CN105022106A - Absorber of ultra wide band of visible and near-infrared band and preparation method thereof - Google Patents
Absorber of ultra wide band of visible and near-infrared band and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses an absorber of an ultra wide band of a visible and near-infrared band and a preparation method thereof. The absorber consists of a substrate and five layers of optical thin films, the thin film at the lowest layer being a metal absorption layer, a layer of germanium being above the metal absorption layer, other three layers, which have gradually decreased refractive indexes of materials from bottom up, being above the layer of germanium. The absorber, based on the combination of the incidence resistance effect of the metal absorption layer and a wide band anti-reflection film layer of the layer of germanium, establishes an anti-reflection structure of wide band without transmission, is capable of absorbing ultra wide band of visible and near-infrared band, with high efficiency and insensitive incident angles, and is completely beyond a traditional absorber in performance. Compared with traditional absorbers and artificial electromagnetic absorbers provided in recent years, the absorber provided by the invention employs a compact multi-layer thin film structure which is more simple so as to prevent complicated nanofabrication technology, thereby the absorber provided by the invention is reduced in cost of production, is greatly shorten in the production cycle, and is convenient for large-scale manufacture in batches.
Description
Technical field
The invention belongs to the fields such as parasitic light elimination, space exploration, imaging, photothermal deformation and electromagnetic absorption, be specifically related to as seen a kind of ultra broadband absorber of-near-infrared band.
Background technology
Because visible-infrared broadband absorption device can play significant role in many different frontiers, thus visible-infrared broadband absorption device obtains extensive research, thus more and more broadband absorber is produced out in recent years.In recent years, researchist proposes the near infrared absorption device of various electromagnetic wave manual electromagnetic structure.Wherein, the method that Chen etc. utilize drop to evaporate forms the gold nanorods of random alignment in the metallic substrates being coated with dielectric layer, realize high-selenium corn (the Near-infrared broadband absorber with film-coupled multilayernanorods of near infrared 900nm-1600nm wave band, Optics Lett.38,2247-2249 (2013)); Zhou etc. utilize the feature of Lateral Deposition to prepare the pyramidal structure of the alternating dielectric/metal of multilayer, realize the broadband higher absorption of near infrared (Experiment and Theory of the Broadband Absorption by a TaperedHyperbolic Metamaterial Array, ACS Photonics 1,618-624 (2014)); Ji etc. propose a kind of structure replacing deposit particle and silicon oxide film in silver-colored mirror surface, thus realize high-selenium corn (the Plasmonic broadband absorberby stacking multiple metallic nanoparticle layers of 300nm-1100nm wave band average more than 96%, Appl.Phys.Lett.106,161107 (2015)).
But said method preparation process is comparatively complicated, consuming time longer, preparation cost is high, is unfavorable for that large area quantizes to produce.
Bibliographical information relevant at present mainly contains:
Application number be 201510163240.8 Chinese patent literature disclose a kind of ultra broadband absorber based on cascade structure Meta Materials, this absorber is by 9 dielectric layers, 9 metal level compositions, 1st ~ 3 dielectric layers and metal level are the cylinder that diameter is identical, 4th ~ 6 dielectric layers and metal level are the cylinder that diameter is identical, 7th ~ 9 dielectric layers and metal level are the cylinder that diameter is identical, and this absorber one-piece construction is comparatively complicated, and require higher to incident angle.
Application number be 201410020841.9 Chinese patent literature disclose a kind of based on seeing near-infrared band absorbing coatings structure, it adopts vapour deposition, liquid deposition growing metal thin layer, dielectric thin film layer successively on any substrate, wherein metallic film layer thickness is 80nm-1 μm, dielectric film layer thickness is 1nm-200nm, in metallic particles disorder distribution layer, equivalent thin layer average height is 5nm-100nm, particle mean size is 10nm-200nm, and surface of metal particles coverage rate is 3%-90%.Structure is relatively simple, but its absorptivity is bad.
