CN110376667B - Broadband electromagnetic wave absorber based on refractory material and preparation method thereof - Google Patents
Broadband electromagnetic wave absorber based on refractory material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a refractory material-based broadband electromagnetic wave absorber and a preparation method thereof. The broadband electromagnetic wave absorber is composed of a three-layer structure of a flat metal film layer, split dielectric nano rings and split metal nano rings from bottom to top in sequence. The metal can be refractory material such as titanium, nickel, chromium or tungsten metal. The process is simple and mature, and can realize large-area production. The absorber has the characteristics of perfect broadband absorption and thermal stability in a complex electromagnetic field environment.
Description
Technical Field
The invention relates to the field of materials and energy, in particular to a refractory material-based broadband electromagnetic wave absorber and a preparation method thereof.
Background
The broadband electromagnetic wave absorber is one of necessary devices for realizing efficient absorption of solar energy spectrums and photoelectric detection of broadband, and the principle of the broadband electromagnetic wave absorber is that the phenomenon of resonance absorption or capture of light waves caused by plasmon resonance, medium wave guide mode, spectrum phase coupling or coherence and the like generally.
Since 2008 reported meta-material absorbers, the international academia has raised a new heat tide. The broadband absorber has good application prospects in the aspects of solar cells, heat radiation, imaging equipment and the like. To date, great progress has been made in the design of absorbers having excellent absorption properties. Many different types of absorbers have been proposed, including single band, dual band, multi-band and broadband absorbers. The metamaterial absorber mainly comprises a metal-medium-metal three-layer structure. The performance of the absorber is not only determined by the material itself, but is also closely related to the shape, size, arrangement and structural combination of the absorber material. The bottom metal layer is to prevent electromagnetic transmission (i.e., transmission of 0) and the top metal structure is to match the absorber impedance to suppress reflection (i.e., reflection of approximately 0). So that a perfect absorption with absorption close to 100% is obtained according to the absorption formula a-1-R-T (where a stands for absorption, R for reflectance and T for transmittance). The existing broadband absorbers absorb only one resonance wavelength, and the absorption band is narrow. In addition, these absorber systems suffer from drawbacks such as narrow absorption bandwidth, low absorption efficiency, complex structure and the need to use precious metal materials and poor thermal stability.
Therefore, designing and realizing perfect absorption in a wide band range only depends on a metal-medium composite system which is simple and easy to operate and can be produced by a large-area process, and the metal-medium composite system has very important practical significance and application value for the difficulty of solar energy absorption.
Disclosure of Invention
In order to solve the defects of the absorbers mentioned in the background art, the invention provides a refractory-based broadband electromagnetic wave absorber and a preparation method thereof.
The invention relates to a refractory-based broadband electromagnetic wave absorber, which comprises:
a flat metal film;
a split dielectric nanoring arrayed on the metal film, the split dielectric nanoring meaning that there are gaps on the dielectric nanoring;
a split metallic nanoring disposed on the split dielectric nanoring, the split metallic nanoring meaning that there are gaps on the metallic nanoring.
Further, the split dielectric nanoring comprises four evenly distributed gaps and the split metal nanoring comprises four evenly distributed gaps.
Further, the thickness of the flat metal film exceeds 150 nanometers, and the material of the flat metal film is titanium, nickel, chromium or tungsten.
Further, the thickness of the split dielectric nanoring is 1-300 nanometers, and the material of the split dielectric nanoring is silicon dioxide, aluminum oxide or magnesium fluoride.
Further, the thickness of the split metal nano ring is 1-300 nanometers, and the split metal nano ring is made of titanium, nickel, chromium or tungsten.
Furthermore, the inner diameter and the outer diameter of the split dielectric nanoring and the split metal nanoring are kept consistent, the inner diameter is 1-300 nanometers, and the outer diameter is 300-800 nanometers.
Further, the period of the array is greater than or equal to the outer diameter of the split dielectric nanorings such that no overlap remains between split nanorings.
