Ultra-thin high-Al content barrier layers can enable improved gate control and high-frequency operation of AlGaN/GaN high electron mobility transistors (HEMTs) but the precise composition control is very challenging. In this work, we investigate the compositional profiles of AlxGa1-xN/GaN HEMT structures with targeted Al content in the barrier layer, x = 0.50, 0.70, and 1, and thickness in the sub-10 nm range in correlation with the two-dimensional electron gas (2DEG) properties. The HEMT structures are grown by metal-organic chemical vapor deposition on SiC. The maximum Al content in the barrier layer, experimentally determined by scanning transmission electron microscopy combined with energy-dispersive x-ray spectroscopy, is found to be lower than that intended and the deviations from the designed structures increase progressively with increasing x. Compositionally sharp interface between GaN and Al0.46Ga0.54N and box-like Al profile is achieved for intended x similar to 0.50 while pronounced Al grading is found in the samples with intended x of 0.70 and 1, with a maximum Al content of 0.78 reached for the HEMT structure with intended AlN barrier layer. The impact of the experimentally determined Al profiles on the 2DEG properties, obtained by contactless and electrical Hall effect measurements and coupled with self-consistent solution of the Poisson-Schrodinger equation, is evaluated and discussed. It is shown that the observed deviations from the intended Al profiles have a negative effect on the 2DEG confinement and result in reduced mobility parameters, which have significant implications for the implementation of high-Al content AlGaN/GaN structures in high-frequency devices.