CN111349432B - Photochromic up-conversion fluorescent switch and preparation method thereof - Google Patents
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Abstract
The invention discloses a photochromic up-conversion fluorescent switch and a preparation method thereof, wherein the photochromic switch is based on rare earth doped crystal materials, and particularly has a three-layer core-shell structure, and comprises a light-emitting crystal nucleus with lower concentration, an inert separation layer and a high-concentration photo-thermal conversion shell layer from inside to outside. The invention reduces the fluorescence intensity of the crystal nucleus under the excitation of another wavelength by utilizing the heating effect of the photo-thermal shell layer under the specific excitation wave band, thereby realizing the function of switching on and off of light under the single particle level. The photochromic switch has the advantages of small size, easy data reading, quick response, simple and convenient operation, high repeatability and the like, and mainly solves the defects of large size, slow response, difficult data reading, complex operation and poor repeatability of the conventional photochromic switch.
Description
Technical Field
The invention relates to a photochromic up-conversion fluorescent switch and a preparation method thereof, in particular to a novel photochromic up-conversion fluorescent switch based on a photo-thermal effect and a preparation method thereof, which relate to construction, preparation and application of micro optical materials and belong to the field of optical materials.
Background
Photochromic phenomena refers to the chemical reaction or physical change of certain substances under the action of light of a certain wavelength and intensity, so as to cause the reversible change of the light absorption or light emission characteristics. Traditional photochromism often involves a change in color of a substance, and is therefore often used in applications such as color changing glasses, smart windows, and the like. Photochromic in a broad sense refers generally to a change of absorption or luminescence characteristics of an object under external light stimulus, wherein a photochromic switching material having a light emission "on-off" function under different external stimuli has important value in practical applications such as optical memory and optical storage, sensors, three-dimensional holographic memories, and the like, and has been receiving more and more attention in recent years.
At present, the photochromic switch material mainly comprises a luminescent dye unit, organic molecules, light activated luminescent proteins, a metal/photochromic material compound and the like, and the organic or inorganic photochromic materials still have the following defects to be overcome. First, conventional photochromic switches are generally based on large-sized blocks or large-particle powders, and cannot be applied to micro-nano integrated optoelectronic systems. Second, their luminescence modulation behavior derives mainly from two quenching mechanisms: intramolecular resonance energy transfer and electron transfer mechanisms. Because of the overlap between the excitation or emission wavelength and the absorption wavelength in the above mechanisms, it is difficult to accurately read the information carried in the emitted light signal. Again, such materials often require additional heat treatment processes such as high temperature annealing or sintering under specific atmospheres to achieve reversible luminescence, often between tens of minutes and hours, resulting in cumbersome operation and long response times for conventional photochromic switches. Finally, the light emission of the conventional photochromic switching material is reversible after heat treatment, but the light emission brightness under different cycles can be significantly different, resulting in poor operation repeatability of the photochromic switching material.
Disclosure of Invention
Aiming at the prior art, the technical problem to be solved by the invention is to provide the photochromic up-conversion fluorescent switch based on photo-thermal conversion, which can realize the operation of the optical switch with high repeatability simply, conveniently and quickly under the micro-nano size, and the preparation method thereof, so as to solve the problems of large size, difficult data reading, complex operation, slow response and poor repeatability of the traditional photochromic switch.
In order to solve the technical problems, the invention relates to a photochromic up-conversion fluorescent switch which adopts three layers of core-shellThe shell structure sequentially comprises a luminous crystal nucleus, an isolating layer and a heating layer from inside to outside, wherein the luminous crystal nucleus adopts Er 3+ /Yb 3+ 、Tm 3+ /Yb 3+ Or Ho 3+ /Yb 3+ Co-doped nano or micron crystal, and Nd is adopted as the heating layer 3+ 、Er 3+ Or Tm 3+ The isolating layer is nano-or micron-sized crystal of pure matrix; the nano-or micron-sized crystal is ALnF 4 Wherein ln=y, gd or Lu, a=li, na or K.
