O Bienek, B Fuchs, M Kuhl, T Rieth, J Kühne, L I Wagner, L M Todenhagen, L Wolz, A Henning, I D Sharp
Engineering Defects and Interfaces of Atomic Layer-Deposited TiOx-Protective Coatings for Efficient III–V Semiconductor Photocathodes Journal Article
In: ACS Photonics, vol. 10, no. 11, pp. 3985-3997, 0000.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Engineering Defects and Interfaces of Atomic Layer-Deposited TiOx-Protective Coatings for Efficient III\textendashV Semiconductor Photocathodes},
author = {O Bienek and B Fuchs and M Kuhl and T Rieth and J K\"{u}hne and L I Wagner and L M Todenhagen and L Wolz and A Henning and I D Sharp},
url = {https://doi.org/10.1021/acsphotonics.3c00818},
doi = {10.1021/acsphotonics.3c00818},
journal = {ACS Photonics},
volume = {10},
number = {11},
pages = {3985-3997},
abstract = {III\textendashV compound semiconductors offer optoelectronic properties that are well suited for the conversion of solar energy to chemical fuels. While such materials suffer from poor stability under photoelectrochemical (PEC) conditions, atomic layer deposition (ALD) of titanium oxide (TiOx) has emerged as a powerful approach for creating corrosion protection layers, thereby enabling efficient and robust interfaces. However, the role of defects within TiOx layers and at the semiconductor/TiOx interface on the PEC performance remains poorly understood and controlled. Here, we use p-type InP as a model III\textendashV semiconductor to investigate the impact of defects in ALD TiOx on junction formation, interfacial charge transport, and photocarrier recombination, which underpin characteristics of PEC devices. We show that defect concentrations in TiOx can be tuned over a broad range, resulting in significant modulation of the optical constants, electrical conductivity, and interface chemistry. While plasma-enhanced ALD yields films with low midgap-state concentrations, it introduces series resistance losses due to oxidation of the substrate. In contrast, thermal ALD suppresses interface oxidation but leads to electronically active defect states within the band gap of TiOx. By controlling these defect states, the nature of junction formation can be tuned, and high photovoltage photocathodes can be achieved. In particular, ALD TiOx layers possessing high carrier concentrations form buried InP/TiOx pn heterojunctions, whereas less defective layers preserve semiconductor/electrolyte junction energetics to achieve large photovoltages and applied bias photon-to-current efficiencies. These results highlight the power of ALD for engineering photoelectrode interfaces and provide a new route for tailoring the junction formation between buried and PEC junctions.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
S Caicedo-Dávila, A Cohen, S G Motti, M Isobe, K M Mccall, M V Kovalenko, O Yaffe, L M Herz, D H Fabini, D A Egger
Disentangling the Effects of Structure and Lone-Pair Electrons in the Lattice Dynamics of Halide Perovskites Journal Article
In: arXiv preprint arXiv:2310.03408, 0000.
Abstract | Links | Tags: Foundry Organic
@article{nokey,
title = {Disentangling the Effects of Structure and Lone-Pair Electrons in the Lattice Dynamics of Halide Perovskites},
author = {S Caicedo-D\'{a}vila and A Cohen and S G Motti and M Isobe and K M Mccall and M V Kovalenko and O Yaffe and L M Herz and D H Fabini and D A Egger},
url = {https://arxiv.org/abs/2310.03408},
doi = {https://doi.org/10.48550/arXiv.2310.03408},
journal = {arXiv preprint arXiv:2310.03408},
abstract = {Metal halide perovskites have shown great performance as solar energy materials, but their outstanding optoelectronic properties are paired with unusually strong anharmonic effects. It has been proposed that this intriguing combination of properties derives from the "lone pair" electrons of the octahedral metal cations, but the precise impact of this chemical feature remains unclear. Here we show that in fact a lone pair of electrons is not a prerequisite for the strong anharmonicity and low-energy lattice dynamics encountered in this class of materials. We combine X-ray diffraction, infrared and Raman spectroscopies, and first-principles molecular dynamics calculations to directly contrast the lattice dynamics of CsSrBr3 with those of CsPbBr3, two compounds which bear close structural similarity but with the former lacking lone pairs on the octahedral metal. We exploit low-frequency diffusive Raman scattering, nominally symmetry-forbidden in the cubic phase, as a fingerprint to detect anharmonicity and reveal that low-frequency tilting occurs irrespective of lone pair presence. This work highlights the key role of structure in perovskite lattice dynamics, providing important design rules for the emerging class of soft perovskite semiconductors for optoelectronic and light-harvesting devices.},
keywords = {Foundry Organic},
pubstate = {published},
tppubtype = {article}
}
M Christis, A Henning, J D Bartl, A Zeidler, B Rieger, M Stutzmann, I D Sharp
Annealing-Free Ohmic Contacts to n-Type GaN via Hydrogen Plasma-Assisted Atomic Layer Deposition of Sub-Nanometer AlOx Journal Article
In: Advanced Materials Interfaces, vol. n/a, no. n/a, pp. 2300758, 0000, ISSN: 2196-7350.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {Annealing-Free Ohmic Contacts to n-Type GaN via Hydrogen Plasma-Assisted Atomic Layer Deposition of Sub-Nanometer AlOx},
author = {M Christis and A Henning and J D Bartl and A Zeidler and B Rieger and M Stutzmann and I D Sharp},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/admi.202300758},
doi = {https://doi.org/10.1002/admi.202300758},
issn = {2196-7350},
journal = {Advanced Materials Interfaces},
volume = {n/a},
number = {n/a},
pages = {2300758},
abstract = {Abstract A plasma-assisted atomic layer deposition (PE-ALD) process is reported for creating ohmic contacts to n-type GaN that combines native oxide reduction, near-surface doping, and encapsulation of GaN in a single processing step, thereby eliminating the need for both wet chemical etching of the native oxide before metallization and thermal annealing after contact formation. Repeated ALD cycling of trimethyl aluminum (TMA) and high-intensity hydrogen (H2) plasma results in the deposition of a sub-nanometer-thin (≈8 r{A}) AlOx layer via the partial transformation of the GaN surface oxide into AlOx. Hydrogen plasma-induced nitrogen vacancies in the near-surface region of GaN serve as shallow donors, promoting efficient out-of-plane electrical transport. Subsequent metallization with a Ti/Al/Ti/Au stack results in low contact resistance, ohmic behavior, and smooth morphology without requiring annealing. This electrical contracting approach thus meets the thermal budget requirements for Si-based complementary metal\textendashoxide\textendashsemiconductor structures and can facilitate the design and fabrication of advanced GaN-on-Si heterodevices.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
H Dong, G Shen, Y Zou, Y Li, Z Lin, Q Cai, X Xu, Q Song, H Duan, P Müller-Buschbaum, C Mu
Synergistic Defect Passivation by Metformin Halides for Improving Perovskite Solar Cell Performance Journal Article
In: The Journal of Physical Chemistry C, vol. 127, no. 25, pp. 11845-11853, 0000, ISSN: 1932-7447.
Abstract | Links | Tags: Foundry Inorganic
@article{nokey,
title = {Synergistic Defect Passivation by Metformin Halides for Improving Perovskite Solar Cell Performance},
author = {H Dong and G Shen and Y Zou and Y Li and Z Lin and Q Cai and X Xu and Q Song and H Duan and P M\"{u}ller-Buschbaum and C Mu},
url = {https://doi.org/10.1021/acs.jpcc.3c02121},
doi = {10.1021/acs.jpcc.3c02121},
issn = {1932-7447},
journal = {The Journal of Physical Chemistry C},
volume = {127},
number = {25},
pages = {11845-11853},
abstract = {Defect passivation plays a critical role in manufacturing high-performance perovskite solar cells (PSCs). Herein, engineered components of metformin halides are introduced to the bulk and surface of perovskite layers in PSCs to realize synergistic defect passivation. It is found that the bulk addition of metformin hydrochloride influences the orientation distribution of perovskite crystals and contributes to better perovskite films. Further, the modification of metformin iodide could treat residual defects on the surface of perovskite films. As a result, the synergistically passivated PSCs shows an improved power conversion efficiency (PCE), which increased from 19.36% to 22.17%, together with a higher short-circuit current and open-circuit voltage than those of the control device. Moreover, the as-treated PSCs exhibit excellent thermal and humidity stabilities, maintaining 95% of their initial PCE after being stored under air conditions for over 1000 h. This work provides a novel strategy to passivate perovskite defects and improve the PCE and stability of PSCs.},
keywords = {Foundry Inorganic},
pubstate = {published},
tppubtype = {article}
}
M Duportal, L M Berger, S A Maier, A Tittl, K Krischer
In: arXiv preprint arXiv:2307.10951, 0000.
