CN114815019A - Conductive particle variable array and preparation and application thereof - Google Patents
Conductive particle variable array and preparation and application thereof Download PDFInfo
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- 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
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Abstract
The invention provides a variable array of conductive particles, belongs to the field of plasma element optics, and provides a plasma element surface lattice resonance device with continuously adjustable electromagnetic field distribution performance of a plasma element, so that continuously adjustable spectroscopy application, second-order nonlinear optical application, chiral optical application and third-order nonlinear optical application are realized. The conductive particle variable array is formed by inserting two sets of conductive particle arrays, and continuous adjustment of the surface lattice resonance property of the plasma element is realized through the relative displacement between the two sets of conductive particle arrays. The invention also provides a manufacturing method of the conductive particle variable array, namely a conductive particle mosaic combination method, which realizes a strong and durable conductive particle variable array by embedding conductive particles into a substrate material, and can effectively prevent the conductive particles from accidentally falling off due to collision, friction and the like when adjusting the relative displacement between two sets of conductive particle arrays.
Description
Technical Field
The invention relates to the technical field of plasma element optics, in particular to a plasma element Surface Lattice Resonance (SLR) array with continuously adjustable plasma element electromagnetic field distribution performance.
Background
Plasmon Surface Lattice Resonance (SLR) is an optical resonance phenomenon, which has a wide range of applications. The surface of a single conductive particle can form Localized Surface Plasmon Resonance (LSPR), namely localized surface plasmon oscillation, and the array of the conductive particles can form a collective oscillation form of the localized surface plasmon oscillation (LSPR) under the irradiation of an external light beam with a specific working wavelength, so as to generate sharp resonant absorption, scattering, reflection spectrum peak values and related light wave phase mutation, namely a plasmon Surface Lattice Resonance (SLR) phenomenon. The plasmon Surface Lattice Resonance (SLR) system is an extremely important electromagnetic and optical research system, as described in the literature Chemical Reviews 2018,118, 5912-5951. The plasmon Surface Lattice Resonance (SLR) system can detect and control the polarization of light, and is used for enhancing Raman, detecting refractive index and detecting chirality; the laser can also be used as a laser resonant cavity to output laser, and can directly obtain various lasers with special properties, such as linear polarization, circular polarization, radial/angular polarization and the like.
The conventional plasma cell Surface Lattice Resonance (SLR) array is fabricated on a substrate such as a glass plate by means of electron beam lithography, and once fabricated, its shape does not change, and thus it lacks flexibility. There are documents such as Optical Materials Express vol.7, No.6,1886(2017) and Applied Physics Letters 96,041904(2010) that report that arrays of metal particles can be fabricated on flexible films, varying the distance between the particles by film stretching to change the plasmon Surface Lattice Resonance (SLR) properties, but are still not flexible enough. Many applications require a series of plasmon Surface Lattice Resonance (SLR) arrays with gradually changing properties, for example, parameters of the plasmon Surface Lattice Resonance (SLR) arrays are continuously adjusted to obtain the most sensitive refractive index detection sensitivity, the strongest nonlinear effect, and the like, for this reason, the conventional method can only prepare a large number of plasmon Surface Lattice Resonance (SLR) arrays with sequentially changing parameters, which is labor-consuming and laborious, and cannot adjust array parameters in real time in an optical test. Therefore, the preparation of the plasma element Surface Lattice Resonance (SLR) array with continuously adjustable plasma element electromagnetic field distribution performance is an urgent need in the fields of optical scientific research, physical scientific research, analytical detection, college teaching and the like.
Disclosure of Invention
The invention aims to provide a plasma element Surface Lattice Resonance (SLR) array with adjustable electromagnetic field distribution performance of a plasma element, in particular to a plasma element Surface Lattice Resonance (SLR) array formed by combining two sub-arrays capable of relatively displacing, and the tunable spectroscopy application, the second-order nonlinear optical application and the third-order nonlinear optical application are realized through the device.
