CN111366991B - Optical super-structured surface, preparation method and processing device - Google Patents
Optical super-structured surface, preparation method and processing device Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
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Abstract
The embodiment of the invention discloses an optical super-structure surface, a preparation method and a processing device. The preparation method comprises the steps of providing an optical reaction tank, wherein the optical reaction tank comprises a first substrate, a second substrate and a metal salt precursor solution positioned between the first substrate and the second substrate, and a polyimide coating is arranged on one side, close to the metal salt precursor solution, of the first substrate; at least two beams with different polarization states are used for irradiating the optical reaction cell, and interference patterns with periodic polarization distribution are formed in the optical reaction cell by the at least two beams with different polarization states, so that an optical super-structure surface is formed in the optical reaction cell. The technical scheme of the embodiment of the invention has the advantages of no mask plate, simple and convenient operation and good effect, and can realize high-efficiency, low-cost, mass and large-area preparation of the optical super-structure surface.
Description
Technical Field
The embodiment of the invention relates to a micro-nano processing technology, in particular to an optical super-structure surface, a preparation method and a processing device.
Background
The optical super-structure surface is an ultrathin artificial interface capable of effectively regulating and controlling the amplitude, the phase and the polarization of electromagnetic waves on a sub-wavelength scale. The concept of the method is derived from three-dimensional metamaterial, the appearance of the three-dimensional metamaterial is similar to that of a traditional binary optical structure device, the practical application of the three-dimensional metamaterial in the optical field is restricted by the challenges and huge optical loss problems of the three-dimensional metamaterial in nano processing, and the two-dimensional metamaterial surface has obvious advantages in energy loss and processing difficulty and is the key of the practicability of the metamaterial. The metamaterial surface is an interface formed by introducing artificial metamaterial functional units with space change on a metal and medium material substrate, the metamaterial surface is novel in concept, is more inspired on the fields of optics, electromagnetics, materials and the like, can break through the limitation of the traditional electromagnetic law, is used for designing novel planar electromagnetics and optical devices, realizes the preparation of optical devices with compact volume and low loss, and provides a brand new technical approach for solving the problems of larger volume and weight, lower integration level and the like of a modern optical system.
At present, the optical super-structure surface is manufactured mainly by using methods such as electron beam etching, focused ion beams, nano-imprint etching technology and the like. The electron beam etching technology is a maskless process, is a common tool for preparing a planar nano structure, and can effectively avoid spots caused by the diffraction limit of light and realize nano-level fine processing because the de broglie wavelength of high-energy electrons is far less than the wavelength of light. The focused ion beam etching does not relate to a post-treatment process, and the operation process is relatively simple and has relatively high time efficiency. The manufacturing process of the nano-imprint etching technology is not limited by any diffraction or scattering effect, the structure with the minimum size of 10nm can be realized, the nano-structure can be prepared in batches, and the cost is reduced.
However, the electron beam lithography is limited by the small beam current of the electron beam and the exposure of the electron beam photoresist to effectively transfer the pattern, and is inefficient, expensive in manufacturing time and cost, expensive in equipment price, and not suitable for manufacturing large-area or batch-preparation of optical ultrastructural surfaces. The focused ion beam etching process is essentially a destructive and contaminating process, which, when a high energy ion beam is injected onto the sample surface, causes changes in the composition and shape of the metamaterial unit, further causes variations in its actual performance, and is not conducive to the fabrication of high quality optical metamaterial surfaces. Both electron beam etching and focused ion beam etching are not suitable for large-area and batch preparation of optical ultrastructural surfaces, but only for preparation of nanostructures with dimensions not exceeding millimeter magnitude. The preparation process of the template required by the nano-imprint etching technology is quite complex, and generally needs to be combined with other etching technologies, such as electron beam etching, focused ion beam, reactive ion etching and the like. Therefore, the development of a method for preparing the optical super-structure surface with higher efficiency, low cost, batch and large area has great significance for the development of the field.
Disclosure of Invention
Compared with the traditional optical super-structure surface preparation method, the optical super-structure surface preparation method has the advantages of no mask plate, simplicity and convenience in operation and good effect, and can realize efficient, low-cost, batch and large-area preparation of the optical super-structure surface.
In a first aspect, an embodiment of the present invention provides a method for preparing an optical nanostructured surface, including:
providing an optical reaction tank, wherein the optical reaction tank comprises a first substrate, a second substrate and a metal salt precursor solution positioned between the first substrate and the second substrate, and a polyimide coating is arranged on one side of the first substrate, which is close to the metal salt precursor solution;
and irradiating the optical reaction tank by using at least two beams of light with different polarization states, wherein the at least two beams of light with different polarization states form interference patterns with periodic polarization distribution in the optical reaction tank, so that an optical super-structure surface is formed in the optical reaction tank.