Abstract | Links | Tags: Solid-Liquid
@article{nokey,
title = {Multi-band metasurface-driven surface-enhanced infrared absorption spectroscopy for improved characterization of in-situ electrochemical reactions},
author = {M Duportal and L M Berger and S A Maier and A Tittl and K Krischer},
url = {https://arxiv.org/abs/2307.10951},
doi = {https://doi.org/10.48550/arXiv.2307.10951},
journal = {arXiv preprint arXiv:2307.10951},
abstract = {Surface-enhanced spectroscopy techniques are the method-of-choice to characterize adsorbed intermediates occurring during electrochemical reactions, which are crucial in realizing a green sustainable future. Characterizing species with low coverages or short lifetimes have so far been limited by low signal enhancement. Recently, metasurface-driven surface-enhanced infrared absorption spectroscopy (SEIRAS) has been pioneered as a promising narrowband technology to study single vibrational modes of electrochemical interfaces during CO oxidation. However, many reactions involve several species or configurations of adsorption that need to be monitored simultaneously requiring reproducible and broadband sensing platforms to provide a clear understanding of the underlying electrochemical processes. Here, we experimentally realize multi-band metasurface-driven SEIRAS for the in-situ study of electrochemical CO2 reduction on a Pt surface. We develop an easily reproducible and spectrally-tunable platinum nano-slot metasurface. Two CO adsorption configurations at 2030 cm-1 and 1840 cm-1 are locally enhanced as a proof of concept that can be extended to more vibrational bands. Our platform provides a 41-fold enhancement in the detection of characteristic absorption signals compared to conventional broadband electrochemically roughened platinum films. A straightforward methodology is outlined starting by baselining our system in CO saturated environment and clearly detecting both configurations of adsorption, in particular the hitherto hardly detectable CO bridge configuration. Then, thanks to the signal enhancement provided by our platform, we find that the CO bridge configuration on platinum does not play a significant role during CO2 reduction in an alkaline environment. We anticipate that our technology will guide researchers in developing similar sensing platforms.},
keywords = {Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
M Eder, M Tschurl, U Heiz
In: The Journal of Physical Chemistry Letters, vol. 14, no. 26, pp. 6193-6201, 0000.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Toward a Comprehensive Understanding of Photocatalysis: What Systematic Studies and Alcohol Surface Chemistry on TiO2(110) Have to Offer for Future Developments},
author = {M Eder and M Tschurl and U Heiz},
url = {https://doi.org/10.1021/acs.jpclett.3c00504},
doi = {10.1021/acs.jpclett.3c00504},
journal = {The Journal of Physical Chemistry Letters},
volume = {14},
number = {26},
pages = {6193-6201},
abstract = {Heterogeneous photocatalytic systems are usually described based on electrochemistry, which the vast majority of interpretations and strategies for optimizing photocatalysts rely on. Charge carrier dynamics are usually in the spotlight, whereas the surface chemistry of the photocatalyst is neglected. This is unjustified, because studies on alcohol photoreforming on metal-decorated rutile single crystals revealed that the electrochemical reaction model is not generally applicable. Hence, many photocatalytic reactions may proceed in a different manner and the thermal chemistry needs to be accounted for. The new mechanism is particularly relevant for reactions in gaseous environments in the absence of solvated ionic species. Here, we compare both mechanisms and highlight their differences and consequences for photocatalysis. Based on alcohol photochemistry, we demonstrate the importance of thermal reactions in photocatalytic mechanisms and the relevance of systematic studies in different environments for a holistic understanding of photocatalysis.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
K Endo, A Raza, L Yao, S Van Gele, A Rodríguez-Camargo, H Vignolo-González, L Grunenberg, B Lotsch
Downsizing Porphyrin Covalent Organic Framework Particles Using Protected Precursors for Electrocatalytic CO2 Reduction Journal Article
In: 0000.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {Downsizing Porphyrin Covalent Organic Framework Particles Using Protected Precursors for Electrocatalytic CO2 Reduction},
author = {K Endo and A Raza and L Yao and S Van Gele and A Rodr\'{i}guez-Camargo and H Vignolo-Gonz\'{a}lez and L Grunenberg and B Lotsch},
url = {https://chemrxiv.org/engage/chemrxiv/article-details/64d12052dfabaf06ffe07a6d},
doi = {10.26434/chemrxiv-2023-skm06},
abstract = {Covalent organic frameworks (COFs) are promising electrocatalyst platforms owing to their designability, porosity, and stability. Recently, COFs with various chemical structures were developed as efficient electrochemical CO2 reduction catalysts. However, controlling the morphology of COF catalysts remains a challenge, which can limit their electrocatalytic performance even if the chemical structure is optimally designed. Especially, while metalated porphyrinoids show great promise as catalytically active COF building blocks, their intermolecular stacking and coordination interactions make it difficult to conduct solution-based COF synthesis which can control the particle size dominated by the aggregation of crystallites. In this work, we report a new synthetic methodology for rationally downsized COF catalyst particles, where a tritylated amine is employed as a novel protected precursor for COF synthesis. Trityl protection provides high solubility to a representative cobalt porphyrin precursor, while its deprotection proceeds in situ under typical solvothermal COF synthesis conditions. This colloidal deprotection\textendashpolycondensation process yields smaller COF particles with less crystallite aggregation than a conventional synthesis, maintaining crystallinity and porosity. The downsized COF particles exhibit superior catalytic performance in electrochemical CO2 reduction, with higher CO production rate and faradaic efficiency with similar stability compared to conventional COF particles. The improved performance of downsized COF particles is attributed to the higher contact area with a conductive agent. This study provides a strategy for the preparation of COF electrocatalysts with controlled morphology and enhanced performance and also reveals an important factor in the evaluation of COF electrocatalysts.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
S Ezendam, J Gargiulo, A Sousa-Castillo, J B Lee, Y S Nam, S A Maier, E Cortés
Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis Journal Article
In: ACS Nano, 0000, ISSN: 1936-0851.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Spatial Distributions of Single-Molecule Reactivity in Plasmonic Catalysis},
author = {S Ezendam and J Gargiulo and A Sousa-Castillo and J B Lee and Y S Nam and S A Maier and E Cort\'{e}s},
url = {https://doi.org/10.1021/acsnano.3c07833},
doi = {10.1021/acsnano.3c07833},
issn = {1936-0851},
journal = {ACS Nano},
abstract = {Plasmonic catalysts have the potential to accelerate and control chemical reactions with light by exploiting localized surface plasmon resonances. However, the mechanisms governing plasmonic catalysis are not simple to decouple. Several plasmon-derived phenomena, such as electromagnetic field enhancements, temperature, or the generation of charge carriers, can affect the reactivity of the system. These effects are convoluted with the inherent (nonplasmonic) catalytic properties of the metal surface. Disentangling these coexisting effects is challenging but is the key to rationally controlling reaction pathways and enhancing reaction rates. This study utilizes super-resolution fluorescence microscopy to examine the mechanisms of plasmonic catalysis at the single-particle level. The reduction reaction of resazurin to resorufin in the presence of Au nanorods coated with a porous silica shell is investigated in situ. This allows the determination of reaction rates with a single-molecule sensitivity and subparticle resolution. By variation of the irradiation wavelength, it is possible to examine two different regimes: photoexcitation of the reactant molecules and photoexcitation of the nanoparticle’s plasmon resonance. In addition, the measured spatial distribution of reactivity allows differentiation between superficial and far-field effects. Our results indicate that the reduction of resazurin can occur through more than one reaction pathway, being most efficient when the reactant is photoexcited and is in contact with the Au surface. In addition, it was found that the spatial distribution of enhancements varies, depending on the underlying mechanism. These findings contribute to the fundamental understanding of plasmonic catalysis and the rational design of future plasmonic nanocatalysts.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
S Ezendam, L Nan, I L Violi, S A Maier, E Cortés, G Baffou, J Gargiulo
Anti Stokes Thermometry of Plasmonic Nanoparticle Arrays Journal Article
In: Advanced Optical Materials, vol. n/a, no. n/a, pp. 2301496, 0000, ISSN: 2195-1071.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Anti Stokes Thermometry of Plasmonic Nanoparticle Arrays},
author = {S Ezendam and L Nan and I L Violi and S A Maier and E Cort\'{e}s and G Baffou and J Gargiulo},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202301496},
doi = {https://doi.org/10.1002/adom.202301496},
issn = {2195-1071},
journal = {Advanced Optical Materials},
volume = {n/a},
number = {n/a},
pages = {2301496},
abstract = {Abstract Metallic nanoparticles possess strong photothermal responses, especially when illuminated as ensembles due to collective effects. However, accurately quantifying the temperature increase remains a significant challenge, impeding progress in several applications. Anti Stokes thermometry offers a promising solution by enabling direct and non-invasive temperature measurements of the metal without the need for labeling or prior calibration. While Anti Stokes thermometry is successfully applied to individual nanoparticles, its potential to study light-to-heat conversion with plasmonic ensembles remains unexplored. In this study, the theoretical framework and the conditions that must be fulfilled for applying Anti Stokes thermometry to ensembles of nanoparticles are discussed. Then, this technique is implemented to measure the light-induced heating of square arrays of Au nanodisks. The obtained temperature measurements are validated using wavefront microscopy, demonstrating excellent agreement between the two thermometry methods. These results showcase the extension of Anti Stokes thermometry to plasmonic ensembles, highlighting its potential for implementation in the diverse photothermal applications involving these systems.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
M J Feil, T L Maier, M Golibrzuch, A C Sterr, M Becherer, K Krischer
Characterization of Different Au/Electrolyte Interfaces via In Situ Differential Cyclic Plasmo-Voltammetry Journal Article
In: The Journal of Physical Chemistry C, vol. 127, no. 40, pp. 20137-20145, 0000, ISSN: 1932-7447.
Abstract | Links | Tags: Solid-Liquid
@article{nokey,
title = {Characterization of Different Au/Electrolyte Interfaces via In Situ Differential Cyclic Plasmo-Voltammetry},
author = {M J Feil and T L Maier and M Golibrzuch and A C Sterr and M Becherer and K Krischer},
url = {https://doi.org/10.1021/acs.jpcc.3c04727},
doi = {10.1021/acs.jpcc.3c04727},
issn = {1932-7447},
journal = {The Journal of Physical Chemistry C},
volume = {127},
number = {40},
pages = {20137-20145},
abstract = {In this article, we describe an improved method that uses in situ plasmonic spectroscopy to reliably track changes of the metal\textendashelectrolyte interface over a large potential window. Utilizing the specific sensitivity of the plasmonic resonance toward changes in the interfacial properties of nanoparticles (NPs), processes such as double-layer charging, surface oxidation/reduction, adsorption and desorption of anions, as well as metal under- and overpotential deposition are resolved. The main contributions to this signal are changes in the charge of the NPs and chemical interface damping due to the adsorbed species. We employ highly homogeneous macroscopic Au nanoarrays with controlled interfaces produced by lift-off nanoimprint lithography (LO-NIL) as the working electrodes for multiparticle differential cyclic plasmo-voltammetry (dCPV). First, plasmonic signals are recorded and compared to known electrochemical processes before the plasmonic signals are used to gain insights beyond those achievable by electrochemical means. These include observation of forced HSO4\textendash and H2PO4\textendash desorption by the onset of the Au oxidation and resolution of the different steps of the monolayer buildup during Cu underpotential deposition on Au.},
keywords = {Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
F A Freire-Moschovitis, R Rizzato, A Pershin, M R Schepp, R D Allert, L M Todenhagen, M S Brandt, A Gali, D B Bucher
The Role of Electrolytes in the Relaxation of Near-Surface Spin Defects in Diamond Journal Article
In: ACS Nano, vol. 17, no. 11, pp. 10474-10485, 0000, ISSN: 1936-0851.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {The Role of Electrolytes in the Relaxation of Near-Surface Spin Defects in Diamond},
author = {F A Freire-Moschovitis and R Rizzato and A Pershin and M R Schepp and R D Allert and L M Todenhagen and M S Brandt and A Gali and D B Bucher},
url = {https://doi.org/10.1021/acsnano.3c01298},
doi = {10.1021/acsnano.3c01298},
issn = {1936-0851},
journal = {ACS Nano},
volume = {17},
number = {11},
pages = {10474-10485},
abstract = {Quantum sensing with spin defects in diamond, such as the nitrogen vacancy (NV) center, enables the detection of various chemical species on the nanoscale. Molecules or ions with unpaired electronic spins are typically probed by their influence on the NV center’s spin relaxation. Whereas it is well-known that paramagnetic ions reduce the NV center’s relaxation time (T1), here we report on the opposite effect for diamagnetic ions. We demonstrate that millimolar concentrations of aqueous diamagnetic electrolyte solutions increase the T1 time of near-surface NV center ensembles compared to pure water. To elucidate the underlying mechanism of this surprising effect, single and double quantum NV experiments are performed, which indicate a reduction of magnetic and electric noise in the presence of diamagnetic electrolytes. In combination with ab initio simulations, we propose that a change in the interfacial band bending due to the formation of an electric double layer leads to a stabilization of fluctuating charges at the interface of an oxidized diamond. This work not only helps to understand noise sources in quantum systems but could also broaden the application space of quantum sensors toward electrolyte sensing in cell biology, neuroscience, and electrochemistry.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
J Gargiulo, M Herran, I L Violi, A Sousa-Castillo, L P Martinez, S Ezendam, M Barella, H Giesler, R Grzeschik, S Schlücker, S A Maier, F D Stefani, E Cortés
Impact of bimetallic interface design on heat generation in plasmonic Au/Pd nanostructures studied by single-particle thermometry Journal Article
In: Nature Communications, vol. 14, no. 1, pp. 3813, 0000, ISSN: 2041-1723.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Impact of bimetallic interface design on heat generation in plasmonic Au/Pd nanostructures studied by single-particle thermometry},
author = {J Gargiulo and M Herran and I L Violi and A Sousa-Castillo and L P Martinez and S Ezendam and M Barella and H Giesler and R Grzeschik and S Schl\"{u}cker and S A Maier and F D Stefani and E Cort\'{e}s},
url = {https://doi.org/10.1038/s41467-023-38982-9},
doi = {10.1038/s41467-023-38982-9},
issn = {2041-1723},
journal = {Nature Communications},
volume = {14},
number = {1},
pages = {3813},
abstract = {Localized surface plasmons are lossy and generate heat. However, accurate measurement of the temperature of metallic nanoparticles under illumination remains an open challenge, creating difficulties in the interpretation of results across plasmonic applications. Particularly, there is a quest for understanding the role of temperature in plasmon-assisted catalysis. Bimetallic nanoparticles combining plasmonic with catalytic metals are raising increasing interest in artificial photosynthesis and the production of solar fuels. Here, we perform single-particle thermometry measurements to investigate the link between morphology and light-to-heat conversion of colloidal Au/Pd nanoparticles with two different configurations: core\textendashshell and core-satellite. It is observed that the inclusion of Pd as a shell strongly reduces the photothermal response in comparison to the bare cores, while the inclusion of Pd as satellites keeps photothermal properties almost unaffected. These results contribute to a better understanding of energy conversion processes in plasmon-assisted catalysis.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
T Guan, W Chen, H Tang, D Li, X Wang, C L Weindl, Y Wang, Z Liang, S Liang, T Xiao, S Tu, S V Roth, L Jiang, P Müller-Buschbaum
Decoding the Self-Assembly Plasmonic Interface Structure in a PbS Colloidal Quantum Dot Solid for a Photodetector Journal Article
In: ACS Nano, vol. 17, no. 22, pp. 23010-23019, 0000, ISSN: 1936-0851.
