rates. Here, we present the results of a comprehensive study of spatial distributions of essential PEMFC parameters using electrochemical impedance spectroscopy across the cell surface of automotive-size fuel cells with an active area of 285cm2. In particular, the results reveal increasing mass transport problems with increasing distance from the air inlet and a tendency of lower proton resistances in the center of the cell. One hundred twenty realistic freeze-start cycles degenerated the cell performance drastically. The outer cell regions, subject to the lowest temperatures, showed the most substantial degradation rates, partly compensated by central cell regions with slightly higher temperatures. These findings bridge the gap between simulation and experiment and provide valuable insights for future fuel cell design and operating strategies.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Li+ Conductivity of Space Charge Layers Formed at Electrified Interfaces Between a Model Solid-State Electrolyte and Blocking Au-Electrodes},

author = {L Katzenmeier and L Carstensen and A S Bandarenka},

url = {https://doi.org/10.1021/acsami.2c00650},

doi = {10.1021/acsami.2c00650},

issn = {1944-8244},

year  = {2022},

date = {2022-04-06},

journal = {ACS Applied Materials \& Interfaces},

volume = {14},

number = {13},

pages = {15811-15817},

abstract = {The formation of space charge layers in solid-state ion conductors has been investigated as early as the 1980s. With the advent of all-solid-state batteries as an alternative to traditional Li-ion batteries, possibly improving performance and safety, the phenomenon of space charge formation caught the attention of researchers as a possible origin for the observed high interfacial resistance. Following classical space charge theory, such high resistances result from the formation of the depletion layers. These layers of up to hundreds of nanometers in thickness are almost free of mobile cations. With the prediction of a Debye-like screening effect, the thickness of the depletion layer is expected to scale with the square root of the absolute temperature. In this work, we studied the temperature dependence of the depletion layer properties in model solid Ohara LICGC Li+ conducting electrolytes using electrochemical impedance spectroscopy. We show that the activation energy inside the depletion layer increases to ca 0.42 eV compared to ca 0.39 eV in the bulk electrolyte. Moreover, the proportionality between temperature and depletion layer thickness, correlating to the Debye length, is tested and validated.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {High-Throughput Fabrication of Triangular Nanogap Arrays for Surface-Enhanced Raman Spectroscopy},

author = {S Luo and A Mancini and F Wang and J Liu and S A Maier and J C De Mello},

url = {https://doi.org/10.1021/acsnano.1c09930},

doi = {10.1021/acsnano.1c09930},

issn = {1936-0851},

year  = {2022},

date = {2022-04-05},

journal = {ACS Nano},

abstract = {Squeezing light into nanometer-sized metallic nanogaps can generate extremely high near-field intensities, resulting in dramatically enhanced absorption, emission, and Raman scattering of target molecules embedded within the gaps. However, the scarcity of low-cost, high-throughput, and reproducible nanogap fabrication methods offering precise control over the gap size is a continuing obstacle to practical applications. Using a combination of molecular self-assembly, colloidal nanosphere lithography, and physical peeling, we report here a high-throughput method for fabricating large-area arrays of triangular nanogaps that allow the gap width to be tuned from ∼10 to ∼3 nm. The nanogap arrays function as high-performance substrates for surface-enhanced Raman spectroscopy (SERS), with measured enhancement factors as high as 108 relative to a thin gold film. Using the nanogap arrays, methylene blue dye molecules can be detected at concentrations as low as 1 pM, while adenine biomolecules can be detected down to 100 pM. We further show that it is possible to achieve sensitive SERS detection on binary-metal nanogap arrays containing gold and platinum, potentially extending SERS detection to the investigation of reactive species at platinum-based catalytic and electrochemical surfaces.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Selective and Cooperative Photocycloadditions within Multistranded Aromatic Sheets},

author = {B Gole and B Kauffmann and A Tron and V Maurizot and N Mcclenaghan and I Huc and Y Ferrand},