Application number be 201110410712.7 Chinese patent literature disclose a kind of solar selectively absorbing coating, this coating is made up of double-deck or three-decker: ground floor is the stainless steel-based end after polishing, the second layer is Cu1.5Mn1.5O4 composite oxides absorption layers, third layer forms anti-reflection layer by TiO2 film, arranges from bottom to top.The absorptivity of this coating is all lower than 0.9, and complicated process of preparation.
Summary of the invention
The invention provides a kind of ultra broadband absorber of Visible-to-Near InfaRed wave band, the absorption bands that this absorber can cover is wider, and absorptive character are better, also have good incident angle insensitivity.
Invention also provides a kind of preparation method of ultra broadband absorber of Visible-to-Near InfaRed wave band, the party's method is easy to prepare, and cost is low, is convenient to extensive, mass production.
A ultra broadband absorber for Visible-to-Near InfaRed wave band, comprises substrate, described substrate is provided with successively metal absorption layer, germanium layer and three layers of broadband anti-reflection rete; Described three layers of broadband anti-reflection rete comprise the bottom be successively set on germanium layer, middle layer and outermost layer respectively, and bottom, middle layer and outermost refractive index reduce gradually.
Be the preferred scheme based on such scheme below:
Base material does not limit, and as preferably, described substrate can select K9, fused quartz, the glass materials such as float glass, also can select silicon, the semiconductor materials such as gallium arsenide.More preferably silicon chip.
As preferably, described metal absorption layer can select the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material; As preferred further, described metal absorption layer can select chromium.The thickness of described metal absorption layer should be greater than 100nm; More preferably 100-500nm; Follow more preferably 150-300nm.
As preferably, described germanium layer is 10nm-40nm;
As preferably, three layers of broadband anti-reflection rete from the bottom to top Refractive Index of Material reduces gradually, and near the bottom film Material selec-tion silicon of germanium layer, thickness is 10nm-40nm, and preferred thickness is 15nm-35nm further; Described intermediate layer film material can select the contour index dielectric material of titania, hafnia, tantalum oxide, silicon nitride, and thickness is 30nm-80nm, and preferred thickness is 35nm-60nm further; Described outermost layer membraneous material can select the low refractive index dielectric materials such as magnesium fluoride, silicon dioxide, yttrium fluoride, and thickness is 70nm-130nm, and preferred thickness is 80nm-120m further.The present invention's three layers of broadband anti-reflection rete are preferably silicon, titania, magnesium fluoride from the bottom to top.
The present invention additionally provides a kind of preparation method of ultra broadband absorber of Visible-to-Near InfaRed wave band simultaneously, comprises the steps:
(1) according to required absorber bandwidth requirement and absorptivity requirement, by optimizing the thickness of each layer film, satisfactory film system is designed; This step can adopt existing software simulating Optimum Operation;
(2) acetone soln is put in substrate ultrasonic, then use ethanol purge substrate; Then ethanolic solution is put in substrate ultrasonic, then use washed with de-ionized water substrate; Finally deionized water for ultrasonic is put in substrate, then again clean substrate with deionized water;
(3) adopt vacuum coating to deposit each rete successively, obtain the ultra broadband absorber of visible-near-infrared band.
As preferably, in step (2), the at every turn ultrasonic time is generally 5-30min; More preferably 5-10min.
The ultra broadband absorber of as seen of the present invention-near-infrared band, compared to traditional absorber, the absorption bands that it can cover is wider, and absorptive character are better, also have good incident angle insensitivity.The ultra wide wave band absorptive character of therefore as seen of the present invention-near-infrared band have surmounted traditional absorber completely.Ultra broadband absorber structure due to as seen of the present invention-near-infrared band is compact multi-layer film structure, and compared to traditional broad band absorber and the artificial electromagnetic absorber that proposed in recent years, structure is simpler.Just due to its compact multi-layer film structure, the ultra broadband absorber of as seen of the present invention-near-infrared band avoids complicated nanofabrication technique, such as electron Beam Machining, focused-ion-beam lithography technology, reactive ion etching technology, photoetching technique etc., thus production cost is significantly declined, production cycle significantly shortens, thus is convenient to extensive, mass production.
