CN112538352A

CN112538352A - Efficient multicolor up-conversion luminescence composite film

Info

Publication number: CN112538352A
Application number: CN201910892517.9A
Authority: CN
Inventors: 丛妍; 杨扬; 董斌; 尚景雨
Original assignee: Dalian Minzu University
Current assignee: Dalian Minzu University
Priority date: 2019-09-20
Filing date: 2019-09-20
Publication date: 2021-03-23
Anticipated expiration: 2039-09-20
Also published as: CN112538352B

Abstract

The invention belongs to the technical field of rare earth doped up-conversion materials, and discloses a high-efficiency multicolor up-conversion luminescent composite film. The high-efficiency multicolor upconversion luminescence composite film is prepared by obtaining rare earth doped NaYF through high-temperature pyrolysis₄Reducing polyhydric alcohol to obtain Ag nano meter with length of 500nm and solvothermally obtaining W growing on FTO glass₁₈O₄₉The nano wire is made of three-layer material, and Ag nano meter and rare earth doped NaYF are subjected to a simple self-assembly process₄Is sequentially deposited on W₁₈O₄₉And the nanowire film is constructed on the nanowire film. Multipolar longitudinal surface using Ag nano meterPlasmon resonance with W₁₈O₄₉The synergistic effect of the ultra-wide surface plasmon resonance effect of the nanowires improves the local electromagnetic field intensity of the surface of the adjacent rare earth-doped up-conversion composite luminescent film under the excitation of incident light, and greatly enhances the multicolor luminous intensity of the rare earth-doped up-conversion composite luminescent film.

Description

Efficient multicolor up-conversion luminescence composite film

Technical Field

The invention belongs to the technical field of rare earth doped up-conversion materials, and relates to a rare earth doped up-conversion materialRare earth doped NaYF₄Ag nano meter/W₁₈O₄₉The high-efficiency multicolor upconversion luminescence composite film is constructed by the nanowires.

Background

The rare earth doped up-conversion material has good stability and can be widely applied to the aspects of biological imaging, solar cells, optical sensing and the like. However, rare earth doped up-conversion nanomaterials have generally low luminous efficiency due to the non-radiative effects of surface defects. At present, researchers have improved the luminescence property of the upconversion nanoparticles through multiple ways such as adjusting doped particles, constructing a core-shell nanostructure, and adjusting and controlling a local field. The regulation and control of the local field based on the local surface plasmon resonance has become one of the effective ways to improve the luminescence property of the upconversion nanoparticles. Noble metal nanoparticles with strong plasmon resonance effect and heavily doped semiconductors with broad spectral absorption have successfully increased the luminescence intensity of up-conversion nanoparticles by enhancing the local electromagnetic field. Due to the limitation of a single-structure local field regulation system, the enhanced luminescence effect of the two plasma nano materials is still not ideal.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the high-efficiency multicolor upconversion luminescence composite film with simple process, good repeatability and excellent luminescence enhancement phenomenon. The high-efficiency multicolor upconversion luminescence composite film is prepared by obtaining rare earth doped NaYF through high-temperature pyrolysis₄Reducing polyhydric alcohol to obtain Ag nano meter with length of 500nm and solvothermally obtaining W growing on FTO glass₁₈O₄₉The nano wire is made of three-layer material, and Ag nano meter and rare earth doped NaYF are subjected to a simple self-assembly process₄Is sequentially deposited on W₁₈O₄₉And the nanowire film is constructed on the nanowire film. Multipolar longitudinal surface plasmon resonance and W using Ag nano meter₁₈O₄₉The synergistic effect of the ultra-wide surface plasmon resonance effect of the nano wire improves the local electromagnetic field intensity of the surface of the adjacent rare earth-doped up-conversion composite luminescent film under the excitation of incident light, and greatly enhances the multicolor luminescence of the rare earth-doped up-conversion composite luminescent filmStrength.

The above purpose of the invention is realized by the following technical scheme:

a high-efficiency multi-color up-conversion luminescent composite film comprises rare earth doped NaYF₄Layer, Ag nano-meter layer and W₁₈O₄₉The nano-wire layer is a composite film with efficient multicolor up-conversion luminescence characteristics.

