CN111313215B - Organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure and preparation method - Google Patents
Organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure and preparation method Download PDFInfo
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
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Abstract
The invention discloses an organic solid laser based on a metal nano core-shell structure-metal film plasma composite structure, which comprises a substrate, a metal film layer, a core-shell structure layer and a gain medium layer which are sequentially stacked; the metal film layer is a metal film capable of generating a non-local surface plasma (SPP) effect; the shell layer material in the core-shell structure layer is an isolation medium material, and the central core material is first metal nano particles capable of realizing the local surface plasma effect LSPR. The shell layer of the core-shell structure is ingeniously used as the isolation layer, the distance between the LSPR and the SPP is regulated and controlled by changing the thickness of the shell layer, coupling between the LSPR and the SPP is achieved, a strong local electric field is further generated, the structure is simpler, and the preparation method is simpler and more convenient.
Description
Technical Field
The invention relates to the technical field of lasers, in particular to an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure and a preparation method thereof.
Background
With the development and application of organic optoelectronic devices, the lasing phenomenon of organic functional materials and the research of organic solid-state laser devices have become hot spots of international research in recent years. Compared with inorganic materials, the laser based on the organic semiconductor material has many advantages, such as simple preparation process, low cost, abundant materials, easy tuning of emergent wavelength and the like, and has great market prospects in the fields of military affairs, medical treatment, communication, scientific research and the like, so that the laser is widely concerned by researchers at home and abroad.
At present, the organic solid laser has made great progress in optical pumping, and with the further understanding of people on optoelectronic devices, the realization of an electrically pumped organic solid laser becomes a target pursued by people. The metal electrode is indispensable in the electrically pumped organic solid-state laser, however, the metal electrode has strong quenching and absorption loss to the emitted light of fluorescent molecules nearby, so that the lasing threshold of the organic functional material is too high, and the electrically pumped organic solid-state laser is difficult to realize.
Currently, fluorescence quenching and loss of metal electrodes to dye molecules have been reduced in a variety of ways. For example, a metal electrode with a distributed feedback grating structure is introduced, a metal cathode with low work function is utilized, and a thin polymer or metal electrode oxide isolation layer is introduced to reduce the negative effect of the metal electrode on a gain medium. However, although the lasing performance of the organic solid-state laser based on the metal thin film is improved to different degrees, quenching of the dye molecules by the metal electrode is still unavoidable, which becomes a key problem in the field of organic solid-state lasers and is one of the obstacles that need to be solved urgently in realizing the electrically pumped organic solid-state laser. Therefore, the optical quenching and absorption loss of the metal electrode to the organic functional material are avoided, the lasing threshold of the organic molecule and the system thereof is further reduced, the realization of the low-threshold optically pumped organic solid laser is facilitated, one of the preconditions for realizing the electrically pumped organic solid laser is also realized, and the method has important research significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an organic solid laser based on a metal nano core-shell structure-metal film plasma composite structure and a preparation method thereof.
The invention provides an organic solid laser based on a metal nano core-shell structure-metal film plasma composite structure, which comprises a substrate, a metal film layer, a core-shell structure layer and a gain medium layer which are sequentially stacked;
the metal film layer is a metal film capable of generating a non-local surface plasma (SPP) effect; the shell layer material in the core-shell structure layer is an isolation medium material, and the central core material is first metal nano particles capable of realizing the local surface plasma effect LSPR.
Preferably, the first metal nanoparticles in the core-shell structure layer are nanospheres, nanorods, nanocubes, nanotrials, nanowires or nanoparticles of various nanometer sizes and shapes made of gold, silver or platinum.
More preferably, the isolation medium material in the core-shell structure layer is a metal or nonmetal oxide with a thickness of 1-100 nm.
More preferably, the isolation medium material in the core-shell structure layer is selected from SiO2Or TiO2。
Preferably, the metal thin film layer is a silver thin film or a gold thin film with a thickness of 10-100 nm.