The present invention is based on the stop incidence effect of metal absorption layer in conjunction with the broadband anti-reflection rete of germanium layer, thus construct the broadband antireflection structure without transmission, thus achieve high-level efficiency, angle as seen insensitive-absorption of near-infrared band ultra broadband.The ultra broadband absorber structure of as seen of the present invention-near-infrared band is simple, and easy to prepare, cost is low, produces with being suitable for large area mass, thus the preparation cost of the ultra broadband absorber of visible-near-infrared band is reduced greatly.Therefore this invention is expected to widespread use in photothermal deformation, electromagnetic absorption, detection and imaging etc., for making contributions in the fields such as Chinese national economy, social development, science and technology and national defense construction.
Accompanying drawing explanation
Fig. 1 be the present invention visible-structural representation of the ultra broadband absorber of near-infrared band;
Fig. 2 be the present invention visible-the preparation flow figure of the ultra broadband absorber of near-infrared band;
Fig. 3 be the present invention visible-the ultra broadband absorption mechanism analysis chart of the ultra broadband absorber of near-infrared band;
Fig. 4 is the abosrption spectrogram of the sample that different Absorber Bandwidth requirement and absorptivity require:
The absorption spectrum of the absorber sample that Fig. 4 (a) is prepared for embodiment 1,400nm-1200nm wave band, average absorption rate more than 98.75%;
The absorption spectrum of the absorber sample that Fig. 4 (b) is prepared for embodiment 2,400nm-2000nm wave band, average absorption rate more than 97.75%;
The absorption spectrum of the absorber sample that Fig. 4 (c) is prepared for embodiment 3,400nm-1200nm wave band, average absorption rate more than 99%;
The absorption spectrum of the absorber sample that Fig. 4 (d) is prepared for embodiment 4,400nm-2000nm wave band, average absorption rate more than 96.2%;
The absorption spectrum of the absorber sample that Fig. 4 (e) is prepared for embodiment 5,400nm-1200nm wave band, average absorption rate more than 98.8%;
The absorption spectrum of the absorber sample that Fig. 4 (f) is prepared for embodiment 6,400nm-2000nm, average absorption rate more than 95.2%.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
As shown in Figure 1, as seen a kind of ultra broadband absorber of-near-infrared band is made up of substrate 1 and five layer films.Substrate 1 material does not limit, and can select K9, fused quartz, the glass materials such as float glass, also can select silicon, the semiconductor materials such as gallium arsenide.Bottom film is metal absorption layer 2, and this layer thickness should be greater than 100nm to stop that incident light transmission enters substrate; Be germanium layer 3 on metal absorption layer, thickness is 10nm-40nm, and be three-layer thin-film (4-6) on germanium layer, Refractive Index of Material reduces gradually from the bottom to top, these the three layers broadband anti-reflection rete can regarding germanium as.Metal absorption layer 2 can select the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material, and metal absorption layer 2 of the present invention is preferably chromium.Three layers of broadband anti-reflection rete (4-6) from the bottom to top Refractive Index of Material reduces gradually, silicon selected by rete 4 membraneous material near germanium layer 3, thickness is 10nm-40nm, middle layer 5 membraneous material can select the contour index dielectric material of titania, hafnia, tantalum oxide, silicon nitride, thickness is 30nm-80nm, outermost layer 6 membraneous material can select the low refractive index dielectric materials such as magnesium fluoride, silicon dioxide, yttrium fluoride, and thickness is 70nm-130nm.The present invention's three layers of broadband anti-reflection rete are preferably silicon, titania, magnesium fluoride from the bottom to top.
