Enhanced surface second harmonic generation in nanolaminates.

Second-harmonic generation (SHG) is a second-order nonlinear optical process that is not allowed in media with inversion symmetry. However, due to the broken symmetry at the surface, surface SHG still occurs, but is generally weak. We experimentally investigate the surface SHG in periodic stacks of alternating, subwavelength dielectric layers, which have a large number of surfaces, thus enhancing surface SHG considerably. To this end, multilayer stacks of SiO2/TiO2 were grown by Plasma Enhanced Atomic Layer Deposition (PEALD) on fused silica substrates. With this technique, individual layers of a thickness of less than 2 nm can be fabricated. We experimentally show that under large angles of incidence (> 20 degrees) there is substantial SHG, well beyond the level, which can be observed from simple interfaces. We perform this experiment for samples with different periods and thicknesses of SiO2/TiO2 and our results are in agreement with theoretical calculations.

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.

Optical properties of black silicon structures ALD-coated with Al2O3.

Atomic layer deposited (ALD) Al2O3coatings were applied on black silicon (b-Si) structures. The coated nanostructures were investigated regarding their reflective and transmissive behaviour. For a systematic study of the influence of the Al2O3coating, ALD coatings with a varying layer thickness were deposited on three b-Si structures with different morphologies. With a scanning electron microscope the morphological evolution of the coating process on the structures was examined. The optical characteristics of the different structures were investigated by spectral transmission and reflection measurements. The usability of the structures for highly efficient absorbers and antireflection (AR) functionalities in the different spectral regions is discussed.

Influence of seed layers on the reflectance of sputtered aluminum thin films.

The fabrication of highly reflective aluminum coatings is still an important part of current research due to their high intrinsic reflectivity in a broad spectral range. By using thin seed layers of Cu, CuOx, Cr, CrOx, Au, and Ag, the morphology of sputtered (unprotected) aluminum layers and, consequently, their reflectance can be influenced. In this long-term study, the reflectance behavior was measured continuously using spectrophotometry. Particular seed layer materials enhance the reflectance of aluminum coatings significantly and reduce their long-term degradation. Combining such seed layers with evaporation processes and suitable protective layers could further increase the reflectance of aluminum coatings.

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.

Light scattering characterization of single-layer nanoporous SiO2 antireflection coating in visible light.

Antireflective coatings are widely applied on transparent optical components to reduce reflections at surfaces. Nanoporous silica (NP SiO2) thin films with tailored refractive index properties are used as single-layer antireflective coatings providing nearly zero reflectivity. In this work, light scattering properties of nanoporous silica single-layer antireflective coatings are investigated in order to determine their optical quality by means of total scattering and detailed roughness analysis. Scattering and roughness characterization of the samples coated with different film thicknesses were realized to distinguish the influences of nanopores and surface roughness on scattering losses in the visible (VIS) spectral range. No significant correlation of scattering losses with the film thickness is found, showing negligible influence of the nanopores to the overall scattering properties compared with the dominating effect of interface roughness. Moreover, the scattering losses from coated fused silica glass were observed as low as 20 ppm (0.002%). It is confirmed that NP SiO2 single-layer antireflective coatings are suitable to be used in optics demanding extremely low scattering characteristics.

Antireflection coating with consistent near-neutral color on complex-shaped substrates prepared by ALD.

Color distortions of common antireflective (AR) multilayer coatings are detrimental to their appearance. These are due to the shift of the reflectance maxima toward shorter wavelengths at oblique incidence angles. Layer thickness variations of coatings on inclined surfaces of complex-shaped components additionally contribute to strong color variations. To improve the residual color consistency, a near-neutral color AR coating has been developed and deposited by atomic layer deposition (ALD) on complex-shaped substrates. This results in a uniform color appearance across the optical surface.

Mechanical, structural, and optical properties of PEALD metallic oxides for optical applications.

