WO2023070731A1 - Metasurface sensor and preparation method therefor - Google Patents
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- WO2023070731A1 WO2023070731A1 PCT/CN2021/128961 CN2021128961W WO2023070731A1 WO 2023070731 A1 WO2023070731 A1 WO 2023070731A1 CN 2021128961 W CN2021128961 W CN 2021128961W WO 2023070731 A1 WO2023070731 A1 WO 2023070731A1
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000004642 Polyimide Substances 0.000 claims abstract description 34
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
- 241000255789 Bombyx mori Species 0.000 claims abstract description 17
- 108010013296 Sericins Proteins 0.000 claims abstract description 14
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- 229920002120 photoresistant polymer Polymers 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
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- 239000010975 amethyst Substances 0.000 claims description 10
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- 239000003292 glue Substances 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 6
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
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- 150000003949 imides Chemical class 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
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- the invention relates to the technical field of terahertz electromagnetic wave metasurface, and more specifically relates to a metasurface sensor and a preparation method thereof.
- Terahertz (THz) wave technology is developed later than microwave and infrared electromagnetic wave technology, and the THz frequency band is called the THz gap.
- Terahertz wave is an electromagnetic wave with a wavelength in the range of 30 ⁇ m to 3000 ⁇ m and a frequency of 0.1 to 10 THz, which is between the microwave and infrared frequency bands. Thanks to the low energy and high penetration of terahertz photons, it can resonate with biological macromolecules and has many characteristics such as biological fingerprints.
- Terahertz wave technology has developed rapidly in the new century and is listed as one of the top 10 new technologies. It has broad application prospects in biomedicine, communications, and public safety.
- terahertz sensing technology has unique advantages, and sensors based on terahertz electromagnetic waves have become a hot research topic. However, the existing terahertz wave sensors are difficult to achieve ultra-sensitive detection performance.
- the present invention provides a metasurface sensor, a device, a system and a preparation method thereof, which can realize ultrasensitive sensing performance by performing qualitative sensing detection on silkworm gum silk.
- silkworm sericin is covalently bonded to graphene, n-doped graphene, changing the Fermi level of graphene, causing a change in the dielectric environment, and then changing the phase of the terahertz wave.
- the terahertz wave After passing through the perovskite, this change can be effectively amplified, and finally ultra-sensitive qualitative detection can be achieved through this phase change.
- the present invention adopts the following technical solutions:
- a metasurface sensor comprising sequentially arranged:
- the surface of the graphene layer is covered with a silkworm glue layer
- the metal microresonator structure layer includes basic metal units.
- the metal microresonator structure layer under the excitation of terahertz photons, the metal microresonator structure layer produces an electromagnetically induced transparent response; - Doping, the covalent adsorption between the silkworm sericin and the graphene layer changes the electrical conductivity of the graphene and affects the dielectric environment of the phase of the terahertz wave.
- the intensity of the doping of the graphene is adjusted to change the magnitude of the electrical conductivity and the degree of the valence environment, and then generate an initial phase of the terahertz photon.
- the phase change signal is amplified to realize ultra-sensitive phase sensing.
- the basic metal unit includes a rectangular metal strip and two elliptical split resonant metal rings located on one side of the rectangular metal strip, and the openings of the two elliptical split resonant metal rings face each other without contact.
- the graphene layer is provided with a blank area not covered by graphene, and the blank area corresponds to the number and position of the basic metal units.
- the thickness of the polyimide layer is 1.5 ⁇ m; the thickness of the perovskite layer is 250 nm; the thickness of the metal microresonator structure layer is 200 nm; the thickness of the polyimide base layer is 10 ⁇ m; The thickness of the amethyst glass layer is 300 ⁇ m.
- the graphene layer is three layers.
- the present invention also provides a method for preparing a metasurface sensor as described in the above technical solution, comprising the following steps:
- the step (2) specifically includes the following steps:
- the step (5) further includes performing photolithography treatment on the graphene layer to obtain a graphene layer with blank areas.
- the present invention discloses a metasurface sensor and its preparation method, which has the following beneficial effects:
- the metasurface sensor of the present invention introduces a metal microresonator structure layer, perovskite and graphene structure layer separated by polyimide, which is similar to electromagnetically induced terahertz response.
- the strength of the doping of the graphene is strengthened to change the magnitude of the electrical conductivity and the degree of the valence environment, thereby producing an initial change to the phase of the terahertz photon, and the phase change passes through the perovskite, so that Phase change signal amplification for ultra-sensitive phase sensing.