The product of the invention further comprises:
1. er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 2 to 5mol% 3+ The concentration of (2) is in the range of 5 to 30mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 60-100mol%.
2. Er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 2 to 3mol% 3+ The concentration of (2) is in the range of 5 to 10mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 60-80mol%.
3. Er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 3 to 4mol% 3+ The concentration of (2) is in the range of 10-20mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 80-90mol%.
4. Er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 4 to 5mol% 3+ The concentration of (2) is in the range of 20-30mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 90-100mol%.
The preparation method of any one of the photochromic up-conversion fluorescent switches comprises the following steps:
s1: preparing a luminous crystal nucleus: ammonium fluoride and AOH were treated as ALnF 4 Preparing water solution in stoichiometric ratio in the molecular formula, wherein A=Li, na or K, adding oleic acid and ethanol, stirring at room temperature until the solution is uniform, and preparing rare earth element according to the luminous crystal nucleus componentAdding the aqueous solution of the materials into a mixed system, stirring for 10-30 minutes at room temperature, then moving the mixed system into a high-pressure reaction kettle, heating to any temperature within the range of 200-230 ℃, keeping the temperature for 10-12 hours, cooling to room temperature, centrifugally separating, washing for 1-2 times by using water and ethanol respectively, and dispersing in the aqueous solution to obtain a No. 1 dispersion;
s2: wrapping an inert isolation layer: according to ALnF 4 Preparing an aqueous solution of raw materials in stoichiometric ratio in a molecular formula, stirring at room temperature to obtain a transparent suspension, adding dilute hydrochloric acid and dilute nitric acid, stirring to obtain a milky suspension, adding a No. 1 dispersion, stirring to be uniform, transferring to a high-pressure reaction kettle, heating to any temperature within the range of 200-230 ℃, continuing to stand for 10-12 hours, cooling to room temperature, centrifuging, washing with water and ethanol for 1-2 times respectively, and dispersing in the aqueous solution to obtain a No. 2 dispersion;
s3, wrapping a heating shell layer: preparing an aqueous solution of raw materials according to the components of the heating layer, stirring to a transparent suspension at room temperature, adding dilute hydrochloric acid and dilute nitric acid, stirring to a milky suspension, adding a No. 2 dispersion, stirring to be uniform, transferring to a high-pressure reaction kettle, heating to any temperature within the range of 200-230 ℃, continuously heating for 10-12 hours, cooling to room temperature, centrifugally separating, washing with water and ethanol for 1-2 times respectively, and dispersing in the aqueous solution to obtain a dispersion of the photochromic switch.
The invention has the beneficial effects that: compared with the traditional optical switch, the invention has the following beneficial effects: 1. the size of the device is small; 2. the data is easy to read; 3. the operation is simple and convenient; 4. the response is rapid; 5. the repeatability is high.
Drawings
FIG. 1 (a) shows Er/Yb: naYF in an optical switch 4 Sample morphology of the crystal nucleus;
FIG. 1 (b) shows the final Er/Yb: naYF in an optical switch 4 @NaYF 4 @NaNdF 4 Core-shell products;
FIG. 2 is a schematic diagram of a typical optical switch structure and operation;
FIG. 3 is an upconversion fluorescence spectrum of an optical switch at 0 watts and 2 watts of 800nm laser power, where 980nm laser power is fixed at 0.2 watts;
FIG. 4 shows the up-conversion fluorescence intensity of an optical switch under 0.2W 980nm excitation with 800nm laser power;
fig. 5 is a schematic diagram of response speed and repeatability of the optical switch.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings.
