CN115895657A - Fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina and preparation method and application thereof - Google Patents

Abstract

The invention provides a fluorescent emitting layer prepared on the basis of metal aluminum-based mesoporous alumina, a preparation method and application of the fluorescent emitting layer. The general chemical formula of the fluorescent emitting layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , where 3≤a≤6, 0.01<b<0.1; under the excitation of blue light at 450nm, the emission spectrum wavelength of the fluorescent emitting layer is The range is between 460-760nm, and the main peak of the emission spectrum is between 530-550nm. Compared with the prior art, the fluorescent emission layer prepared by the present invention based on aluminum-based mesoporous alumina has a simple overall structure and is easy to synthesize; the fluorescent emission layer is directly grown on the aluminum plate, and after the laser excites the fluorescent emission layer , With the good thermal conductivity of the aluminum plate, the heat generated by the fluorescent emitting layer is quickly conducted away, without heat accumulation and obvious temperature rise of the fluorescent emitting layer, so it can be used for laser lighting.

Description

Fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina and its preparation method and application

technical field

The invention relates to the field of lighting technology, in particular to a fluorescent emitting layer prepared based on metal aluminum-based mesoporous alumina, a preparation method and application thereof.

Background technique

With the continuous advancement of industrial technology, lighting technology is also constantly upgraded. From the initial reliance on natural animal and plant materials, to fossil fuels, and then to point light sources such as incandescent and fluorescent lamps. In the 1990s, energy-efficient white LED solid-state lighting began to appear. As the cost of laser diodes gradually decreases and their performance tends to be stable, it becomes possible to use lasers as illumination sources.

Laser lighting technology, the technical principle is similar to that of white light LED technology. In white LED lighting technology, blue light (or purple light, etc.) LED chips excite fluorescent materials, and the light emitted by LED chips is combined with the light emitted by the excited fluorescent materials to finally obtain white light. The implementation of laser lighting technology, as described in Patent Document 1 (Wang Dajian, Song Weiwei, Mao Zhiyong, Li Guanghao, Sun Tao, Lu Zhijuan, A remote fluorescent coating for high-efficiency laser lighting and its application, ZL201410609545.2), usually adopts Laser diodes (laser diodes that can emit blue light are the most common) excite the fluorescent material, and the light emitted by the laser diode is combined with the light emitted by the excited fluorescent material to finally obtain white light.

But laser lighting technology faces many unique technical difficulties. One of the most difficult is: the heating problem of fluorescent materials. This is because, due to the influence of internal defects, energy transfer and other factors, the light conversion efficiency (quantum efficiency) of fluorescent materials under blue laser light is usually less than 100%, so a considerable part of the laser energy will be converted into heat, resulting in The temperature rises, which leads to a significant thermal quenching of the fluorescent material (resulting in a decrease in luminous intensity). In addition, taking the common blue light laser excitation yellow fluorescent material as an example, for yellow fluorescent material, when it absorbs blue light and converts it into yellow light, due to the difference in wavelength between blue light and yellow light, there is an energy difference between blue light and yellow light, that is, Stokes displacement. Therefore, regardless of the quantum efficiency of the fluorescent material, when the blue light excites the yellow fluorescent material, energy loss is inevitable and cannot be eliminated. This part of the energy loss is bound to be converted into heat. However, the fluorescent material has a thermal quenching characteristic, that is, as the temperature increases, the luminous performance of the fluorescent material will decrease. And because the laser is collimated light, the power density of the laser spot is extremely high due to the concentration of the beam. Therefore, when the laser is irradiated on the surface of the fluorescent material, the temperature of the fluorescent material increases more and more obviously.

Therefore, for laser lighting, the most important technical means is how to take away (export) the heat generated by fluorescent materials under laser irradiation. Common technical means include ceramicizing or vitrifying the fluorescent material onto a high thermal conductivity substrate, or dispersing the fluorescent material into a thermally conductive material. In fact, quite a lot of literature has been published in this technical field. For example, Patent Document 2 (R. Coulter, R. R. Drenten, E. J. M. Paulussen, A. Walster, D. Fournier, lamps for laser applications, CN102482576B ) discloses a method to solve the heating problem and alleviate the heat accumulation in the phosphor body. Improve optical performance for laser applications while facilitating heat transfer through phosphor-containing transparent bodies. Specifically, this method is that the attachment between the support and the phosphor is preferably realized by molten glass, ceramic glue, more preferably by transparent pressure ceramics or silicon thermal interface materials. But on the whole, there are many interfaces between the devices, the thermal resistance is high, and the thermal conductivity of the device is average, so the heat generated after the laser is irradiated on the fluorescent material cannot be quickly conducted away.

