CN105022106B - The ultra wide band absorber and preparation method of a kind of visible near-infrared wave band - Google Patents
The ultra wide band absorber and preparation method of a kind of visible near-infrared wave band Download PDFInfo
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Abstract
The invention discloses a kind of ultra wide band absorber of visible-near infrared band and preparation method thereof, including：It can be seen that the ultra wide band absorber of-near infrared band is made up of substrate and five layers of optical thin film, bottom film is metal absorption layer, is germanium layer on metal absorption layer, is remaining three layers above germanium layer, Refractive Index of Material is gradually reduced from the bottom to top.Broadband anti-reflection film layer of the incident effect of stop of the present invention based on metal absorption layer with reference to germanium layer, construct the antireflection structure of broadband no transmission, realize the insensitive visible-near infrared band ultra wide band of high efficiency, angle to absorb, surmount traditional absorber completely in performance.The absorber of the present invention is compact multi-layer film structure, compared to traditional broad band absorber and the artificial electromagnetic absorber proposed in recent years, structure is simpler, avoid the nanofabrication technique of complexity, production cost is remarkably decreased, production cycle significantly shortens, and is easy to extensive, mass production.
Description
Technical field
The invention belongs to the fields such as veiling glare elimination, space exploration, imaging, photothermal deformation and electromagnetic absorption, and in particular to
A kind of ultra wide band absorber of visible-near infrared band.
Background technology
Because visible-infrared broadband absorption device can play significant role in many different frontiers, thus it is near
Year visible-infrared broadband absorption device obtain it is widely studied so that more and more broadband absorber is produced out.
In recent years, researcher proposes the near infrared absorption device of various electromagnetic wave manual electromagnetic structures.Wherein, Chen etc. utilizes drop
The method of evaporation forms the gold nanorods of random alignment in the metallic substrates for be coated with dielectric layer, realize near-infrared 900nm-
High-selenium corn (the Near-infrared broadband absorber with film-coupled of 1600nm wave bands
Multilayer nanorods, Optics Lett.38,2247-2249 (2013))；The characteristics of Zhou etc. is using Lateral Deposition
The pyramidal structure of alternating dielectric/metal of multilayer is prepared, realizes the broadband higher absorption of near-infrared (Experiment and
Theory of the Broadband Absorption by a Tapered Hyperbolic Metamaterial
Array,ACS Photonics 1,618-624(2014))；Ji etc. proposes a kind of in silver-colored mirror surface alternating deposit
The structure of particle and silicon oxide film, so as to realize the high-selenium corn of 300nm -1100nm wave bands average more than 96%
(Plasmonic broadband absorber by stacking multiple metallic nanoparticle
layers,Appl.Phys.Lett.106,161107(2015))。
It is time-consuming longer but above method preparation process is complex, cost height is prepared, is unfavorable for large area and quantifies life
Production.
Presently relevant document report mainly has：
The Chinese patent literature of Application No. 201510163240.8 discloses a kind of super based on cascade structure Meta Materials
Broad band absorber, the absorber is by 9 dielectric layers, and 9 metal level compositions, the 1st~3 dielectric layer and metal level are diameter identical
Cylinder, the 4th~6 dielectric layer and metal level are that diameter identical cylinder, the 7th~9 dielectric layer and metal level are justified for diameter identical
Post, the absorber overall structure is complex, and requires higher to incident angle.
The Chinese patent literature of Application No. 201410020841.9 discloses a kind of based on the suction of visible near infrared band
Winder architecture, it grows metal film layer, dielectric thin film layer successively on any substrate using vapour deposition, liquid deposition,
Wherein metal film layer thickness is 80nm-1 μm, and dielectric thin film layer thickness is 1nm-200nm, and metallic particles disorder distribution layer is medium
It is 5nm-100nm to imitate film layer average height, and particle mean size 10nm-200nm, surface of metal particles coverage rate is 3%-
90%.Structure is relatively simple, but its absorptivity is bad.