Optionally, the at least two light beams with different polarization states include one or two of circularly polarized light, elliptically polarized light, or linearly polarized light.
Optionally, the metal salt precursor solution includes silver nitrate or chloroauric acid.
Optionally, the polyimide coating is subjected to surface hydrophilization and roughening treatment by using ultraviolet ozone.
In a second aspect, an embodiment of the present invention further provides a device for processing an optical metamaterial surface, including a light source, a polarization beam splitting unit, a light path folding unit, and a polarization state adjusting unit;
the polarization beam splitting unit is used for receiving the output light beam of the light source and splitting the output light beam into a first light beam in a first polarization direction and a second light beam in a second polarization direction;
the polarization state adjusting unit is used for adjusting the polarization states of the first light beam and/or the second light beam so as to enable the polarization states of the two light beams to be different;
the light path turning unit is used for adjusting the transmission directions of the two light beams with different polarization states so as to enable the two light beams to form interference patterns with periodic polarization distribution in the optical reaction tank.
Optionally, the polarization beam splitter further includes an intensity adjusting unit disposed on the light path between the light source and the polarization beam splitter, and the intensity adjusting unit is configured to adjust an intensity ratio of the first light beam and the second light beam.
Optionally, the intensity adjustment unit includes a half-wave plate.
Optionally, the polarization beam splitter further includes a filtering unit disposed on an optical path between the light source and the polarization beam splitter.
Optionally, the polarization state adjusting unit includes a first quarter-wave plate and a second quarter-wave plate, the optical path deflecting unit includes a first mirror and a second mirror, the first quarter-wave plate and the first mirror are located on a propagation path of the first light beam, and the second quarter-wave plate and the second mirror are located on a propagation path of the second light beam.
In a third aspect, an embodiment of the present invention further provides an optical metamaterial surface formed by the above manufacturing method.
The preparation method of the optical surface provided by the embodiment of the invention comprises the steps of providing an optical reaction tank, wherein the optical reaction tank comprises a first substrate, a second substrate and a metal salt precursor solution positioned between the first substrate and the second substrate, and a polyimide coating is arranged on one side of the first substrate, which is close to the metal salt precursor solution; at least two beams with different polarization states are used for irradiating the optical reaction cell, and interference patterns with periodic polarization distribution are formed in the optical reaction cell by the at least two beams with different polarization states, so that an optical super-structure surface is formed in the optical reaction cell. Compared with the traditional optical super-structure surface preparation method, the method has the advantages of no mask plate, simplicity and convenience in operation and good effect, and can realize high-efficiency, low-cost, mass and large-area preparation of the optical super-structure surface.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an optical nanostructured surface according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of an optical reaction cell according to an embodiment of the present invention;
FIGS. 3-6 are schematic structural diagrams illustrating a process for forming an optical nanostructured surface according to an embodiment of the present invention;
FIG. 7 is a schematic microstructure of an optical nanostructured surface provided by an embodiment of the present invention;
fig. 8 is a schematic structural diagram of an apparatus for processing an optical meta-surface according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be further noted that, for the convenience of description, only some of the structures related to the present invention are shown in the drawings, not all of the structures.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. It should be noted that the terms "upper", "lower", "left", "right", and the like used in the description of the embodiments of the present invention are used in the angle shown in the drawings, and should not be construed as limiting the embodiments of the present invention. In addition, in this context, it is also to be understood that when an element is referred to as being "on" or "under" another element, it can be directly formed on "or" under "the other element or be indirectly formed on" or "under" the other element through an intermediate element. The terms "first," "second," and the like, are used for descriptive purposes only and not for purposes of limitation, and do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Fig. 1 is a schematic flow chart of a method for manufacturing an optical metamaterial surface according to an embodiment of the present invention, and referring to fig. 1, the present embodiment is applicable to manufacturing an optical metamaterial surface, and the method may be performed by an optical metamaterial surface processing apparatus, and specifically includes the following steps:
step S110, providing an optical reaction cell, where the optical reaction cell includes a first substrate, a second substrate, and a metal salt precursor solution located between the first substrate and the second substrate, and a polyimide coating is disposed on one side of the first substrate close to the metal salt precursor solution.
