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Raman microscopy/spectroscopy measurements are presented on high purity niobium (Nb) samples, including pieces from hot spot regions of a tested superconducting rf cavity that exhibit a high density of etch pits. Measured spectra are compared with density functional theory calculations of Raman-active, vibrational modes of possible surface Nb-O and Nb-H complexes. The Raman spectra inside particularly rough pits in all Nb samples show clear differences from surrounding areas, exhibiting enhanced intensity and sharp peaks. While some of the sharp peaks are consistent with calculated NbH and NbH_{2} modes, there is better overall agreement with C-H modes in chain-type hydrocarbons. Other spectra reveal two broader peaks attributed to amorphous carbon. Niobium foils annealed to >2000°C in high vacuum develop identical Raman peaks when subjected to cold working. Regions with enhanced C and O have also been found by SEM/EDX spectroscopy in the hot spot samples and cold-worked foils, corroborating the Raman results. Such regions with high concentrations of impurities are expected to suppress the local superconductivity and this may explain the correlation between hot spots in superconducting rf (SRF) cavities and the observation of a high density of surface pits. The origin of localized high carbon and hydrocarbon regions is unclear at present but it is suggested that particular processing steps in SRF cavity fabrication may be responsible

Detection of surface carbon and hydrocarbons in hot spot regions of niobium superconducting rf cavities by Raman spectroscopy