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Solar selective coatings based on carbon transition metal carbide nanocomposite absorber layers were designed. Pulsed filtered cathodic arc was used for depositing amorphous carbon: metal carbide (a-C:MeC, Me = V, Mo) thin films. Composition and structure of the samples were characterized by ion beam analysis, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. The optical properties were determined by ellipsometry and spectrophotometry. Three effective medium approximations (EMA), namely Maxwell-Garnett, Bruggeman, and Bergman, were applied to simulate the optical behaviour of the nanocomposite thin films. Excellent agreement was achieved between simulated and measured reflectance spectra in the entire wavelength range by using the Bergman approach, where in-depth knowledge of the nanocomposite thin film microstructure is included. The reflectance is shown to be a function of the metal carbide volume fraction and its degree of percolation, but not dependent on whether the nanocomposite microstructure is homogeneous or a self-organized multilayer. Solar selective coatings based on an optimized a-C:MeC absorber layer were designed exhibiting a maximum solar absorptance of 96% and a low thermal emittance of ~5 and 15% at 25 and 600ºC, respectively. The results of this study can be considered as predictive design tool for nanomaterial-based optical coatings in general.

The design of an efficient and stable solar selective coating for Concentrating Solar Power central receivers requires a complex study of the materials candidates that compose the coating. Carbon-transition metal nanocomposites were studied in this work as absorber materials because they show appropriate optical properties with high absorption in the solar region and low thermal emittance in the infrared. Furthermore metal carbides are thermal and mechanical stable in air at high temperatures. In this work a solar selective coating was grown by a dual source filtered cathodic vacuum arc. The complete stack consists on an infrared reflection layer, an absorber layer of carbon-zirconium carbide nanocomposites and an antireflection layer. The aim of this research is optimize the absorber layer and for that, the metal content was controlled by adjusting the pulse ratio between the two arc sources. The elemental composition was determined by Ion Beam Analysis, X-Ray diffraction measurements show the crystal structure and the optical properties were characterized by spectroscopic ellipsometry measurements. The reflectance spectra of the complete selective coating were simulated with the optical software CODE. Bruggeman effective medium approximation was employed to average the dielectric functions of the two components which constitute the nanocomposite in the absorber layer. The optimized coating exhibited a solar absorptance of 95.41% and thermal emittance of 3.5% for 400ºC. The simulated results were validated with a deposited multilayer selective coating. Unión Europea H2020 FRIENDS2 Centro para el Desarrollo Tecnológico Industrial (CDTI) IDI-20130896 (INDESOL)

Transition metals with carbon deposited by physical vapor deposition techniques, lead the formation of metal nano-clusters or nanocrystalline metallic carbides embedded in a carbon matrix. Interstitial carbides are stable at high temperature, have high melting points and possess a high reflectivity. In contrast, the resulting carbon: transition metal nanocomposites show optical selective properties such as good absorptance in the visible with high reflectance in the infrared. These properties make them very attractive for applications where high temperature resistant materials with selective optical properties are required. In this study, carbon: transition metal nanocomposites were grown using a physical vapor deposition system incorporating two pulsed filtered cathodic arc sources, one provided with a graphite cathode and the other with a metallic cathode (Zr, V or Mo). The metal content in the composite was controlled by adjusting the pulse ratio between the two sources, and determined by Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). Comprehensive structure characterization was carried out using a combination of X-ray diffraction (XRD), Raman spectroscopy and high resolution transmission electron microscopy (HRTEM). Optical characterization has been done using both ellipsometry and spectrophotometer measurements in order to obtain the optical constants and the reflectance spectra of the samples. Together with experimental characterization, a computer program is used to simulate the reflectance spectra of different carbon: transition metal films. Bruggeman effective medium theory was used to average the dielectric functions of the two components which compose the film. According to our simulations, the resulting reflectance of the nanocomposite films is strongly affected by the metal content, independently if it results in metallic nano-clusters or nanocrystalline metallic carbides. Simulated spectra were compared with the measured reflectance of the deposited films obtaining good agreement between simulations and experimental results.

