WO2017020407A1 - 一种可见 - 近红外波段的超宽带吸收器及制备方法 - Google Patents

一种可见 - 近红外波段的超宽带吸收器及制备方法 Download PDF

Info

Publication number
WO2017020407A1
WO2017020407A1 PCT/CN2015/090201 CN2015090201W WO2017020407A1 WO 2017020407 A1 WO2017020407 A1 WO 2017020407A1 CN 2015090201 W CN2015090201 W CN 2015090201W WO 2017020407 A1 WO2017020407 A1 WO 2017020407A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
visible
ultra
infrared band
absorber
Prior art date
Application number
PCT/CN2015/090201
Other languages
English (en)
French (fr)
Inventor
沈伟东
杨陈楹
章岳光
方波
刘旭
Original Assignee
浙江大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201510469463.7A external-priority patent/CN105161141B/zh
Priority claimed from CN201510470432.3A external-priority patent/CN105022106B/zh
Application filed by 浙江大学 filed Critical 浙江大学
Priority to US15/329,569 priority Critical patent/US10481305B2/en
Publication of WO2017020407A1 publication Critical patent/WO2017020407A1/zh

Links

Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/003Light absorbing elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11Anti-reflection coatings
    • G02B1/113Anti-reflection coatings using inorganic layer materials only
    • G02B1/115Multilayers

