CN111239088A - Micro-nano composite structure with fluorescence enhancement and optical amplification effects and preparation method thereof - Google Patents
Micro-nano composite structure with fluorescence enhancement and optical amplification effects and preparation method thereof Download PDFInfo
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a micro-nano composite structure with fluorescence enhancement and optical amplification effects and a preparation method thereof, wherein a noble metal nano structure substrate is prepared by simple modes of spin coating, self-assembly and the like, a micro-nano composite structure of a medium microsphere/a noble metal nano material is prepared by combining a medium microsphere, the effective fluorescence enhancement of various fluorescent materials can be realized by combining the dual effects of nano jet flow of the medium microsphere and plasma resonance of the noble metal nano material, the super-resolution imaging of fluorescent particles with the size of as low as 100nm under an optical microscope can be realized, and the micro-nano composite structure can be used as a structure with fluorescence enhancement and optical amplification effects and used for the detection and fluorescence imaging of weak fluorescence and the visual tracking and detection of the micro-nano fluorescent material. The preparation method of the composite structure is simple and easy to operate.
Description
Technical Field
The invention relates to the technical field of spectroscopic analysis and detection, in particular to a micro-nano composite structure with fluorescence enhancement and optical amplification effects and a preparation method thereof.
Background
The optical detection and imaging technology of fluorescence becomes an important tool and means for exploring the nanometer world due to the characteristics of non-contact, easy integration, electromagnetic interference resistance and the like. Because the fluorescent molecular cluster is small even single-molecule fluorescence under the nanoscale, the fluorescence intensity is weak, and the fluorescence detection is difficult to achieve strong sensitivity; on the other hand, due to the existence of optical diffraction limit, the traditional optical microscopy observation limit can only reach about 200nm, which is not beneficial to the fluorescence imaging of nanometer scale. Therefore, fluorescence enhancement and super-resolution imaging are the focus and focus of research on optical detection and imaging based on fluorescence.
However, to obtain a high enhancement factor requires a complex nano-fabrication process, with a fine design of the structure. The noble metal nano-structure substrate prepared by simple methods such as vacuum sputtering, coating and the like is used for enhancing fluorescence, and the enhancement factor is only several to dozens. Therefore, how to effectively enhance fluorescence by using a simple method or structure remains the focus and difficulty of fluorescence enhancement.
On the other hand, the visual observation of the nanoscale material or structure under the optical microscope needs to break through the optical diffraction limit, but the existing method for breaking through the diffraction limit needs to accurately regulate and control the monomolecular fluorescence and has special requirements on laser beams.
Jun Sun et al reported a plasma-enhanced fluorescent substrate based on a polymethyl methacrylate (PMMA) coating large-area Au @ Ag nanorod array, and assembled Au @ Ag nanorods on SiO2The large-area substrate formed on the/Si wafer showed the greatest fluorescence enhancement factor at the optimum PMMA layer thickness (56 nm). (Jun Sun ect. uniform and random plasma substrate based on PMMA-coated, large-area Au @ Ag nanoarray. Nano Research 2018,11(2): 953-
However, the enhancement factor of enhanced fluorescence is still small (several to tens of times enhancement) for single photon fluorescent materials. Thus, there is a need for a super-resolution imaging system that can achieve effective enhancement of a variety of fluorescent materials and achieve fluorescence in a simple manner.
Disclosure of Invention
The invention aims to solve the technical problem that the existing fluorescence imaging mode cannot meet the requirements of various fluorescent materials, and provides a micro-nano composite structure with fluorescence enhancement and optical amplification effects.
The invention further aims to provide a preparation method of the micro-nano composite structure with fluorescence enhancement and optical amplification effects.
The above purpose of the invention is realized by the following technical scheme:
a micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of polymers and precious metal nano materials, the isolation layer is composed of polymers, the fluorescent layer is composed of fluorescent materials, the protection layer is composed of polymers, and the medium microsphere layer is composed of medium microspheres.