Fig. 2 is a schematic structural diagram of an optical reaction cell according to an embodiment of the present invention. Referring to fig. 2, the optical reaction cell includes a first substrate 10, a second substrate 20, and a metal salt precursor solution 30 between the first substrate 10 and the second substrate 20, and a polyimide coating 40 is disposed on a side of the first substrate 10 adjacent to the metal salt precursor solution 30.
The first substrate 10 and the second substrate 20 may be glass substrates. The metal salt precursor solution 30 contains metal ions that generate photochemical reactions when irradiated with light, and in the present embodiment, the metal salt precursor solution 30 may optionally include silver nitrate or chloroauric acid. The preparation process of the optical reaction tank comprises the following steps: spin-coating polyimide coating glue on a glass substrate with the size of 2cm multiplied by 2cm at 2500rpm, keeping the temperature at 200 ℃ for curing for 2h, and then carrying out ultraviolet ozone treatment for 25min when the glass substrate is cooled to room temperature; using a 300 mu m double-sided adhesive tape as a spacer, and enabling polyimide coated glass (a first substrate) and uncoated glass (a second substrate) to form an optical reaction cell; preparing sodium citrate and silver nitrate solution with the concentration of 0.01mol/L, and taking the equal volume of the sodium citrate and the silver nitrate solution in a 200 mu L centrifugal tube through a liquid transfer gun to be used as a metal growth solution; finally, 45 mu L of metal growth solution is taken by a pipette and injected into the optical reaction tank. The metal salt precursor used is for the purpose of facilitating the explanation of the effects of the production in the examples of the present invention, and is not intended to limit the examples of the present invention.
The polyimide coating 40 serves as a substrate for the growth of metal nanoparticles. Alternatively, the polyimide coating 40 is subjected to surface hydrophilization and roughening treatment using ultraviolet ozone. The polyimide coating treated by ultraviolet ozone plays a key role in the growth of the super surface of the metal nano-particles. The ultraviolet ozone treatment can not only increase the surface roughness of the coating, but also cause the imide ring cracking reaction to ensure that the surface of the coating is rich in hydrophilic groups such as carboxyl (-COOH) and hydroxyl (-OH), and the like, and the metal ions are promoted to be adsorbed at a solid-liquid interface together through the electrostatic attraction effect.
Step S120, at least two beams with different polarization states are used for irradiating the optical reaction cell, and interference patterns with periodic polarization distribution are formed in the optical reaction cell by the at least two beams with different polarization states, so that the optical reaction cell forms an optical super-structure surface.
Optionally, the at least two light beams with different polarization states include one or two of circularly polarized light, elliptically polarized light, or linearly polarized light. For example, the at least two light beams with different polarization states may be two (or more) light beams with circular (or elliptical) polarization interference, such as right-handed circularly polarized light and left-handed circularly polarized light; two (or more) linearly polarized light beams interfere; one (or more) circularly (or elliptically) polarized light and one (or more) linearly polarized light interfere, etc. The light beam can be a gaussian light beam, a vortex light beam and the like, the wave band of the light beam can be from ultraviolet to near infrared, the specific implementation can be selected according to the actual situation, and the embodiment of the invention is not limited.
Taking a metal salt precursor solution comprising sodium citrate and a silver nitrate solution as an example, fig. 3 to 6 are schematic structural diagrams of an optical metamaterial surface forming process provided by an embodiment of the invention. The principle of the preparation method of the optical super-structure surface provided by the embodiment of the invention is as follows:
firstly, a nucleation process. Upon irradiation of at least two consecutive light beams differing in polarization state, the citrate releases carbon dioxide and acts as an electron donor by photochemical oxidative decomposition, and then silver ions are reduced to zero-valent silver atoms, attached to the polyimide coating substrate surface by the following reaction, and serve as nucleation sites for the formation of silver nuclei:
it is noteworthy that the polyimide layer treated with uv ozone plays a key role in the growth of the silver nanoparticle super-surface. The ultraviolet ozone treatment not only can increase the surface roughness of the coating, but also can cause the imide ring cleavage reaction to ensure that the surface of the coating is rich in hydrophilic groups such as carboxyl (-COOH) and hydroxyl (-OH), and the like, and the silver ions are promoted to be adsorbed at a solid-liquid interface together through the electrostatic attraction effect, as shown in figure 3.
