Material that absorbs electromagnetic radiation of wavelengths between 300 nm and 18 microns and app

专利摘要:
Material that absorbs electromagnetic radiation of wavelengths between 300 nm and 18 microns and applications. The present invention relates to a material that absorbs electromagnetic radiation of wavelengths between 300 nm to 18 μm that comprises a polymeric substrate and a plurality of nanocapsules. Furthermore, the present invention relates to an uncooled photodetector, a photomechanical actuator powered by sunlight and a self-regulating artificial dynamic pupil with incident light/radiation and an ocular prosthesis comprising said material. Finally, the present invention relates to the use of the material as a cantilevered support and for the manufacture of a dynamic artificial pupil for the treatment of disorders of the pupil. Thus, the present invention can be found in the area of materials comprising metamaterials and their applications. (Machine-translation by Google Translate, not legally binding)
公开号:ES2832890A1
申请号:ES201931100
申请日:2019-12-11
公开日:2021-06-11
发明作者:Martínez Borja Sepúlveda；Sánchez Mar Alvarez；I Grau Pau Güell；Sanmiguel Josep Nogués；Li Zhi；Sanz Rosa Villa
申请人:Consejo Superior de Investigaciones Cientificas CSIC；Institucio Catalana de Recerca i Estudis Avancats ICREA；Institut Catala de Nanociencia i Nanotecnologia ICN2；
IPC主号:

专利说明:

[0002] Material that absorbs electromagnetic radiation of wavelengths between 300 n mv 18 microns v applications
[0004] The present invention relates to a material that absorbs electromagnetic radiation of wavelengths from 300 nm to 18 pm comprising a polymeric substrate and a plurality of nanocapsules. Furthermore, the present invention relates to an uncooled photodetector, a photomechanical actuator powered by sunlight and a self-regulating artificial dynamic pupil with incident light / radiation and an ocular prosthesis comprising said material. Finally, the present invention relates to the use of the material as a cantilever support and for the manufacture of a dynamic artificial pupil for the treatment of disorders of the pupil.
[0006] Thus, the present invention can be found in the area of materials comprising plasmonic metamaterials and their applications.
[0008] BACKGROUND OF THE INVENTION
[0010] Plasmonic metamaterials are artificial materials based on metallic nanostructures. Electromagnetic waves interact with nanostructures and couple / excite their surface plasmon resonance. Metals like Au or Ag have been widely used due to the strong surface plasmon resonance response they exhibit.
[0012] Plasmonic metamaterials are especially interesting for their efficient absorption capacity at a specific frequency or multi-frequency, in different ranges of the spectrum (adaptive), with much smaller thicknesses than traditionally used devices based on multilayers separated by a quarter of a wavelength. of operation [Watts, CM, Liu, X. & Padilla, WJ Metamaterial ElectromagneticWave Absorbers. Adv. Mater. 24, OP98-OP120 (2012)].
[0014] Achieving absorption over a wide spectrum range by using plasmonic metamaterials represents a challenge due to the inherently narrow bandwidth of localized surface plasmon resonance generated in the surface of metallic nanostructures. Various approaches combine the resonance of nanostructures of different dimensions or the use of multilayers to achieve absorption in a wide bandwidth of the spectrum [Yu, P. et al. Broadband Metamaterial Absorbers. Adv. Opt. Mater. 7, 1800995 (2019)]. However, all of them fail to achieve constant absorption in an ultra-wide range of the spectrum.
[0016] The development of materials capable of achieving efficient absorption of electromagnetic radiation in a wide spectrum bandwidth is essential in applications such as thermo-photovoltaics, photodetection, bolometry and manipulation of mechanical resonances [Yu, P. et al. Broadband Metamaterial Absorbers. Adv. Opt. Mater. 7, 1800995 (2019)]. Other areas of application of these materials include energy accumulation, soft-robotics [Liu, JA-C., Gillen, JH, Mishra, SR, Evans, BA & Tracy, JB Photothermally and magnetically controlled reconfiguration of polymer composites for soft robotics. Sci. Adv. 5, eaaw2897 (2019)] and dynamic pupils [Lapointe, J. Next Generation Artificial Eyes with Dynamic Iris. Int J Ophthalmol Clin Res 3: 062] which could be considered examples of soft-robotics.