Definitions

  • the invention belongs to the fields of stray light elimination, space detection, imaging, photothermal conversion and electromagnetic absorption, and particularly relates to an ultra-wideband absorber with visible_near infrared band.
  • Zhou et al. used the characteristics of lateral deposition to prepare a multi-layered alternating medium/metal cone structure to achieve higher absorption in the near-infrared broad band (Experiment and Theory of the
  • Chinese Patent Application No. 201510163240.8 discloses an ultra-wideband absorber based on a cascading structure metamaterial consisting of 9 dielectric layers, 9 metal layers, and 1 to 3 dielectric layers and The metal layer is a cylinder of the same diameter, the 4th to 6th dielectric layers and the metal layer are cylinders having the same diameter, and the 7th to 9th dielectric layers and the metal layer are cylinders having the same diameter, the overall structure of the absorber is relatively complicated, and the incident angle is Higher demand [0006] Chinese Patent Application No.
  • 201410020841.9 discloses an absorption film structure based on visible to near-infrared band, which sequentially grows a metal film layer and a dielectric film layer by vapor deposition and liquid deposition on any substrate.
  • the thickness of the metal film layer is 80 ⁇ -1 ⁇
  • the thickness of the dielectric film layer is 1 nm-200 nm
  • the average height of the equivalent film layer in the disordered distribution layer of the metal particles is 5 nm-100 nm
  • the average particle size is 10 nm-200 nm
  • the surface coverage of the metal particles is It is 3 ⁇ 3 ⁇ 4-90 ⁇ 3 ⁇ 4.
  • the structure is relatively simple, but its absorption rate is not good.
  • Chinese Patent Application No. 201110410712.7 discloses a solar selective absorbing coating consisting of a two-layer or three-layer structure: the first layer is a polished stainless steel substrate, and the second layer is Cul. .5 Mnl. 504 composite oxide absorber layer, the third layer consists of ⁇ 02 film to form an anti-reflection layer, arranged from bottom to top.
  • the absorption rate of the coating is less than 0.9, and the preparation process is complicated.
  • the present invention provides an ultra-wideband absorber in the visible-near-infrared band, which can cover a wider absorption band, better absorption performance, and better incident angle insensitivity.
  • the present invention provides a method for preparing an ultra-wideband absorber in the visible-near-infrared band, which is convenient to prepare, low in cost, and convenient for large-scale and mass production.
  • a visible-near-infrared ultra-wideband absorber comprising a substrate, wherein the substrate is provided with a bottom metal absorbing layer, a top ruthenium layer and a three-layer wide-band anti-reflection film layer; the three-layer wide-band The anti-reflection film layer respectively comprises a bottom layer, an intermediate layer and an outermost layer which are sequentially disposed on the enamel layer, and the refractive indices of the bottom layer, the intermediate layer and the outermost layer are gradually decreased.
  • a ⁇ layer/metal absorbing layer alternating film layer is disposed between the bottom metal absorbing layer and the top ruthenium layer; the bismuth layer/metal absorbing layer alternating film layer is composed of one or more bismuth layers / Metal absorbing layer unit composition, wherein the ruthenium layer is disposed near the bottom metal absorbing layer.
  • the base material is not limited.
  • the substrate may be a glass material such as K9, fused silica or float glass, or a semiconductor material such as silicon or gallium arsenide. More preferably, it is a silicon wafer.
  • the bottom metal absorbing layer may be selected from the group consisting of chromium, titanium, tantalum, tungsten, nickel, and the like.
  • An alloy; the metal absorbing layer in the alternating layer of the lanthanum/metal absorbing layer may be selected from the group consisting of chromium, titanium, tantalum, tungsten, nickel, and alloys of the above materials; and further preferably, the bottom metal absorbing layer and the ruthenium layer /
  • the metal absorbing layer in the alternating layers of the metal absorbing layer is generally selected from the same material; as a further preferred, the bottom metal absorbing layer may be selected from chromium.
  • the thickness of the bottom metal absorbing layer should be greater than or equal to 100 nm; further preferably from 100 nm to 500 nm; still more preferably from 150 nm to 300 nm.
  • the top ruthenium layer is 10 nm to 40 nm; more preferably 20 nm to 40 nm.
  • the three-layer wide-band anti-reflection film layer gradually decreases in refractive index from the bottom to the top, and the underlying film material near the top germanium layer selects silicon, has a thickness of 10 nm to 40 nm, and further preferably has a thickness of 15 nm to 40 nm, and is further preferred.
  • intermediate layer of the film material may be selected titanium oxide, hafnium oxide, tantalum oxide, silicon nitride, high refractive index dielectric material having a thickness of 30nm_80nm, more preferably a thickness of 35nm_60nm; the outermost film of material may be A low refractive index dielectric material such as magnesium fluoride, silicon dioxide or cesium fluoride is selected to have a thickness of 70 nm to 130 nm, a more preferred thickness of 80 nm to 120 m, and still more preferably 100 nm to 120 nm.
  • the three-layer wide-band anti-reflection film layer of the present invention is preferably silicon, titanium dioxide or magnesium fluoride from bottom to top.
  • the bismuth layer/metal absorbing layer alternating film layer is composed of one or more bismuth layer/metal absorbing layer units, wherein the bismuth layer is disposed near the bottom metal absorbing layer, which can be expressed as ( ⁇ /metal absorbing layer) ) s , where S is a positive integer greater than or equal to 1.
  • the thickness of each layer is 10 nm _ 80 nm; and further preferably, the bismuth layer/metal absorbing layer alternating film layer has a thickness of 33 nm to 80 nm .
  • the material of the metal absorbing layer in the alternating layer of the ruthenium layer/metal absorbing layer is selected from the group consisting of chromium, titanium, tantalum, tungsten, nickel, and an alloy of the above materials; and further preferably, the ruthenium layer/metal absorbing layer is alternately layered
  • the metal absorbing layer may be selected from chromium or titanium; the thickness of the metal absorbing layer in the alternating layer of the bismuth layer/metal absorbing layer is 10 nm to 40 nm ; further preferably 15 nm to 30 nm.
  • S is 1, 2 or 3.
  • the thickness of the bismuth layer may be the same or different, and the thickness of the absorbing layer may be the same or different, and may be adjusted according to actual needs.
  • the present invention also provides a method for preparing an ultra-wideband absorber in the visible-near-infrared band, comprising the following steps:
  • the interval between each ultrasound is generally 5-30 min; further preferably 5-10 min.
  • the visible-near-infrared ultra-wideband absorber of the present invention can cover a wider absorption band, better absorption performance, and better incident angle insensitivity than a conventional absorber. . Therefore, the ultra-wideband absorption performance of the near-infrared band of the present invention completely exceeds that of the conventional absorber. Since the ultra-wideband absorber structure of the visible-near-infrared band of the present invention is a compact multilayer film structure, the structure is simpler than that of the conventional broadband absorber and the artificial electromagnetic absorber proposed in recent years.
  • the visible-near-infrared ultra-wideband absorber of the present invention avoids complex nanofabrication techniques such as electron beam processing techniques, focused ion beam etching techniques, reactive ion etching techniques, Photolithography technology and the like, so that the production cost is significantly reduced, the production cycle is significantly shortened, thereby facilitating large-scale, batch production.
  • the present invention is based on the barrier absorption effect of the metal absorbing layer combined with the wide-band anti-reflection layer of the bismuth layer, thereby constructing a wide-band non-transmissive anti-reflection structure, thereby achieving high efficiency, angle-insensitive visible_near Ultra-wideband absorption in the infrared band.
  • the ultra-wideband absorber of the visible-near-infrared band of the invention has the advantages of simple structure, convenient preparation and low cost, and is suitable for large-area batch production, thereby greatly reducing the preparation cost of the ultra-wideband absorber in the visible-near-infrared band. Therefore, the invention is expected to be widely used in photothermal conversion, electromagnetic absorption, detection, and imaging, and contributes to China's national economy, social development, science and technology, and national defense construction.
  • 1 is a schematic structural view of an ultra-wideband absorber of a visible-near-infrared band according to the present invention
  • 2 is a flow chart of preparing an ultra-wideband absorber of a visible-near-infrared band according to the present invention
  • FIG. 3 is an analysis diagram of an ultra-wideband absorption mechanism of the ultra-wideband absorber of the visible_near-infrared band shown in FIG. 1 according to the present invention
  • Figure 4 is an absorption spectrum of a sample with different absorption bandwidth requirements and absorption requirements:
  • 4(a) is an absorption spectrum of the absorber sample prepared in Example 1, in the range of 400 nm to 1200 nm, and an average absorption rate of 98.75 % or more;
  • 4(b) is an absorption spectrum of the absorber sample prepared in Example 2, in the range of 400 nm to 2000 nm, and the average absorption rate is 97.75% or more;
  • 4(c) is an absorption spectrum of the absorber sample prepared in Example 3, in the range of 400 nm to 1200 nm, and an average absorption rate of 99% or more;
  • 4(d) is an absorption spectrum of the absorber sample prepared in Example 4, with an average absorption rate of 96.2% or more in the range of 400 nm to 2000 nm;
  • 4(e) is an absorption spectrum of the absorber sample prepared in Example 5, in the range of 400 nm to 1200 nm, and an average absorption rate of 98.8% or more;
  • FIG. 5 is a schematic structural view of another embodiment of an ultra-wideband absorber of the visible-near-infrared band according to the present invention.
  • FIG. 6 is an analysis diagram of an ultra-wideband absorption mechanism of an ultra-wideband absorber of the visible_near-infrared band shown in FIG. 5 according to the present invention
  • an ultra-wideband absorber of visible-near-infrared band is composed of a substrate 1 and a five-layer film.
  • the material of the substrate 1 is not limited, and a glass material such as K9, fused silica or float glass may be selected, and a semiconductor material such as silicon or gallium arsenide may be selected.
  • the bottommost film is a metal absorbing layer 2, the thickness of the layer should be greater than or equal to 100 nm to block the transmission of incident light into the substrate; above the metal absorbing layer is a ruthenium layer 3 having a thickness of 10 nm to 40 nm, and a three-layer film on the top of the ruthenium layer ( 4-6), the refractive index of the material from bottom to top is gradually reduced, and the three layers can be regarded as a wide-band anti-reflection layer of germanium.
  • the metal absorbing layer 2 may be selected from the group consisting of chromium, titanium, tantalum, tungsten, nickel, and alloys of the above materials, and the metal absorbing layer 2 of the present invention is preferably chromium.
