Common anti-reflective films on ZnS substrate has low hardness and poor protective effect, so these films cannot function in harsh environment. Diamond-like carbon (DLC) films with high infrared transmittance and high hardness is deposited by quasi-molecule laser in vacuum. Composite anti-reflective and protective films with several common materials including DLC films is developed. The deposition parameters and performance of pure DLC films is optimized. A compound graphite target is made by fix a sector of Ge slice onto a round graphite slice. Unhydrogened Ge doped DLC film is deposited by means of quasi-molecule laser ablation of compound graphite target in vacuum. Compare to pure DLC film, Ge doped DLC film on Si or Ge substrate has higher absorbance in infrared (IR) region, lower transmittance and higher SP3 content. Thus pure DLC films is choosen for the composite films. The adhesion performance of the composite films is improved by introducing adhesive coating, optimizing of the thickness of DLC films and so on. The composite films has many advantages such as high tranmittance in far IR region, good adhesion, anti-scratch and so on, it also pass the boiling water test, tape adhesion test and scrub test.