[0018] The development of artificial dynamic pupils is today a challenge to be solved. Eye prostheses currently used clinically contain a static pupil, with a fixed size, which differs greatly from the dynamic behavior of the real pupil. This limitation impacts on the professional and social life of patients. The only commercially available commercially approved dynamic artificial pupil was developed in 1983 and is based on the use of an external magnet to change the size of the pupil [Art-Lens, ocular prostheses]. The magnet is used by the patient himself and the pupil has two possible sizes. Other approaches use liquid crystals or photochromic materials [Lapointe, J. Next Generation Artificial Eyes with Dynamic Iris. Int J Ophthalmol Clin Res 3: 062], but most of them require the use of batteries which limits the clinical application. A more recent approach uses liquid crystals to develop a dynamic pupil that self-regulates its size depending on the intensity of UV light received [Zeng, H., Wani, OM, Wasylczyk, P., Kaczmarek, R. & Priimagi, A. Self-Regulating Iris Based on Light-Actuated Liquid Crystal Elastomer. Adv. Mater. 29, 1701814 (2017).].
[0019] DESCRIPTION OF THE INVENTION
[0021] The proposed invention simplifies said approaches, and achieves a very high and constant absorption in a wide range of the spectrum due to the combination of the absorption of the elements that make up the material of the invention: a nanostructured material with highly damped plasmonic behavior and a polymer . The absorption spectrum is highly independent of the distance between nanostructures, since the near-field interaction of this material is negligible, thus maintaining a very efficient absorption and reducing light reflection. In comparison, conventional plasmonic materials, such as Au or Ag, suffer from increased light reflection and decreased electromagnetic absorption due to delocalization of the surface plasmon when the distance between them is reduced. Increased reflectance is especially important in the infrared, where conventional plasmonic materials behave almost like a perfect conductor with very little penetration of radiation into the material.
[0023] The advantages of the proposed invention consist of a greater absorption spectral range, an independence of the angle of incidence of light, a higher efficiency of the photothermal conversion and a lower cost. The ferromagnetic properties of the proposed materials also allow the combined or sequential actuation and detection of light and magnetic fields.
[0025] DETAILED DESCRIPTION OF THE INVENTION
[0027] In a first aspect, the present invention refers to a material (hereinafter "the material of the present invention") that absorbs electromagnetic radiation of wavelengths between 300 nm to 18 pm (in accordance with the definition of ultra broadband) and converts that radiation into heat. It absorbs electromagnetic radiation in an ultra-wide spectrum range, from 300 nm to 18 pm, highly efficiently, with an average absorption of 84%. It should be noted that the efficiency of the absorption of said electromagnetic radiation is independent of the angle of incidence of the electromagnetic radiation (light).
[0029] Furthermore, said material is characterized in that it comprises
[0030] • a polymeric substrate, preferably the polymeric substrate is selected from between polydimethylsiloxane (PDMS) or polystyrene.
[0031] • a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-Ai, where each nanocapsule has
[0032] or a vertex,
[0033] or a height between OO nm and 500nm,
[0034] or a thickness of 40 nm and 300 nm
[0035] o and an aperture diameter between 200 nm and 1000 nm,
[0036] where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate.
[0038] In the material of the present invention, the nanocapsules may be partially or completely submerged in the substrate in a similar way to their arrangement on the substrate. The term "the vertex is in direct contact with the substrate" marks the arrangement of all nanocapsules with respect to the substrate (concave side). Note that for the case of nanocapsules partially submerged in the substrate, the part of the nanocapsule that includes the vertex can be submerged in the substrate and the part of the nanocapsule that includes the opening without submerging.
[0040] Preferably, the polymeric substrate of the material of the present invention is an insulator, that is, a non-conductive polymeric substrate. Furthermore, said substrate can be flexible and its surface can be rough.
[0042] The nanocapsules of the material of the present invention have a vertex, a height of between 100 nm and 500 nm, a thickness of between 40 nm and 300 nm and a diameter aperture of between 200 nm and 1000 nm. The composition of the nanocapsules can vary from Fe, Co, Ni or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, preferably the nanocapsules of the present invention comprise Fe.
[0044] The thickness of the material corresponds to the sum of the height of the nanocapsules and the thickness of the substrate and varies depending on its application and therefore will be limited to said application.
[0046] In the material of the present invention the absorption of light / electromagnetic radiation of wavelengths between 300 nm and 18 pm is preferably maximized when the nanocapsules are in contact. Therefore, in a preferred embodiment of the material of the present invention at least two nanocapsules are in contact with each other, preferably said contact is tangential, that is, it occurs at a single point. Even more preferably, all the nanocapsules are the same height.
