(Invited) ALD Metal Fluorides for Ultraviolet Filter and Reflective Coating Applications
Authors: Hennessy John , Jewell April , Nikzad Shouleh 
Published: February 2020

We report on the development of atomic layer deposition (ALD) processes for integrating optical filter coatings directly onto back-illuminated silicon sensors for ultraviolet applications. These devices, including CCD imaging arrays and large-area avalanche photodiodes, are modified with a two-dimensional doping method utilizing molecular beam epitaxy to provide high internal quantum efficiency in the UV. Detector integrated coatings are then required to recover additional external losses due to natural silicon reflectance at these short wavelengths. This includes the development of broadband AR coatings, multilayer narrowband coatings, and metal-dielectric filters for solar-blind devices. The use of ALD is attractive for this purpose because the low deposition temperature and thermal surface reactions do not degrade the 2D doping layers, and therefore do not result in reduced detector quantum efficiency. Applications implementing these coated detectors related to terrestrial and space astronomy, astrophysics missions, and particle physics experiments will be discussed.
Cosmology is experiencing a very exciting time in exploration. Communities of scientists and technology innovators are studying four concepts for flagship future missions selected and supported by NASA. Two of these four missions are Earth-orbiting large aperture telescope observatories that will include UV capabilities. Currently, these ongoing studies have identified high efficiency detectors and high reflectivity mirror coatings as high priority technologies, particularly those that can extend and enhance system performance for UV wavelengths shorter than those previously explored by missions like the Hubble Space Telescope.
At wavelengths below 200 nm, typical ALD dielectric oxide materials like TiO2, HfO2, SiO2, and Al2O3 exhibit large optical losses; we have pursued the development of new processes for ALD metal fluorides to extend coating performance into this far UV wavelength range. Thin films of MgF2, AlF3, and LiF are demonstrated using anhydrous hydrogen fluoride (HF) as the fluorine-containing precursor. This is in contrast to alternate ALD methods for fluoride materials which often utilize reactive metal fluorides as the fluorine precursors, and can result in thin films with components of residual metal oxide contamination. The use of HF has allowed for films with good UV optical properties at deposition temperatures as low 100 °C. This enables compatibility with a variety of 2D-doped silicon sensor formats as well as optical components like polymeric diffraction gratings. The deposition rate of these fluoride materials has a more significant substrate temperature dependence than other common ALD chemistries that often display a ‘window’ of uniform film growth per ALD cycle. Characterization of these coatings is performed with measurements of far UV reflectance and transmittance, x-ray photoelectron spectroscopy, x-ray diffraction, ellipsometry, and atomic force microscopy.
These ALD fluoride materials are also effective protective coatings for reflective aluminum optics. Protected UV Al mirrors with ALD AlF3 overcoats are shown to be competitive with state-of-the-art commercial mirrors made with conventional physical vapor deposition (PVD) methods. The use of ALD in these components holds promise in reducing the thickness of the overcoat relative to PVD approaches. This has significant performance implications for far UV mirrors and the ultimate short wavelength cutoff of Al mirrors for potential future NASA astrophysics missions. The large scale coating uniformity, and corresponding reflectance uniformity of ALD overcoats is also attractive for the same applications. Additionally, the use of HF-based ALD chemistries can also allow for the thermal atomic layer etching (ALE) of a variety of materials including aluminum oxide. By combining these ALE methods with ALD encapsulation, it is possible to chemically strip the oxidation that occurs on metallic aluminum and effectively replace it with thin fluoride layers. Stable Al mirrors with protective fluoride coatings approximately 3 nm thick are demonstrated with this combined ALE/ALD approach. The environmental stability of these coatings will be described in the context of resistance to high-humidity conditions.

Figure 1