CN112538352B - Efficient multicolor up-conversion luminescence composite film - Google Patents

Abstract

The invention belongs to the technical field of rare earth doped up-conversion materials, and discloses an efficient multicolor up-conversion luminescent composite film. The high-efficiency multicolor upconversion luminescent composite film is prepared by obtaining rare earth doped NaYF through high-temperature pyrolysis ₄ Reduction of polyol to Ag nano meter of 500nm length and solvothermal growth of W on FTO glass ₁₈ O ₄₉ The nano wire is made of three-layer material, and Ag nano meter and rare earth doped NaYF are subjected to a simple self-assembly process ₄ Is sequentially deposited on W ₁₈ O ₄₉ And (3) a nanowire film. Multipolar longitudinal surface plasmon resonance and W using Ag nano meter ₁₈ O ₄₉ The 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 luminescent 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 NaYF-based material ₄ Ag nano meter/W ₁₈ O ₄₉ The 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 when the two plasma nano materials are used independently.

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 pyrolysis ₄ Reducing polyhydric alcohol to obtain Ag nano meter with length of 500nm and solvothermally obtaining W growing on FTO glass ₁₈ O ₄₉ The nano wire is made of three-layer material, and Ag nano meter and rare earth doped NaYF are subjected to a simple self-assembly process ₄ Is sequentially deposited on W ₁₈ O ₄₉ And the nanowire film is constructed on the nanowire film. Multipolar longitudinal surface plasmon resonance and W using Ag nano meter ₁₈ O ₄₉ The 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.

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 NaYF ₄ Layer, ag nano-meter layer and W ₁₈ O ₄₉ The nanowire layer has three layers and is constructed with high-efficiency multicolor upper layerA composite film for converting luminescence characteristics.

Further, the rare earth doped NaYF ₄ The layer is composed of Yb ³⁺ As sensitizer and Er ³⁺ Or Tm ³⁺ Rare earth doped NaYF as luminescence center and with uniform particle size ₄ The Ag nano-meter layer assembly is composed of 500nm double-shuttle-shaped Ag nano-meters; w is a group of ₁₈ O ₄₉ The nanowire layer is formed by W grown on an FTO glass substrate ₁₈ O ₄₉ Formed of nanowires.

The NaYF ₄ Layer, ag nano-meter layer, W ₁₈ O ₄₉ The nanowire layer concentration ratio is 4:91-130:45-65.

Furthermore, the FTO glass substrate is SnO doped with fluorine ₂ Transparent 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) W ₁₈ O ₄₉ Preparing a nanowire film:

growing a layer of W on FTO conductive glass by a solvothermal method ₁₈ O ₄₉ A nanowire film, 25-30 mg of tungsten hexacarbonyl is poured into 20-24 mL of absolute ethyl alcohol solution to be stirred for 40-60 min to obtain mixed solution A, the solution A is moved into a 50 mL polytetrafluoroethylene reaction kettle containing 2X 3 cm of FTO conductive glass, an oven is heated to 180-200 ℃, the reaction kettle is then placed into the oven to be insulated for 10-12 h, the reaction kettle is taken out after being cooled to room temperature and is repeatedly washed by absolute ethyl alcohol to finally obtain W ₁₈ O ₄₉ A thin film of nanowires.

Step (2) Ag nano meter/W ₁₈ O ₄₉ Preparing a nanowire film:

step a, preparing Ag nano-meter by adopting a polyol reduction method, adding 10-12 mL of polyethylene glycol into a 100 mL round bottom flask, dripping 2-3 mL of polyvinyl pyrrolidone solution (1M) and 0.2-0.3 mL of newly prepared 1M silver nitrate solution in the stirring process, uniformly stirring for about 10-30 min, transferring the round bottom flask into an oil bath kettle at 113-115 ℃, magnetically stirring for 8-10 h, and cooling to room temperature. 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 10 mL of absolute ethyl alcohol solution to obtain a mixed solution B, namely, the W obtained in the step (1) is subjected to simple self-assembly by a simple self-assembly method ₁₈ O ₄₉ Placing the nanowire film in the solution B and transferring the nanowire film into an oven, heating the oven to 50-70 ℃, preserving heat for 6-8 h, and obtaining Ag nano meter/W after the solution B is completely evaporated ₁₈ O ₄₉ A thin film of nanowires.