In order to solve the technical problems mentioned in the background technology, the invention adopts the following technical scheme:
in one aspect, the present invention provides a variable array of conductive particles, comprising an array one and an array two; the first array and the second array are both two-dimensional crystal arrays consisting of a plurality of conductive particles; the first array is fixed on one plane of the first substrate and marked as a first plane, the second array is fixed on one plane of the second substrate and marked as a second plane, the first plane and the second plane are oppositely and parallelly placed, and a space is reserved between the first plane and the second plane or the first plane and the second plane are attached to each other. The first array and the second array can be moved by moving the first substrate and the second substrate.
Based on the above scheme, preferably, the fixing mode of the conductive particles on the first plane or the second plane is the first mode or the second mode;
the first method is as follows: the first plane and the second plane are both provided with a plurality of depressions, the conductive particles are filled in the depressions and do not protrude out of the first plane and the second plane, and the first plane is attached to the second plane;
the second method comprises the following steps: the conductive particles are directly attached to the first plane and the second plane, the first plane and the second plane are oppositely arranged, the conductive particles on the first plane and the conductive particles on the second plane are distributed in a staggered mode, the first array is not in contact with the second array and the second substrate, and the second array is not in contact with the first array and the first substrate.
Based on the above scheme, preferably, in the second mode, the space between the first plane and the second plane is an air gap excluding the first array and the second array, and the air gap is filled with liquid with the same refractive index as that of the first substrate and the second substrate, so that the refractive index of the environment where the variable array of conductive particles is located is uniform.
Based on the scheme, preferably, the first array and the second array both satisfy the translational symmetry of the two-dimensional crystal (when the array boundary is ignored), and the first array and the second array can be the same or different; the first array and the second array can be relatively displaced, so that the variable array of the conductive particles can be changed in geometric shape.
The geometry change cannot be recovered by simple translation and rotation, and is a substantial change.
The refractive index of the environment in which the variable array of conductive particles is located may be uniform or non-uniform.
The terms of translational symmetry and symmetry center of the two-dimensional crystal, switching of the conductive particles between the paired state and the discrete state are ideal situations of infinite extension of the first array and the second array, and the cutting of the actual first array and the second array is the ideal situation, so that the two arrays are limited.
Based on the above solution, preferably, the conductive particles may be metal particles of silver, gold, aluminum, or the like, or non-metal conductive material particles of titanium nitride, indium tin oxide, or the like, and the material and size thereof can satisfy the well-known condition of light excitation Localized Surface Plasmon Resonance (LSPR) within the wavelength range of 400-2000nm (vacuum wavelength).
Based on the scheme, preferably, the first substrate and the second substrate allow external light beams to irradiate the first array and the second array, and allow transmitted light and reflected light to be output.
Based on the above scheme, preferably, the lattice period of the crystallographic parameters of the first array and the second array is a1, a 2; and a1 is more than or equal to 200nm and less than or equal to 2000nm, a2 is more than or equal to 200nm and less than or equal to 2000nm, so as to meet the physical conditions of the phenomenon of plasma Surface Lattice Resonance (SLR) of visible light and near infrared light under the environment with most refractive indexes, and enhance the effects of spectroscopy application, second-order nonlinear optical application and third-order nonlinear optical application.
The geometry change cannot be recovered by simple translation and rotation, and is a substantial change.
The refractive index of the environment in which the variable array of conductive particles is located may be uniform or non-uniform.