Preferably, second metal nanoparticles are randomly distributed in the gain medium layer, the second metal nanoparticles are metal nanoparticles capable of realizing Localized Surface Plasmon Resonance (LSPR), and the doping concentration of the second metal nanoparticles in the gain medium layer is 1 × 10-8g/cm3-9×10-2g/cm3。
More preferably, the second metal nanoparticles are selected from the group consisting of gold, silver, platinum material nanospheres, nanorods, nanocubes, nanotriangles, nanowires or various nanosized shaped nanoparticles; or, a core-shell structure defined the same as the core-shell structure layer; the second metal nanoparticles are the same as or different from the core-shell structure layer.
More preferably, the doping concentration of the second metal nano-particles in the gain medium layer is 3.8 × 10-6g/cm3-8.65×10-3g/cm3。
Preferably, the material of the gain medium layer comprises a high molecular polymer and a laser dye; the high molecular polymer is polystyrene, polyvinyl alcohol or polymethyl methacrylate; the laser dye is a red laser dye or a blue laser dye, and the light emission wavelength of the laser dye is in the visible light range; the mass ratio of the high molecular polymer to the laser dye is 1-80: 1.
the second purpose of the invention is to provide a preparation method of the organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure, which comprises the following steps:
s1, depositing a metal film on the substrate by a vacuum evaporation method or a magnetron sputtering method to obtain a metal film layer with the thickness of 10-100 nm;
s2, depositing the core-shell structure on the metal film layer compactly in a spin coating or drop coating mode to obtain a core-shell structure layer with the thickness of 2-200 nm;
and S3, preparing a gain medium layer on the surface of the core-shell structure layer, namely finishing the manufacture of the organic solid laser with the thickness of 0.1-3 mu m.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an organic solid laser based on a metal nano core-shell structure-metal film plasma composite structure, which comprises a substrate, a metal film layer, a core-shell structure layer and a gain medium layer, wherein the substrate, the metal film layer, the core-shell structure layer and the gain medium layer are sequentially stacked; the metal film layer is a metal film capable of generating a non-local surface plasma effect (SPP); the first metal nano particles in the core-shell structure layer are metal nano particles capable of realizing the localized surface plasma effect LSPR, and the second metal nano particles capable of realizing the localized surface plasma effect LSPR and having a certain doping concentration are randomly distributed in the gain medium layer. Firstly, when the LSPR of the metal nanoparticles is coupled with the SPP of the metal film, the electric field intensity of the generated local electric field is stronger than that of the single metal nanoparticles or the metal film, and due to the external feedback effect of the metal film, the composite structure has stronger scattering effect than that of the single metal nanoparticles, so that the plasma composite structure formed by the metal nanoparticles and the metal film can have stronger local electric field and scattering intensity, and further the lasing threshold of the gain medium is better reduced.
The shell layer of the core-shell structure is ingeniously used as the isolation layer, the distance between the first metal nano particle LSPR and the metal film SPP in the core-shell structure is adjusted and controlled by changing the thickness of the shell layer, coupling between the first metal nano particle LSPR and the metal film SPP is achieved, a strong local electric field is generated, the structure is simpler, and the preparation method is simpler and more convenient. And secondly, the second metal nano particles with a certain doping amount are randomly distributed in the material of the gain medium layer, so that the device has an additional strong local field and scattering effect generated by the second metal nano particles on the basis of a plasma composite structure, and the lasing performance of the gain medium can be further enhanced. Finally, the first metal nano particles and the metal film in the core-shell structure layer can be respectively coupled with the second metal nano particles in the gain medium nearby the first metal nano particles and the metal film to realize plasma coupling, so that the electric field is further enhanced, and the lasing performance of the gain medium is obviously enhanced.
Drawings
FIG. 1 is a structural view of an organic laser of example 1 of the present invention;
fig. 2 is a structural view of an organic laser of embodiment 2 of the present invention.
Fig. 3 is a graph showing electric field distribution of (a) silver nanospheres (diameter 40nm) alone, (b) a plasma composite structure composed of silver nanospheres (diameter 40nm) spaced at 10nm and a silver thin film (thickness 50nm), (c) two silver nanospheres (diameter 40nm) spaced at 30nm, respectively, under excitation at a wavelength of 435 nm.
