Laser doping plays a crucial role in advanced semiconductor device fabrication. This study introduces a novel method for selectively hyper-doping high-purity (HP) semi-insulating (SI) 4H-silicon carbide (SiC) with p-type dopants like boron and gallium, using a pulsed Nd:YAG laser (λ = 1064 nm) at ambient temperature. Boric acid and gallium nitrate solutions served as precursors for p-type doping in 4H-SiC. Initial challenges arose from insufficient heating-induced diffusion of dopant atoms into transparent HP SI 4H-SiC substrates by the laser. Hence, a laser-assisted deposition technique was adopted, applying a thin film of n-type α-SiC nanoparticles onto the substrate via spin-coating, followed by laser sintering to enhance laser energy absorption and facilitate effective heat conduction from the film to the substrate. The impact of boron and gallium doping on the optical properties, including transmittance, reflectance, and absorptance, of the SiC substrates within the mid-wave infrared range was assessed using FTIR spectrometry. Both dopants created an acceptor energy level at ~ 0.3 eV within the 4H-SiC bandgap, corresponding to 4.3 µm wavelength, resulting in selective photon absorption and notable alterations in the optical properties of the laser-doped regions. The influence of various laser processing parameters on dopant concentration was investigated. Additionally, a new theoretical model was developed to determine and compare variations in refraction and absorption indices induced by both dopants. Morphological, optical, and electrical properties of the as-received (undoped) and doped SiC substrates are comprehensively examined.