In another aspect, the present invention provides a method for preparing the above variable array of conductive particles, the method is method one or method two;
the first method is a mosaic combination method, which comprises the following steps:
manufacturing a first substrate and a second substrate; preparing a first plane and a second plane on the first substrate and the second substrate;
coating polymer layers on the surfaces of the first plane and the second plane, and manufacturing a hole array on the polymer layers to expose the first plane and the second plane at the positions with holes; etching the first plane and the second plane at the position of the hole of the polymer layer to form a concave part; then plating conductive material to fill/level the concave part to obtain conductive particles;
removing the polymer layer and the conductive material layer deposited above the polymer layer to obtain a conductive particle array embedded into the first and second substrates, wherein the conductive particles do not protrude out of the first and second planes; then, the first plane and the second plane are attached to combine the first array and the second array to obtain the variable array of the conductive particles;
the second method comprises the following steps:
manufacturing a first substrate and a second substrate; preparing a first plane and a second plane on the first substrate and the second substrate;
placing a porous plate on the first plane and the second plane, wherein the position and the size of the hole of the porous plate are consistent with the position and the size of the required conductive particles of the first array and the second array in the length and width directions; depositing a conductive material on the porous plate, wherein the thickness of the conductive material is consistent with the height of the conductive particles of the first array and the second array, and then removing the porous plate and the conductive material deposited above the porous plate to obtain a conductive particle array directly attached to the first plane and the second plane;
and then, the first plane and the second plane are arranged in parallel relatively, the first array is not contacted with the second array and the second substrate, the second array is not contacted with the first array and the first substrate, and the first array and the second array are combined to obtain the variable array of the conductive particles.
In still another aspect, the present invention further provides applications of the above variable array of conductive particles in spectroscopy, second-order nonlinear optics, chiral optics, and third-order nonlinear optics. For enhancement, two or three-order strong nonlinear materials can be placed around the conductive particles.
A variable array of conductive particles, and spectroscopic applications thereof, and second order nonlinear optical applications thereof, and chiral optical applications thereof, and third order nonlinear optical applications thereof; the first array and the second array can be relatively displaced, so that the variable conductive particle array is changed in geometric shape; the change of the geometric shape causes the change of the transmission and reflection spectrogram of the variable array of the conductive particles, thus forming the spectroscopy application; the change of the geometric shape causes the appearance or disappearance of the symmetric center of the variable array of the conductive particles, realizes the on or off of the second-order nonlinear optical effect and brings the second-order nonlinear optical application; the change of the geometric shape causes the appearance or disappearance of the symmetrical plane vertical to the first plane and the second plane of the variable array of the conductive particles, realizes the on or off of the chiral optical effect and brings the application of the chiral optical; the change of the geometric shape causes the conductive particles to be switched between a paired/clustered state and a discrete state, thereby realizing the intensity modulation and the weakness modulation of the third-order nonlinear optical effect and bringing about the third-order nonlinear optical application.
For example, the conductive particles may be silver micro-cuboids because metallic silver has a rather good conductivity. The conductive particles are attached to a substrate, which can be a polished fused quartz wafer, which has high transparency and stable and uniform performance. If there are air gaps around the variable array of conductive particles, the variable array of conductive particles may be placed in a uniform refractive index environment using a refractive index matching oil fill. The variable array device of conductive particles of the invention can allow a user to continuously adjust the relative position of the first array and the second array when in operation, thereby realizing the continuous change of spectroscopy application, second-order nonlinear optical application, chiral optical application and third-order nonlinear optical application. The device can be used for scientific research, and can also be applied to double-frequency demonstration experiments, refractive index measurement sensors, four-wave mixing demonstration experiments and the like. The refractive index matching oil can also be replaced by liquid with the refractive index to be measured, so that the effect of judging the refractive index according to the transmission spectrum and the reflection spectrum is achieved.
