We report on the energy level alignment evolution of valence and conduction bands of armchair-oriented graphene nanoribbons (aGNR) as their band gap shrinks with increasing width. We use 4,4-dibromo-para-terphenyl as molecular precursor on Au(111) to form extended poly-para-phenylene nanowires, which can be fused sideways to form atomically precise aGNRs of varying widths. We measure the frontier bands by means of scanning tunneling spectroscopy, corroborating that the nanoribbons band gap is inversely proportional to their width. Interestingly, valence bands are found to show Fermi level pinning as the band gap decreases below a threshold value around 1.7 eV. Such behavior is of critical importance to understand the properties of potential contacts in graphene nanoribbon-based devices. Our measurements further reveal a particularly interesting system for studying Fermi level pinning by modifying an adsorbates band gap while maintaining an almost unchanged interface chemistry defined by substrate and adsorbate.
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