M. Keshavarz
Hedayati
a,
S.
Fahr
b,
C.
Etrich
b,
F.
Faupel
c,
C.
Rockstuhl
b and
M.
Elbahri
*ad
aNanochemistry and Nanoengineering, Institute for Materials Science, Faculty of Engineering, Christian-Albrechts-Universität zu Kiel, Kaiserstrasse 2, 24143 Kiel, Germany
bInstitute of Condensed Matter Theory and Optics, Abbe Center of Photonics, Friedrich-Schiller-Universität, Jena, Max-Wien-Platz 1, 07743 Jena, Germany
cChair for Multicomponent Materials, Institute for Materials Science, Faculty of Engineering, Christian-Albrechts-Universität zu Kiel, Kaiserstrasse 2, 24143 Kiel, Germany
dInstitute of Polymer Research, Helmholtz-Zentrum Geesthacht, Max-Planck-Str. 1, 21502 Geesthacht, Germany. E-mail: me@tf.uni-kiel.de
First published on 20th March 2014
We report on the design, simulation, fabrication, and characterization of a novel two layer anti-reflective coating (ARC) based on a plasmonic metamaterial and a dielectric. Promoted by the strong material dispersion of the plasmonic metamaterial, our novel concept (called hybrid ARC) combines two possible arrangements for layers in an anti-reflection coating into a single structure; albeit at two different wavelengths. This, however, causes a broadband reduction of reflection that is less sensitive against oblique incidence when compared to traditional antireflective coatings. Furthermore, we show that the current metamaterial on a metal reflector can be used for the visualization of different coloration such as plasmonic rainbow despite its sub-wavelength thickness.
The consideration of anti-reflective coatings (ARCs) as being very important is justified from their integration in nearly all photonic devices.11–15 Optical elements where they find use range from ordinary lenses over any laser system up to advanced photonic devices for disruptive technologies. Traditional ARCs made from an individual non-absorbing layer can usually be optimized to operate perfectly at an isolated design wavelength. Then, the refractive index (RI) of the ARC (being directly linked to the square root of the permittivity for non-magnetic, homogenous, isotropic, local materials as considered here) has to be the geometric mean of the RIs of the materials on both sides of the respective interface from which the spurious reflection is encountered, i.e. herein called a substrate and the incident medium. By no means of restriction, we consider in the following the RI of the substrate to be larger than the RI of the incident material (coating). The thickness of the ARC ought to be a quarter of the desired wavelength. However, and quite detrimental, the vanishing reflectivity only occurs at normal incidence and only at the isolated design wavelength. Nevertheless, wider-band ARCs are possible by relying on innovative designs,16,17 plasmonic and metamaterial layers18,19 or multilayer coatings.20 For instance, two-layer ARCs,21i.e. ‘V’ coat, could result in a wide-band ARC by a proper selection of films. In such a case the RI of the top layer should be smaller than the second layer and each layer thickness shall equal a quarter of the desired wavelength. The first suggestion for such a traditional arrangement of the layer materials is linked to the name of Lord Rayleigh; hence hereafter we call it the Rayleigh configuration. In fact, the order of the ARC film is very crucial in such a technique and once the order of layers is inversed (i.e. low and high RI placing as the spacer and the top layer, respectively), the reflection of the device increases and could even turn the substrate (in certain circumstances) into a mirror (Bragg-mirror).22,23 We wish to call such an arrangement in the following the reverse-Rayleigh configuration. Note that the in the reverse-Rayleigh configuration at least two reflection dips surround the central reflection peak.24
Recently, a new class of ARCs has been introduced, specifically for metallic substrates where the coating acts as an absorbing element to reduce the light reflection. In such a configuration, the reflection drops not only due to the interference25 but also by exploiting the absorbing character of the coating combined with losses in the metallic substrate.26–34 The strong optical attenuation through the highly absorbing coating or the strong resonant behavior in layers29 gives rise to low reflection from the metal substrate, although the thickness of the coating is much less than the wavelength of light. This concept works well on gold films which could sustain a plasmonic response under certain conditions as well as a broad intrinsic absorption (i.e. minimum reflection) in the visible range because of interband transition. The question arises whether this concept is equally applicable to semi-conductors as the substrate material. It is known that semi-conductors like silicon exhibit strongly dispersive material properties that complicate the design of efficient ARCs. Therefore, it remains a challenge to perceive an ARC that operates over the entire range of the visible and near-IR for semi-conductors.35
Here, we introduce an ultra-thin bi-layer coating as an ARC. The key-feature of our coatings is the use of a material with a high RI for the layer that faces the incident medium, i.e. the top layer. Moreover, the thicknesses of all involved layers are considerably thinner than a half or even a quarter of a wavelength. By a systematic analysis we show that an excellent anti-reflection performance is possible. While demonstrating the concept in the first stage with a pair of dielectric materials possessing only a weak dispersion, i.e. TiO2/SiO2, we exploit the strong dispersive nature of metamaterials in the second stage to demonstrate the hybrid-concept and eventually achieve a broad-band ARC with only a marginal angular sensitivity.