Step (3) rare earth doping NaYF ₄ Nano particle/Ag nano meter/W ₁₈ O ₄₉ Preparing a nanowire film:

step a, preparing rare earth doped NaYF by utilizing a high-temperature pyrolysis process ₄ Adding yttrium chloride hexahydrate, ytterbium chloride hexahydrate and erbium chloride hexahydrate into a mixed solution C in a three-neck flask containing 6-12 mL of oleic acid and 15-30 mL of octadecene according to a molar ratio of 1. And then dropwise adding a prepared 5-10 mL methanol solution dissolved with 0.148-0.296 g of ammonium fluoride and 0.1-0.2 g of sodium hydroxide into the solution C at a constant speed through a syringe pump, introducing argon for 30-60 min, raising the temperature to 80 ℃, keeping the temperature for 1.5-2 h to remove the methanol, finally raising the temperature to 305-310 ℃, reacting for 1.5-2 h, cooling to room temperature, centrifuging and washing with a liquid with a volume ratio of cyclohexane to ethanol of 1 ₄ And (3) particles.

Step b, doping NaYF with the rare earth obtained in the step a ₄ Dispersing the nano particles into 10 mL 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) ₁₈ O ₄₉ Placing the nanowire film in the solution D and moving the nanowire film into an oven, heating the oven to 50-70 ℃, preserving heat for 6-8 h, and completely evaporating the solution D to ensure that the rare earth is doped with NaYF ₄ Deposition of nanoparticles to Ag nm/W ₁₈ O ₄₉ The surface of the nanowire film can obtain the rare earth doped NaYF ₄ Nano particle/Ag nano meter/W ₁₈ O ₄₉ And (3) a nanowire composite luminescent film.

Further, in the above-mentioned case,the conductive glass in the step (1) is 2-by-3 cm fluorine-doped SnO ₂ Transparent 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 8-10 h in an oil bath pan at the temperature of 113 ℃;

the high-temperature pyrolysis process comprises the steps of firstly heating to 150 ℃, preserving heat for 20-30 min, then cooling to room temperature, heating to 80 ℃ after 30-60 min, preserving heat for 1.5-2 h, and finally continuously heating to 305-310 ℃ and preserving heat for 1.5-2 h.

The Ag nano-meter is a submicron-sized nano-silver structure with 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 NaYF ₄ Layer, ag nano-meter layer and W ₁₈ O ₄₉ The nanowire layers together form the efficient multicolor upconversion luminescent composite film.

2. The technical scheme of the invention is to form a noble metal Ag nano-meter layer with plasma resonance characteristic and a semiconductor W ₁₈ O ₄₉ The local electromagnetic field is enhanced by the nano-wire layer, and Ag nano-meter/W is realized under the excitation of a 980 nm laser diode ₁₈ O ₄₉ Nanowire film regulated and controlled rare earth doped NaYF ₄ The layer emits a bright green or blue colour visible to the naked eyeThe color is luminous.

3. The technical scheme of the invention obtains the high-efficiency multicolor NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ The nanowire up-conversion luminescence composite film can realize the relatively small particle size of 6nm NaYF ₄ :Yb ³⁺ ,Er ³⁺ 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 up-conversion luminescence composite film obtained by the invention ₁₈ O ₄₉ Double plasmon synergistic effect of nanowire film and rare earth doped NaYF ₄ Nano particles/Ag nano meter/W ₁₈ O ₄₉ The 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 invention ₄ :Yb ³⁺ ,Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ Surface scanning electron microscope picture of the nano-wire composite luminescent film.

