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We use scanning tunneling microscopy (STM) and spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS) to investigate the effect of nitrogen doping on the surface electronic and chemical structures of cutouts from superconducting $\mathrm{Nb}$ radio-frequency cavities. The goal of this work is to get insights into the fundamental physics and materials mechanisms behind the striking decrease of the surface resistance with the radio-frequency magnetic field, which has been observed on $N$-doped $\mathrm{Nb}$ cavities. Our XPS measurements reveal significantly more oxidized $\mathrm{Nb}$ $3d$ states and a thinner metallic suboxide layer on the $N$-doped $\mathrm{Nb}$ surfaces, which is also confirmed by tunneling spectroscopy measurements. In turn, tunneling measurements performed on native surfaces as well as on $\mathrm{Ar}$-ion sputtered surfaces allow us to separate the effect of $N$ doping on the surface-oxide layer from that on the density of states in the bulk. Analysis of our tunneling spectra in the framework of a model of a proximity-coupled normal layer at the surface [A. Gurevich and T. Kubo, Phys. Rev. B 96, 184515 (2017)] is consistent with the hypothesis that $N$-doping ameliorates lateral inhomogeneities of superconducting properties on the surface and shrinks the metallic suboxide layer. For the $\mathrm{Ar}$ sputtered surfaces, we also find evidence that $N$ doping changes the contact resistance between the metallic suboxide and the bulk niobium toward an optimum value corresponding to a minimum surface resistance. The totality of our experimental data suggests that the $N$ doping provides an effective tuning of the density of states in such a way that it can result in a decrease of the surface resistance with the radio-frequency field, as predicted by calculations of the nonlinear low-frequency electromagnetic response of dirty superconductors. Furthermore, STM imaging of vortex cores shows a slightly reduced average superconducting gap and a shorter coherence length in the $N$-doped $\mathrm{Nb}$ samples as compared to typically prepared $\mathrm{Nb}$ samples, indicating a stronger impurity scattering caused by nitrogen doping in a moderately disordered material.

Electron Tunneling and X-Ray Photoelectron Spectroscopy Studies of the Superconducting Properties of Nitrogen-Doped Niobium Resonator Cavities