Revisiting W?hler's method (1824), Cs-doped tungsten bronzes were synthesized by reducing Cs-polytungstate at high temperature, and were pulverized into nanoparticles for determining their optical properties. The high-temperature reduced Cs _(4) W _(11) O _(35) crystals absorbed strongly in the near-infrared, providing an improved luminous transparency with a less-bluish tint than normal Cs _(0.32) WO _(3? y ) synthesized in a reductive atmosphere. The high-temperature reduction caused an orthorhombic-to-hexagonal phase transformation and a nonmetal–metal transition, which was monitored by spectrophotometry, X-ray diffraction, and X-ray photoelectron spectroscopy measurements, assisted by a first-principles analysis using a DFT+U method. The high-temperature reduction of Cs _(4) W _(11) O _(35) is concluded to decrease the number of W deficiencies and produce oxygen vacancies, releasing both free and trapped electrons into the conduction band and thereby activating the near-infrared absorption. The comparatively narrow bandgap of Cs _(4) W _(11) O _(35) was identified as the origin of the less-bluish tint of the produced Cs tungsten bronzes.
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