According to the invention, a noble metal nano structure is used as a substrate, and a Micro Sphere (MS) is combined to prepare a micro-nano composite structure of a medium microsphere/noble metal nano material. Because the medium microsphere has the 'nano jet flow' effect, the energy of the light beam can be concentrated in the sub-wavelength range, the energy density of the incident light is improved, and the fluorescence intensity is in direct proportion to the square of the incident field intensity, so that the 'amplification' of the substance can be realized by using the medium microsphere, and the fluorescence can be enhanced at the same time. The invention utilizes the double effects of 'nano jet flow' of the dielectric microsphere and the plasma resonance of the noble metal nano material, can realize effective fluorescence enhancement of various fluorescent materials, and realizes super-resolution imaging of fluorescent particles with the size as low as 100nm under an optical microscope.
Preferably, the polymer is one of polymethyl methacrylate, polystyrene and polypropylene terephthalate vinegar.
More preferably, the polymer is PMMA, produced by cataxinization glass instruments ltd, guangzhou.
Preferably, the noble metal nanomaterial is a gold or silver nanomaterial.
More preferably, the noble metal nanomaterial is a gold nanorod (AuNR).
Preferably, the structure of the nano material is one of a nanorod, a nanoparticle, a nanostar and a nanowire.
Preferably, the fluorescent material is one of Quantum Dots (QDs), organic fluorescent dyes, and up-conversion nanomaterials.
Preferably, the medium microspheres are silicon dioxide microspheres (SiO)2) Polystyrene microspheres (PS), titanium dioxide microspheres (TiO)2) And melamine formaldehyde Microspheres (MF).
Preferably, the thickness of the isolation layer is 4-12 nm.
The invention also provides a preparation method of the micro-nano composite structure with fluorescence enhancement and optical amplification effects, which comprises the following steps:
s1, dispersing a mixed solution of a polymer and a noble metal nano material in a substrate to prepare a structure with a plasmon layer;
s2, coating and dispersing the polymer solution on the structure with the plasmon layer prepared in the step S1, and annealing at 200-300 ℃ to prepare the structure with the isolation layer;
s3, dissolving the fluorescent material in a solvent, and dispersing the fluorescent material on the isolation layer with the structure prepared in the step S2 to prepare a structure with a fluorescent layer;
s4, dispersing the polymer solution on the fluorescent layer with the structure prepared in the step S3 to prepare a structure with a protective layer;
and S5, dissolving the medium microspheres in water, dispersing the medium microspheres on the protective layer of the structure prepared in the step S4, and drying to obtain the micro-nano composite structure with the medium microsphere layer.
Preferably, the preparation method of the substrate is as follows:
firstly, wiping off scraps of a silicon wafer by using ethanol, then respectively carrying out ultrasonic cleaning for 15-30 min in acetone, ethanol and water at 25-30 ℃, then placing the silicon wafer under high-pressure nitrogen flow, and drying the surface of the silicon wafer to obtain a dry and clean silicon wafer serving as a substrate.
Preferably, the mass concentration of the ethanol is 75-95%.
More preferably, the substrate is prepared by the following specific method:
firstly, cutting a silicon wafer into blocks by using a silicon knife, and wiping off scraps by using a piece of lens wiping paper dipped with ethanol (the mass concentration is 75-95%); then, putting the silicon wafer into an acetone solution by using a clean forceps, and carrying out ultrasonic cleaning for 15-30 min at 25-30 ℃; taking out the silicon wafer, putting the silicon wafer into an ethanol solution (the mass concentration is 75-95%), and ultrasonically cleaning the silicon wafer for 15-30 min at 25-30 ℃; taking out the silicon wafer, putting the silicon wafer into deionized water, and ultrasonically cleaning the silicon wafer for 15-30 min at 25-30 ℃; and finally, clamping the silicon wafer by using tweezers, placing under high-pressure nitrogen flow, and quickly drying the surface of the silicon wafer to obtain a dry and clean silicon wafer serving as a substrate.
Preferably, the preparation method of the mixed solution of the polymer and the noble metal nano material comprises the following steps: dissolving a polymer in acetone, adding a noble metal nano material, and uniformly stirring, wherein the mass ratio of the polymer to the metal nano material is 1-3: 1-3, so as to prepare a mixed solution of the polymer and the noble metal nano material.
