Fenestration
elements that enable spectrally selective dynamic
modulation of the near-infrared region of the electromagnetic spectrum
are of great interest as a means of decreasing the energy consumption
of buildings by adjusting solar heat gain in response to external
temperature. The binary vanadium oxide VO
2
exhibits a near-room-temperature
insulator–metal electronic transition accompanied by a dramatic
modulation of the near-infrared transmittance. The low-temperature
insulating phase is infrared transparent but blocks infrared transmission
upon metallization. There is considerable interest in harnessing the
thermochromic modulation afforded by VO
2
in nanocomposite
thin films. However, to prepare a viable thermochromic film, the visible-light
transmittance must be maintained as high as possible while maximizing
thermochromic modulation in the near-infrared region of the electromagnetic
spectrum, which necessitates the development of high-crystalline-quality
VO
2
nanocrystals of the optimal particle size embedded
within the appropriate host matrix and refractive index matched to
the host medium. Here, we demonstrate the preparation of acrylate-based
nanocomposite thin films with varying sizes of embedded VO
2
nanoparticles. The observed strong size dependence of visible-light
transmittance and near-infrared modulation is explicable on the basis
of optical simulations. In this article, we elucidate multiple scattering
and absorption mechanisms, including Mie scattering, temperature-/phase-variant
refractive-index mismatch between VO
2
nanocrystals and
the encapsulating matrix, and the appearance of a surface plasmon
resonance using temperature-variant absorptance and diffuse transmittance
spectroscopy measurements performed as a function of particle loading
for the different sizes of VO
2
nanocrystals. Nanocrystals
with dimensions of 44 ± 30 nm show up to >32% near-infrared
energy
modulation across the near-infrared region of the electromagnetic
spectrum while maintaining high visible-light transmission. The results
presented here, providing mechanistic elucidation of the size dependence
of the different scattering mechanisms, underscore the importance
of nanocrystallite dimensions, refractive-index matching, and individualized
dispersion of particles within the host matrix for the preparation
of viable thermochromic thin films mitigating Mie scattering and differential
refractive-index scattering.