Further, the rare earth doped NaYF₄The layer is composed of Yb³⁺As sensitizer and Er³⁺Or Tm³⁺Rare earth doped NaYF as luminescence center and with uniform particle size₄The Ag nano-meter layer assembly is composed of 500nm double-shuttle-shaped Ag nano-meters; w₁₈O₄₉The nanowire layer is formed by W grown on an FTO glass substrate₁₈O₄₉A nanowire.

The NaYF₄Layer, Ag nano-meter layer, W₁₈O₄₉The nanowire layer concentration ratio is 4: 91-130: 45-65.

Furthermore, the FTO glass substrate is SnO doped with fluorine₂Transparent conductive glass (SnO)₂: F) abbreviated as FTO;

the preparation method of the efficient multicolor up-conversion luminescence composite film comprises the following steps:

step (1) W₁₈O₄₉Preparing a nanowire film:

growing a layer of W on FTO conductive glass by a solvothermal method₁₈O₄₉A nanowire film, 25-30mg of tungsten hexacarbonyl is poured into 20-24mL of absolute ethyl alcohol solution to be stirred for 40-60min to obtain mixed solution A, the solution A is moved into a 50mL polytetrafluoroethylene reaction kettle containing 2 x 3cm of FTO conductive glass, an oven is heated to 180-degree centigrade 200 ℃, then the reaction kettle is put into the oven to be insulated for 10-12h, the reaction kettle is taken out after being cooled to room temperature and is repeatedly washed by absolute ethyl alcohol to finally obtain W₁₈O₄₉A thin film of nanowires.

Step (2) Ag nano meter/W₁₈O₄₉Preparing a nanowire film:

step a, preparing Ag nano rice by adopting a polyol reduction method, adding 10-12mL of polyethylene glycol into a 100mL round bottom flask, dropwise adding 2-3mL of polyvinyl pyrrolidone solution (1M) and 0.2-0.3mL of newly prepared 1M silver nitrate solution in the stirring process, uniformly stirring for about 10-30min, transferring the round bottom flask into an oil bath kettle at the temperature of 113-. Repeatedly centrifuging and washing the mixture for three to four times by using absolute ethyl alcohol to obtain the Ag nano rice.

Step B, dispersing the Ag nano-meter obtained in the step a into 10mL of absolute ethyl alcohol solution to obtain a mixed solution B, and carrying out simple self-assembly on the W obtained in the step (1)₁₈O₄₉Placing the nanowire film in the solution B and transferring the nanowire film into an oven, heating the oven to 50-70 ℃, preserving heat for 6-8h, and obtaining Ag nano meter/W after the solution B is completely evaporated₁₈O₄₉A thin film of nanowires.

Step (3) rare earth doping NaYF₄Nano particle/Ag nano meter/W₁₈O₄₉Preparing a nanowire film:

step a, preparing rare earth doped NaYF by utilizing a high-temperature pyrolysis process₄And (2) up-conversion luminescence nanoparticles, namely adding yttrium chloride hexahydrate, ytterbium chloride hexahydrate and chlorinated bait hexahydrate into a mixed solution C in a three-neck flask containing 6-12mL of oleic acid and 15-30mL of octadecene according to a molar ratio of 1:10:50 or adding yttrium chloride hexahydrate, ytterbium chloride hexahydrate and thulium chloride hexahydrate according to a molar ratio of 1:50:200, vacuumizing for 30-40min, heating to 150 ℃, keeping for 20-30min, and cooling to room temperature. Then, dropwise adding a prepared 5-10mL methanol solution dissolved with 0.148-0.296g of ammonium fluoride and 0.1-0.2g of sodium hydroxide into the solution C at a constant speed through an injection pump, introducing argon for 30-60min, raising the temperature to 80 ℃, keeping the temperature for 1.5-2h to remove the methanol, finally raising the temperature to 305-310 ℃, reacting for 1.5-2h, cooling to room temperature, centrifugally washing three times by using a liquid with a volume ratio of cyclohexane to ethanol of 1:3, and finally obtaining the rare earth doped NaYF₄Particles.

