Publications

@article{nokey,

title = {Transition-Metal-Free Synthesis of Polyfunctional Triarylmethanes and 1,1-Diarylalkanes by Sequential Cross-Coupling of Benzal Diacetates with Organozinc Reagents},

author = {B Wei and Q Ren and T Bein and P Knochel},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202101682},

doi = {https://doi.org/10.1002/anie.202101682},

issn = {1433-7851},

year  = {2021},

date = {2021-02-24},

journal = {Angewandte Chemie International Edition},

volume = {60},

number = {18},

pages = {10409-10414},

abstract = {Abstract A variety of functionalized triarylmethane and 1,1-diarylalkane derivatives were prepared via a transition-metal-free, one-pot and two-step procedure, involving the reaction of various benzal diacetates with organozinc reagents. A sequential cross-coupling is enabled by changing the solvent from THF to toluene, and a two-step SN1-type mechanism was proposed and evidenced by experimental studies. The synthetic utility of the method is further demonstrated by the synthesis of several biologically relevant molecules, such as an anti-tuberculosis agent, an anti-breast cancer agent, a precursor of a sphingosine-1-phosphate (S1P) receptor modulator, and a FLAP inhibitor.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Amine-Linked Covalent Organic Frameworks as a Platform for Postsynthetic Structure Interconversion and Pore-Wall Modification},

author = {L Grunenberg and G Savasci and M W Terban and V Duppel and I Moudrakovski and M Etter and R E Dinnebier and C Ochsenfeld and B V Lotsch},

url = {https://doi.org/10.1021/jacs.0c12249},

doi = {10.1021/jacs.0c12249},

issn = {0002-7863},

year  = {2021},

date = {2021-02-24},

urldate = {2021-02-24},

journal = {Journal of the American Chemical Society},

volume = {143},

number = {9},

pages = {3430-3438},

abstract = {Covalent organic frameworks have emerged as a powerful synthetic platform for installing and interconverting dedicated molecular functions on a crystalline polymeric backbone with atomic precision. Here, we present a novel strategy to directly access amine-linked covalent organic frameworks, which serve as a scaffold enabling pore-wall modification and linkage-interconversion by new synthetic methods based on Leuckart\textendashWallach reduction with formic acid and ammonium formate. Frameworks connected entirely by secondary amine linkages, mixed amine/imine bonds, and partially formylated amine linkages are obtained in a single step from imine-linked frameworks or directly from corresponding linkers in a one-pot crystallization-reduction approach. The new, 2D amine-linked covalent organic frameworks, rPI-3-COF, rTTI-COF, and rPy1P-COF, are obtained with high crystallinity and large surface areas. Secondary amines, installed as reactive sites on the pore wall, enable further postsynthetic functionalization to access tailored covalent organic frameworks, with increased hydrolytic stability, as potential heterogeneous catalysts.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Super-resolution Imaging of Energy Transfer by Intensity-Based STED-FRET},

author = {A M Molszalai and B Siarry and J Lukin and S Giusti and N Unsain and A C\'{a}ceres and F Steiner and P Tinnefeld and D Refojo and T M Jovin and F D Stefani},

url = {https://doi.org/10.1021/acs.nanolett.1c00158},

doi = {10.1021/acs.nanolett.1c00158},

issn = {1530-6984},

year  = {2021},

date = {2021-02-23},

journal = {Nano Letters},

abstract = {F\"{o}rster resonance energy transfer (FRET) imaging methods provide unique insight into the spatial distribution of energy transfer and (bio)molecular interaction events, though they deliver average information for an ensemble of events included in a diffraction-limited volume. Coupling super-resolution fluorescence microscopy and FRET has been a challenging and elusive task. Here, we present STED-FRET, a method of general applicability to obtain super-resolved energy transfer images. In addition to higher spatial resolution, STED-FRET provides a more accurate quantification of interaction and has the capacity of suppressing contributions of noninteracting partners, which are otherwise masked by averaging in conventional imaging. The method capabilities were first demonstrated on DNA-origami model systems, verified on uniformly double-labeled microtubules, and then utilized to image biomolecular interactions in the membrane-associated periodic skeleton (MPS) of neurons.},

keywords = {Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Highly Efficient Resolution-of-Identity Density Functional Theory Calculations on Central and Graphics Processing Units},

author = {J Kussmann and H Laqua and C Ochsenfeld},

url = {https://doi.org/10.1021/acs.jctc.0c01252},

doi = {10.1021/acs.jctc.0c01252},

issn = {1549-9618},

year  = {2021},

date = {2021-02-22},

journal = {Journal of Chemical Theory and Computation},

abstract = {We present an efficient method to evaluate Coulomb potential matrices using the resolution of identity approximation and semilocal exchange-correlation potentials on central (CPU) and graphics processing units (GPU). The new GPU-based RI-algorithm shows a high performance and ensures the favorable scaling with increasing basis set size as the conventional CPU-based method. Furthermore, our method is based on the J-engine algorithm [White; , Head-Gordon, J. Chem. Phys. 1996, 7, 2620], which allows for further optimizations that also provide a significant improvement of the corresponding CPU-based algorithm. Due to the increased performance for the Coulomb evaluation, the calculation of the exchange-correlation potential of density functional theory on CPUs quickly becomes a bottleneck to the overall computational time. Hence, we also present a GPU-based algorithm to evaluate the exchange-correlation terms, which results in an overall high-performance method for density functional calculations. The algorithms to evaluate the potential and nuclear derivative terms are discussed, and their performance on CPUs and GPUs is demonstrated for illustrative calculations.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Activation of 2-Cyclohexenone by BF3 Coordination: Mechanistic Insights from Theory and Experiment},

author = {M Peschel and P Kabacinski and D P Schwinger and E Thyrhaug and G Cerullo and T Bach and J Hauer and R De Vivie-Riedle

},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202016653},

doi = {https://doi.org/10.1002/anie.202016653},

issn = {1433-7851},

year  = {2021},

date = {2021-02-17},

urldate = {2021-02-17},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {Lewis acids have recently been recognized as catalysts enabling enantioselective photochemical transformations. Mechanistic studies on these systems are however rare, either due to their absorption at wavelengths shorter than 260 nm, or due to the limitations of theoretical dynamic studies for larger complexes. In this work, we overcome these challenges and employ sub-30-fs transient absorption in the UV, in combination with a highly accurate theoretical treatment on the XMS-CASPT2 level. We investigate 2-cyclohexenone and its complex to boron trifluoride and analyze the observed dynamics based on trajectory calculations including non-adiabatic coupling and intersystem crossing. This approach explains all ultrafast decay pathways observed in the complex. We show that the Lewis acid remains attached to the substrate in the triplet state, which in turn explains why chiral boron-based Lewis acids induce a high enantioselectivity in photocycloaddition reactions.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Transfer of 1D Photonic Crystals via Spatially Resolved Hydrophobization},

author = {M D\"{a}ntl and S Guderley and K Szendrei-Temesi and D Chatzitheodoridou and P Ganter and A Jim\'{e}nez-Solano and B V Lotsch},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/smll.202007864},

doi = {https://doi.org/10.1002/smll.202007864},

issn = {1613-6810},

year  = {2021},

date = {2021-02-15},

journal = {Small},

volume = {17},

number = {12},

pages = {2007864},

abstract = {Abstract 1D photonic crystals (1DPCs) are well known from a variety of applications ranging from medical diagnostics to optical fibers and optoelectronics. However, large-scale application is still limited due to complex fabrication processes and bottlenecks in transferring 1DPCs to arbitrary substrates and pattern creation. These challenges were addressed by demonstrating the transfer of millimeter- to centimeter-scale 1DPC sensors comprised of alternating layers of H3Sb3P2O14 nanosheets and TiO2 nanoparticles based on a non-invasive chemical approach. By depositing the 1DPC on a sacrificial layer of lithium tin sulfide nanosheets and hydrophobizing only the 1DPC by intercalation of n-octylamine via the vapor phase the 1DPC can be detached from the substrate by immersing the sample in water. Upon exfoliation of the hydrophilic sacrificial layer, the freestanding 1DPC remains at the water\textendashair interface. In a second step, it can be transferred to arbitrary surfaces such as curved glass. In addition, the transfer of patterned 1DPCs is demonstrated by combining the sacrificial layer approach with area-resolved intercalation and etching. The fact that the sensing capability of the 1DPC is not impaired and can be modified after transfer renders this method a generic platform for the fabrication of photonic devices.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Photocatalytic Hydrogen Evolution: Interfacial Engineering for Improved Photocatalysis in a Charge Storing 2D Carbon Nitride: Melamine Functionalized Poly(heptazine imide) (Adv. Energy Mater. 6/2021)},

