Considerations for Utilizing Sodium Chloride in Epitaxial Molybdenum Disulfide.

The utilization of alkali salts, such as NaCl and KI, has enabled the successful growth of large single domain and fully coalesced polycrystalline two-dimensional (2D) transition-metal dichalcogenide layers. However, the impact of alkali salts on photonic and electronic properties is not fully established. In this work, we report alkali-free epitaxy of MoS2 on sapphire and benchmark the properties against alkali-assisted growth of MoS2. This study demonstrates that although NaCl can dramatically increase the domain size of monolayer MoS2 by 20 times, it can also induce strong optical and electronic heterogeneities in as-grown, large-scale films. This work elucidates that utilization of NaCl can lead to variation in growth rates, loss of epitaxy, and high density of nanoscale MoS2 particles (4 ± 0.7/µm2). Such phenomena suggest that alkali atoms play an important role in Mo and S adatom mobility and strongly influence the 2D/sapphire interface during growth. Compared to alkali-free synthesis under the same growth conditions, MoS2 growth assisted by NaCl results in >1% tensile strain in as-grown domains, which reduces photoluminescence by ∼20× and degrades transistor performance.

Large scale 2D/3D hybrids based on gallium nitride and transition metal dichalcogenides.

Two and three-dimensional (2D/3D) hybrid materials have the potential to advance communication and sensing technologies by enabling new or improved device functionality. To date, most 2D/3D hybrid devices utilize mechanical exfoliation or post-synthesis transfer, which can be fundamentally different from directly synthesized layers that are compatible with large scale industrial needs. Therefore, understanding the process/property relationship of synthetic heterostructures is priority for industrially relevant material architectures. Here we demonstrate the scalable synthesis of molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) via metal organic chemical vapor deposition (MOCVD) on gallium nitride (GaN), and elucidate the structure, chemistry, and vertical transport properties of the 2D/3D hybrid. We find that the 2D layer thickness and transition metal dichalcogenide (TMD) choice plays an important role in the transport properties of the hybrid structure, where monolayer TMDs exhibit direct tunneling through the layer, while transport in few layer TMDs on GaN is dominated by p-n diode behavior and varies with the 2D/3D hybrid structure. Kelvin probe force microscopy (KPFM), low energy electron microscopy (LEEM) and X-ray photoelectron spectroscopy (XPS) reveal a strong intrinsic dipole and charge transfer between n-MoS2 and p-GaN, leading to a degraded interface and high p-type leakage current. Finally, we demonstrate integration of heterogeneous 2D layer stacks of MoS2/WSe2 on GaN with atomically sharp interface. Monolayer MoS2/WSe2/n-GaN stacks lead to near Ohmic transport due to the tunneling and non-degenerated doping, while few layer stacking is Schottky barrier dominated.

Near infrared (NIR) strong field ionization and imaging of C60 sputtered molecules: overcoming matrix effects and improving sensitivity.

Strong field ionization (SFI) was applied for the secondary neutral mass spectrometry (SNMS) of patterned rubrene films, mouse brain sections, and Botryococcus braunii algal cell colonies. Molecular ions of rubrene, cholesterol, C31 diene/triene, and three wax monoesters were detected, representing some of the largest organic molecules ever ionized intact by a laser post-ionization experiment. In rubrene, the SFI SNMS molecular ion signal was ~4 times higher than in the corresponding secondary-ion mass spectroscopy (SIMS) analysis. In the biological samples, the achieved signal improvements varied among molecules and sampling locations, with SFI SNMS, in some cases, revealing analytes made completely undetectable by the influence of matrix effects in SIMS.

Investigations Into the Interactions of a MALDI Matrix with Organic Thin Films Using C60+ SIMS Depth Profiling.

Molecular depth profiling of multilayer organic films is now an established protocol for cluster secondary ion mass spectrometry (SIMS). This unique capability is exploited here to study the ionization mechanism associated with matrix-enhanced SIMS and possibly matrix assisted laser desorption/ionization (MALDI). Successful depth profiling experiments were performed on model bi-layer systems using 2,5-dihydroxybenzoic acid (DHB) as the matrix with dipalmitoylphosphatidylcholine (DPPC) or phenylalanine (PHE). The interaction between the matrix and organic analyte is monitored at the interface of the films. Tri-layer films with D2O as a thin-film sandwiched between the matrix and organic layers are also investigated to determine what role, if any, water plays during ionization. The results show successful depth profiles when taken at 90K. Mixing is observed at the interfaces of the films due to primary ion bombardment, but this mixing does not recreate the conditions necessary for ionization enhancement.

Evidence for the formation of dynamically created pre-formed ions at the interface of isotopically enriched thin films.

A novel approach to elucidate the ionization mechanism for the [M + H]+ molecular ion of organic molecules is investigated by molecular depth profiling of isotopically enriched thin films. Using a model bi-layer film of phenylalanine (PHE) and PHE-D8, the results show formation of an [M + D]+ molecular ion for the non-enriched PHE molecule attributed to rearrangements of chemical damage due to successive primary ion impacts. The [M + D]+ ion is observed at the interface for 19.9nm in the enriched-on-top system and 9.9nm for the enriched-on-bottom system. This ion formation is direct evidence for dynamically created pre-formed ions as a result of chemical damage rearrangement induced by previous primary ion bombardment events.

The gas-phase ligand exchange of copper and nickel acetylacetonate, hexafluoroacetylacetonate and trifluorotrimethylacetylacetonate complexes.

The gas-phase ligand-exchange reactions between Cu(II) and Ni(II) complexes containing the acetylacetonate (acac), hexafluoroacetylacetonate (hfac), and trifluorotrimethylacetylacetonate (tftm) ligands were investigated using a triple quadrupole mass spectrometer. The gas-phase mixed-ligand products of [Cu(acac)(tftm)](+), [Ni(acac)(tftm)](+), [Cu(hfac)(tftm)](+), and [Ni(hfac)(tftm)](+) were formed following the co-sublimation of either homo-metal or hetero-metal precursors. The gas-phase formation of [Cu(acac)(tftm)](+), [Cu(hfac)(tftm)](+), [Ni(acac)(tftm)](+), and [Ni(hfac)(tftm)](+) complexes is reported herein for the first time. The corresponding fragmentation patterns of these species along with those of Cu(tftm)(2) and Ni(tftm)(2) are also presented. Mass-selected ion-neutral reactions were investigated.

Gas-phase ligand exchange of select transition-metal acetylacetonate and hexafluoroacetylacetonate complexes.

Gas-phase ligand exchange reactions between M(acac)(2) and M(hfac)(2) species, where M is Cu(II) and/or Ni(II), were observed to occur in a double-focusing reverse-geometry magnetic sector mass spectrometer. The gas-phase mixed ligand product, [M(acac)(hfac)](+), was formed following the co-sublimation of either homo-metal or hetero-metal precursors. The gas-phase formation of [Cu(acac)(hfac)](+) from hetero-metal precursors is reported herein for the first time. The [Ni(acac)(hfac)](+) complex is also observed for the first time to form following the co-sublimation of not only Ni precursors, but also from separate Ni and Cu precursors. The corresponding fragmentation patterns of these species are also presented, and the mixed metal mixed ligand product [NiCu(acac)(2)(hfac)](+) is observed.