In the figure: 1. a substrate; 2. a metal thin film layer; 3. a first core-shell structure layer; 4. a gain medium layer; 5. a second metal nanoparticle layer.
Detailed Description
The technical solutions of the present invention will be further described below with reference to specific embodiments of the present invention and the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
In this embodiment, an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is specifically shown in fig. 1, and includes a substrate 1, a metal thin film layer 2, a core-shell structure layer 3, and a gain medium layer 4, which are sequentially stacked; the metal film layer 2 is capable of generating non-local surface plasma effectThe thickness of the silver thin film layer of the SPP is 50 nm; the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, the central core material is silver nanospheres with the diameter of 40nm, and the core-shell structure nanoparticles are densely deposited on the metal film layer 2; the material of the gain medium layer 4 is prepared from polystyrene and blue laser dye BMT-TPD according to the weight ratio of 4: 1, and the thickness is 300 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/Ag nanospheres @ SiO2(40nm@10nm)/PS:BMT-TPD(300nm)。
The specific preparation method of the organic solid laser is as follows:
s1, depositing a silver film on the substrate 1 by a vacuum evaporation method to obtain a silver film layer with the thickness of 50 nm;
s2, isolating the dielectric material SiO2Core-shell structure (Ag nanospheres @ SiO) formed by coating silver nanospheres2) Compactly depositing on the silver thin film layer in a spin coating manner to obtain a core-shell structure layer 3 with the thickness of 60 nm;
s3, mixing the polystyrene and the laser dye BMT-TPD according to a ratio of 4: 1, adding the mixture into a chloroform solution, performing ultrasonic dissolution, and then spin-coating the mixture on the surface of the core-shell structure layer 3 at a speed of 3000r/min to manufacture a gain medium layer 4 with the thickness of 300nm so as to finish the preparation of the organic solid laser.
Example 2
In this embodiment, an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is specifically shown in fig. 2, and includes a substrate 1, a metal thin film layer 2, a core-shell structure layer 3, and a gain medium layer 4, which are sequentially stacked; the metal film layer 2 is a silver film layer capable of generating a non-local surface plasma (SPP) effect, and the thickness is 50 nm; the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, the central core material is silver nanospheres with the diameter of 40nm, and the core-shell structure nanoparticles are densely deposited on the metal film layer 2; second metal nano particles 5 are randomly distributed in the material of the gain medium layer 4, and the material is prepared from polystyrene and blue laser dye BMT-TPD according to the ratio of 4: 1, these second metal nanoparticlesThe quantum 5 is a silver nanosphere capable of realizing the Localized Surface Plasmon Resonance (LSPR), the diameter of the silver nanosphere is 40nm, and the doping concentration of the second metal nanoparticle 5 in the gain medium layer 4 is 3.65 multiplied by 10-4g/cm3The thickness of the gain medium layer 4 was 300 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/Ag nanospheres @ SiO2(40nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres(300nm)。
The specific preparation method of the organic solid laser is as follows:
s1, depositing a silver film on the substrate 1 by a vacuum evaporation method to obtain a silver film layer with the thickness of 50 nm;
s2, isolating the dielectric material SiO2Core-shell structure (Ag nanospheres @ SiO) formed by coating silver nanospheres2) Compactly depositing on the silver thin film layer in a spin coating manner to obtain a core-shell structure layer 3 with the thickness of 60 nm;
s3, mixing polystyrene with laser dye BMT-TPD according to 4: 1, adding the mixture into chloroform solution for ultrasonic dissolution, adding silver nanospheres with the diameter of 40nm into the mixed solution, and controlling the doping concentration of the silver nanospheres in the gain medium layer 4 to be 3.65 multiplied by 10-4g/cm3And then, coating the surface of the core-shell structure layer 3 with a speed of 3000r/min in a rotating manner to obtain a gain medium layer 4 with the thickness of 300nm so as to finish the preparation of the organic solid laser.