Structural, optical, and mechanical properties of Al2O3, SiO2, and HfO2 materials prepared by plasma-enhanced atomic layer deposition (PEALD) were investigated. Residual stress poses significant challenges for optical coatings since it may lead to mechanical failure, but in-depth understanding of these properties is still missing for PEALD coatings. The tensile stress of PEALD alumina films decreases with increasing deposition temperature and is approximately 100 MPa lower than the stress in thermally grown films. It was associated with incorporation of -OH groups in the film as measured by infrared spectroscopy. The tensile stress of hafnia PEALD layers increases with deposition temperature and was related to crystallization of the film. HfO2 nanocrystallites were observed even at 100°C deposition temperature with transmission electron microscopy. Stress in hafnia films can be reduced from approximately 650 MPA to approximately 450 MPa by incorporating ultrathin Al2O3 layers. PEALD silica layers have shown moderate stress values and stress relaxation with the storage time, which was correlated to water adsorption. A complex interference coating system for a dichroic mirror (DCM) at 355 nm wavelength was realized with a total coating thickness of approximately 2 µm. Severe cracking of the DCM coating was observed, and it propagates even into the substrate material, showing a good adhesion of the ALD films. The reflectance peak is above 99.6% despite the mechanical failure, and further optimization on the material properties should be carried out for demanding optical applications.

Nanoporous SiO2 thin films made by atomic layer deposition and atomic etching.

A new route to prepare nanoporous SiO2 films by mixing atomic-layer-deposited alumina and silica in an Å-scale is presented. The selective removal of Al2O3 from the composites using wet chemical etching with phosphoric acid resulted in nanoporous thin SiO2 layers. A diffusion-controlled dissolution mechanism is identified whereby an interesting reorganization of the residual SiO2 is observed. The atomic scale oxide mixing is decisive in attaining and tailoring the film porosity. The porosity and the refractive index of nanoporous silica films were tailored from 9% to 69% and from 1.40 to 1.13, respectively. The nanoporous silica was successfully employed as antireflection coatings and as diffusion membranes to encapsulate nanostructures.

Encapsulation process for diffraction gratings.

Encapsulation of grating structures facilitates an improvement of the optical functionality and/or adds mechanical stability to the fragile structure. Here, we introduce novel encapsulation process of nanoscale patterns based on atomic layer deposition and micro structuring. The overall size of the encapsulated structured surface area is only restricted by the size of the available microstructuring and coating devices; thus, overcoming inherent limitations of existing bonding processes concerning cleanliness, roughness, and curvature of the components. Finally, the process is demonstrated for a transmission grating. The encapsulated grating has 97.5% transmission efficiency in the -1st diffraction order for TM-polarized light, and is being limited by the experimental grating parameters as confirmed by rigorous coupled wave analysis.

Double-sided structured mask for sub-micron resolution proximity i-line mask-aligner lithography.

Diffractive mask-aligner lithography allows printing structures that have a sub-micrometer resolution by using non-contact mode. For such a purpose, masks are often designed to operate with monochromatic linearly polarized light, which is obtained by placing a spectral filter and a polarizer in the beam path. We propose here a mask design that includes a wire-grid polarizer (WGP) on the top side of a photo-mask and a diffractive element on the bottom one to print a 350 nm period grating by using a classical mask-aligner in proximity exposure mode. Linearly polarizing locally an unpolarized incident beam is only possible by using a WGP on the top side of the mask. This configuration opens the possibility to use different linear polarization orientation on a single mask and allows to print high resolution structures with different orientation within one exposure.

Influence of the oxygen plasma parameters on the atomic layer deposition of titanium dioxide.

The influence of the oxygen plasma parameters on the morphology and optical properties of TiO2 thin films has been extensively analyzed in plasma enhanced atomic layer deposition (PEALD) processes. Crystalline aggregates with the anatase phase have been identified on the film surface at a low deposition temperature (down to 70 °C) under specific plasma conditions. Up to 70% surface coverage by anatase crystallites is obtained at low oxygen gas flow rates and high plasma power. The hillocks abundance is correlated with high ion flux and electron density and with the resulting enhanced ion bombardment of the surface. Altering the plasma conditions is an important parameter besides temperature to control the morphology of the titania film for specific applications such as photocatalysis or functional optical coatings. Specifically, photocatalytic titania coatings on polymer substrates could benefit of such low temperature PEALD processes with abundant anatase crystallites; whereas optical coatings require smooth, high refractive index titania as obtained with low plasma power and high oxygen flow rate.

Multilayer Fresnel zone plates for high energy radiation resolve 21 nm features at 1.2 keV.