- Fig. 1 is the unit structure schematic diagram of the metal microresonator structural layer of the metasurface sensor that the embodiment 1 of the present invention provides;
- Fig. 2 is a side view of the metasurface sensor structure provided by Embodiment 1 of the present invention.
- Fig. 3 is the top view of the graphene circular hole structure of the metasurface sensor provided by Embodiment 1 of the present invention.
- FIG. 4 is a schematic diagram of the metal layer unit structure array arrangement of the metasurface sensor structure provided by Embodiment 1 of the present invention.
- Fig. 5 is the phase spectrogram of the metasurface sensor device provided in Example 1 of the present invention under the action of silkworm colloid protein;
- Fig. 6 is the mechanism diagram of the metasurface sensing device provided by Embodiment 1 of the present invention.
- 1-rectangular metal strip 2-elliptical opening resonant metal ring, 3-terahertz wave, 4-graphene layer, 5-polyimide layer, 6-perovskite layer, 7-metal microresonator layer, 8- Polyimide base layer, 9-Amethyst layer, 10-Blank area.
- a kind of metasurface sensor comprises sequentially arranged:
- the surface of the graphene layer 4 is covered with a silkworm glue layer
- the metal microresonator structure layer 5 includes a basic metal unit.
- the basic metal unit includes a rectangular metal strip 1 and two elliptical opening resonant metal rings 2 on one side of the rectangular metal strip 1. The openings of the two elliptical opening resonant metal rings are opposite and No contact.
- the graphene layer 4 is provided with a blank area 10 not covered by graphene, and the blank area 10 corresponds to the number and position of the basic metal units.
- the graphene layer 4 in this embodiment is a three-layer graphene, which is used to implement the main functional device of the sensing performance.
- the graphene layer 4 is coupled with the terahertz wave, so that the initial terahertz wave
- the phase changes;
- the thickness of the polyimide layer 5 is 1.5 ⁇ m, which has the function of protecting the perovskite and making the perovskite stable.
- the thickness of the perovskite layer 6 is 250nm, which has the effect of amplifying the phase of the terahertz wave, so that the sensitivity of the phase-based sensor is greatly improved.
- the thickness of the metal microresonator structure layer is 200nm, which can be coupled with terahertz waves to generate an electromagnetically induced electromagnetic response, which is the source of the phase characteristic spectrum of the metasurface sensor, and makes the phase mutation occur, thereby enhancing the sensitivity of the metasurface sensor;
- the imide base layer is a flexible layer; the thickness of amethyst glass is 300 ⁇ m, which also plays an important role in the phase accumulation.
- the preparation method of above-mentioned metasurface sensor comprises the following steps:
- step (2) specifically includes the following steps:
- the metasurface sensor can be used as an ultrasensitive qualitative sensing biosensor, and its detection limit for sericin is 780 pg/mL.
- the graphene structure layer 4 and the metal microresonator structure layer 7 form a class of electromagnetically induced transparency with the terahertz electromagnetic wave; the terahertz electromagnetic wave 3 is transmitted to the graphene layer 3
- the conductivity of the graphene changes and the dielectric environment changes, which in turn causes the phase of the terahertz wave to change.
- the terahertz wave passes through the perovskite, this The change can be effectively amplified, and finally ultra-sensitive qualitative detection can be achieved through this phase change.
- each embodiment in this specification is described in a progressive manner, each embodiment focuses on the difference from other embodiments, and the same and similar parts of each embodiment can be referred to each other.
- the description is relatively simple, and for the related information, please refer to the description of the method part.
Abstract
A metasurface sensor and a preparation method therefor, which relate to the technical field of terahertz electromagnetic-wave metasurfaces. The metasurface sensor comprises a graphene layer, a polyimide layer, a perovskite layer, a metal micro-resonator structure layer, a polyimide substrate layer and a fluoritum glass layer. The Fermi level of graphene is changed by means of silkworm sericin, which causes a change in a dielectric environment, such that the phase of a terahertz wave is changed; after the terahertz wave penetrates perovskite, this change can be effectively amplified; and finally, ultra-sensitive qualitative detection is realized by means of this phase change.
Description
本发明涉及太赫兹电磁波超表面技术领域，更具体的说是涉及一种超表面传感器及其制备方法。The invention relates to the technical field of terahertz electromagnetic wave metasurface, and more specifically relates to a metasurface sensor and a preparation method thereof.