  • the refractive index of the three-layer wide-band anti-reflective coating layer (4-6) is gradually reduced from the bottom to the top, and the film material of the film layer 4 near the enamel layer 3 is silicon, and the thickness is 10 nm - 40 ⁇ m.
  • the film material of the intermediate layer 5 can be selected.
  • a high refractive index dielectric material such as titanium dioxide, cerium oxide, cerium oxide or silicon nitride, having a thickness of 30 nm to 80 nm, and a thin film material of the outermost layer 6 may be selected from low refractive index dielectric materials such as magnesium fluoride, silicon dioxide and barium fluoride. 70nm - 130nm.
  • the three-layer wide-band anti-reflection film layer of the present invention is preferably silicon, titanium oxide or magnesium fluoride from the bottom to the top.
  • a method for preparing an ultra-wideband absorber in a visible-near-infrared band includes the following steps, as shown in FIG. 2:
  • the substrate was placed in an acetone solution for 8 minutes, followed by washing the substrate with ethanol; then the substrate (substrate) was placed in an ethanol solution for 8 minutes, followed by washing the substrate with deionized water; The substrate was placed in deionized water for 8 minutes, and then the substrate was washed again with deionized water;
  • the ultra-wideband absorption of an ultra-wideband absorber of the visible-near-infrared band of the present invention is based on the mechanism of forming a plurality of resonances by using a graded-index material stack. As shown in Fig. 3 , with the accumulation of the film layer, each of the originally occurring resonant reflection valleys is translated in the long-wave direction, and the resonant reflection valley corresponding to the film layer appears in the short-wave direction.
  • the refractive index of the outermost layer is gradually reduced, and a graded-index film system having an anti-reflection property is formed, so that the overall reflectance is continuously lowered, so that the absorption is continuously increased. Therefore, the structure of an ultra-wideband absorber which can be seen in the near-infrared band of the present invention is the most important reason for forming ultra-wideband absorption.
  • Example 1 Visible _ near-infrared ultra-wideband absorber, the expected absorption bandwidth is 400 n m- 1200 nm, and the average absorption rate is above 98%.
  • the absorption spectrum of the absorber sample designed and prepared by the present invention is shown in Fig. 4 (a) As shown, the average absorption rate is 98.75% or more, and the corresponding base material is silicon wafer.
  • the corresponding film material is chromium, tantalum, silicon, titanium dioxide, magnesium fluoride, and the thickness of each film layer is 200 nm (chromium), 18 nm ( ⁇ ), 19 nm (silicon), 35 nm (titanium dioxide), 80 nm (magnesium fluoride).
  • Example 2 Visible_near-infrared ultra-wideband absorber, the expected absorption bandwidth is 400 n m- 2000 nm, and the absorption rate of each wavelength is above 90%.
  • the absorption spectrum of the absorber sample designed and prepared by the present invention is shown in FIG. 4 (b) ), the average absorption rate is above 97.75%%, and the corresponding base material is silicon wafer, and the corresponding film material is chromium, tantalum, silicon, titanium dioxide, magnesium fluoride, and the thickness of each film layer. 200 nm (chromium), 33 nm ( ⁇ ), 32 nm (silicon), 56 nm (titanium dioxide), 118 nm (magnesium fluoride)
  • Example 3 Basically the same as Example 1, except that chromium was replaced by titanium, and the rest of the conditions were the same as in Example 1.
  • the absorption spectrum of the design of the present invention is as shown in FIG. 4(c), and the average absorption rate. 99% or more, the film thickness corresponding to each film layer is 200 nm (titanium), 12 nm ( ⁇ ), 17 nm (silicon), 38 nm (titanium dioxide), and 89 nm (magnesium fluoride).
  • Example 4 Basically the same as Example 2, except that chromium was replaced by titanium, and the rest of the conditions were the same as in Example 2.
  • the absorption spectrum of the design of the present invention is shown in FIG. 4(d), and the average absorption rate is the same. 96.2% or more, the film thickness corresponding to each film layer is 200 nm (titanium), 23 nm ( ⁇ ), 31 nm (silicon), 55 nm (titanium dioxide), and 119 nm (magnesium fluoride).
  • Example 5 Basically the same as Example 1, except that titanium dioxide was replaced by cerium oxide, and the rest of the conditions were the same as in Example 1.
  • the absorption spectrum of the design of the present invention is shown in FIG.
  • the rate is 98.8 ⁇ 3 ⁇ 4 or more, and the film thickness corresponding to each film layer is 200 ⁇ (titanium), 18 nm ( ⁇ ), 21 nm (silicon), 48 nm (yttria), and 10 nm (magnesium fluoride).
  • Example 6 Basically the same as Example 2, except that magnesium fluoride was replaced by silica, and the rest of the conditions were the same as in Example 2.
  • the absorption spectrum of the design of the present invention is shown in FIG. 4(f).
  • the average absorption rate is 95.2% or more, and the film thickness corresponding to each film layer is 200 nm (titanium), 32 nm ( ⁇ ), 33 nm (silicon), 56 nm (titanium dioxide), and ll lnm (magnesium fluoride).
  • an ultra-wideband absorber of visible-near-infrared band is composed of a substrate 21 and a five-layer film.
  • the material of the substrate 21 is not limited, and a glass material such as K9, fused silica or float glass may be selected, and a semiconductor material such as silicon or gallium arsenide may be selected.
  • the bottommost film is the bottom metal absorbing layer 22, the thickness of the layer should be greater than or equal to 100 nm to block the transmission of incident light into the substrate; above the bottom metal absorbing layer is a ⁇ layer/metal absorbing layer alternating film layer 27, each layer having a thickness of 10 nm_70 nm,
  • the top layer of the tantalum/metal absorbing layer is the top layer 23, the layer has a thickness of lOnm-40 nm, and the top layer of the top layer is a three-layer film (labeled 24-26 in Figure 5), from bottom to top.
  • the refractive index is gradually reduced, and the three layers can be regarded as a wide-band anti-reflection layer of germanium.
  • the bottom metal absorbing layer 22 may be selected from the group consisting of chromium, titanium, tantalum, tungsten, nickel, and alloys of the above materials, and the bottom metal absorbing layer 22 of the present invention is preferably chromium.
  • the ⁇ layer is the same material as the top ⁇ layer
  • the metal absorbing layer is the same material as the bottom metal absorbing layer 22.
  • the three-layer wide-band anti-reflection film layer (24-26) gradually decreases in refractive index from bottom to top, and the film material near the bottom layer 24 of the top germanium layer 23 is silicon, and the thickness is 10 nm_40 nm.
  • the film of the intermediate layer 25 can be selected from titanium oxide and oxidized.
  • a high refractive index dielectric material such as tantalum, yttria or silicon nitride having a thickness of 30 nm to 80 nm, and a thin film material of the outermost layer 26 may be selected from a low refractive index dielectric material such as magnesium fluoride, silicon oxide or lanthanum fluoride, and has a thickness of 70 nm to 30 nm.
  • the three-layer wide-band anti-reflection film layer of the present invention is preferably silicon, titanium dioxide or magnesium fluoride from bottom to top.
  • This embodiment can adopt the same method as in Embodiment 1, as shown in FIG. 2, including:
  • the substrate is placed in an acetone solution for 8 minutes, followed by washing the substrate with ethanol; then the substrate (base) Bottom) was placed in an ethanol solution for 8 minutes, followed by washing the substrate with deionized water; finally, the substrate was placed in deionized water for 8 minutes, followed by washing the substrate again with deionized water;
  • the ultra-wideband absorption of an ultra-wideband absorber of the visible-near-infrared band of the present invention is based on the use of a gradient refractive index material stacking to form a plurality of resonances. As shown in Fig. 6, with the accumulation of the film layer, each of the original resonant reflection valleys is translated in the long-wave direction, and the resonant reflection valley corresponding to the film layer appears in the short-wave direction. In addition, as the film layer is deposited, the refractive index of the outermost layer is gradually reduced, and a graded-index film system having an anti-reflection property is formed, so that the overall reflectance is continuously lowered, so that the absorption is continuously increased. Therefore, the structure of an ultra-wideband absorber which can be seen in the near-infrared band of the present invention is the most important reason for forming ultra-wideband absorption.
  • Example 7 Visible_near-infrared ultra-wideband absorber, the expected absorption bandwidth is 400 n m_2500 nm, and the absorption rate of each wavelength is above 90%.
  • the absorption spectrum of the absorber sample prepared by the present invention is as shown in FIG.
  • Example 8 Visible _ near-infrared ultra-wideband absorber, the expected absorption bandwidth is 400 n m- 3000 nm, and the absorption rate of each wavelength is above 90%.
  • the absorption spectrum of the membrane system designed by the present invention is shown in FIG.
  • the thickness of the layer corresponding to the layer is 200 nm (chromium), 72 nm ( ⁇ ), 22 nm (chromium), 55 nm ( ⁇ ), 15 nm (chromium), 36 nm ( ⁇ ), 37 nm (silicon), 57 nm (from bottom to top). Titanium dioxide), l lOnm (magnesium fluoride).
  • Example 9 Basically the same as Example 1, except that chromium was replaced by titanium, and the rest of the conditions were the same as in Example 1.
  • the absorption spectrum of the absorber sample designed by the present invention is shown in FIG. The rate is 96.36% or more, and the thickness of the film corresponding to each film layer is 200 nm (titanium), 33 nm ( ⁇ ), 25 nm (titanium), 23 nm ( ⁇ ), 34 nm (silicon), 56 nm (titanium dioxide), respectively.
  • Example 10 Basically the same as Example 8, except that chromium was replaced by titanium, and the rest of the conditions were the same as in Example 8.
  • the absorption spectrum of the absorber sample designed by the present invention is shown in FIG.
  • the rate is 96.36 ⁇ 3 ⁇ 4 or more, and the thickness of the film corresponding to each film layer is 200 nm (titanium), 36 nm ( ⁇ ), 29 nm (titanium), 34 nm ( ⁇ ), 18 nm (titanium), 27 nm ( ⁇ ), respectively, from bottom to top.
  • Example 11 Basically the same as Example 7, except that titanium dioxide was replaced by cerium oxide, and the rest of the conditions were the same as in Example 7.
  • the absorption spectrum of the absorber sample designed by the present invention is shown in FIG.
  • the absorption rate is 96. 9 1 ⁇ 3 ⁇ 4 or more, and the thickness of the film corresponding to each film layer is 200 nm (titanium), 53 nm ( ⁇ ), 20 nm (titanium), 33 nm ( ⁇ ), 35 nm (silicon), respectively, from bottom to top. 60 nm (yttria), 114 ⁇ m (magnesium fluoride).
  • Example 12 Basically the same as Example 8, except that magnesium fluoride was replaced with strontium fluoride fluoride, and the rest of the conditions were the same as in Example 8.
  • the absorption spectrum of the absorber sample designed by the present invention is shown in FIG. As shown, the average absorption rate is 95.28% or more, and the thickness of the film corresponding to each film layer is 200 nm (chromium), 74 nm ( ⁇ ), 22 nm (chromium), 51 nm ( ⁇ ), and 14 nm (chromium), respectively, from bottom to top. 34 nm ( ⁇ ), 36 nm (silicon), 58 nm (titanium dioxide), 105 nm (silicon dioxide).

