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"Hofmann, Mario"
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Controlled Formation of Sharp Zigzag and Armchair Edges in Graphitic Nanoribbons
2009
Graphene nanoribbons can exhibit either quasi-metallic or semiconducting behavior, depending on the atomic structure of their edges. Thus, it is important to control the morphology and crystallinity of these edges for practical purposes. We demonstrated an efficient edge-reconstruction process, at the atomic scale, for graphitic nanoribbons by Joule heating. During Joule heating and electron beam irradiation, carbon atoms are vaporized, and subsequently sharp edges and step-edge arrays are stabilized, mostly with either zigzag- or armchair-edge configurations. Model calculations show that the dominant annealing mechanisms involve point defect annealing and edge reconstruction.
Journal Article
Review of Extrinsic Factors That Limit the Catalytic Performance of Transition Metal Dichalcogenides (TMDs) in Hydrogen Evolution Reactions (HER)
by
Hofmann, Mario
,
Muthu, Jeyavelan
,
Khurshid, Farheen
in
Catalysts
,
Chalcogenides
,
Electrocatalysts
2024
Transition metal dichalcogenides (TMDs) have garnered attention as potential catalysts for water splitting owing to their unique structures, diverse electronic properties, and composition from earth‐abundant elements. While certain TMD catalysts, notably MoS2, have shown promising activity for hydrogen evolution reactions (HER), achieving performance comparable to traditional platinum catalysts remains a challenge. While significant effort has been invested into understanding the effect of TMD's structural properties, such as defectiveness and crystalline phases, recent work has emphasized the role of extrinsic factors on HER. This review summarizes the current understanding of the impact of commonly overlooked electrocatalytic effects that exhibit an enhanced importance in TMD‐based HER. By combining recent advances in theoretical modeling and experimental work, we review the dominating effects of extrinsic factors including electronic resistance, interfacial barriers, surface roughness, oxidation, and valence impurities. Our work aims to provide insights into optimizing TMDs as highly efficient catalysts for HER, facilitating future advancements in hydrogen generation technology. The review explores the influence of extrinsic factors on the hydrogen evolution reaction (HER) performance of transition metal dichalcogenides (TMDs). By combining recent advances in theoretical modeling and experimental work, it examines the dominant effects of electronic resistance, interfacial barriers, surface roughness, oxidation, and valence impurities, providing insights for optimizing TMDs as efficient HER catalysts.
Journal Article
Robust formation of amorphous Sb2S3 on functionalized graphene for high-performance optoelectronic devices in the cyan-gap
2020
Despite significant progress in the fabrication and application of semiconductor materials for optical emitters and sensors, few materials can cover the cyan-gap between 450 and 500 nm. We here introduce a robust and facile method to deposit amorphous Sb
2
S
3
films with a bandgap of 2.8 eV. By exploiting the tunable functionality of graphene, a two-dimensional material, efficient deposition from a chemical was achieved. Ozone-generated defects in the graphene were shown to be required to enhance the morphology and quality of the material and comprehensive characterization of the seed layer and the Sb
2
S
3
film were applied to design an optimal deposition process. The resulting material exhibits efficient carrier transport and high photodetector performance as evidenced by unprecedented responsivity and detectivity in semiconductor/graphene/glass vertical heterostructures. (112 A/W, 2.01 × 10
12
Jones, respectively).
Journal Article
Ferroelectric 2D ice under graphene confinement
2021
We here report on the direct observation of ferroelectric properties of water ice in its 2D phase. Upon nanoelectromechanical confinement between two graphene layers, water forms a 2D ice phase at room temperature that exhibits a strong and permanent dipole which depends on the previously applied field, representing clear evidence for ferroelectric ordering. Characterization of this permanent polarization with respect to varying water partial pressure and temperature reveals the importance of forming a monolayer of 2D ice for ferroelectric ordering which agrees with ab-initio and molecular dynamics simulations conducted. The observed robust ferroelectric properties of 2D ice enable novel nanoelectromechanical devices that exhibit memristive properties. A unique bipolar mechanical switching behavior is observed where previous charging history controls the transition voltage between low-resistance and high-resistance state. This advance enables the realization of rugged, non-volatile, mechanical memory exhibiting switching ratios of 10
6
, 4 bit storage capabilities and no degradation after 10,000 switching cycles.