The invention is based on rare earth doped crystal material, in particular to a three-layer core-shell structure, which comprises a light emitting crystal nucleus with lower concentration, an inert separation layer and a high-concentration photo-thermal conversion shell layer from inside to outside. The invention reduces the fluorescence intensity of the crystal nucleus under the excitation of another wavelength by utilizing the heating effect of the photo-thermal shell layer under the specific excitation wave band, thereby realizing the function of switching on and off of light under the single particle level. The invention utilizes 980nm laser to induce low-concentration rare earth ion doped material to generate up-conversion fluorescence, realizes the on state of the optical switch, utilizes 800nm laser to excite the photo-thermal conversion quenching up-conversion fluorescence of high-concentration rare earth material, realizes the off state of the optical switch, and utilizes a core-shell structure to integrate the on and off functional spaces. The specific implementation mode is as follows:
1. the low-concentration rare earth ion doped nano-or micron-sized crystal material is prepared to be used as a luminous crystal nucleus of the optical switch, and the luminous crystal nucleus efficiently up-converts fluorescence under 980nm excitation to correspond to the 'on' state of the optical switch. Up-conversion fluorescence of rare earth ions is commonly referred to as Er 3+ 、Tm 3+ 、Ho 3+ The alike activator ion emits light in the visible band generated by spontaneous emission of the energy level down to the high excitation state energy level of the population after absorbing two or more near infrared photons. Yb addition to luminescent nuclei 3+ The ions are used as sensitizer and Yb is utilized 3+ Strong absorption in 980nm band and Yb 3+ High-efficiency energy transfer to the activator, improved up-conversion fluorescence efficiency, and improved signal-to-noise ratio of the optical switch. The excitation wave band and the light-emitting wave band of the up-conversion light-emitting process are greatly deviated, so that information carried in a light-emitting signal can be accurately read, and the up-conversion light-emitting device has the advantages of nondestructive reading, safe operation and the like. In addition, the micro-nano-scale nanocrystal core ensures an ultra-small scale of the optical switching deviceCun.
2. And constructing a core-shell structure space to integrate the luminous crystal nucleus and the heating shell, wherein the heating shell is a high-concentration rare earth ion doped micro-nano crystal material. The high-concentration rare earth doped material has a remarkable concentration quenching effect, and the basic principle is that the high-concentration doping greatly reduces the average distance between rare earth ions, so that the ultra-strong energy migration or cross relaxation process between adjacent rare earth ions is caused, and the processes can promote the rare earth ions to transfer absorbed energy to a quenching center, so that light energy is converted into heat through phonon vibration. Nd 3+ 、Tm 3+ 、Er 3+ The activator has strong absorption in the 800nm wave band, so the ion highly doped material excited by 800nm can generate high-efficiency heat under the concentration quenching effect.
3. The up-conversion fluorescence of the rare earth ions has obvious temperature quenching effect and corresponds to the 'off' state of the optical switch. Because the non-radiative relaxation process of each energy level in the rare earth ions towards the adjacent lower energy level is aggravated along with the temperature rise, the non-radiative relaxation process at high temperature dominates the decolonization of the excited state of the rare earth ions, and the fluorescence intensity is obviously quenched, which is the mechanism of the 800nm laser turn-off up-conversion fluorescence signal in the optical switch. Meanwhile, the operation convenience of the optical switch is obviously improved by the all-optical operation of 980nm luminescence and 800nm turn-off.
4. In order to avoid harmful cross relaxation between the luminescent nucleus and rare earth ions in the heating layer, an inert layer is added between the luminescent nucleus and the heating shell layer to isolate unfavorable energy transfer and ensure high intensity of optical signals of the device in an 'on' state. Simultaneously, luminous crystal nucleus, inert isolation layer, shell that generates heat pass through core-shell structure epitaxial growth in proper order, and great area of contact is favorable to mutual heat transfer between each layer, consequently can be quick reach microcosmic heat balance, and be difficult for receiving external environment influence, realized the high-speed response and the high reproducibility of photoswitch.