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Optical Filters (AREA)

Abstract

一种可见-近红外波段的超宽带吸收器及其制备方法。可见-近红外波段的超宽带吸收器由基底(1)和五层光学薄膜组成。最底层薄膜为底部金属吸收层(2),在底部金属吸收层上面是顶部锗层(3),在顶部锗层上面是三层减反射膜(4-6),由下至上三层减反射膜的材料折射率逐渐减小。基于金属吸收层的阻挡入射作用结合锗层的宽波段减反膜层,实现了角度不敏感的可见-近红外波段超宽带吸收,结构更加简单。

Description

一种可见 -近红外波段的超宽带吸收器及制备方法 技术领域
[0001] 本发明属于杂散光消除、 空间探测、 成像、 光热转换及电磁吸收等领域, 具体 涉及一种可见 _近红外波段的超宽带吸收器。
背景技术
[0002] 由于可见一红外宽波段吸收器可以在诸多不同的新领域发挥重大作用, 因而近 些年可见_红外宽波段吸收器获得了广泛研究, 从而使得越来越宽波段的吸收 器被制备出。 近年来, 研究人员提出了各种电磁波人工电磁结构的近红外吸收 器。 其中, Chen等利用液滴蒸发的方法在镀有介质层的金属基底上形成随机排 列的金纳米棒, 实现近红外 900nm_1600nm波段的高吸收 (Near-infrared broadband absorber with film-coupled multilayer nanorods, Optics Lett. 38,
2247-2249 (2013)); Zhou等利用侧向沉积的特点制备出多层的交替介质 /金属的 锥形结构, 实现近红外宽波段的较高吸收 (Experiment and Theory of the
Broadband Absorption by a Tapered Hyperbolic Metamaterial Array, ACS Photonics 1, 618-624 (2014)); Ji等提出了一种在银反射镜表面交替堆积金属颗粒和氧化硅 薄膜的结构, 从而实现 300nm_l lOOnm波段平均 96%以上的高吸收 (Plasmonic broadband absorber by stacking multiple metallic nanoparticle layers, Appl. Phys. Lett. 106, 161107 (2015))。
[0003] 但是上述方法制备过程较为复杂, 耗吋较长, 制备成本高, 不利于大面积量化 生产。
[0004] 目前相关的文献报道主要有:
[0005] 申请号为 201510163240.8的中国专利文献公幵了一种基于级联结构超材料的超 宽带吸收器, 该吸收器由 9个介质层, 9个金属层组成, 第 1~3介质层和金属层为 直径相同的圆柱, 第 4~6介质层和金属层为直径相同的圆柱, 第 7~9介质层和金 属层为直径相同的圆柱, 该吸收器整体结构较为复杂, 且对入射角度要求较高 [0006] 申请号为 201410020841.9的中国专利文献公幵了一种基于可见到近红外波段吸 收膜系结构, 其在任意衬底上采用气相沉积、 液相沉积依次生长金属薄膜层、 介质薄膜层, 其中金属薄膜层厚度为 80ηιη-1μιη, 介质薄膜层厚度为 lnm-200nm , 金属颗粒无序分布层中等效薄膜层平均高度为 5nm-100nm, 颗粒平均尺寸为 10 nm-200nm, 金属颗粒表面覆盖率为 3<¾-90<¾。 结构相对比较简单, 但是其吸收率 不好。
[0007] 申请号为 201110410712.7的中国专利文献公幵了一种太阳能选择性吸收涂层, 该涂层由双层或三层结构组成: 第一层为抛光后的不锈钢基底, 第二层为 Cul.5 Mnl.504复合氧化物吸收层, 第三层由 Ή02薄膜构成减反层, 自下而上排列。 该涂层的吸收率均低于 0.9, 且制备工艺复杂。
技术问题
[0008] 本发明提供了一种可见-近红外波段的超宽带吸收器, 该吸收器所能覆盖的吸 收波段更宽, 吸收性能更好, 还具有较好的入射角度不敏感性。
[0009] 本发明同吋提供了一种可见-近红外波段的超宽带吸收器的制备方法, 该方法 制备方便, 成本低, 便于大规模、 批量化生产。
问题的解决方案
技术解决方案
[0010] 一种可见-近红外波段的超宽带吸收器, 包括基底, 所述基底上依次设有底部 金属吸收层、 顶部锗层以及三层宽波段减反膜层; 所述三层宽波段减反膜层分 别包括依次设置在锗层上的底层、 中间层和最外层, 底层、 中间层和最外层的 折射率逐渐减小。
[0011] 下面为基于上述方案的优选的方案:
[0012] 作为优选, 所述底部金属吸收层与所述顶部锗层之间设有锗层 /金属吸收层交 替膜层; 所述锗层 /金属吸收层交替膜层由一个或多个锗层 /金属吸收层单元组成 , 其中锗层靠近底部金属吸收层设置。
[0013] 基底材料没有限制, 作为优选, 所述基底可以选择 K9, 熔融石英, 浮法玻璃等 玻璃材料, 也可以选择硅, 砷化镓等半导体材料。 进一步优选为硅片。
[0014] 作为优选, 所述底部金属吸收层可以选择铬、 钛、 铱、 钨、 镍以及上述材料的 合金; 所述锗层 /金属吸收层交替膜层中的金属吸收层可以选择铬、 钛、 铱、 钨 、 镍以及上述材料的合金; 作为进一步优选, 所述底部金属吸收层和所述锗层 / 金属吸收层交替膜层中的金属吸收层一般选择相同的材料; 作为进一步优选, 所述底部金属吸收层可以选择铬。 所述底部金属吸收层的厚度应大于等于 lOOnm ; 进一步优选为 100nm-500nm; 更进一步优选为 150nm-300nm。
[0015] 作为优选, 所述顶部锗层为 10nm_40nm; 进一步优选为 20nm_40nm。
[0016] 作为优选, 三层宽波段减反膜层由下至上材料折射率逐渐减小, 靠近顶部锗层 的底层薄膜材料选择硅, 厚度为 10nm_40nm, 进一步优选的厚度为 15nm_40n m, 更进一步优选为 30nm_40nm; 所述中间层薄膜材料可以选择二氧化钛、 氧 化铪、 氧化钽、 氮化硅等高折射率介质材料, 厚度为 30nm_80nm, 进一步优选 的厚度为 35nm_60nm; 所述最外层薄膜材料可以选择氟化镁、 二氧化硅、 氟化 钇等低折射率介质材料, 厚度为 70nm_130nm, 进一步优选的厚度为 80nm_120 m, 更进一步优选为 100nm_120nm。 本发明三层宽波段减反膜层由下至上优选 为硅、 二氧化钛、 氟化镁。
[0017] 作为优选, 所述锗层 /金属吸收层交替膜层由一个或多个锗层 /金属吸收层单元 组成, 其中锗层靠近底部金属吸收层设置, 可表示为 (锗 /金属吸收层) s, 其中 S 为大于等于 1的正整数。 作为优选, 所述锗层 /金属吸收层交替膜层中, 各层的厚 度为 10nm_80nm; 作为进一步优选, 所述锗层 /金属吸收层交替膜层中, 锗层的 厚度为 33nm_80nm。 所述锗层 /金属吸收层交替膜层中金属吸收层的材料选自铬 、 钛、 铱、 钨、 镍以及上述材料的合金; 作为进一步优选, 所述锗层 /金属吸收 层交替膜层中金属吸收层可以选择铬、 钛; 所述锗层 /金属吸收层交替膜层中金 属吸收层的厚度为 10nm_40nm; 进一步优选为 15nm_30nm。 作为优选, S为 1 、 2或 3。 多个锗层 /金属吸收层单元, 锗层的厚度可以相同, 也可以不同; 金属 吸收层的厚度可以相同, 也可以不同, 可根据实际需要调整。
[0018] 本发明同吋还提供了一种可见-近红外波段的超宽带吸收器的制备方法, 包括 如下步骤:
[0019] ( 1 ) 根据所要求的吸收器带宽要求和吸收率要求, 通过优化各层薄膜的厚度 , 设计出符合要求的膜系; 该步骤可采用现有的软件实现优化操作; [0020] (2) 将基底放入丙酮溶液中超声, 接着用乙醇清洗基底; 然后将基底放入乙 醇溶液中超声, 接着用去离子水清洗基底; 最后将基底放入去离子水中超声, 接着用去离子水再次清洗基底;