The Chinese patent literature of Application No. 201110410712.7 discloses a kind of solar selectively absorbing coating, should
Coating is made up of double-deck or three-decker：First layer is the stainless steel base after polishing, and the second layer is that Cu1.5Mn1.5O4 is compound
Oxide absorbed layer, third layer form anti-reflection layer by TiO2 films, arranged from bottom to top.The absorptivity of the coating is below 0.9,
And preparation technology is complicated.
The content of the invention
The invention provides a kind of ultra wide band absorber of Visible-to-Near InfaRed wave band, the absorption that the absorber can cover
Wave band is wider, and absorbent properties are more preferable, also with preferable incident angle insensitivity.
Invention also provides a kind of preparation method of the ultra wide band absorber of Visible-to-Near InfaRed wave band, party's method
It is convenient to prepare, and cost is low, is easy to extensive, mass production.
A kind of ultra wide band absorber of Visible-to-Near InfaRed wave band, including substrate, Metal absorption is sequentially provided with the substrate
Layer, germanium layer and three slice width wave band anti-reflection film layers；The three slice widths wave band anti-reflection film layer includes being successively set on germanium layer respectively
Bottom, intermediate layer and outermost layer, bottom, intermediate layer and outermost refractive index are gradually reduced.
It is the preferable scheme based on such scheme below：
Base material does not limit, preferably, the substrate can select the glass such as K9, vitreous silica, float glass
Material, the semi-conducting materials such as silicon, GaAs can also be selected.More preferably silicon chip.
Preferably, the metal absorption layer can select the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material；As
Further preferably, the metal absorption layer can select chromium.The thickness of the metal absorption layer should be greater than 100nm；It is further excellent
Elect 100-500nm as；With being more preferably 150-300nm.
Preferably, the germanium layer is 10nm -40nm；
Preferably, Refractive Index of Material is gradually reduced three slice width wave band anti-reflection film layers from the bottom to top, close to the bottom of germanium layer
Thin-film material selects silicon, and thickness is 10nm -40nm, and further preferred thickness is 15nm -35nm；The intermediate layer film material
Material can select the high index dielectric material such as titanium dioxide, hafnium oxide, tantalum oxide, silicon nitride, and thickness is 30nm -80nm, is entered
The preferable thickness of one step is 35nm -60nm；The outermost layer membrane materials can select magnesium fluoride, silica, yttrium fluoride etc.
Low refractive index dielectric material, thickness are 70nm -130nm, and further preferred thickness is 80nm -120m.Three slice widths of the invention
Wave band anti-reflection film layer is preferably silicon, titanium dioxide, magnesium fluoride from the bottom to top.
The present invention additionally provides a kind of preparation method of the ultra wide band absorber of Visible-to-Near InfaRed wave band simultaneously, including such as
Lower step：
(1) according to required absorber bandwidth requirement and absorptivity requirement, by optimizing the thickness of each layer film, design
Go out satisfactory membrane system；The step can use existing software to realize optimization operation；
(2) substrate is put into ultrasound in acetone soln, then cleans substrate with ethanol；Then substrate is put into ethanol solution
Middle ultrasound, then cleans substrate with deionized water；Substrate is finally put into ultrasound in deionized water, then with deionized water again
Clean substrate；
(3) each film layer is sequentially depositing using vacuum coating, obtains the ultra wide band absorber of visible-near infrared band.
Preferably, in step (2), the time of each ultrasound is generally 5-30min；More preferably 5-10min.
The ultra wide band absorber of visible-near infrared band of the present invention, compared to traditional absorber, it can be covered
Absorption bands it is wider, absorbent properties are more preferable, also with preferable incident angle insensitivity.Therefore the present invention's is visible-near
Traditional absorber is surmounted completely in the ultra wide wave band absorbent properties of infrared band.Due to visible-near-infrared ripple of the present invention
The ultra wide band absorber structure of section is compact multi-layer film structure, is proposed compared to traditional broad band absorber and in recent years
Artificial electromagnetic absorber, structure is simpler.Just due to its compact multi-layer film structure, visible-near-infrared of the invention
The ultra wide band absorber of wave band avoids the nanofabrication technique of complexity, such as electron Beam Machining, focused-ion-beam lithography
Technology, reactive ion etching technology, photoetching technique etc., so that production cost is remarkably decreased, the production cycle significantly shortens,
Consequently facilitating extensive, mass production.