The invention realizes the ' opening ' -of full-light operation ' based on the high photo-thermal conversion efficiency of rare earth highly doped materials and the temperature quenching phenomenon of rare earth fluorescence by integrating the luminous crystal nucleus and the heating layer through the core-shell structure spaceOff function. The optical switch is composed of a luminous crystal nucleus, an isolation layer and a heating layer. Optical switch is based on ALnF suitable for rare earth ion doping 4 Micro-nano-sized matrix construction, ln=y, gd or Lu, a=li, na or K. Light with 980nm wave band is used as an excitation source of the photochromic switch; the light of 800nm wave band is used as the heating of the photochromic switch, namely the turn-off source. Er with high-efficiency up-conversion fluorescence radiation under 980nm excitation 3+ /Yb 3+ 、Tm 3+ /Yb 3+ And Ho 3+ /Yb 3+ Isodoped crystals as luminescent nuclei, wherein Er 3+ 、Tm 3+ 、Ho 3+ The concentration of Yb ranges from 2 to 5mol% 3+ The concentration of (2) is in the range of (5-30 mol%). High-concentration Nd with high-efficiency heating under 800nm laser 3+ 、Er 3+ 、Tm 3+ A plasma rare earth ion doped crystal is used as a heating layer, wherein Er 3+ 、Tm 3+ 、Ho 3+ The concentration of (2) is in the range of (60-100 mol%). An ALnF layer without pure matrix component doped with activating agent is added between the luminous layer and the heating layer 4 Inert layers ln=y, gd or Lu, a=li, na or K to ensure that the core-shell structure can be formed with the light-emitting nuclei and the heat-generating layer.
As shown in FIGS. 1 (a) and 1 (b), the increase in the size of the nanorods indicates successful construction of the core-shell structure, with the upper insets showing the corresponding crystal structure, where Er/Yb represents Er/Yb: naYF 4 Micron rod crystal nucleus, Y represents NaYF 4 An inert isolation layer, nd represents the outermost NaNdF 4 And (5) heating the layer.
Example 1:
with 2mol% Er 3+ And 18mol% Yb 3+ Doping element as luminous crystal nucleus in optical switch, 100mol% Nd 3+ Doping element as heating shell layer and NaYF synthesized by hydrothermal method 4 The substrate and the inert separator are exemplified. The optical switch component is abbreviated as 2Er/18Yb: naYF 4 @NaYF 4 @NaNdF 4 The invention is described in further detail below with reference to the drawings and detailed description of embodiments:
first, preparing a light-emitting crystal nucleus: ammonium fluoride and sodium hydroxide in a total amount of 9.5 millimoles were added at a ratio of 1:3.75The stoichiometric ratio was set to 2.5 ml of aqueous solution, then 5 ml of oleic acid and 5 ml of ethanol were added and stirred at room temperature until the solution was homogeneous. ErCl was added in a total amount of 1 millimole 3 、YbCl 3 、YCl 3 According to stoichiometric ratio Er 3+ :Yb 3+ :Y 3+ The formulation of =0.02:0.18:0.80 was 2.5 ml of aqueous solution, added to the mixed system and stirred at room temperature for 15 minutes, then transferred to an autoclave and warmed to 220 degrees celsius for 12 hours. Cooling to room temperature, centrifuging, washing with water and ethanol for 1-2 times, dispersing in 2 ml water solution to obtain 2Er/18 Yb/NaYF 4 The morphology of the corresponding luminescent nuclei is shown in FIG. 1 (a).
Then wrapping the inert isolation layer: the total amount was 13.05 mM and the stoichiometric ratio was YCl 3 :EDTA-2Na:NaF:NH 4 17.25 ml of aqueous solution f=0.3:0.75:4:8 was stirred at room temperature to a transparent suspension, diluted hydrochloric acid (1.5 ml 2M) and diluted nitric acid (1.5 ml 15 wt%) were added and stirred to a milky suspension, then dispersion No. 1 was added and stirred to homogeneity, and the mixture was transferred to an autoclave and warmed to 220 ℃ for 12 hours. After cooling to room temperature, the mixture was centrifuged, washed with water and ethanol 1 to 2 times, and dispersed in 2 ml of an aqueous solution to obtain a No. 2 dispersion.