[0021] (3) 采用真空镀膜依次沉积各膜层, 得到可见_近红外波段的超宽带吸收器
[0022] 作为优选, 步骤 (2) 中, 每次超声的吋间一般为 5-30min; 进一步优选为 5-10 min。
发明的有益效果
有益效果
[0023] 本发明的可见 _近红外波段的超宽带吸收器, 相比于传统的吸收器, 它所能覆 盖的吸收波段更宽, 吸收性能更好, 还具有较好的入射角度不敏感性。 因此本 发明的可见一近红外波段的超宽波段吸收性能上完全超越了传统的吸收器。 由 于本发明的可见_近红外波段的超宽带吸收器结构是紧凑的多层薄膜结构, 相 比于传统的宽带吸收器以及近些年提出的人工电磁吸收器, 结构更加简单。 正 由于其紧凑的多层薄膜结构, 本发明的可见 _近红外波段的超宽带吸收器避免 了复杂的纳米加工技术, 例如电子束加工技术、 聚焦离子束刻蚀技术、 反应离 子刻蚀技术、 光刻技术等等, 从而使得生产成本显著下降, 生产周期显著缩短 , 从而便于大规模、 批量化生产。
[0024] 本发明基于金属吸收层的阻挡入射作用结合锗层的宽波段减反膜层, 从而构建 了宽波段的无透射的减反结构, 因而实现了高效率、 角度不敏感的可见 _近红 外波段超宽带吸收。 本发明的可见 _近红外波段的超宽带吸收器结构简单, 制 备方便, 成本低, 适于大面积批量化地生产, 从而使得可见 _近红外波段的超 宽带吸收器的制备成本大大降低。 因此该发明有望在光热转换、 电磁吸收、 探 测以及成像等方面广泛应用, 为我国国民经济、 社会发展、 科学技术和国防建 设等领域作出贡献。
对附图的简要说明
附图说明
[0025] 图 1为本发明可见 _近红外波段的超宽带吸收器的结构示意图; [0026] 图 2为本发明可见 _近红外波段的超宽带吸收器的制备流程图;
[0027] 图 3为本发明制备图 1所示可见_近红外波段的超宽带吸收器的超宽带吸收机理 分析图;
[0028] 图 4为不同吸收带宽要求和吸收率要求的样品的吸收光谱图:
[0029] 图 4 (a) 为实施例 1制备的吸收器样品的吸收光谱, 400nm— 1200nm波段, 平 均吸收率 98.75 %以上;
[0030] 图 4 (b) 为实施例 2制备的吸收器样品的吸收光谱, 400nm— 2000nm波段, 平 均吸收率 97.75%以上;
[0031] 图 4 (c) 为实施例 3制备的吸收器样品的吸收光谱, 400nm— 1200nm波段, 平 均吸收率 99%以上;
[0032] 图 4 (d) 为实施例 4制备的吸收器样品的吸收光谱, 400nm— 2000nm波段, 平 均吸收率 96.2%以上;
[0033] 图 4 (e) 为实施例 5制备的吸收器样品的吸收光谱, 400nm— 1200nm波段, 平 均吸收率 98.8%以上;
[0034] 图 4 (f) 为实施例 6制备的吸收器样品的吸收光谱, 400nm_2000nm, 平均吸 收率 95.2%以上;
[0035] 图 5为本发明可见 _近红外波段的超宽带吸收器的另一种实施方案的结构示意 图;
[0036] 图 6为本发明制备图 5所示可见_近红外波段的超宽带吸收器的超宽带吸收机理 分析图;
[0037] 图 7为实施例 7制备的 S=l, 7层 Cr/Ge/Cr/Ge/Si/TiO 2/MgF 2薄膜结构的吸收光谱 图;
[0038] 图 8为实施例 8制备的 S=2, 9层 Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO 2/MgF 2薄膜结构的吸 收光谱图;
[0039] 图 9为实施例 9制备的 S=l, 7层 Ti/Ge/Ti/Ge/Si/TiO 2/MgF 2薄膜结构的吸收光谱 图;
[0040] 图 10为实施例 10制备的 S=2, 9层 Ti/Ge/Ti/Ge/Ti/Ge/Si/TiO 2/MgF 2薄膜结构的吸 收光谱图; [0041 ] 图 11为实施例 11制备的 S= 1, 7层 Cr/Ge/Cr/Ge/Si/Ta 20 5/MgF 2薄膜结构的吸收 光谱图;
[0042] 图 12为实施例 12制备的 S=2, 9层 Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO 2/SiO 2薄膜结构的吸 收光谱图。
本发明的实施方式
[0043] 下面结合附图对本发明进行详细说明。
[0044] 第一种结构:
[0045] 如图 1所示, 一种可见_近红外波段的超宽带吸收器由基底 1和五层薄膜组成。
基底 1材料没有限制, 可以选择 K9, 熔融石英, 浮法玻璃等玻璃材料, 也可以选 择硅, 砷化镓等半导体材料。 最底层薄膜为金属吸收层 2, 该层厚度应大于等于 lOOnm以阻挡入射光透射进入基板; 在金属吸收层上面是锗层 3, 厚度为 10nm— 40nm, 在锗层的上面为三层薄膜 (4-6), 由下至上材料折射率逐渐减小, 该三层 可看成锗的宽波段减反膜层。 金属吸收层 2可以选择铬、 钛、 铱、 钨、 镍以及上 述材料的合金, 本发明金属吸收层 2优选为铬。 三层宽波段减反膜层 (4-6)由下至 上材料折射率逐渐减小, 靠近锗层 3的膜层 4薄膜材料选择硅, 厚度为 10nm— 40η m, 中间层 5薄膜材料可以选择二氧化钛、 氧化铪、 氧化钽、 氮化硅等高折射率 介质材料, 厚度为 30nm_80nm, 最外层 6薄膜材料可以选择氟化镁、 二氧化硅 、 氟化钇等低折射率介质材料, 厚度为 70nm— 130nm。 本发明三层宽波段减反 膜层由下至上优选为硅、 二氧化钛、 氟化镁。
[0046] 一种可见_近红外波段的超宽带吸收器的制备方法, 包括以下步骤, 如图 2所 示:
[0047] 1) 根据所要求的吸收器带宽要求和吸收率要求, 通过优化各层薄膜的厚度, 设计出符合要求的膜系;
[0048] 2) 将基片放入丙酮溶液中超声 8分钟, 接着用乙醇清洗基片; 然后将基片 (基 底) 放入乙醇溶液中超声 8分钟, 接着用去离子水清洗基片; 最后将基片放入去 离子水中超声 8分钟, 接着用去离子水再次清洗基片;
[0049] 3) 采用真空镀膜技术依次沉积各膜层, 得到可见_近红外波段的超宽带吸收 [0050] 本发明一种可见_近红外波段的超宽带吸收器的超宽带吸收是基于利用了渐变 折射率材料堆积同吋形成了多个谐振的机理。 如图 3, 随着膜层的堆积, 原先出 现的各个谐振反射谷都向长波方向平移, 同吋, 在短波方向出现与该膜层相对 应的谐振反射谷。 除此之外, 随着膜层的堆积, 最外层折射率逐渐减小, 形成 具有减反特性的渐变折射率膜系, 使得整体反射率不断降低, 从而使得吸收不 断增加。 因此, 本发明一种可见一近红外波段的超宽带吸收器的结构是形成超 宽带吸收的最主要原因。
[0051] 具体实施例方式:
[0052] 实施例 1 : 可见 _近红外波段超宽带吸收器, 预期吸收带宽为 400nm_1200nm , 平均吸收率在 98%以上, 本发明设计制备的吸收器样品的吸收光谱如图 4 (a) 所示, 平均吸收率 98.75%以上, 所对应的基底材料为硅片, 所对应的膜层材料 依次为铬、 锗、 硅、 二氧化钛、 氟化镁, 各膜层所对应的膜层厚度分别为 200nm (铬) 、 18nm (锗) 、 19nm (硅) 、 35nm (二氧化钛) 、 80nm (氟化镁) 。
[0053] 实施例 2: 可见 _近红外波段超宽带吸收器, 预期吸收带宽为 400nm_2000nm , 各波长吸收率在 90%以上, 本发明设计制备的吸收器样品的吸收光谱如图 4 (b ) 所示, 平均吸收率 97.75%%以上, 所对应的基底材料为硅片, 所对应的膜层材 料依次为铬、 锗、 硅、 二氧化钛、 氟化镁, 各膜层所对应的膜层厚度分别为 200 nm (铬) 、 33nm (锗) 、 32nm (硅) 、 56nm (二氧化钛) 、 118nm (氟化镁)
