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An electron cyclotron resonance plasma-enhanced chemical vapor deposition apparatus, which is suitable for producing planar fluoride glass films, was developed. A ZrF4-BaF2-EuF3 planar glass film was synthesized by using β-diketonates of Zr, Ba and Eu as starting materials and NF3 as a fluorinating gas. A CaF2 single crystal plate and a fused quartz glass plate were employed as substrates. The planar glass film obtained was colorless and transparent. As an attempt a planar waveguide which has a ZrF4-BaF2/ZrF4-BaF2-EuF3/ZrF4-BaF2 sandwich structure was also formed on a CaF2 substrate. The planar glass film and the planar waveguide were characterized by using techniques such as XPS, X-ray diffraction, DTA, ellipsometry, IR absorption, Mössbauer spectroscopy and SEM.