Ferroelectric ordering of water has been at the heart of intense debates due to its importance in enhancing our understanding of the condensed matter. Here, the authors observe ferroelectric properties of water ice in a two dimensional phase under confinement between two graphene layers.
Journal Article
Impact of growth rate on graphene lattice-defect formation within a single crystalline domain
by
Hofmann, Mario
,
Chin, Hao-Ting
,
Hsieh, Ya-Ping
in
140/133
,
639/301/1005/1007
,
639/301/357/918/1055
2018
Chemical vapor deposition (CVD) is promising for the large scale production of graphene and other two-dimensional materials. Optimization of the CVD process for enhancing their quality is a focus of ongoing effort and significant progress has been made in decreasing the defectiveness associated with grain boundaries and nucleation spots. However, little is known about the quality and origin of structural defects in the outgrowing lattice which are present even in single-crystalline material and represent the limit of current optimization efforts. We here investigate the formation kinetics of such defects by controlling graphene’s growth rate over a wide range using nanoscale confinements. Statistical analysis of Raman spectroscopic results shows a clear trend between growth rate and defectiveness that is in quantitative agreement with a model where defects are healed preferentially at the growth front. Our results suggest that low growth rates are required to avoid the freezing of lattice defects and form high quality material. This conclusion is confirmed by a fourfold enhancement in graphene’s carrier mobility upon optimization of the growth rate.
Journal Article
The Beauty is a beast: Does leachate from the invasive terrestrial plant Impatiens glandulifera affect aquatic food webs?
by
Hofmann, Mario
,
Drescher, Sophia
,
Laforsch, Christian
in
Acutodesmus obliquus
,
Algae
,
Allelochemicals
2022
Invasive alien species are a major threat to ecosystems. Invasive terrestrial plants can produce allelochemicals which suppress native terrestrial biodiversity. However, it is not known if leached allelochemicals from invasive plants growing in riparian zones, such as Impatiens glandulifera, also affect freshwater ecosystems. We used mesocosms and laboratory experiments to test the impact of I. glandulifera on a simplified freshwater food web. Our mesocosm experiments show that leachate from I. glandulifera significantly reduced population growth rate of the water flea Daphnia magna and the green alga Acutodesmus obliquus, both keystone species of lakes and ponds. Laboratory experiments using the main allelochemical released by I. glandulifera, 2‐methoxy‐1,4‐naphthoquinone, revealed negative fitness effects in D. magna and A. obliquus. Our findings show that allelochemicals from I. glandulifera not only reduce biodiversity in terrestrial habitats but also pose a threat to freshwater ecosystems, highlighting the necessity to incorporate cross‐ecosystem effects in the risk assessment of invasive species. Invasive plant species are a major threat to ecosystems. We could show that allelochemicals from I. glandulifera, an invasive terrestrial plant species, not only reduce biodiversity in terrestrial habitats but also pose a threat to freshwater ecosystems, highlighting the necessity to incorporate cross‐ecosystem effects in the risk assessment of invasive species.
Journal Article
Unpinning the magnetic interface between 2D materials and NiFe for ultra-low coercivity spin valves
by
Hofmann, Mario
,
Hsieh, Ya-Ping
,
Lin, Chun-Yi
in
639/301/357/997
,
639/925/918/1052
,
Anisotropy
2025
The integration of two-dimensional (2D) materials into spintronic devices could enable unconventional computing paradigms, such as stochastic computing, that surpass CMOS in energy efficiency and device density. However, their implementation has faced unexpectedly high coercivity values, increasing the energy cost of magnetic switching. Here, we investigate the origin of this magnetic pinning at the interface between ferromagnetic NiFe and graphene. Vertical spin valves were fabricated using an Uninterrupted Contact Deposition (UCD) technique that prevents interfacial oxidation and contamination. The resulting near-pristine devices exhibit a 25-fold reduction in coercivity, approaching the intrinsic limit of NiFe, as confirmed by magneto-optical and Hanle effect measurements. The importance of suppressing antiferromagnetic exchange bias was highlighted through the introduction of a remote NiO interface that dominates the device’s magnetic anisotropy. These findings establish the intrinsic behavior of 2D spintronic interfaces and clarify the spin-transport mechanism in graphene, offering a platform for future low-power spin-based logic.