More preferably, the preparation method of the mixed solution of the polymer and the noble metal nano material comprises the following steps: firstly, cutting PMMA solid into blocks so as to facilitate subsequent dissolution; respectively ultrasonically cleaning PMMA (polymethyl methacrylate) for 15-30 min at 25-30 ℃ by using deionized water and ethanol (the mass concentration is 75% -95%), drying the PMMA under high-pressure nitrogen flow, adding an acetone solution into the PMMA, uniformly stirring the mixture at the rotating speed of 1000-2000 rpm for 24-30 h, and obtaining the acetone solution of PMMA; adding AuNR, stirring uniformly, rotating at 1000-2000 rpm for 5-10 h to prepare a mixed solution of the polymer and the noble metal nano material; mixing an appropriate amount of PMMA solution in the AuNR solution will facilitate dispersion of AuNR upon spin coating and formation of AuNR thin film.
Further, the specific operation of step S1 may be:
and (3) placing the cleaned and dried silicon wafer on a spin coater, dropping 0.05-0.1 mL of mixed solution of the polymer and the metal nano material on the silicon wafer by using a liquid transfer gun, setting the spin coating speed to be 2000-3000 rpm and the spin coating time to be 20-30 s, and spin coating to form a uniform AuNR film, thus obtaining the structure with the plasmon layer.
Preferably, the concentration of the polymer solution in the step S2 and the step S4 is 0.4-2.0 mg/mL.
Further, the specific operation of step S2 may be:
and (4) dripping 0.05-0.1 mL of PMMA solution by using a liquid transfer gun on the structure with the plasmon layer prepared in the step S1, spin-coating for 20-30S at the spin-coating speed of 4000-5000 rpm to form a PMMA nano film with the thickness of 4-12 nm, and then annealing the sample at 200 ℃ for 3min to obtain the structure with the isolation layer.
Further, the specific operation of step S3 may be:
and dispersing the fluorescent material needing fluorescence enhancement into n-hexane, and spin-coating the isolation layer for 20-30 seconds in a spin-coating manner to obtain the structure with the fluorescent layer.
Step S4 is to form a spacer layer on the phosphor layer, which is used as a protective layer to prevent the attenuation of the phosphor due to the photo-bleaching effect, in the same manner as step S2.
Further, the specific operation of step S4 may be:
and dispersing the medium microspheres in water, performing ultrasonic treatment, taking 0.05-0.1 mL of the solution by using a pipette, dispersing the solution on the protective layer prepared in the step S4, and then drying the solution in a drying oven at the temperature of 60-80 ℃ for 24-30 h to obtain the micro-nano composite structure with the medium microsphere layer.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the noble metal nanostructure substrate is prepared in simple manners such as spin coating and self-assembly, the micro-nano composite structure of the dielectric microsphere/the noble metal nanomaterial is prepared by combining the dielectric microsphere, the effective fluorescence enhancement of various fluorescent materials can be realized by combining the dual effects of the nano jet flow of the dielectric microsphere and the plasma resonance of the noble metal nanomaterial, the super-resolution imaging of fluorescent particles with the size of as low as 100nm under an optical microscope can be realized, and the micro-nano composite structure can be used as a structure with the effects of fluorescence enhancement and optical amplification for the detection and fluorescence imaging of weak fluorescence and the visual tracking and detection of the micro-nano fluorescent material. The preparation method of the composite structure is simple and easy to operate.
Drawings
FIG. 1 is a schematic diagram of a fluorescence enhancement principle of a micro-nano composite structure of a dielectric microsphere/noble metal nano material.
FIG. 2 is a picture of the characterization of the QD/AuNR samples with a spacer layer thickness of 4 nm.
FIG. 3 is a picture of the characterization of the QD/AuNR samples with a spacer layer thickness of 8 nm.
FIG. 4 is a picture of the characterization of the QD/AuNR samples with a spacer layer thickness of 12 nm.
Fig. 5 shows the enhanced spectra of AuNR structural substrate for quantum dot fluorescence under different spacer layer thicknesses in examples 1, 4 and 5.
Fig. 6 is an enhancement spectrum of MF microspheres with different diameters for quantum dot fluorescence.
Fig. 7 is a schematic diagram of an enhanced composite structure of a micro-nano composite structure for quantum dot fluorescence.
FIG. 8 shows fluorescence spectra of quantum dots obtained from QD, QD/AuNR, MF/QD, and MF/QD/AuNR samples.