The preparation method of the refractory-based broadband electromagnetic wave absorber comprises the following steps of:
(1) providing a flat substrate;
(2) depositing a metal film layer with a specific thickness on a substrate;
(3) depositing a dielectric film layer with a specific thickness on the metal film layer obtained in the step (2);
(4) depositing a metal film layer with a specific thickness on the dielectric film layer obtained in the step (3);
(5) etching by using a maskless electron beam etching technology and a focused ion beam etching technology to obtain an array structure of split metal nano rings and an array structure of split dielectric nano rings;
(6) and cleaning with absolute ethyl alcohol and acetone to obtain the refractory-based broadband electromagnetic wave absorber.
Further, the substrate is quartz, glass, a silicon wafer, or an organic film.
Furthermore, the deposition method comprises one or a mixture of several methods of a magnetron sputtering method, a vacuum coating method, a metal thermal evaporation coating method, a laser pulse deposition method, a chemical plating method, an atomic layer deposition method and an electrochemical method.
The invention has the beneficial effects that:
1. the materials used by the whole electromagnetic wave absorber have the effect of high temperature resistance, and the melting points of silicon dioxide, aluminum oxide, magnesium fluoride, titanium, nickel, chromium and tungsten are 1650 ℃, 2054 ℃, 1248 ℃, 1668 ℃, 1445 ℃, 1907 ℃ and 3422 ℃ respectively, so that the electromagnetic wave absorber has the thermal stability of high temperature resistance, and can effectively avoid the problems of internal metal ohmic loss, thermal effect, thermal instability and the like which cannot be overcome by the conventional perfect light absorber consisting of systems such as a precious metal particle array or a multi-element metal resonance array composite structure and the like;
2. the perfect absorption from near infrared to intermediate infrared bands is realized by using the strong electromagnetic resonance mode and the broadband resonance absorption characteristic of the refractory metal material;
3. based on the characteristic of periodic arrangement of split metal/dielectric nano rings, plasmon resonance modes in multiple frequency ranges can be generated, and further the perfect absorption characteristic of broadband electromagnetic waves is obtained;
4. the adopted metal material is a refractory material rich in earth, has low cost and has wide application prospect in the fields of solar cells, heat radiation, stealth, infrared imaging and the like;
5. more efficient solar energy wave absorption response is realized, and the average wave absorption efficiency of more than 96.2 percent can be achieved for the solar wave band of 1234-3660 nanometers under the irradiation of incident light, namely sunlight, so that the efficient absorption of the sunlight is realized;
6. the absorber is simple in structure, easy to prepare, simple in experimental preparation process, labor-saving, material-saving, easy to practically popularize and produce and high in practical value.
Drawings
The present invention will be described in further detail below with reference to the accompanying drawings.
Fig. 1 is a schematic structural view of a refractory-based broadband electromagnetic wave absorber according to the present invention.
FIG. 2 is an absorption spectrum of a broadband electromagnetic wave absorber based on a refractory material in example 1 of the present invention.
Fig. 3 is an absorption spectrum diagram of a refractory-based broadband electromagnetic wave absorber in examples 2-4 of the present invention, in which the top layer is a split chromium nanoring and the thickness (h) is 45 nm, 65 nm, and 85 nm.
Fig. 4 is an absorption spectrum diagram corresponding to the thickness (t) of 190, 210 and 230 nm of the split silica nanorings in the middle layer of the broadband electromagnetic wave absorber based on refractory material according to examples 5 to 7 of the present invention.
FIG. 5 is an absorption spectrum of split nanoring inner diameters (r) of 115, 135 and 155 nm of refractory-based broadband electromagnetic wave absorbers in examples 8 to 10 of the present invention.
FIG. 6 is a graph showing absorption spectra corresponding to nanoring gaps (d) of 25, 45 and 65 nm at the time of cleavage in a broadband electromagnetic wave absorber based on a refractory in examples 11 to 13 of the present invention.
Fig. 7 is a schematic structural view of a refractory-based broadband electromagnetic wave absorber according to example 14 of the present invention.
FIG. 8 is an absorption spectrum of a refractory-based broadband electromagnetic wave absorber in example 15 of the present invention.
