Understanding
the nucleation and growth kinetics of thin films
is a prerequisite for their large-scale utilization in devices. For
self-assembled molecular phases near thermodynamic equilibrium the
nucleation–growth kinetic models are still not developed. Here,
we employ real-time low-energy electron microscopy (LEEM) to visualize
a phase transformation induced by the carboxylation of 4,4′-biphenyl
dicarboxylic acid on Ag(001) under ultra-high-vacuum conditions. The
initial (α) and transformed (β) molecular phases are characterized
in detail by X-ray photoemission spectroscopy, single-domain low-energy
electron diffraction, room-temperature scanning tunneling microscopy,
noncontact atomic force microscopy, and density functional theory
calculations. The phase transformation is shown to exhibit a rich
variety of phenomena, including Ostwald ripening of the α domains,
burst nucleation of the β domains outside the α phase,
remote dissolution of the α domains by nearby β domains,
and a structural change from disorder to order. We show that all phenomena
are well described by a general growth–conversion–growth
(GCG) model. Here, the two-dimensional gas of admolecules has a dual
role: it mediates mass transport between the molecular islands and
hosts a slow deprotonation reaction. Further, we conclude that burst
nucleation is consistent with a combination of rather weak intermolecular
bonding and the onset of an additional weak many-body attractive interaction
when a molecule is surrounded by its nearest neighbors. In addition,
we conclude that Ostwald ripening and remote dissolution are essentially
the same phenomenon, where a more stable structure grows at the expense
of a kinetically formed, less stable entity via transport
through the 2D gas. The proposed GCG model is validated through kinetic
Monte Carlo (kMC) simulations.
The realization of complex long-range ordered structures in a Euclidean plane presents a significant challenge en route to the utilization of their unique physical and chemical properties. Recent progress in on-surface supramolecular chemistry has enabled the engineering of regular and semi-regular tilings, expressing translation symmetric, quasicrystalline, and fractal geometries. However, the k-uniform tilings possessing several distinct vertices remain largely unexplored. Here, we show that these complex geometries can be prepared from a simple bitopic molecular precursor-4,4'-biphenyl dicarboxylic acid (BDA)by its controlled chemical transformation on the Ag(001) surface. The realization of 2-and 3-uniform tilings is enabled by partially carboxylated BDA mediating the seamless connection of two distinct binding motifs in a single long-range ordered molecular phase. These results define the basic self-assembly criteria, opening way to the utilization of complex supramolecular tilings.
Synthesis of graphene by chemical vapor deposition is a promising route for manufacturing large-scale high-quality graphene for electronic applications. The quality of the employed substrates plays a crucial role, since the surface roughness and defects alter the graphene growth and cause difficulties in the subsequent graphene transfer. Here, we report on ultrasmooth high-purity copper foils prepared by sputter deposition of Cu thin film on a SiO2/Si template, and the subsequent peeling off of the metallic layer from the template. The surface displays a low level of oxidation and contamination, and the roughness of the foil surface is generally defined by the template, and was below 0.6 nm even on a large scale. The roughness and grain size increase occurred during both the annealing of the foils, and catalytic growth of graphene from methane (≈1000 °C), but on the large scale still remained far below the roughness typical for commercial foils. The micro-Raman spectroscopy and transport measurements proved the high quality of graphene grown on such foils, and the room temperature mobility of the graphene grown on the template stripped foil was three times higher compared to that of one grown on the commercial copper foil. The presented high-quality copper foils are expected to provide large-area substrates for the production of graphene suitable for electronic applications.
Low-energy ion scattering (LEIS) is known for its extreme surface sensitivity, as it yields a quantitative analysis of the outermost surface as well as highly resolved in-depth information for ultrathin surface layers. Hence, it could have been generally considered to be a suitable technique for the analysis of graphene samples. However, due to the low scattering cross section for light elements such as carbon, LEIS has not become a common technique for the characterization of graphene. In the present study we use a high-sensitivity LEIS instrument with parallel energy analysis for the characterization of CVD graphene transferred to thermal silica/silicon substrates. Thanks to its high sensitivity and the exceptional depth resolution typical of LEIS, the graphene layer closure was verified, and different kinds of contaminants were detected, quantified, and localized within the graphene structure. Utilizing the extraordinarily strong neutralization of helium by carbon atoms in graphene, LEIS experiments performed at several primary ion energies permit us to distinguish carbon in graphene from that in nongraphitic forms (e.g., the remains of a resist). Furthermore, metal impurities such as Fe, Sn, and Na located at the graphene-silica interface (intercalated) are detected, and the coverages of Fe and Sn are determined. Hence, high-resolution LEIS is capable of both checking the purity of graphene surfaces and detecting impurities incorporated into graphene layers or their interfaces. Thus, it is a suitable method for monitoring the quality of the whole fabrication process of graphene, including its transfer on various substrates.
The
structure and morphology of organic thin films on solid substrates
influence their functional properties. Therefore, knowledge of molecular
structure, orientation, diffusion, and involved interactions on particular
surfaces is required to gain control over the growth process and prepare
layers with the required functionality. However, the resulting morphology
is dictated by the delicate interplay of several interactions, which
in many cases results in novel and unexpected behavior. Here, we show
that strong interaction of 4,4′-biphenyl dicarboxylic acid
(BDA) with the step edges on Cu(001) results in the formation of densely
packed molecular row, which causes the step edge passivation. The
step edge passivation limits the BDA diffusion over the step edges
and inhibits the attachment of additional BDA molecules preventing
nucleation and growth of molecular islands on the step edges. Our
results thus provide fundamental insight into the anomalous growth
behavior exhibited by certain organic/inorganic systems, which allows
the development of models enabling the control of the growth of organic
heterointerfaces.
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