The metamaterial we will use consists of an ultrathin plasmonic nanocomposite made from ultra-fine metallic nanoparticles (diameter D < 5 nm (ref. 26)). Fig. 1a and b show the cross-sectional and top view TEM images of the sample. It is apparent that the particles' diameters are around 5 nanometers and they are randomly distributed in the matrix. It possesses a dispersive permittivity with a Lorentzian profile centered at the particle plasmon resonance. The homogenous isotropic metamaterial is characterized by a strongly dispersive RI that takes high values at long wavelengths and small values at short wavelengths, taken with respect to the particle plasmon resonance. Such a material can therefore beneficially be used to perceive an ARC that combines the reverse-Rayleigh and the Rayleigh ARC in the same structure, albeit at different wavelengths. Therefore, we call this structure a “Hybrid-Antireflection” structure. We postulate that the broadband anti-reflection performance of the presented metamaterial is facilitated by the anomalous material dispersion around the plasmon resonance. The dispersive refractive index of the composite varies in a way that at wavelengths longer than the resonance the coating serves in a reverse-Rayleigh configuration but at smaller wavelengths the composite's RI is smaller than the second layer and hence the Rayleigh condition is satisfied. In other words, by overlapping the reflection dip of the traditional ARC with that of a Fabry–Perot interferometer, the corresponding reflection dip of our two layer coating is very broad despite its low thickness. This unique dispersive RI of the presented metamaterial leads to the opportunity to observe a hybrid wide-band ARC encompassing the Rayleigh/reverse-Rayleigh configurations. Full wave electro-magnetic simulations of the metamaterial verify that it acts as a homogenous medium rather than an ensemble of plasmonic absorbers. This entails their description in terms of effective material properties which paves the way to consider such a structure in the design of many high efficient ARC devices.
To start with, we consider a bi-layer ARC where the top layer facing air as the incident medium is an ultrathin film of a high RI material. With the final device in mind, the thickness is chosen to be 20 nm. This adheres to the desire to have an ultra-thin and compact ARC. We leave here the exact value of the RI as a free parameter. The second layer shall be made from a low RI material. Silicon dioxide is selected as the low RI film since it is a common material in silicon industry and it can be either deposited or grown on the silicon substrate with good adhesion. We leave as a degree of freedom the thickness of this layer. In such a scheme, the substrate, i.e. silicon wafer, has the highest RI in the stack.
To identify on analytical grounds the conditions where the ARC operates optimal, a thin-film transfer matrix technique is applied to calculate the reflection. Results are shown in Fig. 1c. There, the reflectivity at a design wavelength (in this case at 600 nm) is calculated depending on the RI of the top layer and the thickness of the SiO2 layer. It is apparent that the reflection is suppressed for a rather high value of RI of the ultrathin top layer and a thin SiO2 layer. To suppress reflectivity at longer design wavelengths, the RI should be approximately the same but the thickness of the SiO2 layer should be slightly increased. However, it can always be assured that the reflection can be reduced to a negligible quantity, even though the coating is sub-wavelength in its thickness, i.e. far below the quarter of the design wavelength.
According to the calculated reflection contour (Fig. 1c), a high RI material which suitably matches the required RI is TiO2 (its average RI in the visible region is 2.4 (ref. 36)). The oxide films were prepared by sputtering of a dielectric target (namely SiO2 or TiO2) and the thicknesses were measured with a profilometer. Based on the simulation, 20 nm TiO2 layer and a 50 nm SiO2 coated on silicon could realize low reflection at 570 nm. Indeed, the fabricated stacks with the mentioned geometry and thicknesses provide a broad reflection reduction with a reflection minimum at 570 nm wavelength for silicon as shown in Fig. 1d which agrees well with simulation. By resorting to a traditional order for the layers, i.e. an ordinary Rayleigh configuration where the materials are arranged in the ascending order of their RI, it was observed that the reflection minimum occurs at 410 nm [Fig. 1d (inset)], in agreement with Rayleigh's postulation but it does not vanish totally since its thickness is far below the quarter-wavelength which is required for anti-reflectivity.