Patent document 3 (Wang Dajian, Gao Wenyu, Mao Zhiyong, Chen Jingjing, Tian Hua, Yang Chao, Anna, Shi Yuandong, low melting point glass powder and glass ceramics for laser lighting made thereof, CN106587641B) discloses a low melting point glass powder and its Fabrication of glass ceramics for laser illumination. The low-melting-point glass powder of the invention has a relatively low glass phase transition temperature, and its glass phase transition temperature can be adjusted within the range of 200-500°C. It is suitable for the production of sealing glass and vacuum components and the packaging of LEDs, especially for Used in the manufacture of luminescent glass ceramics with phosphor materials, the luminescent glass ceramics are especially suitable for laser lighting. Forming and sintering glass ceramics at a relatively low temperature can effectively avoid thermal degradation of phosphors at high temperatures, and has important application value in the field of laser lighting. But on the whole, the thermal conductivity of glass is relatively low, and it cannot quickly conduct away the heat generated by laser irradiation on fluorescent materials.

Patent document 4 (Feng Shaowei, Xia Xiaochun, Wang Hong, Zhu Jinchao, Li Chunhui, Zhang Pande, Ye Yong, Li Dongsheng, full-spectrum composite fluorescent ceramics for laser lighting and display and its preparation method, CN111285682A) discloses the use of The invention is a full-spectrum multi-phase fluorescent ceramic used for laser lighting and laser display. The beneficial effects of the invention are: it has a completely dense microstructure, excellent thermal conductivity and mechanical properties, and can effectively improve the heat generated by the luminescent material. Reduce the overall temperature of the device and improve the light extraction efficiency. But overall, compared with glass, the thermal conductivity of fluorescent ceramics has been significantly improved, but the preparation process of fluorescent ceramics is too complicated.

Patent Document 5 (Li Gan, Xu Yanzheng, Wavelength Conversion Device, Its Light Source System, and Projection System, CN203489180U) discloses a wavelength conversion device, its light source system, and projection system. The wavelength conversion device includes a support and multiple wavelength conversion modules that are assembled together, each of the wavelength conversion modules includes a ceramic carrier and phosphor placed on the ceramic carrier, and the support converts the multiple wavelengths The conversion modules remain relatively fixed. Both the light source system and the projection system include the wavelength conversion device. By adopting the utility model, the ceramic material is used as the ceramic carrier of the fluorescent powder, which can withstand high temperature, and will not cause the fluorescent powder to be difficult to attach due to deformation due to high temperature. Obviously, ceramization of fluorescent materials is a common method in this field to conduct heat away and reduce device temperature. Since the fluorescent ceramic itself is light-transmissive, the most suitable device structure is obviously transmissive, that is, the excitation light will pass through the fluorescent ceramic itself.

The ceramicization process is also used, but by generating a second phase, the thermal conductivity of the device can also be improved. Patent document 6 (Zhu Ning, Composite fluorescent ceramics for white light illumination excited by blue light, preparation method and light source device, CN109896852A) discloses a composite fluorescent ceramic for white light illumination excited by blue light, a preparation method and a light source device. The composite fluorescent ceramic has a fluorescent phase with a lutetium aluminum garnet structure and an Al ₂ O ₃ high thermal conductivity phase, and the microcrystals in the Al ₂ O ₃ high thermal conductivity phase are evenly distributed and surround the fluorescent phase of the lutetium aluminum garnet around, and form a three-dimensional network channel directly to the surface of the composite fluorescent ceramics. The invention has the beneficial effects of: effectively solving the problems of weak thermal shock resistance of fluorescent materials in current white light laser lighting, and poor high-temperature fluorescent characteristics such as luminous efficiency of fluorescent materials decreases with increasing temperature. But on the whole, due to the introduction of the second phase, although the thermal conductivity of the material has been significantly improved, the luminous efficiency of the obtained material is lower than that of conventional fluorescent ceramics.

In addition to ceramicization, the thin film process of fluorescent materials combined with low-melting glass powder can also conduct away the heat generated by fluorescent materials under laser excitation. For example, Patent Document 7 (Xie Rongjun, You Shihai, Zheng Peng, Zhou Tianliang, Li Shuxing, Nitride Phosphor Powder/Glass Composite Light Conversion Components for Laser Illumination and Its Preparation, CN108895314B) discloses a nitride phosphor/glass composite light conversion component for laser lighting. Glass composite light conversion components. It consists of a nitride phosphor/glass composite coating and a high thermal conductivity ceramic substrate, and the nitride phosphor powder/glass composite coating is closely grown on the high thermal conductivity ceramic substrate. But on the whole, although the thermal conductivity of the ceramic as the matrix is high, there is an obvious interface at the junction of the phosphor/glass composite coating and the ceramic substrate, and the thermal resistance is relatively large. The effect needs to be improved.

