CN113249700B - Metamaterial with infrared high refractive index and low dispersion and preparation method thereof - Google Patents

Metamaterial with infrared high refractive index and low dispersion and preparation method thereof Download PDF

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CN113249700B
CN113249700B CN202110591053.5A CN202110591053A CN113249700B CN 113249700 B CN113249700 B CN 113249700B CN 202110591053 A CN202110591053 A CN 202110591053A CN 113249700 B CN113249700 B CN 113249700B
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高俊华
王鑫鹏
曹鸿涛
胡海搏
汪湾
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a metamaterial with infrared high refractive index and low dispersion, which comprises a metal nanowire array and a dielectric layer, wherein the metal nanowire array is vertically embedded into the dielectric layer; the metal nanowire array consists of a plurality of metal nanowires, the diameter of each metal nanowire is not less than 2nm, the length is the same as the thickness of the dielectric layer, and the distance between the metal nanowires is 1-6nm; the volume percentage of the metal nano wires in the metamaterial is 5-50%; the dielectric layer is a semiconductor or ceramic dielectric. The invention also discloses a preparation method of the metamaterial with the infrared high refractive index and low dispersion, which comprises the following steps: pretreating a substrate; and selecting metal, ceramic or semiconductor as co-sputtering targets respectively, performing multi-target magnetron co-sputtering, and simultaneously applying plasma bombardment assistance to prepare the metal nanowire array-ceramic or semiconductor composite layer metamaterial. The preparation method is simple and efficient to operate.

Description

Metamaterial with infrared high refractive index and low dispersion and preparation method thereof
Technical Field
The invention belongs to the field of optical films (nano materials), and particularly relates to a metamaterial with infrared high refractive index and low dispersion and a preparation method thereof.
Background
The refractive index is closely related to the electromagnetic property of the material, and particularly for high-refractive-index materials, the material has key effects in the aspects of miniaturization of devices, imaging resolution improvement and the like, however, the refractive index of the natural transparent material is generally limited to be within 4 in the range from visible light to near infrared, and the application of the material in the novel optical fields such as nano imaging, integrated optics and the like is greatly limited. On the other hand, the refractive index of the common material can change along with the different wavelengths of the incident light, and the generated chromatic dispersion can cause residual chromatic aberration problem which is difficult to eliminate, so that the design of optical elements such as lenses and the like is influenced very adversely. Therefore, obtaining a material with high refractive index and low dispersion has urgent demands for nano-optics, super-resolution imaging, miniaturization of optical components and the like.
Since the beginning of the twenty-first century, the rapid development of metamaterials has given researchers a new idea of freely regulating the optical properties of materials, becoming the best way to cross refractive index limitations. Among them, the key to obtain a high refractive index is to increase the dielectric constant epsilon and the magnetic permeability mu and to suppress the diamagnetic response of the material. The metamaterial is an artificial periodic structure with a sub-wavelength scale, the refractive index of the material can be conveniently regulated and controlled, and meanwhile, outside a resonance wave band, the scale of the metamaterial unit is far smaller than the skin depth of metal, so that the absorption of the metamaterial at the moment is negligible, and the chromatic dispersion effect is greatly reduced. By densely arranging the periodic I-shaped metal arrays (the two metal planes are connected through a straight line passing through the mass center), the high refractive index characteristic can be obtained in the terahertz wave band. The principle is that when electromagnetic wave interacts with the periodic structure, equal amount of charges with different polarities are excited on the surface of the adjacent unit structure, the capacitive coupling effect is induced, and the local polarization intensity P (epsilon= 1+P/epsilon) is enhanced 0 E) And finally, the dielectric constant of the material is improved. On the other hand, it is necessary to suppress the diamagnetic effect by the cyclic displacement current in the cell structure by reducing the thickness in a certain dimension so that the magnetic permeability μ can be made as close to 1 as possible. Obtaining a high refractive index metamaterial needs to simultaneously consider the strong capacitive coupling between units and the optimization of the unit structure, and challenges are brought to large-area controllable preparation of the metamaterial.
