期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 12, 页码 4651-4658出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja412868w
关键词
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资金
- European Research Council [ERC-2010-AdG-267374]
- Spanish Grants [FIS2010-21282-C02-01, PIB2010US-00652]
- Grupos Consolidados UPV/EHU del Gobierno Vasco [IT578-13]
- Ikerbasque
- European Commission projects CRONOS [280879-2 CRONOS CP-FP7]
- ERC [247299]
- Spanish Juan de la Cireva program [JCI-2010-08156]
- Mexican CONACyT program
On-surface chemistry for atomically precise sp(2) 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(2)-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(2)-carbon precursors can be graphitized by e-beam treatment at 500 degrees C, demonstrating promising applications in photolithography of graphene nanoarchitectures. Our results present UV-induced reactions on insulators for the formation of all sp(2)-carbon architectures, thereby converging top-down lithography and bottom-up on-surface chemistry into technology.
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