FIG. 2 shows NaYF prepared in example 1 of the present invention ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ A scanning electron microscope picture of the cross section of the nanowire composite luminescent film.

FIG. 3 shows NaYF prepared in example 1 of the present invention ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ And (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 invention ₁₈ O ₄₉ Nanowire and Ag nm/W ₁₈ O ₄₉ UV-NIR absorption spectra of nanowire films.

FIG. 5 shows NaYF prepared in comparative example 1 and example 1 ₄ :Yb ³⁺ ,Er ³⁺ 、NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter, naYF ₄ :Yb ³⁺ ,Er ³⁺ /W ₁₈ O ₄₉ Nanowire and NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ A multicolor upconversion luminescence spectrogram of the nanowire composite luminescent film.

FIG. 6 shows NaYF with different particle sizes prepared in examples 1-4 of the present invention ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ A comparison graph of multicolor luminescence enhancement factors of the nanowire composite luminescent film.

FIG. 7 shows NaYF prepared in comparative example 2 and example 5 ₄ :Yb ³⁺ ,Tm ³⁺ 、NaYF ₄ :Yb ³⁺ ,Tm ³⁺ Ag nano meter, naYF ₄ :Yb ³⁺ , Tm ³⁺ /W ₁₈ O ₄₉ Nanowire and NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ A 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 invention ₄ :Yb ³⁺ ,Tm ³⁺ Ag nano meter/W ₁₈ O ₄₉ A comparison graph of multicolor luminescence enhancement factors of the nanowire composite luminescent film.

FIG. 9 shows Ag nano meter/W prepared in example 1 of the present invention ₁₈ O ₄₉ The nano-wire 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 NaYF prepared in example 1 of the present invention ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ The nanometer line composite luminescent film detects spectrograms of fluorescence of rhodamine B ethanol solutions with different concentrations under the excitation of 980 nm laser.

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 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

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

Uniformly dispersing 1 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ The nano-wire film can determine Ag nano meter/W according to the extinction spectrogram of figure 4 ₁₈ O ₄₉ The nano-wire film has Ag nano-meter and W ₁₈ O ₄₉ The extinction characteristics and strength of the nanowires are improved.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 5 mL/h, after introducing argon gas for 30 min, 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 duration is 1.5 hours, and the temperature is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1The obtained product is 6nm NaYF ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get 200 mu L's NaYF ₄ :Yb ³⁺ ,Er ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing the nanowire film glass in the solution D, and then transferring the nanowire film glass into an oven with the temperature of 50 ℃ for heat preservation for 6 hours to obtain a final product NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ The 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 film ₂ Glass, W ₁₈ O ₄₉ Nanowire, naYF ₄ Nano particles and Ag nano meter components. NaYF ₄ :Yb ³⁺ ,Er ^{3 +} Ag nano meter/W ₁₈ O ₄₉ The 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 NaYF ₄ :Yb ³⁺ ,Er ³⁺ 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

A preparation method of an efficient multicolor up-conversion luminescent composite film;

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ And washing the nanowire film glass with absolute ethyl alcohol repeatedly.

Adding 10 mL of polyethylene glycol, newly prepared 2 mL of polyvinyl pyrrolidone solution (1 mol/L) and 0.2 mL of silver nitrate solution (1 mol/L) into a 100 mL round bottom flask in sequence, stirring at a constant speed for 10 min at room temperature, fixing the round bottom flask in an oil bath kettle at 113 ℃, magnetically stirring for 8 h, cooling, and repeatedly centrifuging and washing with absolute ethyl alcohol for 4 times.