Chinese patent document publication No. CN209249703U discloses a microwave high refractive index metamaterial based on a ring structure and a duplex-type structure. The cell described in this patent consists of two vertically distributed i-shaped copper metals separated by a dielectric layer. The value of the calculated equivalent refractive index is about 27 in the frequency band of 6.55 GHz-10.32 GHz through numerical simulation and electromagnetic parameter extraction, and the equivalent refractive index shows low dispersion. Chinese patent publication No. CN103941316a discloses a polarization insensitive terahertz high refractive index metamaterial and a preparation method thereof. The patent utilizes electron beam vacuum evaporation and photolithography to prepare metamaterial structural units which are two I-shaped metal materials embedded in a dielectric material and vertically and symmetrically arranged. The units are periodically arranged on a plane to form a single-layer two-dimensional metamaterial. The refractive index peak value of the obtained metamaterial is 60 at 1THz, and the refractive index is kept at about 20 when the refractive index is higher than 2 THz. Although the I-shaped metamaterial can obtain a very high refractive index in microwave and terahertz wave bands, the I-shaped metamaterial is difficult to adapt to shorter wavelengths such as visible light, near infrared light and the like, mainly because the size of a structural unit is too large, and meanwhile, a nano-scale gap is difficult to realize by a photoetching process from top to bottom, and the expansion of the high refractive index characteristic of the metamaterial to the visible light and near infrared wave bands still faces a great obstacle.
In recent years, a metal nano cube or particle metamaterial array is prepared by a colloid solution self-assembly method, and research on high refractive index of materials in high-frequency visible light and infrared bands (Huh J H, kim K, et al, amplifying colloidal metamaterials for achieving unnatural optical refractions.Adv.Mater.,2020,32:2001806;Doyle D,Charipar N,Argyropoulos C,et al.Tunable Subnanometer Gap Plasmonic Metasurfaces.ACS Photonics,2017,5:1012) is achieved. The method can realize the particle gap of nanometer level, greatly enhance the capacitive coupling effect among metal nanometer units, and the obtained metamaterial structure has an effective refractive index maximum value of more than 6, and has middle far infrared more than 4.3 and maintains low dispersion characteristic which is higher than that of infrared high refractive index material germanium by 4.0. The large-scale preparation is difficult and the process is complex.
Therefore, how to simply and efficiently obtain the high-refractive index and low-dispersion metamaterial in the high frequency band (visible-infrared) becomes a problem to be solved at present.
Disclosure of Invention
The invention provides a metamaterial with infrared high refractive index and low dispersion, and also provides a preparation method of the metamaterial with infrared high refractive index and low dispersion.
A metamaterial with infrared high refractive index and low dispersion comprises a metal nanowire array and a dielectric layer, wherein the metal nanowire array is vertically embedded into the dielectric layer;
the metal nanowire array consists of a plurality of metal nanowires, the diameter of each metal nanowire is not smaller than 2nm, the length is the same as the thickness of a dielectric layer, and the distance between the metal nanowires is 1-6nm;
the dielectric layer is a semiconductor or ceramic transparent medium;
the volume percentage of the metal nano wire in the metamaterial is 5-50%.
The diameter, the length and the distance between the metal nanowires in the metamaterial can be regulated and controlled by adjusting experimental conditions. From the theory of effective media, the optical properties of the composite structure are the average effect of each set of microscopic media. For the electromagnetic wave which is incident along the normal, the polarization direction is perpendicular to the axial direction of the nanometer line, the isotropy property is shown, the distance between the metal nanometer lines is proper, the stronger capacitive coupling effect is generated, the higher polarization intensity is obtained, and the improvement of the dielectric constant of the material is obvious. Meanwhile, the scale of the metal nanowire array structure is in the nanometer level, so that the antimagnetic response can be effectively inhibited, and the refractive index regulating and controlling capability of the material is further enhanced.
The regulation and control of the refractive index mainly results from the microstructure geometrical parameters in the metamaterial, namely the size and the gap of the metal nanowires, and the dielectric constant of the semiconductor or ceramic dielectric material. The volume percentage of the metal nanowires in the composite layer is the key point for establishing and regulating the capacitive coupling between the nanowires, the larger the volume percentage is, the smaller the line interval is, the stronger the capacitive coupling is, the higher the corresponding refractive index is, the dielectric constant of the semiconductor or ceramic medium determines the initial value of the refractive index of the composite film, and more importantly, the capacitive coupling effect between the nanowires can be further obviously improved. On the other hand, the metal nanowire has a diameter far smaller than the skin depth of bulk metal, so that the loss of the system under the incidence of micron-sized infrared light and non-resonance is almost negligible, and meanwhile, the system can exhibit the advantage of broadband low dispersion due to the large size difference between the incidence wavelength and the nanostructure unit. In particular, in order to weaken the problem of mismatch between the high-refractive index metamaterial and the substrate, the spectrum signal of the material is more conveniently detected, the volume percentage of the metal nanowires in the selected sample is limited to a certain extent, the space between the metal nanowires is 1-5nm, the diameter is 3-7nm, and the volume percentage of the metal nanowires in the metamaterial is 10% -30%. The length of the metal nanowire is 150-300nm.