Detailed Description
As shown in fig. 1, the broadband optical electromagnetic wave absorber based on refractory material of the present invention is formed by connecting a flat metal film 1, a split dielectric nanoring 2 and a split metal nanoring 3 in sequence from bottom to top. Wherein the split dielectric nanorings and the split metallic nanorings are arranged in a periodic array. Each split dielectric nanoring comprises four uniformly distributed gaps and each split metal nanoring comprises four uniformly distributed gaps.
The refractory-based broadband electromagnetic wave absorber can be prepared by the following steps:
(1) cleaning a flat substrate by prepared cleaning solution, then washing the substrate by deionized water, drying the substrate by nitrogen and fixing the substrate in a deposition chamber;
(2) depositing a metal film layer with a specific thickness on a substrate;
(3) depositing a dielectric film layer with a specific thickness on the metal film layer obtained in the step (2);
(4) depositing a metal film layer with a specific thickness on the dielectric film layer obtained in the step (3);
(5) etching by using a maskless electron beam etching technology and a focused ion beam etching technology to obtain an array structure of split metal nano rings and an array structure of split dielectric nano rings;
(6) and cleaning with absolute ethyl alcohol and acetone to obtain the refractory-based broadband electromagnetic wave absorber.
Specifically, the substrate may be quartz, glass, a silicon wafer, or an organic film. The deposition method comprises one or more of magnetron sputtering method, vacuum coating method, metal thermal evaporation coating method, laser pulse deposition method, chemical plating method, atomic layer deposition method and electrochemical method.
Example 1:
the preparation method of the refractory-based broadband optical electromagnetic wave absorber of the embodiment comprises the following steps: firstly, depositing a chromium film with the thickness of 150 nanometers, a silicon dioxide film with the thickness of 210 nanometers and a chromium film with the thickness of 65 nanometers on a substrate silicon dioxide glass sheet in sequence by adopting a physical vacuum coating method; secondly, preparing split chromium/silicon dioxide nanorings on the top chromium film and the middle silicon dioxide film by adopting an electron beam etching technology to form a periodic array, wherein the array period (P) is 400 nanometers; the inner radius (R) of the split nanorings is 135 nanometers, and the outer radius (R) is 200 nanometers; the thickness of the flat metal film (a) is 150 nanometers, the thickness of the split silicon dioxide nanoring (t) is 210 nanometers, and the thickness of the split chromium nanoring (h) is 65 nanometers; the gaps (d) of the split nanorings were all 45 nm.
The test of the refractory-based broadband optical electromagnetic wave absorber of the present embodiment can obtain an absorption spectrum as shown in fig. 2. As can be seen in fig. 2, the absorber achieves a strong absorption response absorption bandwidth of 2426 nm with an absorbance greater than 90% over the near to mid infrared range of wavelengths from 1234 nm to 3660 nm, with an average absorbance up to 96.2%.
Example 2:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the thickness of the top split chromium nanoring is 45 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 3 can be obtained.
Example 3:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the thickness of the split chromium nanoring at the top layer is 65 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 3 can be obtained. When the thickness of the chromium nanoring is 65 nanometers, the absorption rate of the absorber is more than 90 percent of the broadband of the spectrum and reaches 2426 nanometers, and the corresponding absorption spectrum ranges from 1234 nanometers to 3660 nanometers.
Example 4:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the thickness of the top split chromium nanoring is 85 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 3 can be obtained.
Example 5:
in the refractory-based broadband optical electromagnetic wave absorber in this embodiment, the thickness of the silica nanoring split in the intermediate layer is 190 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 4 can be obtained.
Example 6:
in the refractory-based broadband optical electromagnetic wave absorber in this embodiment, the thickness of the silica nanoring split in the intermediate layer is 210 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 4 can be obtained. The best absorber effect is achieved with a split silica nanoring thickness of 210 nm.
Example 7:
in the broadband optical electromagnetic wave absorber based on the refractory material in the embodiment, the thickness of the silica nanoring split in the middle layer is 230 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 4 can be obtained.
Example 8:
in the refractory-based broadband optical electromagnetic wave absorber in this embodiment, the inner radius of the silica nanoring split in the intermediate layer is 115 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 5 can be obtained.