Abstract | Links | Tags: Foundry Organic, Solid-Solid
@article{nokey,
title = {Decoding the Self-Assembly Plasmonic Interface Structure in a PbS Colloidal Quantum Dot Solid for a Photodetector},
author = {T Guan and W Chen and H Tang and D Li and X Wang and C L Weindl and Y Wang and Z Liang and S Liang and T Xiao and S Tu and S V Roth and L Jiang and P M\"{u}ller-Buschbaum},
url = {https://doi.org/10.1021/acsnano.3c08526},
doi = {10.1021/acsnano.3c08526},
issn = {1936-0851},
journal = {ACS Nano},
volume = {17},
number = {22},
pages = {23010-23019},
abstract = {Hybrid plasmonic nanostructures have gained enormous attention in a variety of optoelectronic devices due to their surface plasmon resonance properties. Self-assembled hybrid metal/quantum dot (QD) architectures offer a means of coupling the properties of plasmonics and QDs to photodetectors, thereby modifying their functionality. The arrangement and localization of hybrid nanostructures have an impact on exciton trapping and light harvesting. Here, we present a hybrid structure consisting of self-assembled gold nanospheres (Au NSs) embedded in a solid matrix of PbS QDs for mapping the interface structures and the motion of charge carriers. Grazing-incidence small-angle X-ray scattering is utilized to analyze the localization and spacing of the Au NSs within the hybrid structure. Furthermore, by correlating the morphology of the Au NSs in the hybrid structure with the corresponding differences observed in the performance of photodetectors, we are able to determine the impact of interface charge carrier dynamics in the coupling structure. From the perspective of architecture, our study provides insights into the performance improvement of optoelectronic devices.},
keywords = {Foundry Organic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
R Guo, X Wang, X Jia, X Guo, J Li, Z Li, K Sun, X Jiang, E Alvianto, Z Shi, M Schwartzkopf, P Müller-Buschbaum, Y Hou
Refining the Substrate Surface Morphology for Achieving Efficient Inverted Perovskite Solar Cells Journal Article
In: Advanced Energy Materials, vol. 13, no. 43, pp. 2302280, 0000, ISSN: 1614-6832.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Refining the Substrate Surface Morphology for Achieving Efficient Inverted Perovskite Solar Cells},
author = {R Guo and X Wang and X Jia and X Guo and J Li and Z Li and K Sun and X Jiang and E Alvianto and Z Shi and M Schwartzkopf and P M\"{u}ller-Buschbaum and Y Hou},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202302280},
doi = {https://doi.org/10.1002/aenm.202302280},
issn = {1614-6832},
journal = {Advanced Energy Materials},
volume = {13},
number = {43},
pages = {2302280},
abstract = {Abstract Significant advancements in perovskite solar cells (PSCs) have been driven by the engineering of the interface between perovskite absorbers and charge transport layers. Inverted PSCs offer substantial potential with their high power conversion efficiency (PCE) and enhanced compatibility for tandem solar cell applications. Conventional hole transport materials like poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and poly(triaryl amine) (PTAA) not only constrain the PSC efficiency but also elevate their fabrication costs. In the case of improving inverted structured PSCs according to the aforementioned concerns, utilizing self-assembled monolayers (SAMs) as hole-transporting layers has played a crucial role. However, the growth of self-assembled monolayers on the substrates still limits the performance and reproducibility of inverted structured PSCs. In this study, the authors delve into the growth model of SAMs on different surface morphologies. Moreover, it is found that the plasma treatment can effectively regulate the surface morphologies of substrates and achieve conformal growth of SAMs. This treatment improves the uniformity and suppresses non-radiative recombination at the interface, which leads to a PCE of 24.5% (stabilized at 23.5%) for inverted structured PSCs.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
F Haimerl, S Kumar, M Heere, A S Bandarenka
Electrochemical impedance spectroscopy of PEM fuel cells at low hydrogen partial pressures: efficient cell tests for mass production Journal Article
In: Industrial Chemistry & Materials, 0000, ISSN: 2755-2608.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Electrochemical impedance spectroscopy of PEM fuel cells at low hydrogen partial pressures: efficient cell tests for mass production},
author = {F Haimerl and S Kumar and M Heere and A S Bandarenka},
url = {http://dx.doi.org/10.1039/D3IM00075C},
doi = {10.1039/D3IM00075C},
issn = {2755-2608},
journal = {Industrial Chemistry \& Materials},
abstract = {Quality testing costs hinder the large-scale production of PEM fuel cell systems due to long testing times and high safety measures for hydrogen. While eliminating both issues, electrochemical impedance spectroscopy at low hydrogen concentrations can provide valuable insights into fuel cell processes. However, the influence of high anode stream dilutions on PEM fuel cell performance is not yet completely understood. This study presents a new equivalent circuit model to analyze impedance spectra at low hydrogen partial pressures. The proposed model accurately describes the impedance response and explains the performance decrease at low hydrogen concentrations. First, the reduced availability of hydrogen at the anode leads to rising reaction losses from the hydrogen side. Further, the resulting losses lead to potential changes also influencing the cathode processes. The findings indicate that impedance spectroscopy at low hydrogen partial pressure might provide a reliable fuel cell quality control tool, simplifying production processes, reducing costs, and mitigating risks in fuel cell production. Keywords: PEM fuel cells; Electrochemical impedance spectroscopy; EIS; Large scale PEMFC production; Anodes; Cathodes.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
M Herran, S Juergensen, M Kessens, D Hoeing, A Köppen, A Sousa-Castillo, W J Parak, H Lange, S Reich, F Schulz, E Cortés
Plasmonic bimetallic two-dimensional supercrystals for H2 generation Journal Article
In: Nature Catalysis, vol. 6, no. 12, pp. 1205-1214, 0000, ISSN: 2520-1158.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Plasmonic bimetallic two-dimensional supercrystals for H2 generation},
author = {M Herran and S Juergensen and M Kessens and D Hoeing and A K\"{o}ppen and A Sousa-Castillo and W J Parak and H Lange and S Reich and F Schulz and E Cort\'{e}s},
url = {https://doi.org/10.1038/s41929-023-01053-9},
doi = {10.1038/s41929-023-01053-9},
issn = {2520-1158},
journal = {Nature Catalysis},
volume = {6},
number = {12},
pages = {1205-1214},
abstract = {Sunlight-driven H2 generation is a central technology to tackle our impending carbon-based energy collapse. Colloidal photocatalysts consisting of plasmonic and catalytic nanoparticles are promising for H2 production at solar irradiances, but their performance is hindered by absorption and multiscattering events. Here we present a two-dimensional bimetallic catalyst by incorporating platinum nanoparticles into a well-defined supercrystal of gold nanoparticles. The bimetallic supercrystal exhibited an H2 generation rate of $$139,mathrmmmol,mathrmg_mathrmcat^-1,mathrmh^-1$$via formic acid dehydrogenation under visible light illumination and solar irradiance. This configuration makes it possible to study the interaction between the two metallic materials and the influence of this in catalysis. We observe a correlation between the intensity of the electric field in the hotspots and the boosted catalytic activity of platinum nanoparticles, while identifying a minor role of heat and gold-to-platinum charge transfer in the enhancement. Our results demonstrate the benefits of two-dimensional configurations with optimized architecture for liquid-phase photocatalysis.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
R Hooijer, A Weis, W Kaiser, A Biewald, P Dörflinger, C Maheu, O Arsatiants, D Helminger, V Dyakonov, A Hartschuh, E Mosconi, F De Angelis, T Bein
Cu/Ag–Sb–I Rudorffite Thin Films for Photovoltaic Applications Journal Article
In: Chemistry of Materials, vol. 35, no. 23, pp. 9988-10000, 0000, ISSN: 0897-4756.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {Cu/Ag\textendashSb\textendashI Rudorffite Thin Films for Photovoltaic Applications},
author = {R Hooijer and A Weis and W Kaiser and A Biewald and P D\"{o}rflinger and C Maheu and O Arsatiants and D Helminger and V Dyakonov and A Hartschuh and E Mosconi and F De Angelis and T Bein},
url = {https://doi.org/10.1021/acs.chemmater.3c01837},
doi = {10.1021/acs.chemmater.3c01837},
issn = {0897-4756},
journal = {Chemistry of Materials},
volume = {35},
number = {23},
pages = {9988-10000},
abstract = {In the search for lead-free perovskites, silver pnictohalides recently gained attention as novel perovskite-inspired materials for photovoltaics due to their high stability, low toxicity, and promising early efficiencies, especially for indoor applications. Recent research on such “rudorffites” mainly addresses silver bismuth iodides (Ag\textendashBi\textendashI), while their antimony analogues are hardly investigated due to intrinsic challenges in the synthesis of Sb-based thin films. Here, we establish a synthetic route to prepare Ag\textendashSb\textendashI thin films by employing thiourea as a Lewis-base additive. Thin film morphologies were further optimized by alloying them with Cu, resulting in solar cells with an improved power conversion efficiency of 0.7% by reducing undesired side phases. Density functional theory calculations and optical characterization methods support the incorporation of Cu into a Cu1\textendashxAgxSbI4 phase, keeping the overall stoichiometry and band gap virtually unchanged upon alloying. Our results further reveal the detrimental role of Ag point defects representing trap states in the band gap, being responsible for low open-circuit voltages and subgap absorption and emission features. Moreover, additional minor amounts of Bi are shown to boost the efficiency and stabilize the performance over a wider compositional range. Despite the remaining challenges regarding device performance, we demonstrate a strong increase in external quantum efficiency when reducing the light intensity, highlighting the potential of Ag\textendashSb\textendashI rudorffites for indoor photovoltaics.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
N G Hörmann, S D Beinlich, K Reuter
Converging Divergent Paths: Constant Charge vs. Constant Potential Energetics in Computational Electrochemistry Journal Article
In: arXiv preprint arXiv:2312.00911, 0000.