url = {https://doi.org/10.1021/jacs.2c01269},

doi = {10.1021/jacs.2c01269},

issn = {0002-7863},

year  = {2022},

date = {2022-04-05},

journal = {Journal of the American Chemical Society},

abstract = {A series of aromatic helix-sheet-helix oligoamide foldamers composed of several different photosensitive diazaanthracene units have been designed and synthesized. Molecular objects up to 7 kDa were straightforwardly produced on a 100 mg scale. Nuclear magnetic resonance and crystallographic investigations revealed that helix-sheet-helix architectures can adopt one or two distinct conformations. Sequences composed of an even number of turn units were found to fold in a canonical symmetrical conformation with two helices of identical handedness stacked above and below the sheet segment. Sequences composed of an odd number of turns revealed a coexistence between a canonical fold with helices of opposite handedness and an alternate fold with a twist within the sheet and two helices of identical handedness. The proportions between these species could be manipulated, in some cases quantitatively, being dependent on solvent, temperature, and absolute control of helix handedness. Diazaanthracene units were shown to display distinct reactivity toward [4 + 4] photocycloadditions according to the substituent in position 9. Their organization within the sequences was programmed to allow photoreactions to take place in a specific order. Reaction pathways and kinetics were deciphered and product characterized, demonstrating the possibility to orchestrate successive photoreactions so as to avoid orphan units or to deliberately produce orphan units at precise locations. Strong cooperative effects were observed in which the photoreaction rate was influenced by the presence (or absence) of photoadducts in the structure. Multiple photoreactions within the aromatic sheet eventually lead to structure lengthening and stiffening, locking conformational equilibria. Photoproducts could be thermally reverted.},

keywords = {Foundry Organic, Molecularly Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Transversal Halide Motion Intensifies Band-To-Band Transitions in Halide Perovskites},

author = {C Gehrmann and S Caicedo-D\'{a}vila and X Zhu and D A Egger},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/advs.202200706},

doi = {https://doi.org/10.1002/advs.202200706},

issn = {2198-3844},

year  = {2022},

date = {2022-04-04},

journal = {Advanced Science},

volume = {n/a},

number = {n/a},

pages = {2200706},

abstract = {Abstract Despite their puzzling vibrational characteristics that include strong signatures of anharmonicity and thermal disorder already around room temperature, halide perovskites (HaPs) exhibit favorable optoelectronic properties for applications in photovoltaics and beyond. Whether these vibrational properties are advantageous or detrimental to their optoelectronic properties remains, however, an important open question. Here, this issue is addressed by investigation of the finite-temperature optoelectronic properties in the prototypical cubic CsPbBr3, using first-principles molecular dynamics based on density-functional theory. It is shown that the dynamic flexibility associated with HaPs enables the so-called transversality, which manifests as a preference for large halide displacements perpendicular to the Pb-Br-Pb bonding axis. The authors find that transversality is concurrent with vibrational anharmonicity and leads to a rapid rise in the joint density of states, which is favorable for photovoltaics since this implies sharp optical absorption profiles. These findings are contrasted to the case of PbTe, a material that shares several key properties with CsPbBr3 but cannot exhibit any transversality and, hence, is found to exhibit much wider band-edge distributions. The authors conclude that the dynamic structural flexibility in HaPs and their unusual vibrational characteristics might not just be a mere coincidence, but play active roles in establishing their favorable optoelectronic properties.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Time-Resolved Orientation and Phase Analysis of Lead Halide Perovskite Film Annealing Probed by In Situ GIWAXS},

author = {M A Reus and L K Reb and A F Weinzierl and C L Weindl and R Guo and T Xiao and M Schwartzkopf and A Chumakov and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202102722},

