CN105161141A - Visible-nearinfrared band UWB absorber and making method thereof - Google Patents
Visible-nearinfrared band UWB absorber and making method thereof Download PDFInfo
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Abstract
The invention discloses a visible-near infrared band UWB absorber and a making method thereof. The absorber is composed of a substrate, a bottom metal absorbing layer, alternating germanium layers and metal absorbing layers, a top germanium layer and a three-layer broadband anti-reflection layer with decreased refractive indexes on the top germanium layer. According to the invention, based on the combination of the incidence blocking effect of the metal absorbing layer and the broadband anti-reflection layer on the germanium layer, the broadband non-transmission anti-reflection structure is established and visible-near infrared band UWB absorption of high efficiency and low sensitivity to angles is realized and the absorber provided by the invention transcends a traditional absorber completely in the aspect of performance. The absorber provided by the invention has a compact multi-layer thin film structure. Compared with the traditional broadband absorber and an artificial electromagnetic absorber disclosed in recent years, the structure becomes simple, complex nano processing techniques are avoided, production cost is reduced substantially, production period is shortened distinctively and large-scale and mass production is facilitated.
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-infraredbroadbandabsorberwithfilm-coupledmultilayer nanorods of near infrared 900nm-1600nm wave band, OpticsLett.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 (ExperimentandTheoryoftheBroadbandAbsorptionbyaTaperedHyp erbolicMetamaterialArray, ACSPhotonics1,618-624 (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 Plasmonicbroadbandabsorberbystackingmultiplemetallicnano particlelayers 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 bottom metal absorption layer, germanium layer/metal absorption layer alternate membrane i.e. (germanium/metal absorption layer)
s, top 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 the germanium layer of top, 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 bottom metal absorption layer can select chromium.The thickness of described bottom metal absorption layer should be greater than 100nm; More preferably 100-500nm; Further be preferably 150-300nm.
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 bottom germanium layer, thickness is 10nm-40nm, and preferred thickness is 15nm-40nm further, is further preferably 30nm-40nm; 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, is further preferably 50nm-60nm; 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, is further preferably 100nm-120nm.The present invention's three layers of broadband anti-reflection rete are preferably silicon, titania, magnesium fluoride from the bottom to top.
As preferably, the thickness of described top germanium layer is 10nm-40nm; More preferably 20nm-40nm.
As preferably, described germanium layer/metal absorption layer alternate membrane is made up of one or more germanium layer/Metal absorption layer unit, and wherein germanium layer is arranged near bottom metal absorption layer, can be expressed as (germanium/metal absorption layer)
s, wherein S be more than or equal to 1 positive integer.As preferably, in described germanium layer/metal absorption layer alternate membrane, the thickness of each layer is 10nm-80nm; As preferred further, in described germanium layer/metal absorption layer alternate membrane, the thickness of germanium layer is 33nm-80nm.In described germanium layer/metal absorption layer alternate membrane, the material of metal absorption layer is selected from the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material; As preferred further, in described germanium layer/metal absorption layer alternate membrane, metal absorption layer can select chromium, titanium; In described germanium layer/metal absorption layer alternate membrane, the thickness of metal absorption layer is 10nm-40nm; More preferably 15nm-30nm.As preferably, S is 1,2 or 3.Multiple germanium layer/Metal absorption layer unit, the thickness of germanium layer can be identical, also can be different; The thickness of metal absorption layer can be identical, also can be different, can adjust according to actual needs.
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 S=1 prepared by embodiment 1,7 layers of Cr/Ge/Cr/Ge/Si/TiO
2/ MgF
2the abosrption spectrogram of membrane structure;
Fig. 5 is S=2 prepared by embodiment 2,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO
2/ MgF
2the abosrption spectrogram of membrane structure;
Fig. 6 is S=1 prepared by embodiment 3,7 layers of Ti/Ge/Ti/Ge/Si/TiO
2/ MgF
2the abosrption spectrogram of membrane structure;
Fig. 7 is S=2 prepared by embodiment 4,9 layers of Ti/Ge/Ti/Ge/Ti/Ge/Si/TiO
2/ MgF
2the abosrption spectrogram of membrane structure;
Fig. 8 is S=1 prepared by embodiment 5,7 layers of Cr/Ge/Cr/Ge/Si/Ta
2o
5/ MgF
2the abosrption spectrogram of membrane structure;
Fig. 9 is S=2 prepared by embodiment 6,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO
2/ SiO
2the abosrption spectrogram of membrane structure.
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 bottom metal absorption layer 2, and this layer thickness should be greater than 100nm to stop that incident light transmission enters substrate; It is germanium layer/metal absorption layer alternate membrane 7 on bottom metal absorption layer, each layer thickness is 10nm-70nm, be top germanium layer 3 on germanium layer/metal absorption layer alternate membrane, this layer thickness is 10nm-40nm, it is three-layer thin-film (in Fig. 1, label is 4-6) on the germanium layer of top, Refractive Index of Material reduces gradually from the bottom to top, these the three layers broadband anti-reflection rete can regarding germanium as.Bottom metal absorption layer 2 can select the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material, and bottom metal absorption layer 2 of the present invention is preferably chromium.In germanium layer/metal absorption layer alternate membrane 7, germanium layer is identical with top germanium layer material, and metal absorption layer is identical with bottom metal absorption layer 2 material.Three layers of broadband anti-reflection rete (4-6) from the bottom to top Refractive Index of Material reduces gradually, silicon selected by bottom 4 membraneous material near top 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, monox, 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-2500nm, each wavelength absorption rate is more than 90%, the present invention designs the absorption spectrum of the absorber sample of preparation as shown in Figure 4, average absorption rate more than 96.82%, corresponding structure is S=1,7 layers of Cr/Ge/Cr/Ge/Si/TiO
2/ MgF
2membrane structure, corresponding base material is silicon chip, and the thicknesses of layers corresponding to each rete is respectively 200nm (chromium), 52nm (germanium), 21nm (chromium), 33nm (germanium), 34nm (silicon), 57nm (titania), 111nm (magnesium fluoride) from the bottom to top.