The metamaterial is widely selected, the metal nanowire is any one of gold, silver, platinum, copper and aluminum, the semiconductor transparent medium is any one of silicon, germanium, zinc sulfide, zinc selenide and silicon carbide, and the ceramic transparent medium is any one of oxide, nitride and carbide
The high refractive index property of the metamaterial provided by the invention is closely related to the material and the structural characteristics thereof, namely, the high refractive index and low dispersion metamaterial needs to meet the following requirements: 1. the gaps among the unit structures are nano-scale, so that the degree of capacitive coupling among the unit structures is enhanced; 2. the size of the structure is small, so that the area of a current loop is reduced, and the diamagnetic response is inhibited; 3. the degree of capacitive coupling between the structures is further regulated by changing the dielectric environment. Further, the metal nanowire is any one of gold, silver and platinum, the semiconductor transparent medium is any one of silicon, germanium and zinc selenide, the ceramic transparent medium is any one of silicon dioxide, silicon carbide and aluminum oxide, the distance between the metal nanowires is 2-5nm, and the diameter is 3-6nm.
The choice of low resistance metals such as gold, silver, platinum, etc. as nanowires has the great advantage that, firstly, the absorption of the metamaterial system is greatly reduced due to their low ohmic losses. In addition, the self-organization ordered growth of vertical close-packed can be realized in the preparation process of the nanowires, the consistency of the cavity size between the nanowires is realized, the line size is controlled within the range of 2-5nm, and the necessary condition for generating strong capacitive coupling is met, on the other hand, the diameter of the prepared metal nanowire is 3-6nm, a current loop is difficult to form on the on-line surface under the size, the generation of antimagnetic effect is effectively inhibited, the wavelength difference with infrared waves is large, the low dispersion characteristic is facilitated, and further preferably, the metal nanowire is any one of gold, silver and platinum, the semiconductor transparent medium is any one of silicon, germanium and zinc selenide, and the ceramic transparent medium is any one of silicon dioxide, silicon carbide and aluminum oxide.
In addition, unlike traditional method of preparing high refractive index metamaterial with solution self-organizing method, the method has the advantage of adjustable and controllable dielectric environment, so that the refractive index of the whole metamaterial structure can be effectively regulated and controlled, and when the volume percentage of silver nanowires is 10% -35%, the refractive index of the silver nanowires is between 5-10 in the middle-far infrared band.
The invention also provides a preparation method of the metamaterial with the infrared high refractive index and low dispersion, which comprises the following steps:
(1) Pretreating a substrate;
(2) And (3) selecting metal, ceramic or semiconductor as a co-sputtering target material, and performing multi-target magnetron co-sputtering on the substrate pretreated in the step (1) under the atmosphere of argon at the air pressure of 0.15-0.6Pa, and simultaneously applying plasma bombardment assistance to prepare the metal nanowire array-ceramic or semiconductor composite layer metamaterial.
The preparation method provided by the invention is that metal, ceramic or semiconductor is used as a target material and co-sputtered into a pretreated substrate, and vertical orientation self-organization growth of the nanowires is realized under the assistance of plasma bombardment, so that a metal nanowire array-ceramic or semiconductor composite layer metamaterial is formed.
In the step (1), the substrate comprises an inorganic nonmetallic material, a flexible material or a semiconductor material.
Further, the inorganic nonmetallic material comprises any one of glass, ceramic, oxide and carbide; the flexible material is PET or PP; the semiconductor material is any one of silicon, germanium, zinc sulfide, zinc selenide and silicon carbide.
Further preferably, the substrate is any one of a quartz wafer, a sapphire wafer and a double-polished silicon wafer. To facilitate optical testing.
In the step (1), the specific steps of preprocessing the substrate are as follows:
and cleaning the substrate by adopting acetone, alcohol and deionized water in sequence, simultaneously performing ultrasonic action in the cleaning process, and then performing heating desorption and plasma sputtering cleaning.
