CN113514998B - Flexible tunable focusing lens and preparation method thereof - Google Patents
Flexible tunable focusing lens and preparation method thereof Download PDFInfo
- Publication number
- CN113514998B CN113514998B CN202010278254.5A CN202010278254A CN113514998B CN 113514998 B CN113514998 B CN 113514998B CN 202010278254 A CN202010278254 A CN 202010278254A CN 113514998 B CN113514998 B CN 113514998B
- Authority
- CN
- China
- Prior art keywords
- focusing lens
- flexible
- tunable focusing
- functional layer
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/008—Surface plasmon devices
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a flexible tunable focusing lens and a preparation method thereof, wherein the lens comprises an array formed by a plurality of structural units, each structural unit comprises a flexible first transparent substrate, and a transparent bottom electrode, a metal functional layer, an electrochromic layer and a transparent top electrode which are sequentially arranged on the flexible first transparent substrate from bottom to top; the metal functional layer comprises a nanorod array structure formed by periodically arranging a plurality of metal nanorods, and when different voltages are applied to the electrochromic layer through the bottom electrode and the top electrode, the refractive index and the extinction coefficient of the electrochromic layer are changed. The flexible tunable focusing lens can obtain images with different brightness by only loading a little voltage on the device, has simple and reasonable structure, is ultrathin, light, easy to integrate, low in power consumption and low in cost, is relatively easy to manufacture, is completely compatible with the existing semiconductor manufacturing process, and overcomes the defect that the tunable focusing lens can be obtained only by needing a complicated manufacturing process in the prior art.
Description
Technical Field
The invention relates to the technical field of optical element preparation, in particular to a flexible tunable focusing lens and a preparation method thereof.
Background
In conventional optical devices, the manipulation of optical waves is achieved by light propagating through a medium of a given refractive index, the changes in amplitude, phase and polarization are accumulated by propagation through the medium, and the associated optical components are cumbersome and difficult to integrate.
The object of miniaturization and integration of modern industry promotes the birth and development of micro-nano optics. The explosive development of super surfaces in recent years has provided a means to break through the above limitations. The super surface is an ultrathin artificial material and is formed by a micro-nano structure array with sub-wavelength size. Research shows that in the sub-wavelength size, light and the micro-nano structure act to generate a surface plasmon resonance phenomenon, and the resonance wavelength is accompanied with a phase mutation. By regulating and controlling the geometric shape and parameters of the micro-nano unit structure, the optical response of transmitted or reflected light can be accurately controlled, special phase mutation is generated at a specified wavelength, the purposes of deflecting, converging and separating light beams are achieved, and a new door is opened for the research of optical phase control. However, in general, the nanostructure constituting the super surface has only a single function once prepared, and lacks flexibility of active control, thereby greatly limiting the practical use thereof.
The future integrated optoelectronic devices need more adjustable, light and easy-to-integrate optical devices, and how to combine the super-surface with a tunable intelligent material to create an optoelectronic device capable of efficiently, flexibly and actively modulating electromagnetic waves in real time is a hot problem for research of scientists of various countries. However, the existing technology for manufacturing the focusing lens requires a cumbersome manufacturing process to be implemented, and requires considerable technical resources, financial resources, and time costs. This greatly restricts the market spread and application of the focusing lens.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a flexible tunable focusing lens based on a super-surface-electrochromic material, which has the advantages of excellent focusing performance, high modulation depth, fast response speed, low power consumption and low cost, and is easy to produce, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flexible tunable focusing lens comprises an array formed by a plurality of structural units, wherein each structural unit comprises a flexible first transparent substrate, and a transparent bottom electrode, a metal functional layer, an electrochromic layer and a transparent top electrode which are sequentially arranged on the flexible first transparent substrate from bottom to top; the metal functional layer comprises a nanorod array structure formed by periodically arranging a plurality of metal nanorods, and when different voltages are applied to the electrochromic layer through the bottom electrode and the top electrode, the refractive index and the extinction coefficient of the electrochromic layer are changed.
In one embodiment, the material of the metal functional layer includes gold or silver, or a combination of both.
In one embodiment, the flexible tunable focusing lens further includes a flexible second transparent substrate covering the outer surface of the top electrode.
As one embodiment, each nanorod in the metal functional layer is a cuboid with a preset rotation angle along the circumferential direction of the lens, and the array formed by the structural units has a plurality of different preset rotation angles.
As one of the embodiments, the phase delay Φ (x, y) of the rectangular parallelepiped at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the central point thereof, phi (0, 0) refers to the phase corresponding to the geometric central position of the flexible tunable focusing lens, x refers to the x-axis coordinate of the position corresponding to the cuboid, y refers to the y-axis coordinate of the position corresponding to the cuboid structure, lambda is the incident wavelength, and n is a positive integer.
In one embodiment, the electrochromic layer coats the top and side surfaces of the nanorod and is formed on the surface of the bottom electrode.
In one embodiment, the nanorods in the metal functional layer are spaced apart, and there is no space between the structural units.
Another objective of the present invention is to provide a method for manufacturing a flexible tunable focusing lens, comprising:
providing a transparent bottom electrode on a flexible first transparent substrate;
arranging a metal functional layer on the first transparent substrate, and processing and forming a nanorod array structure with periodically arranged metal nanorods in the metal functional layer to form a metal super surface;
disposing an electrochromic layer on the bottom electrode;
a transparent top electrode is disposed over the electrochromic layer.
As one embodiment, each nanorod in the metal functional layer is a cuboid with a preset rotation angle along the circumferential direction of the lens, and the array formed by the structural units has a plurality of different preset rotation angles.
As one of the embodiments, the phase delay Φ (x, y) of the rectangular parallelepiped at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the central point thereof, phi (0, 0) refers to the phase corresponding to the geometric central position of the flexible tunable focusing lens, x refers to the x-axis coordinate of the position corresponding to the cuboid, y refers to the y-axis coordinate of the position corresponding to the cuboid structure, lambda is the incident wavelength, and n is a positive integer.