author = {J Kr\"{o}ger and A Jim\'{e}nez-Solano and G Savasci and P Rov\'{o} and I Moudrakovski and K K\"{u}ster and H Schlomberg and H A Vignolo-Gonz\'{a}lez and V Duppel and L Grunenberg and C B Dayan and M Sitti and F Podjaski and C Ochsenfeld and B V Lotsch},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202170028},

doi = {https://doi.org/10.1002/aenm.202170028},

issn = {1614-6832},

year  = {2021},

date = {2021-02-11},

journal = {Advanced Energy Materials},

volume = {11},

number = {6},

pages = {2170028},

abstract = {In article number 2003016, Bettina V. Lotsch and co-workers demonstrate that covalent surface modifications of the 2D carbon nitride poly(heptazine imide) with melamine groups strongly influence its polarity and photo(electrochemical) properties. This potent tuning pathway also results in the boosting of photocatalytic hydrogen evolution due to increased donor interactions and enhanced hole extraction.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Addressable nanoantennas with cleared hotspots for single-molecule detection on a portable smartphone microscope},

author = {K Trofymchuk and V Glembockyte and L Grabenhorst and F Steiner and C Vietz and C Close and M Pfeiffer and L Richter and M L Sch\"{u}tte and F Selbach and R Yaadav and J Z\"{a}hringer and Q Wei and A Ozcan and B Lalkens and G P Acuna and P Tinnefeld},

url = {https://doi.org/10.1038/s41467-021-21238-9},

doi = {10.1038/s41467-021-21238-9},

issn = {2041-1723},

year  = {2021},

date = {2021-02-11},

urldate = {2021-02-11},

journal = {Nature Communications},

volume = {12},

number = {1},

pages = {950},

abstract = {The advent of highly sensitive photodetectors and the development of photostabilization strategies made detecting the fluorescence of single molecules a routine task in many labs around the world. However, to this day, this process requires cost-intensive optical instruments due to the truly nanoscopic signal of a single emitter. Simplifying single-molecule detection would enable many exciting applications, e.g., in point-of-care diagnostic settings, where costly equipment would be prohibitive. Here, we introduce addressable NanoAntennas with Cleared HOtSpots (NACHOS) that are scaffolded by DNA origami nanostructures and can be specifically tailored for the incorporation of bioassays. Single emitters placed in NACHOS emit up to 461-fold (average of 89 ± 7-fold) brighter enabling their detection with a customary smartphone camera and an 8-US-dollar objective lens. To prove the applicability of our system, we built a portable, battery-powered smartphone microscope and successfully carried out an exemplary single-molecule detection assay for DNA specific to antibiotic-resistant Klebsiella pneumonia on the road.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Perovskite Nanocrystals: Synthesis, Stability, and Optoelectronic Applications},

author = {S Wang and Yousefi A A Amin and L Wu and M Cao and Q Zhang and T Ameri},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/sstr.202000124},

doi = {https://doi.org/10.1002/sstr.202000124},

issn = {2688-4062},

year  = {2021},

date = {2021-02-07},

journal = {Small Structures},

volume = {n/a},

number = {n/a},

pages = {2000124},

abstract = {Metal halide perovskite (MHP) materials, named as the game changers, have attracted researchers’ attention worldwide for over a decade. Among them, nanometer-scale perovskite nanocrystals (PNCs) have exhibited attractive photophysical properties, such as tunable bandgaps, narrow emission, strong light-absorption coefficients, and high defect tolerance, because they combined the excellent optoelectronic properties of bulk perovskite materials with strong quantum confinement effects of the nanoscale. These materials possess a great potential to be applied in the optoelectronic devices. For commercial applications in devices like solar cells (SCs), light-emitting diodes (LEDs), and photodetectors (PDs), the stability of PNCs against ambient atmosphere like oxygen and moisture, as well as light and high temperature is crucial. Herein, the synthetic methods and stability issues of the PNCs are introduced first, followed by the introduction of the strategies for improving their stability by encapsulation. The applications of PNCs in various optoelectronic devices are then briefly presented. Finally, the remained challenges in improving the stability of PNCs toward the PNC-based optoelectronics with high performance and great durability are addressed.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Properties of the Space Charge Layers Formed in Li-Ion Conducting Glass Ceramics},

author = {L Katzenmeier and S Helmer and S Braxmeier and E Knobbe and A S Bandarenka},

url = {https://doi.org/10.1021/acsami.0c21304},

doi = {10.1021/acsami.0c21304},

issn = {1944-8244},

year  = {2021},

date = {2021-02-03},

journal = {ACS Applied Materials \& Interfaces},

volume = {13},

number = {4},

pages = {5853-5860},

abstract = {For years, the space charge layer formation in Li-conducting solid electrolytes and its relevance to so-called all solid-state batteries have been controversially discussed from experimental and theoretical perspectives. In this work, we observe the phenomenon of space charge layer formation using impedance spectroscopy at different electrode polarizations. We analyze the properties of these space charge layers using a physical equivalent circuit describing the response of the solid electrolytes and solid/solid electrified interfaces under blocking conditions. The elements corresponding to the interfacial layers are identified and analyzed with different electrode metals and applied biases. The effective thickness of the space charge layer was calculated to be ∼60 nm at a bias potential of 1 V. In addition, it was possible to estimate the relative permittivity of the electrolytes, specific resistance of the space charge layer, and the effective thickness of the electric double layer (∼0.7 nm).},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Electronic properties of semiconducting Zn(Si, Ge, Sn)N2 alloys},

author = {M Ogura and D Han and M M Pointner and L S Junkers and S S Rudel and W Schnick and H Ebert},

url = {https://link.aps.org/doi/10.1103/PhysRevMaterials.5.024601},

doi = {10.1103/PhysRevMaterials.5.024601},

year  = {2021},

date = {2021-02-02},

urldate = {2021-02-02},

journal = {Physical Review Materials},

volume = {5},

number = {2},

pages = {024601},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Examination of possible high-pressure candidates of SnTiO3: The search for novel ferroelectric materials},

author = {F Pielnhofer and L Diehl and A Jim\'{e}nez-Solano and A Bussmann-Holder and J C Sch\"{o}n and B V Lotsch},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0029968},

doi = {10.1063/5.0029968},

year  = {2021},

date = {2021-02-02},

journal = {APL Materials},

volume = {9},

number = {2},

pages = {021103},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Origin of Hole Transport in Small Molecule Dilute Donor Solar Cells},

author = {W Kaiser and L N S Murthy and C-L Chung and K-T Wong and J W P Hsu and A Gagliardi},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aesr.202000042},

doi = {https://doi.org/10.1002/aesr.202000042},

issn = {2699-9412},

year  = {2021},

date = {2021-02-01},

journal = {Advanced Energy and Sustainability Research},

volume = {2},

number = {3},

pages = {2000042},

abstract = {Dilute donor organic solar cells (OSCs) are a promising technology to circumvent the trade-off between open-circuit voltage (Voc) and short-circuit current density (Jsc). The origin of hole transport in OSCs with donor concentrations below the percolation threshold is diversely discussed in the community. Herein, both hole back transfer and long-range hopping (tunneling) are analyzed as possible mechanisms of photocurrent in small molecule dilute donor OSCs using kinetic Monte Carlo (kMC) simulations. In contrast to previous kMC studies, the driving force for exciton dissociation is accounted for. As a study system, nitrogen-bridged terthiophene (NBTT) molecules in a [6,6]-phenyl-C70-butyric acid methyl ester (PC71BM) matrix are investigated. The simulations show that hole back transfer from the small molecule donor to the fullerene matrix explains the measured concentration dependences of the photocurrents as well as the Jsc dependence on the light intensity for donor concentrations below 5 wt%. For 5 wt%, distances between NBTT molecules decrease to reasonable ranges that long-range hopping or tunneling cannot be discounted. Compared with polymer donors, larger hole localization is observed. The results emphasize that the barrier for hole back transfer is not only due to the highest occupied molecular orbital (HOMO) offset, but also by hole localization.},

