The invention relates to a nanoparticle antireflection layer and, in particular, though not necessarily, to a nanoparticle thin-film broadband antireflection layer, to optical elements and optoelectronic devices comprising such antireflection layer and to the use of such nanoparticles in an antireflection layer.
Antireflection (AR) coatings (layers) are well known optical coatings used in optical devices or elements in order to reduce reflection of light. The use of such AR coatings cover a wide range of important optical applications including AR coatings for optical elements, e.g. lenses, and optoelectronic devices, e.g. solar cells, light emitting diodes, lasers, and displays. Conventional AR coatings are based on interference effects in one or more dielectric layers of a specific thickness and refractive index. A single layer AR coating is inherently unable to reduce reflection over a broad range of wavelengths. This is particularly important in solar cells that convert the broad spectral range emitted by the sun to electricity. Moreover such conventional AR coatings suffer from undesired angle dependences.
In order to solve this problem typically multilayer graded-index AR coatings are used. For example, Chhajed et al. describe in their article “Nanostructured multilayer graded-index antireflection coating for Si solar cells with broadband and omnidirectional characteristics” (Applied Physics Letters 93, 251108 (2008)) the use of multilayer graded-index AR coatings comprising a low refractive index nanostructured porous silicon dioxide top layer. Other ways of achieving graded index antireflection coatings are described in U.S. Pat. No. 7,170,666, which describes a method for etching nanostructures into a thin film oxide layer thereby realizing a graded index oxide surface. Such broadband graded index multilayer antireflection coatings however require tight control of process parameters, e.g. the layer thicknesses and layer compositions, and are thus not suitable for implementation in mass produced optical devices and elements.
US2008/0171192 suggests the use of a nanoparticle array of relatively small size and pitch for use as an AR layer in the visible range (400-800 nm). For particular applications however, such as solar cell applications, extreme broadband AR coatings are desired which provide optimal transmission of the whole solar spectrum, including UV, visible, near infrared and infrared radiation.
Hence, there is a need in the art for providing improved AR coatings, which provide effective broadband antireflection properties over a wide range of incident angles. Moreover, there is a need in the art for broadband AC coatings, which are simple to fabricate.
It is an object of the invention to reduce or eliminate at least one of the drawbacks in the prior art. In one aspect, the invention may relate to a thin-film broadband antireflection layer for use with an optical element or an optoelectronic device, wherein said antireflection layer comprises: at least one thin-film dielectric layer; and, at least one array of nanoparticles disposed onto or in said thin-film dielectric layer, wherein the dielectric constants of said nano-particles is substantially distinct from the dielectric constant of said dielectric layer. Such nanoparticle antireflection layer provides improved antireflective properties over a broad range of wavelengths, including the UV and IR spectrum range.
In one embodiment, the thickness of the antireflection layer, the size of the nanoparticles in the nanoparticle array and the pitch of the nanoparticle array is selected such that transmittance of photons associated with the solar spectrum between 300 and 1100 nm is more than 80%, preferably more than 85%.
In one embodiment said thin-film dielectric layer may comprise silicon dioxide, silicon nitride, tetraethylorthosilicate (TEOS), a organic resin, a polymer, a semiconducting layer and/or combinations thereof.
In one embodiment said thin-film dielectric may have a thickness approximately between 10 and 300 nm, preferably between 50 and 100 nm.
In yet another embodiment the average dimensions of said nanoparticles may be selected between approximately 50 and 300 nm and wherein the average distance between said particles is selected between 200 and 700 nm.
In a further embodiment at least part of said nanoparticles may be metal nanoparticles. In yet a further embodiment said metal may be selected from the group of Au, Ag, Cu, Al and/or alloys thereof.
In one variant at least part of said nanoparticles may be semiconducting nanoparticles. In another variant said semiconducting material may be selected from the group IV semiconductors, the III-V or II-VI semiconducting compounds and/or combinations thereof.
In a further variant, at least part of said nanoparticles may be metaloxide nanoparticles. In yet a further variant said metaloxide may relate to high-refractive index oxides selected from the group of Al2O3, Ta2O5, Ti3O5, TiO2, ZiO2, Nb2O5, CeO2 and Si3N4.
In one embodiment at least part of said nanoparticles has a substantially spheroidal shape; in another embodiment at least part of said nanoparticles are substantially cylindrically shaped.
In a further aspect, the invention may relate to a multilayer structure comprising at least one antireflection layer according to any of the embodiments and/or variants as described above.