太赫兹(THz)波普技术比微波和红外电磁波技术发展晚，太赫兹频带被称为THz空隙。太赫兹波是一种波长在30μm到3000μm范围内，频率在0.1到10THz的电磁波，介于微波与红外线频带之间。得益于太赫兹的光子能量很低、穿透性很高，能与生物大分子发生共振，具有生物指纹图谱等众多特征。太赫兹波普技术在新世纪迅速发展，被列为10大新型技术之一，在生物医疗、通讯、公共安全等方面存在广泛的应用前景。特别地，太赫兹传感技术具有独特的优势，基于太赫兹电磁波的传感器成为目前科研的热点。而目前现有的太赫兹波传感器难以实现超灵敏探测性能。Terahertz (THz) wave technology is developed later than microwave and infrared electromagnetic wave technology, and the THz frequency band is called the THz gap. Terahertz wave is an electromagnetic wave with a wavelength in the range of 30 μm to 3000 μm and a frequency of 0.1 to 10 THz, which is between the microwave and infrared frequency bands. Thanks to the low energy and high penetration of terahertz photons, it can resonate with biological macromolecules and has many characteristics such as biological fingerprints. Terahertz wave technology has developed rapidly in the new century and is listed as one of the top 10 new technologies. It has broad application prospects in biomedicine, communications, and public safety. In particular, terahertz sensing technology has unique advantages, and sensors based on terahertz electromagnetic waves have become a hot research topic. However, the existing terahertz wave sensors are difficult to achieve ultra-sensitive detection performance.
因此，如何提供一种新型的太赫兹波传感器是本领域技术人员亟待解决的问题。Therefore, how to provide a novel terahertz wave sensor is an urgent problem to be solved by those skilled in the art.
发明内容Contents of the invention
有鉴于此，本发明提供了一种超表面传感器、装置、***及其制备方法，通过对家蚕胶丝进行定性传感检测，实现超灵敏传感性能。首先，家蚕丝胶与石墨烯发生共价结合，对石墨烯n掺杂，改变石墨烯的费米能级，引起介电环境的改变，进而使得太赫兹波的相位发生变化，当太赫兹波穿过钙钛矿 后，这种变化可以被有效的放大，最后通过这种相位的变化实现超灵敏定性检测。In view of this, the present invention provides a metasurface sensor, a device, a system and a preparation method thereof, which can realize ultrasensitive sensing performance by performing qualitative sensing detection on silkworm gum silk. First, silkworm sericin is covalently bonded to graphene, n-doped graphene, changing the Fermi level of graphene, causing a change in the dielectric environment, and then changing the phase of the terahertz wave. When the terahertz wave After passing through the perovskite, this change can be effectively amplified, and finally ultra-sensitive qualitative detection can be achieved through this phase change.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种超表面传感器，包括依次设置的：A metasurface sensor comprising sequentially arranged:
石墨烯层、聚酰亚胺层、钙钛矿层、金属微谐振器结构层、聚酰亚胺基底层、紫石英玻璃层；Graphene layer, polyimide layer, perovskite layer, metal microresonator structure layer, polyimide base layer, amethyst glass layer;
所述石墨烯层表面覆盖有家蚕胶丝层；The surface of the graphene layer is covered with a silkworm glue layer;
所述金属微谐振器结构层包括基本金属单元。The metal microresonator structure layer includes basic metal units.
上述技术方案的原理是：在太赫兹光子激发下，所述金属微谐振器结构层产生类电磁诱导透明响应；在家蚕胶丝与石墨烯层产生共价吸附时，所述石墨烯层被n-掺杂，所述家蚕丝胶与石墨烯层之间的共价吸附作用，使得石墨烯的电导率改变，对太赫兹波的相位的介电环境产生影响。在工作状态下，通过调节家蚕胶丝的浓度参数，调节所述石墨烯的参杂的强度，以改变所述电导率的大小与价电环境的程度，进而对太赫兹光子的相位产生初始的改变，所述太赫兹波经过钙钛矿后，使得相位变化信号放大，实现超灵敏的相位传感。The principle of the above technical solution is: under the excitation of terahertz photons, the metal microresonator structure layer produces an electromagnetically induced transparent response; - Doping, the covalent adsorption between the silkworm sericin and the graphene layer changes the electrical conductivity of the graphene and affects the dielectric environment of the phase of the terahertz wave. In the working state, by adjusting the concentration parameters of the silkworm gum silk, the intensity of the doping of the graphene is adjusted to change the magnitude of the electrical conductivity and the degree of the valence environment, and then generate an initial phase of the terahertz photon. After the terahertz wave passes through the perovskite, the phase change signal is amplified to realize ultra-sensitive phase sensing.