It can be seen that the ARC in the Rayleigh configuration is spectrally narrower than the reverse-Rayleigh configuration and its remaining reflection almost doubled. However, since those results might be affected by experimental uncertainties, we would like to stress the major advantage of the reverse-Rayleigh concept that can be better appreciated while comparing the angular dependency of both configurations (i.e. Rayleigh and reverse-Rayleigh). The average reflection at higher incidence angles for the case of the Rayleigh configuration is almost twice the intensity of a similar film but in reverse order (Fig. 2a). In fact, the reflection drop considerably red-shifts upon changing the geometry from traditional to the reverse-one which proves that the performance of ultra-thin reverse-Rayleigh ARC is more promising for an operation in the visible spectrum.
The more pronounced reflection drop and red-shift of the curve in reverse-Rayleigh compared to the Rayleigh configuration can be well explained by interference.37 In principle, destructive interference of the direct reflected light and the light reflected at consecutive interfaces requires a phase accumulation of π by the wave traversing the layers back and forth. This easily explains the dogma on using quarter wavelength layers with a small RI as the first (top) layer. However, in the case of a top-film with high RI (reverse-Rayleigh), the light which travels through the low RI layer and the reflected wave have a π phase difference38 which ends up with a destructive interference. In other words, in the case of a top-film with high RI, π phase accumulation comes for free as the impinging light reflected at the various interfaces experiences π–0–π phase shifts. The phase difference of the incoming and reflected light in the cavity is39 where n and d are the RI and thickness of the spacer layer, respectively. By inserting the values of thickness and RI of SiO2 in the mentioned equation, it ends up with , which provides the condition of destructive interference. Color changes of the coating by changing the thickness of the spacer layer (i.e. SiO2 film) from 10 to 50 nm, further prove the interference role in the reverse-Rayleigh coating. Fig. 2b shows the true color photograph of the silicon samples coated with 30 nm TiO2 film atop of 10, 30 and 50 nm SiO2 on the silicon substrate.
Nevertheless, neither ARC based on reverse-Rayleigh concept nor Rayleigh provide the desired properties of a wide-band ARC (i.e. whole solar spectrum range) owing to high reflection that appears at short and long wavelengths of the visible for both configurations. Additionally, for shifting the reflection dip to NIR, increasing the layer thickness and/or using a high RI material is needed. Note that there are only a limited number of materials with high refractive index which could fulfill the required RI contrast for the reverse-Rayleigh configuration.
In our opinion, and from technological point of view, the field is revolutionized if a coating is used that would enable both Rayleigh and reverse-Rayleigh configurations simultaneously, at different wavelengths though. Suppressing the reflections at multiple wavelengths would automatically enable a broadband ARC based on ultrathin films. However, this requires the use of strongly dispersive materials in the design of the ARC. Ideally, the geometrical dispersion that degrades the anti-reflection action beyond the target wavelength in an ARC design where non-dispersive materials are used has to be compensated by a suitable material dispersion. This perfect balancing, however, requires an anomalous dispersion in the material properties, which is always accompanied by absorption. Nonetheless, motivated by the recent work on ARC coatings on metals using weakly absorbing materials,29 we may conclude that if the ARC coating is sufficiently thin and contains ultrafine plasmonic nanoparticles, the absorption might not be detrimental. To evaluate the potential of this idea, we sought out a way to design a new concept for a coating that considers artificial materials (metamaterial) in their design that possesses a strong chromatic anomalous dispersion.
Accordingly, we consider a plasmonic nanocomposite of tiny metallic nanoparticles embedded in a dielectric host as a metamaterial with the required highly dispersive refractive index. The properties of the nanocomposite can be tuned by many parameters which constitute a great degree of freedom. They constitute an extraordinary material platform with many intriguing advantages. The fabrication of these nanocomposites is based on self-assembly processes using sputter techniques, which is well established,40–42 and they can be deposited on a large surface in a short time and at low costs (for more details see the Methods section).
This metamaterial derives its unique properties from the excitation of localized plasmon polaritons in the metallic nanoparticles.43 The nanoparticles are sufficiently small and arranged sufficiently dense, such that the material can be considered as effectively homogenous and isotropic. The material is characterized by a Lorentzian resonance in the effective permittivity which is centered at the plasmon resonance wavelength. Due to the isotropy of the material and the vanishing of any magnetic response, the permittivity uniquely defines the effective refractive index. The material can be perceived as a strongly dispersive dielectric with some finite absorption in resonance.
