Evolution of PTCDA-derived seeds prior to graphene nanoribbon growth on Ge(001)

Zheng, Xiaoqi; Meng, Jun; Guisinger, Nathan P.; Guest, Jeffrey R.; Su, Katherine A.; Morgan, Dane; Arnold, Michael S.

doi:10.1016/j.carbon.2024.119468

Evolution of PTCDA-derived seeds prior to graphene nanoribbon growth on Ge(001)

Journal Article · Sat Jul 20 00:00:00 EDT 2024 · Carbon

DOI:https://doi.org/10.1016/j.carbon.2024.119468· OSTI ID:2432427

^[1]; Meng, Jun ^[1]; Guisinger, Nathan P. ^[2]; ^[2]; ^[1]; Morgan, Dane ^[1]; ^[1]

Univ. of Wisconsin, Madison, WI (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

The synthesis of graphene nanoribbons (GNRs) can be realized via CH4 chemical vapor deposition (CVD) on substrates such as Ge(001) that promote highly anisotropic growth kinetics. Small polycyclic aromatic hydrocarbons (PAHs) are first sublimed onto Ge near room temperature to form graphene-like seeds that subsequently initiate GNR growth with CH4 exposure at 1173 K. The behaviors of PAHs in the time in between their sublimation onto Ge and GNR growth are unclear. Here, we study an archetypical PAH, perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA), on Ge(001) using both scanning tunneling microscopy (STM) and density functional theory (DFT) to characterize PAH conformation, surface diffusivity, and clustering, versus temperature. PTCDA becomes mobile above 673 K (consistent with a DFT calculated diffusion barrier of 2.01 eV). The mobile PTCDA molecules meet, cluster, and fuse at Ge step edges. These clusters have an apparent height of 0.4 nm, similar to small graphene islands, and grow laterally with increasing temperature – reaching 1.2 – 2.1 nm in width at 1173 K, consistent with the seed size extrapolated from CVD experiments. These results provide a plausible picture for how PTCDA forms seeds for anisotropic GNR CVD and show that PAHs with reduced surface diffusivity and inter-molecular reactivity are needed to enable more monodisperse PAH-seeded GNR synthesis.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2432427

Journal Information:: Carbon, Journal Name: Carbon Vol. 229; ISSN 0008-6223

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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