The incident effect of stop of the present invention based on metal absorption layer combines the broadband anti-reflection film layer of germanium layer, so as to construct
The antireflection structure of broadband no transmission, it is thus achieved that visible-near infrared band ultra wide band that high efficiency, angle are insensitive
Absorb.The ultra wide band absorber structure of visible-near infrared band of the present invention is simple, and it is convenient to prepare, and cost is low, suitable for big face
Produce, so that the preparation cost of the ultra wide band absorber of visible-near infrared band substantially reduces product mass.Therefore
The invention is expected in photothermal deformation, electromagnetic absorption, detection and imaging etc. extensive use, is Chinese national economy, society
Make contributions in the fields such as development, science and technology and national defense construction.
Brief description of the drawings
Fig. 1 is the structural representation of the ultra wide band absorber of visible-near infrared band of the invention；
Fig. 2 is the preparation flow figure of the ultra wide band absorber of visible-near infrared band of the invention；
Fig. 3 is the ultra wide band absorption mechanism analysis chart of the ultra wide band absorber of visible-near infrared band of the invention；
Fig. 4 is the abosrption spectrogram of the sample of the requirement of different Absorber Bandwidths and absorptivity requirement：
The absorption spectrum for the absorber sample that Fig. 4 (a) is prepared for embodiment 1,400nm -1200nm wave bands, average absorption
Rate more than 98.75%；
The absorption spectrum for the absorber sample that Fig. 4 (b) is prepared for embodiment 2,400nm -2000nm wave bands, average absorption
Rate more than 97.75%；
The absorption spectrum for the absorber sample that Fig. 4 (c) is prepared for embodiment 3,400nm -1200nm wave bands, average absorption
Rate more than 99%；
The absorption spectrum for the absorber sample that Fig. 4 (d) is prepared for embodiment 4,400nm -2000nm wave bands, average absorption
Rate more than 96.2%；
The absorption spectrum for the absorber sample that Fig. 4 (e) is prepared for embodiment 5,400nm -1200nm wave bands, average absorption
Rate more than 98.8%；
The absorption spectrum for the absorber sample that Fig. 4 (f) is prepared for embodiment 6,400nm -2000nm, average absorption ratio
More than 95.2%.
Embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
As shown in figure 1, a kind of ultra wide band absorber of visible-near infrared band is made up of the layer film of substrate 1 and five.Base
The material of bottom 1 does not limit, and can select the glass materials such as K9, vitreous silica, float glass, can also select silicon, GaAs etc.
Semi-conducting material.Bottom film is metal absorption layer 2, and the thickness degree should be greater than 100nm to stop that incident light is transmitted into base
Plate；It is germanium layer 3 on metal absorption layer, thickness is 10nm -40nm, is three-layer thin-film (4-6) above germanium layer, under
Supreme Refractive Index of Material is gradually reduced, this three layers broadband anti-reflection film layer that can regard germanium as.Metal absorption layer 2 can select chromium,
Titanium, iridium, tungsten, the alloy of nickel and above-mentioned material, metal absorption layer 2 of the present invention are preferably chromium.Three slice width wave band anti-reflection film layer (4-
6) Refractive Index of Material is gradually reduced from the bottom to top, and close to the thin-film material of the film layer 4 selection silicon of germanium layer 3, thickness is 10nm -40nm,
The thin-film material of intermediate layer 5 can select the high index dielectric material such as titanium dioxide, hafnium oxide, tantalum oxide, silicon nitride, and thickness is
30nm -80nm, the thin-film material of outermost layer 6 can select the low refractive index dielectric material such as magnesium fluoride, silica, yttrium fluoride, thick
Spend for 70nm -130nm.Three slice width wave band anti-reflection film layers of the invention are preferably silicon, titanium dioxide, magnesium fluoride from the bottom to top.