doi = {https://doi.org/10.1002/adom.202102722},

issn = {2195-1071},

year  = {2022},

date = {2022-04-03},

journal = {Advanced Optical Materials},

volume = {n/a},

number = {n/a},

pages = {2102722},

abstract = {Abstract Scalable thin-film deposition methods are increasingly important for hybrid lead halide perovskite thin films. Understanding the structure evolution during non-equilibrium processes helps to find suitable materials and processing parameters to produce films with well-performing optoelectronic properties. Here, spin-cast and slot-die coated bilayers of lead iodide (PbI2) and methylammonium iodide (MAI) are investigated by in situ grazing-incidence wide-angle X-ray scattering during the thermal annealing process, which converts the bilayer into methylammonium lead iodide (MAPI). Photoluminescence (PL) and UV/Vis measurements show increasing crystallinity during the annealing process and a slight PL red-shift of the spin-cast film, attributed to crystallite coalescence that is not prominent for the slot-die coated film. The disintegration of the solvent-precursor complex (MA)2(Pb3I8) ⋅ 2 DMSO and conversion into perovskite are followed in situ and differences in the morphology and time evolution are observed. In both, spin-cast and slot-die coated thin-films, the isotropic orientation is dominant, however, in the slot-die coated films, the perovskite crystallites have an additional face-on orientation ((110) parallel to substrate) that is not detected in spin-cast films. An Avrami model is applied for the perovskite crystal growth that indicates reduced dimensionality of the growth for the printed thin films.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Selectivity Trends and Role of Adsorbate-Adsorbate Interactions in CO Hydrogenation on Rhodium Catalysts},

author = {M Deimel and H Prats and M Seibt and K Reuter and M Andersen},

url = {https://arxiv.org/abs/2203.15746},

doi = {https://doi.org/10.48550/arXiv.2203.15746},

year  = {2022},

date = {2022-03-29},

journal = {arXiv preprint arXiv:2203.15746},

abstract = {Predictive-quality computational modeling of heterogeneously catalyzed reactions has emerged as an important tool for the analysis and assessment of activity and activity trends. In contrast, more subtle selectivities and selectivity trends still pose a significant challenge to prevalent microkinetic modeling approaches that typically employ a mean-field approximation (MFA). Here, we focus on CO hydrogenation on Rh catalysts with the possible products methane, acetaldehyde, ethanol and water. This reaction has already been subject to a number of experimental and theoretical studies with conflicting views on the factors controlling activity and selectivity towards the more valuable higher oxygenates. Using accelerated first-principles kinetic Monte Carlo (KMC) simulations and explicitly and systematically accounting for adsorbate-adsorbate interactions through a cluster expansion approach, we model the reaction on the low-index Rh(111) and stepped Rh(211) surfaces. We find that the Rh(111) facet is selective towards methane, while the Rh(211) facet exhibits a similar selectivity towards methane and acetaldehyde. This is consistent with the experimental selectivity observed for larger, predominantly (111)-exposing Rh nanoparticles and resolves the discrepancy to earlier first-principles MFA microkinetic work that found the Rh(111) facet to be selective towards acetaldehyde. While the latter work tried to approximately account for lateral interactions through coverage-dependent rate expressions, our analysis demonstrates that this fails to sufficiently capture concomitant correlations among the adsorbed reaction intermediates that crucially determine the overall selectivity.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Self-doping behavior and cation disorder in MgSnN2},

author = {D Han and S S Rudel and W Schnick and H Ebert},

url = {https://link.aps.org/doi/10.1103/PhysRevB.105.125202},

doi = {10.1103/PhysRevB.105.125202},

year  = {2022},

date = {2022-03-28},

journal = {Physical Review B},

volume = {105},

number = {12},

pages = {125202},

abstract = {Investigations on II−Sn−N2(II=Mg, Ca) have been started very recently compared to the intense research of Zn−IV−N2 (IV=Si, Ge, Sn). In this work, we study the phase stability of MgSnN2 and ZnSnN2 in wurtzite and rocksalt phases by first principles calculations. The calculated phase diagram agrees with the experimental observation; i.e., MgSnN2 can form in the wurtzite and rocksalt phases while ZnSnN2 only crystallizes in the wurtzite phase. Due to the higher ionicity of Mg-N bonds compared to Sn-N bonds and Zn-N bonds, wurtzite-type 