X-ray microscopy is a successful technique with applications in several key fields. Fresnel zone plates (FZPs) have been the optical elements driving its success, especially in the soft X-ray range. However, focusing of hard X-rays via FZPs remains a challenge. It is demonstrated here, that two multilayer type FZPs, delivered from the same multilayer deposit, focus both hard and soft X-rays with high fidelity. The results prove that these lenses can achieve at least 21 nm half-pitch resolution at 1.2 keV demonstrated by direct imaging, and sub-30 nm FWHM (full-pitch) resolution at 7.9 keV, deduced from autocorrelation analysis. Reported FZPs had more than 10% diffraction efficiency near 1.5 keV.

Two-Color Spatially Resolved Tuning of Polymer-Coated Metasurfaces.

For the realization of truly reconfigurable metasurface technologies, dynamic spatial tuning of the metasurface resonance is required. Here we report the use of organic photoswitches as a means for the light-induced spatial tuning of metasurface resonances. Coating of a dielectric metasurface, hosting high-quality-factor resonances, with a spiropyran (SPA)-containing polymer enabled dynamic resonance tuning up to 4 times the resonance full-width at half-maximum with arbitrary spatial precision. A major benefit of employing photoswitches is the broad toolbox of chromophores available and the unique optical properties of each. In particular, SPA and azobenzene (AZO) photoswitches can both be switched with UV light but exhibit opposite refractive index changes. When applied to the metasurface, SPA induced a red shift in the metasurface resonance with a figure of merit of 97 RIU-1, while AZO caused a blue shift in the resonance with an even greater sensitivity of 100 RIU-1. Critically, SPA and AZO can be individually recovered with red and blue light, respectively. To exploit this advantage, we coated a dielectric metasurface with spatially offset SPA- and AZO-containing polymers to demonstrate wavelength-dependent, spatially resolved control over the metasurface resonance tuning.

Efficient focusing of 8 keV X-rays with multilayer Fresnel zone plates fabricated by atomic layer deposition and focused ion beam milling.

Fresnel zone plates (FZPs) recently showed significant improvement by focusing soft X-rays down to ~10 nm. In contrast to soft X-rays, generally a very high aspect ratio FZP is needed for efficient focusing of hard X-rays. Therefore, FZPs had limited success in the hard X-ray range owing to difficulties of manufacturing high-aspect-ratio zone plates using conventional techniques. Here, employing a method of fabrication based on atomic layer deposition (ALD) and focused ion beam (FIB) milling, FZPs with very high aspect ratios were prepared. Such multilayer FZPs with outermost zone widths of 10 and 35 nm and aspect ratios of up to 243 were tested for their focusing properties at 8 keV and shown to focus hard X-rays efficiently. This success was enabled by the outstanding layer quality thanks to ALD. Via the use of FIB for slicing the multilayer structures, desired aspect ratios could be obtained by precisely controlling the thickness. Experimental diffraction efficiencies of multilayer FZPs fabricated via this combination reached up to 15.58% at 8 keV. In addition, scanning transmission X-ray microscopy experiments at 1.5 keV were carried out using one of the multilayer FZPs and resolved a 60 nm feature size. Finally, the prospective of different material combinations with various outermost zone widths at 8 and 17 keV is discussed in the light of the coupled wave theory and the thin-grating approximation. Al2O3/Ir is outlined as a promising future material candidate for extremely high resolution with a theoretical efficiency of more than 20% for as small an outermost zone width as 10 nm at 17 keV.

Carrier-envelope phase on-chip scanner and control of laser beams.

The carrier-envelope phase (CEP) is an important property of few-cycle laser pulses, allowing for light field control of electronic processes during laser-matter interactions. Thus, the measurement and control of CEP is essential for applications of few-cycle lasers. Currently, there is no robust method for measuring the non-trivial spatial CEP distribution of few-cycle laser pulses. Here, we demonstrate a compact on-chip, ambient-air, CEP scanning probe with 0.1 µm3 resolution based on optical driving of CEP-sensitive ultrafast currents in a metal-dielectric heterostructure. We successfully apply the probe to obtain a 3D map of spatial changes of CEP in the vicinity of an oscillator beam focus with pulses as weak as 1 nJ. We also demonstrate CEP control in the focal volume with a spatial light modulator so that arbitrary spatial CEP sculpting could be realized.