FIG. 9 shows super-resolution imaging under an optical microscope of each sample prepared in example 1: (a) transmission electron microscope pictures of the nano fluorescent particles; (b) the focus is on the picture of the surface of the fluorescent layer under the bright field; (c) a fluorescent layer picture at the medium microsphere; (d) the focus is on the picture on the surface of the fluorescent layer in a dark field; (e) and (5) a fluorescent layer picture at the medium microsphere.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The invention provides a micro-nano composite structure with fluorescence enhancement and optical amplification effects and a preparation method thereof, and the following embodiments specifically illustrate the micro-nano composite structure.
Example 1
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of CdSe quantum dots, the protective layer is composed of PMMA, and the medium microsphere layer is composed of MF medium microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
s1, firstly, cutting a silicon wafer to 1cm multiplied by 1cm by a silicon knife, and wiping off scraps by using a piece of lens wiping paper dipped with ethanol with the mass concentration of 75%; then putting the silicon wafer into an acetone solution by using a clean forceps, and carrying out ultrasonic cleaning for 15min at normal temperature; taking out the silicon wafer, adding 75% ethanol by mass, and ultrasonically cleaning again for 15min at normal temperature; taking out the silicon wafer, putting the silicon wafer into deionized water, and ultrasonically cleaning the silicon wafer for 15min at normal temperature; finally, clamping the silicon wafer by using tweezers, placing the silicon wafer under high-pressure nitrogen flow, and quickly drying the surface of the silicon wafer to obtain a dry and clean silicon wafer which is used as a substrate;
cutting PMMA solid (provided by Catalphos chemical glass instruments Co., Ltd., Guangzhou) into small blocks for subsequent dissolution; ultrasonically cleaning PMMA with deionized water and alcohol at normal temperature for 15min, and blowing under high pressure nitrogen flow; weighing PMMA solid, putting the PMMA solid into a conical flask, adding 25mL of acetone solution, stirring, putting the conical flask into a magnetic stirrer, and stirring for 24 hours at the normal temperature at the rotating speed of 1000rpm to obtain the acetone solution of PMMA;
taking out AuNR dispersed in acetone by using a liquid transfer gun, preparing a mixed solution according to the mass ratio of the AuNR to PMMA of 1:1, placing the mixed solution in a magnetic stirrer, setting the rotating speed to be 1000rpm, and stirring for 5 hours at 25 ℃ to obtain a uniform mixed solution;
and (3) placing the cleaned and dried silicon wafer on a spin coater, dripping 0.05mL of the mixed solution on the silicon wafer by using a liquid transfer gun, setting the spin coating speed to be 2000rpm and the spin coating time to be 20s, and spin-coating to form a uniform AuNR film, namely completing the preparation of the plasma excited layer.
S2, dripping 0.05mL of 0.4mg/mL PMMA solution on the sample prepared in the step S1 by using a liquid transfer gun, spin-coating for 20S at the spin-coating speed of 4000rpm to form a PMMA nano film with the thickness of 4nm, and then annealing the sample at 200 ℃ for 3min to finish the preparation of the isolation layer.
S3, using n-hexane as a solvent to prepare a CdSe quantum dot solution of 0.3 mg/mL; placing the sample prepared in the step S2 on a spin coating platform; measuring 0.05mL of quantum dot solution by using a liquid transfer gun and dispersing the quantum dot solution on a sample; setting the spin-coating speed at 2000rpm for 20s, and carrying out spin-coating to transfer the quantum dots to the substrate to form an even film layer, thereby facilitating the subsequent observation.
S4, measuring 0.05mL of 2.0mg/mL PMMA acetone solution by using a liquid transfer gun, dispersing the PMMA acetone solution on the quantum dot film, setting the spin-coating speed to 4000rpm for 20s, and performing spin-coating to complete the preparation of the PMMA protective layer.
S5, dispersing MF medium microspheres (the diameter is 10 microns) in deionized water, performing ultrasonic dispersion for 15min to uniformly disperse the microspheres, measuring 0.05mL of the MF medium microsphere solution by using a liquid transfer gun, dispersing the MF medium microsphere solution on the surface of the sample prepared in the step S4, and drying the sample in a drying oven at 60 ℃ for 24h to obtain the micro-nano composite structure MF/QD/AuNR.
Example 2
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of CdSe quantum dots, the protective layer is composed of PMMA, and the medium microsphere layer is composed of MF medium microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the manufacturing method of this example is the same as example 1 except that the annealing temperature is replaced with 300 c in step S2.
