Field emission gun (FEG) nanoprobe scanning electron transmission microscopy (STEM) techniques coupled with energy dispersive X-ray (EDX) and electron energy loss spectroscopy (EELS) are evaluated for the detection of the n-type dopant arsenic, in silicon semiconductor devices with nanometer-scale. Optimization of the experimental procedure, data extraction and the signal-to-noise ratio versus electron dose, show that arsenic detection below 0.1% should be possible. STEM EDX and EELS spectrum profiles have been quantified and compared with secondary ion mass spectrometry (SIMS) analyses which show a good agreement. In addition, the arsenic doping level found inside large and small epitaxial devices have been compared using STEM EDX-EELS profiling. The average doping level is found to be similar but variable interface segregation has been observed. Finally, STEM EDX arsenic mapping acquired in a BiCMOS transistor cross-section shows strong heterogeneities and segregation in the epitaxially grown emitter part.