Example 3
In this embodiment, as shown in fig. 2, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that: the doping concentration of the second metal nanoparticles 5 in the gain medium layer 4 is different, and in this embodiment, the doping concentration is 8.65 × 10-3g/cm3。
The specific fabrication method of this organic solid-state laser is also the same as that provided in example 2, except that: when the gain medium layer 4 is prepared, the doping concentration of the second metal nanoparticles 5 in the gain medium layer 4 is controlled to be a corresponding value, which is not described in detail herein.
Example 4
In this embodiment, as shown in fig. 2, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that: the doping concentration of the second metal nanoparticles 5 in the gain medium layer 4 is different, and is 3.8 × 10 in this embodiment-6g/cm3。
The specific fabrication method of this organic solid-state laser is also the same as that provided in example 2, except that: when the gain medium layer 4 is prepared, the doping concentration of the second metal nanoparticles 5 in the gain medium layer 4 is controlled to be a corresponding value, which is not described in detail herein.
Example 5
In this embodiment, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that:
the shell layer material in the core-shell structure layer 3 is an isolation medium material TiO2The thickness is 10nm, and the central core material is silver nanosphere with the diameter of 40 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/Ag nanospheres @ TiO2(40nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres(300nm)。
The specific preparation method of the organic solid laser is also the same as that provided in example 2, and the difference is that the manufacturing process of the core-shell structure layer 3 in S2 is different, and the shell material used in this example is TiO2。
Example 6
In this embodiment, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that: the second metal nano-particle 5 is also in a core-shell structure, and the shell material is an isolation medium material SiO2The thickness is 10nm, and the central core material is silver nanosphere with the diameter of 40 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/Ag nanospheres@SiO2(40nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres@SiO2(300nm)。
The specific preparation method of the organic solid-state laser is also the same as that provided in embodiment 2, and the difference is that in S3, the material of the second metal nanoparticles 5 in the gain medium layer 4 is different.
Example 7
In this embodiment, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that: the metal film layer 2 is made of a gold film layer with the thickness of 50 nm.
The specific device structure is expressed as follows: glass/Au film (50nm)/Ag nanospheres @ SiO2(40nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres(300nm)
The specific preparation method of the organic solid laser is also the same as that provided in example 2, and the difference is also only that the material selection of the metal thin film layer 2 in S1 is different, and the metal thin film layer 2 used in this example is a gold thin film layer with a thickness of 50nm, and is prepared by a magnetron sputtering method.
Example 8
In this embodiment, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 2, except that:
the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, and the central core material is gold nano cubes (Au nanocubes) with the side length of 50 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/Au nanocubes @ SiO2(50nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres(300nm)。
The specific preparation method of the organic solid laser is also the same as that provided in example 1, and the difference is that the manufacturing process of the core-shell structure layer 3 in S2 is different, and the central core material used in this example is a gold nanocube with a side length of 50 nm.
Example 9
In this embodiment, a specific structure of an organic solid laser based on a metal nano core-shell structure-metal thin film plasma composite structure is the same as that in embodiment 8, except that: the gain medium layer is made of different materials, in this embodiment, the gain medium layer 4 is made of polymethyl methacrylate (PMMA) and fluorescent molecules (Alq)3The Forster energy transfer system formed by the dye DCJTB and the red laser dye is taken as the laser dye (PS: Alq)3:DCJTB＝200:100:3.5，wt％)。
The specific device structure is expressed as follows: glass/Ag film (50nm)/Au nanocubes @ SiO2(50nm@10nm)/PMMA:Alq3:DCJTB mingled with Ag nanospheres(300nm)。
The organic solid-state lasers with the metal nano core-shell structure-metal thin film plasma composite structure and excellent performance are prepared in the above embodiments 1 to 9, and it should be noted that all the devices provided in the embodiments 1 to 8 in the organic solid-state lasers are blue-light devices, the material of the gain medium layer is composed of high-molecular polymer and blue-light laser dye, the high-molecular polymer adopts polystyrene, and the blue-light laser dye adopts BMT-TPD as an example. Example 9 provides a red light device, the gain medium layer is made of polymethyl methacrylate (PMMA), and fluorescent molecules are Alq3And the red laser dye DCJTB. It should be noted that the present invention is not limited by the choice of the material of the gain medium layer given in the embodiments of the present invention. Of course, the purpose of the invention can be achieved only by adopting the device with the metal nano core-shell structure-metal film plasma composite structure.