[0048] In another preferred embodiment of the material of the present invention, all of the plurality of nanocapsules are separated from each other.
[0050] In a preferred embodiment of the material of the present invention, the polymeric substrate has
[0051] • a first side periodically corrugated with a periodicity between 800 nm and 20000 nm and
[0052] • a second side,
[0053] and where the nanocapsules are arranged on the second side of the polymeric substrate. This material is capable of being used as a cantilever support in photodetection and photomechanical actuation applications, where the absorbed radiation is converted into mechanical energy, and in a displacement of the free end of the cantilever. The corrugated side changes the color diffracted by the material as the radiation is absorbed. As another aspect of the present invention refers to the use of said material as a cantilever or cantilever support, preferably for photodetectors or photomechanical actuators.
[0055] Another aspect of the invention is an uncooled photodetector, preferably an uncooled infrared photodetector, characterized in that it comprises the material of the present invention. Since the material absorbs radiation in a longer range of lengths, between 300 nm and 18 pm, it maximizes the efficiency of the photodetector. The material of the present invention is the sensor layer in photodetectors based on thermal response, such as pyroelectric photodetectors, bolometers or thermopiles.
[0057] In nanomechanical IR photodetectors, the material of the present invention is used as the only component (material of the invention in the form of a cantilever). Optionally it can have a corrugated side. If it has a corrugated side, it directly converts the absorption into a color change, if it does not have it, the cantilever responds to the absorption, but does not change color and another technique can be used to measure the deflection of it.
[0059] Another aspect of the present invention is a light-powered photomechanical actuator. solar characterized in that it comprises the material of the present invention. Since the material efficiently converts light or electromagnetic radiation between 300 nm and 18 pm into heat, the mechanical response will be higher, since the mechanical response is directly related to the heat generated in the material and the coefficients of thermal expansion.
[0061] Another aspect of the present invention refers to the use of the material characterized in that it comprises the material of the present invention which in turn comprises
[0062] • a non-conductive polymeric substrate, preferably the polymeric substrate is selected from polydimethylsiloxane (PDMS) or polystyrene.
[0063] • a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, where each nanocapsule has
[0064] or a vertex,
[0065] or a height between 100nm and 500nm,
[0066] or a thickness of 40 nm and 300 nm
[0067] o and an aperture diameter between 200 nm and 1000 nm,
[0068] where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate, for the manufacture of a self-regulated dynamic artificial pupil with incident light / radiation for the treatment of pupil disorders such as unequal size of the pupils (anisocoria), unreactive pupils, miotic pupils, isochoric pupils, etc.
[0070] Another aspect of the present invention refers to the self-regulated dynamic artificial pupil with incident light / radiation characterized in that it comprises the material of the present invention which in turn comprises
[0071] • a non-conductive polymeric substrate, preferably the polymeric substrate is selected from polydimethylsiloxane (PDMS) or polystyrene.
[0072] • a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, where each nanocapsule has
[0073] or a vertex,
[0074] or a height between 100nm and 500nm,
[0075] or a thickness of 40 nm and 300 nm
[0076] o and an aperture diameter between 200 nm and 1000 nm,
[0077] where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate and where the substrate is a contact lens.
[0079] The dynamic artificial pupil comprising the material of the present invention consists of a circle of material with several cuts, in a preferred form of the invention with radial cuts from the center to near the edge, which give rise to triangular shaped cantilevers raised due to to the stress of the materials. Due to this design, the space in the center of the circle, which would correspond to the size of the pupil, has a fixed size in the absence of light and decreases in size proportionally to the intensity of incident light due to the change in the deflection of the triangular cantilevers, simulating the real response of the pupil.
[0081] The dynamic pupil solves one of the main limitations of ocular prostheses, where the absence of change in pupil size in different environments undermines the effort to achieve a realistic artificial eye, impacting on the quality of professional and social life of patients. Compared to other approaches where the artificial pupil also responds to changes in light, the advantages of the material of the present invention include:
[0082] • response to a wide range of the spectrum (not just UV),
[0083] • mechanically adjustable response (depending on the final thickness of the material and the cutting design).
[0085] Another aspect of the present invention refers to the ocular prosthesis that comprises the artificial pupil self-regulated with incident light / radiation that comprises the material of the present invention, which in turn comprises
[0086] • a non-conductive polymeric substrate, preferably the polymeric substrate is selected from polydimethylsiloxane (PDMS) or polystyrene.