As one embodiment, the step of processing to form a nanorod array structure with periodically arranged metal nanorods in the metal functional layer includes:
forming a patterned photoresist mask on the metal functional layer;
and etching the metal functional layer by adopting an ion beam etching technology to form the patterned metal functional layer.
As one embodiment, the step of disposing an electrochromic layer on the bottom electrode includes:
spin-coating an electrochromic material on the metal super-surface, wherein the electrochromic material uniformly covers the metal super-surface structure and is in contact with the bottom electrode;
and baking at the temperature of 80 ℃ for 60 minutes to cure the electrochromic material to form the electrochromic layer.
The flexible tunable focusing lens based on the super-surface-electrochromic material can dynamically switch the output energy of the device in real time only by loading a little voltage on the device so as to obtain images with different brightness, and an unexpected technical effect is achieved; meanwhile, the flexible tunable focusing lens provided by the invention has the advantages of simple and reasonable structure, ultra-thin, light and easy integration, low power consumption and low cost, is relatively easy to manufacture, and the preparation method of the flexible tunable focusing lens is completely compatible with the existing semiconductor manufacturing process, thereby overcoming the defect that the tunable focusing lens can be obtained only by a complicated preparation process in the prior art.
Drawings
Fig. 1 is a schematic view of a rotation state of a rectangular parallelepiped in a structural unit of a flexible tunable focusing lens based on a super surface-electrochromic material in embodiment 1 of the present invention;
fig. 2 is a schematic diagram of the internal structure of the flexible tunable focusing lens in the front view direction according to embodiment 1 of the present invention;
fig. 3 is a front view of a flexible tunable focusing lens of embodiment 1 of the present invention;
FIG. 4 is a schematic diagram of a flexible tunable focusing lens and a nanorod array therein according to example 1 of the present invention;
fig. 5 is a schematic view of a rotated state of a rectangular parallelepiped in a top view state in a structural unit of a flexible tunable focusing lens of embodiment 1 of the present invention;
fig. 6 is a transmittance curve of the electrochromic material of the flexible tunable focusing lens of example 1 in the visible light band, which is measured by an ultraviolet spectrophotometer, wherein a gray curve is the transmittance of the electrochromic material in the transparent state, and a black curve is the transmittance of the electrochromic material in the colored state;
fig. 7 is a refractive index curve of the electrochromic material of the flexible tunable focusing lens in embodiment 1 of the present invention in the visible light band, which is measured by using a j.a. woollam M-2000 ellipsometer and calculated by fitting using wvaso 32 software, wherein a gray dotted line is the refractive index of the electrochromic material in the transparent state, and a black solid line is the refractive index of the electrochromic material in the colored state;
fig. 8 is an extinction coefficient curve of the electrochromic material of the flexible tunable focusing lens in embodiment 1 of the present invention in the visible light band, which is measured by using a j.a. woollam M-2000 variable angle ellipsometer and calculated by fitting using WVase32 software, wherein the gray dotted line is the extinction coefficient of the electrochromic material in the transparent state, and the black solid line is the extinction coefficient of the electrochromic material in the colored state;
fig. 9 is a graph showing the transmission phase of the transmitted light with the rotation angle of the metal nanorods in different states of the electrochromic material when the single left-handed circularly polarized plane light with a wavelength of 632.8nm of example 1 of the present invention is vertically incident from right below the lens, where the dotted gray line is the transmission phase of the electrochromic material in the transparent state, and the solid black line is the transmission phase of the electrochromic material in the colored state;
FIG. 10 is a graph showing the transmission amplitude of the transmitted light with the rotation angle of the metal nanorods as a function of the transmission amplitude of the electrochromic material in the transparent state and the transmission amplitude of the electrochromic material in the colored state in different states of the electrochromic material when the single levorotatory circularly polarized plane light with the wavelength of 632.8nm of example 1 of the present invention is vertically incident from directly below the lens;
FIG. 11 is a diagram illustrating the Ey electric field intensity distribution of the surface scattering light of the super surface of the metal nanorods when the electrochromic material is in a transparent state, i.e., the tunable focusing lens is in a "strong" state, when a single plane of left-handed circular polarization with a wavelength of 632.8nm is vertically incident from directly below the lens in example 1 of the present invention;
FIG. 12 is a diagram showing Ey electric field intensity distribution of surface scattering light of the super surface of the metal nanorods when the electrochromic material is in a colored state, i.e. the tunable focusing lens is in a "weak" state, when a single plane of left-handed circular polarization with a wavelength of 632.8nm is vertically incident from directly below the lens in example 1 of the present invention;
FIG. 13 is an x-z cut normalized energy distribution curve of far field radiation of a transmitted beam when the electrochromic material is in a colored state (grey lines) and a transparent state (black lines), respectively, when light of a single left-handed circularly polarized plane having a wavelength of 632.8nm is vertically incident from directly below the lens, according to example 1 of the present invention.
Fig. 14 is a schematic diagram of a method for manufacturing a flexible tunable focusing lens according to embodiment 2 of the present invention.
Description of reference numerals:
10-a first transparent substrate; 20 a-bottom electrode; 20 b-top electrode; 30-a metal functional layer; 40-an electrochromic layer; 50-a second transparent substrate; 60-ion storage layer; 70-electrolyte layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1, the flexible tunable focusing lens according to the embodiment of the present invention is a structure based on a super-surface-electrochromic material technology, and includes an array structure formed by a plurality of structural units, where each structural unit includes a flexible first transparent substrate 10, and a transparent bottom electrode 20a, a metal functional layer 30, an electrochromic layer 40, and a transparent top electrode 20b sequentially disposed on the flexible first transparent substrate 10 from bottom to top. The metal functional layer 30 includes a nanorod array structure formed by periodically arranging a plurality of metal nanorods, and when different voltages are applied to the electrochromic layer 40 through the bottom electrode 20a and the top electrode 20b, the refractive index and the extinction coefficient of the electrochromic layer 40 are changed, that is, the complex dielectric constant is changed.