The physical vapour deposition of transition metals with carbon leads to the formation of metal nano-clusters or nanocrystalline metallic carbides embedded in a carbon matrix. Interstitial carbides are very stable at high temperature, have high melting points and possess a high reflectivity. In contrast, carbon: transition metal nanocomposites can show optical selective properties such as good absorptance in the visible with high reflectance in the infrared. These properties make them very attractive for applications were high temperature resistant materials with selective optical properties are required. In this study, Carbon: transition metal nanocomposites were grown using a physical vapour deposition system incorporating two pulsed filtered cathodic arc sources, one provided with a graphite cathode and the other with a metal cathode (Zr, V and Mo). The metal content in the composite was controlled by adjusting the ICarbon/IMetal pulse ration between the two sources, and determined by Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA). Comprehensive structure characterization was carried out using a combination of X-ray diffraction (XRD), Raman spectroscopy and high resolution transmission electron microscopy (HRTEM). Optical characterization has been done using both with ellipsometry and spectrophotometer measurements in order to obtain the optical constants and the reflectance spectra of the samples. Together with experimental characterization, the computer program CODE is used to simulate the reflectance spectra of different carbon: transition metal films. Bruggeman effective medium theory was used to average the dielectric functions of the two components which compose the film. According to our simulations, the resulting reflectance of the nanocomposite films is strongly affected by the same metal content, independently if it results in metallic nano-clusters or nanocrystalline metallic carbides. Simulated spectra were compared with the measured reflectance of the deposited films obtaining good agreement between simulations and experimental results.

Ion assistance provides unique opportunities to influence the microstructure of growing films due to energy and momentum transfer. Here, ion effects on the microstructure of C:Ni nanocomposite thin films grown at RT to 500°C by ion-beam sputtering with assisting oblique incidence angle Ar+ ion beam irradiation (50 – 130 eV) are studied by SEM, (c)AFM, TEM, GISAXS, and TRI3DYN simulations. Two types of ordered metallic nanostructures in an amorphous carbon matrix are identified and characterized: i) tilted parallel columns [1] and ii) rippled, periodic three-dimensional nanoparticle arrays [2]. For the former one, the tilt angle and diameter of the nanocolumns are controlled by the deposition parameters. Ion-enhanced diffusivity and ion-induced surface drift are responsible for the tilted column microstructure. Complex secondary structures like chevrons with partially epitaxial junctions are grown by sequential deposition. For a given composition of the depositing flux, the transition from the columnar growth to the 3D pattern formation regime as a function of the assisting ion energy is demonstrated. The 3D pattern is attributed to the transfer of compositionally modulated surface ripples into the bulk of the C:Ni thin film. The essential experimental features are reproduced by three-dimensional binary collision computer simulations. This agreement points to ion-induced preferential displacements as the driving force for the 3D pattern formation.

Nano structured Si absorber layers are candidates to improve efficiencies of thin film Si solar cells without increasing costs. Si-SiO2 nano sponge-like nanocomposites are promising materials as they exhibit a widened band gap due to quantum confinement and electrical interconnectivity due to percolation of the nanostructured Si. The sponge-like structures can be formed upon annealing of substoichiometric SiOx films (x

Ion assistance during film growth provides unique opportunities to influence the microstructure due to energy transfer and imposed directionality. During nanocomposite film growth at low temperatures (RT to 300°C), phase separation occurs at the growing film surface. A systematic study of ion irradiation as a pure energy and momentum transfer agent in the context of surface diffusion assisted phase separations is, however, lacking. Here the influence of low energy (50-140 eV) assisting Ar+ ion irradiation on the morphology of C:Ni (~ 5 at.% Ni to ~ 50 at.% Ni) thin films will be reported. Two types of ordered nanostructures, - tilted columns and self-organized 3D patterns with well-defined surface periodicity - are identified and characterized. For a given composition of the depositing flux, the transition from the column to the self-organized 3D pattern formation regime as a function of the assisting ion energy is demonstrated. Tilt angle and diameter of the nanocolumns are controlled by the deposition parameters. Complex secondary structures like chevrons with partially epitaxial junctions are grown by sequential deposition. The effects of the metal content and the assisting ion current on the self-organized 3D patterns and surface periodicity are studied. Mechanical and tribological properties of both types of nanostructures will be reported. Acknowledgement: The work is funded by the European Union, LEI Folgeprojekt D1, "C-basierte Funktionsschichten für tribologische Anwendungen (CarboFunctCoat)", No. 7310000211.