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

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Formation Mechanisms for Phosphorene and SnIP},

author = {M R P Pielmeier and T Nilges},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202016257},

doi = {https://doi.org/10.1002/anie.202016257},

issn = {1433-7851},

year  = {2021},

date = {2021-01-29},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {Abstract Phosphorene\textemdashthe monolayered material of the element allotrope black phosphorus (Pblack)\textemdashand SnIP are 2D and 1D semiconductors with intriguing physical properties. Pblack and SnIP have in common that they can be synthesized via short way transport or mineralization using tin, tin(IV) iodide and amorphous red phosphorus. This top-down approach is the most important access route to phosphorene. The two preparation routes are closely connected and differ mainly in reaction temperature and molar ratios of starting materials. Many speculative intermediates or activator side phases have been postulated especially for top-down Pblack/phosphorene synthesis, such as Hittorf's phosphorus or Sn24P19.3I8 clathrate. The importance of phosphorus-based 2D and 1D materials for energy conversion, storage, and catalysis inspired us to elucidate the formation mechanisms of these two compounds. Herein, we report on the reaction mechanisms of Pblack/phosphorene and SnIP from P4 and SnI2 via direct gas phase formation.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Identification of Potential Optoelectronic Applications for Metal Thiophosphates},

author = {D Han and H Ebert},

url = {https://doi.org/10.1021/acsami.0c17818},

doi = {10.1021/acsami.0c17818},

issn = {1944-8244},

year  = {2021},

date = {2021-01-27},

urldate = {2021-01-27},

journal = {ACS Applied Materials \& Interfaces},

volume = {13},

number = {3},

pages = {3836-3844},

abstract = {Metal thiophosphates are a large family of compounds that received far less attention than conventional chalcogenides. Recently, however, metal thiophosphates arouse research interest in regard of energy harvesting and conversion due to their structural and chemical diversity. Nevertheless, there remain many unexplored metal thiophosphates. Here, we performed a comprehensive investigation on the electronic and optoelectronic properties of a series of metal thiophosphates using first-principles calculations and identified several highly promising compounds as p-type transparent conductors, photovoltaic absorbers, and single visible-light-driven photocatalysts for water splitting. Our investigation reveals the intrinsic features of a series of typical metal thiophosphates, identifies their new optoelectronic applications, and validates that metal thiophosphates are promising materials deserving exploration.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Gate-Switchable Arrays of Quantum Light Emitters in Contacted Monolayer MoS2 van der Waals Heterodevices},

author = {A H\"{o}tger and J Klein and K Barthelmi and L Sigl and F Sigger and W M\"{a}nner and S Gyger and M Florian and M Lorke and F Jahnke and T Taniguchi and K Watanabe and K D J\"{o}ns and U Wurstbauer and C Kastl and K M\"{u}ller and J J Finley and A W Holleitner},

url = {https://doi.org/10.1021/acs.nanolett.0c04222},

doi = {10.1021/acs.nanolett.0c04222},

issn = {1530-6984},

year  = {2021},

date = {2021-01-27},

journal = {Nano Letters},

volume = {21},

number = {2},

pages = {1040-1046},

abstract = {We demonstrate electrostatic switching of individual, site-selectively generated matrices of single photon emitters (SPEs) in MoS2 van der Waals heterodevices. We contact monolayers of MoS2 in field-effect devices with graphene gates and hexagonal boron nitride as the dielectric and graphite as bottom gates. After the assembly of such gate-tunable heterodevices, we demonstrate how arrays of defects, that serve as quantum emitters, can be site-selectively generated in the monolayer MoS2 by focused helium ion irradiation. The SPEs are sensitive to the charge carrier concentration in the MoS2 and switch on and off similar to the neutral exciton in MoS2 for moderate electron doping. The demonstrated scheme is a first step for producing scalable, gate-addressable, and gate-switchable arrays of quantum light emitters in MoS2 heterostacks.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Relaxed Current Matching Requirements in Highly Luminescent Perovskite Tandem Solar Cells and Their Fundamental Efficiency Limits},

author = {A R Bowman and F Lang and Y-H Chiang and A Jim\'{e}nez-Solano and K Frohna and G E Eperon and E Ruggeri and M Abdi-Jalebi and M Anaya and B V Lotsch and S D Stranks},

url = {https://doi.org/10.1021/acsenergylett.0c02481},

doi = {10.1021/acsenergylett.0c02481},

year  = {2021},

date = {2021-01-22},

journal = {ACS Energy Letters},

volume = {6},

number = {2},

pages = {612-620},

abstract = {Perovskite-based tandem solar cells are of increasing interest as they approach commercialization. Here we use experimental parameters from optical spectroscopy measurements to calculate the limiting efficiency of perovskite\textendashsilicon and all-perovskite two-terminal tandems, employing currently available bandgap materials, as 42.0% and 40.8%, respectively. We show luminescence coupling between subcells (the optical transfer of photons from the high-bandgap to low-bandgap subcell) relaxes current matching when the high-bandgap subcell is a luminescent perovskite. We calculate that luminescence coupling becomes important at charge trapping rates (≤106 s\textendash1) already being achieved in relevant halide perovskites. Luminescence coupling increases flexibility in subcell thicknesses and tolerance to different spectral conditions. For maximal benefit, the high-bandgap subcell should have the higher short-circuit current under average spectral conditions. This can be achieved by reducing the bandgap of the high-bandgap subcell, allowing wider, unstable bandgap compositions to be avoided. Lastly, we visualize luminescence coupling in an all-perovskite tandem through cross-section luminescence imaging.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Sensing a binding event through charge transport variations using an aromatic oligoamide capsule},

author = {P Mateus and A Jacquet and A M\'{e}ndez-Ardoy and A Boulloy and B Kauffmann and G Pecastaings and T Buffeteau and Y Ferrand and D M Bassani and I Huc},

url = {http://dx.doi.org/10.1039/D0SC06060G},

doi = {10.1039/D0SC06060G},

issn = {2041-6520},

year  = {2021},

date = {2021-01-22},

journal = {Chemical Science},

volume = {12},

number = {10},

pages = {3743-3750},

abstract = {The selective binding properties of a 13-mer oligoamide foldamer capsule composed of 4 different aromatic subunits are reported. The capsule was designed to recognize dicarboxylic acids through multiple-point interactions owing to a combination of protonation/deprotonation events, H-bonding, and geometrical constraints imparted by the rigidity of the foldamer backbone. Compared to tartaric acid, binding of 2,2-difluorosuccinic acid or 2,2,3,3-tetrafluorosuccinic acid resulted in symmetry breaking due to deprotonation of only one of the two carboxylic acid groups of the encapsulated species as shown by NMR studies in solution and by single-crystal X-ray diffraction in the solid state. An analogous 14-mer foldamer capsule terminated with a thiol anchoring group was used to probe the complexation event in self-assembled monolayers on Au substrates. Ellipsometry and polarization-modulation infrared absorption-reflection spectroscopy studies were consistent with the formation of a single molecule layer of the foldamer capsule oriented vertically with respect to the surface. The latter underwent smooth complexation of 2,2-difluorosuccinic acid with deprotonation of one of the two carboxylic acid groups. A significant (80-fold) difference in the charge transport properties of the monolayer upon encapsulation of the dicarboxylic acid was evidenced from conducting-AFM measurements (S = 1.1 × 10−9vs. 1.4 × 10−11 ohm−1 for the empty and complexed capsule, respectively). The modulation in conductivity was assigned to protonation of the aromatic foldamer backbone.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Engineering the Luminescence and Generation of Individual Defect Emitters in Atomically Thin MoS2},

author = {J Klein and L Sigl and S Gyger and K Barthelmi and M Florian and S Rey and T Taniguchi and K Watanabe and F Jahnke and C Kastl and V Zwiller and K D J\"{o}ns and K M\"{u}ller and U Wurstbauer and J J Finley and A W Holleitner},