Finally, wrapping a heating shell layer: the total amount was 13.05 mM, and the stoichiometric ratio was NdCl 3 :EDTA-2Na:NaF:NH 4 17.25 ml of aqueous solution f=0.3:0.75:4:8 was stirred at room temperature to a transparent suspension, diluted hydrochloric acid (1.5 ml 2M) and diluted nitric acid (1.5 ml 15 wt%) were added and stirred to a milky suspension, then dispersion No. 2 was added and stirred to homogeneity, and the mixture was transferred to an autoclave and warmed to 220 ℃ for 12 hours. Cooling to room temperature, centrifuging, washing with water and ethanol for 1-2 times, and dispersing in 2 ml of aqueous solution to obtain the dispersion liquid of the photochromic switch provided by the invention, wherein the corresponding morphology is shown in figure 1 (b).
The operation steps of the photochromic switch are as follows: as shown in FIG. 2, under 980nm laser irradiation with 0.1-0.5W output power, 2Er/18Yb: naYF 4 The crystal nucleus emits bright up-converted green lightI.e., the "on" function of photochromic switching on; simultaneously adding 800nm laser irradiation with 1-3W output power, naNdF 4 The shell layer generates high-efficiency photo-thermal conversion, and rapidly transmits heat to the luminous crystal nucleus to remarkably quench green light emitted by photo-on light (figure 3), so that the off function of the photochromic switch is realized. As shown in FIG. 4, the more pronounced the fluorescence quenching with increasing 800nm laser power, the more the fluorescence intensity decay of the optical switch at 2 Watts of power is approaching 90%. As shown in fig. 5, the response time of the optical switch is in microsecond level, the fluctuation of the fluorescence intensity in the "on" and "off" states is less than 20%, and the faster response speed and the higher repeatability of the optical switch provided by the invention are proved.
Example 2:
at 0.5mol% Tm 3+ And 18mol% Yb 3+ Doping element as luminous crystal nucleus in photochromic switch and 100mol% Er 3+ Doping element and NaLuF as heating shell layer 4 As an example of the substrate and the inert isolation layer, the specific composition of the optical switch in this example is abbreviated as 0.5Tm/18Yb: naLuF 4 @NaLuF 4 @NaErF 4 The specific embodiment is the same as the procedure of example 1, except that Er is used in the preparation of the luminescent nucleus 3+ :Yb 3+ :Y 3+ The stoichiometric ratio=0.02:0.18:0.80 is changed to Tm 3+ :Yb 3+ :Lu 3+ YCl of inert isolation layer was applied to =0.005:0.180:0.815 3 :EDTA-2Na:NaF:NH 4 The stoichiometric ratio of f=0.3:0.75:4:8 was changed to LuCl 3 :EDTA-2Na:NaF:NH 4 F=0.3:0.75:4:8, and finally NdCl in the heat-generating shell layer 3 :EDTA-2Na:NaF:NH 4 The stoichiometric ratio of f=0.3:0.75:4:8 was changed to ErCl 3 :EDTA-2Na:NaF:NH 4 F=0.3:0.75:4:8.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1.A photochromic up-conversion fluorescent switch, characterized by: adopts a three-layer core-shell structure, comprises a luminous crystal nucleus, an isolating layer and a heating layer from inside to outside, wherein the luminous crystal nucleus adopts Er 3+ /Yb 3+ 、Tm 3+ /Yb 3+ Or Ho 3+ /Yb 3+ Co-doped nano or micron crystal, and Nd is adopted as the heating layer 3+ 、Er 3+ Or Tm 3+ The isolating layer is nano-or micron-sized crystal of pure matrix; the nano-or micron-sized crystal is ALnF 4 Wherein ln=y, gd or Lu, a=li, na or K.
2. A photochromic upconversion fluorescent switch according to claim 1, wherein: er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 2 to 5mol% 3+ The concentration of (2) is in the range of 5 to 30mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 60-100mol%.
3. A photochromic upconversion fluorescent switch according to claim 1, wherein: er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 2 to 3mol% 3+ The concentration of (2) is in the range of 5 to 10mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 60-80mol%.