Step b, doping NaYF with the rare earth obtained in the step a₄Dispersing the nano particles into 10mL of cyclohexane solution to obtain a mixed solution D, and performing nano-meter/W treatment on the Ag nano particles obtained in the step (2)₁₈O₄₉Placing the nanowire film in the solution D and moving the nanowire film into an oven, heating the oven to 50-70 ℃, preserving heat for 6-8h, and completely evaporating the solution DSo that the rare earth is doped with NaYF₄Deposition of nanoparticles to Ag nm/W₁₈O₄₉The surface of the nanowire film can be obtained to be the rare earth doped NaYF₄Nano particle/Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

Further, the conductive glass in the step (1) is 2 x 3cm fluorine-doped SnO₂Transparent conductive glass (SnO)₂：F)，

Further, the solvothermal method described in the step (1) refers to a reaction at 180 ℃ for 12 hours.

Further, the simple self-assembly method in the step (2) is to keep the temperature at 50-70 ℃ for 6-8 h.

The polyol reduction method is characterized in that the polyol reduction method is to continuously stir for 8-10h in an oil bath pan at the temperature of 113 ℃;

the high-temperature pyrolysis process is that the temperature is firstly raised to 150 ℃ and is preserved for 20-30min, then the temperature is lowered to room temperature, the temperature is raised to 80 ℃ after 30-60min and is preserved for 1.5-2h, and finally the temperature is continuously raised to 305 ℃ and 310 ℃ and is preserved for 1.5-2 h.

The Ag nano meter is a submicron-sized silver nano structure with a uniform shape, which is prepared by adopting a polyol reduction method.

According to the invention, the noble metal with the surface plasmon effect and the semiconductor are compounded by a simple self-assembly method, so that the composite film with the dual surface plasmon synergistic effect is obtained, the limitation of regulating an up-conversion luminescent system by using single plasma is overcome, the luminous efficiency of the up-conversion luminescent film is improved to a greater extent, and meanwhile, the composite luminescent film with repeatability is further applied to two aspects of monitoring a surface enhanced Raman signal and testing fluorescence emission intensity to detect the concentration of dye molecules.

Compared with the prior art, the invention has the beneficial effects that:

1. the technical scheme of the invention is to obtain the rare earth doped NaYF₄Layer, Ag nano-meter layer and W₁₈O₄₉The nanowire layers together form the efficient multicolor upconversion luminescent composite film.

2. The technical scheme of the invention is to use the noble metal Ag nano with plasma resonance characteristicRice layer and semiconductor W₁₈O₄₉The nano-wire layer is compounded with a reinforced local electromagnetic field, and Ag nano meter/W is realized under the excitation of a 980nm laser diode₁₈O₄₉Nanowire film regulated rare earth doped NaYF₄The layer emits a bright green or blue luminescence visible to the naked eye.

3. The technical scheme of the invention obtains the high-efficiency multicolor NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉The nanowire up-conversion luminescence composite film can realize the NaYF with relatively small particle size of 6nm₄:Yb³⁺,Er³⁺The up-conversion nano particle film has the advantages that the luminous intensity is improved by two orders of magnitude, and the up-conversion nano particle film has the excellent characteristics of simplicity in preparation, high repeatability, safety and no toxicity.

4. Ag nano meter/W in the high-efficiency multicolor upconversion luminescent composite film obtained by the invention₁₈O₄₉Double plasmon synergistic effect of nanowire film and rare earth doped NaYF₄Nano particle/Ag nano meter/W₁₈O₄₉The efficient up-conversion luminescence performance of the nanowire film respectively utilizes the characteristics of local electromagnetic field enhancement and energy effective transfer, and can be applied to high-sensitivity dye detection which is firstly qualitative and then quantitative.

Drawings

FIG. 1 shows NaYF prepared in example 1 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉And (3) a surface scanning electron microscope picture of the nanowire composite luminescent film.

FIG. 2 shows NaYF prepared in example 1 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉And (3) a cross section scanning electron microscope picture of the nanowire composite luminescent film.

FIG. 3 shows NaYF prepared in example 1 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉And (3) an X-ray diffraction spectrum of the nanowire composite luminescent film.

FIG. 4 shows Ag nanoparticles and W prepared in example 1 of the present invention₁₈O₄₉Nanowire and Ag nm/W₁₈O₄₉UV-NIR absorption spectra of the nanowire films.

FIG. 5 shows NaYF prepared in comparative example 1 and example 1₄:Yb³⁺,Er³⁺、NaYF₄:Yb³⁺,Er³⁺Ag nano meter, NaYF₄:Yb³⁺,Er³⁺/W₁₈O₄₉Nanowire and NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉A multicolor upconversion luminescence spectrogram of the nanowire composite luminescent film.