In other aspects the invention may relate to an optical element, preferably an optical lens or a display screen, comprising an antireflection layer according to any of the embodiments and/or variants as described above or to an optoelectronic device, preferably a light-receiving or a light-emitting device, comprising an antireflection layer according to any of the embodiments and/or variants as described above.
In one embodiment said antireflection layer is deposited onto a thin-film light absorbing or light-emitting layer associated with an optoelectronic device.
In yet a further aspect, the invention relates to the use of an array of dielectric nanoparticles, preferably metallic nanoparticles, as at least part of an antireflective coating. In one embodiment, the average dimensions of said used nanoparticles may be selected between approximately 100 and 300 nm and wherein the average distance between said particles is selected between 200 and 700 nm. In another embodiment, at least part of said used nanoparticles may be metal nanoparticles, preferably said metal being selected from the group of Au, Ag, Cu, Al and/or alloys thereof; and/or, wherein at least part of said used nanoparticles may be semiconducting nanoparticles, preferably said semiconducting material being selected from the group IV semiconductors, the III-V or II-VI semiconducting compounds and/or combinations thereof; and/or wherein at least part of said used nanoparticles may be metaloxide nanoparticles, preferably high-refractive index oxides selected from the group of Ta2O5, Ti3O5, TiO2, ZiO2, Nb2O5, CeO2 and Si3N4.
The invention will be further illustrated with reference to the attached drawings, which schematically show embodiments according to the invention. It will be understood that the invention is not in any way restricted to these specific embodiments.
In contrast with conventional AR coatings, which are designed to match the refractive index of air with the refractive index of the optical element or optoelectronic device using a stack of dielectrics having a low refractive top dielectric layer and a relatively high refractive index bottom dielectric layer, the present invention uses an array of nanoparticles provided onto the surface or embedded into the surface of a thin-film dielectric.
Further, the use of metals in antireflection coatings is uncommon, as metal films are know as good reflectors. In the present invention the nanostructure of the metal particles, and their assembly in regular arrays or random geometries, leads to efficient anti-reflective properties.
In particular, the present invention uses the scattering properties of light, which depend on the optical constants of the nanoparticles, the optical constants of the surrounding dielectric and the optical constants of the substrate. Light is preferentially scattered by the nanoparticles into the high-refractive index substrate material, thereby rendering the metal nanoparticle arrays effective anti-reflective coatings. A further advantage of this invention for applications for example in solar cells is that the scattered light acquires an angular spread in the substrate, which can lead to more effectively absorption of light in the solar cell. This is a particularly important advantage for thin-film solar cells.
Although the effect at 650 nm is not so high as for a standard AR coating, the total enhancement is larger due to the broadband effect provided by the nanoparticles. This is illustrated in more detail in
a) and (b) depict the enhancement factor for different particle parameters. These figures show that the nanoparticle thin-film AR coating allows improved AR properties, in particular a more than 8% improvement, when compared with the conventional Si3N4 AR coating. The improvement in the AR effect is dependent on various parameters, including e.g. particle height (
a) and (b) depict the enhancement factor for a particle thin-film AR coating according to another embodiment of the invention.
b) depicts an embodiment wherein the enhancement factor is measured for a nanoparticle AR coating as a function of the thin-film dielectric layer, in this case a thin-film Indium Tin Oxide (ITO) layer, i.e. a transparent conducting layer (TCO), on top of an a-Si substrate. In this example Ag spheroids of 200 nm width and 125 nm height and an array pitch of approximately 450 nm were used. Such nanoparticle AR coating may be advantageously used in a photovoltaic cell based on a-Si. From this figure it follows that a substantial enhancement factor is present over a wide range of ITO thicknesses, in this case between approximately 20 and 60 nm, preferably between 30 nm and 55 nm, more preferably between 35 and 50 nm.
Hence, the inventors have discovered that combining a thin-film dielectric layer with nanoparticles comprising a material having a dielectric constant distinctly different than that of their surrounding forms a very simple and effective broadband AR coating. The present invention is based on the insight that such nanoparticles may be used as strong light scatters. For example, for metallic nanoparticles, e.g. Ag or Au nanoparticles of sufficiently large size, there is almost no absorption in the particles and the scattering cross section may well exceed the particle's geometrical cross section. Such particles may thus be used as effective light scatters requiring a relatively small surface coverage. Depending on particle size, such optimized coverage may be in the order of approximately 10-20% of the surface area.
Due to the presence of an array of nanoparticles on top of a substrate having a higher dielectric index than air, light scattered by the nanoparticles will preferentially scatter into the substrate.
