We report a comprehensive quantitative ARXPS study of 20-cycle ALD-grown HfO2 films on Si (001) substrates with and without remote plasma nitridation. The films comprised 0.6 nm HfO2 layer atop 1 nm hafnium-rich silicate interlayer. A detailed analysis of the Hf 4f, Si 2p, O 1s, C 1s, and N 1s core level spectra is presented for samples with and without nitridation. The fitting of the Hf 4f spectra reveals four contributing components associated with silicate, hafnia, and their respective nitrided species. The Hf 4f, O 1s, and C 1s spectra exhibit a negative binding energy shift of about 0.2 eV upon nitridation induced by a Si2+-N dipole formed at the interface. Quantitative ARXPS analysis, employing the MultiLayer Model, enabled the determination of the thicknesses, and composition together with their associated uncertainties. The analysis showed that the composition of the nitrided hafnia is HfO1.66N0.33. There is a higher degree of nitridation in the silicate interlayer compared to the overlying hafnia layer. The degree of nitridation is found to increase with plasma power; N2+ is identified as the primary plasma species responsible for the nitridation of hafnia.