It is known that, with filling fractions for the metallic nanoparticles between 20% and 40%, the effective properties cannot be derived from canonical effective medium theories such as Clausius–Mossotti.44 Instead, we used finite-difference time-domain (FDTD) simulations of a sufficiently large super-cell and calculated the dispersive complex reflection and transmission coefficient45 (cf. Methods section). From these coefficients effective properties were retrieved for the composite. These parameters were afterwards fueled into a thin-film transfer matrix technique to simulate all quantities of interest. Selected configurations were equally simulated by the FDTD method to cross-check the predictive power of the effective properties. Identical results were always predicted, justifying the treatment of the nanocomposite as an effective medium (for more details see the Methods section). The dispersive RIs of the nanocomposites with different filling factors are shown in Fig. 2c. It is apparent from this dispersion graph that at resonance the absorption is maximal and the real part of the RI undergoes anomalous dispersion. At wavelengths longer than the resonance wavelength the material is characterized by a large RI (large permittivity) and hence would be suitable to serve in the reverse-Rayleigh configuration as the top material (ntop > nspacer). In contrast, at wavelengths smaller than the resonance wavelength, the medium is characterized by a rather small RI (small permittivity) and accordingly would be appropriate to be used in the Rayleigh configuration as the top material (ntop < nspacer). Therefore, plasmonic nanocomposites can be considered as the hybrid ARC that meets the condition of both Rayleigh and reverse-Rayleigh geometries resulting in a broad-band ARC coating.
We demonstrate the hybrid concept by coating a polished silicon wafer with a 20 nm silver–silicon dioxide nanocomposite separated from the substrate by a thin layer (50 nm) of silicon dioxide as shown schematically in Fig. 2d. Such a stack gives rise to the realization of a black silicon with a homogeneous ultrathin layer coating. Fig. 3a shows the reflection spectra of 20% and 30% nanocomposites deposited on 50 nm SiO2 coated silicon and the inset is the true color photograph of the sample with 30%, which looks black indeed.
Fig. 3 (a) Reflection spectra of 20 nm Ag–SiO2 with 20% (red) and 30% (blue) filling factors deposited atop of 50 nm SiO2 coated silicon. The inset shows the true color photograph of the silicon coated with the optimized film, which turns black in its appearance. (b) Reflection spectra of the film as in Fig. 2c measured at different angles of incidence with s-(solid lines) and p-polarization (dotted lines), (c) reflection spectra of hybrid ARC with 30% filling fraction of metal in the top layer deposited on spacer layers with three different thicknesses. The ARC is deposited again on silicon. Black, red and blue curves showing the spectra of 50, 70 and 100 nm thick spacer layers, correspondingly. (d) Reflection contour of the 20 nm film with various RIs on the SiO2 film with different thicknesses at (left) 800 nm and (right) 900 nm wavelengths. |
Angular reflectance measurement of the coating with 30% filling factor (Fig. 3b) shows the marginal angular and polarization dependency of the plasmonic hybrid ARC.46 More details on the angular behavior,33 especially for the angular domain that is not shown here, can be found in the literature.26
The spectra possess two main dips in the reflection spectra. The small wavelength dip is attributed to the graded AR (i.e. in analogue to a configuration where 50 nm SiO2 is deposited atop of 20 nm TiO2 (cf.Fig. 1d (inset))) and the second reflection dip originates from the destructive interference of the reflected field (i.e. in analogy with the TiO2 film atop of SiO2 (cf.Fig. 1d (black curve))).
In spite of the expected wavelength shifts of the antireflection dips [cf.Fig. 3b (inset)], one peak at 450 nm (i.e. where the plasmon of the nanocomposite arise) is also revealed that is invariant against the angle of incidence and hence we attribute it to the plasmon resonance of the composite. Indeed, the wavelength of the peak remains unchanged by angle variation, which confirms the localized nature of the (particle plasmon) resonance.
To demonstrate the tunability of the hybrid ARC coating and meanwhile to gain more understanding about the role of plasmon in the observed phenomena, the effect of the spacer layer on the optical responses was examined. Keeping the top layer thickness and composition constant while increasing the thickness of SiO2 from 50 nm to 100 nm, a red-shift of the reverse-Rayleigh as well as Rayleigh antireflection dips was observed (Fig. 3c). This behavior is in good agreement with our simulation (Fig. 3d) which shows that an increase of the spacer results in a broad ARC in NIR (800–900 nm) for the case of the reverse-Rayleigh configuration. On the other hand, ARC performance of the graded configuration (small wavelength regime) in the hybrid is deteriorated by thickening the spacer layer. Indeed, the origin of the mentioned high reflection with a thicker inter-layer could be attributed to two phenomena; firstly the constructive interference of the incident and the reflected light, and secondly, the spectral overlap of the plasmonic resonance of the nanocomposite and the Rayleigh antireflection dip. Such an overlap occurred because of the red-shift of the Rayleigh originated dip via thickening of the spacer layer.
