This paper presents details on a new experimental apparatus implementing the hot electron nanoscopy (HENs) technique introduced for advanced spectroscopies on structure and chemistry in few molecules and interface problems. A detailed description of the architecture used for the laser excitation of surface plasmons at an atomic force microscope (AFM) tip is provided. The photogenerated current from the tip to the sample is detected during the AFM scan. The technique is applied to innovative semiconductors for applications in electronics: 2D MoS2 single crystal and a p-type SnO layer. Results are supported by complementary scanning Kelvin probe microscopy, traditional conductive AFM, and Raman measurements. New features highlighted by HEN technique reveal details of local complexity in MoS2 and polycrystalline structure of SnO at nanometric scale otherwise undetected. The technique set in this paper is promising for future studies in nanojunctions and innovative multilayered materials, with new insight on interfaces.