When the electrochromic material is injected or extracted with charges (ions or electrons) to change the refractive index and extinction coefficient of the electrochromic material, incident light enters the metal functional layer structure to excite surface plasmon to generate resonance. The electrochromic then acts to modulate the resonance characteristics. The dielectric constant of the electrochromic composite material changes with a change in voltage, resulting in a change in the frequency of resonance, thereby changing the amplitude and phase. According to the working principle of the metal focusing super-structure lens, the focal length is only determined by the relative phase distribution of the whole super-surface array. When the electrochromic material changes from a transparent state to a colored state, a parallel shift of the phase distribution occurs, while the relative phase distribution remains unchanged. However, the transmission amplitude is changed and varied due to the resonance absorption between the metal and the material, so that the focusing intensity of the transmitted light can be easily modulated by the voltage without changing the focal length, and the effect of adjusting the imaging brightness is finally achieved.
The top of the flexible tunable focusing lens may further include a flexible second transparent substrate 50, and the second transparent substrate 50 covers the outer surface of the top electrode 20b, so that the first transparent substrate 10 and the second transparent substrate 50 are respectively disposed on the outer surfaces of the bottom electrode 20a and the top electrode 20b, which can protect the internal structure of the lens and allow light to pass through.
In addition to the above-mentioned structural layers, as shown in fig. 1 and 3, the flexible tunable focusing lens of the present embodiment may further include an ion storage layer 60 and an electrolyte layer 70, wherein the top electrode 20b is disposed on the ion storage layer 60, the electrolyte layer 70 is disposed on the electrochromic layer 40 and provides a channel for transporting ions, and the ion storage layer 60 is disposed on the electrolyte layer 70 and is used for storing desired ions. The first transparent substrate 10, the bottom electrode 20a, the metal functional layer 30, the electrochromic layer 40, the electrolyte layer 70, the ion storage layer 60, the transparent top electrode 20b, and the second transparent substrate 50 are sequentially stacked from bottom to top.
The material of the first transparent substrate 10 preferably includes one or a combination of two or more of a poly (terephthalic acid) Plastic (PET), Polydimethylsiloxane (PDMS), and Polyimide (PI), and has a thickness of 2 to 125 μm. For example, the first transparent substrate 10 may be composed of a poly-p-phenylene-series plastic.
Preferably, the material of the bottom electrode 20a includes one or a combination of two or more of Indium Tin Oxide (ITO), zinc oxide (ZnO), silver silk ink, and single-layer graphene, and the thickness H1 is 50nm to 190nm, preferably 130nm to 160 nm.
Preferably, the material of the metal functional layer 30 is one or a combination of two of gold, silver and other materials that are easy to excite surface plasmon polariton, and the thickness H2 is 60nm to 100nm, preferably 70nm to 90 nm. The metal functional layer 30 is preferably made of gold because the gold has a mature manufacturing process, stable performance, is not easily corroded and oxidized, and has a long service life.
Preferably, the electrochromic layer 40 includes poly (ethylenedioxythiophene) -poly (styrenesulfonate) having a thickness H3 of 0.6 μm to 1.2 μm. For example, the electrochromic layer 40 is composed of a continuous polyethylenedioxythiophene-poly (styrenesulfonate) film.
Preferably, the electrolyte layer 70 is made of polyacrylate and has a thickness H4 of 40-80 μm. The material of the ion storage layer 60 is lithium fluoride, and its thickness H5 is 1 to 2 μm. The top electrode 20b has a thickness H6 of 50nm to 190nm, preferably 130nm to 160 nm. The bottom electrode 20a and the top electrode 20b may be made of the same material, and are both Indium Tin Oxide (ITO).
In the present embodiment, it is preferable that each nanorod in the metal functional layer 30 of each structural unit is a cuboid with a preset rotation angle along the circumferential direction of the lens, the array formed by the structural units has a plurality of different preset rotation angles, and the nanorod structure array is embedded in the electrochromic layer 40.
As shown in fig. 2, the length and width of the rectangular parallelepiped nanorod with a certain rotation angle in the nanorod array structure are both smaller than the period of the structural unit where the rectangular parallelepiped nanorod is located. Here, the definition "period" refers to a dimension of each structure in the arrangement direction when a plurality of structures are periodically arranged adjacent to each other. Preferably, each structural unit is the same, and each structural unit is closely connected, that is, there is no space between each structural unit, but there is a space between each nanorod in the metal functional layer 30, and the period of the structural unit is the length and width corresponding to the structural unit. In a specific embodiment, each structural unit includes a metal nanorod in the middle and a multi-layered film structure of upper and lower layers (i.e., the first transparent substrate 10, the bottom electrode 20a, the metal functional layer 30, the electrochromic layer 40, the electrolyte layer 70, the ion storage layer 60, the top electrode 20b, the second transparent substrate 50). The length and the width of the cuboid with the rotation angle in the nanorod array structure are both smaller than the period of the structural unit where the cuboid is located, namely, the cuboid nanorod is completely located in the structural unit and does not exceed the boundary of the structural unit.
Preferably, the multilayer film structures are squares with equal length and width, and are connected with each other without intervals, and the metal nanorods are all in the positive center of the structural unit in the arrangement direction, wherein, the distance between the nanorods is related to the period of the structural unit and the length and the rotation angle of the nanorods. Here, the period of each structural unit is 300nm to 340nm, preferably, the side length of each layer of square film structure is 320nm, then the period of each structural unit is 320nm, for different wavelengths, a good focusing function can be obtained by changing the side length of the cuboid nanorod, the length L of the cuboid is 240nm to 280nm (preferably 240nm to 250nm), the width W of the cuboid is 80nm to 120nm, the central rotation angle is changed at 0 to 180 °, and the height of the cuboid is 60nm to 100 nm. The optimized parameters can make the structure achieve the advantages of best adjustability and better focusing performance.