Example 3
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of up-conversion nano materials, the protective layer is composed of PMMA, and the medium microsphere layer is composed of MF medium microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as example 1 except that the CdSe quantum dots are replaced with the up-converting nanomaterial at step S2.
Example 4
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of up-conversion nano materials, the protective layer is composed of PMMA, and the medium microsphere layer is composed of MF medium microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as example 1 except that the concentration of the PMMA solution in step S2 is replaced with 1 mg/mL.
Example 5
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of up-conversion nano materials, the protective layer is composed of PMMA, and the medium microsphere layer is composed of MF medium microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as that of example 1 except that the concentration of the PMMA solution is replaced with 2mg/mL in step S2.
Example 6
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of an up-conversion nano material, the protective layer is composed of PMMA, and the medium microsphere layer is composed of silicon dioxide microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as that of example 1, except that the MF media microspheres are replaced with silica microspheres in step S5.
Example 7
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PMMA and AuNR, the isolation layer is composed of PMMA, the fluorescent layer is composed of up-conversion nano materials, the protective layer is composed of PMMA, and the medium microsphere layer is composed of PS microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as that of example 1, except that the MF media microspheres described in step S5 are replaced with PS microspheres with a diameter of 100 nm.
Example 8
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PS and AuNR, the isolation layer is composed of PS, the fluorescent layer is composed of up-conversion nano-materials, the protection layer is composed of PS, and the medium microsphere layer is composed of MF microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as example 1 except that PMMA is replaced with PS.
Example 9
A micro-nano composite structure with fluorescence enhancement and optical amplification effects comprises a plasmon layer, an isolation layer, a fluorescent layer, a protection layer and a medium microsphere layer; the plasmon layer is composed of PS and silver nanoparticles, the isolation layer is composed of PS, the fluorescent layer is composed of up-conversion nano materials, the protection layer is composed of PS, and the medium microsphere layer is composed of MF microspheres.
The preparation method of the micro-nano composite structure comprises the following steps:
the preparation method of this example is the same as example 1 except that AuNR is replaced with silver nanoparticles at step S1.
Comparative example 1
This comparative example was prepared in the same manner as example 1 except that it did not include step S5, and QD/AuNR was prepared.
Comparative example 2
The comparative example was prepared in the same manner as in comparative example 1 except that the concentration of the PMMA solution was adjusted to 1mg/mL in step S2 of the comparative example, to obtain QD/AuNR.
Comparative example 3
The comparative example was prepared in the same manner as in comparative example 1 except that the concentration of the PMMA solution was adjusted to 2mg/mL in step S2 of the comparative example, to obtain QD/AuNR.
Comparative example 4
The comparative example was prepared in the same manner as in example 1 except that it included cleaning and preparation of the silicon substrate in step S1, did not include fabrication of the plasma excimer layer in step S1, and the MF media microsphere diameter of step S5 was replaced with 1 μm to prepare MF/QD.
Comparative example 5
The preparation method of the comparative example is the same as that of the comparative example 4, except that the diameter of the MF medium microsphere of the comparative example is replaced by 5 μm, so as to prepare MF/QD.
Comparative example 6
The preparation method of the comparative example is the same as that of the comparative example 4, except that the diameter of the MF medium microsphere of the comparative example is replaced by 8 μm, so that MF/QD is prepared.
Comparative example 7
This comparative example was prepared in the same manner as example 7 except that it did not include step S5, and QD/AuNR was prepared.
Fig. 1 is a schematic diagram of a fluorescence enhancement principle of a micro-nano composite structure of a dielectric microsphere/noble metal nano material, the left diagram is an effect diagram of a fluorescent material without a micro-nano composite structure under excitation light, the right diagram is an effect diagram of fluorescence enhancement generated by the fluorescent material in the composite structure under the excitation light, and the micro-nano composite structure combines a nano jet flow effect of the dielectric microsphere and a plasma effect of a gold nanorod and can realize remarkable fluorescence enhancement under the same excitation condition.
Performance testing
1. Test method
Test sample 1 group: comparative examples 1, 2 and 3
Test sample 2 group: comparative examples 4, 5 and 6
Test sample 3 groups: example 1
Test sample 4 groups: example 7 and comparative example 7
Meanwhile, QD samples with the same concentration are selected and manufactured on a silicon substrate in a spin coating mode and used as reference.