Journal Article
Increasing the doping efficiency by surface energy control for ultra-transparent graphene conductors
2017
Graphene’s attractiveness in many applications is limited by its high resistance. Extrinsic doping has shown promise to overcome this challenge but graphene’s performance remains below industry requirements. This issue is caused by a limited charge transfer efficiency (CTE) between dopant and graphene. Using AuCl
3
as a model system, we measure CTE as low as 5% of the expected values due to the geometrical capacitance of small adsorbate clusters. We here demonstrate a strategy for enhancing the CTE by a two-step optimization of graphene’s surface energy prior to AuCl
3
doping. First, exposure to UV ozone modified the hydrophilicity of graphene and was found to decrease the cluster’s geometric capacitance, which had a direct effect on the CTE. Occurrence of lattice defects at high UV exposure, however, deteriorated graphene’s transport characteristics and limited the effectiveness of this pretreatment step. Thus, prior to UV exposure, a functionalized polymer layer was introduced that could further enhance graphene’s surface energy while protecting it from damage. Combination of these treatment steps were found to increase the AuCl
3
charge transfer efficiency to 70% and lower the sheet resistance to 106 Ω/γ at 97% transmittance which represents the highest reported performance for doped single layer graphene and is on par with commercially available transparent conductors.
Journal Article
Uncovering Stability Origins in Layered Ferromagnetic Electrocatalysts Through Homolog Comparison
by
Hofmann, Mario
,
Gujela, Om Prakash
,
Hsieh, Ya-Ping
in
Catalysis
,
Catalytic activity
,
Crystal structure
2025
Magnetic 2D materials offer a compelling platform for next-generation electrocatalysis by enabling spin-dependent reaction pathways. Among them, layered ferromagnets such as Fe3GeTe2 (FGT) have garnered attention for combining intrinsic ferromagnetism with high predicted oxygen evolution activity. However, the stability of non-oxide ferromagnets in electrochemical environments remains an unresolved challenge, limiting their envisioned applications. In this study, we introduce a structural homolog approach to investigate the origin of FGT’s catalytic behavior and the mechanisms underlying its degradation. By comparing FGT with its isostructural analog Fe3GaTe2 (FGaT), we demonstrate that the electrochemical activity of FGT arises primarily from Fe orbitals and is largely insensitive to changes in sublayer composition. Although both materials exhibit similar basal-plane hydrogen evolution performance, FGaT demonstrates significantly lower long-term stability. Density functional theory calculations reveal that this instability arises from weaker Te bonding introduced by Ga substitution. These findings establish structural homologs as a powerful strategy for decoupling catalytic activity from electrochemical deterioration and for guiding the rational design of stable magnetic electrocatalysts.
Journal Article
Mediator-assisted synthesis of WS2 with ultrahigh-optoelectronic performance at multi-wafer scale
by
Hsieh, Ya-Ping
,
Chen, Yu-Siang
,
Yao, Yu-Chi
in
639/925/357/1017
,
639/925/357/1018
,
Chemical vapor deposition
2022
The integration of 2D materials into future applications relies on advances in their quality and production. We here report a synthesis method that achieves ultrahigh optoelectronic performance at unprecedented fabrication scales. A mediator-assisted chemical vapor deposition process yields tungsten-disulfide (WS
2
) with near-unity photoluminescence quantum yield, superior photosensitivity and improved environmental stability. This enhancement is due to the decrease in the density of lattice defects and charge traps brought about by the self-regulating nature of the growth process. This robustness in the presence of precursor variability enables the high-throughput growth in atomically confined stacks and achieves uniform synthesis of single-layer WS
2
on dozens of closely packed wafers. Our approach enhances the scientific and commercial potential of 2D materials as demonstrated in producing large-scale arrays of record-breaking optoelectronic devices.
Journal Article