[0087] • a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, where each nanocapsule has
[0088] or a vertex,
[0089] or a height between OO nm and 500nm,
[0090] or a thickness of 40 nm and 300 nm
[0091] o and an aperture diameter between 200 nm and 1000 nm,
[0092] where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate and where the substrate is a lens.
[0093] In the present invention, "ocular prosthesis" is understood as that artificial tissue or structure intended to be used as an ocular implant.
[0095] The last aspect of the present invention refers to the material of the present invention characterized in that it comprises
[0096] • a non-conductive polymeric substrate, preferably the polymeric substrate is selected from polydimethylsiloxane (PDMS), polystyrene or a silicone hydrogel,
[0097] • a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, where each nanocapsule has
[0098] or a vertex,
[0099] or a height of betweenOOnmy500nm,
[0100] or a thickness of 40 nm and 300 nm
[0101] o and an aperture diameter between 200 nm and 1000 nm,
[0102] where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate, for the treatment of pupil disorders.
[0104] Throughout the description and claims the word "comprise" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
[0106] BRIEF DESCRIPTION OF THE FIGURES
[0108] Fig. 1 SEM images of the nanostructured monolayer and scheme of the material of the present invention.
[0110] Fig. 2 Experimental measurement of the absorption of two types of different monolayers on a PDMS layer depending on the material (Fe and Au), carried out by UV-visible spectrometry and by FTIR.
[0112] Fig. 3 Experimental measurement of the reflection and transmission of two types of monolayers different on PDMS layer depending on the material (Fe and Au), performed by UV-visible spectrometry and by FTIR.
[0114] Fig. 4 Experimental measurement of the temperature change suffered by the material of the invention for two different types of monolayers depending on the material (Fe and Au) on PDMS when radiated by a source with a wavelength of 808 nm and 1470 nm , at two different angles (0 ° and 450).
[0116] Fig. 5 Color change suffered by the material of the invention with the shape of a cantilever represented by the change in the value of H (HSV space) obtained from the RGB analysis of the image, for different radiation powers, and the profile of the cantilever for three different powers.
[0118] Fig. 6. Shows the change in pupil diameter (open space in the center of the circle of material) measured experimentally when the material of the invention is radiated with different powers, and the dynamic change, and sequence of images corresponding to said powers radiation.
[0120] EXAMPLES
[0122] The invention will now be illustrated by means of tests carried out by the inventors, which show the effectiveness of the product of the invention.
[0124] Manufacture of the material of the invention
[0126] Figure 1 shows images obtained by scanning electron microscopy (SEM) of the material obtained from the assembly of polystyrene nanoparticles and the subsequent deposition of Fe or Au on said assembly. It also shows a diagram of the material object of the invention, where the size and thickness, t, of the nanocapsules are shown.
[0128] Figure 2 shows the absorption of the material in a range between 300 nm and 1600 nm, performed with a UV-visible spectrometer (a), and between 1000 nm and 18000 nm, performed with a Fourier transform infrared transmission spectrometer (FTIR ) (b), showing an average absorption of 84% for wavelengths of at least less until 18 pm in the Fe-polymer metamaterial. At the same time, the absorption in the case of the Au-polymer metamaterial presents an average absorption of 65-70%, being at least 17% lower than that obtained for Fe (See Figure 2).
[0130] Figure 3 shows the experimental measurements of reflection and transmission, with a range from 300 nm to 1600 nm and from 1000 nm to 18000 nm, for metamaterials comprising nanocome made with two different materials (Fe or Au) on PDMS. From these measures the absorption of each material is obtained. It can be seen how the reflection is lower in the case of the metamaterial that comprises Fe nanocapsules, while the transmission is the same, which shows the greater absorption of radiation in the case of Fe.
[0132] In comparison, in the material comprising Au nanocapsules there is an increase in reflection, as is already beginning to be observed in the simulations and experiments presented.
[0134] The experimental measurement of the temperature change suffered by the metamaterial with Fe or Au nanocapsules when radiated by a source with a wavelength of 808 nm and another of 1470 nm was also carried out, as shown in figure 5. The response of the metamaterial is the same in both cases, which shows the stability of the thermal response in a wide range of the spectrum, but it is much higher in the case of Fe nano-domes.