Uniformly dispersing 1.2 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting the nanowire film glass into the solution B with the right side facing upwards, then transferring the nanowire film glass into an oven with the temperature of 50 ℃ for heat preservation for 6 hours, and taking out Ag nano meter/W ₁₈ O ₄₉ A thin film of nanowires.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 7 mL/h, after introducing argon gas for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get NaYF of 180 mu L ₄ :Yb ³⁺ ,Er ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ Nano-wire composite luminescent film, relative to 15 nmNaYF ₄ :Yb ³⁺ ,Er ³⁺ 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

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

2X 3 cm FTO glass conductive side down was placed in a polytetrafluoroethylene autoclave (50 mL) while 25 mg of tungsten hexacarbonyl was addedAdding 20 mL of absolute ethyl alcohol solution, magnetically stirring for 40min, pouring into a reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the growth W ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

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

Uniformly dispersing 0.8 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was extracted using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, the solution was added dropwise into the flask at an injection rate of 10 mL/h, argon gas was introduced for 30 min, 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 duration is 1.5 hours, and the temperature is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get 220 mu L's NaYF ₄ :Yb ³⁺ ,Er ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ Nano-wire composite luminous film, relative to 30 nmNaYF ₄ :Yb ³⁺ ,Er ³⁺ 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

A preparation method of an efficient multicolor up-conversion luminescent composite film;

placing 2 x 3 cm FTO glass with conductive surface facing downwards into polytetrafluoroethylene high pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, placing into 180 deg.C oven, maintaining temperature for 12 hr, cooling to room temperature, taking out grown W ₁₈ O ₄₉ And washing the nanowire film glass with absolute ethyl alcohol repeatedly.

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

Uniformly dispersing 1.5 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Bait chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 15 mL/h, after introducing argon gas for 30 min, the temperature was raised to 80 ℃ to remove the methanol, and the temperature was maintained for 1.5 h. Finally the temperature is measuredIncreasing the temperature to 305 ℃, keeping the temperature for 1.5 h, cooling the temperature to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Taking 250 mu L NaYF ₄ :Yb ³⁺ ,Er ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ Nano-wire composite luminescent film, corresponding to 50 nmNaYF ₄ :Yb ³⁺ ,Er ³⁺ 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

A preparation method of an efficient multicolor up-conversion luminescent composite film;

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

Adding 10 mL of polyethylene glycol, newly prepared 2 mL of polyvinyl pyrrolidone solution (1 mol/L) and 0.2 mL of silver nitrate solution (1 mol/L) into a 100 mL round bottom flask in sequence, stirring at a constant speed for 10 min at room temperature, fixing the round bottom flask in an oil bath kettle at 113 ℃, magnetically stirring for 8 h, cooling, and repeatedly centrifuging and washing with absolute ethyl alcohol for 4 times.

Uniformly dispersing 1.2 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6 mL/h, after introducing argon gas for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ Solution, washed three times by liquid centrifugation with cyclohexane to ethanol at a volume ratio of 1:3, and the obtained product, 10 nm NaYF ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Get 500 mu L's NaYF ₄ :Yb ³⁺ , Tm ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nano meter/W ₁₈ O ₄₉ The nanowire composite luminescent film has the advantages that the luminescent intensity of the composite film is obviously enhanced according to a luminescent spectrum as shown in figure 7, and the luminescent intensity is higher than that of 10 nm NaYF ₄ :Yb ³⁺ ,Tm ³⁺ The luminescence enhancement of the film is shown in fig. 8 at 1, with enhancement factors at three different emission sites 337, 374, 87, respectively.

Example 6

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

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

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

Uniformly dispersing 1 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution, and when all of them were dissolved, the entire methanol solution was extracted using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 7 mL/h, and after 30 min of argon gas introduction, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Get 600 mu L's NaYF ₄ :Yb ³⁺ , Tm ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ Nano-wire composite luminous film, relative to 15 nmNaYF ₄ :Yb ^{3 +} ,Tm ³⁺ Luminescence enhancement of the film is shown in FIG. 8, 2, at three different emission sitesAre 166, 145, 55, respectively.

Example 7

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

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

Adding 10 mL of polyethylene glycol, newly prepared 2 mL of polyvinyl pyrrolidone solution (1 mol/L) and 0.2 mL of silver nitrate solution (1 mol/L) into a 100 mL round bottom flask in sequence, stirring at a constant speed for 10 min at room temperature, fixing the round bottom flask in an oil bath kettle at 113 ℃, magnetically stirring for 8 h, cooling, and repeatedly centrifuging and washing with absolute ethyl alcohol for 4 times.