FIG. 6 is a schematic diagram of NaYF with different particle sizes prepared in examples 1-4 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉A comparison graph of multicolor luminescence enhancement factors of the nanowire composite luminescent film.

FIG. 7 shows NaYF prepared in comparative example 2 and example 5₄:Yb³⁺,Tm³⁺、NaYF₄:Yb³⁺,Tm³⁺Ag nano meter, NaYF₄:Yb³⁺,Tm³⁺/W₁₈O₄₉Nanowire and NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉A multicolor upconversion luminescence spectrogram of the nanowire composite luminescent film.

FIG. 8 illustrates NaYF with different particle sizes prepared in examples 5-8 of the present invention₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉A comparison graph of multicolor luminescence enhancement factors of the nanowire composite luminescent film.

FIG. 9 shows Ag nm/W particles prepared in example 1 of the present invention₁₈O₄₉The nanowire composite luminescent film is used as a substrate to detect surface enhanced Raman spectrograms of rhodamine B ethanol solutions with different concentrations.

FIG. 10 shows Ag nm/W particles prepared in example 1 of the present invention₁₈O₄₉The nanowire composite luminescent film is used as a substrate to detect surface enhanced Raman signal intensity maps of rhodamine B ethanol solutions with different concentrations.

FIG. 11 shows NaYF prepared in example 1 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉Nanowire and method of manufacturing the sameThe composite luminescent film detects spectrograms of fluorescence of rhodamine B ethanol solutions with different concentrations under the excitation of 980nm laser.

FIG. 12 shows NaYF prepared in example 1 of the present invention₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉And (3) an integral area diagram of the fluorescence detection spectrum of the nanowire composite luminescent film on rhodamine B ethanol solutions with different concentrations under 980nm laser excitation.

Detailed Description

The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.

Example 1

A preparation method of an efficient multicolor upconversion luminescent composite film;

putting 2 x 3cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50mL), simultaneously adding 25mg of tungsten hexacarbonyl into 20mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12h, cooling to room temperature, taking out the W to grow₁₈O₄₉The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

10mL of polyethylene glycol, a newly prepared 2mL of polyvinyl alcohol pyrrolidone solution (1mol/L) and 0.2mL of silver nitrate solution (1mol/L) are sequentially added into a 100mL round bottom flask, stirred at a constant speed for 10min at room temperature, then the round bottom flask is fixed in an oil bath pan at 113 ℃, stirred magnetically for 8h, cooled, and repeatedly centrifuged and washed with absolute ethyl alcohol for 4 times.

Uniformly dispersing 1mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉The nano-wire film can determine Ag nano meter/W according to the extinction spectrogram of figure 4₁₈O₄₉The nano-wire film has Ag nano-meter and W₁₈O₄₉The extinction characteristic and the strength of the nano wire are improved.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 5mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 6nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Collecting 200 μ L NaYF₄:Yb³⁺,Er³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉The nano-wire composite luminescent film is determined by the X-ray diffraction spectrum of the composite luminescent film shown in the figure 3, wherein the figures 1 and 2 are respectively the surface and cross-section scanning electron microscope photo of the composite luminescent film₂Glass, W₁₈O₄₉Nanowire, NaYF₄Nano particles and Ag nano meter components. NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉The luminescence spectrum of the nanowire composite luminescent film is shown in fig. 5, the luminescent intensity of the composite film is obviously enhanced, and the composite film is relatively to 6nm NaYF₄:Yb³⁺,Er³⁺The luminescence enhancement of the film is shown in fig. 6 at 1, with enhancement factors 263, 324, 192 at three different emission sites, respectively.

Example 2

Uniformly dispersing 1.2mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉A thin film of nanowires.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 7mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product 15nm NaYF is obtained₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Taking 180 mu L of NaYF₄:Yb³⁺,Er³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, relative to 15nmNaYF₄:Yb³⁺,Er³⁺The enhancement of the luminescence of the film is shown in fig. 6 at 2, with enhancement factors at three different emission sites being 152, 54, 113, respectively.