Indeed, integrating the plasmonic structure as a hybrid ARC coating provides an additional degree of freedom for tuning the performance of the ARC coating. In other words, by using the hybrid plasmonic ARC, the designer can reach the desired optical properties not only by alteration of the layer thickness but also by adjusting the filling factor (RI) and type of the metallic constituents of the nanocomposite. Generally, the performance of the hybrid ARC depends on the contrast of the RIs between the layers. At the wavelengths where the top layer shows higher RI, the reverse-Rayleigh condition is satisfied but the traditional Rayleigh would be realized once the top film possesses the lower RI in the stack. The presented plasmonic anti-reflector shows such a low and tunable reflectivity due to the extreme dispersive RI of the metamaterial (cf.Fig. 2c), which has been shown formerly.47–50 The RI of the nanocomposite with 40% filling factor changes from 0.9 up to 3.15 from small to long wavelengths. In other words, the relative RI changes of the host matrix before and after embedding of the nanoparticles can vary from −30% to +140%.
In fact, the tunability of the plasmon resonance and correspondingly the reflection change29 by changing the filling factor of the nanocomposite provide the possibility for the coloring of metals using our hybrid concept. Fig. 4a shows a true photograph of samples of 25 nm SiO2 coated gold film which is covered with 20 nm gold–SiO2 nanocomposite with a variety of filling factors, creating a spectrum of colors including yellow, orange, blue and green. The colors originated from the different reflection drops associated with each filling factor demonstrating the potential of the hybrid concept for realization of plasmonic rainbow colors.51 Note that demonstration of various colors on the silicon substrate is not possible under the same conditions (i.e. constant thickness of layers while varying the filling factor). It seems that, the surface plasmon of the gold film (which is absent on silicon) in parallel with the hybrid ARC contributes to the rainbow colors.
We believe that the hybrid concept could pave the way for new highly efficient ARCs for a variety of applications ranging from photovoltaics52 and optics to solar absorbers and stealth technology53,54 as well as other fields where high reflection is undesired. But for energy applications, not only the low reflectance rather high transmission is desired. Calculation showed that the light transmission into the substrate (silicon) is enhanced by using the plasmonic coating. Fig. 4b shows the light absorbed by silicon (i.e. light transmitted into silicon) by means of current plasmonic coating. The light reaching the substrate is apparently increased through the coating, which shows the potential of such an approach for energy harvesting purposes. However, the preliminary results on photocurrent measurements of presented coating on p-silicon showed some current loss that we attributed to the poor interface of the prepared films which acts as the sites for electron–hole recombination. Nevertheless, a more sophisticated design is required to better explore the role of the present ARC for electron–hole generation which is beyond the scope of this manuscript.
The thickness of the films was measured with a profilometer (Dektak 8000 surface profile measuring system) and the thickness of dielectric was further measured with an ellipsometer (M2000 (J.A. Woollam Co., Inc.)). Optical properties of the samples at normal incidence were measured with a UV/vis/NIR spectrometer (Lambda900, Perkin Elmer). For transmission measurements, the base line was collected by measuring the empty compartment (i.e. air considered as the reference) while for reflection measurements, the mirror provided by the company was used. To extract the absolute value of reflection, the measured reflection spectra of the samples were normalized to the tabulated data of the mirror provided by the manufacturing company (PerkinElmer). In all types of measurements, the scan step was fixed to 4 nm and the base line was collected twice by a full sweep across the spectral domain of interest while the integration and acquisition times were kept constant.
Polarization-dependent and variable angle spectroscopic Ellipsometry reflection measurements of the films was carried out with J.A. Woollam Co., Inc. M2000 UI (spectroscopic ellipsometer) with a dual lamp system with deuterium and Quartz Tungsten Halogen (QTH) lamps as light sources (data provided by LOT catalogue Europe). The angle sweep step was selected to be 5° or 10° and the angle variation from 45° to 85° was performed. In order to have a comparable study and achieve the best signal-to-noise, 5 second acquisition time was applied for all experiments. Accordingly, the measurement did not take more than few seconds. For analyzing the data, CompleteEASE® software package provided by the company was used.
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