As seen a kind of preparation method of ultra broadband absorber of-near-infrared band, comprises the following steps, as shown in Figure 2:
1) according to required absorber bandwidth requirement and absorptivity requirement, by optimizing the thickness of each layer film, satisfactory film system is designed;
2) substrate is put into acetone soln ultrasonic 8 minutes, then use ethanol purge substrate; Then substrate (substrate) is put into ethanolic solution ultrasonic 8 minutes, then use washed with de-ionized water substrate; Finally substrate is put into deionized water for ultrasonic 8 minutes, then again clean substrate with deionized water;
3) adopt vacuum coating technology to deposit each rete successively, obtain the ultra broadband absorber of visible-near-infrared band;
The present invention is a kind of visible-and it is pile up based on make use of graded index materials the mechanism simultaneously defining multiple resonance that the ultra broadband of the ultra broadband absorber of near-infrared band absorbs.As Fig. 3, along with the accumulation of rete, all to the translation of long wave direction, meanwhile, there is the tuned reflection paddy corresponding with this rete in shortwave direction in original each tuned reflection paddy occurred.In addition, along with the accumulation of rete, outermost layer refractive index reduces gradually, forms the graded index film system with anti-reflection characteristic, overall reflectivity is constantly reduced, thus makes to absorb continuous increase.Therefore, the present invention a kind of visible-structure of the ultra broadband absorber of near-infrared band forms the main reason that ultra broadband absorbs.
Specific embodiment mode:
Embodiment 1: visible-near-infrared band ultra broadband absorber, expection Absorber Bandwidth is 400nm-1200nm, average absorption rate is more than 98%, the present invention designs the absorption spectrum of the absorber sample of preparation as shown in Fig. 4 (a), average absorption rate more than 98.75%, corresponding base material is silicon chip, corresponding film material is followed successively by chromium, germanium, silicon, titania, magnesium fluoride, thicknesses of layers corresponding to each rete is respectively 200nm (chromium), 18nm (germanium), 19nm (silicon), 35nm (titania), 80nm (magnesium fluoride).
Embodiment 2: visible-near-infrared band ultra broadband absorber, expection Absorber Bandwidth is 400nm-2000nm, each wavelength absorption rate is more than 90%, the present invention designs the absorption spectrum of the absorber sample of preparation as shown in Fig. 4 (b), average absorption rate more than 97.75%%, corresponding base material is silicon chip, corresponding film material is followed successively by chromium, germanium, silicon, titania, magnesium fluoride, thicknesses of layers corresponding to each rete is respectively 200nm (chromium), 33nm (germanium), 32nm (silicon), 56nm (titania), 118nm (magnesium fluoride).
Embodiment 3: substantially the same manner as Example 1, difference is chromium to replace with titanium, all the other conditions are identical with embodiment 1, the absorption spectrum of the present invention's design is as shown in Fig. 4 (c), average absorption rate more than 99%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 12nm (germanium), 17nm (silicon), 38nm (titania), 89nm (magnesium fluoride).
Embodiment 4: substantially the same manner as Example 2, difference is chromium to replace with titanium, all the other conditions are identical with embodiment 2, the absorption spectrum of the present invention's design is as shown in Fig. 4 (d), average absorption rate more than 96.2%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 23nm (germanium), 31nm (silicon), 55nm (titania), 119nm (magnesium fluoride).
Embodiment 5: substantially the same manner as Example 1, difference is titania to replace with tantalum oxide, all the other conditions are identical with embodiment 1, the absorption spectrum of the present invention's design is as shown in Fig. 4 (e), average absorption rate more than 98.8%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 18nm (germanium), 21nm (silicon), 48nm (tantalum oxide), 101nm (magnesium fluoride).
Embodiment 6: substantially the same manner as Example 2, difference is magnesium fluoride to replace with silicon dioxide, all the other conditions are identical with embodiment 2, the absorption spectrum of the present invention's design is as shown in Fig. 4 (f), average absorption rate more than 95.2%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 32nm (germanium), 33nm (silicon), 56nm (titania), 111nm (magnesium fluoride).