url = {https://doi.org/10.1021/acsphotonics.0c01907},

doi = {10.1021/acsphotonics.0c01907},

year  = {2021},

date = {2021-01-21},

journal = {ACS Photonics},

abstract = {We demonstrate the on-demand creation and positioning of photon emitters in atomically thin MoS2 with very narrow ensemble broadening and negligible background luminescence. Focused helium-ion beam irradiation creates 100s to 1000s of such mono-typical emitters at specific positions in the MoS2 monolayers. Individually measured photon emitters show antibunching behavior with a g2(0) ∼ 0.23 and 0.27. From a statistical analysis, we extract the creation yield of the He-ion induced photon emitters in MoS2 as a function of the exposed area, as well as the total yield of single emitters as a function of the number of He ions when single spots are irradiated by He ions. We reach probabilities as high as 18% for the generation of individual and spectrally clean photon emitters per irradiated single site. Our results firmly establish 2D materials as a platform for photon emitters with unprecedented control of position as well as photophysical properties owing to the all-interfacial nature.},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Synergistic Interplay between Asymmetric Backbone Conformation, Molecular Aggregation, and Charge-Carrier Dynamics in Fused-Ring Electron Acceptor-Based Bulk Heterojunction Solar Cells},

author = {X Song and L Hou and R Guo and Q Wei and L Yang and X Jiang and S Tu and A Zhang and Z Kan and W Tang and G Xing and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.0c19700},

doi = {10.1021/acsami.0c19700},

issn = {1944-8244},

year  = {2021},

date = {2021-01-20},

urldate = {2021-01-20},

journal = {ACS Applied Materials \& Interfaces},

volume = {13},

number = {2},

pages = {2961-2970},

abstract = {Asymmetric fused-ring electron acceptors (a-FREAs) have proved to be a promising type of electron acceptor for high-performance organic solar cells (OSCs). However, the relationship among molecular structures of a-FREAs and their nanoscale morphology, charge-carrier dynamics, and device performance remains unclear. In this contribution, two FREAs differing in conjugated backbone geometry with an asymmetric conformation (IPT-2F) or symmetric one (INPIC-2F) are selected to systematically explore the superiorities of the asymmetric conformation. Despite the frailer extinction coefficient and weaker crystallinity, IPT-2F shows stronger dipole interactions in the asymmetrical backbone, which would induce a closer lamellar packing than that of the symmetrical counterpart. Using PBDB-T as the electron donor, the IPT-2F-based OSCs achieve the best power conversion efficiency of 14.0%, which is ca. 67% improvement compared to the INPIC-2F-based ones (8.37%), resulting from a simultaneously increased short-circuited current density (Jsc) and fill factor. Systematical investigations on optoelectronic and morphological properties show that the asymmetric conformation-structured IPT-2F exhibits better miscibility with the polymer donor to induce a favorable blend ordering with small domain sizes and suitable phase separation compared to the INPIC-2F symmetric molecule. This facilitates an efficient charge generation and transport, inhibits charge-carrier recombination, and promotes valid charge extraction in IPT-2F-based devices.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {3D Deep Learning Enables Accurate Layer Mapping of 2D Materials},

author = {X Dong and H Li and Z Jiang and T Gr\"{u}nleitner and \.{I} G\"{u}ler and J Dong and K Wang and M H K\"{o}hler and M Jakobi and B H Menze and A K Yetisen and I D Sharp and A V Stier and J J Finley and A W Koch},

url = {https://doi.org/10.1021/acsnano.0c09685},

doi = {10.1021/acsnano.0c09685},

issn = {1936-0851},

year  = {2021},

date = {2021-01-19},

journal = {ACS Nano},

volume = {15},

number = {2},

pages = {3139-3151},

abstract = {Layered, two-dimensional (2D) materials are promising for next-generation photonics devices. Typically, the thickness of mechanically cleaved flakes and chemical vapor deposited thin films is distributed randomly over a large area, where accurate identification of atomic layer numbers is time-consuming. Hyperspectral imaging microscopy yields spectral information that can be used to distinguish the spectral differences of varying thickness specimens. However, its spatial resolution is relatively low due to the spectral imaging nature. In this work, we present a 3D deep learning solution called DALM (deep-learning-enabled atomic layer mapping) to merge hyperspectral reflection images (high spectral resolution) and RGB images (high spatial resolution) for the identification and segmentation of MoS2 flakes with mono-, bi-, tri-, and multilayer thicknesses. DALM is trained on a small set of labeled images, automatically predicts layer distributions and segments individual layers with high accuracy, and shows robustness to illumination and contrast variations. Further, we show its advantageous performance over the state-of-the-art model that is solely based on RGB microscope images. This AI-supported technique with high speed, spatial resolution, and accuracy allows for reliable computer-aided identification of atomically thin materials.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Raman spectrum of Janus transition metal dichalcogenide monolayers WSSe and MoSSe},

author = {M M Petri\'{c} and M Kremser and M Barbone and Y Qin and Y Sayyad and Y Shen and S Tongay and J J Finley and A R Botello-M\'{e}ndez and K M\"{u}ller},

url = {https://link.aps.org/doi/10.1103/PhysRevB.103.035414},

doi = {10.1103/PhysRevB.103.035414},

year  = {2021},

date = {2021-01-15},

journal = {Physical Review B},

volume = {103},

number = {3},

pages = {035414},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Pulsed Interleaved MINFLUX},

author = {L A Masullo and F Steiner and J Z\"{a}hringer and L F Lopez and J Bohlen and L Richter and F Cole and P Tinnefeld and F D Stefani},

url = {https://doi.org/10.1021/acs.nanolett.0c04600},

doi = {10.1021/acs.nanolett.0c04600},

issn = {1530-6984},

year  = {2021},

date = {2021-01-13},

urldate = {2021-01-13},

journal = {Nano Letters},

volume = {21},

number = {1},

pages = {840-846},

abstract = {We introduce p-MINFLUX, a new implementation of the highly photon-efficient single-molecule localization method with a simplified experimental setup and additional fluorescence lifetime information. In contrast to the original MINFLUX implementation, p-MINFLUX uses interleaved laser pulses to deliver the doughnut-shaped excitation foci at a maximum repetition rate. Using both static and dynamic DNA origami model systems, we demonstrate the performance of p-MINFLUX for single-molecule localization nanoscopy and tracking, respectively. p-MINFLUX delivers 1\textendash2 nm localization precision with 2000\textendash1000 photon counts. In addition, p-MINFLUX gives access to the fluorescence lifetime enabling multiplexing and super-resolved lifetime imaging. p-MINFLUX should help to unlock the full potential of innovative single-molecule localization schemes.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Pure non-local machine-learned density functional theory for electron correlation},

author = {J T Margraf and K Reuter},

url = {https://doi.org/10.1038/s41467-020-20471-y},

doi = {10.1038/s41467-020-20471-y},

issn = {2041-1723},

year  = {2021},

date = {2021-01-12},

urldate = {2021-01-12},

journal = {Nature Communications},

volume = {12},

number = {1},

pages = {344},

abstract = {Density-functional theory (DFT) is a rigorous and (in principle) exact framework for the description of the ground state properties of atoms, molecules and solids based on their electron density. While computationally efficient density-functional approximations (DFAs) have become essential tools in computational chemistry, their (semi-)local treatment of electron correlation has a number of well-known pathologies, e.g. related to electron self-interaction. Here, we present a type of machine-learning (ML) based DFA (termed Kernel Density Functional Approximation, KDFA) that is pure, non-local and transferable, and can be efficiently trained with fully quantitative reference methods. The functionals retain the mean-field computational cost of common DFAs and are shown to be applicable to non-covalent, ionic and covalent interactions, as well as across different system sizes. We demonstrate their remarkable possibilities by computing the free energy surface for the protonated water dimer at hitherto unfeasible gold-standard coupled cluster quality on a single commodity workstation.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Charged Exciton Kinetics in Monolayer MoSe2 near Ferroelectric Domain Walls in Periodically Poled LiNbO3},

author = {P Soubelet and J Klein and J Wierzbowski and R Silvioli and F Sigger and A V Stier and K Gallo and J J Finley},