MgSnN2 appears under Mg-rich conditions. The defect properties and doping behavior of MgSnN2 in the wurtzite phase are further investigated. We find that MgSnN2 exhibits self-doped n-type conductivity, and donor-type antisite defect SnMg is the primary source of free electrons. The high possibility of forming the stoichiometry-preserving MgSn+SnMg defect complex leads to our study of cation disorder in MgSnN2 by using the cluster expansion method with first principles calculations. It is found that cation disorder in MgSnN2 induces a band-gap reduction because of a violation of the octet rule. The local disorder, namely, forming (4,0) or (0,4) tetrahedra, leads to an appreciable band-gap reduction and hinders the enhancement of the optical absorption.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Band gap and electronic structure of defects in the ternary nitride BP3N6: experiment and theory},

author = {T De Boer and M F A Fattah and M R Amin and S J Ambach and S Vogel and W Schnick and A Moewes},

url = {https://doi.org/10.1039/D1TC06009K},

doi = {10.1039/D1TC06009K},

issn = {2050-7526},

year  = {2022},

date = {2022-03-28},

urldate = {2022-03-28},

journal = {Journal of Materials Chemistry C},

volume = {10},

pages = {6429-6434},

abstract = {Recent advances in methods to access nitride systems by a high-pressure high-temperature approach have made possible the one-step synthesis of mixed ternary non-metal nitrides. As a prerequisite to use in a practical device, it is important to understand important bulk electronic properties, such as the band gap, as well as characterizing the presence and effect of defects that are present. In this work, the novel ternary nitride BP3N6 is studied using techniques sensitive to the partial electronic density of states, specifically X-ray absorption spectroscopy and X-ray emission spectroscopy. Complementary full-potential all-electron density functional theory (DFT) calculations allow important bulk electronic parameters, such as the band gap, to be elucidated. The band gap of BP3N6 has been determined to be 3.9 ± 0.2 eV and 4.1 ± 0.4 eV at the B K- and N K-edges, respectively. This is close to a theoretical value of 4.3 eV predicted by the PBEsol exchange\textendashcorrelation functional and considerably less than a value of 5.8 eV predicted by the modified Becke\textendashJohnson exchange\textendashcorrelation functional. X-Ray excited optical luminescence (XEOL) measurements are performed to interrogate the presence of point defects in this system. Together with DFT calculations, these measurements reveal the presence of nitrogen vacancies which lead to multiple mid-gap trap states.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Wafer-scale epitaxial modulation of quantum dot density},

author = {N Bart and C Dangel and P Zajac and N Spitzer and J Ritzmann and M Schmidt and H G Babin and R Schott and S R Valentin and S Scholz and Y Wang and R Uppu and D Najer and M C L\"{o}bl and N Tomm and A Javadi and N O Antoniadis and L Midolo and K M\"{u}ller and R J Warburton and P Lodahl and A D Wieck and J J Finley and A Ludwig},

url = {https://doi.org/10.1038/s41467-022-29116-8},

doi = {10.1038/s41467-022-29116-8},

issn = {2041-1723},

year  = {2022},

date = {2022-03-28},

journal = {Nature Communications},

volume = {13},

number = {1},

pages = {1633},

abstract = {Precise control of the properties of semiconductor quantum dots (QDs) is vital for creating novel devices for quantum photonics and advanced opto-electronics. Suitable low QD-densities for single QD devices and experiments are challenging to control during epitaxy and are typically found only in limited regions of the wafer. Here, we demonstrate how conventional molecular beam epitaxy (MBE) can be used to modulate the density of optically active QDs in one- and two- dimensional patterns, while still retaining excellent quality. We find that material thickness gradients during layer-by-layer growth result in surface roughness modulations across the whole wafer. Growth on such templates strongly influences the QD nucleation probability. We obtain density modulations between 1 and 10 QDs/µm2 and periods ranging from several millimeters down to at least a few hundred microns. This method is universal and expected to be applicable to a wide variety of different semiconductor material systems. We apply the method to enable growth of ultra-low noise QDs across an entire 3-inch semiconductor wafer.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Process-aid solid engineering triggers delicately modulation of Y-series non-fullerene acceptor for efficient organic solar cells},

