Low-energy electron irradiation induced synthesis of molecular nanosheets: influence of the electron beam energy.

Aromatic self-assembled monolayers (SAMs) can be cross-linked into molecular nanosheets - carbon nanomembranes (CNMs) -via low-energy electron irradiation. Due to their favorable mechanical stability and tunable functional properties, they possess a high potential for various applications including nanosensors and separation membranes for osmosis or energy conversion devices. Despite this potential, the mechanistic details of the electron irradiation induced cross-linking process still need to be understood in more detail. Here, we studied the cross-linking of 4'-nitro-1,1'-biphenyl-4-thiol SAM on gold. The SAM samples were irradiated with different electron energies ranging from 2.5 to 100 eV in ultra-high vacuum and subsequently analysed by complementary techniques. We present results obtained via spectroscopy and microscopy characterization by high-resolution X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction with micrometre sized electron beams (μLEED) and low-energy electron microscopy (LEEM). To demonstrate the formation of CNMs, the formed two-dimensional molecular materials were transferred onto grids and oxidized wafer and analyzed by optical, scanning electron microscopy (SEM) and atomic force microscopy (AFM). We found a strong energy dependence for the cross section for the cross-linking process, the rate of which decreases exponentially towards lower electron energies by about four orders of magnitude. We conduct a comparative analysis of the cross sections for the C-H bond scission via electron impact ionization and dissociative electron attachment and find that these different ionization mechanisms are responsible for the variation of the cross-linking cross section with electron energy.