url = {https://doi.org/10.1021/acs.nanolett.0c03810},

doi = {10.1021/acs.nanolett.0c03810},

issn = {1530-6984},

year  = {2021},

date = {2021-01-11},

journal = {Nano Letters},

volume = {21},

number = {2},

pages = {959-966},

abstract = {Monolayer semiconducting transition metal dichalcogenides are a strongly emergent platform for exploring quantum phenomena in condensed matter, building novel optoelectronic devices with enhanced functionalities. Because of their atomic thickness, their excitonic optical response is highly sensitive to their dielectric environment. In this work, we explore the optical properties of monolayer thick MoSe2 straddling domain wall boundaries in periodically poled LiNbO3. Spatially resolved photoluminescence experiments reveal spatial sorting of charge and photogenerated neutral and charged excitons across the boundary. Our results reveal evidence for extremely large in-plane electric fields of ≃4000 kV/cm at the domain wall whose effect is manifested in exciton dissociation and routing of free charges and trions toward oppositely poled domains and a nonintuitive spatial intensity dependence. By modeling our result using drift-diffusion and continuity equations, we obtain excellent qualitative agreement with our observations and have explained the observed spatial luminescence modulation using realistic material parameters.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Growth dynamics and compositional structure in periodic InAsSb nanowire arrays on Si (111) grown by selective area molecular beam epitaxy},

author = {D Ruhstorfer and A Lang and S Matich and M D\"{o}blinger and H Riedl and J J Finley and G Koblm\"{u}ller},

issn = {0957-4484},

year  = {2021},

date = {2021-01-08},

journal = {Nanotechnology},

volume = {32},

number = {13},

pages = {135604},

keywords = {Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Layer-by-Layer Spray-Coating of Cellulose Nanofibrils and Silver Nanoparticles for Hydrophilic Interfaces},

author = {Q Chen and C J Brett and A Chumakov and M Gensch and M Schwartzkopf and V K\"{o}rstgens and L D S\"{o}derberg and A Plech and P Zhang and P M\"{u}ller-Buschbaum and S V Roth},

url = {https://doi.org/10.1021/acsanm.0c02819},

doi = {10.1021/acsanm.0c02819},

year  = {2021},

date = {2021-01-05},

urldate = {2021-01-05},

journal = {ACS Applied Nano Materials},

volume = {4},

number = {1},

pages = {503-513},

abstract = {Silver nanoparticles (AgNPs) and AgNP-based composite materials have attracted growing interest due to their structure-dependent optical, electrical, catalytic, and stimuli-responsive properties. For practical applications, polymeric materials are often combined with AgNPs to provide flexibility and offer a scaffold for homogenous distribution of the AgNPs. However, the control over the assembly process of AgNPs on polymeric substrates remains a big challenge. Herein, we report the fabrication of AgNP/cellulose nanofibril (CNF) thin films via layer-by-layer (LBL) spray-coating. The morphology and self-assembly of AgNPs with increasing number of spray cycles are characterized by atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), and grazing-incidence wide-angle X-ray scattering (GIWAXS). We deduce that an individual AgNP (radius = 15 ± 3 nm) is composed of multiple nanocrystallites (diameter = 2.4 ± 0.9 nm). Our results suggest that AgNPs are assembled into large agglomerates on SiO2 substrates during spray-coating, which is disadvantageous for AgNP functionalization. However, the incorporation of CNF substrates contributes to a more uniform distribution of AgNP agglomerates and individual AgNPs by its network structure and by absorbing the partially dissolved AgNP agglomerates. Furthermore, we demonstrate that the spray-coating of the AgNP/CNF mixture results in similar topography and agglomeration patterns of AgNPs compared to depositing AgNPs onto a precoated CNF thin film. Contact-angle measurements and UV/vis spectroscopy suggest that the deposition of AgNPs onto or within CNFs could increase the hydrophilicity of AgNP-containing surfaces and the localized surface plasmon resonance (LSPR) intensity of AgNP compared to AgNPs sprayed on SiO2 substrates, suggesting their potential applications in antifouling coatings or label-free biosensors. Thereby, our approach provides a platform for a facile and scalable production of AgNP/CNF films with a low agglomeration rate by two different methods as follows: (1) multistep layer-by-layer (LBL) spray-coating and (2) direct spray-coating of the AgNP/CNF mixture. We also demonstrate the ability of CNFs as a flexible framework for directing the uniform assembly of AgNPs with tailorable wettability and plasmonic properties.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Ultrafast hot carrier relaxation in silicon monitored by phase-resolved transient absorption spectroscopy},

author = {M W\"{o}rle and A W Holleitner and R Kienberger and H Iglev},

year  = {2021},

date = {2021-01-05},

journal = {arXiv preprint arXiv:2101.01439},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Entrapped Molecular Photocatalyst and Photosensitizer in Metal\textendashOrganic Framework Nanoreactors for Enhanced Solar CO2 Reduction},

author = {P M Stanley and C Thomas and E Thyrhaug and A Urstoeger and M Schuster and J Hauer and B Rieger and J Warnan and R A Fischer},

url = {https://doi.org/10.1021/acscatal.0c04673},

doi = {10.1021/acscatal.0c04673},

year  = {2021},

date = {2021-01-05},

urldate = {2021-01-05},

journal = {ACS Catalysis},

volume = {11},

number = {2},

pages = {871-882},

abstract = {Herein, we report on a molecular catalyst embedding metal\textendashorganic framework (MOF) that enables enhanced photocatalytic CO2 reduction activity. A benchmark photocatalyst fac-ReBr(CO)3(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)2(5,5′-dcbpy)Cl2 (bpy = 2,2′-bipyridine) were synergistically entrapped inside the cages of the nontoxic and inexpensive MIL-101-NH2(Al) through noncovalent host\textendashguest interactions. The heterogeneous material improved Re catalyst stabilization under photocatalytic CO2 reduction conditions as selective CO evolution was prolonged from 1.5 to 40 h compared to the MOF-free photosystem upon reactivation with additional photosensitizer. By varying ratios of immobilized catalyst to photosensitizer, we demonstrated and evaluated the effect of reaction environment modulation in defined MOF cages acting as a nanoreactor. This illustrated the optimal efficiency for two photosensitizers and one catalyst per cage and further led to the determination of ad hoc relationships between molecular complex size, MOF pore windows, and number of hostable molecules per cage. Differing from typical homogeneous systems, photosensitizer\textemdashand not catalyst\textemdashdegradation was identified as a major performance-limiting factor, providing a future route to higher turnover numbers via a rational choice of parameters.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Morphology Control in 2D Carbon Nitrides: Impact of Particle Size on Optoelectronic Properties and Photocatalysis},

author = {J Kr\"{o}ger and A Jim\'{e}nez-Solano and G Savasci and V W H Lau and V Duppel and I Moudrakovski and K K\"{u}ster and T Scholz and A Gouder and M-L Schreiber and F Podjaski and C Ochsenfeld and B V Lotsch},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202102468},

doi = {https://doi.org/10.1002/adfm.202102468},

issn = {1616-301X},

year  = {2021},

date = {2021-01-01},

urldate = {2021-01-01},

journal = {Advanced Functional Materials},

volume = {31},

number = {28},

pages = {2102468},

abstract = {Abstract The carbon nitride poly(heptazine imide), PHI, has recently emerged as a powerful 2D carbon nitride photocatalyst with intriguing charge storing ability. Yet, insights into how morphology, particle size, and defects influence its photophysical properties are virtually absent. Here, ultrasonication is used to systematically tune the particle size as well as concentration of surface functional groups and study their impact. Enhanced photocatalytic activity correlates with an optimal amount of those defects that create shallow trap states in the optical band gap, promoting charge percolation, as evidenced by time-resolved photoluminescence spectroscopy, charge transport studies, and quantum-chemical calculations. Excessive amounts of terminal defects can act as recombination centers and hence, decrease the photocatalytic activity for hydrogen evolution. Re-agglomeration of small particles can, however, partially restore the photocatalytic activity. The type and amount of trap states at the surface can also influence the deposition of the co-catalyst Pt, which is used in hydrogen evolution experiments. Optimized conditions entail improved Pt distribution, as well as enhanced wettability and colloidal stability. A description of the interplay between these effects is provided to obtain a holistic picture of the size\textendashproperty\textendashactivity relationship in nanoparticulate PHI-type carbon nitrides that can likely be generalized to related photocatalytic systems.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {DNA origami based superconducting nanowires},

author = {L Shani and P Tinnefeld and Y Fleger and A Sharoni and B Y Shapiro and A Shaulov and O Gang and Y Yeshurun},