Fig. 5 is a schematic view of a rotated state of a rectangular parallelepiped in a top view state in a structural unit of a flexible tunable focusing lens according to embodiment 1 of the present invention.
As shown in FIGS. 2-5, the distance d between nanorods is the product of the period p of the structural unit minus the cosine value between the length L of the nanorod and the rotation angle nanorod, i.e.: d-p-L cos (θ).
It can be seen from fig. 4 that the nanorod array mode of this embodiment has a certain rule, and the rotation angle θ of the nanorod structure and the phase delay Φ (x, y) at the corresponding position thereof satisfy a preset condition, which is directly related to the phase delay of each nanorod structure. Specifically, the phase delay Φ (x, y) of the rectangular parallelepiped at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the central point thereof, phi (0, 0) refers to the phase (unit: radian) corresponding to the geometric central position of the flexible tunable focusing lens, x refers to the x-axis coordinate (unit: um) at the position corresponding to the cuboid, y refers to the y-axis coordinate (unit: um) at the position corresponding to the cuboid structure, lambda is the incident wavelength (unit: um), and n is a positive integer.
The nanorod structure array is embedded in the electrochromic layer 40, and specifically, the electrochromic layer 40 coats the top and side surfaces of the nanorods and is formed on the surface of the bottom electrode 20 a.
The flexible tunable focusing lens comprises a plurality of structural units, each structural unit is a device, the electrochromic layer 40 changes the refractive index and extinction coefficient of the electrochromic material, namely changes the complex dielectric constant of the electrochromic material, by injecting or extracting charges (ions or electrons) under the action of alternating high-low or positive-negative external electric fields, so that reversible change is generated between a coloring state with low transmissivity and a decoloring state with high transmissivity, the reversible change is expressed in appearance performance as reversible change of color and transmissivity, and the flexible tunable focusing lens has the excellent properties of high reaction speed, continuous tunable property, low power consumption, open-circuit memory property and the like.
Referring to fig. 6 to 13, in the embodiment of the present invention, the refractive index and extinction coefficient curves of the electrochromic material in the visible light band are measured by an ellipsometer.
FIG. 6 is a graph of transmittance of an electrochromic material of a flexible tunable focusing lens in the visible light band, as measured by an ultraviolet spectrophotometer, where the gray curve is the transmittance of the electrochromic material in the transparent state and the black curve is the transmittance of the electrochromic material in the colored state;
fig. 7 is a refractive index curve of the electrochromic material of the flexible tunable focusing lens in the visible light band, which is measured by using a j.a. woollam M-2000 ellipsometer and calculated by fitting using wvasose 32 software, where a gray dotted line is a refractive index of the electrochromic material in a transparent state, and a black solid line is a refractive index of the electrochromic material in a colored state;
fig. 8 is an extinction coefficient curve of the electrochromic material of the flexible tunable focusing lens in the visible light band, which is measured by using a j.a.woollam M-2000 ellipsometer and calculated by fitting using wvasose 32 software, where a gray dotted line is an extinction coefficient of the electrochromic material in a transparent state, and a black solid line is an extinction coefficient of the electrochromic material in a colored state;
FIG. 9 is a graph showing the transmission phase of the transmitted light with the rotation angle of the metal nanorods in different states of the electrochromic material when the single levorotatory circularly polarized plane light with a wavelength of 632.8nm is vertically incident from right below the lens according to the embodiment of the present invention, wherein the gray dotted line is the transmission phase of the electrochromic material in the transparent state, and the black solid line is the transmission phase of the electrochromic material in the colored state;
FIG. 10 is a graph showing the transmission amplitude of the transmitted light with the rotation angle of the metal nanorods in different states of the electrochromic material when the single levorotatory circularly polarized plane light with a wavelength of 632.8nm is vertically incident from right under the lens according to the embodiment of the present invention, wherein the gray dotted line is the transmission amplitude of the electrochromic material in the transparent state, and the black solid line is the transmission amplitude of the electrochromic material in the colored state;
FIG. 11 is a diagram illustrating the Ey electric field intensity distribution of the surface scattering light of the super surface of the metal nanorods when the electrochromic material is in a transparent state, i.e., the tunable focusing lens is in a "strong" state, when a single levorotatory circularly polarized plane light with a wavelength of 632.8nm is vertically incident from directly below the lens according to an embodiment of the present invention; according to the distribution of the electric field intensity, different gold nanorods modulate the phase and amplitude of transmitted light, the transmitted light can obtain a special emission angle by arraying the arranged mode of the designed gold nanorod formula, and finally a focusing effect is formed.
FIG. 12 is a diagram showing Ey electric field intensity distribution of surface scattering light of the super surface of the metal nanorods when the electrochromic material is in a colored state, i.e. the tunable focusing lens is in a "weak" state, when a single plane of left-handed circular polarization with a wavelength of 632.8nm is vertically incident from directly below the lens according to an embodiment of the present invention. According to the distribution of the electric field intensity, different gold nanorods modulate the phase and amplitude of transmitted light, and the transmitted light can obtain a special emission angle and can still form a good focusing effect finally by arraying the arranged mode of the designed gold nanorod formula, but at the moment, the electrochromic material and the metal structure generate extremely strong resonance and absorption loss on the incident light, so that the energy of the transmitted light is greatly reduced, and only weak energy focusing can be obtained finally.
FIG. 13 is an x-z cut normalized energy distribution curve of transmitted beam far field radiation when the electrochromic material is in the colored state (grey lines) and transparent state (black lines), respectively, for a single levorotatory circularly polarized planar light having a wavelength of 632.8 nanometers, incident normally from directly below the lens, according to an embodiment of the present invention.