The processed substrate has higher cleanliness, and provides conditions for better growth of the metal nanowire-semiconductor or ceramic composite structure.
In the step (2), the driving mode of the metal target is pulse, radio frequency or direct current power supply, the semiconductor target is driven by the pulse, radio frequency or direct current power supply, and the ceramic target is driven by the radio frequency power supply.
In the step (2), the power range adopted by the metal target material is 0.5-2W/cm 2 The power range of the adopted semiconductor target material is 2-8W/cm 2 The power range of the ceramic target material is 4-12W/cm 2 Furthermore, the target is at a distance of 75-90mm from the substrate.
Further, when copper and aluminum active metals are used as nanowire metal materials, the power adopted is 0.8-2W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The power of the semiconductor targets such as silicon, germanium and the like is 2-7W/cm 2 。
Further, the substrate is silicon dioxide, silicon, sapphire or zinc selenide, the metal target is gold or silver, and the power range adopted is 0.5-2.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The semiconductor target material is silicon, germanium or zinc selenide, and the power range adopted is 2-7W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The ceramic target material is silicon dioxide, silicon carbide or aluminum oxide, and the power range adopted is 2-10W/cm 2 。
By suitable combination of the substrate, metal target, semiconductor target or ceramic target, and the power ranges employed respectively, for example silver and silicon, gold and silicon carbide, and co-sputter growth of the metal nanowires with the medium. The obtained metamaterial structure is that the vertically grown metal nanowires are embedded in corresponding media, wherein the distance between the nanowires is generally 3-4nm, the capacitive coupling effect between the nanowires is greatly enhanced, so that the dielectric constant is remarkably improved, on the other hand, the diameter of the nanowires is generally 3-5nm, the nanoscale size makes it difficult to form a current loop in the nanowire structure, so that the antimagnetic response is reduced, the dielectric environment where the nanowires are located is improved through the high-refractive-index media, the refractive index values are greatly improved, and the lifting amplitude is 1-5.
Compared with the prior art, the invention has the following advantages:
(1) For the condition of incidence perpendicular to the surface of the material, the highest refractive index peak value of the material can reach more than 7 in the near infrared band, and the refractive index of the material can be kept unchanged by a certain value between 4.3 and 10 in the middle and far infrared band, so that the requirement of broadband low-dispersion high refractive index can be effectively met. In addition, the result of calculation simulation shows that the metamaterial has low extinction coefficient at the same time, and is expected to bring new application in the fields of infrared transparent media and the like.
(2) Compared with the traditional micro-nano structure preparation method, such as photoetching, solution self-assembly growth method and the like, the magnetron sputtering method adopted by the invention for growing the metal nanowire metamaterial structure has the advantages of simple process, low cost, convenient parameter regulation and control, contribution to large-area production, and uniform and stable property of the obtained composite structure.
(3) From the microstructure, the metal nanowire distance of the invention reaches the nanometer level, which greatly improves the capacitive coupling effect between the nanowires and can realize the great improvement of the refractive index of the near infrared band. Compared with a solution self-assembly method, the metal nanowire provided by the invention has the advantages of uniform size, few defects, high quality of the vertically compact grown nanowire and no need of further etching correction.
(4) The invention has loose choice for metal, semiconductor or ceramic matrix, and can select proper materials for preparation according to different refractive index requirements, namely the broadband high refractive index low dispersion property of the nanowire metamaterial mainly comes from the coupling property between micro-nano structures.
(5) The invention has wider selection range for the substrate material, and the selectable material is not limited to rigidity, flexibility, semiconductor or metal, and the like, thus having positive effect on the application of the high-refractive-index low-dispersion metamaterial.
(6) The invention is different from other metamaterial preparation methods, and can regulate and control the dielectric environment among micro-nano structures, namely a semiconductor or ceramic parent phase with high refractive index, further improve the capacitive coupling effect among metal nano wires, thereby obtaining higher refractive index and low dispersion.
