CN114276810B - Double-local-field synergistic enhanced up-conversion luminescence composite film and preparation method thereof - Google Patents
Double-local-field synergistic enhanced up-conversion luminescence composite film and preparation method thereof Download PDFInfo
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Abstract
The application relates to a double-local-field synergic enhancement up-conversion luminescence composite film, which comprises a substrate, a photonic crystal layer, a noble metal layer, a dielectric layer and an up-conversion luminescence layer. The preparation method of the composite film comprises the steps of preparing NaGdF by a solvothermal method 4 :Yb 3+ /Er 3+ /Al 3+ Nanocrystalline, then preparing a photonic crystal layer on the substrate, then preparing a noble metal layer on the photonic crystal layer, then preparing a dielectric layer on the noble metal layer, finally up-converting luminescent NaGdF 4 The nanocrystalline is spin-coated on the dielectric layer to prepare the up-conversion luminescent layer. The composite film and the preparation method thereof are beneficial to improving the up-conversion luminescence performance and simple in preparation.
Description
Technical Field
The application belongs to the field of up-conversion luminescent materials, and particularly relates to a double-local-field synergic enhanced up-conversion luminescent composite film and a preparation method thereof.
Background
The up-conversion luminescent material can convert near infrared light into short-wave visible light, so that the up-conversion luminescent material has wide application in aspects of biological fluorescence imaging, sensing, photodynamic therapy, solar cells and the like. Currently, fluorides are the more desirable low phonon energy up-conversion matrix materials in which NaGdF 4 Is one of known matrix materials with high efficiency, and has high refractive index, high radiation luminescence and good infrared transmissionAnd the jettability and the like.
The up-conversion composite film structure can regulate up-conversion luminescence, and compared with block and nano-crystal up-conversion luminescent materials, the up-conversion luminescent film has attractive prospects in the aspects of solar cells, optoelectronic devices, near infrared detectors and the like. The dual local fields of the excitation field and the metal local surface plasmon resonance coupling emission field are coupled by utilizing the Bragg reflection effect of the photonic crystal surface to enhance the up-conversion luminous intensity, and a transparent dielectric layer is inserted between the up-conversion material and the metal film, so that the luminous intensity of the film is further regulated and controlled. The photonic crystal band gap, the morphology and the size of silver film particles and the thickness of a dielectric layer have great influence on up-conversion luminous intensity, so that NaGdF is prepared 4 The film adopts a simple and easy method to strengthen NaGdF 4 The up-conversion luminous intensity of the film has important potential application value.
Disclosure of Invention
The application aims to provide a double-local-field synergic enhancement up-conversion luminescence composite film and a preparation method thereof, and the composite film and the preparation method thereof are beneficial to improving up-conversion luminescence performance and are simple to prepare.
In order to achieve the above purpose, the application adopts the following technical scheme: a composite film with double local fields for synergistically enhancing up-conversion luminescence comprises a substrate, a photonic crystal layer, a noble metal layer, a dielectric layer and an up-conversion luminescence layer.
Further, the substrate is a glass sheet; the photonic crystal layer PCs is a 400nm polystyrene photonic crystal template; the noble metal layer is an Ag layer, and the thickness of the noble metal layer is 8nm; the dielectric layer is Al 2 O 3 A film having a thickness of 5-12 a nm a; the up-conversion luminescent layer is formed by NaGdF 4 :Yb 3+ /Er 3+ /Al 3+ The up-conversion luminescent material is prepared by uniformly spin-coating the up-conversion luminescent material on the surface of the dielectric layer, and the thickness of the up-conversion luminescent material is 100-500 nm.
The preparation method of the double-local-field synergistic enhanced up-conversion luminescence composite film comprises the steps of preparing NaGdF by a solvothermal method 4 :Yb 3+ /Er 3+ /Al 3+ Nanocrystalline, then liningPreparing a photonic crystal layer on the bottom, preparing a noble metal layer on the photonic crystal layer, preparing a medium layer on the noble metal layer, and finally up-converting luminescent NaGdF 4 The nanocrystalline is spin-coated on the dielectric layer to prepare the up-conversion luminescent layer.