[0054] 实施例 3: 与实施例 1基本相同, 不同之处在于将铬替换为钛, 其余条件与实施 例 1相同, 本发明设计的吸收光谱如图 4 (c) 所示, 平均吸收率 99%以上, 各膜 层所对应的膜层厚度分别为 200nm (钛) 、 12nm (锗) 、 17nm (硅) 、 38nm ( 二氧化钛) 、 89nm (氟化镁) 。
[0055] 实施例 4: 与实施例 2基本相同, 不同之处在于将铬替换为钛, 其余条件与实施 例 2相同, 本发明设计的吸收光谱如图 4 (d) 所示, 平均吸收率 96.2%以上, 各 膜层所对应的膜层厚度分别为 200nm (钛) 、 23nm (锗) 、 31nm (硅) 、 55nm (二氧化钛) 、 119nm (氟化镁) 。 [0056] 实施例 5: 与实施例 1基本相同, 不同之处在于将二氧化钛替换为氧化钽, 其余 条件与实施例 1相同, 本发明设计的吸收光谱如图 4 (e) 所示, 平均吸收率 98.8 <¾以上, 各膜层所对应的膜层厚度分别为 200匪 (钛) 、 18nm (锗) 、 21nm ( 硅) 、 48nm (氧化钽) 、 lOlnm (氟化镁) 。
[0057] 实施例 6: 与实施例 2基本相同, 不同之处在于将氟化镁替换为二氧化硅, 其余 条件与实施例 2相同, 本发明设计的吸收光谱如图 4 (f) 所示, 平均吸收率 95.2% 以上, 各膜层所对应的膜层厚度分别为 200nm (钛) 、 32nm (锗) 、 33nm (硅 ) 、 56nm (二氧化钛) 、 l l lnm (氟化镁) 。
[0058] 第二种结构:
[0059] 如图 5所示, 一种可见_近红外波段的超宽带吸收器由基底 21和五层薄膜组成 。 基底 21材料没有限制, 可以选择 K9, 熔融石英, 浮法玻璃等玻璃材料, 也可 以选择硅, 砷化镓等半导体材料。 最底层薄膜为底部金属吸收层 22, 该层厚度 应大于等于 lOOnm以阻挡入射光透射进入基板; 在底部金属吸收层上面是锗层 / 金属吸收层交替膜层 27, 各层厚度为 10nm_70nm, 在锗层 /金属吸收层交替膜层 的上面为顶部锗层 23, 该层厚度为 lOnm— 40nm, 在顶部锗层的上面为三层薄膜 (图 5中标号为 24-26) , 由下至上材料折射率逐渐减小, 该三层可看成锗的宽波 段减反膜层。 底部金属吸收层 22可以选择铬、 钛、 铱、 钨、 镍以及上述材料的 合金, 本发明底部金属吸收层 22优选为铬。 锗层 /金属吸收层交替膜层 27中, 锗 层与顶部锗层材质相同, 金属吸收层与底部金属吸收层 22材质相同。 三层宽波 段减反膜层 (24-26)由下至上材料折射率逐渐减小, 靠近顶部锗层 23的底层 24薄 膜材料选择硅, 厚度为 10nm_40nm, 中间层 25薄膜材料可以选择二氧化钛、 氧 化铪、 氧化钽、 氮化硅等高折射率介质材料, 厚度为 30nm_80nm, 最外层 26薄 膜材料可以选择氟化镁、 氧化硅、 氟化钇等低折射率介质材料, 厚度为 70nm— 1 30nm。 本发明三层宽波段减反膜层由下至上优选为硅、 二氧化钛、 氟化镁。
[0060] 本实施例可采用同实施例 1中的方法, 如图 2所示, 包括:
[0061] 1) 根据所要求的吸收器带宽要求和吸收率要求, 通过优化各层薄膜的厚度, 设计出符合要求的膜系;
[0062] 2) 将基片放入丙酮溶液中超声 8分钟, 接着用乙醇清洗基片; 然后将基片 (基 底) 放入乙醇溶液中超声 8分钟, 接着用去离子水清洗基片; 最后将基片放入去 离子水中超声 8分钟, 接着用去离子水再次清洗基片;
[0063] 3) 采用真空镀膜技术依次沉积各膜层, 得到可见_近红外波段的超宽带吸收
[0064] 本发明一种可见_近红外波段的超宽带吸收器的超宽带吸收是基于利用了渐变 折射率材料堆积同吋形成了多个谐振的机理。 如图 6, 随着膜层的堆积, 原先出 现的各个谐振反射谷都向长波方向平移, 同吋, 在短波方向出现与该膜层相对 应的谐振反射谷。 除此之外, 随着膜层的堆积, 最外层折射率逐渐减小, 形成 具有减反特性的渐变折射率膜系, 使得整体反射率不断降低, 从而使得吸收不 断增加。 因此, 本发明一种可见一近红外波段的超宽带吸收器的结构是形成超 宽带吸收的最主要原因。
[0065] 具体实施例方式:
[0066] 实施例 7: 可见 _近红外波段超宽带吸收器, 预期吸收带宽为 400nm_2500nm , 各波长吸收率在 90%以上, 本发明设计制备的吸收器样品的吸收光谱如图 7所 示, 平均吸收率 96.82%以上, 所对应的结构为 S=l, 7层 Cr/Ge/Cr/Ge/Si TiO 2 /MgF 2薄膜结构, 所对应的基底材料为硅片, 各膜层所对应的膜层厚度由下至上 分别为 200nm (铬) 、 52nm (锗) 、 21nm (铬) 、 33nm (锗) 、 34nm (硅) 、 57nm (二氧化钛) 、 l l lnm (氟化镁) 。
[0067] 实施例 8: 可见 _近红外波段超宽带吸收器, 预期吸收带宽为 400nm_3000nm , 各波长吸收率在 90%以上, 本发明设计的膜系的吸收光谱如图 8所示, 平均吸 收率 94.9%以上, 所对应的结构为 S=2, 9层 Cr/Ge/Cr/Ge/Cr/Ge/Si/TiO 2/MgF 2薄膜 结构, 所对应的基底材料为硅片, 各膜层所对应的膜层厚度由下至上分别为 200 nm (铬) 、 72nm (锗) 、 22nm (铬) 、 55nm (锗) 、 15nm (铬) 、 36nm (锗 ) 、 37nm (硅) 、 57nm (二氧化钛) 、 l lOnm (氟化镁) 。
[0068] 实施例 9: 与实施例 1基本相同, 不同之处在于将铬替换为钛, 其余条件与实施 例 1相同, 本发明设计的吸收器样品的吸收光谱如图 9所示, 平均吸收率 96.36% 以上, 各膜层所对应的膜层厚度由下至上分别为 200nm (钛) 、 33nm (锗) 、 2 5nm (钛) 、 23nm (锗) 、 34nm (硅) 、 56nm (二氧化钛) 、 l l lnm (氟化镁 [0069] 实施例 10: 与实施例 8基本相同, 不同之处在于将铬替换为钛, 其余条件与实 施例 8相同, 本发明设计的吸收器样品的吸收光谱如图 10所示, 平均吸收率 96.36 <¾以上, 各膜层所对应的膜层厚度由下至上分别为 200nm (钛) 、 36nm (锗) 、 29nm (钛) 、 34nm (锗) 、 18nm (钛) 、 27nm (锗) 、 38nm (硅) 、 57nm ( 二氧化钛) 、 l lOnm (氟化镁) 。
[0070] 实施例 11 : 与实施例 7基本相同, 不同之处在于将二氧化钛替换为氧化钽, 其 余条件与实施例 7相同, 本发明设计的吸收器样品的吸收光谱如图 11所示, 平均 吸收率 96.91<¾以上, 各膜层所对应的膜层厚度由下至上分别为 200nm (钛) 、 53 nm (锗) 、 20nm (钛) 、 33nm (锗) 、 35nm (硅) 、 60nm (氧化钽) 、 114η m (氟化镁) 。
[0071] 实施例 12: 与实施例 8基本相同, 不同之处在于将氟化镁替换为氟化钇钨, 其 余条件与实施例 8相同, 本发明设计的吸收器样品的吸收光谱如图 12所示, 平均 吸收率 95.28%以上, 各膜层所对应的膜层厚度由下至上分别为 200nm (铬) 、 74 nm (锗) 、 22nm (铬) 、 51nm (锗) 、 14nm (铬) 、 34nm (锗) 、 36nm (硅 ) 、 58nm (二氧化钛) 、 105nm (二氧化硅) 。