Drawings
FIG. 1 is a schematic structural diagram of a metamaterial with infrared high refractive index and low dispersion provided by the invention;
FIG. 2 is a TEM image of a cross section of a silver nanowire-silicon medium composite structure prepared in example 1;
FIG. 3 is an infrared transmission spectrum corresponding to the silver nanowire-silicon medium composite structure prepared in example 1;
FIG. 4 is a comparison of refractive index corresponding to the silver nanowire-silicon dielectric composite structure prepared in example 1 with that of pure silicon;
FIG. 5 is an infrared transmission spectrum corresponding to the silver nanowire-silicon medium composite structure prepared in example 2;
FIG. 6 is a comparison of refractive index corresponding to the silver nanowire-silicon dielectric composite structure prepared in example 2 with that of pure silicon;
FIG. 7 is an infrared transmission spectrum corresponding to the silver nanowire-germanium dielectric composite structure prepared in example 3;
FIG. 8 is a comparison of refractive index corresponding to the silver nanowire-germanium dielectric composite structure prepared in example 3 with pure germanium refractive index;
FIG. 9 is a comparison of refractive index corresponding to the gold nanowire-silicon carbide composite structure prepared in example 4 with that of pure silicon carbide;
Detailed Description
The following detailed description of the present patent refers to the accompanying drawings and specific embodiments thereof, which are included to provide a further understanding of the invention, and are not to be construed as limiting the scope of the invention.
Example 1
Firstly, cleaning a substrate, and respectively ultrasonically cleaning a double-polished silicon wafer, a single-polished silicon wafer, a quartz wafer and sapphire by using acetone, ethanol and deionized water for 10 minutes in sequence to remove surface pollutants; drying the cleaned substrate by nitrogen and fixing the substrate on a substrate tray; loading the tray into a preparation chamber of a magnetron sputtering device, and vacuumizing to 10 counts by using a mechanical pump and a molecular pump in sequence -4 Pa or less; opening an argon gas path, introducing argon gas flow to keep the pressure of a deposition chamber at 0.35-0.6 Pa, cleaning a silver target by using radio frequency sputtering, cleaning a silicon target by using a direct current power supply for 10min, and applying bias voltage to clean a substrate for 10min; after the cleaning is finished, the air pressure of the deposition chamber is regulated to 0.3Pa, and the sputtering power density of the silver target is controlled to be 0.75W/cm 2 The sputtering power of the silicon target is 6W/cm 2 With the aid of plasma bombardment, the power density of the power supply is 2W/cm 2 And simultaneously opening a baffle plate in front of the silver target and the silicon target, and starting sputtering, wherein the deposition time is 3h10 min. And after the time is over, closing the silver target, the silicon target and the bias driving power supply to obtain the metal nanowire metamaterial film with high refractive index and low dispersion, wherein the schematic diagram of the obtained composite structure is shown in figure 1.
The cross-sectional morphology of the film sample was observed and analyzed by Transmission Electron Microscopy (TEM). Fig. 2 shows the cross-sectional TEM morphology of the metal nanowire metamaterial thin film in the embodiment 1, and it is clear from the figure that the cross section comprises a substrate and a metal nanowire-semiconductor composite structure, wherein the thickness of the metal nanowire-semiconductor composite layer is 200-210 nm. The silver nanowires are vertically embedded in a silicon medium in a certain periodic arrangement, wherein the average diameter of the silver nanowires is 3.5nm, the interval between the nanowires is 2.5nm, and the volume percentage of the metal nanowires is 15%.
FIG. 3 is a Fourier IR spectrum of the metal nanowire metamaterial in example 1. The substrate selected by the sample is a double-polished silicon wafer, and the infrared spectrum obtained by the sample is compared with the infrared transmission spectrum of a pure double-polished silicon substrate, so that the transmittance of the sample obtained by the embodiment 1 is obviously reduced about 2 mu m, and the refractive index reaches a peak value due to the strong coupling resonance effect among the metal nanowires, so that the refractive index mismatch degree between the silver nanowire-silicon composite layer and the air and the substrate is improved. Meanwhile, in the middle and far infrared bands, the transmittance curve obtained by the sample keeps consistent with the transmittance curve trend of the double-polished silicon substrate, only the numerical value is reduced, and the side surface proves that the obtained silver nanowire-silicon composite layer has low dispersion characteristic similar to that of pure silicon and has a refractive index larger than that of silicon.
Theoretical calculation of the refractive index of the silver nanowire-silicon composite layer of example 1 shows that the refractive index of the composite structure is greatly improved compared with pure silicon, and at the filling rate, the obtained refractive index has a maximum value of 5.8 at 1.4 μm and keeps 4.3 unchanged at more than 1.4 μm as shown in fig. 4.