Precision Tailoring Quasi-BIC Resonance of a-Si:H Metasurfaces.

The capability of tailoring the resonance wavelength of metasurfaces is important as it can alleviate the manufacturing precision required to produce the exact structure according to the design of the nanoresonators. Tuning of Fano resonances by applying heat has been theoretically predicted in the case of silicon metasurfaces. Here, we experimentally demonstrate the permanent tailoring of quasi-bound states in the continuum (quasi-BIC) resonance wavelength in an a-Si:H metasurface and quantitatively analyze the modification in the Q-factor with gradual heating. A gradual increment in temperature leads to a spectral shift in the resonance wavelength. With the support of ellipsometry measurements, the spectral shift resulting from the short-duration (ten minutes) heating is identified to be due to refractive index variations in the material rather than a geometric effect or amorphous/polycrystalline phase transition. In the case of quasi-BIC modes in the near-infrared, resonance wavelength could be adjusted from T = 350 °C to T = 550 °C without affecting the Q-factor considerably. Apart from the temperature-induced resonance trimming, large Q-factors can be attained at the highest analyzed temperature (T = 700 °C) in the near-infrared quasi-BIC modes. Resonance tailoring is just one of the possible applications of our results. We expect that our study is also insightful in the design of a-Si:H metasurfaces where large Q-factors are required at high temperatures.

Atomically Thin Metal-Dielectric Heterostructures by Atomic Layer Deposition.

Heterostructures increasingly attracted attention over the past several years to enable various optoelectronic and photonic applications. In this work, atomically thin interfaces of Ir/Al2O3 heterostructures compatible with micro-optoelectronic technologies are reported. Their structural and optical properties were determined by spectroscopic and microscopic techniques (XRR, XPS, HRTEM, spectroscopic ellipsometry, and UV/vis/NIR spectrophotometry). The XRR and HRTEM analyses reveal a layer-by-layer growth mechanism of Ir in atomic scale heterostructures, which is different from the typical island-type growth of metals on dielectrics. Alongside, XPS investigations imply the formation of Ir-O-Al bonding at the interfaces for lower Ir concentrations, in contrast to the nanoparticle core-shell structure formation. Precisely tuning the ratio of the constituents ensures the control of the dispersion profile along with a transition from effective dielectric to metallic heterostructures. The Ir coating thickness was varied ranging from a few angstroms to films of about 7 nm in the heterostructures. The transition has been observed in the structures containing individual Ir coating thicknesses of about 2-4 nm. Following this, we show epsilon-near-zero metamaterials with tunable dielectric constants by precisely varying the composition of such heterostructures. Overall, a comprehensive study on structural and optical properties of the metal-dielectric interfaces of Ir/Al2O3 heterostructures was addressed, indicating an extension of the material portfolio available for novel optical functionalities.

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.

Optical bandgap control in Al2O3/TiO2 heterostructures by plasma enhanced atomic layer deposition: Toward quantizing structures and tailored binary oxides.

Atomically thin heterostructures and superlattices are promising candidates for various optoelectronic and photonic applications. Different combinations of Al2O3/TiO2 composites are obtained by plasma enhanced atomic layer deposition (PEALD). Their growth, composition, dispersion relation, and optical bandgap are systematically studied by means of UV/VIS spectrophotometry, spectroscopic ellipsometry (SE), x-ray reflectometry (XRR), scanning transmission electron microscopy(STEM) and x-ray photoelectron spectroscopy (XPS). Besides, an effective medium approximation (EMA) approach is applied to model the heterostructures theoretically. The refractive index and the indirect bandgap of the heterostructures depend on the ratio of the two oxides, while the bandgap is very sensitive to the thicknesses of the barrier and quantum well layers. A large blue shift of the absorption edge from 400 nm to 320 nm is obtained by changing the TiO2 (quantum well) thickness from ~2 nm to ~0.1 nm separated by ~2 nm of Al2O3 (barrier) layers. PEALD unfolds the possibility of achieving optical quantizing effects within complex heterostructures enabling control of their structures down to atomic scale. It enables a path towards atomic scale processing of new 'artificial' materials with desired refractive indices and bandgap combinations by precise control of their compositions.