The technological capabilities of the method of liquid-phase epitaxy from a limited volume of Sn solution-melt for obtaining films of substitutional solid solution (Si2)1−x(GaN)x on Si (111) substrates are shown. The grown films had a single-crystal structure with (111) orientation, n-type conductivity with a resistivity of ρ ~ 1.38 Ω∙cm, a carrier concentration of n ~ 3.4∙1016 cm− 3, and a charge carrier mobility of µ ~ 133 cm2/(V⋅sec). The relatively narrow width (FWHM = 780 arcsec) and high intensity (2⋅105 pulses/sec) of the main structural reflection (111)Si/GaN indicate a high degree of perfection of the crystal lattice of the epitaxial layer (Si2)1−x(GaN)x. The photosensitivity region of p-Si–n-(Si2)1−x(GaN)x heterostructures covers the photon energy range from 1.2 to 2.4 eV, with a maximum at 1.9 eV.