The substrate may be a glass substrate, a silicon substrate, or a flexible substrate, and is not particularly limited in the present invention.
In order to further illustrate the excellent effects of the technical solutions provided by the above embodiments of the present invention, the present invention further provides the following comparative examples for verification and explanation.
Comparative example 1
The comparative example is an organic solid laser comprising a first electrode and a second electrodeThe core-shell structure comprises a substrate 1, a core-shell structure layer 3 and a gain medium layer 4 which are sequentially stacked; wherein, the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, the central core material is silver nanospheres with the diameter of 40nm, and the core-shell structure nanoparticles are densely deposited on the substrate 1; the material of the gain medium layer 4 is prepared from polystyrene and blue laser dye BMT-TPD according to the weight ratio of 4: 1, and the thickness of the gain medium layer 4 is 300 nm.
The specific device structure is expressed as follows: glass/Ag nanospheres @ SiO2(40nm@10nm)/PS:BMT-TPD(300nm)。
Comparative example 2
The organic solid laser comprises a glass substrate 1, a metal thin film layer 2, an isolation dielectric layer and a gain dielectric layer 4 which are sequentially stacked from bottom to top; wherein, the metal film layer 2 is a silver film with the thickness of 50 nm; the isolating medium layer is a LiF isolating layer with the thickness of 20 nm; the material of the gain medium layer 4 is prepared from polystyrene and blue laser dye BMT-TPD according to the weight ratio of 4: 1, and the thickness of the gain medium layer 4 is 300 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/LiF (20nm)/PS BMT-TPD (300 nm).
Comparative example 3
The organic solid laser comprises a glass substrate 1, a core-shell structure layer 3 and a gain medium layer 4 which are sequentially stacked from bottom to top; wherein, the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, the central core material is silver nanospheres with the diameter of 40nm, and the core-shell structure nanoparticles are densely deposited on the substrate 1; the gain medium layer 4 is made of polystyrene PS and BMT-TPD according to the weight ratio of 4: 1, the gain medium layer 4 is doped with silver nanospheres with the diameter of 40nm, and the doping concentration of the silver nanospheres is 3.65 multiplied by 10-4g/cm3The thickness of the gain medium layer 4 was 300 nm.
The specific device structure is expressed as follows: glass/Ag nanospheres @ SiO2(40nm@10nm)/PS:BMT-TPD mingled with Ag nanospheres(300nm)。
Comparative example 4
The organic solid laser comprises a glass substrate 1, a metal thin film layer 2, an isolation dielectric layer and a gain dielectric layer 4 which are sequentially stacked from bottom to top; wherein the metal film layer 2 is a silver film layer with a thickness of 50 nm; the isolating medium layer is a LiF isolating layer with the thickness of 20 nm; the gain medium layer 4 is made of polystyrene and BMT-TPD according to the weight ratio of 4: 1, the gain medium layer 4 is doped with silver nanospheres with the diameter of 40nm, and the doping concentration of the silver nanospheres is 3.65 multiplied by 10-4g/cm3The thickness of the gain medium layer 4 was 300 nm.
The specific device structure is expressed as follows: glass/Ag film (50nm)/LiF (20nm)/PS BMT-TPD finished with Ag nanoparticles (300 nm).
