To reduce the energy consumption of cooling in the hot summer days, searching for novel NIR
shielding materials for buildings is of great value. In this report, monodispersed F doped TiO
2 nanocrystals with an average size of 8.6 nm were synthesized as novel solar
shielding materials for energy-saving windows. All the products adopted an anatase TiO
2 structure. After doping of F ions, the morphology of TiO
2 was transformed from an irregular shape to a pseudospherical shape. The Raman shift and XPS depth analysis confirmed the successful doping of F
− ions into the lattice oxygen sites in the TiO
2 structure. The introduction of F
− ions generated free electrons and bulk Ti
3+ in TiO
2 crystals, which activated a localized surface plasmon resonance (LSPR) absorption in the NIR region. Correspondingly, the NIR shielding performance of the TiO
2 films improved with increasing F doping amounts. The NIR shielding value of the films increased from 1.3% to 43.2% when the molar ratio of F to Ti increased from 0 to 0.3. The reason can be attributed to the enhanced NIR absorption induced by the increased electron concentration after doping of fluorine ions. The F–TiO
2 films showed superior visible transmittance (90.1–96.7%). Moreover, the F–TiO
2 films lowered the indoor temperature of the heat box by 5.3 °C in the thermal tests. Overall, the prepared F–TiO
2 nanocrystals show a great potential to be used for energy-saving windows.
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