A graph of phase and amplitude of a light field is simulated and calculated by using FDTD Solution (Canada) software, a 3D mode is selected for building a structure, and a periodic boundary condition is set in the horizontal direction. In the vertical direction, due to the existence of various media, a perfect matching layer is utilized in the boundary condition, the simulated light source is a plane wave, the simulated light source is arranged right below the bottom of the flexible tunable focusing lens based on the super-surface-electrochromic material, and the wavelength of the simulated light source is 632.8 nm. Aiming at the structural optimization and the performance analysis of the flexible tunable focusing lens with 632.8nm wavelength, when lambda is0632.8 nm: p-320 nm, H1-185 nm, H2-80 nm, H3-1 μm, H4-80 μm, H5-1 μm, H6-185 nm, L-260 nm, and W-100 nm. The circularly polarized plane wave is vertically incident to the lower surface of the gold nanorod unit, the transmission phase and the amplitude are scanned while the rotation angle of the gold nanorod is changed, when the electrochromic material is in a transparent state, the light transmission phase changes in a gradient way along with the change of the rotation angle of the gold nanorod, and the change of the transmission phase is twice of the rotation angle, which means that the distribution of the transmission phase in 360 degrees can be obtained by rotating the nanopillars by 180 degrees, and at the same time, when the nanorods are rotated, which has a high transmission amplitude and remains substantially unchanged, when the electrochromic material is in the colored state, with the change of the rotation angle of the gold nanorod, the light transmission phase also has gradient change, compared with the transparent state, the transmission phases are increased and the increased values are basically the same, and at the same time, the transmission amplitude is greatly reduced, and only a small transmission amplitude can be obtained.
According to the phase response curves shown in the respective figures, in this case, a transmission phase distribution close to 360 ° can be obtained by changing the rotation angle of the rectangular parallelepiped regardless of whether the electrochromic material is in a transparent or colored state. And according to preset conditions, periodically arranging the gold nanorods with different rotation angles according to the formula, and thus obtaining the lens with the focusing function.
In the structural unit, the electrochromic layer 40 is arranged above the transparent bottom electrode 20a and covers the upper surface and the side surface of the metal nanorod array structure, when a negative (-2.3v) voltage is applied to the device, ions stored in the ion storage layer 60 are transported towards the electrochromic layer 40 through the channel of the electrolyte layer 70 and are injected into the electrochromic layer 40, at this time, the electrochromic material and the ions are subjected to a chemical reaction to form a colored state, the refractive index is 1.437, and the extinction coefficient is 0.101; when a forward (2.5v) voltage is applied to the device, ions in the electrochromic material are extracted, transported towards the electrochromic layer 40 through the channel of the electrolyte layer 70, and returned to the ion storage layer 60, and at this time, the electrochromic material also undergoes a corresponding chemical reaction, and is in a transparent state, the refractive index is 1.412, and the extinction coefficient is 0.018. Therefore, when the electrochromic material injects or extracts charges (ions or electrons) to change the refractive index and the extinction coefficient (namely, the complex dielectric constant is changed), incident light enters the metal structure to excite surface plasmon to generate resonance. The electrochromic then acts to modulate the resonance characteristics. The dielectric constant of the electrochromic composite material changes with the change of voltage, resulting in the change of the frequency of resonance, thereby changing the amplitude and phase. According to the working principle of the metal focusing super-structure lens, the focal length is only determined by the relative phase distribution of the whole super-surface array, when the electrochromic material is changed from a transparent state to a colored state, the parallel movement of the phase distribution can occur, and the relative phase distribution is kept unchanged. However, the transmission amplitude is changed and varied due to the resonance absorption between the metal and the material, so that the focusing intensity of the transmitted light can be easily modulated by the voltage without changing the focal length, and the effect of adjusting the imaging brightness is finally achieved.
Therefore, the gold nanorods which are distributed with the rotation angle of 0-180 degrees are covered on the transparent bottom electrode 20a according to the arrangement mode described by the formula, the electrochromic layer 40 is covered on the super-surface structure, the electrolyte layer 70, the ion storage layer 60, the top electrode 20b and the second transparent substrate 50 are sequentially covered on the electrochromic material, when the electrochromic material is adjusted to be in a transparent state by loading voltage, the device has a good focusing function and can obtain stronger focusing energy, and when the electrochromic material is adjusted to be in a colored state, the device still has the focusing function but can only obtain weaker focusing energy, so that the amplitude tunable focusing lens with good performance is obtained.
Analysis shows that when the electrochromic material has color changing characteristics, the refractive index and the extinction coefficient of the electrochromic material are changed, namely the dielectric property of the electrochromic material is changed. When the dielectric properties of the surrounding environment of the nanostructure change, the resonant frequency shifts. By utilizing the characteristic, the flexible tunable focusing lens based on the super-surface-electrochromic material is designed by combining the super-surface structure and the electrochromic material. Therefore, the flexible tunable focusing lens provided by the embodiment of the invention has the following characteristics:
(1) different from components of a pure electrochromic material structure, the flexible tunable focusing lens provided by the embodiment of the invention utilizes the property that the refractive index and the extinction coefficient of the flexible tunable focusing lens can be regulated and controlled by voltage, and is combined with a super surface consisting of metal nano structures to dynamically regulate and control incident visible light in real time;
(2) the device is easier to realize in theory and experiment (no structure is needed on the electrochromic material), and has operability of voltage regulation and control.