Abstract | Links | Tags: Solid-Liquid
@article{nokey,
title = {Converging Divergent Paths: Constant Charge vs. Constant Potential Energetics in Computational Electrochemistry},
author = {N G H\"{o}rmann and S D Beinlich and K Reuter},
url = {https://arxiv.org/abs/2312.00911},
doi = {https://doi.org/10.48550/arXiv.2312.00911},
journal = {arXiv preprint arXiv:2312.00911},
abstract = {Using the example of a proton adsorption process, we analyze and compare two prominent modelling approaches in computational electrochemistry at metallic electrodes - electronically canonical, constant-charge and electronically grand-canonical, constant-potential calculations. We first confirm that both methodologies yield consistent results for the differential free energy change in the infinite cell size limit. This validation emphasizes that, fundamentally, both methods are equally valid and precise. In practice, the grand-canonical, constant-potential approach shows superior interpretability and size convergence as it aligns closer to experimental ensembles and exhibits smaller finite-size effects. On the other hand, constant-charge calculations exhibit greater resilience against discrepancies, such as deviations in interfacial capacitance and absolute potential alignment, as their results inherently only depend on the surface charge, and not on the modelled charge vs. potential relation. The present analysis thus offers valuable insights and guidance for selecting the most appropriate ensemble when addressing diverse electrochemical challenges.},
keywords = {Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
P Hosseini, A Rodríguez-Camargo, L Yao, B Lotsch, K Tschulik
Identifying the active species in a cobalt-based covalent organic framework for the electrochemical oxygen evolution reaction Journal Article
In: 0000.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {Identifying the active species in a cobalt-based covalent organic framework for the electrochemical oxygen evolution reaction},
author = {P Hosseini and A Rodr\'{i}guez-Camargo and L Yao and B Lotsch and K Tschulik},
url = {https://chemrxiv.org/engage/chemrxiv/article-details/650cfd18b927619fe79761cb},
doi = {10.26434/chemrxiv-2023-7dl21},
abstract = {While considerable efforts have been devoted to developing functionalized covalent organic frameworks (COFs) as oxygen evolution electrocatalysts in recent years, studies related to the identification of the true catalytically active species for the oxygen evolution reaction (OER) remain lacking in the field. In this work, we investigated the active species of a cobalt-functionalized COF (TpBpy-Co) as electrochemical OER catalyst through a series of electrochemical measurements and post-electrolysis characterizations. Our results demonstrate that Co(II) ions, coordinated to the COF backbone, are transformed to cobalt-based nanoparticles when exposing TpBpy-Co to alkaline media. These nanoparticles act as the true active species for oxygen evolution. It remains unclear whether intact TpBpy-Co acts as a secondary catalytic species, due to its structural instability in alkaline electrolyte and its inferred lower catalytic activity compared to cobalt-based nanoparticles. Our results highlight that caution is warranted when identifying the active species for COF electrocatalysts formed under catalyst working conditions. Specifically, strong coordination between COFs and metal centers under electrochemical operation conditions is crucial to avoid unintended transformation of COF electrocatalysts. Our study thus contributes to the rational development of earth-abundant COF OER catalysts for the production of green hydrogen from renewable resources.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
A Hötger, W Männer, T Amit, D Hernangómez-Pérez, T Taniguchi, K Watanabe, U Wurstbauer, J J Finley, S Refaely-Abramson, C Kastl, A W Holleitner
Photovoltage and Photocurrent Absorption Spectra of Sulfur Vacancies Locally Patterned in Monolayer MoS2 Journal Article
In: Nano Letters, 0000, ISSN: 1530-6984.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Photovoltage and Photocurrent Absorption Spectra of Sulfur Vacancies Locally Patterned in Monolayer MoS2},
author = {A H\"{o}tger and W M\"{a}nner and T Amit and D Hernang\'{o}mez-P\'{e}rez and T Taniguchi and K Watanabe and U Wurstbauer and J J Finley and S Refaely-Abramson and C Kastl and A W Holleitner},
url = {https://doi.org/10.1021/acs.nanolett.3c03517},
doi = {10.1021/acs.nanolett.3c03517},
issn = {1530-6984},
journal = {Nano Letters},
abstract = {We report on the optical absorption characteristics of selectively positioned sulfur vacancies in monolayer MoS2, as observed by photovoltage and photocurrent experiments in an atomistic vertical tunneling circuit at cryogenic and room temperature. Charge carriers are resonantly photoexcited within the defect states before they tunnel through an hBN tunneling barrier to a graphene-based drain contact. Both photovoltage and photocurrent characteristics confirm the optical absorption spectrum as derived from ab initio GW and Bethe\textendashSalpeter equation approximations. Our results reveal the potential of single-vacancy tunneling devices as atomic-scale photodiodes.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
H Hu, A K Pal, A Berestennikov, T Weber, A Stefancu, E Cortes, S A Maier, A Tittl
Semiconductor Metasurfaces for Surface-enhanced Raman Scattering Journal Article
In: arXiv preprint arXiv:2309.10732, 0000.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Semiconductor Metasurfaces for Surface-enhanced Raman Scattering},
author = {H Hu and A K Pal and A Berestennikov and T Weber and A Stefancu and E Cortes and S A Maier and A Tittl},
url = {https://arxiv.org/abs/2309.10732},
doi = {https://doi.org/10.48550/arXiv.2309.10732},
journal = {arXiv preprint arXiv:2309.10732},
abstract = {Semiconductor-based surface-enhanced Raman spectroscopy (SERS) substrates, as a new frontier in the field of SERS, are hindered by their poor electromagnetic field confinement, and weak light-matter interaction. Metasurfaces, a class of 2D artificial materials based on the electromagnetic design of nanophotonic resonators, enable strong electromagnetic field enhancement and optical absorption engineering for a wide range of semiconductor materials. However, the engineering of semiconductor substrates into metasurfaces for improving SERS activity remains underexplored. Here, we develop an improved SERS metasurface platform that leverages the combination of titanium oxide (TiO2) and the emerging physical concept of optical bound states in the continuum (BICs) to boost the Raman emission. Moreover, fine-tuning of BIC-assisted resonant absorption offers a pathway for maximizing the photoinduced charge transfer effect (PICT) in SERS. We achieve ultrahigh values of BIC-assisted electric field enhancement (|E/E0|^2 ~ 10^3), challenging the preconception of weak electromagnetic (EM) field enhancement on semiconductor SERS substrates. Our BIC-assisted TiO2 metasurface platform offers a new dimension in spectrally-tunable SERS with earth-abundant and bio-compatible semiconductor materials, beyond the traditional plasmonic ones.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
R Jiang, T Tian, B Ke, Z Kou, P Müller-Buschbaum, F Huang, Y-B Cheng, T Bu
Insights into the effects of oriented crystallization on the performance of quasi-two-dimensional perovskite solar cells Journal Article
In: Next Materials, vol. 1, no. 4, pp. 100044, 0000, ISSN: 2949-8228.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Insights into the effects of oriented crystallization on the performance of quasi-two-dimensional perovskite solar cells},
author = {R Jiang and T Tian and B Ke and Z Kou and P M\"{u}ller-Buschbaum and F Huang and Y-B Cheng and T Bu},
url = {https://www.sciencedirect.com/science/article/pii/S2949822823000448},
doi = {https://doi.org/10.1016/j.nxmate.2023.100044},
issn = {2949-8228},
journal = {Next Materials},
volume = {1},
number = {4},
pages = {100044},
abstract = {Long-term operational stability is one of the key problems for the commercialization of the perovskite photovoltaics. During the past decade, a tremendous amount of work has aimed at addressing the stability issues of perovskite solar cells (PSCs). Among them, the intrinsic instability of the ionic crystal structure of perovskite materials is foremost where proper strategies are highly required to complete the crystallization. Reducing the dimensional structure of the photoactive three-dimensional (3D) perovskites by the introduction of a non-photoactive two-dimensional (2D) perovskite phase is a rising topic recently, which generates a quasi-2D perovskite for improving the corresponding device stability. However, the power conversion efficiency (PCE) of quasi-2D perovskite solar cells decreases unfortunately with the increase of the 2D contents, which obviously depends on the orientation of the crystals. In this review, we first review the effect of the crystal orientation on the performance of quasi-2D PSCs. Then, the growth mechanism of the preferred crystal orientation is discussed in detail. The research progress of the modulation strategies which are key segments for the preferred oriented growth of quasi-2D perovskite crystals is summarized emphatically. Finally, we identify some challenges and opportunities for chasing efficient quasi-2D PSCs in furthering our understanding of the above themes.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
H Jin, M Herran, E Cortés, J Lischner
Theory of Hot-Carrier Generation in Bimetallic Plasmonic Catalysts Journal Article
In: ACS Photonics, vol. 10, no. 10, pp. 3629-3636, 0000.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Theory of Hot-Carrier Generation in Bimetallic Plasmonic Catalysts},
author = {H Jin and M Herran and E Cort\'{e}s and J Lischner},
url = {https://doi.org/10.1021/acsphotonics.3c00715},
doi = {10.1021/acsphotonics.3c00715},
journal = {ACS Photonics},
volume = {10},
number = {10},
pages = {3629-3636},
abstract = {Bimetallic nanoreactors in which a plasmonic metal is used to funnel solar energy toward a catalytic metal have recently been studied experimentally, but a detailed theoretical understanding of these systems is lacking. Here, we present theoretical results of hot-carrier generation rates of different Au\textendashPd nanoarchitectures. In particular, we study spherical core\textendashshell nanoparticles with a Au core and a Pd shell as well as antenna\textendashreactor systems consisting of a large Au nanoparticle that acts as an antenna and a smaller Pd satellite nanoparticle separated by a gap. In addition, we investigate an antenna\textendashreactor system in which the satellite is a core\textendashshell nanoparticle. Hot-carrier generation rates are obtained from an atomistic quantum-mechanical modeling technique which combines a solution of Maxwell’s equation with a tight-binding description of the nanoparticle electronic structure. We find that antenna\textendashreactor systems exhibit significantly higher hot-carrier generation rates in the catalytic material than the core\textendashshell system as a result of strong electric field enhancements associated with the gap between the antenna and the satellite. For these systems, we also study the dependence of the hot-carrier generation rate on the size of the gap, the radius of the antenna nanoparticle, and the direction of light polarization. Overall, we find a strong correlation between the calculated hot-carrier generation rates and the experimentally measured chemical activity for the different Au\textendashPd photocatalysts. Our insights pave the way toward a microscopic understanding of hot-carrier generation in heterogeneous nanostructures for photocatalysis and other energy-conversion applications.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
Z Kang, Y Tong, K Wang, Y Chen, P Yan, G Pan, P Müller-Buschbaum, L Zhang, Y Yang, J Wu, H Xie, S Liu, H Wang
Tailoring Low-Dimensional Phases for Improved Performance of 2D–3D Tin Perovskite Solar Cells Journal Article
In: ACS Materials Letters, pp. 1-9, 0000.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Tailoring Low-Dimensional Phases for Improved Performance of 2D\textendash3D Tin Perovskite Solar Cells},
author = {Z Kang and Y Tong and K Wang and Y Chen and P Yan and G Pan and P M\"{u}ller-Buschbaum and L Zhang and Y Yang and J Wu and H Xie and S Liu and H Wang},
url = {https://doi.org/10.1021/acsmaterialslett.3c00929},
doi = {10.1021/acsmaterialslett.3c00929},
journal = {ACS Materials Letters},
pages = {1-9},
abstract = {2D\textendash3D tin perovskites are considered as promising candidates for realizing efficient lead-free perovskite solar cells (PSCs). However, the ultrathin 2D phases could unfavorably affect charge transport and device performance. In the present work, we demonstrate that the introduction of D-homoserine lactone hydrochloride (D-HLH) can tailor the low-dimensional phases and improve the quality of 2D\textendash3D tin perovskite films. The functional group in D-HLH can interact with FA+ and I\textendash as well as Sn2+ in the precursor solution. These interactions not only affect the formation of tin perovskite film and favor the formation of thicker 2D phases but also decrease the defect density and suppress the nonradiative recombination. As a result, the efficiency of tin PSCs is significantly improved from 7.97 to 12.45%, and the stability of the device is also enhanced. This work provides a feasible strategy to regulate the low-dimensional phases in 2D\textendash3D tin PSCs toward realizing high efficiency.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
L Katzenmeier, M Gößwein, L Carstensen, J Sterzinger, M Ederer, P Müller-Buschbaum, A Gagliardi, A S Bandarenka
Mass transport and charge transfer through an electrified interface between metallic lithium and solid-state electrolytes Journal Article
In: Communications Chemistry, vol. 6, no. 1, pp. 124, 0000, ISSN: 2399-3669.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Mass transport and charge transfer through an electrified interface between metallic lithium and solid-state electrolytes},
author = {L Katzenmeier and M G\"{o}\sswein and L Carstensen and J Sterzinger and M Ederer and P M\"{u}ller-Buschbaum and A Gagliardi and A S Bandarenka},
url = {https://doi.org/10.1038/s42004-023-00923-4},
doi = {10.1038/s42004-023-00923-4},
issn = {2399-3669},
journal = {Communications Chemistry},
volume = {6},
number = {1},
pages = {124},
abstract = {All-solid-state Li-ion batteries are one of the most promising energy storage devices for future automotive applications as high energy density metallic Li anodes can be safely used. However, introducing solid-state electrolytes needs a better understanding of the forming electrified electrode/electrolyte interface to facilitate the charge and mass transport through it and design ever-high-performance batteries. This study investigates the interface between metallic lithium and solid-state electrolytes. Using spectroscopic ellipsometry, we detected the formation of the space charge depletion layers even in the presence of metallic Li. That is counterintuitive and has been a subject of intense debate in recent years. Using impedance measurements, we obtain key parameters characterizing these layers and, with the help of kinetic Monte Carlo simulations, construct a comprehensive model of the systems to gain insights into the mass transport and the underlying mechanisms of charge accumulation, which is crucial for developing high-performance solid-state batteries.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
A Klumpp, R Hooijer, N Krüger, J Boudaden, F Wolf, M Döblinger, T Bein
Study on the properties of wafer-scale grown MoS2 deposited via thermally induced chemical vapor deposition with Mo(CO)6 and H2S precursors Journal Article
In: Materials Research Express, vol. 10, no. 9, pp. 095903, 0000, ISSN: 2053-1591.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {Study on the properties of wafer-scale grown MoS2 deposited via thermally induced chemical vapor deposition with Mo(CO)6 and H2S precursors},
author = {A Klumpp and R Hooijer and N Kr\"{u}ger and J Boudaden and F Wolf and M D\"{o}blinger and T Bein},
url = {https://dx.doi.org/10.1088/2053-1591/acf7ae},
doi = {10.1088/2053-1591/acf7ae},
issn = {2053-1591},
journal = {Materials Research Express},
volume = {10},
number = {9},
pages = {095903},
abstract = {To realize profitable applications with 2D-materials the transition from research scale to microelectronic fabrication methods is needed. This means the use of equipment for larger substrates and assessment of the process flows. In this study we demonstrate an effective way to assess MoS2 as semiconducting material, deposited with the lower priced precursors Mo(CO)6 and H2S on 200 mm silicon wafers. We could show how the evolution of layer quality develops depending on temperature and interface pretreatment. It is not possible to achieve mono-layers of 0.6 nm with high quality due to seeding kinetics and mechanism. In contrast, layers with thicknesses above 3 nm have suitable electrical and optical qualities to proceed with the design of active devices on 200 mm wafers.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
E Kolodzeiski, C J Stein
Automated, Consistent, and Even-handed Selection of Active Orbital Spaces for Quantum Embedding Journal Article
In: arXiv preprint arXiv:2306.09488, 0000.