优选的，所述基本金属单元为多个且呈阵列式周期性排列。Preferably, there are multiple basic metal units arranged periodically in an array.
优选的，所述基本金属单元包括一个长方形金属条和位于所述长方形金属条一侧的两个椭圆开口谐振金属环，两个所述椭圆开口谐振金属环开口相对且无接触。Preferably, the basic metal unit includes a rectangular metal strip and two elliptical split resonant metal rings located on one side of the rectangular metal strip, and the openings of the two elliptical split resonant metal rings face each other without contact.
优选的，所述石墨烯层设置有无石墨烯覆盖的空白区域，所述空白区域与所述基本金属单元数量及位置相对应。Preferably, the graphene layer is provided with a blank area not covered by graphene, and the blank area corresponds to the number and position of the basic metal units.
优选的，所述聚酰亚胺层的厚度为1.5μm；所述钙钛矿层厚度为250nm；所述金属微谐振器结构层的厚度200nm；所述聚酰亚胺基底层的厚度为10μm；所述紫石英玻璃层的厚度为300μm。Preferably, the thickness of the polyimide layer is 1.5 μm; the thickness of the perovskite layer is 250 nm; the thickness of the metal microresonator structure layer is 200 nm; the thickness of the polyimide base layer is 10 μm; The thickness of the amethyst glass layer is 300 μm.
优选的，所述石墨烯层为三层。Preferably, the graphene layer is three layers.
本发明还提供了一种如上技术方案所述的超表面传感器的制备方法，包括以下步骤：The present invention also provides a method for preparing a metasurface sensor as described in the above technical solution, comprising the following steps:
(1)通过甩胶工艺，在紫石英玻璃层上旋涂聚酰亚胺基底层；(1) Spin-coat the polyimide base layer on the amethyst glass layer by spinning the glue process;
(2)通过光刻工艺，在所述聚酰亚胺基底层的正面制备金属微谐振器层；(2) preparing a metal microresonator layer on the front side of the polyimide base layer by photolithography;
(3)将钙钛矿旋涂在所述金属微谐振器层上；(3) Perovskite is spin-coated on the metal microresonator layer;
(4)通过甩胶工艺，在所述钙钛矿层上旋涂聚酰亚胺层；(4) Spin-coat polyimide layer on the perovskite layer by spinning glue process;
(5)利用化学气相沉积法制备石墨烯层，然后将所述石墨烯层转移至所述聚酰亚胺层上；(5) Utilize chemical vapor deposition to prepare a graphene layer, and then transfer the graphene layer to the polyimide layer;
(6)在所述石墨烯层表面滴加家蚕丝胶得到家蚕丝胶层。(6) adding silkworm sericin dropwise on the surface of the graphene layer to obtain a silkworm sericin layer.
优选的，步骤(2)中具体包括以下步骤：Preferably, the step (2) specifically includes the following steps:
(2.1)在所述聚酰亚胺基底层旋涂光刻胶；(2.1) spin coating photoresist on the polyimide base layer;
(2.2)在所述聚酰亚胺基底层上放置光刻板；(2.2) placing a photoresist plate on the polyimide base layer;
(2.3)将所述光刻胶进行曝光和显影处理；(2.3) exposing and developing the photoresist;
(2.4)利用测控溅射工艺，在所述未被光刻胶覆盖区域上生长金属微谐振器结构层，并剥离所述光刻胶。(2.4) Using a measurement and control sputtering process, growing a metal microresonator structure layer on the region not covered by the photoresist, and stripping the photoresist.
优选的，步骤(5)中还包括对所述石墨烯层进行光刻处理，得到具有空白区域的石墨烯层。Preferably, the step (5) further includes performing photolithography treatment on the graphene layer to obtain a graphene layer with blank areas.
经由上述的技术方案可知，与现有技术相比，本发明公开提供了一种超表面传感器及其制备方法，具有如下有益效果：It can be seen from the above technical solutions that, compared with the prior art, the present invention discloses a metasurface sensor and its preparation method, which has the following beneficial effects:
本发明的超表面传感器引入了类电磁诱导太赫兹响应的金属微谐振器结构层、钙钛矿和石墨烯结构层由聚酰亚胺隔开的设计方案，在家蚕丝胶的参杂作用下，所述石墨烯的参杂的强度被加强，以改变所述电导率的大小与价电环境的程度，进而对太赫兹光子的相位产生初始的改变，所述相位变化经过钙钛矿后，使得相位变化信号放大，实现超灵敏的相位传感。The metasurface sensor of the present invention introduces a metal microresonator structure layer, perovskite and graphene structure layer separated by polyimide, which is similar to electromagnetically induced terahertz response. Under the doping effect of silkworm sericin, The strength of the doping of the graphene is strengthened to change the magnitude of the electrical conductivity and the degree of the valence environment, thereby producing an initial change to the phase of the terahertz photon, and the phase change passes through the perovskite, so that Phase change signal amplification for ultra-sensitive phase sensing.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can also obtain other drawings according to the provided drawings without creative work.
图1为本发明实施例1提供的超表面传感器的金属微谐振器结构层的单元结构示意图；Fig. 1 is the unit structure schematic diagram of the metal microresonator structural layer of the metasurface sensor that the embodiment 1 of the present invention provides;
图2为本发明实施例1提供的超表面传感器结构侧视图；Fig. 2 is a side view of the metasurface sensor structure provided by Embodiment 1 of the present invention;
图3为本发明实施例1提供的超表面传感器的石墨烯圆孔结构俯视图；Fig. 3 is the top view of the graphene circular hole structure of the metasurface sensor provided by Embodiment 1 of the present invention;
图4为本发明实施例1提供的超表面传感器结构的金属层单元结构阵列式排列的示意图；4 is a schematic diagram of the metal layer unit structure array arrangement of the metasurface sensor structure provided by Embodiment 1 of the present invention;
图5为本发明实施例1提供的超表面传感器装置在家蚕胶丝蛋白作用下的相位谱图；Fig. 5 is the phase spectrogram of the metasurface sensor device provided in Example 1 of the present invention under the action of silkworm colloid protein;
图6为本发明实施例1提供的超表面传感装置机理图；Fig. 6 is the mechanism diagram of the metasurface sensing device provided by Embodiment 1 of the present invention;
其中：in:
1-长方形金属条、2-椭圆开口谐振金属环、3-太赫兹波、4-石墨烯层、5-聚酰亚胺层、6-钙钛矿层、7-金属微谐振器层、8-聚酰亚胺基底层、9-紫石英层，10-空白区域。1-rectangular metal strip, 2-elliptical opening resonant metal ring, 3-terahertz wave, 4-graphene layer, 5-polyimide layer, 6-perovskite layer, 7-metal microresonator layer, 8- Polyimide base layer, 9-Amethyst layer, 10-Blank area.
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
如附图2所示，一种超表面传感器，包括依次设置的：As shown in accompanying drawing 2, a kind of metasurface sensor comprises sequentially arranged:
石墨烯层4、聚酰亚胺层3、钙钛矿层4、金属微谐振器结构层5、聚酰亚胺基底层6、紫石英玻璃层7； Graphene layer 4, polyimide layer 3, perovskite layer 4, metal microresonator structure layer 5, polyimide base layer 6, amethyst glass layer 7;
石墨烯层4表面覆盖有家蚕胶丝层；The surface of the graphene layer 4 is covered with a silkworm glue layer;
金属微谐振器结构层5包括基本金属单元，基本金属单元包括一个长方形金属条1和位于长方形金属条1一侧的两个椭圆开口谐振金属环2，两个椭圆开口谐振金属环2开口相对且无接触。The metal microresonator structure layer 5 includes a basic metal unit. The basic metal unit includes a rectangular metal strip 1 and two elliptical opening resonant metal rings 2 on one side of the rectangular metal strip 1. The openings of the two elliptical opening resonant metal rings are opposite and No contact.
如附图4所示，当基本金属单元为多个时，沿着x和y方向周期性排列。As shown in Fig. 4, when there are multiple basic metal units, they are arranged periodically along the x and y directions.
如附图3所示，石墨烯层4设置有无石墨烯覆盖的空白区域10，空白区域10与基本金属单元数量及位置相对应。As shown in FIG. 3 , the graphene layer 4 is provided with a blank area 10 not covered by graphene, and the blank area 10 corresponds to the number and position of the basic metal units.
作为一种优选的实施方式，本实施例中石墨烯层4为三层石墨烯，用于实施传感性能的主要功能器件，石墨烯层4与太赫兹波发生耦合，使得太赫兹波的初始相位发生变化；聚酰亚胺层5的厚度1.5μm，具有保护钙钛矿的作用，使得钙钛矿稳定。钙钛矿层6的厚度为250nm，具有放大太赫兹波相位的作用，使得基于相位的传感器的灵敏度大幅提高。金属微谐振器结构层的厚度为200nm，能够与太赫兹波耦合产生类电磁诱导电磁响应，是超表面传感器的相位特征谱来源，并且使得相位突变发生，增强所述超表面传感器的灵敏度；聚酰亚胺基底层为柔性层；紫石英玻璃成的厚度为300μm，也对相位积累起到重要的作用。As a preferred embodiment, the graphene layer 4 in this embodiment is a three-layer graphene, which is used to implement the main functional device of the sensing performance. The graphene layer 4 is coupled with the terahertz wave, so that the initial terahertz wave The phase changes; the thickness of the polyimide layer 5 is 1.5 μm, which has the function of protecting the perovskite and making the perovskite stable. The thickness of the perovskite layer 6 is 250nm, which has the effect of amplifying the phase of the terahertz wave, so that the sensitivity of the phase-based sensor is greatly improved. The thickness of the metal microresonator structure layer is 200nm, which can be coupled with terahertz waves to generate an electromagnetically induced electromagnetic response, which is the source of the phase characteristic spectrum of the metasurface sensor, and makes the phase mutation occur, thereby enhancing the sensitivity of the metasurface sensor; The imide base layer is a flexible layer; the thickness of amethyst glass is 300 μm, which also plays an important role in the phase accumulation.
上述超表面传感器的制备方法，包括以下步骤：The preparation method of above-mentioned metasurface sensor, comprises the following steps:
(1)通过甩胶工艺，在紫石英玻璃层上旋涂聚酰亚胺基底层；(1) Spin-coat the polyimide base layer on the amethyst glass layer by spinning the glue process;
(2)通过光刻工艺，在所述聚酰亚胺基底层的正面制备金属微谐振器层；(2) preparing a metal microresonator layer on the front side of the polyimide base layer by photolithography;
(3)将钙钛矿旋涂在所述金属微谐振器层上；(3) Perovskite is spin-coated on the metal microresonator layer;
(4)通过甩胶工艺，在所述钙钛矿层上旋涂聚酰亚胺层；(4) Spin-coat polyimide layer on the perovskite layer by spinning glue process;
(5)利用化学气相沉积法制备石墨烯层，然后将所述石墨烯层转移至所述聚酰亚胺层上；(5) Utilize chemical vapor deposition to prepare a graphene layer, and then transfer the graphene layer to the polyimide layer;
(6)利用光刻工艺，对所述石墨烯层进行空白区域结构的制备；(6) using a photolithography process to prepare a blank region structure for the graphene layer;
(7)在石墨烯层表面旋涂家蚕丝胶层。(7) Spin-coat the silkworm sericin layer on the surface of the graphene layer.
其中，步骤(2)中具体包括以下步骤：Wherein, the step (2) specifically includes the following steps:
(2.1)在所述聚酰亚胺基底层旋涂光刻胶；(2.1) spin coating photoresist on the polyimide base layer;
(2.2)在所述聚酰亚胺基底层上放置光刻板；(2.2) placing a photoresist plate on the polyimide base layer;
(2.3)将所述光刻胶进行曝光和显影处理；(2.3) exposing and developing the photoresist;
(2.4)利用测控溅射工艺，在所述未被光刻胶覆盖区域上生长金属微谐振器结构层，并剥离所述光刻胶。(2.4) Using a measurement and control sputtering process, growing a metal microresonator structure layer on the region not covered by the photoresist, and stripping the photoresist.
如图5所示，超表面传感器在家蚕胶丝蛋白作用下的相位谱图，由图5可知，为超表面传感器结构检测丝胶的实验测试透射谱，检测浓度范围为780pg/mL至1.25μg/mL。从图中可以看出，与裸所述超表面传感器样品相比，含有丝胶的所述超表面传感器样品的相位谱透明度窗口显着增强，因而所述超表面传感器可用作蛋白质的定性传感。为了更清楚地阐明传感性能，定义ΔP/P＝(P
protein-P
bare)/P
bare×100％，其中P
protein(P
bare)为有(无)丝胶时透明窗口处的相位值。从图5可看出，超表面传感器在检测1.25μg/mL(最高浓度)浓度的丝胶时ΔP/P为6.7％，略高于1.17ng/mL浓度，其ΔP/P＝5.0％，但远低于780pg/mL(最低浓度)的ΔP/P＝21％。基于上述结果可以得知，超表面传感器能够作为一种超灵敏的定性传感生物传感器，其检测丝胶的检测限为780pg/mL。
As shown in Figure 5, the phase spectrum of the metasurface sensor under the action of silkworm colloid protein, as can be seen from Figure 5, is the experimental test transmission spectrum of the metasurface sensor structure to detect sericin, and the detection concentration range is 780pg/mL to 1.25μg /mL. It can be seen from the figure that compared with the bare metasurface sensor sample, the phase spectrum transparency window of the metasurface sensor sample containing sericin is significantly enhanced, so the metasurface sensor can be used as a qualitative sensor for protein. feel. In order to clarify the sensing performance more clearly, define ΔP/P=(P protein -P bare )/P bare ×100%, where P protein (P bare ) is the phase value at the transparent window with (without) sericin. It can be seen from Figure 5 that the ΔP/P of the metasurface sensor is 6.7% when detecting sericin at a concentration of 1.25 μg/mL (the highest concentration), which is slightly higher than the concentration of 1.17ng/mL, and its ΔP/P=5.0%, but ΔP/P = 21% well below 780 pg/mL (lowest concentration). Based on the above results, it can be known that the metasurface sensor can be used as an ultrasensitive qualitative sensing biosensor, and its detection limit for sericin is 780 pg/mL.
如图6所示，为超表面传感材料吸收装置机理；当太赫兹波3通过石墨烯层4时，由于石墨烯中的生物掺杂，
变为
其中
是太赫兹波的初始相位，
是电导率变化引起的相位变化。太赫兹波3通过钙钛矿层6后，
变为
其中ω为频率，c为光速，n为钙钛矿的折射率，l 为钙钛矿的厚度。由于钙钛矿具有相对较高的折射率，图6显示较小的
可以实现较大的相位变化，并且
的变化随着
的增加而增加。因此，钙钛矿层6在基于相位的传感中起着重要作用。
As shown in Figure 6, it is the mechanism of the metasurface sensing material absorption device; when the terahertz wave 3 passes through the graphene layer 4, due to the biological doping in the graphene, becomes in is the initial phase of the terahertz wave, is the phase change caused by the change in conductivity. After the terahertz wave 3 passes through the perovskite layer 6, becomes where ω is the frequency, c is the speed of light, n is the refractive index of the perovskite, and l is the thickness of the perovskite. Due to the relatively high refractive index of perovskite, Fig. 6 shows a small large phase changes can be achieved, and change with increased by the increase. Therefore, the perovskite layer 6 plays an important role in phase-based sensing.
本实施例的超表面传感器在在家蚕胶丝蛋白作用下，石墨烯结构层4和金属微谐振器结构层7与太赫兹电磁波形成类电磁诱导透明；在太赫兹电磁波3传递至石墨烯层3时，在石墨烯层3发生n参杂，使得石墨烯的电导率发生改变引起介电环境的改变，进而使得太赫兹波的相位发生变化，当太赫兹波穿过钙钛矿后，这种变化可以被有效的放大，最后通过这种相位的变化实现超灵敏定性检测。In the metasurface sensor of this embodiment, under the action of silkworm colloid protein, the graphene structure layer 4 and the metal microresonator structure layer 7 form a class of electromagnetically induced transparency with the terahertz electromagnetic wave; the terahertz electromagnetic wave 3 is transmitted to the graphene layer 3 When n doping occurs in the graphene layer 3, the conductivity of the graphene changes and the dielectric environment changes, which in turn causes the phase of the terahertz wave to change. When the terahertz wave passes through the perovskite, this The change can be effectively amplified, and finally ultra-sensitive qualitative detection can be achieved through this phase change.
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。Each embodiment in this specification is described in a progressive manner, each embodiment focuses on the difference from other embodiments, and the same and similar parts of each embodiment can be referred to each other. As for the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and for the related information, please refer to the description of the method part.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
- 一种超表面传感器，其特征在于，包括依次设置的：A metasurface sensor is characterized in that, comprising sequentially arranged:石墨烯层、聚酰亚胺层、钙钛矿层、金属微谐振器结构层、聚酰亚胺基底层、紫石英玻璃层；Graphene layer, polyimide layer, perovskite layer, metal microresonator structure layer, polyimide base layer, amethyst glass layer;所述石墨烯层表面覆盖有家蚕胶丝层；The surface of the graphene layer is covered with a silkworm glue layer;所述金属微谐振器结构层包括基本金属单元。The metal microresonator structure layer includes basic metal units.
- 根据权利要求1所述的一种超表面传感器，其特征在于，所述基本金属单元为多个且呈阵列式周期性排列。The metasurface sensor according to claim 1, wherein the basic metal units are multiple and arranged periodically in an array.
- 根据权利要求1或2所述的一种超表面传感器，其特征在于，所述基本金属单元包括一个长方形金属条和位于所述长方形金属条一侧的两个椭圆开口谐振金属环，两个所述椭圆开口谐振金属环开口相对且无接触。A kind of metasurface sensor according to claim 1 or 2, it is characterized in that, described basic metal unit comprises a rectangular metal strip and two ellipse opening resonant metal rings that are positioned at one side of described rectangular metal strip, two described The openings of the elliptical opening resonant metal ring are opposite to each other without contact.
- 根据权利要求1或2所述的一种超表面传感器，其特征在于，所述石墨烯层设置有无石墨烯覆盖的空白区域，所述空白区域与所述基本金属单元数量及位置相对应。A metasurface sensor according to claim 1 or 2, wherein the graphene layer is provided with a blank area without graphene coverage, and the blank area corresponds to the number and position of the basic metal units.
- 根据权利要求1所述的一种超表面传感器，其特征在于，所述聚酰亚胺层的厚度为1.5μm；所述钙钛矿层厚度为250nm；所述金属微谐振器结构层的厚度200nm；所述聚酰亚胺基底层的厚度为10μm；所述紫石英玻璃层的厚度为300μm。A kind of metasurface sensor according to claim 1, is characterized in that, the thickness of described polyimide layer is 1.5 μ m; The thickness of described perovskite layer is 250nm; The thickness 200nm of described metal microresonator structure layer ; The thickness of the polyimide base layer is 10 μm; the thickness of the amethyst glass layer is 300 μm.
- 根据权利要求1所述的一种超表面传感器，其特征在于，所述石墨烯层为三层。A kind of metasurface sensor according to claim 1, is characterized in that, described graphene layer is three layers.
- 一种权利要求1-6任一项所述的超表面传感器的制备方法，其特征在于，包括以下步骤：A preparation method of the metasurface sensor described in any one of claims 1-6, characterized in that, comprising the following steps:(1)通过甩胶工艺，在紫石英玻璃层上旋涂聚酰亚胺基底层；(1) Spin-coat the polyimide base layer on the amethyst glass layer by spinning the glue process;(2)通过光刻工艺，在所述聚酰亚胺基底层的正面制备金属微谐振器层；(2) preparing a metal microresonator layer on the front side of the polyimide base layer by photolithography;(3)将钙钛矿旋涂在所述金属微谐振器层上；(3) Perovskite is spin-coated on the metal microresonator layer;(4)通过甩胶工艺，在所述钙钛矿层上旋涂聚酰亚胺层；(4) Spin-coat polyimide layer on the perovskite layer by spinning glue process;(5)利用化学气相沉积法制备石墨烯层，然后将所述石墨烯层转移至所述聚酰亚胺层上；(5) Utilize chemical vapor deposition to prepare a graphene layer, and then transfer the graphene layer to the polyimide layer;(6)在所述石墨烯层表面滴加家蚕丝胶，得到家蚕丝胶层。(6) Add silkworm sericin dropwise on the surface of the graphene layer to obtain a silkworm sericin layer.
- 根据权利要求7所述的一种超表面传感器的制备方法，其特征在于，步骤(2)中具体包括以下步骤：The preparation method of a kind of metasurface sensor according to claim 7, is characterized in that, specifically comprises the following steps in step (2):(2.1)在所述聚酰亚胺基底层旋涂光刻胶；(2.1) spin coating photoresist on the polyimide base layer;(2.2)在所述聚酰亚胺基底层上放置光刻板；(2.2) placing a photoresist plate on the polyimide base layer;(2.3)将所述光刻胶进行曝光和显影处理；(2.3) exposing and developing the photoresist;(2.4)利用测控溅射工艺，在所述未被光刻胶覆盖区域上生长金属微谐振器结构层，并剥离所述光刻胶。(2.4) Using a measurement and control sputtering process, growing a metal microresonator structure layer on the region not covered by the photoresist, and stripping the photoresist.
- 根据权利要求7所述的一种超表面传感器的制备方法，其特征在于，步骤(5)中还包括对所述石墨烯层进行光刻处理，得到具有空白区域的石墨烯层。The preparation method of a kind of metasurface sensor according to claim 7, is characterized in that, in step (5), also comprises carrying out photolithographic treatment to described graphene layer, obtains the graphene layer with blank area.
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| CN111766221A (en) * | 2020-07-17 | 2020-10-13 | 南昌大学 | Terahertz super-surface biosensor based on Fano resonance and preparation method thereof |
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