PowerWindow is a luminescent solar concentrator which employs a Tm2+-doped material to strongly absorb sunlight and produce a sharp emission in the near-infrared spectrum for energy-harvesting purposes. The absence of self-absorption and the large spectral overlap with the solar spectrum make it an attractive addition to current building-integrated photovoltaics development. Such Tm2+-doped materials have so far been limited to halides that are susceptible to decomposition when exposed to air, which compromises its stability and limits the application. The solutions to functionalize the characteristic Tm2+ photoluminescence properties are two-fold: by an alternative inorganic host (CaSi2O2N2) that is insensitive to moisture, or by using a protective barrier (silicone) that protects halides against decomposition upon exposure to air. The proposed alternative phosphor CaSi2O2N2:Tm is synthesized by solid-state reaction and its luminescent property is examined. The Tm dopant is found to exist in trivalent state (Tm3+) and no luminescence of Tm2+ is found in the material. Besides Tm2O3, different starting powders with other oxidation states (TmI2 and Tm metal powder) were tested to reduce Tm3+ ion to Tm2+ but no change has been observed. It is concluded that the high-lying Tm2+ 4f electronic ground state in CaSi2O2N2 is susceptible to oxidization by losing electrons to its conduction band and therefore unlikely to be stabilized with this synthesis method. The protective barrier approach applied to the NaCl:Tm2+ phosphors was realized by a polydiphenylsiloxane silicone encapsulant. The precursors and the phosphors are cured together in a lamination scheme between two pieces of glass. From the optical properties derived from its absorption and transmission spectra, it is concluded that the Tm2+ valence state of NaCl:Tm2+ is stable in the polymer with no sign of Tm3+ formation at all. While its production process and the relative amount of phosphor still need to be further optimized, a proof-of concept has been attained.