Uniformly dispersing 1.5 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was extracted using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, the solution was added dropwise into the flask at an injection rate of 10 mL/h, argon gas was introduced for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Tm ³⁺ Putting the solution into glassPreserving in glass bottle.

Get NaYF of 450 mu L ₄ :Yb ³⁺ , Tm ³⁺ Re-dispersing the solution into 10 mL cyclohexane solution to obtain mixed solution D, and mixing Ag with nano meter/W ₁₈ O ₄₉ Placing the nanowire film glass in the solution D, and then transferring the nanowire film glass into an oven with the temperature of 50 ℃ for heat preservation for 6 hours to obtain a final product NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ Nano-wire composite luminescent film, relative to 30 nmNaYF ₄ :Yb ^{3 +} ,Tm ³⁺ The luminescence enhancement of the film is shown in fig. 8 at 3, with enhancement factors at three different emission sites of 70, 56, 22, respectively.

Example 8

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

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ And washing the nanowire film glass with absolute ethyl alcohol repeatedly.

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

Uniformly dispersing 1.2 mL of Ag nano-meter solution into 10 mL of ethanol to obtain a mixed solution B, and then uniformly dispersing W ₁₈ O ₄₉ Putting 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/W ₁₈ O ₄₉ A thin film of nanowires.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1And after 20 min, adjusting to room temperature. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution, and when all of them were dissolved, the whole methanol solution was extracted using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 15 mL/h, and after 30 min of argon gas introduction, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Taking 650 mu L of NaYF ₄ :Yb ³⁺ , Tm ³⁺ Dispersing the solution into 10 mL cyclohexane solution again to obtain mixed solution D, and mixing Ag nano meter/W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ Nano-wire composite luminescent film, corresponding to 50 nmNaYF ₄ :Yb ^{3 +} ,Tm ³⁺ 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

NaYF ₄ :Yb ³⁺ ,Er ³⁺ A luminescent film preparation method;

weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 5 mL/h, after introducing argon gas for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get 200 mu L of NaYF ₄ :Yb ³⁺ ,Er ³⁺ The solution was again dispersed in 10 mL of cyclohexane solution to obtain a mixed solution M ₁ 2 x 3 cm FTO glass conductive side up was placed in solution M ₁ Then the mixture is moved into an oven with the temperature of 50 ℃ for heat preservation for 6 h to obtain the final product NaYF ₄ :Yb ³⁺ ,Er ³⁺ The luminescence spectrum of the luminescent film is shown in FIG. 5, from which NaYF can be seen ₄ :Yb ³⁺ ,Er ³⁺ The luminous intensity of the luminous film is obviously lower than NaYF ₄ :Yb ³⁺ , Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ The nano-wire is compounded with a luminescent film.

NaYF ₄ :Yb ³⁺ ,Er ³⁺ /W ₁₈ O ₄₉ A preparation method of a nanowire composite luminescent film;

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

Weighing bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and was added dropwise into the flask at an injection rate of 5 mL/h, after introducing argon gas for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ Solutions from cyclohexane and ethaneAlcohol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get 200 mu L's NaYF ₄ :Yb ³⁺ ,Er ³⁺ The solution was redispersed in 10 mL of cyclohexane solution to give a mixed solution D, and W was ₁₈ O ₄₉ The nanowire film glass is placed in the solution D with the right side facing upwards, and then the nanowire film glass is moved into an oven with the temperature of 50 ℃ for heat preservation for 6 hours to obtain a final product NaYF ₄ :Yb ³⁺ ,Er ³⁺ / W ₁₈ O ₄₉ The light emission spectrum of the nanowire composite light-emitting film is shown in FIG. 5, from which NaYF can be seen ₄ :Yb ³⁺ ,Er ³⁺ /W ₁₈ O ₄₉ The luminous intensity of the nano-wire composite luminous film is obviously lower than NaYF ₄ :Yb ³⁺ , Er ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ And (3) a nanowire composite luminescent film.