The design of an efficient and stable solar selective coating for photo-thermal conversion plants requires a complex study of the materials that composed the coating. The optimal optical properties for those absorber coatings are high solar absorptance in the wavelength range of 0.3 to 2.5 μm which corresponds to solar spectrum under atmospheric conditions and low thermal emittance in the infrared wavelength range. Carbon-transition metal nanocomposites have been selected as absorber materials because they show appropriate optical properties as well as thermal and mechanical stability at high temperatures. The refractory metal carbide nanoparticles have been experimentally shown to stabilize the surrounding carbon matrix at least up to 700°C. The computer simulation program CODE has been used to calculate solar absorptance and thermal emittance of various multilayers coatings material combinations of carbon - metal nanocomposites (NCTM). The optical properties of the inhomogeneous composite material were simulated with a physical model proposed by Bruggeman and Maxwell Garnett which average the dielectric function of the components of the composite. This allows treating the composite system as an effective medium. This contribution compares simulated optical properties for different nanocomposite structural configurations (layer thickness, metal to carbon ratio). The calculated results are in the range of 0.91-0.97 for solar absorptance and 0.02 - 0.07 for thermal emittance at 300K.

Phase separation occurring on the surface of growing films provides unique means to influence the microstructure of composite materials. Here, the influence of ion assistance on the morphology of carbon-nickel nanocomposite thin films for different metal contents is investigated. Carbon-transition metal nanocomposites are relevant in the context of solar-thermal energy conversion, fusion, fuel cells, tribology or sensing. The films were grown by dual ion beam sputtering in a temperature range of RT-300°C. The growing films were irradiated by an assisting Ar ion beam with energies ranging from 50 to 130 eV. It is found that the nickel content drastically influences the morphology of the films: while films with low Ni contents show regular self-organized structures consisting of ordered Ni nanoparticles embedded in the carbon matrix, higher Ni contents predominantly exhibit a columnar morphology. The results are discussed on the basis of the interplay of ion-induced effects and phase separation modes. Acknowledgements: Funding by the European Union, ECEMP-Project D1, "Nanoskalige Funktionsschichten auf Kohlenstoffbasis", Projektnummer 13857 / 2379 is gratefully acknowledged.

Ion irradiation of multielement surfaces can induce regular compositionally modulated surface roughness nanopattern formation such as ripples or nanodots. This kind of bottom-up nanopatterning can provide means to not only structure the solid surfaces but also to create ordered heterogeneous structures in three dimensions (3D) when performed in growth mode: the compositional surface nanopattern is continuously buried by incoming species while the surface is again restructured due to ion irradiation. The present work is an experimental demonstration of this concept: 3D ordered nanocomposites are grown via ion induced two dimensional (2D, surface) nanopattern formation during bi-component film growth. The influence of low energy (50-140 eV) assisting Ar+ ion irradiation on the morphology of C:Ni (~ 5 at.% Ni to ~ 30 at.% Ni) thin films will be reported. It will be shown that for certain growth conditions surface ripples form during oblique incidence low energy ion beam assisted deposition of C:Ni films. These surface ripples are compositionally modulated: Ni is located on the crests and carbon in the valleys. The film cross sections show periodic distribution of metal nanoparticles in a carbon matrix with the same periodicity as the surface ripples. As this 3D patterning effect has a physical origin, it can be expected to occur in many material systems. Such an approach holds high potential for the growth of functional nanocomposite films for a wide range of applications.

Carbon-based metal nanocomposites have been shown to be good material candidates for applications requiring optical selectivity. However their true potential usage largely depends on the optimization of their composition and microstructure. Diamond Like Carbon with different transition metals were grown on stainless steel and Inconel substrates using pulse filtered cathodic arc deposition from two repetitively pulsed cathodic arc sources with separate macroparticle filters. The influence of several transition metals (Ti, Zr, Cr, W, Mo, V and Nb) on their optical selectivity was investigated. Carbon metal-containing samples were prepared using two cathodic arc sources provided with a carbon cathode and a pure transition metal cathode. Different metal concentrations in the coatings were obtained by varying the average arc current of the metal pulsed cathodic arc source (Imetal). The volume fraction of metal was determined by combined Rutherford Backscattering Spectroscopy (RBS) and Nuclear Reaction Analysis (NRA) measurements. The structure of the deposited films was analyzed by Transmission Electron Microscopy (TEM), X-ray diraction (XRD) and Raman spectroscopy. In this study, the computer simulation program Coating Design (CODE) has been used to calculate optical properties of the different carbon-transition metal nanocomposites. The optical constants of various carbon-based nanocomposites were simulated using a physical model proposed by Bruggeman and Maxwell Garnett which averages the dielectric function of the components of the composite, which allows treating the composite system as an effective medium. The performed simulations allowed calculating the solar absorptance and thermal emittance of the nanocomposites. Varying the nanocomposite material configurations such as layer thickness, volume metal fraction, number of layers and multilayer stack resulted in new configurations that enhance the optical selectivity of these materials. Simulated reflectance was compared with spectrophotometry measurements of the deposited films with good agreement between them.

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