4. A photochromic upconversion fluorescent switch according to claim 1, wherein: er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration of Yb ranges from 3 to 4mol% 3+ The concentration of (2) is in the range of 10-20mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 80-90mol%.
5. A photochromic upconversion fluorescent switch according to claim 1, wherein: er in luminous crystal nucleus 3+ 、Tm 3+ Or Ho 3+ The concentration range of (2) is4-5mol％，Yb 3+ The concentration of (2) is in the range of 20-30mol%; nd in heating layer 3+ 、Er 3+ Or Tm 3+ The concentration range is 90-100mol%.
6. A method of manufacturing a photochromic up-conversion fluorescent switch according to any one of claims 1 to 5, comprising the steps of:
s1: preparing a luminous crystal nucleus: ammonium fluoride and AOH were treated as ALnF 4 Preparing an aqueous solution according to a stoichiometric ratio in a molecular formula, wherein A=Li, na or K, adding oleic acid and ethanol, stirring at room temperature until the solution is uniform, preparing an aqueous solution of a rare earth raw material according to a luminescent crystal nucleus component, adding the aqueous solution into a mixed system, stirring at room temperature for 10-30 minutes, then moving the mixed system into a high-pressure reaction kettle, heating to any temperature within a range of 200-230 ℃, continuing the temperature for 10-12 hours, cooling to room temperature, performing centrifugal separation, washing with water and ethanol for 1-2 times respectively, and dispersing in the aqueous solution to obtain a No. 1 dispersion;
s2: wrapping an inert isolation layer: according to ALnF 4 Preparing an aqueous solution of raw materials in stoichiometric ratio in a molecular formula, stirring at room temperature to obtain a transparent suspension, adding dilute hydrochloric acid and dilute nitric acid, stirring to obtain a milky suspension, adding a No. 1 dispersion, stirring to be uniform, transferring to a high-pressure reaction kettle, heating to any temperature within the range of 200-230 ℃, continuing to stand for 10-12 hours, cooling to room temperature, centrifuging, washing with water and ethanol for 1-2 times respectively, and dispersing in the aqueous solution to obtain a No. 2 dispersion;
s3, wrapping a heating shell layer: preparing an aqueous solution of raw materials according to the components of the heating layer, stirring to a transparent suspension at room temperature, adding dilute hydrochloric acid and dilute nitric acid, stirring to a milky suspension, adding a No. 2 dispersion, stirring to be uniform, transferring to a high-pressure reaction kettle, heating to any temperature within the range of 200-230 ℃, continuously heating for 10-12 hours, cooling to room temperature, centrifugally separating, washing with water and ethanol for 1-2 times respectively, and dispersing in the aqueous solution to obtain a dispersion of the photochromic switch.
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| CN102268259A (en) * | 2011-06-14 | 2011-12-07 | 中国科学院长春光学精密机械与物理研究所 | Luminescent centre regionally doped rare earth upconversion luminescent material and preparation method thereof |
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| CN105176515A (en) * | 2015-09-01 | 2015-12-23 | 国家纳米科学中心 | Rare earth upconversion nanoparticles, preparation method and uses thereof |
| CN107286924A (en) * | 2017-06-13 | 2017-10-24 | 复旦大学 | Upper conversion nano crystalline material of the infrared ray excited orthogonal fluorescent emission of redgreenblue and preparation method thereof |
| CN107828408A (en) * | 2017-10-12 | 2018-03-23 | 复旦大学 | The lower conversion nano fluorescence probe of the window of near-infrared second transmitting and its synthetic method |
| CN107739603A (en) * | 2017-10-23 | 2018-02-27 | 合肥工业大学 | Conversion nano particle and preparation method thereof on a kind of red green luminescence rare earth of exciting light regulation and control |
| CN110423615A (en) * | 2019-07-05 | 2019-11-08 | 哈尔滨工程大学 | A kind of individual particle nanocrystal and preparation method thereof having three-color light-emitting |
| CN110878207A (en) * | 2019-11-21 | 2020-03-13 | 广州大学 | Up-conversion nanometer optical switch material and preparation method thereof |
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