Comparative example 5
The organic solid laser comprises a glass substrate 1, a core-shell structure layer 3 and a gain medium layer 4 which are sequentially stacked from bottom to top; wherein, the shell layer material in the core-shell structure layer 3 is an isolation medium material SiO2The thickness is 10nm, the central core material is gold nano cubes (Au nanocubes) with the side length of 50nm, and the core-shell structure nano particles are densely deposited on the substrate 1; the material of the gain medium layer 4 is polymethyl methacrylate (PMMA), fluorescent molecules Alq3The red laser dye DCJTB is mixed according to the mass ratio of 200:100:3.5, silver nanospheres with the diameter of 40nm are doped in the gain medium layer 4, and the doping concentration of the silver nanospheres is 3.65 multiplied by 10-4g/cm3The thickness of the gain medium layer 4 was 300 nm.
The specific device structure is expressed as follows: glass/Au nanocubes @ SiO2(50nm@10nm)/PMMA:Alq3:DCJTB mingled with Ag nanospheres(300nm)。
Comparative example 6
The organic solid laser comprises a glass substrate 1, a metal thin film layer 2, an isolation dielectric layer and a gain dielectric layer 4 which are sequentially stacked from bottom to top; wherein the metal film layer 2 is a silver film layer with a thickness of 50 nm; the isolating medium layer is a LiF isolating layer with the thickness of 20 nm; the material of the gain medium layer 4 is polymethyl methacrylate (PMMA), fluorescent molecules Alq3With red laser dye DCJTBThe gain medium layer 4 is doped with silver nanospheres with the diameter of 40nm, and the doping concentration of the silver nanospheres is 3.65 multiplied by 10-4g/cm3The thickness of the gain medium layer 4 was 300 nm.
The specific device structure is expressed as follows:
glass/Ag film(50nm)/LiF(20nm)/PMMA:Alq3:DCJTB mingled with Ag nanospheres(300nm)。
the method ingeniously utilizes the shell layer of the core-shell structure as the isolation layer, adjusts and controls the distance between the metal nano particle LSPR and the metal film SPP by changing the thickness of the shell layer, realizes the coupling between the metal nano particle LSPR and the metal film SPP, further generates a strong local electric field, and prepares the laser with excellent performance. The pumping threshold of the device was obtained by pumping the device with an incident light of 355nm with a pulse duration of 5.5ns and a repetition frequency of 10hz using a Nd: YAG nanosecond laser.
Examples 1-9 provide lasers with excellent performance, and the specific results of these laser performance tests are shown in table 1 below.
Table 1 examples 1-9 and comparative examples 1-6 provide a comparison of the emission performance of the devices
First, as can be seen from the data provided in table 1, the device threshold provided in example 1 is lower than the device threshold of comparative examples 1 and 2, the device threshold provided in example 2 is lower than the device threshold of comparative examples 3 and 4, and the device threshold provided in example 9 is lower than the device threshold of comparative examples 5 and 6, which sufficiently demonstrates that the composite of the metal film 2 and the core-shell structure layer 3 in example is composed of the metal film 2 and the core-shell structure layer 3, compared to the device alone in comparative examples, by introducing the metal film 2 or the core-shell structure layer 3 aloneThe structure can better reduce the laser threshold, because the plasma composite structure formed by the metal nanoparticles and the metal film has stronger local electric field (as shown in fig. 3a and b) and scattering intensity compared with the metal nanoparticles or the metal film. In the patent, the metal film 2 and the nuclear shell structure layer 3 form a plasma composite structure, and a dielectric material SiO is isolated2The thickness of the shell layer is optimized, so that the distance between the first metal nano particle LSPR and the metal film SPP in the core-shell structure can be regulated, and the coupling between the first metal nano particle LSPR and the metal film SPP is realized, thereby generating a stronger local electric field; and due to the external feedback effect of the metal film 2, compared with the single core-shell structure nano particle, the composite structure has a stronger scattering effect, so that the plasma composite structure formed by the core-shell structure layer 3 and the metal film 2 can have stronger local electric field and scattering strength, and further, the lasing threshold of the gain medium is better reduced. The structure is simpler, and the preparation method is simpler and more convenient. Secondly, the device threshold provided in embodiment 2 is lower than that of embodiment 1, the device threshold provided in comparative example 3 is lower than that of comparative example 1, and the device threshold provided in