Example 9:
in the refractory-based broadband optical electromagnetic wave absorber in this embodiment, the inner radius of the silica nanoring split in the intermediate layer is 135 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 5 can be obtained. The absorption of the absorber at an inner radius of 135 nm is wider than the absorption bandwidth of 90%.
Example 10:
in the refractory-based broadband optical electromagnetic wave absorber of the present embodiment, the inner radius of the silica nanoring split in the intermediate layer is 155 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 5 can be obtained.
Example 11:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the gaps of the split nanorings are all 25 nm, and other parameters are the same as those in embodiment 1. The corresponding absorption spectrum as shown in fig. 6 can be obtained.
Example 12:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the gaps of the split nanorings are all 45 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 6 can be obtained. The absorption response of the absorber is best when the gap is 45 nm.
Example 13:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, the gaps of the split nanorings are all 65 nm, and other parameters are the same as those in embodiment 1. A corresponding absorption spectrum as shown in fig. 6 can be obtained.
Example 14:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, an anti-reflection silica layer (with a thickness of 50 nm to 300 nm) is added on top of the absorber in embodiment 1, so as to obtain a broadband optical electromagnetic wave absorber based on refractory material with a four-layer structure as shown in fig. 7.
Example 15:
in the broadband optical electromagnetic wave absorber based on refractory material in this embodiment, an anti-reflection silica layer with a thickness of 130 nm is added on top of the absorber in embodiment 1. The silica anti-reflection layer on the top layer of the absorption spectrum shown in fig. 8 has a thickness of 130 nm, and the absorption effect is the best. The absorber achieves a broad band absorption of greater than 90% at 3386 nm, from 685 nm to 4071 nm. The average absorbance is as high as 94.35% in the spectral range from 600 nm to 4200 nm.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the present invention pertains, numerous and varied simplifications or substitutions can be made without departing from the spirit of the invention, which should be construed as falling within the scope of the invention.
Claims (4)
1. A refractory-based broadband electromagnetic wave absorber, comprising:
a flat metal film;
an array of split dielectric nanorings on the metal film, the split dielectric nanorings meaning that there are gaps on the dielectric nanorings;
a split metal nanoring disposed on the split dielectric nanoring, the split metal nanoring meaning that there are gaps on the metal nanoring;
wherein the split dielectric nanorings comprise four uniformly distributed gaps, the split metal nanorings comprise four uniformly distributed gaps, the thickness of the flat metal film exceeds 150 nm, the flat metal film is made of titanium, nickel, chromium or tungsten, the thickness of the split dielectric nanorings is 1-300 nm, the split dielectric nanorings are made of silicon dioxide, aluminum oxide or magnesium fluoride, the thickness of the split metal nanorings is 1-300 nm, the split metal nanorings are made of titanium, nickel, chromium or tungsten, the inner diameters and the outer diameters of the split dielectric nanorings and the split metal nanorings are kept consistent, the inner diameter is 1-300 nm, the outer diameter is 300-800 nm, the period of the array is greater than or equal to the outer diameter of the split dielectric nanorings, the split dielectric nanorings correspond one-to-one with the gaps of the split metal nanorings.
2. The method for manufacturing a refractory-based broadband electromagnetic wave absorber according to claim 1, comprising the steps of:
(1) providing a flat substrate;
(2) depositing a metal film layer with a specific thickness on a substrate;
(3) depositing a dielectric film layer with a specific thickness on the metal film layer obtained in the step (2);
(4) depositing a metal film layer with a specific thickness on the dielectric film layer obtained in the step (3);
(5) etching by using a mask-free electron beam etching and focused ion beam etching technology to obtain an array structure of split metal nanorings and an array structure of split dielectric nanorings;
(6) and cleaning with absolute ethyl alcohol and acetone to obtain the refractory-based broadband electromagnetic wave absorber.
3. The method of claim 2, wherein: the substrate is quartz, glass, a silicon wafer or an organic film.
4. The method of claim 2, wherein: the deposition comprises one or a mixture of a plurality of methods of a magnetron sputtering method, a vacuum coating method, a metal thermal evaporation coating method, a laser pulse deposition method, a chemical plating method, an atomic layer deposition method and an electrochemical method.
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