Embodiment 2: visible-near-infrared band ultra broadband absorber, expection Absorber Bandwidth is 400nm-3000nm, each wavelength absorption rate is more than 90%, the absorption spectrum of the film system of the present invention's design as shown in Figure 5, average absorption rate more than 94.9%, corresponding structure is S=2,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO
2/ MgF
2membrane structure, corresponding base material is silicon chip, and the thicknesses of layers corresponding to each rete is respectively 200nm (chromium), 72nm (germanium), 22nm (chromium), 55nm (germanium), 15nm (chromium), 36nm (germanium), 37nm (silicon), 57nm (titania), 110nm (magnesium fluoride) from the bottom to top.
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 absorber sample of the present invention's design as shown in Figure 6, average absorption rate more than 96.36%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 33nm (germanium), 25nm (titanium), 23nm (germanium), 34nm (silicon), 56nm (titania), 111nm (magnesium fluoride) from the bottom to top.
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 absorber sample of the present invention's design as shown in Figure 7, average absorption rate more than 96.36%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 36nm (germanium), 29nm (titanium), 34nm (germanium), 18nm (titanium), 27nm (germanium), 38nm (silicon), 57nm (titania), 110nm (magnesium fluoride) from the bottom to top.
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 absorber sample of the present invention's design as shown in Figure 8, average absorption rate more than 96.91%, the thicknesses of layers corresponding to each rete is respectively 200nm (titanium), 53nm (germanium), 20nm (titanium), 33nm (germanium), 35nm (silicon), 60nm (tantalum oxide), 114nm (magnesium fluoride) from the bottom to top.
Embodiment 6: substantially the same manner as Example 2, difference is magnesium fluoride to replace with yttrium fluoride tungsten, all the other conditions are identical with embodiment 2, the absorption spectrum of the absorber sample of the present invention's design as shown in Figure 9, average absorption rate more than 95.28%, the thicknesses of layers corresponding to each rete is respectively 200nm (chromium), 74nm (germanium), 22nm (chromium), 51nm (germanium), 14nm (chromium), 34nm (germanium), 36nm (silicon), 58nm (titania), 105nm (silicon dioxide) from the bottom to top.
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 bottom metal absorption layer, germanium layer/metal absorption layer alternate membrane, top 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 the germanium layer of top, middle layer and outermost layer respectively, and bottom, middle layer and outermost refractive index reduce gradually; Described germanium layer/metal absorption layer alternate membrane is made up of one or more germanium layer/Metal absorption layer unit, and wherein germanium layer is arranged near bottom metal absorption layer.
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 bottom 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 bottom metal absorption layer is greater than 100nm.
5. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 1, is characterized in that, in described germanium layer/metal absorption layer alternate membrane, each layer thickness is 10nm-80nm.
6. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 1, is characterized in that, described top germanium layer thickness is 10nm-40nm.
7. 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.
8. the ultra broadband absorber of Visible-to-Near InfaRed wave band according to claim 6, is characterized in that, the thickness of described bottom is 10nm-40nm; The thickness in described middle layer is 30nm-80nm; Described outermost thickness is 70nm-130nm.
9. 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.
10. a preparation method for the ultra broadband absorber of the Visible-to-Near InfaRed wave band described in the arbitrary claim of claim 1-9, 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.
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| CN201510469463.7A CN105161141B (en) | 2015-08-04 | 2015-08-04 | The ultra wide band absorber and preparation method 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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| CN109491002A (en) * | 2018-12-26 | 2019-03-19 | 浙江大学 | A kind of colored filter and preparation method thereof that the incident angle based on porous aluminas is insensitive |
| CN110093583A (en) * | 2018-01-29 | 2019-08-06 | 蓝思科技（长沙）有限公司 | A kind of photochromic decorating film and preparation method thereof |
| CN113314849A (en) * | 2021-04-20 | 2021-08-27 | 上海海事大学 | Periodic unit of metamaterial broadband wave absorber and metamaterial broadband wave absorber |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110093583A (en) * | 2018-01-29 | 2019-08-06 | 蓝思科技（长沙）有限公司 | A kind of photochromic decorating film and preparation method thereof |
| CN110093583B (en) * | 2018-01-29 | 2024-01-30 | 蓝思科技（长沙）有限公司 | Photochromic decorative film and manufacturing method thereof |
| CN109491002A (en) * | 2018-12-26 | 2019-03-19 | 浙江大学 | A kind of colored filter and preparation method thereof that the incident angle based on porous aluminas is insensitive |
| CN109491002B (en) * | 2018-12-26 | 2020-01-31 | 浙江大学 | porous alumina-based color filter insensitive to incident angle and preparation method thereof |
| CN113314849A (en) * | 2021-04-20 | 2021-08-27 | 上海海事大学 | Periodic unit of metamaterial broadband wave absorber and metamaterial broadband wave absorber |
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Effective date of registration: 20220825 Address after: 201806 zone B, 1st floor, building 2, No. 4500 Baoqian highway, Jiading District, Shanghai Patentee after: Shanghai high energy Yu Plating Technology Co.,Ltd. Address before: 310027 No. 38, Zhejiang Road, Hangzhou, Zhejiang, Xihu District Patentee before: ZHEJIANG University |