CN105161141B - The ultra wide band absorber and preparation method of visible near-infrared wave band - Google Patents
The ultra wide band absorber and preparation method 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 wave band and preparation method thereof, three slice width wave band anti-reflection film layers that absorber is gradually reduced by germanium layer at the top of substrate, bottom metal absorbed layer, germanium layer/metal absorption layer alternate membrane and the refractive index above the germanium layer of 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, bottom metal is sequentially provided with the substrate
Absorbed layer, germanium layer/metal absorption layer alternate membrane are (germanium/metal absorption layer)S, top germanium layer and three slice width wave band antireflective films
Layer；The three slice widths wave band anti-reflection film layer includes bottom, intermediate layer and the outermost layer being successively set on the germanium layer of top, bottom respectively
Layer, 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 bottom metal absorbed layer can select chromium.The thickness of the bottom metal absorbed layer should be greater than 100nm；
More preferably 100-500nm；Still more preferably it is 150-300nm.
Preferably, Refractive Index of Material is gradually reduced three slice width wave band anti-reflection film layers from the bottom to top, close to bottom germanium layer
Bottom film material selects silicon, and thickness is 10nm -40nm, and further preferred thickness is 15nm -40nm, still more preferably
For 30nm -40nm；The intermediate layer film material can select the contour refraction of titanium dioxide, hafnium oxide, tantalum oxide, silicon nitride
Rate dielectric material, thickness are 30nm -80nm, and further preferred thickness is 35nm -60nm, still more preferably for 50nm -
60nm；The outermost layer membrane materials can select the low refractive index dielectric material such as magnesium fluoride, silica, yttrium fluoride, thickness
For 70nm -130nm, further preferred thickness is 80nm -120m, is still more preferably 100nm -120nm.The present invention
Three slice width wave band anti-reflection film layers are preferably silicon, titanium dioxide, magnesium fluoride from the bottom to top.
Preferably, the thickness of the top germanium layer is 10nm -40nm；More preferably 20nm -40nm.
Preferably, the germanium layer/metal absorption layer alternate membrane is by one or more germanium layers/Metal absorption layer unit group
Into wherein germanium layer is set close to bottom metal absorbed layer, is represented by (germanium/metal absorption layer)S, wherein S is more than or equal to 1
Positive integer.Preferably, in the germanium layer/metal absorption layer alternate membrane, the thickness of each layer is 10nm -80nm；As entering one
Step is preferred, and in the germanium layer/metal absorption layer alternate membrane, the thickness of germanium layer is 33nm -80nm.Germanium layer/the Metal absorption
The material of metal absorption layer is selected from the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material in layer alternate membrane；As further excellent
Select, metal absorption layer can select chromium, titanium in the germanium layer/metal absorption layer alternate membrane；The germanium layer/metal absorption layer is handed over
Thickness for metal absorption layer in film layer is 10nm -40nm；More preferably 15nm -30nm.Preferably, S be 1,2 or
3.Multiple germanium layers/Metal absorption layer unit, the thickness of germanium layer can be with identical, can also be different；The thickness of metal absorption layer can be with
It is identical, can also be different, it can be adjusted according to being actually needed.
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 S=1,7 layers of Cr/Ge/Cr/Ge/Si/TiO prepared by embodiment 12/MgF2The absorption spectrum of membrane structure
Figure；
Fig. 5 is S=2,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO prepared by embodiment 22/MgF2The absorption of membrane structure
Spectrogram；
Fig. 6 is S=1,7 layers of Ti/Ge/Ti/Ge/Si/TiO prepared by embodiment 32/MgF2The absorption spectrum of membrane structure
Figure；
Fig. 7 is S=2,9 layers of Ti/Ge/Ti/Ge/Ti/Ge/Si/TiO prepared by embodiment 42/MgF2The absorption of membrane structure
Spectrogram；
Fig. 8 is S=1,7 layers of Cr/Ge/Cr/Ge/Si/Ta prepared by embodiment 52O5/MgF2The absorption spectrum of membrane structure
Figure；
Fig. 9 is S=2,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO prepared by embodiment 62/SiO2The absorption of membrane structure
Spectrogram.
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 bottom metal absorbed layer 2, and the thickness degree should be greater than 100nm to stop that incident light transmission is entered
Enter substrate；It is germanium layer/metal absorption layer alternate membrane 7 on bottom metal absorbed layer, each thickness degree is 10nm -70nm,
It is top germanium layer 3 above germanium layer/metal absorption layer alternate membrane, the thickness degree is 10nm -40nm, and at top, germanium layer is upper
Face is three-layer thin-film (marked as 4-6 in Fig. 1), and Refractive Index of Material is gradually reduced from the bottom to top, this three layers wide ripple that can regard germanium as
Section anti-reflection film layer.Bottom metal absorbed layer 2 can select the alloy of chromium, titanium, iridium, tungsten, nickel and above-mentioned material, bottom of the present invention
Metal absorption layer 2 is preferably chromium.In germanium layer/metal absorption layer alternate membrane 7, germanium layer is identical with top germanium layer material, and metal is inhaled
It is identical with the material of bottom metal absorbed layer 2 to receive layer.Refractive Index of Material gradually subtracts three slice width wave band anti-reflection film layers (4-6) from the bottom to top
Small, close to the thin-film material of the bottom 4 selection silicon of top germanium layer 3, thickness is 10nm -40nm, and 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 is selected, thickness is 30nm -80nm, and outermost layer 6 is thin
Membrane material can select the low refractive index dielectric material such as magnesium fluoride, silica, yttrium fluoride, and thickness is 70nm -130nm.The present invention
Three slice width wave band anti-reflection film layers 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 -2500nm, each ripple
Long absorptivity is more than 90%, and the absorption spectrum of absorber sample prepared by present invention design is as shown in figure 4, average absorption ratio
More than 96.82%, corresponding structure is S=1,7 layers of Cr/Ge/Cr/Ge/Si/TiO2/MgF2Membrane structure, corresponding base
Bottom material is silicon chip, the thicknesses of layers corresponding to each film layer from the bottom to top be respectively 200nm (chromium), 52nm (germanium), 21nm (chromium),
33nm (germanium), 34nm (silicon), 57nm (titanium dioxide), 111nm (magnesium fluoride).