The test samples 1, 2 and 3 are sequentially placed on a three-dimensional moving platform of a micro spectrophotometer connected with a Charge-coupled device (CCD), the position of the platform and the position of a focus are adjusted under a white light source, and a clear sample surface image is found in a computer picture connected with an instrument. And switching a light source, selecting 365nm light as exciting light, and observing the fluorescence intensity of the quantum dots in different samples under a dark field.
The 4 groups of nano fluorescent materials of the test sample are placed on a three-dimensional moving platform of a microspectrophotometer, the magnification of the selected microscope lens is 40 times, the numerical aperture is 0.6, and the working distance is 1.8 mm. And observing by adjusting the three-dimensional moving platform and the focal distance under white light. The light source was then switched and the nanofluorescent materials of example 7 and comparative example 7 (with/without microspheres) were observed under excitation from a 365nm light source.
2. Analysis of results
And drawing a height-position curve graph along the position of a blue dotted line in the graph, wherein the thickness of the isolation layer can be obtained according to the average height difference of the steps as shown in the graph. The fluorescence enhancement effect of PMMA isolation layers with different thicknesses obtained by spin coating PMMA solutions with different concentrations is analyzed as follows: when the concentration of PMMA solution was 0.4, 1 and 2mg/mL, the thickness of the obtained spacer layer was 4 (FIG. 2), 8 (FIG. 3) and 12nm (FIG. 4), respectively. Fig. 5 shows the enhanced spectra of AuNR structural substrates for quantum dot fluorescence at different spacer layer thicknesses. The thickness of the isolation layer is changed, different enhancement effects of the gold nanostructure substrate on fluorescence can be observed, when the isolation layer is absent, the plasma resonance effect of AuNR shows that the fluorescence is quenched, and the fluorescence of the quantum dots is weakened; when the thickness of the isolation layer is gradually increased, the plasma resonance effect is gradually changed from quenching to enhancing the fluorescence, when the thickness of the isolation layer is 8nm, the enhancement effect is strongest, and the fluorescence of the quantum dots is enhanced by 22 times; when the thickness of the isolation layer is further increased, the plasmon resonance effect is weakened, and the fluorescence enhancement effect is also weakened accordingly. Therefore, the comparison experiment results show that the optimal fluorescence enhancement effect can be obtained under the thickness of the isolation layer of 8 nm.
Fig. 6 is an enhancement spectrum of MF microspheres with different diameters for quantum dot fluorescence. The fluorescence enhancement effect of MF microspheres with different diameters on quantum dots is analyzed as follows: due to the nano jet flow effect of the medium microspheres, the MF microspheres have a convergence effect on incident light, so that the energy density of the incident light can be improved, and fluorescence can be enhanced, so that the fluorescence intensity in the MF/QD sample is stronger than that of the QD sample. This concentration of light increases with increasing diameter of the MF microspheres, and thus the fluorescence intensity of the MF/QD sample increases with increasing diameter of the microspheres, which increases by a factor of 26 when the MF microspheres are 10 μm in diameter.
The enhancement effect of the micro-nano composite structure on the fluorescence can be observed quantitatively through spectral measurement.
Fig. 7 is a schematic diagram of the micro-nano composite structure prepared in example 1, and it can be seen that the micro-nano composite structure is composed of six parts, from bottom to top, of a substrate, a plasmon layer, a polymer isolation layer, a fluorescent layer, a polymer protection layer and a medium microsphere layer, wherein the thickness of the polymer isolation layer is 8nm, and the diameter of the microsphere is 10 μm.
Fig. 8 is a fluorescence enhancement spectrum of the micro-nano composite structure prepared in example 1 for quantum dots, and four curves in the graph are fluorescence spectra of quantum dots in four samples, namely QD, QD/AuNR prepared in comparative example 1, MF/QD prepared in comparative example 4, and MF/QD/AuNR prepared in example 1. The inset is a dark field fluorescence picture of the optical microscope of the composite structure under 365nm excitation, wherein the red bright spot is the position of the microsphere. It can be seen that compared with a pure Quantum Dot (QD) sample, the quantum dot fluorescence in the MF/QD/AuNR composite structure is enhanced by up to 260 times, while in the presence of microspheres, the quantum dot fluorescence in the MF/QD structure is enhanced by 26 times, and in the presence of plasmon layer, the quantum dot fluorescence in the QD/AuNR structure is enhanced by 22 times. As can be seen, the fluorescence enhancement effect of the micro-nano composite structure on the fluorescent layer is improved by one order of magnitude compared with that of the fluorescent layer in the presence of the single microsphere or plasmon layer.