Further, the photonic crystal layer PCs is formed by vertically inserting 0.2ml of 400nm monodisperse polystyrene microspheres into 2.25ml deionized water and 0.75ml absolute ethyl alcohol, vertically inserting the glass substrate, and baking at 55 ℃ for vertical self-assembly.
Further, the noble metal layer is prepared by evaporating Ag particles on the photonic crystal layer by adopting a vacuum thermal evaporation method; the technological conditions of the vacuum thermal evaporation method are as follows: background vacuum less than 1X 10 -4 Pa, a source base distance of 150mm, and a heating current of 88A.
Further, the dielectric layer is formed by sputtering a layer of Al on the Ag film by adopting a radio frequency magnetron sputtering method 2 O 3 Film preparation; the technological conditions of the radio frequency magnetron sputtering method are as follows: the background vacuum degree is less than 1 multiplied by 10 by adopting an alumina ceramic target -3 Pa, a target base distance of 12.8mm, an argon flow of 35sccm, a sputtering gas pressure of 0.5Pa, and a sputtering power of 50W.
Further, the preparation method of the up-conversion luminescent layer comprises the following steps:
(1) Adding 50mg polymethyl methacrylate PMMA particles into a 5mL chloroform solvent, performing ultrasonic treatment for 15min, and then placing the mixture into a magnetic stirrer to stir for 30min to obtain a transparent colloid solution for standby;
(2) 0.2g NaGdF was added 4 :Yb 3+ /Er 3+ /Al 3+ Adding the powder into absolute ethyl alcohol of 4mL, carrying out ultrasonic treatment for 15min, and then placing into a magnetic stirrer to stir for 30min to obtain a solution for standby;
(3) In Glass/PCs/Ag/Al 2 O 3 Spin-coating a layer of the solution containing the up-conversion powder prepared in the step (2) on the composite film through a spin-coating machine, and spin-coating a layer of the colloidal solution prepared in the step (1); the spin coating conditions are as follows: forward rotation speed 2500rmp, time 30s; the back rotation speed is 1000rmp, and the time is 30s.
Compared with the prior art, the application has the following beneficial effects: the application provides a double-local field synergic enhanced up-conversion luminescence composite film and a preparation method thereof, and the application uses NaGdF co-doped with metal ions and rare earth ions 4 As an up-conversion luminescent material, the thickness of the noble metal silver layer and the size of the photonic crystal are controlled to couple the electromagnetic field of emitted light and absorbed light, and the distance between the luminescent layer and the silver layer is isolated by regulating the thickness of the dielectric layer to enhance the up-conversion luminescent intensity. The up-conversion composite film can be applied to the fields of light emitting devices, solar cells and the like, and has simple preparation process, easy operation and wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a composite film structure with dual local field synergistic enhancement up-conversion luminescence according to an embodiment of the present application;
FIG. 2 is an SEM image of a photonic crystal layer prepared in accordance with embodiments of the present application;
FIG. 3 is an SEM image of PCs/Ag film prepared in the examples of the present application;
FIG. 4 shows PCs/Ag/Al prepared in example 1 of the present application 2 O 3 UC film under 980 nm excitation of different Al 2 O 3 Up-conversion emission map of thickness;
FIG. 5 shows PCs/Ag/Al prepared in example 1 of the present application 2 O 3 UC film under 980 nm excitation of different Al 2 O 3 Light emission enhancement multiple of thickness.
Detailed Description
The application will be further described with reference to the accompanying drawings and examples.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As shown in FIG. 1, the embodiment provides a composite film with dual local fields synergistically enhanced up-conversion luminescence, which comprises a substrate, a photonic crystal layer, a noble metal layer, a dielectric layer and an up-conversion luminescence layer.
