The present invention relates to a three-dimensional isotropic metamaterial. More specifically, the present invention relates to a three-dimensional isotropic metamaterial, a terahertz region optical element including the three-dimensional isotropic metamaterial, and a method of producing a three-dimensional isotropic metamaterial.
Terahertz waves are electromagnetic waves having a frequency of about 0.1 to 10 THz, and have a fingerprint spectrum specific to material, and high permeability. Because terahertz waves exert small influence on a biological body, terahertz waves are considered to be usable in sensing in security and medical fields, and active research has been recently conducted. For example, it has been reported that success has been achieved in determination of medicine in an envelope based on a difference in transmission spectra of terahertz waves (Optics Express, vol. 11, 2549 to 2554, 2003; Non Patent Literature 1).
Nevertheless, a sensing technology in a terahertz region is nonfully-developed. The reason lies in that low-loss materials that can be used as an optical element in a terahertz band are as listed in Table 1, and a design freedom degree is small.
Thus, as a material that can control optical characteristics such as transmission and refraction, a metamaterial being an artificial structure formed of minute metal smaller than a wavelength has been proposed. It is indicated that, in a terahertz region, by producing a pattern of a metal wire on a polymer film, a refractive index equal to or larger than double of a refractive index of a conventional material can be obtained in a specific frequency (Infrared Milli Terahz Waves, vol. 38, 1130 to 1139, 2017; Non Patent Literature 2), and the metamaterial is expected to be used in compact and high-performance lens, prism, and the like. A split ring resonator (hereinafter, abbreviated as an SRR) illustrated in
Both metamaterials described in Non Patent Literatures 2 and 3 have a planar periodic structure, and a response is limited to a specific incident direction. Nevertheless, a structure of similarly responding in all incident directions is actually demanded. In addition, a thickness structure of being equal to or larger than a millimeter (mm) order is also demanded for ensuring a sufficient interaction distance with electromagnetic waves.
For solving this issue, a metamaterial having a three-dimensional structure having isotropic optical characteristics by a minute structure becomes necessary. Nevertheless, in a generally-used lithography method, it is difficult to create a thick structure, and a new method is demanded.
So far, there has been proposed a method of producing an SRR on a resin wall surface as a three-dimensional metamaterial (Adv. Mater. vol. 22, 5053 to 5057, 2010; Non Patent Literature 4). This method constructs one layer on the outside of a substrate plane, and has a limitation in manufacturable thickness. In addition, a metamaterial in which a layer patterned with an SRR is overlaid on a substrate has been reported (Nature Materials, vol. 7, 31 to 37, 2008; Non Patent Literature 5). According to Non patent Literature 5, a limitation in manufacturable thickness is eliminated, but there is a limitation in the direction of the SRR, and there is such a problem that characteristics vary depending on the direction. Accordingly, in the current situation, a metamaterial having complete isotropy has not been realized yet.
The present invention provides a metamaterial in which meta-atoms (metamaterial unit structure) such as SRRs are buried in such a manner as to three-dimensionally disperse in a transparent medium (resin) independent of direction, and a method of producing the same, and verifies that a produced metamaterial has desired optical characteristics (isotropy, refractive index control property).
Using methods to be described later in the section of mode for carrying out the invention, the present inventors have performed design (calculation and response), producing, and experiment of a three-dimensional model as for a metamaterial structure for a three-dimensional isotropic terahertz region, showed the usefulness of a three-dimensional metamaterial having a random structure, by calculation using a finite integration technique (FIT), established a method of producing a three-dimensional metamaterial in which SRRs disperse in a cycloolefin polymer (COP) independent of direction, and verified and confirmed that polarization dependence of the produced three-dimensional metamaterial has been resolved as compared with a planar periodic structure, by measuring optical characteristics (isotropy, refractive index control property) of the produced metamaterial. Then, it has been confirmed that a refractive index of 1.50 to 1.60 is realized in a 0.35 THz band, and a refractive index of 1.43 to 1.60 is realized in a 0.7 THz band, by the produced three-dimensional metamaterial, and the present invention has been completed.