A kind of preparation method of the ultra wide band absorber of visible-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, design
Go out satisfactory membrane system；
2) substrate is put into ultrasound 8 minutes in acetone soln, then cleans substrate with ethanol；Then substrate (substrate) is put
Enter ultrasound 8 minutes in ethanol solution, then clean substrate with deionized water；Substrate is finally put into 8 points of ultrasound in deionized water
Clock, substrate is then cleaned again with deionized water；
3) each film layer is sequentially depositing using vacuum coating technology, obtains the ultra wide band absorber of visible-near infrared band；
It is to be based on make use of gradual change that the ultra wide band of the ultra wide band absorber of the visible-near infrared band of one kind of the invention, which absorbs,
Refraction materials accumulation forms the mechanism of multiple resonance simultaneously.Such as Fig. 3, with the accumulation of film layer, what is originally occurred is each humorous
The reflection paddy that shakes all translates to long wave direction, meanwhile, occur the tuned reflection paddy corresponding with the film layer in shortwave direction.Except this it
Outside, as the accumulation of film layer, outermost layer refractive index are gradually reduced, the graded index membrane system with anti-reflection characteristic is formed so that
Overall reflectivity constantly reduces, and is continuously increased so that absorbing.Therefore, a kind of ultra-wide of visible-near infrared band of the present invention
Structure with absorber is to form the main reason of ultra wide band absorption.
Specific embodiment mode：
Embodiment 1：It can be seen that-near infrared band ultra wide band absorber, it is contemplated that Absorber Bandwidth is 400nm -1200nm, average
Absorptivity is more than 98%, shown in absorption spectrum such as Fig. 4 (a) of absorber sample prepared by present invention design, average absorption ratio
More than 98.75%, corresponding base material is silicon chip, and corresponding film material is followed successively by chromium, germanium, silicon, titanium dioxide, fluorine
Change magnesium, the thicknesses of layers corresponding to each film layer be respectively 200nm (chromium), 18nm (germanium), 19nm (silicon), 35nm (titanium dioxide),
80nm (magnesium fluoride).
Embodiment 2：It can be seen that-near infrared band ultra wide band absorber, it is contemplated that Absorber Bandwidth is 400nm -2000nm, each ripple
Long absorptivity is more than 90%, shown in absorption spectrum such as Fig. 4 (b) of absorber sample prepared by present invention design, average absorption
Rate more than 97.75%%, corresponding base material are silicon chip, and corresponding film material is followed successively by chromium, germanium, silicon, titanium dioxide
Titanium, magnesium fluoride, the thicknesses of layers corresponding to each film layer are respectively 200nm (chromium), 33nm (germanium), 32nm (silicon), 56nm (titanium dioxides
Titanium), 118nm (magnesium fluoride).
Embodiment 3：Substantially the same manner as Example 1, difference is chromium replacing with titanium, remaining condition and embodiment 1
It is identical, shown in absorption spectrum such as Fig. 4 (c) that the present invention designs, average absorption ratio more than 99%, the film layer thickness corresponding to each film layer
Degree is respectively 200nm (titanium), 12nm (germanium), 17nm (silicon), 38nm (titanium dioxide), 89nm (magnesium fluoride).
Embodiment 4：Substantially the same manner as Example 2, difference is chromium replacing with titanium, remaining condition and embodiment 2
It is identical, shown in absorption spectrum such as Fig. 4 (d) that the present invention designs, average absorption ratio more than 96.2%, the film layer corresponding to each film layer
Thickness is respectively 200nm (titanium), 23nm (germanium), 31nm (silicon), 55nm (titanium dioxide), 119nm (magnesium fluoride).
Embodiment 5：Substantially the same manner as Example 1, difference is titanium dioxide replacing with tantalum oxide, remaining condition
It is same as Example 1, shown in absorption spectrum such as Fig. 4 (e) that the present invention designs, average absorption ratio more than 98.8%, each film layer institute
Corresponding thicknesses of layers 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 replacing with silica, remaining condition
It is same as Example 2, shown in absorption spectrum such as Fig. 4 (f) that the present invention designs, average absorption ratio more than 95.2%, each film layer institute
Corresponding thicknesses of layers is respectively 200nm (titanium), 32nm (germanium), 33nm (silicon), 56nm (titanium dioxide), 111nm (magnesium fluoride).
