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To improve the transmittance of chemical vapor deposition (CVD) diamond, erbium(III) oxide (Er 2 O 3) antireflective films were deposited on CVD diamond substrates by radio frequency (RF) magnetron sputtering. Effects of deposition temperature on structure, chemical composition and properties of the samples were investigated. A strong correlation was observed between the deposition temperature and crystalline structure evolution of the Er 2 O 3 antireflective films. With rising deposition temperature, the deposition rate, grain size and surface roughness of the Er 2 O 3 antireflective films increased. Changes of composition and chemical bonding of the films were analyzed. Results showed that the amount of bonding between Er and O atoms surface as the temperature increased. The films were structured by amorphous, monoclinic and cubic phase, with preferential orientations of C-Er 2 O 3 {222} at deposition temperature increased to 400 °C. A thickness of 10 nm transition layer was observed between the Er 2 O 3 antireflective films and the CVD diamond substrates by transmission electron microscopy (TEM). Moreover, the transition layer feature primarily consisted of Er, O and C. The hardness and modulus of Er 2 O 3 antireflective films were increased for higher deposition temperature, which positively affects the IR transmittance and adhesion strength of the Er 2 O 3 antireflective films on CVD diamond substrates. • The maximum transmittance of Er 2 O 3 /diamond sample was 80% in 7–11 μm range. • Texturization of Er 2 O 3 film interface was studied by HRTEM. • The higher deposition temperature favors crystallization of Er 2 O 3 film. • This study meets the requirements of windows for infrared (IR) imaging systems coating in the LWIR range. [ABSTRACT FROM AUTHOR]