url = {https://doi.org/10.1063/5.0029781},

doi = {10.1063/5.0029781},

year  = {2021},

date = {2021-01-01},

urldate = {2021-01-01},

journal = {AIP Advances},

volume = {11},

number = {1},

pages = {015130},

keywords = {Foundry Inorganic, Foundry Organic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {A Solution-Processable Polymer-Based Thin-Film Thermoelectric Generator},

author = {R M Kluge and N Saxena and P M\"{u}ller-Buschbaum},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aesr.202000060},

doi = {https://doi.org/10.1002/aesr.202000060},

issn = {2699-9412},

year  = {2021},

date = {2021-01-01},

urldate = {2021-01-01},

journal = {Advanced Energy and Sustainability Research},

volume = {2},

number = {1},

pages = {2000060},

abstract = {Thermoelectric modules are capable of transforming thermal energy into electrical power. Implementing earth-abundant and cost-effective organic materials, they can contribute to an eco-friendly way of energy production out of low-grade waste heat and natural heat sources via the Seebeck effect. Moreover, the flexibility of organic materials can allow for adaption to curved surfaces such as the human skin and wearable electronics. Herein, a solution-processable thermoelectric generator (TEG) using exclusively polymers as active materials is presented. The high-mobility n-type polymer poly[[N,N-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5-(2,2-bithiophene)] (P(NDI2OD-T2)) and the widely studied p-type polymer blend poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) are combined into a thin-film TEG. The presented device design is not limited to this system but is applicable to any pair of organic materials processable from solution and can be easily upscaled to fully flexible devices via, e.g., printing and roll-to-roll processing.},

keywords = {Foundry Organic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Electrochemical top-down synthesis of C-supported Pt nano-particles with controllable shape and size: Mechanistic insights and application},

author = {B Garlyyev and S Watzele and J Fichtner and J Michali\v{c}ka and A Sch\"{o}kel and A Senyshyn and A Perego and D Pan and H A El-Sayed and J M Macak and P Atanassov and I V Zenyuk and A S Bandarenka},

url = {https://doi.org/10.1007/s12274-020-3281-z},

doi = {10.1007/s12274-020-3281-z},

issn = {1998-0000},

year  = {2020},

date = {2020-12-29},

journal = {Nano Research},

volume = {14},

number = {8},

pages = {2762-2769},

abstract = {In this work, we demonstrate the power of a simple top-down electrochemical erosion approach to obtain Pt nanoparticle with controlled shapes and sizes (in the range from ~ 2 to ~ 10 nm). Carbon supported nanoparticles with narrow size distributions have been synthesized by applying an alternating voltage to macroscopic bulk platinum structures, such as disks or wires. Without using any surfactants, the size and shape of the particles can be changed by adjusting simple parameters such as the applied potential, frequency and electrolyte composition. For instance, application of a sinusoidal AC voltage with lower frequencies results in cubic nanoparticles; whereas higher frequencies lead to predominantly spherical nanoparticles. On the other hand, the amplitude of the sinusoidal signal was found to affect the particle size; the lower the amplitude of the applied AC signal, the smaller the resulting particle size. Pt/C catalysts prepared by this approach showed 0.76 A/mg mass activity towards the oxygen reduction reaction which is ~ 2 times higher than the state-of-the-art commercial Pt/C catalyst (0.42 A/mg) from Tanaka. In addition to this, we discussed the mechanistic insights about the nanoparticle formation pathways.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Challenges in Plasmonic Catalysis},

author = {E Cort\'{e}s and L V Besteiro and A Alabastri and A Baldi and G Tagliabue and A Demetriadou and P Narang},

url = {https://doi.org/10.1021/acsnano.0c08773},

doi = {10.1021/acsnano.0c08773},

issn = {1936-0851},

year  = {2020},

date = {2020-12-22},

urldate = {2020-12-22},

journal = {ACS Nano},

volume = {14},

number = {12},

pages = {16202-16219},

abstract = {The use of nanoplasmonics to control light and heat close to the thermodynamic limit enables exciting opportunities in the field of plasmonic catalysis. The decay of plasmonic excitations creates highly nonequilibrium distributions of hot carriers that can initiate or catalyze reactions through both thermal and nonthermal pathways. In this Perspective, we present the current understanding in the field of plasmonic catalysis, capturing vibrant debates in the literature, and discuss future avenues of exploration to overcome critical bottlenecks. Our Perspective spans first-principles theory and computation of correlated and far-from-equilibrium light\textendashmatter interactions, synthesis of new nanoplasmonic hybrids, and new steady-state and ultrafast spectroscopic probes of interactions in plasmonic catalysis, recognizing the key contributions of each discipline in realizing the promise of plasmonic catalysis. We conclude with our vision for fundamental and technological advances in the field of plasmon-driven chemical reactions in the coming years.},

keywords = {Foundry Inorganic, Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Interfacial Engineering for Improved Photocatalysis in a Charge Storing 2D Carbon Nitride: Melamine Functionalized Poly(heptazine imide)},

author = {J Kr\"{o}ger and A Jim\'{e}nez-Solano and G Savasci and P Rov\'{o} and I Moudrakovski and K K\"{u}ster and H Schlomberg and H A Vignolo-Gonz\'{a}lez and V Duppel and L Grunenberg and C B Dayan and M Sitti and F Podjaski and C Ochsenfeld and B V Lotsch},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/aenm.202003016},

doi = {https://doi.org/10.1002/aenm.202003016},

issn = {1614-6832},

year  = {2020},

date = {2020-12-21},

journal = {Advanced Energy Materials},

volume = {11},

number = {6},

pages = {2003016},

abstract = {Abstract Carbon nitrides constitute a class of earth-abundant polymeric semiconductors, which have high potential for tunability on a molecular level, despite their high chemical and thermal inertness. Here the first postsynthetic modification of the 2D carbon nitride poly(heptazine imide) (PHI) is reported, which is decorated with terminal melamine (Mel) moieties by a functional group interconversion. The covalent attachment of this group is verified based with a suite of spectroscopic and microscopic techniques supported by quantum\textendashchemical calculations. Using triethanolamine as a sacrificial electron donor, Mel-PHI outperforms most other carbon nitrides in terms of hydrogen evolution rate (5570 µmol h−1 g−1), while maintaining the intrinsic light storing properties of PHI. The origin of the observed superior photocatalytic performance is traced back to a modified surface electronic structure and enhanced interfacial interactions with the amphiphile triethanolamine, which imparts improved colloidal stability to the catalyst particles especially in contrast to methanol used as donor. However, this high activity can be limited by oxidation products of donor reversibly building up at the surface, thus blocking active centers. The findings lay out the importance of surface functionalization to engineer the catalyst\textendashsolution interface, an underappreciated tuning parameter in photocatalytic reaction design.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Optoelectronic processes in covalent organic frameworks},

author = {N Keller and T Bein},

url = {http://dx.doi.org/10.1039/D0CS00793E},

doi = {10.1039/D0CS00793E},

issn = {0306-0012},

year  = {2020},

date = {2020-12-17},

journal = {Chemical Society Reviews},

abstract = {Covalent organic frameworks (COFs) are crystalline porous materials constructed from molecular building blocks using diverse linkage chemistries. Their modular construction system allows not only for tailor-made design but also for an immense variety of building blocks, opening the door to numerous different functionalities and potential applications. As a consequence, a large number of building blocks that can act as light-harvesters, semiconductors, ligands, binding sites or redox centers have recently been integrated into the scaffolds of COFs. This unique combination of reticular chemistry with the molecular control of intrinsic properties paves the way towards the design of new semiconducting materials for (opto-)electronic applications such as sensors, photocatalysts or -electrodes, supercapacitor and battery materials, solar-harvesting devices or light emitting diodes. With new developments regarding the linkage motif, highly stable but still tunable COFs have been developed for applications even under harsh conditions. Further, the molecular stacking modes and distances in the COFs have been investigated as a powerful means to control optical and electrical characteristics of these self-assembled frameworks. Advanced understanding of optoelectronic processes in COFs has enabled their implementation in optoelectronic devices with promising potential for real-world applications. This review highlights the key developments of design concepts for the synthesis of electro- and photoactive COFs as well as our understanding of optoelectronic processes in these frameworks, hence establishing a new paradigm for the rational construction of well-defined novel optoelectronic materials and devices.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {In Situ Study of Order Formation in Mesoporous Titania Thin Films Templated by a Diblock Copolymer during Slot-Die Printing},

