Conformal antireflection coatings for optical dome covers by atomic layer deposition.

Complex 3D-shaped optics are difficult to coat with conventional technologies. In this research, large top-open optical glass cubes with a 100 mm side length were functionalized to simulate large dome-shaped optics. Antireflection coatings for the visible range (420-670 nm) and for a single wavelength (550 nm) were applied by atomic layer deposition simultaneously on two and six demonstrators, respectively. Reflectance measurements on both the inner and outer glass surfaces confirm a conformal AR coating with a residual reflectance significantly below 0.3% for visible wavelengths and 0.2% for single wavelengths on nearly the entire surface of the cubes.

Plasma-Enhanced Atomic Layer Deposition of HfO2 with Substrate Biasing: Thin Films for High-Reflective Mirrors.

Tuning ion energies in plasma-enhanced atomic layer deposition (PEALD) processes enables fine control over the material properties of functional coatings. The growth, structural, mechanical, and optical properties of HfO2 thin films are presented in detail toward photonic applications. The influence of the film thickness and bias value on the properties of HfO2 thin films deposited at 100 °C using tetrakis(dimethylamino)hafnium (TDMAH) and oxygen plasma using substrate biasing is systematically analyzed. The HfO2 films deposited without a substrate bias show an amorphous microstructure with a low density, low refractive index, high incorporation of residual hydroxyl (OH) content, and high residual tensile stress. The material properties of HfO2 films significantly improved at a low bias voltage due to the interaction with oxygen ions accelerated to the film. Such HfO2 films have a higher density, higher refractive index, and lower residual OH incorporation than films without bias. The mechanical stress becomes compressive depending on the bias values. Further increasing the ion energies by applying a larger substrate bias results in a decrease of the film density, refractive index, and a higher residual OH incorporation as well as crystalline inclusions. The comparable material properties of the HfO2 films have been reported using tris(dimethylamino)cyclopentadienyl hafnium (TDMACpH) in a different apparatus, indicating that this approach can be transferred to various systems and is highly versatile. Finally, the substrate biasing technique has been introduced to deposit stress-compensated, crack- and delamination-free high-reflective (HR) mirrors at 355 and 532 nm wavelengths using HfO2 and SiO2 as high and low refractive index materials, respectively. Such mirrors could not be obtained without the substrate biasing during the deposition because of the high tensile stress of HfO2, leading to cracks in thick multilayer systems. An HR mirror for 532 nm wavelength shows a high reflectance of 99.93%, a residual transmittance of ∼530 ppm, and a low absorption of ∼11 ppm, as well as low scattering losses of ∼4 ppm, high laser-induced damage threshold, low mechanical stress, and high environmental stability.

Structural, optical, and mechanical properties of TiO2 nanolaminates.

The structural, optical, and mechanical properties of TiO2 nanolaminate films grown by plasma-enhanced atomic layer deposition are discussed. Several TiO2/Al2O3 and TiO2/SiO2 compositions have been investigated to study the effect of the relative number of ALD oxide cycles on the film properties to obtain a high refractive index coating with low optical losses, low roughness, and low mechanical stress. The formation of crystalline TiO2 observed at high deposition temperature, or film thickness was inhibited by periodically introducing ultra-thin amorphous layers into the film. Only 4 ALD cycles of Al2O3 (corresponding to ca. 0.5 nm) between 335 ALD cycles of TiO2 (ca. 11 nm) form a closed, distinct layer suppressing the crystallization in TiO2 film. Consequently, the roughness of the pure TiO2 film is reduced from ca. 20 nm rms to 1 nm rms in the 335/4 nanolaminate, with only a slight decrease of the refractive index from 2.46 to 2.44 in 100 nm pure TiO2 and the nanolaminate, respectively. The refractive indices of the nanolaminates in various compositions vary between 2.38 and 2.50 at 632 nm, and the corresponding optical losses from the films are low. The mechanical stress was reduced to about 140 MPa in several TiO2/Al2O3 nanolaminates; however, lower mechanical stress has not been obtained with the studied compositions. The nanolaminate structure is preserved up to 600 °C annealing temperature. After annealing at 800 °C, the individual layers interdiffuse into each other so that no distinct nanolaminate structure is detected. By using TiO2/Al2O3 nanolaminates with reduced mechanical stress, a narrow bandpass filter was realized on various substrates, including half-ball and aspherical lenses.

Effect of an electric field during the deposition of silicon dioxide thin films by plasma enhanced atomic layer deposition: an experimental and computational study.

The growth, chemical, structural, mechanical, and optical properties of oxide thin films deposited by plasma enhanced atomic layer deposition (PEALD) are strongly influenced by the average-bias voltage applied during the reaction step of surface functional groups with oxygen plasma species. Here, this effect is investigated thoroughly for SiO2 deposited in two different PEALD tools at average-bias voltages up to -300 V. Already at a very low average-bias voltage (< -10 V), the SiO2 films have significantly lower water content than films grown without biasing together with the formation of denser films having a higher refractive index and nearly stoichiometric composition. Substrate biasing during PEALD also enables control of mechanical stress. The experimental findings are supported by density functional theory and atomistic simulations. They demonstrate that the application of an electric field during the plasma step results in an increased energy transfer between energetic ions and the surface, directly influencing relevant surface reactions. Applying an electric field during the PEALD process leads to SiO2 thin films with significantly improved properties comparable to films grown by ion beam sputtering.

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies.

Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiO x and HfO x and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiN x and HfN x films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiO x were slightly improved whereas those of SiN x were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.