Abstract | Links | Tags: Foundry Inorganic
@article{nokey,
title = {Automated, Consistent, and Even-handed Selection of Active Orbital Spaces for Quantum Embedding},
author = {E Kolodzeiski and C J Stein},
url = {https://arxiv.org/abs/2306.09488},
doi = {https://doi.org/10.48550/arXiv.2306.09488},
journal = {arXiv preprint arXiv:2306.09488},
abstract = {A widely used strategy to reduce the computational cost in quantum-chemical calculations is to partition the system into an active subsystem, which is the focus of the computational efforts and an environment that is treated at a lower computational level. The system partitioning is mostly based on localized molecular orbitals. When reaction paths or energy differences are to be calculated, it is crucial to keep the orbital space consistent for all structures. Inconsistencies in the orbital space can lead to unpredictable errors in the potential energy surface. While successful strategies to ensure this consistency have been established for organic and even metal-organic systems, these methods often fail for metal clusters or nanoparticles with a high density of near-degenerate and delocalized molecular orbitals. However, such systems are highly relevant for catalysis. Accurate yet feasible quantum-mechanical ab initio calculations are therefore highly desired. In this work, we present an approach based on the SPADE algorithm that allows us to ensure an automated and consistent partitioning even for systems with delocalized and near-degenerate molecular orbitals and demonstrate the validity of this method for the binding energies of small molecules on transition-metal clusters.},
keywords = {Foundry Inorganic},
pubstate = {published},
tppubtype = {article}
}
M Krinninger, N Bock, S Kaiser, J Reich, T Bruhm, F Haag, F Allegretti, U Heiz, K Köhler, B J Lechner, F Esch
On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine Journal Article
In: Chemistry of Materials, vol. 35, no. 17, pp. 6762-6770, 0000, ISSN: 0897-4756.
Abstract | Links | Tags: Solid-Liquid
@article{nokey,
title = {On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine},
author = {M Krinninger and N Bock and S Kaiser and J Reich and T Bruhm and F Haag and F Allegretti and U Heiz and K K\"{o}hler and B J Lechner and F Esch},
url = {https://doi.org/10.1021/acs.chemmater.3c01030},
doi = {10.1021/acs.chemmater.3c01030},
issn = {0897-4756},
journal = {Chemistry of Materials},
volume = {35},
number = {17},
pages = {6762-6770},
abstract = {Carbon nitrides have recently come into focus for photo- and thermal catalysis, both as support materials for metal nanoparticles as well as photocatalysts themselves. While many approaches for the synthesis of three-dimensional carbon nitride materials are available, only top-down approaches by exfoliation of powders lead to thin-film flakes of this inherently two-dimensional material. Here, we describe an in situ on-surface synthesis of monolayer 2D carbon nitride films as a first step toward precise combination with other 2D materials. Starting with a single monomer precursor, we show that 2,5,8-triazido-s-heptazine can be evaporated intact, deposited on a single crystalline Au(111) or graphite support, and activated via azide decomposition and subsequent coupling to form a covalent polyheptazine network. We demonstrate that the activation can occur in three pathways, via electrons (X-ray illumination), via photons (UV illumination), and thermally. Our work paves the way to coat materials with extended carbon nitride networks that are, as we show, stable under ambient conditions.},
keywords = {Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
X Lamprecht, P Zellner, G Yesilbas, L Hromadko, P Moser, P Marzak, S Hou, R Haid, F Steinberger, T Steeger, J M Macak, A S Bandarenka
Fast-Charging Capability of Thin-Film Prussian Blue Analogue Electrodes for Aqueous Sodium-Ion Batteries Journal Article
In: ACS Applied Materials & Interfaces, vol. 15, no. 19, pp. 23951-23962, 0000, ISSN: 1944-8244.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Fast-Charging Capability of Thin-Film Prussian Blue Analogue Electrodes for Aqueous Sodium-Ion Batteries},
author = {X Lamprecht and P Zellner and G Yesilbas and L Hromadko and P Moser and P Marzak and S Hou and R Haid and F Steinberger and T Steeger and J M Macak and A S Bandarenka},
url = {https://doi.org/10.1021/acsami.3c02633},
doi = {10.1021/acsami.3c02633},
issn = {1944-8244},
journal = {ACS Applied Materials \& Interfaces},
volume = {15},
number = {19},
pages = {23951-23962},
abstract = {Prussian blue analogues are considered as promising candidates for aqueous sodium-ion batteries providing a decently high energy density for stationary energy storage. However, suppose the operation of such materials under high-power conditions could be facilitated. In that case, their application might involve fast-response power grid stabilization and enable short-distance urban mobility due to fast re-charging. In this work, sodium nickel hexacyanoferrate thin-film electrodes are synthesized via a facile electrochemical deposition approach to form a model system for a robust investigation. Their fast-charging capability is systematically elaborated with regard to the electroactive material thickness in comparison to a ″traditional″ composite-type electrode. It is found that quasi-equilibrium kinetics allow extremely fast (dis)charging within a few seconds for sub-micron film thicknesses. Specifically, for a thickness below ≈ 500 nm, 90% of the capacity can be retained at a rate of 60C (1 min for full (dis)charge). A transition toward mass transport control is observed when further increasing the rate, with thicker films being dominated by this mode earlier than thinner films. This can be entirely attributed to the limiting effects of solid-state diffusion of Na+ within the electrode material. By presenting a PBA model cell yielding 25 Wh kg\textendash1 at up to 10 kW kg\textendash1, this work highlights a possible pathway toward the guided design of hybrid battery\textendashsupercapacitor systems. Furthermore, open challenges associated with thin-film electrodes are discussed, such as the role of parasitic side reactions, as well as increasing the mass loading.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
C Li, A V Scherbakov, P Soubelet, A K Samusev, C Ruppert, N Balakrishnan, V E Gusev, A V Stier, J J Finley, M Bayer, A V Akimov
Coherent Phonons in van der Waals MoSe2/WSe2 Heterobilayers Journal Article
In: Nano Letters, vol. 23, no. 17, pp. 8186-8193, 0000, ISSN: 1530-6984.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Coherent Phonons in van der Waals MoSe2/WSe2 Heterobilayers},
author = {C Li and A V Scherbakov and P Soubelet and A K Samusev and C Ruppert and N Balakrishnan and V E Gusev and A V Stier and J J Finley and M Bayer and A V Akimov},
url = {https://doi.org/10.1021/acs.nanolett.3c02316},
doi = {10.1021/acs.nanolett.3c02316},
issn = {1530-6984},
journal = {Nano Letters},
volume = {23},
number = {17},
pages = {8186-8193},
abstract = {The increasing role of two-dimensional (2D) devices requires the development of new techniques for ultrafast control of physical properties in 2D van der Waals (vdW) nanolayers. A special feature of heterobilayers assembled from vdW monolayers is femtosecond separation of photoexcited electrons and holes between the neighboring layers, resulting in the formation of Coulomb force. Using laser pulses, we generate a 0.8 THz coherent breathing mode in MoSe2/WSe2 heterobilayers, which modulates the thickness of the heterobilayer and should modulate the photogenerated electric field in the vdW gap. While the phonon frequency and decay time are independent of the stacking angle between the MoSe2 and WSe2 monolayers, the amplitude decreases at intermediate angles, which is explained by a decrease in the photogenerated electric field between the layers. The modulation of the vdW gap by coherent phonons enables a new technology for the generation of THz radiation in 2D nanodevices with vdW heterobilayers.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
K Liang, F Ristow, K Li, J Pittrich, N Fehn, L Dörringer, U Heiz, R Kienberger, G Pescitelli, H Iglev, A Kartouzian
Negative Nonlinear CD–ee Dependence in Polycrystalline BINOL Thin Films Journal Article
In: Journal of the American Chemical Society, 0000, ISSN: 0002-7863.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {Negative Nonlinear CD\textendashee Dependence in Polycrystalline BINOL Thin Films},
author = {K Liang and F Ristow and K Li and J Pittrich and N Fehn and L D\"{o}rringer and U Heiz and R Kienberger and G Pescitelli and H Iglev and A Kartouzian},
url = {https://doi.org/10.1021/jacs.3c12253},
doi = {10.1021/jacs.3c12253},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
abstract = {Generally, the relationship between the observed circular dichroism and the enantiomeric excess in chiral systems (CD\textendashee dependence) is linear. While positive nonlinear behavior has often been reported in the past, examples of negative nonlinear (NN) behavior in CD\textendashee dependence are rare and not well understood. Here, we present a strong NN CD\textendashee dependence within polycrystalline thin films of BINOL by using second-harmonic-generation circular dichroism (SHG-CD) and commercial CD spectroscopy studies. Theoretical calculations, microscopy, and FTIR studies are employed to further clarify the underlying cause of this observation. This behavior is attributed to the changing supramolecular chirality of the system. Systems exhibiting NN CD\textendashee dependence hold promise for highly accurate enantiomeric excess characterization, which is essential for the refinement of enantio-separating and -purifying processes in pharmaceuticals, asymmetric catalysis, and chiral sensing. Our findings suggest that a whole class of single-species systems, i.e., racemate crystals, might possess NN CD\textendashee dependence and thus provide us a vast playground to better understand and exploit this phenomenon.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
T Lin, T Yang, Y Cai, J Li, G Lu, S Chen, Y Li, L Guo, S A Maier, C Liu, J Huang
Transformation-Optics-Designed Plasmonic Singularities for Efficient Photocatalytic Hydrogen Evolution at Metal/Semiconductor Interfaces Journal Article
In: Nano Letters, vol. 23, no. 11, pp. 5288-5296, 0000, ISSN: 1530-6984.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Transformation-Optics-Designed Plasmonic Singularities for Efficient Photocatalytic Hydrogen Evolution at Metal/Semiconductor Interfaces},
author = {T Lin and T Yang and Y Cai and J Li and G Lu and S Chen and Y Li and L Guo and S A Maier and C Liu and J Huang},
url = {https://doi.org/10.1021/acs.nanolett.3c01287},
doi = {10.1021/acs.nanolett.3c01287},
issn = {1530-6984},
journal = {Nano Letters},
volume = {23},
number = {11},
pages = {5288-5296},
abstract = {Inspired by transformation optics, we propose a new concept for plasmonic photocatalysis by creating a novel hybrid nanostructure with a plasmonic singularity. Our geometry enables broad and strong spectral light harvesting at the active site of a nearby semiconductor where the chemical reaction occurs. A proof-of-concept nanostructure comprising Cu2ZnSnS4 (CZTS) and Au\textendashAu dimer (t-CZTS@Au\textendashAu) is fabricated via a colloidal strategy combining templating and seeded growth. On the basis of numerical and experimental results of different related hybrid nanostructures, we show that both the sharpness of the singular feature and the relative position to the reactive site play a pivotal role in optimizing photocatalytic activity. Compared with bare CZTS, the hybrid nanostructure (t-CZTS@Au\textendashAu) exhibits an enhancement of the photocatalytic hydrogen evolution rate by up to ∼9 times. The insights gained from this work might be beneficial for designing efficient composite plasmonic photocatalysts for diverse photocatalytic reactions.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
Z Lou, J Tao, B Wei, X Jiang, S Cheng, Z Wang, C Qin, R Liang, H Guo, L Zhu, P Müller-Buschbaum, H-M Cheng, X Xu
Near-Infrared Organic Photodetectors toward Skin-Integrated Photoplethysmography-Electrocardiography Multimodal Sensing System Journal Article
In: Advanced Science, vol. n/a, no. n/a, pp. 2304174, 0000, ISSN: 2198-3844.