Secondly, growing. When the concentration of silver atoms near the polyimide interface fails to form new nucleation sites, it can only help the formed silver nuclei to grow into silver seeds, as shown in fig. 4. As the silver seed crystal continuously grows to form silver balls, when the size of the silver balls is close to the propagation distance of the surface plasmon, as shown in fig. 5, the electromagnetic field caused by the local plasmon resonance effect is greatly enhanced, the growth rate of the silver nanoparticles in the dipole direction thereof is much greater than that in other directions, and the particle size in the direction is significantly increased. Moreover, the action of gradient forces in the strong optical field causes silver cations or atoms to migrate more preferentially to the polarization direction, thereby creating an anisotropic ellipsoidal morphology oriented along the polarization direction, as shown in fig. 6. Furthermore, this polarization-oriented growth mechanism can be used for controlled oriented growth of particles immobilized on the substrate surface. In fact, the use of lower light intensity in this example, which is caused by single photon absorption during the formation and growth of the silver nanostructures, is compared to the multiphoton absorption process in pulsed laser-induced photochemical reactions.
FIG. 7 is a schematic view of a microstructure of an optical microstructured surface according to an embodiment of the present invention. Referring to fig. 7, the metal nanostructure is observed by a Scanning Electron Microscope (SEM), the prepared optical nanostructure has a good surface morphology, the direction of the metal silver particles shows periodic growth distribution, which is consistent with the adopted light polarization interference pattern, and it is proved that the method for imprinting the optical nanostructure surface by light polarization is feasible and has a good effect.
According to the technical scheme of the embodiment, the growth direction of the metal nanostructure is regulated and controlled by changing the light polarization pattern, the polyimide coating substrate is used as the substrate for growth, and the optical super-structured surface is constructed.
Fig. 8 is a schematic structural diagram of an optical metamaterial surface processing apparatus according to an embodiment of the present invention, the optical metamaterial surface processing apparatus according to the embodiment is used for performing the manufacturing method according to the embodiment to manufacture an optical metamaterial surface, and referring to fig. 8, the optical metamaterial surface processing apparatus includes a light source 100, a polarization beam splitting unit 200, an optical path folding unit 300, and a polarization state adjusting unit 400; the polarization beam splitting unit 200 is configured to receive an output light beam of the light source 100 and split the output light beam into a first light beam a with a first polarization direction and a second light beam b with a second polarization direction; the polarization state adjusting unit 400 is configured to adjust the polarization states of the first light beam a and/or the second light beam b, so that the polarization states of the two light beams are different; the optical path folding unit 300 is configured to adjust the transmission directions of the two light beams with different polarization states, so that the two light beams form an interference pattern with a periodic polarization distribution in the optical reaction cell 500.
In this embodiment, the light source 100 may be a laser, the light source 100 may be a 488nm continuous laser, the polarization beam splitting unit 200 may be a polarization beam splitting prism, the first light beam a may be a transmission light beam, the first polarization direction is P polarization, the second light beam b may be a reflection light beam, and the second polarization direction is S polarization.
Alternatively, the polarization state adjustment unit 400 includes a first quarter-wave plate 401 and a second quarter-wave plate 402, the optical path folding unit 300 includes a first mirror 301 and a second mirror 302, the first quarter-wave plate 401 and the first mirror 301 are located on the propagation path of the first light beam a, and the second quarter-wave plate 402 and the second mirror 302 are located on the propagation path of the second light beam b. The first quarter waveplate 401 and the second quarter waveplate 402 may modulate the two light beams into right-hand polarized light and left-hand polarized light, respectively.
According to the technical scheme of the embodiment, the output light beam of the light source is received through the polarization beam splitting unit, and the output light beam is split into a first light beam in a first polarization direction and a second light beam in a second polarization direction; the polarization state of the first light beam and/or the second light beam is adjusted through a polarization state adjusting unit, so that the polarization states of the two light beams are different; the transmission directions of the two light beams with different polarization states are adjusted through the light path turning unit, so that the two light beams form interference patterns with periodic polarization distribution in the optical reaction tank, the preparation method provided by the embodiment is utilized to realize the preparation of the optical super-structure surface, the preparation method has the advantages of no mask plate, simplicity and convenience in operation and good effect, and the high-efficiency, low-cost, mass and large-area preparation of the optical super-structure surface can be realized.
On the basis of the above technical solution, optionally, with reference to fig. 8, the processing apparatus further includes an intensity adjusting unit 600 disposed on the light path between the light source 100 and the polarization beam splitting unit 200, wherein the intensity adjusting unit 600 is configured to adjust an intensity ratio of the first light beam a to the second light beam b.
Optionally, the intensity adjustment unit 600 includes a one-half wave plate.