Example 3

Uniformly dispersing 0.8mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉A thin film of nanowires.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution to be completely dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 10mL/h, followed by introduction of argon gasAfter 30min, the temperature is raised to 80 ℃ to remove the methanol, and the temperature is kept for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, namely 30nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Taking 220 mu L NaYF₄:Yb³⁺,Er³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, relative to 30nmNaYF₄:Yb³⁺,Er³⁺The luminescence enhancement of the film is shown in fig. 6 at 3, with enhancement factors 69, 20, 23 at three different emission sites, respectively.

Example 4

Uniformly dispersing 1.5mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉Nanowire and method of manufacturing the sameA film.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 15mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 50nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Taking 250 mu L NaYF₄:Yb³⁺,Er³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, corresponding to 50nmNaYF₄:Yb³⁺,Er³⁺The luminescence enhancement of the film is shown at 4 in fig. 6, with enhancement factors of 10, 4, 5 at three different emission sites, respectively.

Example 5

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 10nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

500 μ L of NaYF was taken₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉The nanowire composite luminescent film has the advantages that the luminescent intensity of the composite film is obviously enhanced according to the luminescent spectrum shown in figure 7, and the luminescent intensity is higher than that of 10nm NaYF₄:Yb³⁺,Tm³⁺The luminescence enhancement of the film is shown in fig. 8 at 1, with enhancement factors at three different emission sites being 337, 374, 87, respectively.

Example 6

Uniformly dispersing 1mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 7mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product 15nm NaYF is obtained₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

Taking 600 mu L NaYF₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, relative to 15nmNaYF₄:Yb³⁺,Tm³⁺The enhancement of the luminescence of the film is shown in fig. 8 at 2, with enhancement factors at three different emission sites being 166, 145, 55, respectively.

Example 7

Uniformly dispersing 1.5mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours, and taking out Ag nano meter/W₁₈O₄₉A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g ammonium fluoride and 0.1g sodium hydroxide powder were poured into 5mL of methanol solution and, after all had dissolved, the solution was aspirated using a syringe (10mL)All the methanol solution is taken and fixed in a fixed groove of an injector of an injection pump, the methanol solution is dropwise added into the flask at the injection speed of 10mL/h, argon is introduced for 30min, the temperature is raised to 80 ℃, the methanol is removed, and the temperature is kept for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, namely 30nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

Taking 450 mu L NaYF₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, relative to 30nmNaYF₄:Yb³⁺,Tm³⁺The luminescence enhancement of the film is shown in fig. 8 at 3, with enhancement factors of 70, 56, 22 at three different emission sites, respectively.

Example 8

Uniformly dispersing 1.2mL of Ag nano-meter solution into 10mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W₁₈O₄₉Nanowire thin film glassPlacing the glass with the right side facing upwards into the solution B, then transferring into an oven at 50 ℃ for heat preservation for 6h, and taking out Ag nano meter/W₁₈O₄₉A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 15mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 50nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

Taking 650 mu L NaYF₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉Nano-wire composite luminescent film, corresponding to 50nmNaYF₄:Yb³⁺,Tm³⁺The luminescence enhancement of the film is shown in fig. 8 at 4, with enhancement factors at three different emission sites of 19, 16, 13, respectively.

Comparative example 1

NaYF₄:Yb³⁺,Er³⁺A luminescent film preparation method;

weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were mixedPouring into 5mL of methanol solution, dissolving completely, pumping out all methanol solution by using a syringe (10mL) and fixing in a syringe fixing groove of a syringe pump, dropwise adding into the flask at the injection speed of 5mL/h, introducing argon for 30min, raising the temperature to 80 ℃, removing methanol, and keeping the temperature for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 6nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Collecting 200 μ L NaYF₄:Yb³⁺,Er³⁺The solution was again dispersed in 10mL of cyclohexane solution to obtain a mixed solution M₁Placing 2 x 3cm FTO glass with conductive side facing upwards in the solution M₁Then transferring the mixture into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺The luminescence spectrum of the luminescent film is shown in FIG. 5, from which NaYF can be seen₄:Yb³⁺,Er³⁺The luminous intensity of the luminous film is obviously lower than NaYF₄:Yb³⁺,Er ³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

NaYF₄:Yb³⁺,Er³⁺/W₁₈O₄₉A preparation method of the nanowire composite luminescent film;