author = {N Li and W Chen and L Song and R Guo and M A Scheel and D Yang and V K\"{o}rstgens and M Schwartzkopf and S V Roth and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsami.0c18851},

doi = {10.1021/acsami.0c18851},

issn = {1944-8244},

year  = {2020},

date = {2020-12-09},

urldate = {2020-12-09},

journal = {ACS Applied Materials \& Interfaces},

volume = {12},

number = {51},

pages = {57627-57637},

abstract = {Slot-die printing, a large-scale deposition technique, is applied to fabricate mesoporous titania films. Printing is interesting, for example, for scaling up solar cells where titania films with an interconnected mesoporous network and a large surface-to-volume ratio are desired as photoanodes. A fundamental understanding of the structure evolution during printing is of high significance in tailoring these films. In this work, we provide important insights into the self-assembly of the slot-die-printed titania/polystyrene-block-poly(ethylene oxide) (PS-b-PEO) micelles into ordered hybrid structures in real time via in situ grazing-incidence small-angle X-ray scattering (GISAXS). GISAXS allows for tracking both vertical and lateral structure development of the film formation process. In the hybrid film, a face-centered cubic (FCC) structure is preferentially formed at the interfaces with air and with the substrate, while a defect-rich mixed FCC and body-centered cubic (BCC) structure forms in the bulk. After calcination, the surface and inner morphologies of the obtained nanostructured titania films are compared with the spin-coated analogues. In the printed films, the initially formed nanoscale structure of the hybrid film is preserved, and the resulting mesoporous titania film shows a superior order as compared with the spin-coated thin films which can be beneficial for future applications.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Covalent Graphene-MOF Hybrids for High-Performance Asymmetric Supercapacitors},

author = {K Jayaramulu and M Horn and A Schneemann and H Saini and A Bakandritsos and V Ranc and M Petr and V Stavila and C Narayana and B Scheibe and \v{S} Kment and M Otyepka and N Motta and D Dubal and R Zbo\v{r}il and R A Fischer},

url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.202004560},

doi = {https://doi.org/10.1002/adma.202004560},

issn = {0935-9648},

year  = {2020},

date = {2020-12-04},

journal = {Advanced Materials},

volume = {33},

number = {4},

pages = {2004560},

abstract = {Abstract In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2 = Zr6O4(OH)4(bdc-NH2)6; bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g−1, significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3C2TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg−1 and an energy density of up to 73 Wh kg−1, which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.},

keywords = {Foundry Inorganic, Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Template Dissolution Interfacial Patterning of Single Colloids for Nanoelectrochemistry and Nanosensing},

author = {J B Lee and H Walker and Y Li and T W Nam and A Rakovich and R Sapienza and Y S Jung and Y S Nam and S A Maier and E Cort\'{e}s},

url = {https://doi.org/10.1021/acsnano.0c09319},

doi = {10.1021/acsnano.0c09319},

issn = {1936-0851},

year  = {2020},

date = {2020-12-03},

urldate = {2020-12-03},

journal = {ACS Nano},

abstract = {Deterministic positioning and assembly of colloidal nanoparticles (NPs) onto substrates is a core requirement and a promising alternative to top-down lithography to create functional nanostructures and nanodevices with intriguing optical, electrical, and catalytic features. Capillary-assisted particle assembly (CAPA) has emerged as an attractive technique to this end, as it allows controlled and selective assembly of a wide variety of NPs onto predefined topographical templates using capillary forces. One critical issue with CAPA, however, lies in its final printing step, where high printing yields are possible only with the use of an adhesive polymer film. To address this problem, we have developed a template dissolution interfacial patterning (TDIP) technique to assemble and print single colloidal AuNP arrays onto various dielectric and conductive substrates in the absence of any adhesion layer, with printing yields higher than 98%. The TDIP approach grants direct access to the interface between the AuNP and the target surface, enabling the use of colloidal AuNPs as building blocks for practical applications. The versatile applicability of TDIP is demonstrated by the creation of direct electrical junctions for electro- and photoelectrochemistry and nanoparticle-on-mirror geometries for single-particle molecular sensing.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Time-domain photocurrent spectroscopy based on a common-path birefringent interferometer},

author = {L Wolz and C Heshmatpour and A Perri and D Polli and G Cerullo and J J Finley and E Thyrhaug and J Hauer and A V Stier},

url = {https://aip.scitation.org/doi/abs/10.1063/5.0023543},

doi = {10.1063/5.0023543},

year  = {2020},

date = {2020-12-02},

urldate = {2020-12-02},

journal = {Review of Scientific Instruments},

volume = {91},

number = {12},

pages = {123101},

keywords = {Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Spray-deposited PbS colloidal quantum dot solid for near-infrared photodetectors},

author = {W Chen and H Tang and Y Chen and J E Heger and N Li and L P Kreuzer and Y Xie and D Li and C Anthony and Z Pikramenou and K W Ng and X W Sun and K Wang and P M\"{u}ller-Buschbaum},

url = {https://www.sciencedirect.com/science/article/pii/S2211285520308326},

doi = {https://doi.org/10.1016/j.nanoen.2020.105254},

issn = {2211-2855},

year  = {2020},

date = {2020-12-01},

urldate = {2020-12-01},

journal = {Nano Energy},

volume = {78},

pages = {105254},

abstract = {Colloidal PbS quantum dots (QDs) are promising candidates for various optoelectronic applications based on solution-processed thin-film techniques. In this work, a versatile layer-by-layer (LBL) spray deposition of the QDs is introduced aiming for a future large-scale fabrication process of optoelectronic devices. As compared to spin-coated QD solids, a smaller inter-dot distance and a better-ordered superlattice stacking behavior of the QDs are found in the spray-deposited QD solids as confirmed by grazing-incidence small-angle X-ray scattering (GISAXS). The spectral mapping combined time-resolved photoluminescence analysis indicates a longer charge carrier lifetime and better order of the energy state distribution of the spray-deposited QD solid comparing with the spin-coated one. Thus, photodetectors based on spray deposition of QD solids demonstrate an excellent device performance, with the responsivity achieving 365.1 A/W and the detectivity reaching up to 1.4 × 1012 Jones under an illumination power of 63.5 μW/cm2 at a wavelength of 1250 nm. The spray-deposited device performances indicate a great potential of spray deposition of large sized QDs in large-scale fabrications for optoelectronics using longer wavelengths.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Anharmonic host-lattice dynamics enable fast ion conduction in superionic AgI},

author = {T M Brenner and C Gehrmann and R Korobko and T Livneh and D A Egger and O Yaffe},

url = {https://link.aps.org/doi/10.1103/PhysRevMaterials.4.115402},

doi = {10.1103/PhysRevMaterials.4.115402},

year  = {2020},

date = {2020-11-30},

urldate = {2020-11-30},

journal = {Physical Review Materials},

volume = {4},

number = {11},

pages = {115402},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Mode-Matching Enhancement of Second-Harmonic Generation with Plasmonic Nanopatch Antennas},

author = {A Noor and A R Damodaran and I-H Lee and S A Maier and S-H Oh and C Cirac\`{i}},

url = {https://doi.org/10.1021/acsphotonics.0c01545},

doi = {10.1021/acsphotonics.0c01545},

year  = {2020},

date = {2020-11-25},

journal = {ACS Photonics},

volume = {7},

number = {12},

pages = {3333-3340},

abstract = {Plasmonic enhancement of nonlinear optical processes confront severe limitations arising from the strong dispersion of metal susceptibilities and small interaction volumes that hamper the realization of desirable phase-matching-like conditions. Maximizing nonlinear interactions in nanoscale systems require simultaneous excitation of resonant modes that spatially and constructively overlap at all wavelengths involved in the process. Here, we present a hybrid rectangular patch antenna design for optimal second-harmonic generation (SHG) that is characterized by a non-centrosymmetric dielectric/ferroelectric material at the plasmonic hot spot. The optimization of the rectangular patch allows for the independent tuning of various modes of resonances that can be used to enhance the SHG process. We explore the angular dependence of SHG in these hybrid structures and highlight conditions necessary for the maximal SHG efficiency. Furthermore, we propose a novel configuration with a periodically poled ferroelectric layer for an orders-of-magnitude enhanced SHG at normal incidence. Such a platform may enable the development of integrated nanoscale light sources and on-chip frequency converters.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Optoelectronic Properties of Cs2AgBiBr6 Thin Films: The Influence of Precursor Stoichiometry},

