Infrared (IR) absorption and Raman scattering are reported from the localized vibrational modes (LVM) of Al and Si δ-layer superlattices in MBE (100) GaAs grown at 400°C as a function of the total areal concentrations, [A1]A and [Si]A respectively. The Al superlattices show the expected behavior on passing from sub-monolayer (ML) to thicker layers (thin AlAs) since the impurities still occupy only Ga-sites. The behavior is very different from that found for Si δ-layers. In addition to SiGa reported previously, we now show that SiAs, SiGa-SiAs pairs and the electron trap Si-X are also present in Si δ-layers and superlattices for 0.05 ≤ [Si]A≤ 0.5 ML. The conductivity of these structures and the concentrations of substitutional Si in GaAs at all sites fall to zero for [Si]A> 0.5 ML but a Raman feature at 470–490 cm−1, attributed to the vibrations of covalent Si-Si bonds is then detected. This feature is not observed in structures containing very closely spaced dilute (0.01 ML) Si δ-planes. It is inferred that long-range Si diffusion does not occur in the bulk crystal, although there could be surface diffusion during Si deposition. The maximum measured carrier concentrations are always less than 2 × 1019 cm−3, the DX limit. The redistribution of Si amongst the various lattice sites is discussed in terms of SiGa DX-like displacements occurring during growth, followed by local thermally activated diffusion jumps. It is speculated that AsGa antisite defects and Ga-vacancies are produced by this process. The reason why the Si δ-layer is non-conducting remains unclear.