Embodiment 2：It can be seen that-near infrared band ultra wide band absorber, it is contemplated that Absorber Bandwidth is 400nm -3000nm, each ripple
Long absorptivity more than 90%, the absorption spectrum of membrane system that the present invention designs as shown in figure 5, average absorption ratio more than 94.9%,
Corresponding structure is S=2,9 layers of Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO2/MgF2Membrane structure, corresponding base material
For silicon chip, the thicknesses of layers corresponding to each film layer is respectively 200nm (chromium), 72nm (germanium), 22nm (chromium), 55nm from the bottom to top
(germanium), 15nm (chromium), 36nm (germanium), 37nm (silicon), 57nm (titanium dioxide), 110nm (magnesium fluoride).
Embodiment 3：Substantially the same manner as Example 1, difference is chromium replacing with titanium, remaining condition and embodiment 1
Identical, the absorption spectrum for the absorber sample that the present invention designs is as shown in fig. 6, average absorption ratio more than 96.36%, each film layer institute
Corresponding thicknesses of layers from the bottom to top be respectively 200nm (titanium), 33nm (germanium), 25nm (titanium), 23nm (germanium), 34nm (silicon),
56nm (titanium dioxide), 111nm (magnesium fluoride).
Embodiment 4：Substantially the same manner as Example 2, difference is chromium replacing with titanium, remaining condition and embodiment 2
Identical, the absorption spectrum for the absorber sample that the present invention designs is as shown in fig. 7, average absorption ratio more than 96.36%, each film layer institute
Corresponding thicknesses of layers from the bottom to top be respectively 200nm (titanium), 36nm (germanium), 29nm (titanium), 34nm (germanium), 18nm (titanium),
27nm (germanium), 38nm (silicon), 57nm (titanium dioxide), 110nm (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, the absorption spectrum of absorber sample that the present invention designs as shown in figure 8, average absorption ratio 96.91% with
On, thicknesses of layers corresponding to each film layer be respectively from the bottom to top 200nm (titanium), 53nm (germanium), 20nm (titanium), 33nm (germanium),
35nm (silicon), 60nm (tantalum oxide), 114nm (magnesium fluoride).
Embodiment 6：Substantially the same manner as Example 2, difference is magnesium fluoride replacing with yttrium fluoride tungsten, remaining condition
It is same as Example 2, the absorption spectrum of absorber sample that the present invention designs as shown in figure 9, average absorption ratio 95.28% with
On, thicknesses of layers corresponding to each film layer be respectively from the bottom to top 200nm (chromium), 74nm (germanium), 22nm (chromium), 51nm (germanium),
14nm (chromium), 34nm (germanium), 36nm (silicon), 58nm (titanium dioxide), 105nm (silica).
Claims (10)
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 bottom metal absorbed layer, germanium layer/metal absorption layer alternate membrane, top germanium layer and three slice width wave band anti-reflection film layers；It is described
Three slice width wave band anti-reflection film layers include bottom, intermediate layer and the outermost layer being successively set on the germanium layer of top, bottom, centre respectively
Layer and outermost refractive index are gradually reduced；The germanium layer/metal absorption layer alternate membrane is inhaled by one or more germanium layers/metal
Layer unit composition is received, wherein germanium layer is set close to bottom metal absorbed layer；The primer is silicon.
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 bottom gold
Category absorbs the alloy that layer material is selected from chromium, titanium, iridium, tungsten, nickel and above-mentioned material.
4. the ultra wide band absorber of the Visible-to-Near InfaRed wave band according to claim 1 or 3, it is characterised in that the bottom
The thickness of metal absorption layer is more than 100nm.
5. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the germanium layer/gold
It is 10nm -80nm to belong to each thickness degree in absorbed layer alternate membrane.
6. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the top germanium
Thickness degree is 10nm -40nm.
7. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 1, it is characterised in that the intermediate layer
Material is selected from titanium dioxide, hafnium oxide, tantalum oxide, silicon nitride；The outermost material is selected from magnesium fluoride, silica, fluorination
Yttrium.
8. the ultra wide band absorber of Visible-to-Near InfaRed wave band according to claim 6, it is characterised in that the bottom
Thickness is 10nm -40nm；The thickness in the intermediate layer is 30nm -80nm；The outermost thickness is 70nm -130nm.
9. the ultra wide band absorber of the Visible-to-Near InfaRed wave band according to claim 6 or 7, it is characterised in that the centre
Layer material is titanium dioxide, and the outermost material is magnesium fluoride.
A kind of 10. preparation side of the ultra wide band absorber of the Visible-to-Near InfaRed wave band described in claim 1-9 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.
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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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| CN201510469463.7A CN105161141B (en) | 2015-08-04 | 2015-08-04 | The ultra wide band absorber and preparation method of visible near-infrared wave band |
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| 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 |