Drawings
FIG. 1: the variable array of conductive particles has a state of symmetry center;
FIG. 2: the conductive particle variable array has no symmetric center state;
FIG. 3: the variable array of conductive particles has no state of being vertical to the symmetrical plane of the paper surface;
FIG. 4: the conductive particle variable array is in a weak third-order nonlinear effect state;
FIG. 5: the conductive particle variable array is in a strong third-order nonlinear effect state;
FIG. 6: a side view of a variable array of conductive particles and their substrate;
FIG. 7: a side view of a variable array of conductive particles and its substrate made by conductive particle damascene integration.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1: frequency doubling/chiral switch conductive particle variable array
The top view of the plane of the variable array of the frequency doubling switch conductive particles is shown in fig. 1 and fig. 2. In fig. 1 and 2, the array is indicated by a solid line, the array is indicated by a dashed line, the array i and the array ii both have conductive particles with the same size, each conductive particle is made of silver metal and is a cuboid, the size is 150nm (length) by 50nm (width) by 50nm (height), the horizontal and vertical repetition period of the conductive particles of the array i and the array ii is 728.8nm, namely, the distance between every two transversely or longitudinally adjacent conductive particles in the array i is 728.8nm, and the same also applies to the array ii; however, the first array and the second array have different directions of arrangement of the conductive particles, such as right-leaning direction and left-leaning direction, as shown in fig. 1 and 2. In a variable array of conductive particles consisting of array one and array two, the geometric centers of all particles are located on the same plane (allowing for some assembly error), the bottom planes of all particles are located on the same plane (allowing for some assembly error), and the top planes of all particles are also located on the same plane (allowing for some assembly error). It should be noted that both the first array and the second array can have a plurality of repetition periods, and can be regarded as two-dimensional crystal structures extending infinitely in the plane thereof, and fig. 1 and 2 only show 5 periods in the horizontal direction and the vertical direction as an illustration; the whole variable array of frequency doubling switch conductive particles is placed in an environment with a refractive index of 1.46 (aiming at light with wavelengths of 1064nm and 532 nm), a piezoelectric ceramic actuator is used for moving one array, and the array can move along front, back, left and right, as shown in figures 1 and 2, the two typical situations of the relative relation of the first array and the second array are shown, wherein the conductive particles are spliced into a plurality of ^ shapes as the graph of figure 2, obviously, the variable array of conductive particles consisting of the first array and the second array does not have a symmetry center (when describing two-dimensional crystal symmetry in the crystallography concept, the used point symmetry operation group element for describing inversion symmetry: the symmetry center corresponds to the international symbol: i.), the variable array can have a nonzero second-order nonlinear optical effect, when 1064nm laser is incident perpendicular to the plane of the array of the conductive particles, the variable array can generate 532nm frequency doubling light, when the polarization of 1064nm laser is vertical, 532nm double frequency light is strongest. Similarly, the position relationship between the first array and the second array can be moved, so that the conductive particles are spliced into a plurality of shapes of < ", >, or 'v', to change the selection direction of the frequency doubling effect on the polarization of the laser. When the position relation between the first array and the second array is switched to the graph 1, the central point of the position connecting line of every two adjacent conductive particles in the horizontal direction of the first array is one conductive particle belonging to the second array, and vice versa, at this time, the two-dimensional crystal structure corresponding to the conductive particle variable array formed by the first array and the second array has a symmetry center, namely, any two particles belonging to the first array or the second array are the same, the midpoint of the central connecting line is a symmetry center, the second-order nonlinear optical effect is zero, and the double frequency phenomenon disappears. In conclusion, the double-frequency switching effect is realized. When the double frequency is set to be on, the selection of the size of the conductive particles is suitable for 1064nm laser to generate a Localized Surface Plasmon Resonance (LSPR) effect, so that the effect of enhancing the surface electric field intensity of the conductive particles is achieved, and the Surface Lattice Resonance (SLR) effect of the plasma elements is generated under the action of the variable array of the conductive particles in cooperation with the oscillation of the electromagnetic field, so that the surface electric field intensity of the conductive particles is further enhanced, and the double frequency light generation effect of the conductive particles is enhanced.
The top view of the plane of the variable array of chiral switch conductive particles is shown in fig. 1 and 3. The array I and the array II contained in the variable array are consistent with the array I and the array II contained in the variable array of the frequency doubling switch conductive particles. It is obvious that fig. 1 possesses a symmetry plane (point symmetry operational group element: symmetry plane, international symbol: m) perpendicular to the first and second planes, and a projection of the symmetry plane on fig. 1 will be a vertical line, which may be a bisector of any two adjacent conductive particles in the horizontal direction of the variable array of conductive particles. At the moment, the spectrums of transmission, reflection, absorption and the like of the variable array of the conductive particles have no chirality. Fig. 1 is a diagram 3, the second array is moved to switch from the second array to the third array, the conductive particles are spliced into a plurality of "√" (opposite-hook) shapes, which are different from the "v" shapes in that the shapes of the two opposite lines are different in length, at this time, the symmetric planes disappear, and the spectrums of the variable array of the conductive particles, such as transmission, reflection, absorption, and the like, are chiral, that is, the spectrums of the left-handed circularly polarized light and the right-handed circularly polarized light in the same optical path are different. Switching between the two situations as shown in fig. 1 and fig. 3 can realize the switching of the chiral spectrum. The second array can also be moved to make the conductive particles form a plurality of horizontally reversed "√" shapes, in which case the chiral inversion operation of the chiral spectrum is realized relative to fig. 3.
Example 2: transmission reflection spectrum and three-order nonlinear optical effect adjustable conductive particle variable array
Fig. 4 and 5 show top views of the adjustable conductive particle variable array with transflective spectrum and third-order nonlinear optical effect. In fig. 4 and 5, the array is shown by a solid line and the array is shown by a dashed line, the array i and the array ii both have conductive particles with the same size, are cylinders, each conductive particle is made of metal silver, and has a size of 100nm (diameter) × 100nm (height), and the horizontal and vertical repetition periods are both 500nm, that is, the distance between every two transversely or longitudinally adjacent conductive particles in the array i is 500nm, and the same is true for the array ii; in array one or array two, the geometric centers of all particles are located on the same plane (allowing for small assembly errors), the basal planes of all particles are located on the same plane (allowing for small assembly errors), and the apical planes of all particles are also located on the same plane (allowing for small assembly errors). It should be noted that both the first array and the second array can have a plurality of repetition periods, and can be regarded as two-dimensional crystal structures extending infinitely in the plane thereof, and fig. 4 and 5 only show 5 periods in the horizontal direction and the vertical direction as an illustration; the whole variable array of conductive particles is placed in an environment with a refractive index of 1.46, and a piezoelectric ceramic actuator is used to move one array, so that the array can move back and forth and left and right, as shown in fig. 4 and 5, which are two typical cases of the relative relationship between the first array and the second array, wherein in fig. 4, the conductive particles are uniformly distributed in the transverse direction, and in fig. 5, the conductive particles are non-uniformly distributed in the transverse direction, so that a plurality of 'dimers' are formed. Different from the embodiment 1, one of the first array and the second array is moved transversely and longitudinally, the variable array of the conductive particles always has a symmetrical center, and therefore, the second-order nonlinear optical effect is avoided. However, the size of the conductive particles is selected to be suitable for laser with the wavelength of about 730nm to generate the Localized Surface Plasmon Resonance (LSPR) effect, so that the electric field intensity of the surface layer of the conductive particles is enhanced, and the Surface Lattice Resonance (SLR) effect of the plasmons is generated under the synergistic effect of the variable array of the conductive particles, so that the electric field intensity of the surface layer of the conductive particles is further enhanced. When one of the first array and the second array is moved, the conductive particles can change the shape of the array, and the shape is a typical shape as shown in fig. 4 and 5; at this time, the intensity of the plasmon Surface Lattice Resonance (SLR) effect and the electric field distribution are also changed, which results in the change of the transflective spectrum, such as light intensity and light wave phase, etc., which is particularly good when the light beam incident into the variable array of conductive particles has transverse polarization, and the transflective spectrum is also closely related to the refractive index environment of the variable array of conductive particles, so that the variable array of conductive particles can be used as a refractive index sensor. The variable array of conductive particles shown in fig. 5 has a plurality of dimers of conductive particles, and if the polarization direction of the external light is transverse, the surface electric fields of two conductive particles contained in the dimer are mutually superimposed and enhanced, and are strongest at the gap between the two conductive particles, so that a third-order nonlinear effect, such as a surface-enhanced raman spectrum, a four-wave mixing spectrum and the like, which is enhanced by the induction of the surface of the conductive particle or other substances at the gap between the two conductive particles can be achieved. If simple expansion is performed, for example, the number of conductive particles per lattice of the first array and the second array is increased, the "dimer" can be expanded into a "polymer" with a variable shape, when external light is used to irradiate the conductive particle variable array, an oscillating electromagnetic field is induced on the surface of the conductive particle, a plurality of conductive particles contained in each "polymer" can be influenced by the surface electric field, a plurality of electromagnetic field resonance modes are formed on the surface of the conductive particle and the space near the conductive particle, the frequencies of the electromagnetic field resonance modes are different, and the plurality of electromagnetic field resonance modes can be mutually interfered but are not independent, so that the Fano resonance effect in physics and the like can be induced. The application can be used for teaching demonstration and can also be used in the field of detection and analysis.
Example 3: variable array of conductive particles fixed to a substrate
In the above embodiment, only the material and the geometric structure of the variable array of conductive particles are specified, and the mechanical fixing manner of the variable array of conductive particles is not specified, and a specific scheme is given in this embodiment, as shown in fig. 6, a side view of the variable array of conductive particles is given, a large solid line rectangle is a first substrate made of a flat transparent glass sheet, a plane below the glass sheet is a first plane, and small solid line rectangles are conductive particles of the first array (only 3 are given for illustration), and the first array is attached to the first plane; the large dotted rectangle is a second substrate, the material of the large dotted rectangle is the same as that of the first substrate, the plane above the large dotted rectangle is a second plane, the small dotted rectangle is conductive particles (only 3 are shown for illustration) of a second array, and the second array is attached to the second plane. When the first plane and the second plane are close to each other, the first array and the second array can be inserted and combined into the variable array of the conductive particles. In order to prevent collision and friction, the first array, the second array and the second substrate are not contacted, and a little gap is reserved; similarly, the second array is not in contact with the first array and the first substrate, and a little gap is left. The space between the first substrate and the second substrate except the first array and the second array is an air gap, and in order to better meet the physical phenomenon of plasma cell Surface Lattice Resonance (SLR), the air gap can be filled with liquid with the same refractive index as the first substrate and the second substrate, so that the refractive index of the environment where the variable array of the conductive particles is located is uniform. In fig. 6, the whole device is in a horizontal flat plate shape, so that external light can irradiate the whole device from bottom to top or from top to bottom, thereby realizing the variable array effect of the light and the conductive particles and obtaining the transmission, reflection or scattering spectrum. The scheme of the embodiment 3 is obviously compatible with the schemes of the embodiments 1 and 2, and can be combined for use. This embodiment corresponds to the second mode of the claims.
Example 4: conductive particle variable array prepared by conductive particle mosaic combination method
This embodiment corresponds to the first mode of the claims. The preparation mentioned here, the main steps are:
(1) manufacturing a first substrate and a second substrate of a transparent flat fused silica glass sheet;
(2) the first substrate and the second substrate respectively designate a plane for placing conductive particles, and the plane is the first plane and the second plane;
(3) coating polymer layers (such as polymethyl methacrylate (PMMA)) on the surfaces of the first plane and the second plane, and forming a micropore array on the polymer layers by using an electron beam lithography method so that the first plane and the second plane are exposed out of holes of the polymer layers;
(4) the polymer layer is thinned without holes through non-selective uniform etching, and small recesses are etched on the positions with the holes on the first plane and the second plane (selective etching means can also be selected to directly act on the first plane and the second plane to obtain the small recesses);
(5) then, metal silver is evaporated, the evaporation time is controlled until the silver is filled in or fills up the small recesses, namely silver particles embedded into the first substrate and the second substrate are obtained, the polymer layer and the metal silver layer deposited above the polymer layer are removed together, conductive particle arrays embedded into the first substrate and the second substrate are obtained, and the conductive particles do not protrude out of the first plane and the second plane;
(6) and then attaching the first plane and the second plane to obtain the variable array of the conductive particles.
The cross-sectional schematic of the finished product is shown in fig. 7: the large solid line rectangles on the upper side are a first substrate, the lower plane of the first substrate is designated as a first plane, the first array is embedded, the small solid line rectangles in the first substrate are embedded conductive particles forming the first array, and only three solid line rectangles are drawn for simplicity; the large dotted rectangle below is a second substrate, the upper plane of the second substrate is designated as a second plane, the second array is embedded, and the small dotted rectangles in the second substrate are conductive particles forming the second array, and only three conductive particles are drawn for simplicity; and (3) bonding the first plane and the second plane to realize the combination of the first array and the second array to obtain the variable conductive particle array. Compared with embodiment 3, this embodiment has an advantage that the embedded conductive particles can effectively prevent the conductive particles from colliding with each other and falling off. In addition, protective layers (such as silicon dioxide and aluminum oxide coatings) can be plated on the first plane and the second plane to protect the surfaces of the conductive particles facing the outside of the small recesses, so that the oxidation of outside air, the corrosion of outside liquid and the like can be prevented. The first and second arrays in this embodiment are not strictly located in the same plane, but have a shift amount, but the shift amount may be much smaller than the repetition period of the first and second conductive particles, and it can be approximately considered that the centroids of all the first and second conductive particles are still located in the same plane, so that the first and second arrays are also suitable for applications such as plasma Surface Lattice Resonance (SLR) physical effect of example 1, double frequency switch, chiral switch, change of the transflective spectrum of example 2, refractive index sensor, fanno resonance effect, and third-order nonlinear optical effect such as surface enhanced raman spectrum and four-wave mixing spectrum. This embodiment is also applicable to the operations mentioned in embodiment 3, such as filling the air gap with a liquid having the same refractive index as the first substrate and the second substrate, and obtaining the transmission, reflection or scattering spectra.
The above description is some examples of the present invention, but the scope of the present invention is not limited thereto. Any person skilled in the art can apply the technical solution according to the present invention and the embodiments of the inventive concept without any inventive step and shall fall within the scope of the present invention.
Claims (10)
1. The variable array of conductive particles is characterized by comprising a first array and a second array; the first array and the second array are two-dimensional crystal arrays consisting of a plurality of conductive particles; the first array is fixed on one plane of the first substrate and marked as a first plane, the second array is fixed on one plane of the second substrate and marked as a second plane, the first plane and the second plane are oppositely and parallelly placed, and a space is reserved between the first plane and the second plane or the first plane and the second plane are attached to each other.
2. The variable array of conductive particles of claim 1,
the fixing mode of the conductive particles on the first plane or the second plane is a first mode or a second mode;
the first method is as follows: the first plane and the second plane are both provided with a plurality of depressions, the conductive particles are filled in the depressions and do not protrude out of the first plane and the second plane, and the first plane is attached to the second plane;
the second method comprises the following steps: the conductive particles are directly attached to the first plane and the second plane, the first plane and the second plane are oppositely arranged, the conductive particles on the first plane and the conductive particles on the second plane are distributed in a staggered mode, the first array is not in contact with the second array and the second substrate, and the second array is not in contact with the first array and the first substrate.
3. The variable array of conductive particles of claim 2, wherein in the second mode, the space between the first plane and the second plane is an air gap except the first plane and the second plane, and the air gap is filled with a liquid having the same refractive index as the first substrate and the second substrate, so that the refractive index of the environment in which the variable array of conductive particles is located is uniform.
4. The variable array of conductive particles of claim 1, wherein both array one and array two satisfy translational symmetry of a two-dimensional crystal, and the array one and array two may be the same or different; the first array and the second array can be relatively displaced, so that the variable array of the conductive particles can be changed in geometric shape.
5. The variable array of conductive particles according to claim 1, wherein the conductive particles are metal particles or particles of a non-metallic conductive material; the metal particles are silver, gold or aluminum; the non-metal conductive material particles are titanium nitride or indium tin oxide, and the material and the size of the conductive particles meet the condition that light excites localized surface plasmon oscillation within the wavelength range of vacuum wavelength of 400-2000 nm.
6. The variable array of conductive particles according to claim 1, wherein the first substrate and the second substrate allow external light beams to illuminate the first array and the second array and allow transmitted light and reflected light to be output.
7. The variable array of conductive particles of claim 1, wherein the conductive particles of array one, array two have a lattice period of a1, a 2; and a1 is more than or equal to 200nm and less than or equal to 2000nm, and a2 is more than or equal to 200nm and less than or equal to 2000 nm.
8. A method of making a variable array of conductive particles according to claim 1, wherein the method is method one or method two;
the first method is a mosaic combination method, and comprises the following steps:
manufacturing a first substrate and a second substrate; preparing a first plane and a second plane on the first substrate and the second substrate;
coating polymer layers on the surfaces of the first plane and the second plane, and manufacturing a hole array on the polymer layers to expose the first plane and the second plane at the positions with holes; etching the first plane and the second plane at the position of the hole of the polymer layer to form a concave part; then plating conductive material to fill/level the concave part to obtain conductive particles;
removing the polymer layer and the conductive material layer deposited above the polymer layer to obtain a conductive particle array embedded into the first and second substrates, wherein the conductive particles do not protrude out of the first and second planes; then, the first plane and the second plane are attached to combine the first array and the second array to obtain the variable conductive particle array;
the second method comprises the following steps:
manufacturing a first substrate and a second substrate; preparing a first plane and a second plane on the first substrate and the second substrate;
placing a porous plate on the first plane and the second plane, wherein the position and the size of the hole of the porous plate are consistent with the position and the size of the required conductive particles of the first array and the second array in the length and width directions; depositing a conductive material on the porous plate, wherein the thickness of the conductive material is consistent with the height of the conductive particles of the required first array and the second array, and then removing the porous plate and the conductive material deposited above the porous plate to obtain a conductive particle array directly attached to the first plane and the second plane;
and then, the first plane and the second plane are arranged in parallel relatively, the first array is not contacted with the second array and the second substrate, the second array is not contacted with the first array and the first substrate, and the first array and the second array are combined to obtain the variable array of the conductive particles.
9. Use of a variable array of conductive particles according to claim 1 in spectroscopy, second order nonlinear optics, chiral optics and third order nonlinear optics.
10. The use of claim 9, wherein the variable array of conductive particles comprises a first array and a second array that are relatively displaceable to cause a change in geometry of the variable array of conductive particles; the change of the geometric shape causes the change of the transmission and reflection spectrogram of the variable array of the conductive particles, thus forming the spectroscopy application; the change of the geometric shape causes the appearance or disappearance of the symmetric center of the variable array of the conductive particles, realizes the on or off of the second-order nonlinear optical effect and brings the second-order nonlinear optical application; the change of the geometric shape causes the appearance or disappearance of the symmetrical plane vertical to the first plane and the second plane of the variable array of the conductive particles, realizes the on or off of the chiral optical effect and brings the application of the chiral optical; the change of the geometric shape causes the conductive particles to be switched between a paired/clustered state and a discrete state, thereby realizing the intensity modulation and the weakness modulation of the third-order nonlinear optical effect and bringing about the third-order nonlinear optical application.
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