Abstract | Links | Tags: Foundry Organic, Solid-Solid
@article{nokey,
title = {Near-Infrared Organic Photodetectors toward Skin-Integrated Photoplethysmography-Electrocardiography Multimodal Sensing System},
author = {Z Lou and J Tao and B Wei and X Jiang and S Cheng and Z Wang and C Qin and R Liang and H Guo and L Zhu and P M\"{u}ller-Buschbaum and H-M Cheng and X Xu},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/advs.202304174},
doi = {https://doi.org/10.1002/advs.202304174},
issn = {2198-3844},
journal = {Advanced Science},
volume = {n/a},
number = {n/a},
pages = {2304174},
abstract = {Abstract In the fast-evolving landscape of decentralized and personalized healthcare, the need for multimodal biosensing systems that integrate seamlessly with the human body is growing rapidly. This presents a significant challenge in devising ultraflexible configurations that can accommodate multiple sensors and designing high-performance sensing components that remain stable over long periods. To overcome these challenges, ultraflexible organic photodetectors (OPDs) that exhibit exceptional performance under near-infrared illumination while maintaining long-term stability are developed. These ultraflexible OPDs demonstrate a photoresponsivity of 0.53 A W−1 under 940 nm, shot-noise-limited specific detectivity of 3.4 × 1013 Jones, and cut-off response frequency beyond 1 MHz at −3 dB. As a result, the flexible photoplethysmography sensor boasts a high signal-to-noise ratio and stable peak-to-peak amplitude under hypoxic and hypoperfusion conditions, outperforming commercial finger pulse oximeters. This ensures precise extraction of blood oxygen saturation in dynamic working conditions. Ultraflexible OPDs are further integrated with conductive polymer electrodes on an ultrathin hydrogel substrate, allowing for direct interface with soft and dynamic skin. This skin-integrated sensing platform provides accurate measurement of photoelectric and biopotential signals in a time-synchronized manner, reproducing the functionality of conventional technologies without their inherent limitations.},
keywords = {Foundry Organic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
W Lu, L D S Menezes, A Tittl, H Ren, S A Maier
Active Huygens' metasurface based on in-situ grown conductive polymer Journal Article
In: arXiv preprint arXiv:2305.07356, 0000.
Abstract | Links | Tags: Solid-Solid
@article{nokey,
title = {Active Huygens' metasurface based on in-situ grown conductive polymer},
author = {W Lu and L D S Menezes and A Tittl and H Ren and S A Maier},
url = {https://arxiv.org/abs/2305.07356},
doi = {https://doi.org/10.48550/arXiv.2305.07356},
journal = {arXiv preprint arXiv:2305.07356},
abstract = {Active metasurfaces provide unique advantages for on-demand light manipulation at a subwavelength scale for emerging applications of 3D displays, augmented/virtual reality (AR/VR) glasses, holographic projectors and light detection and ranging (LiDAR). These applications put stringent requirements on switching speed, cycling duration, controllability over intermediate states, modulation contrast, optical efficiency and operation voltages. However, previous demonstrations focus only on particular subsets of these key performance requirements for device implementation, while the other performance metrics have remained too low for any practical use. Here, we demonstrate an active Huygens' metasurface based on in-situ grown conductive polymer with holistic switching performance, including switching speed of 60 frames per second (fps), switching duration of more than 2000 switching cycles without noticeable degradation, hysteresis-free controllability over intermediate states, modulation contrast of over 1400%, optical efficiency of 28% and operation voltage range within 1 V. Our active metasurface design meets all foundational requirements for display applications and can be readily incorporated into other metasurface concepts to deliver high-reliability electrical control over its optical response, paving the way for compact and robust electro-optic metadevices.},
keywords = {Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
F Zoller, S Häringer, D Böhm, J Luxa, Z Sofer, D Fattakhova-Rohlfing
Carbonaceous Oxygen Evolution Reaction Catalysts: From Defect and Doping-Induced Activity over Hybrid Compounds to Ordered Framework Structures Journal Article
In: Small, pp. e2007484, 0000, ISSN: 1613-6810.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{,
title = {Carbonaceous Oxygen Evolution Reaction Catalysts: From Defect and Doping-Induced Activity over Hybrid Compounds to Ordered Framework Structures},
author = {F Zoller and S H\"{a}ringer and D B\"{o}hm and J Luxa and Z Sofer and D Fattakhova-Rohlfing},
doi = {10.1002/smll.202007484},
issn = {1613-6810},
journal = {Small},
pages = {e2007484},
abstract = {Oxygen evolution reaction (OER) is expected to be of great importance for the future energy conversion and storage in form of hydrogen by water electrolysis. Besides the traditional noble-metal or transition metal oxide-based catalysts, carbonaceous electrocatalysts are of great interest due to their huge structural and compositional variety and unrestricted abundance. This review provides a summary of recent advances in the field of carbon-based OER catalysts ranging from "pure" or unintentionally doped carbon allotropes over heteroatom-doped carbonaceous materials and carbon/transition metal compounds to metal oxide composites where the role of carbon is mainly assigned to be a conductive support. Furthermore, the review discusses the recent developments in the field of ordered carbon framework structures (metal organic framework and covalent organic framework structures) that potentially allow a rational design of heteroatom-doped 3D porous structures with defined composition and spatial arrangement of doping atoms to deepen the understanding on the OER mechanism on carbonaceous structures in the future. Besides introducing the structural and compositional origin of electrochemical activity, the review discusses the mechanism of the catalytic activity of carbonaceous materials, their stability under OER conditions, and potential synergistic effects in combination with metal (or metal oxide) co-catalysts.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
X Ma, D J Zheng, S Hou, S Mukherjee, R Khare, G Gao, Q Ai, B Garlyyev, W Li, M Koch, J Mink, Y Shao-Horn, J Warnan, A S Bandarenka, R A Fischer
Structure–Activity Relationships in Ni- Carboxylate-Type Metal–Organic Frameworks’ Metamorphosis for the Oxygen Evolution Reaction Journal Article
In: ACS Catalysis, vol. 13, no. 11, pp. 7587-7596, 0000.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {Structure\textendashActivity Relationships in Ni- Carboxylate-Type Metal\textendashOrganic Frameworks’ Metamorphosis for the Oxygen Evolution Reaction},
author = {X Ma and D J Zheng and S Hou and S Mukherjee and R Khare and G Gao and Q Ai and B Garlyyev and W Li and M Koch and J Mink and Y Shao-Horn and J Warnan and A S Bandarenka and R A Fischer},
url = {https://doi.org/10.1021/acscatal.3c00625},
doi = {10.1021/acscatal.3c00625},
journal = {ACS Catalysis},
volume = {13},
number = {11},
pages = {7587-7596},
abstract = {Metal\textendashorganic frameworks (MOFs) have been reported to catalyze the oxygen evolution reaction (OER). Despite the established links between the pristine MOFs and their derived metal hydroxide electrocatalysts, several limitations still preclude understanding of the critical factors determining the OER performance. Of prime importance appears the choice of MOF and how its compositions relate to the catalyst stability and in turn to the reconstruction or metamorphosis mechanisms into the active species under OER conditions. An isoreticular series of Ni-carboxylate-type MOFs [Ni2(OH)2L] was chosen to elucidate the effects of the carboxylate linker length expansion and modulation of the linker\textendashlinker π\textendashπ interactions (L = 1,4-benzodicarboxylate, 2,6-napthalenedicarboxylate, biphenyl-4,4′-dicarboxylate, and p-terphenyl-4,4″-dicarboxylate). Degradation and reconstruction of MOFs were systematically investigated. The linker controls the transformation of Ni-MOF into distinct nickel hydroxide phases, and the conversion from α-Ni(OH)2 to β-Ni(OH)2, thus correlating the Ni-MOF composition with the OER activity of the Ni-MOF-derived metastable nickel hydroxide phase mixture.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
R V Mom, L-E Sandoval-Diaz, D Gao, C-H Chuang, E A Carbonio, T E Jones, R Arrigo, D Ivanov, M Hävecker, B Roldan Cuenya, R Schlögl, T Lunkenbein, A Knop-Gericke, J-J Velasco-Vélez
Assessment of the Degradation Mechanisms of Cu Electrodes during the CO2 Reduction Reaction Journal Article
In: ACS Applied Materials & Interfaces, vol. 15, no. 25, pp. 30052-30059, 0000, ISSN: 1944-8244.