Claims

权利要求书
[权利要求 1] 一种可见-近红外波段的超宽带吸收器, 包括基底, 其特征在于, 所 述基底上依次设有底部金属吸收层、 顶部锗层以及三层宽波段减反膜 层; 所述三层宽波段减反膜层分别包括依次设置在顶部锗层上的底层 、 中间层和最外层, 底层、 中间层和最外层的折射率逐渐减小。
[权利要求 2] 根据权利要求 1所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述底部金属吸收层与所述顶部锗层之间设有锗层 /金属吸收层交 替膜层; 所述锗层 /金属吸收层交替膜层由一个或多个锗层 /金属吸收 层单元组成, 其中锗层靠近底部金属吸收层设置。
[权利要求 3] 根据权利要求 1或 2所述的可见-近红外波段的超宽带吸收器, 其特征 在于, 所述基底材料选自 K9、 熔融石英、 浮法玻璃、 硅、 砷化镓。
[权利要求 4] 根据权利要求 1所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述底部金属吸收层材料选自铬、 钛、 铱、 钨、 镍以及上述材料的 合金。
[权利要求 5] 根据权利要求 4所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述锗层 /金属吸收层交替膜层中金属吸收层材料与底部金属吸收 层材料相同。
[权利要求 6] 根据权利要求 1或 2所述的可见-近红外波段的超宽带吸收器, 其特征 在于, 所述底部金属吸收层的厚度大于等于 100nm。
[权利要求 7] 根据权利要求 6所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述底部金属吸收层的厚度为 100nm_500nm。
[权利要求 8] 根据权利要求 1或 2所述的可见-近红外波段的超宽带吸收器, 其特征 在于, 所述顶部锗层为 10nm_40nm。
[权利要求 9] 根据权利要求 2所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述锗层 /金属吸收层交替膜层中各层厚度为 10nm_80nm。
[权利要求 10] 根据权利要求 9所述的可见-近红外波段的超宽带吸收器, 其特征在于
, 所述锗层 /金属吸收层交替膜层中: 锗层的厚度为 33nm_80nm, 金 属吸收层的厚度为 10nm_40nm。
[权利要求 11] 根据权利要求 1或 2所述的可见-近红外波段的超宽带吸收器, 其特征 在于, 所述底层材料为硅; 所述中间层材料选自二氧化钛、 氧化铪、 氧化钽、 氮化硅; 所述最外层材料选自氟化镁、 二氧化硅、 氟化钇。
[权利要求 12] 根据权利要求 11所述的可见-近红外波段的超宽带吸收器, 其特征在 于, 所述底层厚度为 10nm_40nm; 所述中间层厚度为 30nm_80nm ; 所述最外层厚度为 70nm_130nm。
[权利要求 13] 根据权利要求 11所述的可见-近红外波段的超宽带吸收器, 其特征在 于, 所述底层材料为硅, 所述中间层材料为二氧化钛, 所述最外层材 料为氟化镁。
[权利要求 14] 根据权利要求 12所述的可见-近红外波段的超宽带吸收器, 其特征在 于, 所述底层材料为硅, 所述中间层材料为二氧化钛, 所述最外层材 料为氟化镁。
[权利要求 15] —种权利要求 1-14任一权利要求所述的可见-近红外波段的超宽带吸 收器的制备方法, 其特征在于, 包括如下步骤:
( 1) 根据所要求的吸收器带宽要求和吸收率要求, 通过优化设计得 出各层薄膜的厚度, 确定符合要求的膜系;
(2) 将基底放入丙酮中超声, 用乙醇清洗基底; 然后将基底放入乙 醇中超声, 用去离子水清洗基底; 最后将基底放入去离子水中超声, 接着用去离子水再次清洗基底;
(3) 采用真空镀膜依次沉积各膜层, 得到可见_近红外波段的超宽 带吸收器。
[权利要求 16] 根据权利要求 15所述的可见 -近红外波段的超宽带吸收器的制备方法 , 其特征在于, 步骤 (2) 中, 每次超声的吋间为 5-30min。
PCT/CN2015/090201 2015-08-04 2015-09-21 一种可见 - 近红外波段的超宽带吸收器及制备方法 WO2017020407A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/329,569 US10481305B2 (en) 2015-08-04 2015-09-21 Visible near-infrared ultra-broadband absorber and its preparation method