In other words, the present invention provides a three-dimensional isotropic metamaterial according to [1] to [14] described below, a method of producing the same, and a product including the metamaterial.
[1] A three-dimensional isotropic metamaterial, including an aggregate of meta-atom block pieces in which meta-atoms are buried in a transparent resin, in a transparent resin member.
[2] The three-dimensional isotropic metamaterial according to the previous item 1, wherein the meta-atom is an SRR.
[3] The three-dimensional isotropic metamaterial according to the previous item 2, wherein an SRR block piece aggregate in which SRRs are buried in a central part of the transparent resin member cube or a vicinity of the central part is included in the transparent resin member.
[4] The three-dimensional isotropic metamaterial according to the previous item 2 or 3, wherein a size of the SRR block is set to a ring width w of 1 μm or more, an average radius r of 1 to 500 μm, and a period (one piece) a of 3 to 3,000 μm.
[5] The three-dimensional isotropic metamaterial according to the previous item 4, wherein the SRR is formed of a conductive material (conductive member).
[6] The three-dimensional isotropic metamaterial according to the previous item 5, wherein the conductive member is at least one type selected from the group consisting of a metal material, a transparent conductive oxide, and a carbon material.
[7] The three-dimensional isotropic metamaterial according to any of the previous items 1 to 6, wherein a material of the transparent resin member is a transparent nonconductive material for light in a terahertz region.
[8] A method of producing a three-dimensional isotropic metamaterial, including the steps of:
a step (P1) of forming a conductive member film on a transparent resin film (1a) and etching the conductive member film to form a meta-atom block aggregate;
a step (p2) of bonding transparent resin films (1b) after coating the meta-atom block aggregate with transparent resin solution;
a step (p3) of splicing the transparent resin film (1a) to a substrate sheet (2) after drying;
a step (p4) of dicing the meta-atom block aggregate into a predetermined size, and then removing the diced aggregate from the substrate sheet (2) as a block piece in which a meta-atom is buried in a transparent resin (1); and
a step (p5) of uniformly dispersing the meta-atom buried block pieces in transparent resin solution in a mold and then causing curing, and extracting a cured molded member from the mold.
[9] The method of producing a three-dimensional isotropic metamaterial according to the previous item 8, wherein the meta-atom block is an SRR block.
[10] The method of producing a three-dimensional isotropic metamaterial according to the previous item 9, wherein a size of an SRR block is set to a ring width w of 1 μm or more, an average radius r of 1 to 500 μm, and a length a of a period (one piece) of 3 to 3,000 μm.
[11] The method of producing a three-dimensional isotropic metamaterial according to any of the previous items 8 to 10, wherein the conductive member is at least one type selected from the group consisting of a metal material, a transparent conductive oxide, and a carbon material.
[12] The method of producing a three-dimensional isotropic metamaterial for a terahertz region optical element according to any of the previous items 8 to 11, wherein a resin material of the transparent resin film and transparent resin solution is a transparent nonconductive material for light in a terahertz region.
[13] A product, including the three-dimensional isotropic metamaterial according to any of the previous items 1 to 7.
[14] The product according to the previous item 13, wherein the product is a terahertz region optical element.
By the realization of a three-dimensional isotropic metamaterial and a terahertz region optical element including the same according to the present invention, the use of electromagnetic waves of terahertz waves (frequency 0.1 to 10 THz) that have a fingerprint spectrum specific to material, and high permeability, and exert small influence on a biological body has become practical. The application field of terahertz region light is not specifically limited, and a three-dimensional isotropic metamaterial is applied to, for example, a filter without angle dependence, a thin lens, a spectroscope that uses a prism, and the like.