[0136] Application: uncooled mechanical radiation sensor
[0138] Figure 5 shows the color change experienced by the end of the cantilever calculated from the Hue (H) value (HSV space) of the image. The change in H demonstrates the deflection of a cantilever exposed to radiation of a wavelength of 808 nm and another of 1470 nm of different magnitudes. It also includes the cantilever profile for three different radiation magnitudes. The cantilever consists of a PDMS polymeric substrate with one of its faces periodically corrugated (diffraction grating); Fe nanocapsules are placed on its opposite side. Exposure to radiation produces an absorption by the material that generates a change in temperature in the material, as shown in figure 4. This change in temperature induces a change in the curvature of the cantilever due to the differences in the coefficients of expansion of the materials used. When a white light falls on the corrugated surface, the diffraction of the white light takes place in its different components of the spectrum, giving rise to a structural coloration of the cantilever. This coloration will change along the cantilever due to changes in its curvature, induced by changes in temperature of the material of the invention.
[0140] Application: Dynamic Iris
[0142] Figure 6 shows a self-regulating dynamic artificial pupil using the material of the present invention. The dynamic pupil made of the material of the present invention consists of a circle of material with several radial cuts from the center to near the edge, resulting in triangular shaped cantilevers raised due to the stress of the materials. Due to this design, the space that remains in the center of the circle, which would correspond to the size of the pupil, has a fixed size in the absence of light and decreases in size proportionally to the intensity of incident light due to the change in light. deflection of the triangular cantilevers, simulating the real response of the pupil (see sequence of images in Fig. 6). The change in deflection of the triangular cantilevers is due to the increase in temperature of the material when exposed to radiation, which gives rise to a change in surface tension in the cantilevers due to the difference in coefficients of expansion of the materials that form the material of the invention (polymer and Fe).

权利要求:
Claims (14)
[1]
1. Material that absorbs electromagnetic radiation of wavelengths between 300nm to 18pm characterized by comprising
• a polymeric substrate and
• a plurality of Fe, Co, Ni nanocapsules or an Fe alloy selected from Fe-Ni, Fe-Co, Fe-Ga or Fe-AI, where each nanocapsule has
or a vertex,
or a height between 100 nm and 500 nm,
or a thickness between 40 nm and 300 nm,
o and an aperture diameter between 200 nm and 1000 nm,
where each nanocapsule is arranged on the polymeric substrate so that its vertex is in direct contact with the polymeric substrate.
[2]
2. Material according to claim 1, wherein the polymeric substrate is selected from PDMS and polystyrene.
[3]
3. Material according to any of claims 1 or 2, wherein at least two nanocapsules are in contact with each other.
[4]
4. Material according to claim 3, wherein the contact is tangential.
[5]
5. Material according to any of claims 3 or 4, where all the nanocapsules have the same height.
[6]
6. Material according to any one of claims 1 or 2, wherein all the nanocapsules of the plurality are separated from each other.
[7]
7. Material according to any of claims 1 to 6, wherein the polymeric substrate has
• a first side periodically corrugated with a periodicity between 800 nm and 20000 nm and
• a second side,
and where the nanocapsules are arranged on the second side of the polymeric substrate.
[8]
Use of the material according to claim 7 as a cantilever support, preferably for photodetectors or photomechanical actuators.
[9]
An uncooled photodetector, characterized in that the sensor layer of the photodetector comprises the material according to claims 1 to 7.
[10]
10. Solar-powered photomechanical actuator characterized in that it comprises the material according to claims 1 to 7.
[11]
Use of the material according to claims 1 to 7 for the manufacture of a self-regulating dynamic artificial pupil with incident light / radiation for the treatment of disorders of the pupil.
[12]
12. Self-regulating dynamic artificial pupil with incident light / radiation characterized in that it comprises the material according to claims 1 to 7, wherein the non-conductive polymeric substrate is a lens.
[13]
An ocular prosthesis comprising the artificial pupil self-regulating with incident light / radiation according to claim 12.
[14]
14. Material according to any one of claims 1 to 7 for the treatment of pupil disorders.

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ES2832890B2|2021-10-27|

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WO2021116522A1|2021-06-17|

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ES201931100A|ES2832890B2|2019-12-11|2019-12-11|Material that absorbs electromagnetic radiation of wavelengths between 300 nm and 18 microns and applications|ES201931100A| ES2832890B2|2019-12-11|2019-12-11|Material that absorbs electromagnetic radiation of wavelengths between 300 nm and 18 microns and applications|

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PCT/ES2020/070778| WO2021116522A1|2019-12-11|2020-12-10|Material that absorbs electromagnetic radiation of wavelengths between 300 nm and 18 microns, and applications|