Photoinduced
C–C Reactions on Insulators toward
Photolithography of Graphene Nanoarchitectures
- Publication date
- Publisher
Abstract
On-surface chemistry for atomically
precise sp<sup>2</sup> macromolecules
requires top-down lithographic methods on insulating surfaces in order
to pattern the long-range complex architectures needed by the semiconductor
industry. Here, we fabricate sp<sup>2</sup>-carbon nanometer-thin
films on insulators and under ultrahigh vacuum (UHV) conditions from
photocoupled brominated precursors. We reveal that covalent coupling
is initiated by C–Br bond cleavage through photon energies
exceeding 4.4 eV, as monitored by laser desorption ionization (LDI)
mass spectrometry (MS) and X-ray photoelectron spectroscopy (XPS).
Density functional theory (DFT) gives insight into the mechanisms
of C–Br scission and C–C coupling processes. Further,
unreacted material can be sublimed and the coupled sp<sup>2</sup>-carbon
precursors can be graphitized by e-beam treatment at 500 °C,
demonstrating promising applications in photolithography of graphene
nanoarchitectures. Our results present UV-induced reactions on insulators
for the formation of all sp<sup>2</sup>-carbon architectures, thereby
converging top-down lithography and bottom-up on-surface chemistry
into technology