Through the embodiments, it can be found that the flexible tunable focusing lens based on the super-surface-electrochromic material can modulate the working wavelength band according to the structural parameters. The flexible tunable focusing lens based on the super-surface-electrochromic material has excellent electrical regulation performance, one beam of circularly polarized visible light (632.8nm) synthesized by two linearly polarized lights with the same amplitude, the polarization directions of the linearly polarized lights respectively along the x direction and the y direction and the phase difference of 90 degrees vertically enters the flexible tunable focusing lens from the position right below the bottom of a device, voltage is loaded on the structure, when the voltage is regulated, the refractive index n of the electrochromic material is 1.412, and the extinction coefficient k is 0.018, the focusing lens is in a strong state, the good focusing performance is displayed, the normally incident elliptically polarized visible light can be focused, and the transmission energy is strong; when the voltage is adjusted so that the refractive index n of the electrochromic material is 1.437 and the extinction coefficient k is 0.101, the focusing lens is in a "weak" state, and can also exhibit good focusing performance, but the transmitted energy is greatly reduced. The output energy of the device can be dynamically switched from time to time only by loading a little voltage on the device so as to obtain images with different brightness, an unexpected technical effect is obtained, and when other parameters are fixed and unchanged, the phase and amplitude of transmitted light can change along with the change of the rotation angle of the metal nano rod, but the frequency of light does not change; meanwhile, the flexible tunable focusing lens based on the super-surface-electrochromic material has the advantages of simple and reasonable structure, ultra-thin, light and easy integration, low power consumption, low cost and relative easy manufacture, and the preparation method is completely compatible with the existing semiconductor manufacturing process; the defect that the tunable focusing lens can be obtained only by a complicated preparation process in the prior art is overcome.
The nanorod array structure arranged periodically is formed in the metal functional layer 30 by etching, and it is necessary to ensure that the slits penetrate through the metal layer in the etching process, and the transparent bottom electrode 20a arranged below the metal functional layer 30 cannot be damaged. In a specific implementation process, a working waveband corresponding to the structural parameter of the flexible tunable focusing lens is a visible light waveband, and the specific working waveband can be modulated according to the selection of the structural parameter.
Example 2
As shown in fig. 14, the present invention further provides a method for preparing the flexible tunable focusing lens based on the super-surface-electrochromic material in embodiment 1, including the following steps:
s01, disposing a transparent bottom electrode 20a on a flexible first transparent substrate 10.
Specifically, the bottom electrode 20a may be formed on the first transparent substrate 10 using an optical coating technique, or the bottom electrode 20a may also be formed on the first transparent substrate 10 using a magnetron sputtering coating technique. Here, it is preferable to plate a continuous indium tin oxide thin film according to the range of the operating wavelength.
The material of the first transparent substrate 10 is preferably cleaned in advance to remove dirty spots and oil stains on the surface, so that the surface of the first transparent substrate 10 has better cleanliness and adhesion;
s02, arranging a metal functional layer 30 on the first transparent substrate 10, and processing to form a nanorod array structure with periodically arranged metal nanorods in the metal functional layer 30 to form a metal super surface.
In a specific embodiment, the metal functional layer 30 may be formed on the first transparent substrate 10 using an electron beam evaporation coating technique.
The step of processing to form a nanorod array structure with periodically arranged metal nanorods in the metal functional layer 30 may include:
coating (for example, spin-coating) photoresist on the metal functional layer 30, and etching a photoresist structure of a pattern corresponding to the periodic nanorod array by using an electron beam exposure technology to form a patterned photoresist mask;
and etching the metal functional layer 30 by adopting an ion beam etching technology to pattern the metal functional layer, removing the photoresist remained on the metal functional layer 30, and forming the patterned metal functional layer 30, namely manufacturing the nanorod array structure in periodic gradient arrangement. The photoresist can be removed by placing the etched sample into a beaker filled with acetone, and ultrasonically removing the residual photoresist to obtain the metal super-surface structure.
S03, disposing the electrochromic layer 40 on the bottom electrode 20 a.
This step is specifically to make the electrochromic layer 40 coat the side and top surfaces of the metal nanostructure at the same time, and includes:
spin-coating an electrochromic material uniformly covering the metal super-surface structure and contacting the bottom electrode 20a on the metal super-surface;
the electrochromic material was cured by baking at a temperature of 80 deg.c for 60 minutes to form the electrochromic layer 40.
After disposing the electrochromic layer 40 on the bottom electrode 20a, forming a transparent top electrode 20b above the electrochromic layer 40, specifically including:
s04, disposing the electrolyte layer 70 on the electrochromic layer 40.
In a particular embodiment, the electrolyte layer 70 may be formed on the cured electrochromic layer 40 using a printing (e.g., doctor blading) technique.
S05, the ion storage layer 60 is provided on the electrolyte layer 70.
In a specific embodiment, the ion storage layer 60 can also be formed on the electrolyte layer 70 by a printing (e.g., doctor blading) technique in the same manner as the step of forming the electrolyte layer 70.
S06, disposing the transparent top electrode 20b and the flexible second transparent substrate 50 on the ion storage layer 60, disposing the second transparent substrate 50 plated with the transparent top electrode 20b on the ion storage layer 60, and attaching the top electrode 20b and the ion storage layer 60 together to form the tunable focusing lens.
Each nanorod in the metal functional layer 30 is a cuboid with a preset rotation angle along the circumferential direction of the lens, and an array formed by the structural units has a plurality of different preset rotation angles.
The rotation angle theta of the nanorod structures and the phase delay phi (x, y) at the corresponding positions thereof satisfy a preset condition that is directly related to the phase delay of each nanorod structure. Specifically, the phase delay Φ (x, y) of the rectangular parallelepiped at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the center point thereof, phi (0, 0) refers to the phase corresponding to the geometric center position of the flexible tunable focusing lens, x refers to the x-axis coordinate of the corresponding position of the cuboid, y refers to the y-axis coordinate of the corresponding position of the cuboid structure, lambda is the incident wavelength, and n is a positive integer.