Furthermore, in a case where a three-dimensional isotropic metamaterial is used in a terahertz region optical element, examples include products, systems, apparatuses, and the like that are related to the application of a transparent mantle for terahertz, a stealth technology equipped product (terahertz wave reflection/absorption suppression technique), a radio disturbance resolution technique equipped product (operate a direction of terahertz waves), a high-sensitive ultracompact antenna, an IC tag, a high-angle beam scanning antenna, a near-field microscope device, a high-efficiency detector, terahertz waveband optical waveguide/optical fiber, a dangerous object inspection device, an airport security inspection device, a body scanner (used in finance, information terminal room, airport, etc.), a doping test device, a biometric authentication device (used in finance, information terminal room, airport, etc.), a food quality safety inspection device, a food quality management device, an agricultural crop inspection device, a medicinal product inspection device, a biotip/DNA analysis device, a cancer diagnosis device, a semiconductor wafer evaluation device, an LSI failure inspection device, an atmosphere environment analysis device, and the like.
A structure of a three-dimensional isotropic terahertz metamaterial of the present invention will be described in the order of design (calculation and response) of a three-dimensional model, a producing, and an experiment result.
First of all, calculation for predicting a response of a metamaterial to be produced was performed using a finite integration technique. First of all, a model obtained by periodically arraying an SRR of one pattern in xy directions was used as a two-dimensional model, and a response made when an SRR is slanted was checked as a basic response to electromagnetic wave while assuming that almost all SRRs are obliquely arranged with respect to an incident wave in random arrangement (
A basic operation of a split ring (SRR) will be described. An SRR indicates a response indicating whether an electric field component of an incident wave basically goes along a gap, using a specific frequency when a magnetic field component is vertical to a ring plane and a magnetic field penetrates through a ring.
Next, a response made when an SRR is slanted with respect to vertical incidence was checked (
Next, a response of a three-dimensional metamaterial with SRR random arrangement that is to be produced was predicted by simulation. In a case where an SRR is arranged so as to be orthogonal to each axis, directions of six patterns illustrated in (1) to (6) of
When seven transmission characteristics calculated while changing an angle are averaged, it was revealed that a transmittance largely drops near 0.7 terahertz (
Next, a change in a response made when a period and a size of an SRR are changed was checked by simulation. First of all, when a period is changed from 120 μm to 280 μm, a spectrum shape changes, but a response frequency band did not change (
A change in a response made when the number of layers of the above-described three-dimensional model of SRR 3 layer arrangement is changed was checked. From this calculation, it is considered that, as a thickness of a metamaterial increases, a drop in transmittance becomes larger (
Next, polarization dependence and incident angle dependence were compared with those of a planar structure (
From the above-described calculation results, it was predicted that a metamaterial to be produced makes a response at a specific frequency irrespective of periodicity, and the response does not depend on an incident direction of terahertz waves. If the characteristics can be realized, direction dependence existing in a conventional optical filter can be resolved.
The details (steps) of an example of a producing process are illustrated in (
A metal film (Au film) is formed on a transparent resin film (COP film)(1a), the Au film is etched by photolithography, and an SRR block aggregate with an SRR ring width w (μm), an average radius r (μm), and a length a (μm) of a period (one piece) is formed (a), the SRR block aggregate is coated with resin solution (COP solution)(1b) (b), and then, the transparent resin films (COP film)(1b) are bonded (c). Herein, instead of bonding resin films, a film of transparent resin material may be formed by a technique such as spin coating, sputtering, or CVD. Note that the average radius r (μm) corresponds to a radius up to the center of an SRR ring width w (μm) as illustrated in
Subsequently, after performing drying in a vacuum (d), the COP film (1c) is spliced to a tape shaped substrate (2) (e). The SRR block aggregate is diced into individual SRR blocks (f), an SRR-buried block is removed from the tape shaped substrate (2) (g), and an SRR-buried block aggregate is obtained. The aggregate of SRR-buried blocks is put into a mold (3) (h), and transparent resin (COP) (1b) solution is poured and blocks are uniformly dispersed (i), and then, drying and curing are performed (j). A three-dimensional metamaterial (4) is obtained as a cured molded member (k).