NaYF ₄ :Yb ³⁺ ,Er ³⁺ A preparation method of the Ag nano-meter composite luminescent film;

adding 10 mL of polyethylene glycol, newly prepared 2 mL of polyvinyl pyrrolidone solution (1 mol/L) and 0.2 mL of silver nitrate solution (1 mol/L) into a 100 mL round bottom flask in sequence, stirring at a constant speed for 10 min at room temperature, fixing the round bottom flask in an oil bath kettle at 113 ℃, magnetically stirring for 8 h, cooling, and repeatedly centrifuging and washing with absolute ethyl alcohol for 4 times.

Uniformly dispersing 1 mL of Ag nano meter solution into 10 mL of ethanol to obtain a mixed solution B, putting the solution B with the 2X 3 cm FTO glass conductive surface 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 bait hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution and, after all of them were dissolved, all of the methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and the solution was gradually injected at an injection rate of 5 mL/hDropwise adding into a flask, introducing argon for 30 min, heating to 80 ℃ to remove methanol, and keeping the temperature for 1.5 h. Finally, the temperature is increased to 305 ℃, the duration is 1.5 hours, and the temperature is cooled to room temperature to obtain the rare earth doped NaYF ₄ The solution was washed three times with cyclohexane to ethanol 1 ₄ :Yb ³⁺ ,Er ³⁺ The solution was stored in a glass bottle.

Get 200 mu L's NaYF ₄ :Yb ³⁺ ,Er ³⁺ Dispersing the solution into 10 mL 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, and preserving heat for 6 hours to obtain a final product NaYF ₄ :Yb ³⁺ ,Er ³⁺ The luminescence spectrum of the/Ag nano meter composite luminescent film is shown in figure 5, from which the NaYF can be seen ₄ :Yb ³⁺ ,Er ³⁺ The luminescence intensity of the Ag nano-meter composite luminescent film is obviously lower than that of NaYF ₄ :Yb ³⁺ ,Er ³⁺ Ag nano meter/W ₁₈ O ₄₉ And (3) a nanowire composite luminescent film.

Comparative example 2

NaYF ₄ :Yb ³⁺ ,Tm ³⁺ A luminescent film preparation method;

thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6 mL/h, after introducing argon gas for 30 min, 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 1.5 h, and the mixture is cooled to room temperature to obtain the rare earth doped NaYF ₄ Solution, washed three times by liquid centrifugation with cyclohexane to ethanol at a volume ratio of 1:3, and the obtained product, 10 nm NaYF ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Taking 500 mu LNaYF ₄ :Yb ³⁺ , Tm ³⁺ Dispersing the solution into 10 mL of cyclohexane solution again to obtain a mixed solution D, placing the solution D with a 2 x 3 cm FTO glass conductive surface facing upwards, and then transferring the solution D into an oven at 50 ℃ for heat preservation for 6 h to obtain a final product NaYF ₄ :Yb ³⁺ ,Tm ³⁺ The luminescence spectrum of the luminescent film is shown in FIG. 7, from which NaYF can be seen ₄ :Yb ³⁺ ,Tm ³⁺ The luminous intensity of the luminous film is obviously lower than NaYF ₄ :Yb ³⁺ ,Tm ³⁺ Ag nano meter/W ₁₈ O ₄₉ The nano-wire is compounded with a luminescent film.

NaYF ₄ :Yb ³⁺ , Tm ³⁺ /W ₁₈ O ₄₉ A preparation method of a nanowire composite luminescent film;

putting 2X 3 cm FTO glass with conductive surface facing downwards into a polytetrafluoroethylene high-pressure reaction kettle (50 mL), simultaneously adding 25 mg of tungsten hexacarbonyl into 20 mL of anhydrous ethanol solution, magnetically stirring for 40min, pouring into the reaction kettle, putting into a 180 ℃ oven, keeping the temperature for 12 h, cooling to room temperature, taking out the W to grow ₁₈ O ₄₉ The nanowire film glass is repeatedly washed by absolute ethyl alcohol.

