The two-dimensional (2D) superconducting state is a fragile state of matter susceptible to quantum phase fluctuations. Although superconductivity has been observed in ultrathin metal films down to a few layers 1-10 , it is still not known whether a single layer of ordered metal atoms, which represents the ultimate 2D limit of a crystalline film, could be superconducting. Here we report scanning tunnelling microscopy measurements on single atomic layers of Pb and In grown epitaxially on Si(111) substrate, and demonstrate unambiguously that superconductivity does exist at such a 2D extreme. The film shows a superconducting transition temperature of 1.83 K for an atom areal density n = 10.44 Pb atoms nm −2 , 1.52 K for n = 9.40 Pb atoms nm −2 and 3.18 K for n = 9.40 In atoms nm −2 , respectively. We confirm the occurrence of superconductivity by the presence of superconducting vortices under magnetic field. In situ angle-resolved photoemission spectroscopy measurements reveal that the observed superconductivity is due to the interplay between the Pb-Pb (In-In) metallic and the Pb-Si (In-Si) covalent bondings.The one-atomic-layer films of Pb and In studied here were grown with atomic precision on bulk-terminated Si(111) substrate using molecular beam epitaxy. The one-atomic-layer films of Pb have two different structural phases depending on the coverage (for sample preparation, see the Methods section). Figure 1a,d shows the schematic structure and scanning tunnelling microscopy (STM) topograph of the so-called striped incommensurate (SIC) phase, which has a Pb coverage of 4/3 monolayers (ML;. Here 1 ML is defined as the surface atomic density of the Si(111) with areal density n = 7.84 atoms nm −2 . In a unit cell of the SIC-Pb phase, there are four Pb atoms per three surface Si atoms. Three of the four Pb atoms each form a covalent bond with an underlying Si atom, leaving one Pb atom without bonding to the Si substrate. Besides the covalent bonds with the Si substrate, the metal atoms also form metallic bonds within the metal overlayer. As all Pb atoms are located exactly in the same atomic-layer sheet (see the large-scale STM image and cross-section height profiles in Supplementary Fig. S1), the resulting areal density of Pb atoms is 10.44 nm −2 . Compared with the bulk Pb(111) plane, the lattice of the SIC phase is compressed by 5%.Ultralow-temperature (down to 0.40 K) scanning tunnelling spectroscopy (STS) on the SIC phase reveals a clear signature of superconductivity. Figure 2a shows the tunnelling spectra taken on the SIC phase using a superconducting Nb tip. At 0.42 K,

In situ angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy (STS) have been used to study the electronic structure of Pb thin films grown on a Si (111) substrates. The experiments reveal that the electronic structure near the Fermi energy is dominated by a set of m-shaped subbands because of strong quantum confinement in the films, and the tops of the m-shaped subbands form an intriguing ring-like Van Hove singularity. Combined with theoretical calculations, we show that it is the Van Hove singularity that leads to an extremely high density of states near the Fermi energy and the recently reported strong oscillations (with a period of two monolayers) in various properties of Pb films.