In this embodiment, the substrate is a glass sheet; the photonic crystal layer (PCs) is a 400nm polystyrene photonic crystal template; the noble metal layer is an Ag layer, and the thickness of the noble metal layer is 8nm; the dielectric layer is Al 2 O 3 A film having a thickness of 5-12 a nm a; the up-conversion luminescent layer is formed by NaGdF 4 :Yb 3+ /Er 3+ /Al 3+ The up-conversion luminescent material is prepared by uniformly spin-coating the up-conversion luminescent material on the surface of the dielectric layer, and the thickness of the up-conversion luminescent material is 100-500 nm. In this example, the SEM of the photonic crystal layer is shown in FIG. 2, and the SEM of the PCs/Ag film is shown in FIG. 3.
In this embodiment, the preparation method of the composite film with dual local fields synergistically enhanced up-conversion luminescence includes: firstly, preparing NaGdF by using solvothermal method 4 :Yb 3+ /Er 3+ /Al 3+ Nanocrystalline, then preparing a photonic crystal layer on the substrate, then preparing a noble metal film on the photonic crystal layer, then preparing a dielectric layer on the noble metal film, finally up-converting luminescent NaGdF 4 The nanocrystalline is spin-coated on the dielectric layer to prepare the up-conversion luminescent layer.
In order to make the contents of the present application more easily understood, the following two specific embodiments are used to further describe the technical solution of the present application, but the present application is not limited thereto.
Example 1 PC/Ag/Al 2 O 3 UC film luminous structure
(1) 50mg Polymethylmethacrylate (PMMA) particles were weighed into a 5mL chloroform solvent, sonicated for 15min, and then placed into a magnetic stirrer for stirring for 30 min. To obtain a transparent colloid solution for standby.
(2) Weigh 0.2g NaGdF 4 :Yb 3+ /Er 3+ /Al 3+ Adding the powder into absolute ethanol of 4mL, performing ultrasonic treatment for 15min, and stirring in a magnetic stirrer for 30 min. A ready-to-use solution was obtained.
(3) The common glass substrate is cleaned and dried.
(4) The glass substrate was placed vertically in a solution of 0.2ml of 400. 400nm monodisperse polystyrene microspheres in 2.25ml deionized water and 0.75. 0.75ml absolute ethanol, and baked at 55 ℃ to vertically self-assemble the photonic crystal.
(5) Vacuum evaporating the Ag film on the photonic crystal to a thickness of about 8a nm a; the technological conditions for evaporating Ag in vacuum are as follows: vacuum degree is less than 8.5X10 -5 Pa, source base 15 cm, heating current 88A.
(6) Magnetron sputtering of Al on Ag films 2 O 3 A film with a thickness of 5-12 a nm a; magnetron sputtering Al 2 O 3 The process conditions of (2) are as follows: by Al 2 O 3 Ceramic target, deposition gas pressure less than 7.5X10 -4 Pa, an argon gas flow rate of 35sccm, a target base distance of 12.8 cm, a sputtering gas pressure of 0.5Pa, and a sputtering power of 50W.
(7) In Glass/PCs/Ag/Al 2 O 3 Spin coating (2) the standby solution and (1) the colloid solution on the composite film by using a spin coating machine, wherein the specific parameters are as follows: forward rotation speed 2500rmp, time 30s; the back rotation speed is 1000rmp, and the time is 30s.
FIG. 4 shows PCs/Ag/Al prepared in example 1 2 O 3 UC film under 980 nm excitation of different Al 2 O 3 Up-conversion emission map of thickness, al 2 O 3 Maximum fluorescence enhancement was obtained at a film thickness of 10 nm;
FIG. 5 shows PCs/Ag/Al prepared in example 1 2 O 3 UC film under 980 nm excitation of different Al 2 O 3 Light emission enhancement times for film thickness. As can be seen from FIG. 5, in Al 2 O 3 At a thickness of 10 nm, the red and green light are respectively enhanced by 94 times and 183 times.