author = {M T Sirtl and M Armer and L K Reb and R Hooijer and P D\"{o}rflinger and M A Scheel and K Tvingstedt and P Rieder and N Gl\"{u}ck and P Pandit and S V Roth and P M\"{u}ller-Buschbaum and V Dyakonov and T Bein},

url = {https://doi.org/10.1021/acsaem.0c01308},

doi = {10.1021/acsaem.0c01308},

year  = {2020},

date = {2020-11-25},

journal = {ACS Applied Energy Materials},

abstract = {Lead-free double perovskites have recently attracted growing attention as possible alternatives to lead-based halide perovskites in photovoltaics and other optoelectronic applications. The most prominent compound Cs2AgBiBr6, however, presents issues such as a rather large and indirect band gap, high exciton binding energies, and poor charge carrier transport, especially in thin films. In order to address some of these challenges, we systematically modified the stoichiometry of the precursors used for the synthesis of thin films toward a BiBr3-deficient system. In combination with a stoichiometric excess of AgBr, we obtained highly oriented double perovskite thin films. These modifications directly boost the lifetime of the charge carriers up to 500 ns as observed by time-resolved photoluminescence spectroscopy. Moreover, time-resolved microwave conductivity studies revealed an increase of the charge carrier mobility from 3.5 to around ∼5 cm2/(V s). Solar cells comprising the modified films as planar active layers reached power conversion efficiency (PCE) values up to 1.11%, exceeding the stoichiometric reference film (∼0.97%), both on average and with champion cells. The results in this work underline the importance of controlling the nanomorphology of the bulk film. We anticipate that control of precursor stoichiometry will also offer a promising approach for enhancing the efficiency of other perovskite photovoltaic absorber materials and thin films.},

keywords = {Foundry Inorganic, Solid-Solid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Hierarchical Structures from Nanocrystalline Colloidal Precursors within Hybrid Perovskite Thin Films: Implications for Photovoltaics},

author = {S Pratap and J Schlipf and L Bie\ssmann and P M\"{u}ller-Buschbaum},

url = {https://doi.org/10.1021/acsanm.0c03000},

doi = {10.1021/acsanm.0c03000},

year  = {2020},

date = {2020-11-23},

urldate = {2020-11-23},

journal = {ACS Applied Nano Materials},

volume = {3},

number = {12},

pages = {11701-11708},

abstract = {Originating from stochastic nanocrystalline colloidal precursors with differential chemical compositions, crystalline thin films exhibit hierarchical structures originating at the crystallographic level and scaling up to mesoscale structures, manifested within their nanocrystalline morphology and mesoscale topology. We interlink morphogenetic signatures within thin films to differential precursor chemistry and explain the cooperative impact of structure-defining inorganic and organic counterparts on perovskite hybrids. Understanding the effect of chemical species on the structural characteristics of thin films and leveraging complex assembly processes present facile routes to tuning multiscale morphologies in thin films, pertinent for engineering functional performance metrics within thin-film perovskite photovoltaics.},

keywords = {Foundry Inorganic, Solid-Liquid},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Anharmonic Molecular Motion Drives Resonance Energy Transfer in peri-Arylene Dyads},

author = {V Sl\'{a}ma and V Perl\'{i}k and H Langhals and A Walter and T Man\v{c}al and J Hauer and F \v{S}anda},

url = {https://www.frontiersin.org/article/10.3389/fchem.2020.579166},

doi = {10.3389/fchem.2020.579166},

issn = {2296-2646},

year  = {2020},

date = {2020-11-23},

urldate = {2020-11-23},

journal = {Frontiers in Chemistry},

volume = {8},

abstract = {Spectral and dynamical properties of molecular donor-acceptor systems strongly depend on the steric arrangement of the constituents with exciton coupling J as a key control parameter. In the present work we study two peri-arylene based dyads with orthogonal and parallel transition dipoles for donor and acceptor moieties, respectively. We show that the anharmonic multi-well character of the orthogonal dyad's intramolecular potential explains findings from both stationary and time-resolved absorption experiments. While for a parallel dyad, standard quantum chemical estimates of J at 0 K are in good agreement with experimental observations, J becomes vanishingly small for the orthogonal dyad, in contrast to its ultrafast experimental transfer times. This discrepancy is not resolved even by accounting for harmonic fluctuations along normal coordinates. We resolve this problem by supplementing quantum chemical approaches with dynamical sampling of fluctuating geometries. In contrast to the moderate Gaussian fluctuations of J for the parallel dyad, fluctuations for the orthogonal dyad are found to follow non-Gaussian statistics leading to significantly higher effective J in good agreement with experimental observations. In effort to apply a unified framework for treating the dynamics of optical coherence and excitonic populations of both dyads, we employ a vibronic approach treating electronic and selected vibrational degrees on an equal footing. This vibronic model is used to model absorption and fluorescence spectra as well as donor-acceptor transport dynamics and covers the more traditional categories of F\"{o}rster and Redfield transport as limiting cases.},

keywords = {Molecularly-Functionalized},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Self-Regeneration and Self-Healing in DNA Origami Nanostructures},

author = {J M Scheckenbach and P Tinnefeld and V Glembockyte and T Schubert and C Forthmann},

url = {https://doi.org/10.1002/anie.202012986},

doi = {https://doi.org/10.1002/anie.202012986},

issn = {1433-7851},

year  = {2020},

date = {2020-11-23},

journal = {Angewandte Chemie International Edition},

volume = {n/a},

number = {n/a},

abstract = {DNA nanotechnology and advances in the DNA origami technique have enabled facile design and synthesis of complex and functional nanostructures. Molecular devices are, however, prone to rapid functional and structural degradation due to the high proportion of surface atoms at the nanoscale and due to complex working environments. Besides stabilizing mechanisms, approach for the self-repair of functional molecular devices are desirable. Here we exploit the self-assembly and reconfigurability of DNA origami nanostructures to induce the self-repair of defects of photoinduced and enzymatic damage. With different examples of repair in DNA nanostructures, we distinguish between unspecific self-regeneration and damage specific self-healing mechanisms. Using DNA origami nanorulers studied by atomic force and superresolution DNA PAINT microscopy, quantitative preservation of fluorescence properties is demonstrated with direct potential for improving nanoscale calibration samples.},

keywords = {Foundry Organic},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Wafer-Scale Epitaxial Positioning of Quantum Dots},

author = {N Bart and C Dangel and P Zajac and N Spitzer and J Ritzmann and M Schmidt and K M\"{u}ller and A Wieck and J J Finley and A Ludwig},

url = {https://arxiv.org/abs/2011.10632v2},

doi = {arXiv:2011.10632v2},

year  = {2020},

date = {2020-11-20},

urldate = {2020-11-20},

journal = {arXiv e-prints},

pages = {arXiv: 2011.10632},

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

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}

@article{,

title = {Core\textendashShell Bimetallic Nanoparticle Trimers for Efficient Light-to-Chemical Energy Conversion},

author = {S Lee and H Hwang and W Lee and D Schebarchov and Y Wy and J Grand and B Augui\'{e} and D H Wi and E Cort\'{e}s and S W Han},

url = {https://doi.org/10.1021/acsenergylett.0c02110},

doi = {10.1021/acsenergylett.0c02110},

year  = {2020},

date = {2020-11-19},

journal = {ACS Energy Letters},

pages = {3881-3890},

abstract = {Incorporation of catalytically active materials into plasmonic metal nanostructures can efficiently merge the reactivity and energy-harvesting abilities of both types of materials for visible light photocatalysis. Herein, we explore the influence of electromagnetic hotspots in the ability of plasmonic core\textendashshell colloidal structures to induce chemical transformations. For this study, we developed a synthetic strategy for the fabrication of Au nanoparticle (NP) trimers in aqueous solution through fine controlled galvanic replacement between Ag nanoprisms and Au precursors. Core\textendashshell Au@M NP trimers with catalytically active metals (M = Pd, Pt) were subsequently synthesized using Au NP trimers as templates. Our experimental and computational results highlight the synergy of geometry and composition in plasmonic catalysts for plasmon-driven chemical reactions.},

keywords = {Foundry Inorganic},

pubstate = {published},

tppubtype = {article}

}