QUICK COATER SC-701HMCII manufactured by Sanyu Electron Co., Ltd. was used for sputtering. An SUSS aligner was user for photolithography. A designed dimension of an SRR block was set to an average radius r=46 μm, an SRR ring width w=15 μm, a gap g=10 μm, and a length a of a period (one piece)=200 μm. An interval (period) between SRRs was set to 225 μm in consideration of a width to be cut in dicing. ZeonorFilm (registered trademark) ZF14 produced by Zeon Corporation and having a thickness of 100 μm was used for a COP film. Here, a method of cutting into a block piece is not limited to dicing, and a cutting method of pressing a blade, a method of cutting like a cutter, a mold press work of a pressing a mold, cutting using a wire saw, a precise machining work that uses a cutting tool such as a turning tool, or the like may be employed.
Note that a lithography range of an SRR pattern was set to 6 cm×6 cm (corresponds to 70756 SRRs per film).
A COP pellet (product name; Zeonex) manufactured by Zeon Corporation was used for preparation of COP solution. The COP solution was obtained by putting Zeonex into xylene, and completely dissolving Zeonex by stirring. The same films obtained by performing spin coating of COP solution was bonded.
A produced SRR block was put into an aluminum mold, and was molded using COP solution. In other words, after putting an SRR block into a mold, a step of pouring COP solution and drying was executed. Both surfaces of the molded metamaterial were polished using Automatic Lapping Polishing Machine MA-200D produced by Musashino Denshi, INC.
The produced three-dimensional metamaterial was observed using a microscope.
[Producing in Case where Block Dimension is Changed]
An SRR block having one side of 100 μm was produced, and producing of a dimensional metamaterial was similarly performed.
[Producing of Prism that Uses Three-Dimensional Metamaterial]
A prism-shaped metamaterial was produced using the above-described producing method. A designed dimension was set to r=86 μm, w=15 μm, g=10 μm, and a=200 μm. This is because a refractive index change larger than r=46 μm was obtained by measurement to be described later. A molding die for a prism shape was prepared, and molding and polishing were performed similarly to the above-described metamaterial.
Optical characteristics of the produced three-dimensional metamaterial were measured using a terahertz time-domain spectroscopy (THz-TDS). Note that the THz-TDS is a method of obtaining an absorbing spectrum in a terahertz band from a Fourier-transform spectrum ratio of waveforms by measuring a waveform of an electromagnetic wave when a terahertz wave is emitted and transmitted through a sample, and a waveform of an electromagnetic wave when a sample does not exist (Terahertz Spectroscopy, J. Phys. Chem., vol. 106, 7146 to 7159, 2002, C. R. Acad Sci., vol. 4, 983 to 988, 2001).
Transmission characteristics obtained when a terahertz wave vertically enters a sample of a metamaterial was checked. A metamaterial obtained by ending film splicing in the producing process illustrated in
Next, a measurement result of a three-dimensional metamaterial will be described. Although directions of SRRs are not uniform in a three-dimensional metamaterial, for checking characteristics caused by polarized light, a direction of polarized light in
Similarly to the metamaterial shown in
[Math. 1]
δ=sin−1(n2 sin α)−α (1)
When the prism of the metamaterial shown in
As described above, the present inventor et al. has performed verification of isotropy and refractive index control property as for a three-dimensional metamaterial in which SRRs disperse at random in COP. In a three-dimensional metamaterial proposed by calculation using a finite integration technique, anisotropy can be resolved as compared with a two-dimensional structure, and response frequency and intensity can be controlled by a dimension parameter. In addition, by a method of integrating cubic blocks each including one buried SRR, and molding the blocks, producing of a three-dimensional metamaterial was performed, the produced three-dimensional metamaterial was measured by the THz-TDS, and transmission characteristics and refractive index characteristics were evaluated.
By the calculation of a two-dimensional model, the first dipole resonance corresponding to LC resonance of an SRR is useful in creating a random structure without periodicity because a frequency shift caused by a change in periodicity is smaller as compared with resonance of another mode. When the same SRR is expanded to a three-dimensional model and calculation is performed, a response near 0.7 THz corresponding to a response frequency band of a two-dimensional model was confirmed. When calculation is performed while changing the dimension of the SRR, it was identified that, as an average radius of SRRs becomes larger, a response frequency band shifts toward a low-frequency side. In addition, when calculation is performed while changing the density of the SRR, it was identified that, although a response frequency band does not change, as a density becomes higher, a drop in transmittance and a variation in refractive index become larger. Furthermore, it was identified that, in the three-dimensional model, incident angle dependence and polarization dependence are resolved.