In one embodiment, the specific operation steps are as follows: firstly, the total output power of the light source 100 is adjusted to be 0.836W, then the intensity of the double light beams is adjusted to be 68.6mW by adjusting the intensity adjusting unit 600, the irradiation time is set to be 50min, the polyimide coated glass substrate is taken down after the reaction is finished, a layer of metal silver nano film grows on the surface of the polyimide coated glass substrate, the size of the metal silver nano film is about 1cm, and the preparation of a metal nano structure with a larger size can be realized by changing the size of a light spot interference area.
Optionally, with continued reference to fig. 8, the processing apparatus further includes a filtering unit 700 disposed on the optical path between the light source 100 and the polarization beam splitting unit 200.
Illustratively, the filtering unit 700 in this embodiment includes a stop 701 and a pinhole spatial filter 702, where the stop 701 is used to eliminate stray light, and the pinhole spatial filter 702 may be a precision pinhole and a lens set to improve beam quality.
It is understood that the structure and the optical path shown in fig. 8 are only schematic, and in the implementation, optical elements may be added or reduced according to actual situations, for example, a third mirror 800 may be further included, and the third mirror 800 reflects the light beam emitted from the light source 100 to the polarization beam splitting unit 200. In other embodiments, the optical path folding unit 300 may only have one mirror, and the order of the optical elements may be adjusted without affecting the function, so that only at least two light beams with different polarization states are required to irradiate the optical reaction cell.
The embodiment of the invention also provides an optical super-structure surface which is formed by adopting the preparation method provided by the embodiment.
The optical super-structure surface provided by the embodiment of the invention directly prepares the metal nano-structure on the surface of the substrate by using a light polarization imprinting method, and has the advantages of no mask plate, simple and convenient operation and good effect.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (10)
1. A method of making an optical nanostructured surface comprising:
providing an optical reaction tank, wherein the optical reaction tank comprises a first substrate, a second substrate and a metal salt precursor solution positioned between the first substrate and the second substrate, and a polyimide coating is arranged on one side of the first substrate, which is close to the metal salt precursor solution;
irradiating the optical reaction tank by using at least two beams of light with different polarization states, wherein the at least two beams of light with different polarization states form interference patterns with periodic polarization distribution in the optical reaction tank so as to form an optical ultrastructure surface in the optical reaction tank;
wherein the metal salt precursor solution contains metal ions that produce a photochemical reaction upon illumination.
2. The method of claim 1, wherein the at least two light beams having different polarization states comprise one or both of circularly polarized light, elliptically polarized light, or linearly polarized light.
3. The production method according to claim 1, wherein the metal salt precursor solution includes silver nitrate or chloroauric acid.
4. The method of claim 1, wherein the polyimide coating is surface hydrophilized and roughened using uv ozone.
5. An optical metamaterial surface processing apparatus for performing the fabrication method of any one of claims 1 to 4 to fabricate an optical metamaterial surface, comprising a light source, a polarization beam splitting unit, a light path folding unit, and a polarization state adjusting unit;
the polarization beam splitting unit is used for receiving the output light beam of the light source and splitting the output light beam into a first light beam in a first polarization direction and a second light beam in a second polarization direction;
the polarization state adjusting unit is used for adjusting the polarization states of the first light beam and/or the second light beam so as to enable the polarization states of the two light beams to be different;
the light path turning unit is used for adjusting the transmission directions of the two light beams with different polarization states so as to enable the two light beams to form interference patterns with periodic polarization distribution in the optical reaction tank.
6. The processing apparatus as claimed in claim 5, further comprising an intensity adjusting unit disposed on an optical path between the light source and the polarization beam splitting unit, the intensity adjusting unit being configured to adjust an intensity ratio of the first light beam and the second light beam.
7. The processing apparatus as claimed in claim 6, wherein the intensity adjustment unit comprises a half-wave plate.
8. The processing apparatus as claimed in claim 5, further comprising a filter unit disposed on an optical path between the light source and the polarization beam splitting unit.
9. The processing apparatus according to claim 5, wherein the polarization state adjustment unit comprises a first quarter wave plate and a second quarter wave plate, the optical path folding unit comprises a first mirror and a second mirror, the first quarter wave plate and the first mirror are located on a propagation path of the first light beam, and the second quarter wave plate and the second mirror are located on a propagation path of the second light beam.
10. An optical nanostructured surface formed by the production method according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010304921.2A CN111366991B (en) | 2020-04-17 | 2020-04-17 | Optical super-structured surface, preparation method and processing device |
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| CN202010304921.2A CN111366991B (en) | 2020-04-17 | 2020-04-17 | Optical super-structured surface, preparation method and processing device |
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