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50, adding the bait hexahydrate, the ytterbium chloride hexahydrate and the yttrium chloride hexahydrate into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, vacuumizing for 30min, raising the temperature to 150 ℃ to dissolve rare earth, and adjusting the temperature to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of methanol solution and, after dissolving all, the whole was withdrawn using a syringe (10mL)The methanol solution is partially fixed in a fixing groove of an injector of an injection pump, the methanol solution is dropwise added into the flask at the injection speed of 5mL/h, argon is introduced for 30min, the temperature is raised to 80 ℃, the methanol is removed, and the temperature is kept for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 6nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Collecting 200 μ L NaYF₄:Yb³⁺,Er³⁺The solution was redispersed in 10mL of cyclohexane solution to give a mixed solution D, and W was₁₈O₄₉The nanowire film glass is placed in the solution D with the right side facing upwards, and then the nanowire film glass is moved into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺/W₁₈O₄₉The light emission spectrum of the nanowire composite light-emitting film is shown in FIG. 5, from which NaYF can be seen₄:Yb³⁺,Er³⁺/W₁₈O₄₉The luminous intensity of the nano-wire composite luminous film is obviously lower than NaYF₄:Yb³⁺,Er ³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

NaYF₄:Yb³⁺,Er³⁺A preparation method of the Ag nano-meter composite luminescent film;

Uniformly dispersing 1mL of Ag nano meter solution into 10mL of ethanol to obtain a mixed solution B, putting the solution B with the conductive surface of 2X 3cm FTO glass facing upwards, then transferring the solution B into a 50 ℃ oven, preserving heat for 6 hours, and taking out the Ag nano meter film.

Weighing baits chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:10:50 into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, fixing the flask into a heating jacket, and vacuumizing for 30 DEGAfter min, the temperature is raised to 150 ℃ to dissolve the rare earth, and after 20min, the temperature is adjusted to room temperature. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 5mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 6nm NaYF₄:Yb³⁺,Er³⁺The solution was stored in a glass bottle.

Collecting 200 μ L NaYF₄:Yb³⁺,Er³⁺Dispersing the solution into 10mL of cyclohexane solution again to obtain a mixed solution D, placing Ag nano-meter film glass into the solution D, then transferring the solution into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Er³⁺The luminescence spectrum of the/Ag nano meter composite luminescent film is shown in figure 5, from which the NaYF can be seen₄:Yb³⁺,Er³⁺The luminescence intensity of the Ag nano-meter composite luminescent film is obviously lower than that of NaYF₄:Yb³⁺,Er ³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

Comparative example 2

NaYF₄:Yb³⁺,Tm³⁺A luminescent film preparation method;

thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally increasing the temperature to 305 ℃ for 1.5h, cooling to room temperature to obtainRare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 10nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

500 μ L of NaYF was taken₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL of cyclohexane solution again to obtain a mixed solution D, placing the solution D with the 2X 3cm FTO glass conductive surface facing upwards, and then transferring the solution into a 50 ℃ oven for heat preservation for 6h to obtain a final product NaYF₄:Yb³⁺,Tm³⁺The luminescence spectrum of the luminescent film is shown in FIG. 7, from which NaYF can be seen₄:Yb³⁺,Tm³⁺The luminous intensity of the luminous film is obviously lower than NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

NaYF₄:Yb³⁺,Tm³⁺/W₁₈O₄₉A preparation method of the nanowire composite luminescent film;

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6mL/h, after introducing argon gas for 30min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3The obtained product is 10nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

500 μ L of NaYF was taken₄:Yb³⁺,Tm³⁺The solution was redispersed in 10mL of cyclohexane solution to give a mixed solution D, and W was₁₈O₄₉Placing the nanowire film glass in the solution D, then transferring the nanowire film glass into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺/W₁₈O₄₉The light emission spectrum of the nanowire composite light-emitting film is shown in FIG. 7, from which NaYF can be seen₄:Yb³⁺,Tm³⁺/W₁₈O₄₉The luminous intensity of the nano-wire composite luminous film is obviously lower than NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

NaYF₄:Yb³⁺,Tm³⁺A preparation method of the Ag nano-meter composite luminescent film;