When measurement is performed using the THz-TDS, a response of the produced three-dimensional metamaterial approximately conform with a designed frequency. A metamaterial produced with an average radius r=46 μm and one side a of a block=200 μm has a transmittance dropping in a 0.7 THz band and a refractive index change of 1.51 to 1.53. In addition, also in a case where polarized light is rotated by 90°, a similar response is indicated, and it was confirmed that polarization dependence is resolved as compared with a two-dimensional structure. A metamaterial produced with r=86 μm and a=200 μm indicates a drop in a transmittance in a 0.35 THz band, and a refractive index change of 1.50 to 1.60 was obtained. In addition, the response conformed well with a response made when polarized light is rotated by 90°. A metamaterial produced with r=46 μm and a=100 μm has a transmittance dropping largely in a 0.7 THz band than that produced with a=200 μm, and the largest refractive index change of 1.43 to 1.60 was obtained.
A refractive index 1.60 realized by the present invention is a refractive index drastically higher than a resin material used as a conventional optical element.
As described above, the metamaterial obtained by the present invention realizes a refractive index that cannot be obtained by a natural material, in a terahertz region. According to the metamaterial of the present invention, because a refractive index can be freely set, a design freedom degree of an optical element increases. Specific examples to which the metamaterial of the present invention can be applied include a filter without angle dependence, a thin lens, a terahertz wave spectroscope that uses a prism, and the like, but the application is not limited to these.
Heretofore, regarding the three-dimensional isotropic metamaterial of the present invention, the mode of an SRR-buried block for a terahertz region optical element has been described in detail, but the three-dimensional isotropic metamaterial of the present invention is not limited to a terahertz region. In addition, a meta-atom that can be used in a metamaterial is not limited to an SRR, and can be applied to metamaterial unit structures (meta-atoms) with various structures. For example, a three-dimensional isotropic metamaterial in which paired metal cut wires disclosed in applied physics, vol. 86, 897 to 902 (2017), omega-type metamaterials disclosed in Optic Communications, 283, 2547 to 2551 (2010), or double split rings disclosed in IEEE Photonics journal, vol. 1, No. 2, 99 to 118, August (2009) are buried in a transparent resin member similarly to the case of an SRR can be considered.
The material of an SRR is only required to be an electricity-conducting material, and examples include a metal material, a transparent conductive oxide (ITO, IZO, ZnO, IGZO, etc.) used in a transparent electrode, and a carbon material such as graphene. Representative examples of the metal material include gold (Au), silver (Ag), copper (Cu), and aluminum (Al).
The material of a transparent resin member that buries (encompasses) an SRR in the present invention is only required to be a transparent nonconductive material for light in a terahertz region. The material is not specifically limited, and examples include polymethylpentene, polyethylene, cycloolefin polymer (COP) silicon, polytetrafluoroethane (Teflon; registered trademark), SiO2, and the like. Among these materials, COP is preferable.
The metamaterial of the present invention is preferably used for a terahertz region optical element with a frequency of 0.1 to 10 THz (wavelength of 30 to 3000 μm). Accordingly, a size of an SRR to be buried in a transparent resin material member is preferably set to a range of a ring width w of 1 μm or more, an average radius r of 1 to 500 μm, and a period (one piece) a of 3 to 3000 μm. More preferably, a size is set to w of 5 μm or more, r of 2 to 400 μm, and a of 10 to 2000 μm. Further preferably, a size is set to w of 10 μm or more, r of 3 to 300 μm, and a of 20 to 1000 μm. In addition, the ring width w of the metamaterial of the present invention is used in 1500 μm or less because a length of a period is limited.
Filing Document | Filing Date | Country | Kind |
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PCT/JP2019/013481 | 3/27/2019 | WO | 00 |