Thulium chloride hexahydrate, ytterbium chloride hexahydrate and yttrium chloride hexahydrate in a molar ratio of 1. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6 mL/h, after introducing argon gas for 30 min, 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 duration is 1.5 hours, and the temperature is cooled to room temperature to obtain the rare earth doped NaYF ₄ Solution, washed three times by liquid centrifugation with cyclohexane to ethanol at a volume ratio of 1:3, and the obtained product, 10 nm NaYF ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Get 500 mu L's NaYF ₄ :Yb ³⁺ , Tm ³⁺ Solution(s)Dispersing again in 10 mL of cyclohexane solution to obtain a mixed solution D, and adding W ₁₈ O ₄₉ Placing 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 NaYF ₄ :Yb ³⁺ , Tm ³⁺ /W ₁₈ O ₄₉ The light emission spectrum of the nanowire composite light-emitting film is shown in FIG. 7, from which NaYF can be seen ₄ :Yb ³⁺ ,Tm ³⁺ /W ₁₈ O ₄₉ The luminous intensity of the nano-wire composite luminous film is obviously lower than NaYF ₄ :Yb ³⁺ ,Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ The nano-wire is compounded with a luminescent film.

NaYF ₄ :Yb ³⁺ ,Tm ³⁺ A preparation method of the Ag nano-meter composite luminescent film;

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

Uniformly dispersing 1.2 mL of Ag nano meter solution into 10 mL of ethanol to obtain a mixed solution B, then placing the solution B with the 2 x 3 cm FTO glass conductive surface 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. 0.148 g of ammonium fluoride and 0.1 g of sodium hydroxide powder were poured into 5 mL of the methanol solution until all were dissolved, the entire methanol solution was withdrawn using a syringe (10 mL) and fixed in a syringe fixing groove of a syringe pump, and added dropwise into the flask at an injection rate of 6 mL/h, after introducing argon gas for 30 min, 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 duration is 1.5 hours, and the temperature is cooled to room temperature to obtain the rare earth doped NaYF ₄ Solution, washed with cyclohexane to ethanol 1Secondly, the obtained product 10 nm NaYF is added ₄ :Yb ³⁺ ,Tm ³⁺ The solution was stored in a glass bottle.

Taking 500 mu L NaYF ₄ :Yb ³⁺ , Tm ³⁺ Dispersing the solution into 10 mL 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 NaYF ₄ :Yb ³⁺ , Tm ³⁺ The luminescence spectrum of the/Ag nano composite luminescent film is shown in figure 7, from which the NaYF can be seen ₄ :Yb ³⁺ ,Tm ³⁺ The luminescent intensity of the Ag nano composite luminescent film is obviously lower than that of NaYF ₄ :Yb ³⁺ , Tm ³⁺ Ag nanometer meter/W ₁₈ O ₄₉ The 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 ^-3 And (3) obtaining solutions with other concentrations by continuously diluting the rhodamine B dye in mol/L, extracting the same volume of 50 mu L, and respectively dripping the solution on the surface of the composite luminescent film. Firstly, the Ag is passed through a nanometer meter/W ₁₈ O ₄₉ The nanowire composite film is used as a Raman test substrate, the excitation wavelength is 532.8 nm, the power is 0.5W, the integration time is 30 s, the qualitative detection is carried out on the organic fluorescent molecules by utilizing the fingerprint characteristic of the 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 980 nm 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 only preferred embodiments of the invention, and are not all possible embodiments for the practical implementation 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 (2)