Uniformly dispersing 1.2mL of Ag nano meter solution into 10mL of ethanol to obtain a mixed solution B, putting the solution B with the conductive surface of 2 x 3cm FTO glass facing upwards, then transferring the solution B into a 50 ℃ oven, preserving heat for 6 hours, and taking out the Ag nano meter film.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1:50:200 are weighed and added into a three-neck flask containing 6mL of oleic acid and 15mL of octadecene, the flask is fixed into a heating sleeve, the flask is vacuumized for 30min, the temperature is raised to 150 ℃ to dissolve rare earth, and the flask is adjusted to room temperature after 20 min. 0.148g of ammonium fluoride and 0.1g of sodium hydroxide powder were poured into 5mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10mL) and fixed in a syringe fixing groove of a syringe pump, added dropwise into the flask at an injection rate of 6mL/h, argon was introduced for 30min, the temperature was raised to 80 ℃ to remove the methanol,and preserving the heat for 1.5 h. Finally, the temperature is increased to 305 ℃, the reaction lasts for 1.5h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF₄The solution is centrifugally washed three times by liquid with the volume ratio of cyclohexane to ethanol being 1:3, and the obtained product, 10nm NaYF₄:Yb³⁺,Tm³⁺The solution was stored in a glass bottle.

500 μ L of NaYF was taken₄:Yb³⁺,Tm³⁺Dispersing the solution into 10mL of cyclohexane solution again to obtain a mixed solution D, placing Ag nano-meter film glass into the solution D, then transferring the solution into a 50 ℃ oven for heat preservation for 6 hours to obtain a final product NaYF₄:Yb³⁺,Tm³⁺The luminescence spectrum of the/Ag nano meter composite luminescent film is shown in figure 7, from which the NaYF can be seen₄:Yb³⁺,Tm³⁺The luminescence intensity of the Ag nano-meter composite luminescent film is obviously lower than that of NaYF₄:Yb³⁺,Tm³⁺Ag nano meter/W₁₈O₄₉The nano-wire is compounded with a luminescent film.

The efficient multicolor up-conversion luminescence composite film can be applied to the aspect of double detection of dye molecules.

The invention discloses application of a high-efficiency multicolor upconversion luminescence composite film based on dual plasmon synergistic regulation in the field of aqueous phase fluorescence detection, and mainly examines performance detection based on an organic fluorescent molecular ethanol solution of the film. The method comprises preparing a solution with a concentration of 10^-3And (3) continuously diluting the mol/L rhodamine B dye to obtain solutions with other concentrations, extracting 50 mu L of the same volume, and respectively dropwise adding the solutions to the surface of the composite luminescent film. Firstly, the Ag nano meter/W is passed₁₈O₄₉The nanowire composite film is used as a Raman test substrate, the excitation wavelength is 532.8nm, the power is 0.5W, the integration time is 30s, qualitative detection is carried out on organic fluorescent molecules by utilizing the fingerprint characteristic of a Raman spectrum characteristic peak, and the fluorescent molecules are determined to be rhodamine B dye. But because of the saturation limitation of Raman detection of high-concentration solution, secondary detection is carried out by utilizing the fluorescence characteristic of dye molecules, a 980nm laser diode is used as an excitation light source to irradiate a sample, the power is 0.5W, the current is 1A, and a spectrometer receives a fluorescence signal, so that quantitative detection is carried out on rhodamine B dye solution with different concentrations.

The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.

Claims

1. A high-efficiency multi-color up-conversion luminescence composite film is characterized by comprising rare earth doped NaYF₄Layer, Ag nano-meter layer and W₁₈O₄₉The nano-wire layer is a composite film with efficient multicolor up-conversion luminescence characteristics constructed by three layers; through simple self-assembling process, Ag nano-meter and rare earth doped NaYF are mixed₄Is sequentially deposited on W₁₈O₄₉Constructed on the nanowire film;

the rare earth doped NaYF₄The layer is composed of Yb³⁺As sensitizer and Er³⁺Or Tm³⁺Rare earth doped NaYF as luminescence center and with uniform particle size₄The Ag nano-meter layer is formed by 500nm double-shuttle-shaped Ag nano-meters; w₁₈O₄₉The nanowire layer is formed by W grown on an FTO glass substrate₁₈O₄₉Is composed of nano-wires;

2. The efficient multicolor upconversion luminescent composite film according to claim 1, wherein the FTO glass substrate is SnO doped with fluorine₂Transparent conductive glass.

3. The use of the highly efficient multicolor upconversion luminescent composite film according to claim 1 for dual detection of dye molecules.

4. The use of the highly efficient multicolor upconversion luminescent composite film according to claim 1 for aqueous phase fluorescence detection.