Example 2
Firstly, cleaning a substrate, and respectively ultrasonically cleaning a double-polished silicon wafer, a single-polished silicon wafer, a quartz wafer and sapphire by using acetone, ethanol and deionized water for 10 minutes in sequence to remove surface pollutants; drying the cleaned substrate by nitrogen and fixing the substrate on a substrate tray; loading the tray into a preparation chamber of a magnetron sputtering device, and vacuumizing to 10 counts by using a mechanical pump and a molecular pump in sequence -4 Pa or less; opening an argon gas path, introducing argon gas flow to keep the pressure of a deposition chamber at 0.5-0.7 Pa, cleaning a silver target by using radio frequency sputtering, cleaning a silicon target by using a direct current power supply for 10min, and applying bias voltage to clean a substrate for 10min; after the cleaning is finished, the air pressure of the deposition chamber is regulated to 0.3Pa, and the sputtering power density of the silver target is controlled to be 1.25W/cm 2 The sputtering power of the silicon target is 7W/cm 2 With the aid of plasma bombardment, the power density of the power supply is 2W/cm 2 And simultaneously opening a baffle plate in front of the silver target and the silicon target, and starting sputtering, wherein the deposition time is 3h. And after the time is over, closing the silver target, the silicon target and the bias driving power supply to obtain the metal nanowire metamaterial film with high refractive index and low dispersion.
The average diameter of the obtained silver nanowires was 6nm, the spacing between nanowires was 2.5nm, and the volume percentage of the metal nanowires was significantly improved by 25% compared to the sample obtained in example 1. Fig. 5 is a fourier infrared spectrum of the metal nanowire metamaterial in example 2. The substrate selected by the sample is a double-polished silicon wafer, and the infrared spectrum obtained by the sample is compared with the infrared transmission spectrum of a pure double-polished silicon substrate, so that the transmittance of the sample in the embodiment 2 is still obviously reduced at about 2 mu m similar to the sample obtained in the embodiment 1. Meanwhile, in the mid-far infrared band, the transmittance curve obtained by the sample keeps consistent with the transmittance curve trend of the double-polished silicon substrate, and the transmittance curve is reduced in value compared with the sample in the embodiment 1, which shows that the silver nanowire-silicon composite layer obtained in the embodiment 2 has low dispersion characteristic similar to pure silicon and has a refractive index larger than that of the sample in the embodiment 1.
Theoretical calculations were made on the refractive index of the silver nanowire-silicon composite layer of example 2, and as a result, as shown in fig. 6, the refractive index of the composite structure is improved more than that of pure silicon, and at this filling rate, the obtained refractive index has a maximum value of 7 at 2.1 μm and remains unchanged at 5.8 at more than 2.7 μm.
By changing experimental parameters, the microstructure of the metal nanowire-semiconductor composite layer can be effectively regulated and controlled, so that a series of gradient high-refractive-index low-dispersion metamaterial optical films are obtained.
Example 3
Firstly, cleaning a substrate, and respectively ultrasonically cleaning a double-polished silicon wafer, a single-polished silicon wafer, a quartz wafer and sapphire by using acetone, ethanol and deionized water for 10 minutes in sequence to remove surface pollutants; drying the cleaned substrate by nitrogen and fixing the substrate on a substrate tray; loading the tray into a preparation chamber of a magnetron sputtering device, and vacuumizing to 10 counts by using a mechanical pump and a molecular pump in sequence -4 Pa or less; opening an argon gas path, introducing argon gas flow to keep the pressure of a deposition chamber at 0.35-0.6 Pa, cleaning a silver target by using radio frequency sputtering, cleaning a germanium target by using a direct current power supply for 10min, and applying bias voltage to clean a substrate for 10min; after the cleaning is finished, the air pressure of the deposition chamber is regulated to 0.3Pa, and the sputtering power density of the silver target is controlled at the momentIs 0.70W/cm 2 The sputtering power of the germanium target is 7W/cm 2 With the aid of plasma bombardment, the power density of the power supply is 2W/cm 2 And simultaneously opening a baffle plate in front of the silver target and the germanium target, and starting sputtering, wherein the deposition time is 3h50 min. And after the time is over, closing the silver target, the germanium target and the bias driving power supply to obtain the metal nanowire metamaterial film with high refractive index and low dispersion.