1. An application of a high-efficiency multicolor up-conversion luminescence composite film in double detection of dye molecules; the preparation method is characterized in that the preparation method of the efficient multicolor up-conversion luminescence composite film comprises the following steps:

step (1) W ₁₈ O ₄₉ Preparing a nanowire film:

growing a layer of W on FTO conductive glass by a solvothermal method ₁₈ O ₄₉ A nanowire film, 25-30 mg of tungsten hexacarbonyl is poured into 20-24 mL of absolute ethyl alcohol solution to be stirred for 40-60 min to obtain mixed solution A, the solution A is moved into a 50 mL polytetrafluoroethylene reaction kettle containing 2X 3 cm of FTO conductive glass, an oven is heated to 180-200 ℃, the reaction kettle is then placed into the oven to be insulated for 10-12 h, the reaction kettle is taken out after being cooled to room temperature and is repeatedly washed by absolute ethyl alcohol to finally obtain W ₁₈ O ₄₉ A nanowire film;

step (2) Ag nano meter/W ₁₈ O ₄₉ Preparing a nanowire film:

step a, preparing Ag nano rice by adopting a polyol reduction method, adding 10-12 mL of polyethylene glycol into a 100 mL round-bottom flask, dripping 2-3 mL of polyvinyl pyrrolidone solution (1M) and 0.2-0.3 mL of newly prepared 1M silver nitrate solution in the stirring process, uniformly stirring for about 10-30 min, transferring the round-bottom flask into an oil bath kettle at 113-115 ℃, magnetically stirring for 8-10 h, and cooling to room temperature; repeatedly centrifuging and washing the mixture for three to four times by using absolute ethyl alcohol to obtain Ag nano rice;

step B, dispersing the Ag nano-meter obtained in the step a into 10 mL of absolute ethyl alcohol solution to obtain a mixed solution B, namely, the W obtained in the step (1) is subjected to simple self-assembly by a simple self-assembly method ₁₈ O ₄₉ Placing the nanowire film in the solution B, transferring into an oven, heating the oven to 50-70 deg.C, keeping the temperature for 6-8 h, and evaporating the solution B completely to obtain Ag nano meter/W ₁₈ O ₄₉ A nanowire film;

step (3) rare earth doping NaYF ₄ Nano particle/Ag nano meter/W ₁₈ O ₄₉ Preparing a nanowire film:

step a, preparing rare earth doped NaYF by utilizing a high-temperature pyrolysis process ₄ Adding yttrium chloride hexahydrate, ytterbium chloride hexahydrate and erbium chloride hexahydrate into a mixed solution C in a three-neck flask containing 6-12 mL of oleic acid and 15-30 mL of octadecene according to a molar ratio of 1;

and then dropwise adding a prepared 5-10 mL methanol solution dissolved with 0.148-0.296 g of ammonium fluoride and 0.1-0.2 g of sodium hydroxide into the solution C at a constant speed through a syringe pump, introducing argon for 30-60 min, raising the temperature to 80 ℃, keeping the temperature for 1.5-2 h to remove the methanol, finally raising the temperature to 305-310 ℃, reacting for 1.5-2 h, cooling to room temperature, centrifuging and washing with a liquid with a volume ratio of cyclohexane to ethanol of 1 ₄ Particles;

step b, doping NaYF with the rare earth obtained in the step a ₄ Dispersing the nano particles into 10 mL 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) ₁₈ O ₄₉ Placing the nanowire film in the solution D and moving the nanowire film into an oven, heating the oven to 50-70 ℃, preserving heat for 6-8 h, and completely evaporating the solution D to ensure that the rare earth is doped with NaYF ₄ Deposition of nanoparticles to Ag nm/W ₁₈ O ₄₉ The surface of the nanowire film can obtain the rare earth doped NaYF ₄ Nano particle/Ag nano meter/W ₁₈ O ₄₉ And (3) a nanowire composite luminescent film.

2. The use of the highly efficient multicolor upconversion luminescent composite film according to claim 1 for dual detection of dye molecules; it is characterized in that the FTO conductive glass is SnO doped with fluorine ₂ Transparent conductive glass.

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