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201510469463.7 2015-08-04
CN201510469463.7A CN105161141B (zh) 2015-08-04 2015-08-04 可见‑近红外波段的超宽带吸收器及制备方法
CN201510470432.3 2015-08-04
CN201510470432.3A CN105022106B (zh) 2015-08-04 2015-08-04 一种可见‑近红外波段的超宽带吸收器及制备方法

Publications (1)

Publication Number Publication Date
WO2017020407A1 true WO2017020407A1 (zh) 2017-02-09

Family

ID=57942357

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/090201 WO2017020407A1 (zh) 2015-08-04 2015-09-21 一种可见 - 近红外波段的超宽带吸收器及制备方法

Country Status (2)

Country Link
US (1) US10481305B2 (zh)
WO (1) WO2017020407A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110389398A (zh) * 2019-07-25 2019-10-29 江西师范大学 一种超宽带完美吸收器及其制备方法
CN112764132A (zh) * 2021-01-27 2021-05-07 厦门大学 近红外超宽带完美反射与隧穿透射的全介质超材料
CN113009606A (zh) * 2021-02-04 2021-06-22 江西师范大学 一种五层纳米材料超宽带完美吸收器及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114442202B (zh) * 2017-08-31 2024-03-26 康宁股份有限公司 混合梯度干涉硬涂层
WO2019046762A1 (en) 2017-08-31 2019-03-07 Corning Incorporated HYBRID GRADIENT HARD INTERFERENCE COATINGS
CN112799159B (zh) * 2021-01-28 2022-08-05 浙江大学 一种紫外-可见-红外全波段吸收器及其制备方法
CN115657176B (zh) * 2022-11-10 2023-04-21 微集电科技(苏州)有限公司 一种镧系钙钛矿陶瓷基光吸收体及其应用与制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018132A2 (en) * 2000-08-30 2002-03-07 Cpfilms, Inc. Heat reflecting film with low visible refectance
CN102328475A (zh) * 2011-08-23 2012-01-25 北京天瑞星真空技术开发有限公司 一种具有SiO2和TiO2的双陶瓷结构高温太阳能选择性吸收涂层及其制备方法
CN102514280A (zh) * 2011-12-12 2012-06-27 武汉理工大学 一种太阳能选择性吸收涂层及其制备方法
CN103574949A (zh) * 2012-08-07 2014-02-12 益科博能源科技(上海)有限公司 选择性吸收腔式集热器
CN204345956U (zh) * 2014-11-14 2015-05-20 中国建筑材料科学研究总院 一种吸收边连续可调的太阳光谱选择性吸收涂层

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018132A2 (en) * 2000-08-30 2002-03-07 Cpfilms, Inc. Heat reflecting film with low visible refectance
CN102328475A (zh) * 2011-08-23 2012-01-25 北京天瑞星真空技术开发有限公司 一种具有SiO2和TiO2的双陶瓷结构高温太阳能选择性吸收涂层及其制备方法
CN102514280A (zh) * 2011-12-12 2012-06-27 武汉理工大学 一种太阳能选择性吸收涂层及其制备方法
CN103574949A (zh) * 2012-08-07 2014-02-12 益科博能源科技(上海)有限公司 选择性吸收腔式集热器
CN204345956U (zh) * 2014-11-14 2015-05-20 中国建筑材料科学研究总院 一种吸收边连续可调的太阳光谱选择性吸收涂层

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110389398A (zh) * 2019-07-25 2019-10-29 江西师范大学 一种超宽带完美吸收器及其制备方法
CN112764132A (zh) * 2021-01-27 2021-05-07 厦门大学 近红外超宽带完美反射与隧穿透射的全介质超材料
CN113009606A (zh) * 2021-02-04 2021-06-22 江西师范大学 一种五层纳米材料超宽带完美吸收器及其制备方法

Also Published As

Publication number Publication date
US20170242162A1 (en) 2017-08-24
US10481305B2 (en) 2019-11-19

Similar Documents

Publication Publication Date Title
WO2017020407A1 (zh) 一种可见 - 近红外波段的超宽带吸收器及制备方法
CN105022106B (zh) 一种可见‑近红外波段的超宽带吸收器及制备方法
US11088291B2 (en) Ultra-low reflectance broadband omni-directional anti-reflection coating
WO2020024566A1 (zh) 辐射制冷滤光片及其制备方法和应用
KR101194257B1 (ko) 광대역 반사방지 다층코팅을 갖는 태양전지용 투명 기판 및 그 제조방법
CN216624291U (zh) 太阳能电池正面钝化膜层
WO2024093105A1 (zh) 一种弱吸收低反清底色防蓝光树脂镜片及其制备方法
WO2022253082A1 (zh) 基于过渡金属膜层的可见光宽带完美吸收器及制备方法
CN113721310A (zh) 一种大角度宽波段减反射膜及其制作方法
CN105161141B (zh) 可见‑近红外波段的超宽带吸收器及制备方法
CN103066161B (zh) 一种太阳电池复合减反射膜的制备工艺
CN105585253A (zh) 减反膜玻璃及其制备方法
CN108515743B (zh) 一种金属/介质超宽带吸收薄膜及其制备方法
KR101194258B1 (ko) 광대역 반사방지 다층코팅을 갖는 태양전지용 투명 기판 및 그 제조방법
CN102681055B (zh) 一种硅铝合金/锆极紫外多层膜反射镜及其制备方法
Baryshnikova et al. Nanostructural antireflecting coatings: Classification analysis (A review)
CN110634966B (zh) 一种超薄太阳光黑硅吸波器及其制备方法
KR101456220B1 (ko) 반사방지 코팅층을 가지는 투명기판 및 그 제조방법
AU2012266168B2 (en) Process for producing an element for absorbing solar radiation for a thermal concentrating solar power plant
CN112201705A (zh) 一种硅基超宽谱光子吸收器及其制备方法
CN103048712B (zh) 一种极紫外多层膜反射镜及其制作方法
CN102520470A (zh) 一种硬铝/碳化硅极紫外多层膜反射镜及其制备方法
CN112799159B (zh) 一种紫外-可见-红外全波段吸收器及其制备方法
CN100345001C (zh) 一种具有低透射率、反射率和发射率的表面涂层
CN208315558U (zh) 一种减反射膜、太阳能电池及光伏组件

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 15329569

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15900178

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15900178

Country of ref document: EP

Kind code of ref document: A1