Fig. 9 is a magnified image of the micro-nano composite structure prepared in example 7 on fluorescent particles. Wherein, fig. 9a is a transmission electron microscope image of the nano fluorescent particles, and it can be seen that the diameter distribution of the selected fluorescent particles is uniform, and is about 100 nm. Fig. 9b and c are bright-field optical microscope pictures of the micro-nano composite structure with the fluorescent layer at the position of the fluorescent layer and the microsphere at the focal plane, respectively, and fig. 9d and e are dark-field fluorescent pictures (the excitation light wavelength is 365nm) corresponding to b and c, respectively. It was found that due to the presence of the optical diffraction limit, we could not resolve the fluorescent particles under the optical microscope (fig. 9 b). With the help of microspheres, we can see fluorescent particles under an optical microscope due to the optical magnification of the microspheres, adjusting the focal plane, but the imaging is not clear enough (fig. 9 c). Under 365nm excitation, the brightness of the fluorescent particles is more obvious due to the enhancement effect of the micro-nano composite structure on the fluorescence (fig. 9d), and due to the fluorescence enhancement and the optical amplification effect of the medium microspheres, single nano fluorescent particles can be distinguished, and super-resolution imaging of the fluorescent material under the 100nm scale under an optical microscope is successfully realized (fig. 9 e).
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A micro-nano composite structure with fluorescence enhancement and optical amplification effects is characterized by comprising a plasmon layer, an isolation layer, a fluorescent layer, a protective layer and a medium microsphere layer; the plasmon layer is composed of polymers and precious metal nano materials, the isolation layer is composed of polymers, the fluorescent layer is composed of fluorescent materials, the protection layer is composed of polymers, and the medium microsphere layer is composed of medium microspheres.
2. The method of claim 1, wherein the polymer is one of polymethylmethacrylate, polystyrene, and polypropylene glycol terephthalate vinegar.
3. The production method according to claim 1, wherein the noble metal nanomaterial is a gold or silver nanomaterial.
4. The method according to claim 1, wherein the fluorescent material is one of quantum dots, organic fluorescent dyes and up-conversion nanomaterials.
5. The preparation method according to claim 1, wherein the dielectric microspheres are one of silica microspheres, polystyrene microspheres, titanium dioxide microspheres, and melamine formaldehyde microspheres.
6. The method according to claim 1, wherein the thickness of the isolation layer is 4 to 12 nm.
7. The method for preparing the micro-nano composite structure according to any one of claims 1 to 6, characterized by comprising the following steps:
s1, dispersing a mixed solution of a polymer and a noble metal nano material in a substrate to prepare a structure with a plasmon layer;
s2, coating and dispersing the polymer solution on the structure with the plasmon layer prepared in the step S1, and annealing at 200-300 ℃ to prepare the structure with the isolation layer;
s3, dissolving the fluorescent material in a solvent, and dispersing the fluorescent material on the isolation layer with the structure prepared in the step S2 to prepare a structure with a fluorescent layer;
s4, dispersing the polymer solution on the fluorescent layer with the structure prepared in the step S3 to prepare a structure with a protective layer;
and S5, dissolving the medium microspheres in water, dispersing the medium microspheres on the protective layer of the structure prepared in the step S4, and drying to obtain the micro-nano composite structure with the medium microsphere layer.
8. The method of claim 7, wherein the substrate is prepared by:
firstly, wiping off scraps of a silicon wafer by using ethanol, then respectively carrying out ultrasonic cleaning for 15-30 min in acetone, ethanol and water at 25-30 ℃, then placing the silicon wafer under high-pressure nitrogen flow, and drying the surface of the silicon wafer to obtain a dry and clean silicon wafer serving as a substrate.
9. The method of claim 7, wherein the mixed solution of the polymer and the noble metal nanomaterial is prepared by: dissolving a polymer in acetone, adding a metal nano material, and uniformly stirring to prepare a mixed solution of the polymer and the metal nano material, wherein the mass ratio of the polymer to the metal nano material is 1-3: 1-3.
10. The method of claim 7, wherein the polymer solution of the steps S2 and S4 has a concentration of 0.4-2.0 mg/mL.
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