The application provides a double local field cooperative enhancement up-conversion transmitterThe optical composite film and the preparation method thereof utilize Bragg reflection effect of the photonic crystal, noble metal Ag plasma effect and the regulating and controlling dual-local field synergistic effect of the transparent dielectric layer to improve NaGdF 4 :Yb 3+ /Er 3+ /Al 3+ Up-conversion luminous intensity of the film; the application has controllable film thickness, simple preparation method and equipment, easy realization and can be applied to the fields of light-emitting devices, solar cells and the like.
The above description is only a preferred embodiment of the present application, and is not intended to limit the application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present application still fall within the protection scope of the technical solution of the present application.
Claims (1)
1. The composite film is characterized by comprising a substrate, a photonic crystal layer, a noble metal layer, a dielectric layer and an up-conversion luminescent layer; the substrate is a glass sheet; the photonic crystal layer PCs is a 400nm polystyrene photonic crystal template; the noble metal layer is an Ag layer, and the thickness of the noble metal layer is 8nm; the dielectric layer is Al 2 O 3 A thin film having a thickness of 5-12nm; the up-conversion luminescent layer is formed by NaGdF 4 :Yb 3+ /Er 3+ /Al 3+ The up-conversion luminescent material is prepared by uniformly spin-coating the up-conversion luminescent material on the surface of a dielectric layer, and the thickness of the up-conversion luminescent material is 100-500nm;
the preparation method of the double-local-field synergistic enhanced up-conversion luminescence composite film comprises the steps of preparing NaGdF by a solvothermal method 4 :Yb 3+ /Er 3+ /Al 3+ Nanocrystalline, then preparing a photonic crystal layer on the substrate, then preparing a noble metal layer on the photonic crystal layer, then preparing a dielectric layer on the noble metal layer, finally up-converting luminescent NaGdF 4 The nanocrystalline is spin-coated on the dielectric layer to prepare an up-conversion luminescent layer;
the photonic crystal layer PCs is formed by vertically inserting 0.2ml of 400nm monodisperse polystyrene microspheres into 2.25ml of deionized water and 0.75ml of absolute ethyl alcohol into a glass substrate, and vertically self-assembling by baking at the temperature of 55 ℃;
the noble metal layer is prepared by evaporating Ag particles on the photonic crystal layer by adopting a vacuum thermal evaporation method; the technological conditions of the vacuum thermal evaporation method are as follows: background vacuum less than 1X 10 -4 Pa, a source base distance of 150mm, and a heating current of 88A;
the dielectric layer is formed by sputtering a layer of Al on the Ag film by adopting a radio frequency magnetron sputtering method 2 O 3 Film preparation; the technological conditions of the radio frequency magnetron sputtering method are as follows: the background vacuum degree is less than 1 multiplied by 10 by adopting an alumina ceramic target -3 Pa, a target base distance of 12.8mm, an argon flow of 35sccm, a sputtering air pressure of 0.5Pa and a sputtering power of 50W;
the preparation method of the up-conversion luminescent layer comprises the following steps:
(1) 50mg of polymethyl methacrylate PMMA particles are added into 5mL of chloroform solvent, ultrasonic treatment is carried out for 15min, and then the mixture is put into a magnetic stirrer to be stirred for 30min, thus obtaining a transparent colloid solution for standby;
(2) 0.2g NaGdF was added 4 :Yb 3+ /Er 3+ /Al 3+ Adding the powder into 4mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, and then placing into a magnetic stirrer to stir for 30min to obtain a solution for standby;
(3) In Glass/PCs/Ag/Al 2 O 3 Spin-coating a layer of the solution containing the up-conversion powder prepared in the step (2) on the composite film through a spin-coating machine, and spin-coating a layer of the colloidal solution prepared in the step (1);
the spin coating conditions are as follows: forward rotation speed 2500rmp, time 30s; the back rotation speed is 1000rmp and the time is 30s.
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| Title |
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| 王鹤.光子晶体与等离子体共振效应增强光致发光及其应用探索.《中国博士学位论文全文数据库基础科学辑》.2018,(第undefined期),第A005-26页. * |
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