Claims (10)
1. a ultra broadband absorber for Visible-to-Near InfaRed wave band, comprises substrate, it is characterized in that, described substrate is provided with successively metal absorption layer, germanium layer and three layers of broadband anti-reflection rete; Described three layers of broadband anti-reflection rete comprise the bottom be successively set on germanium layer, middle layer and outermost layer respectively, and bottom, middle layer and outermost refractive index reduce gradually.
2. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 1, is characterized in that, described base material is selected from K9, fused quartz, float glass, silicon, gallium arsenide.
3. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 1, is characterized in that, described Metal absorption layer material is selected from the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material.
4. the ultra broadband absorber of the Visible-to-Near InfaRed wave band according to claim 1 or 3, is characterized in that, the thickness of described metal absorption layer is greater than 100nm.
5. the ultra broadband absorber of the Visible-to-Near InfaRed wave band according to claim 1 or 3, is characterized in that, described germanium layer is 10nm-40nm.
6. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 1, is characterized in that, described primer is silicon; Described intermediate layer material is selected from titania, hafnia, tantalum oxide, silicon nitride; Described outermost material is selected from magnesium fluoride, silicon dioxide, yttrium fluoride.
7. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 6, is characterized in that, described underlayer thickness is 10nm-40nm; Described intermediate layer thickness is 30nm-80nm; Described outermost layer thickness is 70nm-130nm.
8. the ultra broadband absorber of the Visible-to-Near InfaRed wave band according to claim 6 or 7, is characterized in that, described primer is silicon, and described intermediate layer material is titania, and described outermost material is magnesium fluoride.
9. a preparation method for the ultra broadband absorber of the Visible-to-Near InfaRed wave band described in the arbitrary claim of claim 1-8, is characterized in that, comprise the steps:
(1) according to required absorber bandwidth requirement and absorptivity requirement, drawn the thickness of each layer film by optimal design, determine satisfactory film system;
(2) acetone is put in substrate ultrasonic, use ethanol purge substrate; Then ethanol is put in substrate ultrasonic, use washed with de-ionized water substrate; Finally deionized water for ultrasonic is put in substrate, then again clean substrate with deionized water;
(3) adopt vacuum coating to deposit each rete successively, obtain the ultra broadband absorber of visible-near-infrared band.
10. the preparation method of the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 9, is characterized in that, in step (2), the at every turn ultrasonic time is 5-30min.
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| CN201510470432.3A CN105022106B (en) | 2015-08-04 | 2015-08-04 | The ultra wide band absorber and preparation method of a kind of visible near-infrared wave band |
| US15/329,569 US10481305B2 (en) | 2015-08-04 | 2015-09-21 | Visible near-infrared ultra-broadband absorber and its preparation method |
| PCT/CN2015/090201 WO2017020407A1 (en) | 2015-08-04 | 2015-09-21 | Visible and near-infrared light ultra-broadband absorber and manufacturing method thereof |
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| CN105652354A (en) * | 2016-01-25 | 2016-06-08 | 中国科学院上海光学精密机械研究所 | Polarization-independent broadband absorber based on conical metal-dielectric multilayer grating structure |
| CN106324740A (en) * | 2016-11-16 | 2017-01-11 | 天津津航技术物理研究所 | Broad band absorbing film preparation method |
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| CN106324740A (en) * | 2016-11-16 | 2017-01-11 | 天津津航技术物理研究所 | Broad band absorbing film preparation method |
| CN108515743A (en) * | 2018-05-09 | 2018-09-11 | 同济大学 | A kind of medium/metal ultra wide band absorbing membrane and preparation method thereof |
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| CN111596388A (en) * | 2020-05-27 | 2020-08-28 | 中国科学院上海硅酸盐研究所 | Near-infrared broadband perfect absorber based on dielectric constant near-zero film and preparation method thereof |
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