author = {X Song and K Zhang and R Guo and K Sun and Z Zhou and S Huang and L Huber and M Reus and J Zhou and M Schwartzkopf and S V Roth and W Liu and Y Liu and W Zhu and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202200907},

doi = {https://doi.org/10.1002/adma.202200907},

issn = {0935-9648},

year  = {2022},

date = {2022-03-22},

journal = {Advanced Materials},

volume = {n/a},

number = {n/a},

pages = {2200907},

abstract = {Abstract Volatile solids with symmetric π-backbone have been intensively implemented on manipulating the nanomorphology for improving the operability and stability of organic solar cells. However, due to the isotropic stacking, the announced solids with symmetric geometry cannot modify the microscopic phase separation and component distribution collaboratively, which would constrain the promotion of exciton splitting and charge collection efficiency. Inspired by the superiorities of asymmetric configuration, a novel process-aid solid (PAS) engineering is proposed. By coupling with BTP core unit in Y-series molecule, an asymmetric, volatile 1, 3-dibromo-5-chlorobenzene (DBCl) solid can induce the anisotropic dipole direction, elevated dipole moment, and interlaminar interaction spontaneously. Due to the synergetic effects on the favorable phase separation and desired component distribution, the PAS treated devices feature the evident improvement of exciton splitting, charge transport, and collection, accompanied by the suppressed trap-assisted recombination. Consequently, we achieve an impressive fill factor of 80.2% with maximum power conversion efficiency (PCE) of 18.5% in the PAS treated device. More strikingly, the PAS treated devices demonstrate a promising thickness-tolerance character, where a record PCE of 17.0% is yielded in PAS devices with a 300 nm thickness photoactive layer, which represents the highest PCE for thick-film OSCs. This article is protected by copyright. All rights reserved},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Hydrophobic Graphene Quantum Dots for Defect Passivation and Enhanced Moisture Stability of CH3NH3PbI3 Perovskite Solar Cells},

author = {E Khorshidi and B Rezaei and D Bl\"{a}tte and A Buyruk and M A Reus and J Hanisch and B B\"{o}ller and P M\"{u}ller-Buschbaum and T Ameri},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/solr.202200023},

doi = {https://doi.org/10.1002/solr.202200023},

issn = {2367-198X},

year  = {2022},

date = {2022-03-19},

journal = {Solar RRL},

volume = {n/a},

number = {n/a},

pages = {2200023},

abstract = {Passivating the defects and grain boundaries (GBs) of perovskite films at the interface by interface engineering is a promising route to achieve efficient and stable perovskite solar cells (PSCs). Herein, a new type of graphene, that is, hydrophobic graphene quantum dots (HGQDs) containing amide linkages, which consist of carbonyl and dodecyl amine groups, is successfully used as a bifunctional interface modifier to engineer the interface of the perovskite/hole transport layer. A comprehensive characterization including X-ray photoelectron spectroscopy, Fourier-transform photocurrent spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and space-charge-limited current measurements is performed to identify the underlying passivation mechanisms. It can be demonstrated that the HGQDs, due to the bifunctional groups containing N and O atoms, effectively passivate the uncoordinated Pb2+ ions at the perovskite film surface and GBs and consequently induce a lower trap state density. Moreover, HGQDs enhance the quality of the perovskite film which reduces the charge recombination at the interface. Therefore, the power conversion efficiency of PSCs treated with HGQDs is significantly increased from 16.00% to 18.30%, mainly based on the improved open-circuit voltage and fill factor. Importantly, the HGQDs featuring hydrophobicity due to alkyl chains significantly enhance moisture stability.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Scalable, Highly Crystalline, 2D Semiconductor Atomic Layer Deposition Process for High Performance Electronic Applications},

author = {N Aspiotis and K Morgan and B M\"{a}rz and K M\"{u}ller-Caspary and M Ebert and C-C Huang and D W Hewak and S Majumdar and I Zeimpekis},