From
Further, from
One of the advantageous of using metal nanoparticles in the formation of a nanoparticle AR coating on e.g. a solar cell, is that metals (e.g. Ag or Al) are used for the formation of the electrical top contact of the solar cell. In this way deposition of electrical contacts and a nanoparticle AR coating may be realized in a single processing step using the same metal. In some embodiments, it is found that the transmittance of light is improved by placing the nanoparticles on a thin dielectric spacer layer on the substrate. Such spacer layers may e.g. be the thin passivation layer that is already present in a standard semiconductor manufacturing process.
The reflection coefficients shown in this figure are calculated by averaging the measured reflectivity over the solar spectrum, for wavelengths up to the band gap of c-Si. The graph shows that selection of both the particle array geometry and the Si3N4 spacer layer may be used to minimize reflection, due to the strong coupling between the particles and Si3N4 spacer layer properties.
As will be described in more detail hereunder, the nanoparticle AR coating according to the invention is not limited to the materials as described with reference to
In
From these graphs it can be derived that due to the interaction between the dielectric spacer layer and the nanoparticle AR layer, the dielectric spacer layer especially improves the transmission of light in the UV and visible part of the spectrum, while the nanoparticle AR layer comprising nanoparticles having a dielectric constant substantially distinct from the dielectric constant of the dielectric layer improves transmission in the near IR and IR spectral range. Combination of these AR layers provides significant broadband transmission enhancement over the entire solar spectrum.
This embodiment also illustrates that the broadband enhancement in the transmittance spectrum stems from the combined effect of the nanoparticle layer improving the transmittance in the near IR and IR spectral range and of the dielectric AR layer improving the transmittance in the blue and visible parts of the spectrum wherein the nanoparticles have a dielectric constant which is substantially distinct from the dielectric constant ∈ of the dielectric layer.
Values of the dielectric constant of the materials used in the nanoparticle AR coatings according to the invention are well known in the art e.g.: polymers ∈˜1.4; SiO2∈˜2.15; Si3N4∈˜4; TiO2∈˜7.5; Si∈˜12.25 (1100 nm wavelength) and ∈˜15 (500 nm). Further, it is well known in the art that the dielectric constant of metals are complex, wavelength-dependent functions, e.g. for Ag the real part of ∈ may vary between −55 (1100 nm) and 2 (300 nm) and the imaginary part of ∈ may vary between 0.5 and 3.5 and for Au the real part of ∈ may vary between −60 (1100 nm) and 0 (300 nm) and the imaginary part of ∈ may vary between 1 and 7. A stronger scattering effects requires a larger difference between the dielectric constant of the materials used for the spacer layer and the nanoparticles.
In a further embodiments metal nanoparticles as described with reference to
The materials and AR coating structures used in the embodiments described with reference to
Moreover, it is submitted that the nanoparticle AR coating may be part of a multilayered structure comprising e.g. one or more passivation layers deposited on top of the nanoparticles. Such passivation layer may for example comprise a UV curable resin well known in the art. Further, an array of nanoparticles may both include two-dimensional arrangements with a predetermined pitch and random arrangements of nanoparticles. In such randomized arrangements instead of the array pitch the effective surface coverage (% per unit of area) may be used as one of the parameters defining the nanoparticle AR coating.
The nanoparticle AR coating may be fabricated using various known lithography techniques such as UV, X-ray, e-beam lithography and other related techniques in combination with known thin-film deposition methods such as for example sputtering, thermal evaporation, chemical vapour deposition or sol-gel techniques.
Further, an adapted screen-print or inkjet printing technique may be used which allowing direct printing of nano-sized metal structures (see e.g. Zhao et al., “Self-aligned inkjet printing of highly conducting gold electrodes with submicron resolution”, Journal of Applied Physics 101, 064513, 2007).
One particular useful technique for large area application is the imprint lithography technique. One embodiment of this technique is for example described in US patent application US2008/0011934, which is hereby incorporated by reference into this application. Using this method an imprint template corresponding to the pattern of a predetermined nanoparticle array with typical dimensions as described in relation with
It is to be understood that any feature described in relation to any one embodiment may be used alone, or in combination with other features described, and may also be used in combination with one or more features of any other of the embodiments, or any combination of any other of the embodiments. Moreover, the invention is not limited to the embodiments described above, which may be varied within the scope of the accompanying claims.
Number | Date | Country | Kind |
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10159174.1 | Apr 2010 | EP | regional |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2011/055323 | 4/6/2011 | WO | 00 | 3/1/2013 |