In a more specific embodiment, the preparation method may specifically include:
firstly, forming a bottom electrode 20a on a first transparent substrate 10 by using an optical coating technology, forming a metal functional layer 30 on the first transparent substrate 10 by using an electron beam evaporation coating technology, then coating a layer of photoresist on the metal functional layer 30, etching a nanorod array photoresist structure with periodic gradient arrangement according to a position defined by a formula of phase delay phi (x, y) by using an electron beam exposure technology, etching the functional metal layer 30 by using an ion beam etching process to pattern the functional metal layer, then removing residual photoresist to obtain a metal super surface structure, then, coating an electrochromic layer 40 on the processed metal super surface to uniformly cover the super surface structure and contact with the transparent bottom electrode 20a, baking for 60 minutes at the temperature of 80 ℃ to solidify the super surface structure, and then forming an electrolyte layer 70 on the solidified electrochromic layer 40 by using a printing (such as blade coating) technology, and then, forming an ion storage layer 60 on the electrolyte layer 70 by using a printing (such as knife coating) technology, finally, placing the second transparent substrate 50 plated with the transparent top electrode 20b on the ion storage layer 60, and attaching the top electrode 20b and the ion storage layer 60 to form the flexible tunable focusing lens based on the super-surface-electrochromic material.
In the technical scheme, electron beams can be adopted for direct exposure and development, then the photoresist is etched by an ion beam etching technology, and residual photoresist is removed by utilizing acetone.
By adopting the preparation method, the preparation method has wide raw material sources, simple preparation, lower financial and time cost and excellent performance compared with the prior art, and has great application value in optical communication systems, advanced nano-photonic devices and integrated optical systems.
Example 3
The embodiment provides the application of the flexible tunable focusing lens based on the super-surface-electrochromic material in the preparation of an optical communication system, a nano-photonic device or an integrated optical system. The flexible tunable focusing lens has the characteristics of simple structure, flexible regulation, thinness, portability, easy integration, low power consumption, low cost and relative easy manufacture, and has great application value in optical communication systems, portable photographic equipment, micro-imaging systems and integrated optical systems.
In summary, the flexible tunable focusing lens and the preparation method thereof of the present invention have the following advantages:
1) the flexible tunable focusing lens based on the super-surface-electrochromic material has excellent beam splitting performance and excellent electric regulation performance, and when the voltage is regulated, the refractive index and extinction coefficient of the electrochromic material are as follows: when the refractive index n is 1.412 and the extinction coefficient k is 0.018, the focusing lens is in a "strong" state, exhibits good focusing performance, can focus elliptically polarized visible light that is normally incident, and has high transmission energy. When the voltage is adjusted so that the refractive index and extinction coefficient of the electrochromic material are: when the refractive index n is 1.437 and the extinction coefficient k is 0.101, the focusing lens is in a "weak" state, and can exhibit good focusing performance, but the transmitted energy is greatly reduced. The output energy of the device can be dynamically switched in real time only by loading a little voltage on the device so as to obtain images with different brightness, and an unexpected technical effect is achieved.
2) The flexible tunable focusing lens based on the super-surface-electrochromic material has a simple and reasonable structure, is different from a pure electrochromic material or a super-surface component, utilizes the property that the complex refractive index, namely the complex dielectric constant, of the electrochromic material can be regulated and controlled by voltage, is easier to realize theoretically and experimentally due to no need of manufacturing a structure on the electrochromic material, is ultrathin, light, easy to integrate, low in power consumption and cost, relatively easy to manufacture, completely compatible with the existing semiconductor manufacturing process, overcomes the defect that the focusing lens can be obtained only by a complicated manufacturing process in the prior art, and has operability of voltage regulation and control.
3) The preparation method has the advantages of wide raw material source, simple preparation, lower financial and time cost and excellent performance compared with the prior art, and has great application value in optical communication systems, advanced nano-photonic devices and integrated optical systems.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (12)
1. The flexible tunable focusing lens is characterized by comprising an array formed by a plurality of structural units, wherein each structural unit comprises a flexible first transparent substrate (10), and a transparent bottom electrode (20a), a metal functional layer (30), an electrochromic layer (40) and a transparent top electrode (20b) which are sequentially arranged on the flexible first transparent substrate (10) from bottom to top; the metal functional layer (30) comprises a nanorod array structure formed by periodically arranging a plurality of metal nanorods, and when different voltages are applied to the electrochromic layer (40) through the bottom electrode (20a) and the top electrode (20b), the refractive index and the extinction coefficient of the electrochromic layer (40) are changed.
2. The flexible tunable focusing lens according to claim 1, wherein the material of the metal functional layer (30) comprises gold or silver, or a combination of both.
3. The flexible tunable focusing lens of claim 1, further comprising a flexible second transparent substrate (50), the second transparent substrate (50) overlying an outer surface of the top electrode (20 b).
4. The flexible tunable focusing lens of any one of claims 1 to 3, wherein each nanorod in the metal functional layer (30) is a cuboid with a preset rotation angle along the circumferential direction of the lens, and the array formed by the structural units has a plurality of different preset rotation angles.
5. The flexible tunable focusing lens of claim 4, wherein the phase delay φ (x, y) of the cuboid at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the central point thereof, phi (0, 0) refers to the phase corresponding to the geometric central position of the flexible tunable focusing lens, x refers to the x-axis coordinate of the position corresponding to the cuboid, y refers to the y-axis coordinate of the position corresponding to the cuboid structure, lambda is the incident wavelength, and n is a positive integer.
6. The flexible tunable focusing lens of claim 5, wherein the electrochromic layer (40) coats the top and side surfaces of the nanorods and is formed on the surface of the bottom electrode (20 a).
7. The flexible tunable focusing lens of claim 4, wherein each nanorod in the metal functional layer (30) is spaced apart, and each structural unit is free of space.
8. A method of making a flexible tunable focusing lens, comprising:
providing a transparent bottom electrode (20a) on a flexible first transparent substrate (10);
arranging a metal functional layer (30) on the first transparent substrate (10), and processing and forming a nanorod array structure with periodically arranged metal nanorods in the metal functional layer (30) to form a metal super surface;
-providing an electrochromic layer (40) on said bottom electrode (20 a);
a transparent top electrode (20b) is disposed over the electrochromic layer (40).