Fig. 7 is a fourier infrared spectrum of the metal nanowire metamaterial in example 3. The substrate selected by the sample is a double-polished silicon wafer, and the infrared spectrum obtained by the sample is compared with the infrared transmission spectrum of a pure double-polished silicon substrate, so that the transmittance curve obtained by the sample is consistent with the transmittance curve trend of the double-polished silicon substrate in the middle and far infrared band, and compared with the transmittance of the double-polished silicon substrate, the transmittance of the silver nanowire-germanium composite layer obtained by the embodiment 3 is reduced by 30%, and the silver nanowire-germanium composite layer has low dispersion characteristic similar to that of pure silicon and has larger effective refractive index.
Theoretical calculation of the refractive index of the silver nanowire-germanium composite layer of example 3 shows that the refractive index of the composite structure is also greatly improved compared with that of the infrared high refractive index material germanium, and at the filling rate, the obtained refractive index has a maximum value of 8.9 at 2.5 μm and keeps 7.9 unchanged at more than 2.5 μm as shown in fig. 8.
Example 3 shows that the invention can effectively regulate and control the refractive index of the system by regulating and controlling the semiconductor/ceramic medium in the metal nanowire-semiconductor/ceramic medium, so that the material selection and the refractive index range are greatly improved.
Example 4
Firstly, cleaning a substrate, and respectively ultrasonically cleaning a double-polished silicon wafer, a single-polished silicon wafer, a quartz wafer and sapphire by using acetone, ethanol and deionized water for 10 minutes in sequence to remove surface pollutants; drying the cleaned substrate by nitrogen and fixing the substrate on a substrate tray; loading the tray into a preparation chamber of a magnetron sputtering device, and vacuumizing to 10 counts by using a mechanical pump and a molecular pump in sequence -4 Pa or less; opening an argon gas path, introducing argon gas flow to maintain the pressure of the deposition chamber at 0.5-0.7 Pa, and cleaning by using radio frequency sputteringWashing the gold target, washing the silicon carbide target by using a direct current power supply for 10min, and applying bias voltage to wash the substrate for 10min; after the cleaning is finished, the air pressure of the deposition chamber is regulated to 0.3Pa, and the sputtering power density of the gold target is controlled to be 0.75W/cm 2 The sputtering power of the silicon carbide target is 10W/cm 2 With the aid of plasma bombardment, the power density of the power supply is 2W/cm 2 And simultaneously opening a baffle plate in front of the gold target and the silicon carbide target, and starting sputtering, wherein the deposition time is 3h10 min. And after the time is over, the gold target, the silicon carbide target and the bias driving power supply are turned off, so that the metal nanowire metamaterial film with high refractive index and low dispersion is obtained.
The average diameter of the obtained gold nanowires is 3.5nm, the spacing between the nanowires is 3nm, and the volume percentage of the metal nanowires is 22.7%. Theoretical calculation is performed on the refractive index of the gold nanowire-silicon carbide composite layer in example 4, and as shown in fig. 9, the refractive index of the composite structure is greatly improved compared with that of pure silicon carbide, and the refractive index value is 5.8 on average and the maximum value reaches 6.2 at the filling rate.
Example 4 demonstrates that high refractive index low dispersion metamaterial optical films can be conveniently obtained as well, using different combinations of metals and ceramics to form nanowires.
The foregoing detailed description of the preferred embodiments and advantages of the invention will be appreciated that the foregoing description is merely illustrative of the presently preferred embodiments of the invention, and that no changes, additions, substitutions and equivalents of those embodiments are intended to be included within the scope of the invention.

Claims (9)

1. The metamaterial with the infrared high refractive index and low dispersion is characterized by comprising a metal nanowire array and a dielectric layer, wherein the metal nanowire array is vertically embedded into the dielectric layer;
the metal nanowire array consists of a plurality of metal nanowires, the length of the metal nanowire array is the same as the thickness of the dielectric layer, and the distance between the metal nanowires is 1-6nm;
the dielectric layer is a semiconductor; the semiconductor transparent medium is silicon, germanium or zinc selenide;
the volume percentage of the metal nano wire in the metamaterial is 5-50%;
the diameter of the metal nanowire is 3-7nm.
2. The metamaterial with infrared high refractive index and low dispersion according to claim 1, wherein the distance between the metal nanowires is 1-5nm, and the volume percentage of the metal nanowires in the metamaterial is 10% -30%.
3. The metamaterial with infrared high refractive index and low dispersion according to claim 1, wherein the length of the metal nanowires is 150-300nm.
4. The metamaterial with infrared high refractive index and low dispersion according to claim 2, wherein the metal nanowires are any one of gold, silver, platinum, copper and aluminum.
5. The metamaterial with infrared high refractive index and low dispersion according to claim 4, wherein the metal nanowires are gold, silver or platinum, the distance between the metal nanowires is 2-5nm, and the diameter of the metal nanowires is 3-6nm.
6. The method for producing a metamaterial having a high refractive index and low dispersion for infrared rays according to any one of claims 1 to 5, comprising:
(1) Pretreating a substrate;
(2) Selecting metals and semiconductors as co-sputtering targets respectively, and performing multi-target magnetron co-sputtering on the substrate pretreated in the step (1) under the atmosphere of argon at the air pressure of 0.15-0.6Pa, and simultaneously applying plasma bombardment assistance to prepare the metal nanowire array-semiconductor composite layer metamaterial.
7. The metamaterial with infrared high refractive index and low dispersion according to claim 6, wherein in step (1), the specific steps of pre-treating the substrate are as follows:
and cleaning the substrate by adopting acetone, alcohol and deionized water in sequence, simultaneously performing ultrasonic action in the cleaning process, and then performing heating desorption and plasma sputtering cleaning.
8. The metamaterial with infrared high refractive index and low dispersion according to claim 6, wherein in step (2), the power of the metal target is in the range of 0.5-3W/cm 2 The power range of the adopted semiconductor target material is 2-8W/cm 2 。
9. The metamaterial with infrared high refractive index and low dispersion according to claim 8, wherein the substrate is silicon dioxide, silicon, sapphire or zinc selenide, the metal target is silver or platinum, and the power used is in the range of 0.5-2.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The semiconductor target material is silicon, germanium or zinc selenide, and the power range adopted is 2-7W/cm 2 。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8681428B1 (en) * 2012-04-03 2014-03-25 Rockwell Collins, Inc. High refractive index, polarization insensitive nano-rod based plasmonic metamaterials for lenses
WO2017111546A1 (en) * 2015-12-23 2017-06-29 한국과학기술원 Broadband high-refractive index metamaterial nano-composite structure
WO2018136972A1 (en) * 2017-01-23 2018-07-26 The Regents Of The University Of California Broadband absorbers via nanostructures

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7592255B2 (en) * 2004-12-22 2009-09-22 Hewlett-Packard Development Company, L.P. Fabricating arrays of metallic nanostructures
US20090040132A1 (en) * 2007-07-24 2009-02-12 Northeastern University Anisotropic metal-dielectric metamaterials for broadband all-angle negative refraction and superlens imaging
KR20150067141A (en) * 2012-08-13 2015-06-17 프레지던트 앤드 펠로우즈 오브 하바드 칼리지 Multispectral imaging using silicon nanowires
CN108598273A (en) * 2018-05-04 2018-09-28 华中科技大学 Based on the high-efficiency soft light emitting diode with quantum dots of nano silver wire electrode and its preparation
CN109581564B (en) * 2018-11-14 2021-04-06 中国科学院宁波材料技术与工程研究所 Multilayer metal ceramic film with structural color and preparation method thereof
CN109687282B (en) * 2019-02-11 2020-08-07 中国科学院微电子研究所 Three-dimensional metamaterial surface plasmon laser
CN109972090B (en) * 2019-04-04 2020-12-11 中国科学院宁波材料技术与工程研究所 Perfect absorber coating and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8681428B1 (en) * 2012-04-03 2014-03-25 Rockwell Collins, Inc. High refractive index, polarization insensitive nano-rod based plasmonic metamaterials for lenses
WO2017111546A1 (en) * 2015-12-23 2017-06-29 한국과학기술원 Broadband high-refractive index metamaterial nano-composite structure
WO2018136972A1 (en) * 2017-01-23 2018-07-26 The Regents Of The University Of California Broadband absorbers via nanostructures

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Nanowire-based ultra-wideband absorber for visible and ultraviolet light";Qingqing Chen et al.;《Optics and Laser Technology》;102-105 *
Yanyan Huang et al.."Goos–Hänchen shift of the reflected wave through an anisotropic metamaterial containing metal/dielectric nanocomposites".《Optical Society of America》.2012,1436-1444. *

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