comparative example 4 is lower than that of comparative example 2, it can be seen that, by randomly distributing a certain doping amount of the second metal nanoparticles 5 in the gain medium layer 4, the device has an additional strong local field (as shown in fig. 3a) and a scattering effect generated by the second metal nanoparticles 5 on the basis of the plasma composite structure composed of the core-shell structure layer 3 and the metal thin film 2, and the lasing performance of the gain medium can be further enhanced. Finally, the core-shell structure layer 3 and the metal film 2 can also be coupled with the second metal nanoparticles 5 doped in the gain medium layer 4 near the core-shell structure layer respectively to realize plasma coupling, so as to cause electric field enhancement (as shown in fig. 3b and c), thereby further reducing the laser threshold and achieving further optimization of the laser performance, which is also the inherent reason why the device provided by the above embodiment of the present invention has a lower laser threshold.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. An organic solid laser based on a metal nano core-shell structure-metal film plasma composite structure is characterized by comprising a substrate (1), a metal film layer (2), a core-shell structure layer (3) and a gain medium layer (4) which are sequentially stacked;
the metal film layer (2) is a metal film capable of generating a non-local surface plasma (SPP);
the shell layer material in the core-shell structure layer (3) is an isolation medium material, and the central core material is first metal nano particles capable of realizing the local surface plasma effect LSPR.
2. The organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 1, wherein the first metal nanoparticles in the core-shell structure layer (3) are nano spheres, nano rods, nano cubes, nano triangles, nano wires or nano particles of various nano-size shapes of gold, silver and platinum materials.
3. The organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 2, wherein the isolation dielectric material in the core-shell structure layer (3) is a metal or nonmetal oxide with a thickness of 1-100 nm.
4. The organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 3, wherein the isolation medium material in the core-shell structure layer (3) is selected from SiO2Or TiO2。
5. The organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 1, wherein the metal thin film layer (2) is a silver thin film or a gold thin film with a thickness of 10-100 nm.
6. The organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 1, wherein the gain medium layer (4) is randomly distributed with second metal nanoparticles (5), the second metal nanoparticles (5) are metal nanoparticles capable of realizing Localized Surface Plasmon Resonance (LSPR), and the doping concentration of the second metal nanoparticles (5) in the gain medium layer (4) is 1 x 10-8g/cm3-9×10-2g/cm3。
7. The organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure according to claim 6, wherein the second metal nanoparticles (5) are selected from nanospheres, nanorods, nanocubes, nanotrians, nanowires or nanoparticles of various nano-size shapes of gold, silver, platinum material;
or, a core-shell structure defined the same as the core-shell structure layer (3); the second metal nano-particles (5) are the same as or different from the core-shell structure layer (3).
8. The organic solid laser based on metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 6, wherein the doping concentration of the second metal nano particles (5) in the gain medium layer (4) is 3.8 x 10-6g/cm3-8.65×10-3g/cm3。
9. The organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure as claimed in claim 1, wherein the material of the gain medium layer (4) comprises a high molecular polymer and a laser dye; the high molecular polymer is polystyrene, polyvinyl alcohol or polymethyl methacrylate; the laser dye is a red laser dye or a blue laser dye, and the light emission wavelength of the laser dye is in the visible light range;
the mass ratio of the high molecular polymer to the laser dye is 1-80: 1.
10. the method for preparing the organic solid laser based on the metal nano core-shell structure-metal thin film plasma composite structure according to claim 1, comprising the following steps:
s1, depositing a metal film on the substrate (1) by a vacuum evaporation method or a magnetron sputtering method to obtain a metal film layer (2) with the thickness of 10-100 nm;
s2, depositing core-shell structure material on the metal film layer (2) densely in a spin coating or drop coating mode to obtain a core-shell structure layer (3) with the thickness of 2-200 nm;
and S3, preparing a gain medium layer (4) with the thickness of 0.1-3 mu m on the surface of the core-shell structure layer (3), and finishing the manufacture of the organic solid laser.
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