Abstract | Links | Tags: Foundry Inorganic, Solid-Solid
@article{nokey,
title = {Assessment of the Degradation Mechanisms of Cu Electrodes during the CO2 Reduction Reaction},
author = {R V Mom and L-E Sandoval-Diaz and D Gao and C-H Chuang and E A Carbonio and T E Jones and R Arrigo and D Ivanov and M H\"{a}vecker and B Roldan Cuenya and R Schl\"{o}gl and T Lunkenbein and A Knop-Gericke and J-J Velasco-V\'{e}lez},
url = {https://doi.org/10.1021/acsami.2c23007},
doi = {10.1021/acsami.2c23007},
issn = {1944-8244},
journal = {ACS Applied Materials \& Interfaces},
volume = {15},
number = {25},
pages = {30052-30059},
abstract = {Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO2 on copper electrodes. Yet, these aspects are often overlooked. Here, we combine in situ X-ray spectroscopy, in situ electron microscopy, and ex situ characterization techniques to follow the long-term evolution of the catalyst morphology, electronic structure, surface composition, activity, and product selectivity of Cu nanosized crystals during the CO2 reduction reaction. We found no changes in the electronic structure of the electrode under cathodic potentiostatic control over time, nor was there any build-up of contaminants. In contrast, the electrode morphology is modified by prolonged CO2 electroreduction, which transforms the initially faceted Cu particles into a rough/rounded structure. In conjunction with these morphological changes, the current increases and the selectivity changes from value-added hydrocarbons to less valuable side reaction products, i.e., hydrogen and CO. Hence, our results suggest that the stabilization of a faceted Cu morphology is pivotal for ensuring optimal long-term performance in the selective reduction of CO2 into hydrocarbons and oxygenated products.},
keywords = {Foundry Inorganic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
A L Oechsle, T Schöner, L Deville, T Xiao, T Tian, A Vagias, S Bernstorff, P Müller-Buschbaum
Ionic Liquid-Induced Inversion of the Humidity-Dependent Conductivity of Thin PEDOT:PSS Films Journal Article
In: ACS Applied Materials & Interfaces, vol. 15, no. 40, pp. 47682-47691, 0000, ISSN: 1944-8244.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Ionic Liquid-Induced Inversion of the Humidity-Dependent Conductivity of Thin PEDOT:PSS Films},
author = {A L Oechsle and T Sch\"{o}ner and L Deville and T Xiao and T Tian and A Vagias and S Bernstorff and P M\"{u}ller-Buschbaum},
url = {https://doi.org/10.1021/acsami.3c08208},
doi = {10.1021/acsami.3c08208},
issn = {1944-8244},
journal = {ACS Applied Materials \& Interfaces},
volume = {15},
number = {40},
pages = {47682-47691},
abstract = {The humidity influence on the electronic and ionic resistance properties of thin post-treated poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films is investigated. In particular, the resistance of these PEDOT:PSS films post-treated with three different concentrations (0, 0.05, and 0.35 M) of ethyl-3-methylimidazolium dicyanamide (EMIM DCA) is measured while being exposed to a defined humidity protocol. A resistance increase upon elevated humidity is observed for the 0 M reference sample, while the EMIM DCA post-treated samples demonstrate a reverse behavior. Simultaneously performed in situ grazing-incidence small-angle X-ray scattering (GISAXS) measurements evidence changes in the film morphology upon varying the humidity, namely, an increase in the PEDOT domain distances. This leads to a detriment in the interdomain hole transport, which causes a rise in the resistance, as observed for the 0 M reference sample. Finally, electrochemical impedance spectroscopy (EIS) measurements at different humidities reveal additional contributions of ionic charge carriers in the EMIM DCA post-treated PEDOT:PSS films. Therefrom, a model is proposed, which describes the hole and cation transport in different post-treated PEDOT:PSS films dependent on the ambient humidity.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
A L Oechsle, T Schöner, C Geiger, S Tu, P Wang, R Cubitt, P Müller-Buschbaum
In: Macromolecules, vol. 56, no. 22, pp. 9117-9126, 0000, ISSN: 0024-9297.
Abstract | Links | Tags: Foundry Organic, Solid-Solid
@article{nokey,
title = {Unraveling the Humidity Influence on the Electrical Properties of Ionic Liquid Posttreated Poly(3,4-ethylene dioxythiophene):Poly(styrenesulfonate) Films},
author = {A L Oechsle and T Sch\"{o}ner and C Geiger and S Tu and P Wang and R Cubitt and P M\"{u}ller-Buschbaum},
url = {https://doi.org/10.1021/acs.macromol.3c01842},
doi = {10.1021/acs.macromol.3c01842},
issn = {0024-9297},
journal = {Macromolecules},
volume = {56},
number = {22},
pages = {9117-9126},
abstract = {The conductive polymer blend poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), popular for numerous organic applications, is investigated in terms of the influences that ionic liquid (IL) treatment and ambient humidity have on its conductivity properties. PEDOT:PSS thin films posttreated with different concentrations of the IL 1-ethyl-3-methylimidazolium dicyanamide (EMIM DCA) are exposed to different relative humidity (RH) steps from 0% RH up to 90% RH. Simultaneously, the film swelling and increase in the scattering length density (SLD), indicating a water uptake of the films, are monitored in situ with spectral reflectance (SR) and time-of-flight neutron reflectometry (ToF-NR). Additional in situ electrochemical impedance spectroscopy (EIS) shows that the pristine PEDOT:PSS has only an electronic conductivity, while for the IL-treated samples, an additional ionic conductivity contribution is observed. Upon humidity increase, the electronic conductivity of all PEDOT:PSS thin films decreases, while the ionic conductivity for IL posttreated thin films is enhanced by the intake of water molecules.},
keywords = {Foundry Organic, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
C L M Palenzuela, D Spurling, A Szalai, T Schröder, V Nicolosi, P Tinnefeld
MXene-induced nonradiative energy transfer Journal Article
In: 0000.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {MXene-induced nonradiative energy transfer},
author = {C L M Palenzuela and D Spurling and A Szalai and T Schr\"{o}der and V Nicolosi and P Tinnefeld},
url = {https://chemrxiv.org/engage/chemrxiv/article-details/6544ea8948dad23120fe8d2a},
doi = {10.26434/chemrxiv-2023-r54g8},
abstract = {Since their discovery in 2011, MXenes have risen to prominence for energy storage, electromagnetic shielding, and optoelectronics. Yet, the nonradiative energy transfer properties of this family of 2D materials remain elusive, which may have implications in optoelectronics, photovoltaics and biosensing. Here, we use single-molecule fluorescence confocal microscopy and DNA origami nanopositioners to investigate, for the first time, the distance-dependent energy transfer of an organic emitter (ATTO 542) placed on transparent thin films made of spincast Ti3C2Tx flakes. We propose a specific immobilization chemistry for DNA origami nanostructures based on glycine-MXene interaction, allowing us to precisely control their orientation on the surface. Each DNA origami structure is designed to carry a single dye molecule at predetermined heights. Our findings reveal that when the dye is located at distances of 1 nm \< d \< 8 nm from the surface, the fluorescence is quenched following a distance dependence of d-3. This is in agreement with the F\"{o}rster-type mechanism of energy transfer in transparent conductors at the bulk level. 50% of energy transfer efficiency is reached at 2.7 nm (d0). MXenes could therefore be used as short-distance spectroscopic nanorulers, sensitive at a distance regime that common energy transfer tools cannot access.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
G Posnjak, X Yin, P Butler, O Bienek, M Dass, I D Sharp, T Liedl
Diamond photonic crystals assembled from DNA origami Journal Article
In: arXiv preprint arXiv:2310.10884, 0000.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {Diamond photonic crystals assembled from DNA origami},
author = {G Posnjak and X Yin and P Butler and O Bienek and M Dass and I D Sharp and T Liedl},
url = {https://arxiv.org/abs/2310.10884},
doi = {https://doi.org/10.48550/arXiv.2310.10884},
journal = {arXiv preprint arXiv:2310.10884},
abstract = {Colloidal self-assembly allows rational design of structures on the micron and submicron scale, potentially leading to physical material properties that are rare or non-existent in nature. One of the architectures that can generate complete 3D photonic band gaps is the diamond cubic lattice, which has remained difficult to realize at length scales comparable to the wavelength of visible light. Here, we demonstrate 3D photonic crystals self-assembled from DNA origami that act as precisely programmable patchy colloids. Our DNA-based nanoscale tetrapods crystallize into a rod-connected diamond cubic lattice with a periodicity of 170 nm that serves as a scaffold for atomic layer deposition of high refractive index materials such as TiO2, yielding a tunable photonic band gap in the near UV range.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
M A Reus, A Krifa, Q A Akkerman, A Biewald, Z Xu, D P Kosbahn, C L Weindl, J Feldmann, A Hartschuh, P Müller-Buschbaum
Layer-By-Layer Printed Metal Hybrid (Cs:FA)PbI3 Perovskite Nanocrystal Solar Cells Journal Article
In: Advanced Optical Materials, vol. n/a, no. n/a, pp. 2301008, 0000, ISSN: 2195-1071.
Abstract | Links | Tags: Foundry Inorganic
@article{nokey,
title = {Layer-By-Layer Printed Metal Hybrid (Cs:FA)PbI3 Perovskite Nanocrystal Solar Cells},
author = {M A Reus and A Krifa and Q A Akkerman and A Biewald and Z Xu and D P Kosbahn and C L Weindl and J Feldmann and A Hartschuh and P M\"{u}ller-Buschbaum},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adom.202301008},
doi = {https://doi.org/10.1002/adom.202301008},
issn = {2195-1071},
journal = {Advanced Optical Materials},
volume = {n/a},
number = {n/a},
pages = {2301008},
abstract = {Abstract Mixed halide perovskite nanocrystals in the form of cesium/formamidinium lead triiodide ((Cs:FA)PbI3) offer great potential for efficient and stable solar cells. To date, large-scale production with roll-to-roll compatible deposition methods remains difficult and requires detailed research on each involved processing step. Here, a proof-of-concept study about slot-die coating (printing) the active layer of (Cs:FA)PbI3-based nanocrystal solar cells is presented. Structural and morphological changes during ligand exchange of long-chain oleic acid and oleylamine by Pb(NO3)2, and top-layer FAI passivation are investigated. Ligand exchange improves the processability of the nanocrystal layer and enhances charge transport. It also changes texture from face-on toward edge-on orientation as grazing-incidence X-ray scattering studies indicate. Ligand exchange and FAI passivation redshift photoluminescence and prolong charge carrier lifetime in the printed nanocrystal films. The proof-of-concept feasibility of printing metal halide perovskite nanocrystal films for solar cells is shown by building 20 devices with a median power conversion efficiency of 6.39%.},
keywords = {Foundry Inorganic},
pubstate = {published},
tppubtype = {article}
}
L Richter, A M Szalai, C L Manzanares-Palenzuela, I Kamińska, P Tinnefeld
Exploring the Synergies of Single-Molecule Fluorescence and 2D Materials Coupled by DNA Journal Article
In: Advanced Materials, vol. 35, no. 41, pp. 2303152, 0000, ISSN: 0935-9648.
Abstract | Links | Tags: Foundry Organic, Molecularly-Functionalized
@article{nokey,
title = {Exploring the Synergies of Single-Molecule Fluorescence and 2D Materials Coupled by DNA},
author = {L Richter and A M Szalai and C L Manzanares-Palenzuela and I Kami\'{n}ska and P Tinnefeld},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202303152},
doi = {https://doi.org/10.1002/adma.202303152},
issn = {0935-9648},
journal = {Advanced Materials},
volume = {35},
number = {41},
pages = {2303152},
abstract = {Abstract The world of 2D materials is steadily growing, with numerous researchers attempting to discover, elucidate, and exploit their properties. Approaches relying on the detection of single fluorescent molecules offer a set of advantages, for instance, high sensitivity and specificity, that allow the drawing of conclusions with unprecedented precision. Herein, it is argued how the study of 2D materials benefits from fluorescence-based single-molecule modalities, and vice versa. A special focus is placed on DNA, serving as a versatile adaptor when anchoring single dye molecules to 2D materials. The existing literature on the fruitful combination of the two fields is reviewed, and an outlook on the additional synergies that can be created between them provided.},
keywords = {Foundry Organic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
K Rickmeyer, M Huber, C R Hess
Influence of a neighbouring Cu centre on electro- and photocatalytic CO2 reduction by Fe-Mabiq Journal Article
In: Chemical Communications, 0000, ISSN: 1359-7345.