9. The method for preparing a flexible tunable focusing lens according to claim 8, wherein each nanorod in the metal functional layer (30) is a rectangular parallelepiped with a predetermined rotation angle along the circumferential direction of the lens, and the array formed by the structural units has a plurality of different predetermined rotation angles.
10. The method of manufacturing a flexible tunable focusing lens of claim 9, wherein the phase retardation Φ (x, y) of the cuboid at each position satisfies:
wherein f refers to the focal length from the focal point of the flexible tunable focusing lens to the central point thereof, phi (0, 0) refers to the phase corresponding to the geometric central position of the flexible tunable focusing lens, x refers to the x-axis coordinate of the position corresponding to the cuboid, y refers to the y-axis coordinate of the position corresponding to the cuboid structure, lambda is the incident wavelength, and n is a positive integer.
11. The method for preparing a flexible tunable focusing lens according to any one of claims 8 to 10, wherein the step of processing and forming a nanorod array structure with periodically arranged metal nanorods in the metal functional layer (30) comprises:
forming a patterned photoresist mask on the metal functional layer (30);
and etching the metal functional layer (30) by adopting an ion beam etching technology to form the patterned metal functional layer (30).
12. The method of manufacturing a flexible tunable focusing lens according to any one of claims 8 to 10, wherein the step of disposing an electrochromic layer (40) on the bottom electrode (20a) comprises:
spin-coating an electrochromic material on the metallic super-surface, which uniformly covers the metallic super-surface structure and is in contact with the bottom electrode (20 a);
baking at 80 ℃ for 60 minutes to cure the electrochromic material, forming the electrochromic layer (40).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010278254.5A CN113514998B (en) | 2020-04-10 | 2020-04-10 | Flexible tunable focusing lens and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010278254.5A CN113514998B (en) | 2020-04-10 | 2020-04-10 | Flexible tunable focusing lens and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113514998A CN113514998A (en) | 2021-10-19 |
| CN113514998B true CN113514998B (en) | 2022-07-05 |
Family
ID=78061108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010278254.5A Active CN113514998B (en) | 2020-04-10 | 2020-04-10 | Flexible tunable focusing lens and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113514998B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115236773A (en) * | 2022-07-01 | 2022-10-25 | 天津山河光电科技有限公司 | Super-surface device, manufacturing method thereof and optical imaging system |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1801636B1 (en) * | 2004-09-10 | 2008-10-08 | Sumitomo Electric Industries, Ltd. | Transluscent display panel and method for manufacturing the same |
| CN104252055B (en) * | 2008-06-21 | 2019-08-02 | 凌威光电公司 | Use the electro-optical device of the dynamic restructuring of active electrode structure |
| CN101968593B (en) * | 2010-09-07 | 2013-01-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nano tube-polyurethane composite dimming film and preparation method thereof |
| EP3679110A1 (en) * | 2017-09-04 | 2020-07-15 | ABDULHALIM, Ibrahim | Spectral and phase modulation tunable birefringence devices |
| CN110837140A (en) * | 2019-11-14 | 2020-02-25 | 合肥工业大学 | Preparation method of gel microlens array |
-
2020
- 2020-04-10 CN CN202010278254.5A patent/CN113514998B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113514998A (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10775648B2 (en) | Systems and methods for implementing electrically tunable metasurfaces | |
| US20140085693A1 (en) | Metasurface nanoantennas for light processing | |
| Fang et al. | Broadband cross-circular polarization carpet cloaking based on a phase change material metasurface in the mid-infrared region | |
| Papadakis et al. | Field-effect induced tunability in hyperbolic metamaterials | |
| Wang et al. | Selective excitation of resonances in gammadion metamaterials for terahertz wave manipulation | |
| CN113514998B (en) | Flexible tunable focusing lens and preparation method thereof | |
| Shevchenko et al. | Bifacial metasurface with quadrupole optical response | |
| de Galarreta et al. | All-dielectric silicon/phase-change optical metasurfaces with independent and reconfigurable control of resonant modes | |
| Wang et al. | Metasurface empowered lithium niobate optical phased array with an enlarged field of view | |
| Bibbò et al. | Radiation-direction steerable nanoantennae | |
| Moitra et al. | Electrically tunable reflective metasurfaces with continuous and full-phase modulation for high-efficiency wavefront control at visible frequencies | |
| EP4058828A1 (en) | Method of manufacture of a metasurface | |
| CN112180649B (en) | Flexible tunable beam splitter and preparation method thereof | |
| Chung et al. | Tunable metasurface inverse design for 80% switching efficiencies and 144$^\circ $ angular steering | |
| Tang et al. | Dynamic beam scanning metasurface with high reflectivity and independent phase control based on phase change materials | |
| CN111999954A (en) | Optical device based on super-surface-electric dimming material and preparation method thereof | |
| Naserpour et al. | Plano-concave microlenses with epsilon-near-zero surface-relief coatings for efficient shaping of nonparaxial optical beams | |
| Gupta et al. | Longwave infrared tunable notch filters | |
| Hemmatyar et al. | Fano resonant all-dielectric metasurfaces for polarization-sensitive structural coloration | |
| Breedlove | Perovskite Material Development for Use in Plasmonic Devices | |
| KR102577916B1 (en) | Switchable metasurface device at visible light by changing temperature | |
| Lesina et al. | Nanophotonic optical phased arrays: opportunities and limitations | |
| CN118169907A (en) | All-medium tunable beam splitter, preparation method and application thereof | |
| Shalaginov et al. | Reconfigurable all-dielectric metalens based on phase change materials | |
| Chatterjee et al. | Generalized Brewster effect in aluminum-doped ZnO nanopillars |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |