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CN119322412B - On-chip plasma scattering microscope based on one-dimensional photonic crystal - Google Patents

On-chip plasma scattering microscope based on one-dimensional photonic crystal Download PDF

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CN119322412B
CN119322412B CN202411879244.1A CN202411879244A CN119322412B CN 119322412 B CN119322412 B CN 119322412B CN 202411879244 A CN202411879244 A CN 202411879244A CN 119322412 B CN119322412 B CN 119322412B
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photonic crystal
dimensional photonic
scattering
gold film
imaging
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CN119322412A (en
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张斗国
尤新祥
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Hefei National Laboratory
University of Science and Technology of China USTC
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Hefei National Laboratory
University of Science and Technology of China USTC
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Abstract

本发明公开了一种基于一维光子晶体的片上等离子体散射显微镜,属于表面波对小颗粒弱信号的成像与探测领域,包括:像面探测器、成像管镜、空气物镜、金膜、一维光子晶体、散射层、LED光源。金膜与一维光子晶体之间、光子晶体与散射层之间滴有折射率匹配油来黏附。由LED光源发出的光束经过散射层后,光束被散射到各种角度,经过一维光子晶体在动量空间的过滤筛选,可以全方向激发金膜和空气界面的表面等离激元,照明放置在金膜上的纳米尺寸颗粒物,颗粒物的散射光被放置在上方的空气物镜收集。本发明极大的提高光与纳米颗粒物的相互作用,增大颗粒物的散射信号强度,同时提高了成像质量,可以对散射信号很小的纳米颗粒进行成像与探测。

The invention discloses an on-chip plasma scattering microscope based on one-dimensional photonic crystal, which belongs to the field of imaging and detection of small particle weak signals by surface waves, and includes: an image plane detector, an imaging tube lens, an air objective lens, a gold film, a one-dimensional photonic crystal, a scattering layer, and an LED light source. Refractive index matching oil is dripped between the gold film and the one-dimensional photonic crystal, and between the photonic crystal and the scattering layer for adhesion. After the light beam emitted by the LED light source passes through the scattering layer, the light beam is scattered to various angles. After filtering and screening by the one-dimensional photonic crystal in momentum space, the surface plasmons of the interface between the gold film and the air can be excited in all directions, and the nano-sized particles placed on the gold film can be illuminated. The scattered light of the particles is collected by the air objective lens placed above. The invention greatly improves the interaction between light and nano-particles, increases the scattering signal intensity of the particles, and improves the imaging quality at the same time, and can image and detect nano-particles with very small scattering signals.

Description

On-chip plasma scattering microscope based on one-dimensional photonic crystal
Technical Field
The invention relates to the field of imaging and detecting small particle weak signals by surface waves, in particular to an on-chip plasma scattering microscope based on one-dimensional photonic crystals.
Background
Imaging and detection of individual nanoparticles using optical label-free methods is critical for environmental monitoring, understanding of chemical reaction mechanisms, and research of biological processes. Surface plasmon resonance microscopy is a popular label-free detection technique due to its exceptional sensitivity to minute signals. Surface plasmons are evanescent fields that can greatly enhance the interaction of light with nanoparticles. Therefore, surface plasmons can be used to develop label-free imaging methods with high sensitivity, such as surface plasmon resonance microscopy, which have been used to image and detect weak signal objects such as single cells, subcellular organelles, viruses, nanoparticles, exosomes, etc., due to their extremely high sensitivity. Then, the surface plasmon resonance microscope has a certain limitation, and the problems are that:
(1) The spatial resolution is poor, which is caused by interference between reflected waves and scattered waves, has parabolic tailing of micrometer scale along the illumination direction, and the imaging quality is poor due to the existence of laser speckles, so that the surface plasmon resonance microscope has poor imaging resolution and imaging quality.
(2) Surface plasmon resonance microscopes require complicated optical means such as high numerical aperture oil immersion objectives for exciting surface plasmons, various collimating lenses, polarizers and half wave plates, and precise optical path adjustment such as precise adjustment of the angle of incident light to excite surface plasmons, which limit the wide use of surface plasmon resonance microscopes.
(3) Surface plasmon resonance microscopy has a limited imaging field of view, and conventional oil immersion objective excitation methods provide it with a small imaging field of view (micron by micron order), which limits its imaging and detection capabilities over a large area.
Disclosure of Invention
The invention aims to overcome the defects of the surface plasmon resonance microscope and provides an on-chip plasmon scattering microscope based on one-dimensional photonic crystals, which is used for unmarked imaging and sensing of single nanoparticles. The on-chip plasma scattering microscope excites surface plasmons by using a one-dimensional photonic crystal, so that the setting of the traditional surface plasmon resonance microscope is greatly simplified, and the operation is simple without optical adjustment. And the LED light source is used for avoiding laser speckle, only collecting scattered light of particles has no interference tail, the imaging resolution is improved, and the imaging device can have a large-scale imaging view field in the order of centimeters by centimeters. The on-chip plasma scattering microscope realizes imaging and detection of tens of nanometer level particles, such as a sodium chloride aerosol moisture absorption process of 50nm and a chemical reaction process of perovskite nanocrystals with a side length of about 10 nm, and has the characteristics of no mark, high sensitivity, large field of view, high imaging quality, simple device and no need of optical path adjustment.
The technical scheme of the invention for realizing the purpose is that the on-chip plasma scattering microscope based on the one-dimensional photonic crystal comprises an image plane detector, an imaging tube mirror, an air objective lens, a gold film, the one-dimensional photonic crystal, a scattering layer and an 660nm broadband LED light source, wherein the gold film, the one-dimensional photonic crystal, the scattering layer and the 660nm broadband LED light source are sequentially laminated from top to bottom to form a compact planar optical device for exciting surface plasmons, and refractive index matching oil is dripped between the gold film and the one-dimensional photonic crystal and between the photonic crystal and the scattering layer for adhesion. The low-coherence light emitted by the LED light source is scattered to all directions after passing through the scattering layer, then is incident to the one-dimensional photonic crystal, the emergent light with the emergent angle in the range of the excitation angle of the surface plasmon is screened by utilizing the filtering characteristic of the one-dimensional photonic crystal in the momentum space, the surface plasmon of the gold film and the air interface is excited, the illumination of the small particle in the azimuth angle direction and the omnidirectional surface plasmon is realized, then the air objective lens collects the scattered light of the small particle, and finally the scattered light is imaged on the image plane detector through the imaging tube lens.
Further, the one-dimensional photonic crystal is formed by alternately performing chemical vapor deposition on a cover glass of 0.17 mm by using a SiO 2 dielectric film with a refractive index of 1.46 and a thickness of 110 nm and a Si 3N4 dielectric film with a refractive index of 2.45 and a thickness of 75 nm, wherein the cycle number is 15.
According to the invention, a gold film is placed on a one-dimensional photonic crystal, the surface plasmons of the gold film and an air interface are excited by adjusting the energy band structure of the one-dimensional photonic crystal, a sample placed on the gold film is irradiated, compared with a dark field microscope based on the one-dimensional photonic crystal, the surface plasmons have extremely large field enhancement compared with dark field illumination light, the intensity of interaction between light and substances can be improved, the imaging contrast is remarkably improved, nanoparticles with smaller scattering intensity (diameter) can be imaged, the gold film can further block residual light transmitted from the one-dimensional photonic crystal at a small angle compared with the dark field microscope based on the one-dimensional photonic crystal, the dark field imaging effect is improved, meanwhile, the filtering range of the one-dimensional photonic crystal in the momentum space is enlarged to be more than 1, compared with the dark field microscope based on the one-dimensional photonic crystal, dark field imaging can be performed by using a higher NA objective lens, and finally, the cost is lower, the LED light source is more integrated, and the optical operation is reduced.
Compared with the traditional optical method (such as a surface plasmon resonance microscope) for detecting and imaging small particles, the invention has the following beneficial effects:
1. The optical device is simple, and a surface plasmon excitation light path, such as an oil immersed objective lens with high numerical aperture, a polaroid, a half wave plate, an imaging lens and the like, is not needed.
2. The optical operation is not needed, the use is convenient, the light path is not required to be strictly regulated to excite the surface plasmon, the optical path can be combined with a traditional commercial microscope, and the light path adjustment is not required.
3. In the device, the imaging field is determined by the illumination area (in the order of centimeters by centimeters) of the gold film surface and the numerical aperture of the air objective lens, and the air objective lens with small numerical aperture can be used for realizing the imaging of the large field.
4. The use cost is low, the use of consumables is less based on a pure optical detection means, the processing of the multilayer dielectric film is simple and cheap, and the use of the multilayer dielectric film is combined with a commercial common microscope, so that the cost is low.
5. The imaging effect is good, and the LED light source with weak coherence is used, so that laser speckles are avoided, and the imaging quality is improved.
Drawings
FIG. 1 is a schematic diagram of the structure of an on-chip plasma scattering microscope based on one-dimensional photonic crystals of the present invention;
FIG. 2 is a graph showing the distribution of the transmittance of a one-dimensional photonic crystal and the reflectance of a gold film;
FIG. 3 is a graph of polystyrene beads of different diameters versus scattering intensity as measured using an on-chip plasma scattering microscope;
FIG. 4 is a graph showing the variation of scattering intensity of 50 nm sodium chloride particles measured by an on-chip plasma scattering microscope during moisture absorption;
Fig. 5 is a graph of the results of measuring 10 nm gold particles and perovskite having a side length of about 10 nm using the microscope.
In fig. 1, 1 is an image plane detector, 2 is an imaging tube mirror, 3 is an air objective lens, 4 is a gold film, 5 is a one-dimensional photonic crystal, 6 is a scattering layer, and 7 is an LED light source.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other. In order to achieve the above purpose, the present invention adopts the following technical scheme.
The invention provides an on-chip plasma scattering microscope based on one-dimensional photonic crystals, which is used for detecting and imaging single nano particles and comprises an image plane detector 1, an imaging tube mirror 2, an air objective lens 3, a gold film 4, one-dimensional photonic crystals 5, a scattering layer 6 and an LED light source 7, as shown in figure 1. The light with low coherence emitted by the LED light source 7 is scattered randomly to all directions after passing through the scattering layer 6, then the one-dimensional photonic crystal 5 filters in momentum space, the emergent light with the emergent angle in the range of the surface plasmon excitation angle is screened, the surface plasmon of the gold film 4 and the air interface is excited, the omnidirectional surface plasmon illumination of small particles is realized, then the air objective lens 3 collects the scattered light of the small particles, and finally the scattered light passes through the imaging tube lens 2 and is imaged on the image plane detector 1. The LED light source 7 adopts an 660nm broadband LED light source, and refractive index matching oil is dripped between the gold film 4 and the one-dimensional photonic crystal 5 and between the photonic crystal 5 and the scattering layer 6 for adhesion.
The 660nm broadband LED light source 7 emits light beams with a divergence angle of about 30 degrees, the light beams are incident to the scattering layer 6 and scattered to all directions and have random polarization, the light beams are incident to the one-dimensional photonic crystal 5, the light beams with an emergent angle in a surface plasmon excitation angle range are screened by utilizing the filtering characteristic of the one-dimensional photonic crystal 5 in a momentum space and have transverse magnetic fields (TRANSVERSE MAGNETIC, TM) polarization, then the emergent light excites the gold film 4 and the surface plasmon of an air interface, the small-particle all-direction surface plasmon illumination is realized, then the air objective 3 collects scattered light of the small particles, the scattered light passes through the imaging tube mirror 2 and finally images on the image plane detector 1, the scattered light of the surface roughness of the gold film 4 is also collected and imaged by the air objective, the scattered light of the small particles interferes with the scattered light of a rough surface, and the detection of the small-particle with weak signal is facilitated. Polystyrene pellets (diameter at minimum 40 nm a) and gold pellets (diameter at minimum 10a nm a) of various particle sizes were imaged and detected using this on-chip plasma scattering microscope, and perovskite nanocrystalline chemistry with scattering intensity variation during absorption of a 50 a nm a sodium chloride aerosol and a side length of about 10a nm a was imaged and detected.
Further, the divergence angle of the used 660 nm broadband LED light source 7 is not limited, the wavelength bandwidth is about 20nm, the LED light source 7 is formed by a plurality of LED lamp beads through a rectangular scattering plate, the time and space coherence is low, laser speckles are removed, and the imaging quality is improved.
Further, the light beam emitted from the LED light source 7 is scattered in all directions by the scattering layer 6, the scattering layer 6 is made by spin-coating titanium dioxide particles having a diameter of about 60nm a on a common glass sheet, the spin-coating thickness is about 2 μm, and then the scattered light in all directions is incident on the one-dimensional photonic crystal 5.
Further, the one-dimensional photonic crystal 5 is formed by alternately performing chemical vapor deposition on a cover glass by using a SiO 2 dielectric film with a refractive index of 1.46 and a thickness of 110 nm and a Si 3N4 dielectric film with a refractive index of 2.45 and a thickness of 75 nm, wherein the period number is 15. The one-dimensional photonic crystal 5 is used for screening light emitted by the scattering layer 6 at all angles, so that the light is emitted near the excitation angle of the surface plasmon, and the emitted light has polarization of a transverse magnetic field (TRANSVERSE MAGNETIC, TM), so that the omnidirectional surface plasmon illumination of small particles is realized.
Further, the gold film 4 is formed by depositing 50 nm of gold on a clean cover glass by using a magnetron sputtering technology, and the surface of the gold film 4 is not completely flat, and the light is scattered by the rough surface. The gold film 4 can be replaced by other metal films capable of exciting surface plasmons, including silver films, copper films and aluminum films.
Further, the air objective lens 3, the imaging tube lens 2 and the image plane detector 1 are used for collecting and imaging scattered light of small particles placed on the surface of the gold film 4, and air objective lenses with different numerical apertures can be selected to realize different imaging fields of view and resolutions.
The invention images and detects various standard polystyrene beads (diameter is the lowest 30 nm) and gold particle beads (diameter is 10 nm and 5 nm), and images and detects scattering intensity change in the process of absorbing sodium chloride aerosol of 50 nm and perovskite nano crystal chemical reaction process with side length of about 10 nm.
Referring to fig. 2, after the filtering of the one-dimensional photonic crystal 5 in the momentum space, the emitted light has a transverse magnetic field component, and most of the emitted light is concentrated in a range where K/K 0 (K is a wave vector of the emitted light from 1DPC, and K 0 is a wave vector of the light freely propagating in vacuum) is greater than 1, so as to excite surface plasmons of the gold film and the air interface, wherein the excitation angle is as low as Gu Suoshi of the reflection of the gold film 4 in fig. 2, and is on the side of the transverse magnetic field component where K/K 0 is slightly greater than 1.
Referring to fig. 3, a graph of polystyrene beads of different diameters versus scattering intensity as measured using an on-chip plasma scattering microscope is shown. An alcohol solution of polystyrene beads of standard diameter is dropped onto a gold film, spin-coated for a period of time, and the particles are deposited on the gold film surface and then imaged. It can be found that when the particle diameter is small, the scattering intensity (square of the scattered light field) is approximately proportional to the six-degree of diameter, and when the particle diameter is small, the scattering intensity is mainly due to interference between the scattered light of the roughness of the surface of the gold film 4 and the scattered light of the particle, so the scattering intensity is approximately proportional to the three-degree of the particle diameter (one term of the scattered light field), which makes it convenient for the microscope to detect a weak signal of a small particle.
Referring to FIG. 4, a graph of the variation in scattering intensity of the moisture absorption process of 50 nm sodium chloride particles is shown using an on-chip plasma scattering microscope. As shown in fig. 4 (b), when the relative humidity is 75% or less, the scattering intensity of the particulate matter is slowly changed, when the relative humidity is 77%, the scattering intensity is greatly increased, and this humidity is called a decomposition point, the experimental moisture absorption curve is better matched with the extended inorganic aerosol model theoretical model, that is, fig. 4 (b) is a solid line, fig. 4 (a) is an experimental imaging diagram under different humidity, and it can be found that the scattering intensity is greatly changed when the humidity is 77%.
Referring to fig. 5, a graph of the results of measuring 10nm gold particles and perovskite having a side length of about 10nm using the microscope is shown. Using standard diameter gold particles, disposing the gold particles in an alcohol solution, dripping the gold particles drop by drop on a gold film, spin-coating the gold film, standing the gold film, and imaging the gold film by using a microscope of the invention, for example, depositing C SPbI3 perovskite particles on the gold film, respectively introducing HCl and HI gases into the particles, and imaging three states of the particles, as shown in figure 5, respectively, wherein the perovskite particles can be found to undergo an anion replacement process, namely C SPbI3 is changed into C SPbCl3 and then into C SPbI3. Detection and imaging of small particles are achieved. Wherein figure A, B is the result of imaging 10nm gold particles, three figures B are enlarged views of the relevant area of figure a, and figure C, D, E of figure 5 is the result of imaging C SPbI3、CSPbI3 (HCl vapor is introduced) and C SPbI3 (HCl vapor is introduced and HI vapor is introduced), respectively.
Parts of the invention not described in detail are well known in the art.

Claims (8)

1. The on-chip plasma scattering microscope based on the one-dimensional photonic crystal is used for detecting and imaging single nano particles and is characterized by comprising an image plane detector (1), an imaging tube mirror (2), an air objective lens (3), a gold film (4), the one-dimensional photonic crystal (5), a scattering layer (6) and an LED light source (7) with a 660nm broadband, wherein the gold film (4), the one-dimensional photonic crystal (5), the scattering layer (6) and the LED light source (7) are sequentially laminated from top to bottom to form a planar optical device for exciting surface plasmons, and refractive index matching oil is dripped between the gold film (4) and the one-dimensional photonic crystal (5) and between the one-dimensional photonic crystal (5) and the scattering layer (6) to adhere;
The light source (7) of the 660nm broadband LED emits light beams with a divergence angle of 30 degrees, the light beams are incident to the scattering layer (6) and scattered to all directions, the light beams have random polarization, the light beams are incident to the one-dimensional photonic crystal (5), the light beams with the exit angle in the range of a surface plasmon excitation angle are screened by utilizing the filtering characteristic of the one-dimensional photonic crystal (5) in a momentum space, the light beams have transverse magnetic field polarization, then the light beams excite the surface plasmon of a gold film (4) and an air interface, the full-direction surface plasmon illumination of the nano particles in the azimuth direction is realized, then the air objective lens (3) collects the scattered light of the nano particles, and finally the scattered light beams are imaged on the image plane detector (1) through the imaging tube mirror (2).
2. An on-chip plasma scattering microscope based on one-dimensional photonic crystal according to claim 1, characterized in that the wavelength bandwidth of the used 660 nm LED light source (7) is 20 nm, and the LED light source (7) is composed of a plurality of LED light beads through a rectangular scattering plate.
3. An on-chip plasma scattering microscope based on one-dimensional photonic crystal according to claim 1, characterized in that the scattering layer (6) scatters the light beam emitted from the LED light source (7) in all directions, the scattering layer (6) is made by spin-coating titanium dioxide particles with a diameter of about 60 nm on a glass sheet, the spin-coating thickness is 2 μm, after which the scattered light in all directions is incident on the one-dimensional photonic crystal (5).
4. The on-chip plasma scattering microscope based on the one-dimensional photonic crystal according to claim 1, wherein the one-dimensional photonic crystal (5) is formed by alternately performing chemical vapor deposition on a cover glass by a SiO 2 dielectric film with a refractive index of 1.46 and a thickness of 110 nm and a Si 3N4 dielectric film with a refractive index of 2.45 and a thickness of 75nm, the period number is 15, the one-dimensional photonic crystal (5) is used for screening light emitted by the scattering layer (6) at all angles so as to emit the light at a surface plasmon excitation angle, and the emitted light has transverse magnetic field polarization so as to realize omnidirectional surface plasmon illumination of nano particles.
5. An on-chip plasma scattering microscope based on one-dimensional photonic crystal according to claim 1, characterized in that the gold film (4) is made by depositing 50 nm gold on a clean cover glass using magnetron sputtering technique, with a rough surface roughness.
6. An on-chip plasma scattering microscope based on one-dimensional photonic crystal according to claim 1, characterized in that the gold film (4) is replaced by a metal film capable of exciting surface plasmons, the metal film comprising a silver film, a copper film, an aluminum film.
7. An on-chip plasma scattering microscope based on one-dimensional photonic crystal according to claim 1, wherein the air objective (3), the imaging tube lens (2) and the image plane detector (1) are used for collecting and imaging the scattered light of the nano particles placed on the surface of the gold film (4), and the air objective (3) with different numerical apertures is selected to realize different imaging fields of view and resolutions.
8. The one-dimensional photonic crystal-based on-chip plasma scattering microscope according to claim 5, wherein scattered light caused by the surface roughness of the gold film (4) is collected and imaged by the air objective lens (3), and the scattered light of the nanoparticles interferes with the scattered light of the rough surface to realize detection of the weak signal nanoparticles.
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