url = {https://arxiv.org/abs/2203.10309},

doi = {https://doi.org/10.48550/arXiv.2203.10309},

year  = {2022},

date = {2022-03-19},

journal = {arXiv preprint arXiv:2203.10309},

abstract = {This work demonstrates a large area process for atomically thin 2D semiconductors to unlock the technological upscale required for their commercial uptake. The new atomic layer deposition (ALD) and conversion technique yields large area performance uniformity and tunability. Like graphene, 2D Transition Metal Dichalcogenides (TMDCs) are prone to upscaling challenges limiting their commercial uptake. They are challenging to grow uniformly on large substrates and to transfer on alternative substrates while they often lack in large area electrical performance uniformity. The scalable ALD process of this work enables uniform growth of 2D TMDCs on large area with independent control of layer thickness, stoichiometry and crystallinity while allowing chemical free transfers to application substrates. Field effect transistors (FETs) fabricated on flexible substrates using the process present a field effect mobility of up to 55 cm^2/Vs, subthreshold slope down to 80 mV/dec and on/off ratios of 10^7. Additionally, non-volatile memory transistors using ferroelectric FETs (FeFETs) operating at +-5 V with on/off ratio of 107 and a memory window of 3.25 V are demonstrated. These FeFETs demonstrate state-of-the-art performance with multiple state switching, suitable for one-transistor non-volatile memory and for synaptic transistors revealing the applicability of the process to flexible neuromorphic applications.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electron\textendashHole Binding Governs Carrier Transport in Halide Perovskite Nanocrystal Thin Films},

author = {M F Lichtenegger and J Drewniok and A Bornschlegl and C Lampe and A Singldinger and N A Henke and A S Urban},

url = {https://doi.org/10.1021/acsnano.2c00369},

doi = {10.1021/acsnano.2c00369},

issn = {1936-0851},

year  = {2022},

date = {2022-03-18},

journal = {ACS Nano},

abstract = {Two-dimensional halide perovskite nanoplatelets (NPLs) have exceptional light-emitting properties, including wide spectral tunability, ultrafast radiative decays, high quantum yields (QY), and oriented emission. Due to the high binding energies of electron\textendashhole pairs, excitons are generally considered the dominant species responsible for carrier transfer in NPL films. To realize efficient devices, it is imperative to understand how exciton transport progresses therein. We employ spatially and temporally resolved optical microscopy to map exciton diffusion in perovskite nanocrystal (NC) thin films between 15 °C and 55 °C. At room temperature (RT), we find the diffusion length to be inversely correlated to the thickness of the nanocrystals (NCs). With increasing temperatures, exciton diffusion declines for all NC films, but at different rates. This leads to specific temperature turnover points, at which thinner NPLs exhibit higher diffusion lengths. We attribute this anomalous diffusion behavior to the coexistence of excitons and free electron hole-pairs inside the individual NCs within our temperature range. The organic ligand shell surrounding the NCs prevents charge transfer. Accordingly, any time an electron\textendashhole pair spends in the unbound state reduces the FRET-mediated inter-NC transfer rates and, consequently, the overall diffusion. These results clarify how exciton diffusion progresses in strongly confined halide perovskite NC films, emphasizing critical considerations for optoelectronic devices.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Finding efficient catalyst designs: A high-precision method to reveal active sites},

author = {R W Haid and R M Kluge and T O Schmidt and A S Bandarenka},

url = {https://www.sciencedirect.com/science/article/pii/S2667109322001695},

doi = {https://doi.org/10.1016/j.checat.2022.03.024},

issn = {2667-1093},

year  = {2022},

date = {2022-03-16},

journal = {Chem Catalysis},

volume = {2},

number = {4},

pages = {657-659},

abstract = {Designing efficient electrocatalytic structures requires reliable guidelines. For this purpose, experimental approaches for the characterization of model electrodes in operando conditions are valuable. Reporting in Joule, Agnoli et al. showcase the determination of site-specific reaction onset potentials and Tafel slopes by using electrochemical scanning tunneling microscopy.},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}