Claims (7)
1. a kind of ultra wide band absorber of Visible-to-Near InfaRed wave band, including substrate, it is characterised in that set successively in the substrate
There are metal absorption layer, germanium layer and three slice width wave band anti-reflection film layers；The three slice widths wave band anti-reflection film layer includes setting successively respectively
Bottom, intermediate layer and outermost layer on germanium layer are put, bottom, intermediate layer and outermost refractive index are gradually reduced；
The Metal absorption layer material is chromium；
The primer is silicon, and the intermediate layer material is titanium dioxide, and the outermost material is magnesium fluoride.
2. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the substrate material
Material is selected from K9, vitreous silica, float glass, silicon, GaAs.
3. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the metal is inhaled
The thickness for receiving layer is more than 100nm.
4. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the germanium layer is
10nm—40nm。
5. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the bottom is thick
Spend for 10nm -40nm；The intermediate layer thickness is 30nm -80nm；The outermost layer thickness is 70nm -130nm.
A kind of 6. preparation side of the ultra wide band absorber of the Visible-to-Near InfaRed wave band described in claim 1-5 any claims
Method, it is characterised in that comprise the following steps：
(1) required according to required absorber bandwidth requirement and absorptivity, the thickness of each layer film drawn by optimization design,
It is determined for compliance with desired membrane system；
(2) substrate is put into ultrasound in acetone, substrate is cleaned with ethanol；Then substrate is put into ultrasound in ethanol, uses deionization
Water cleans substrate；Substrate is finally put into ultrasound in deionized water, then cleans substrate again with deionized water；
(3) each film layer is sequentially depositing using vacuum coating, obtains the ultra wide band absorber of visible-near infrared band.
7. the preparation method of the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 6, it is characterised in that
In step (2), the time of ultrasound is 5-30min every time.
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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 |
| CN106324740B (en) * | 2016-11-16 | 2018-12-18 | 天津津航技术物理研究所 | A kind of wide band absorption film and preparation method thereof |
| CN108515743B (en) * | 2018-05-09 | 2020-07-28 | 同济大学 | Metal/medium ultra-wideband absorption film and preparation method thereof |
| CN109085669B (en) * | 2018-08-14 | 2020-09-29 | 深圳市融光纳米科技有限公司 | Conical array broadband absorber and preparation method thereof |
| CN110196464B (en) * | 2019-07-01 | 2022-07-29 | 江南大学 | Method for realizing ultra-wideband light absorption and composite microstructure |
| CN110422345B (en) * | 2019-07-26 | 2022-07-19 | 中国电子科技集团公司第三十三研究所 | OSR thermal control coating based on photonic crystal |
| CN113050205B (en) * | 2019-12-27 | 2021-09-21 | 比亚迪股份有限公司 | Black material and preparation method and application thereof |
| CN111240085B (en) * | 2020-03-26 | 2022-07-29 | 合肥工业大学 | Infrared absorber based on bias regulation |
| 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 |
| CN112526663A (en) * | 2020-11-04 | 2021-03-19 | 浙江大学 | Atomic layer deposition-based absorption film and manufacturing method thereof |
| CN112799159B (en) * | 2021-01-28 | 2022-08-05 | 浙江大学 | Ultraviolet-visible-infrared all-band absorber and preparation method thereof |
| CN113009606A (en) * | 2021-02-04 | 2021-06-22 | 江西师范大学 | Five-layer nano-material ultra-wideband perfect absorber and preparation method thereof |
| CN113188669B (en) * | 2021-04-29 | 2023-06-27 | 上海翼捷工业安全设备股份有限公司 | Infrared absorption composite film structure and carbon dioxide pyroelectric infrared detector |
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| JPWO2013077252A1 (en) * | 2011-11-21 | 2015-04-27 | コニカミノルタ株式会社 | Infrared shielding film and infrared shielding body |
| JP2014170171A (en) * | 2013-03-05 | 2014-09-18 | Toppan Printing Co Ltd | Transparent heat shield film with anti-reflection properties |
| CN204345956U (en) * | 2014-11-14 | 2015-05-20 | 中国建筑材料科学研究总院 | The continuously adjustable coating for selective absorption of sunlight spectrum of a kind of ABSORPTION EDGE |
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Effective date of registration: 20220822 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 |