Abstract | Links | Tags: Foundry Organic
@article{nokey,
title = {Influence of a neighbouring Cu centre on electro- and photocatalytic CO2 reduction by Fe-Mabiq},
author = {K Rickmeyer and M Huber and C R Hess},
url = {http://dx.doi.org/10.1039/D3CC04777F},
doi = {10.1039/D3CC04777F},
issn = {1359-7345},
journal = {Chemical Communications},
abstract = {Electrocatalytic and photocatalytic CO2 reduction by a heterobimetallic Cu/Fe\textendashMabiq complex were examined and compared to the monometallic [Fe(Mabiq)]+. The neighbouring Cu\textendashXantphos unit leads to marked changes in the electrocatalytic mechanism and enhanced photocatalytic performance.},
keywords = {Foundry Organic},
pubstate = {published},
tppubtype = {article}
}
M Rieger, V Villafane, L M Todenhagen, S Matthies, S Appel, M S Brandt, K Mueller, J J Finley
Fast optoelectronic charge state conversion of silicon vacancies in diamond Journal Article
In: arXiv preprint arXiv:2310.12288, 0000.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Solid
@article{nokey,
title = {Fast optoelectronic charge state conversion of silicon vacancies in diamond},
author = {M Rieger and V Villafane and L M Todenhagen and S Matthies and S Appel and M S Brandt and K Mueller and J J Finley},
url = {https://arxiv.org/abs/2310.12288},
doi = {https://doi.org/10.48550/arXiv.2310.12288},
journal = {arXiv preprint arXiv:2310.12288},
abstract = {Group IV vacancy color centers in diamond are promising spin-photon interfaces with strong potential for applications for photonic quantum technologies. Reliable methods for controlling and stabilizing their charge state are urgently needed for scaling to multi-qubit devices. Here, we manipulate the charge state of silicon vacancy (SiV) ensembles by combining luminescence and photo-current spectroscopy. We controllably convert the charge state between the optically active SiV− and dark SiV2− with MHz rates and 90% contrast by judiciously choosing the local potential applied to in-plane surface electrodes and the laser excitation wavelength. We observe intense SiV− photoluminescence under hole-capture, measure the intrinsic conversion time from the dark SiV2− to the bright SiV− to be 36.4(6.7)ms and demonstrate how it can be enhanced by a factor of 105 via optical pumping. Moreover, we obtain new information on the defects that contribute to photo-conductivity, indicating the presence of substitutional nitrogen and divacancies.},
keywords = {Molecularly-Functionalized, Solid-Solid},
pubstate = {published},
tppubtype = {article}
}
M Righetto, S Caicedo-Dávila, M T Sirtl, V J Y Lim, J B Patel, D A Egger, T Bein, L M Herz
Alloying Effects on Charge-Carrier Transport in Silver–Bismuth Double Perovskites Journal Article
In: The Journal of Physical Chemistry Letters, vol. 14, no. 46, pp. 10340-10347, 0000.
Abstract | Links | Tags: Foundry Organic, Solid-Liquid
@article{nokey,
title = {Alloying Effects on Charge-Carrier Transport in Silver\textendashBismuth Double Perovskites},
author = {M Righetto and S Caicedo-D\'{a}vila and M T Sirtl and V J Y Lim and J B Patel and D A Egger and T Bein and L M Herz},
url = {https://doi.org/10.1021/acs.jpclett.3c02750},
doi = {10.1021/acs.jpclett.3c02750},
journal = {The Journal of Physical Chemistry Letters},
volume = {14},
number = {46},
pages = {10340-10347},
abstract = {Alloying is widely adopted for tuning the properties of emergent semiconductors for optoelectronic and photovoltaic applications. So far, alloying strategies have primarily focused on engineering bandgaps rather than optimizing charge-carrier transport. Here, we demonstrate that alloying may severely limit charge-carrier transport in the presence of localized charge carriers (e.g., small polarons). By combining reflection\textendashtransmission and optical pump\textendashterahertz probe spectroscopy with first-principles calculations, we investigate the interplay between alloying and charge-carrier localization in Cs2AgSbxBi1\textendashxBr6 double perovskite thin films. We show that the charge-carrier transport regime strongly determines the impact of alloying on the transport properties. While initially delocalized charge carriers probe electronic bands formed upon alloying, subsequently self-localized charge carriers probe the energetic landscape more locally, thus turning an alloy’s low-energy sites (e.g., Sb sites) into traps, which dramatically deteriorates transport properties. These findings highlight the inherent limitations of alloying strategies and provide design tools for newly emerging and highly efficient semiconductors.},
keywords = {Foundry Organic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
R Rizzato, M Schalk, S Mohr, J C Hermann, J P Leibold, F Bruckmaier, G Salvitti, C Qian, P Ji, G V Astakhov, U Kentsch, M Helm, A V Stier, J J Finley, D B Bucher
Extending the coherence of spin defects in hBN enables advanced qubit control and quantum sensing Journal Article
In: Nature Communications, vol. 14, no. 1, pp. 5089, 0000, ISSN: 2041-1723.
Abstract | Links | Tags: Molecularly-Functionalized, Solid-Liquid
@article{nokey,
title = {Extending the coherence of spin defects in hBN enables advanced qubit control and quantum sensing},
author = {R Rizzato and M Schalk and S Mohr and J C Hermann and J P Leibold and F Bruckmaier and G Salvitti and C Qian and P Ji and G V Astakhov and U Kentsch and M Helm and A V Stier and J J Finley and D B Bucher},
url = {https://doi.org/10.1038/s41467-023-40473-w},
doi = {10.1038/s41467-023-40473-w},
issn = {2041-1723},
journal = {Nature Communications},
volume = {14},
number = {1},
pages = {5089},
abstract = {Negatively-charged boron vacancy centers ($$V_B^-$$) in hexagonal Boron Nitride (hBN) are attracting increasing interest since they represent optically-addressable qubits in a van der Waals material. In particular, these spin defects have shown promise as sensors for temperature, pressure, and static magnetic fields. However, their short spin coherence time limits their scope for quantum technology. Here, we apply dynamical decoupling techniques to suppress magnetic noise and extend the spin coherence time by two orders of magnitude, approaching the fundamental T1 relaxation limit. Based on this improvement, we demonstrate advanced spin control and a set of quantum sensing protocols to detect radiofrequency signals with sub-Hz resolution. The corresponding sensitivity is benchmarked against that of state-of-the-art NV-diamond quantum sensors. This work lays the foundation for nanoscale sensing using spin defects in an exfoliable material and opens a promising path to quantum sensors and quantum networks integrated into ultra-thin structures.},
keywords = {Molecularly-Functionalized, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}
D Sandner, H Esmaielpour, F D Giudice, S Meder, M Nuber, R Kienberger, G Koblmüller, H Iglev
Hot Electron Dynamics in InAs–AlAsSb Core–Shell Nanowires Journal Article
In: ACS Applied Energy Materials, vol. 6, no. 20, pp. 10467-10474, 0000.
Abstract | Links | Tags: Foundry Inorganic, Molecularly-Functionalized
@article{nokey,
title = {Hot Electron Dynamics in InAs\textendashAlAsSb Core\textendashShell Nanowires},
author = {D Sandner and H Esmaielpour and F D Giudice and S Meder and M Nuber and R Kienberger and G Koblm\"{u}ller and H Iglev},
url = {https://doi.org/10.1021/acsaem.3c01565},
doi = {10.1021/acsaem.3c01565},
journal = {ACS Applied Energy Materials},
volume = {6},
number = {20},
pages = {10467-10474},
abstract = {Semiconductor nanowires (NWs) have shown evidence of robust hot-carrier effects due to their small dimensions, making them attractive for advanced photoenergy conversion concepts. Especially, indium arsenide (InAs) NWs are promising candidates for harvesting hot carriers due to their high absorption coefficient, high carrier mobility, and large effective electron-to-hole mass difference. Here, we investigate the cooling and recombination dynamics of photoexcited hot carriers in pure and passivated InAs NWs by using ultrafast near-infrared pump\textendashprobe spectroscopy. We observe reduced Auger recombination in pure InAs NWs compared to that in passivated ones and associate this with charge-carrier separation by surface band bending. Similarly, faster carrier cooling by electron\textendashhole scattering is observed in passivated InAs\textendashAlAsSb NWs at high carrier densities in excess of 1018 cm\textendash3, where hot electron lifetimes in this regime increase substantially with the pump fluence due to Auger heating. These results emphasize the importance of type-II alignment for charge-carrier separation in hot-carrier devices to suppress carrier-mediated cooling channels. In addition, a separate charge-carrier population lasting up to several nanoseconds is observed for photoexcitation of the NW shell. Despite the high conduction band offset, carrier migration is not observed in the range of 40 ps to 2 ns. This observation may open avenues for core\textendashshell NW multijunction solar cells.},
keywords = {Foundry Inorganic, Molecularly-Functionalized},
pubstate = {published},
tppubtype = {article}
}
M J Schilcher, D J Abramovitch, M Z Mayers, L Z Tan, D R Reichman, D A Egger
Correlated Anharmonicity and Dynamic Disorder Control Carrier Transport in Halide Perovskites Journal Article
In: arXiv preprint arXiv:2305.13682, 0000.
Abstract | Links | Tags: Foundry Organic
@article{nokey,
title = {Correlated Anharmonicity and Dynamic Disorder Control Carrier Transport in Halide Perovskites},
author = {M J Schilcher and D J Abramovitch and M Z Mayers and L Z Tan and D R Reichman and D A Egger},
url = {https://arxiv.org/abs/2305.13682},
doi = {https://doi.org/10.48550/arXiv.2305.13682},
journal = {arXiv preprint arXiv:2305.13682},
abstract = {Halide pervoskites are an important class of semiconducting materials which hold great promise for optoelectronic applications. In this work we investigate the relationship between vibrational anharmonicity and dynamic disorder in this class of solids. Via a multi-scale model parameterized from first-principles calculations, we demonstrate that the non-Gaussian lattice motion in halide perovskites is microscopically connected to the dynamic disorder of overlap fluctuations among electronic states. This connection allows us to rationalize the emergent differences in temperature-dependent mobilities of prototypical MAPbI3 and MAPbBr3 compounds across structural phase-transitions, in agreement with experimental findings. Our analysis suggests that the details of vibrational anharmonicity and dynamic disorder can complement known predictors of electronic conductivity and can provide structure-property guidelines for the tuning of carrier transport characteristics in anharmonic semiconductors.},
keywords = {Foundry Organic},
pubstate = {published},
tppubtype = {article}
}
T O Schmidt, A Wark, R W Haid, R M Kluge, S Suzuki, K Kamiya, A S Bandarenka, J Maruyama, E Skúlason
Elucidating the Active Sites and Synergies in Water Splitting on Manganese Oxide Nanosheets on Graphite Support Journal Article
In: Advanced Energy Materials, vol. 13, no. 43, pp. 2302039, 0000, ISSN: 1614-6832.
Abstract | Links | Tags: Foundry Inorganic, Solid-Liquid
@article{nokey,
title = {Elucidating the Active Sites and Synergies in Water Splitting on Manganese Oxide Nanosheets on Graphite Support},
author = {T O Schmidt and A Wark and R W Haid and R M Kluge and S Suzuki and K Kamiya and A S Bandarenka and J Maruyama and E Sk\'{u}lason},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202302039},
doi = {https://doi.org/10.1002/aenm.202302039},
issn = {1614-6832},
journal = {Advanced Energy Materials},
volume = {13},
number = {43},
pages = {2302039},
abstract = {Abstract Photosystem II is nature's solution for driving the oxygen evolution reaction to oxidize water. A manganese-oxide cluster is this protein's active center for water splitting, while the most efficient man-made catalysts are costly noble metal-based oxides. Facing the climate change, research on affordable and abundant electrocatalysts is crucial. To mimic the biological solution, manganese oxide nanosheets are synthesized and deposited on highly-oriented pyrolytic graphite. This electrocatalyst is then examined with spectroscopic and electrochemical measurements, electrochemical noise scanning tunneling microscopy, and density functional theory calculations. The detailed investigation assigns the origin of its enhanced water-splitting performance to detected activity at the nanosheet edges which the proposed mechanism explains further. Therefore, the results provide a blueprint for how to design efficient electrocatalysts for water oxidation with abundant materials.},
keywords = {Foundry Inorganic, Solid-Liquid},
pubstate = {published},
tppubtype = {article}
}