In addition, it is also of great significance to consider the heat generated by both the laser diode and the fluorescent material, and perform necessary thermal management. For example, Patent Document 8 (Cao Yongge, Xia Zeqiang, Shen Xiaofei, Ma Chaoyang, Laser white light emitting device for lighting or display, CN105826457B) discloses a laser white light emitting device for lighting or display. The invention combines the transparent fluorescent ceramic with the chip of the excitation light source, avoiding the decline of luminous efficiency or the failure of the light source caused by the heating of the fluorescent powder and silica gel; if according to the application requirements, the heat resistance of the transparent fluorescent ceramic enables the device to work at high current High temperature environment avoids the decline of device output power and electro-optical conversion efficiency when working at high temperature or high injection current. But overall, the preparation process of the device is too complicated.

Non-Patent Document 1 (Caiman Yan, Xinrui Ding, Mingqi Chen, Yifu Liang, Shu Yang, Yong Tang, Research on Laser Illumination Based on Phosphor in Metal (PiM) by Utilizing the Boron Nitride-Coated Copper Foams, ACS Appl. Mater. Interfaces2021 , 13,25,29996–30007) reported a laser lighting device. The device is a mixture of yellow phosphor and silica gel embedded in BN/copper foam to form a metal phosphor (PiM) converter. Copper foam serves as an internally connected heat transfer channel; BN coating effectively solves the light absorption problem of copper foam. It should be pointed out that although this solution can conduct away the heat generated by the fluorescent material to a certain extent through the foamed copper, because the fluorescent material and the foamed copper are not tightly connected (the thermal conductivity coefficient is used when the fluorescent material is fixed on the foamed copper). lower silica gel), so this technical solution cannot well solve the heat conduction problem of fluorescent materials under laser lighting conditions.

Of course, based on Non-Patent Document 1, it is easy to think of an improved technical solution. That is to use low-melting point glass powder instead of silica gel, and then heat the copper foam as a whole, so that the glass powder turns into glass liquid. After cooling, the fluorescent material is fixed in the foam copper by the glass liquid. But this scheme also has certain deficiencies. This is because glass obviously cannot form a chemical bond with copper foam. Although its thermal conductivity is better than that of silica gel combined with fluorescent materials placed in copper foam, the improvement effect will not be too significant.

Mesoporous alumina is a versatile support material. As described in patent document 9 (Pan Dahai, Li Ruifeng, Wang Xu, Guo Min, Yu Feng, He Min, Ma Jinghong, a highly thermally stable ordered mesoporous alumina material and its preparation method, CN103539173B), mesoporous alumina The material has the advantages of good mechanical strength, high chemical stability, suitable isoelectric point, adjustable surface acid/alkaline and a variety of different crystal phase structures, and has become the most widely used in the chemical and petroleum industries. Catalyst or catalyst carrier plays an important role in the reaction processes of petroleum group cracking, hydrofining, hydrodesulfurization, hydrocarbon reforming, hydrogen production, gas phase oil component purification, and automobile exhaust purification.

And as disclosed in patent document 10 (Lu Yong, Wang Chunzheng, Han Lupeng, Zhao Anqi, Liu Ye, an aluminum matrix-mesoporous alumina composite material and its preparation method and application, CN104148040B), the metal aluminum-based mesoporous Compared with traditional mesoporous alumina, alumina has the advantages of good thermal conductivity, high permeability, easy molding, easy filling, easy storage, etc. It is an ideal catalyst carrier and can be used as a catalyst carrier for the preparation of loaded active metals or Catalysts supporting active metals and auxiliary metal oxides. Obviously, the aluminum matrix-mesoporous alumina composite material, like mesoporous alumina, is also a recognized catalyst support material.

All in all, it can be seen from the existing public literature that for metal aluminum-based mesoporous alumina, it is not an easy-to-think material in the laser lighting technology route, and it is difficult to apply to laser lighting technology.

Contents of the invention

The first object of the present invention is to provide a fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina.

The metal aluminum-based mesoporous alumina is a metal aluminum plate containing mesoporous alumina with a pore size of 2-50 nm and a thickness of 20-200 μm on one side; the general chemical formula of the fluorescent emission layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , where 3≤a≤6, 0.01<b<0.1. Under the excitation of blue light at 450nm, the emission spectrum wavelength range of the fluorescent emitting layer prepared by metal aluminum-based mesoporous alumina is between 460-760nm, and the main peak of the emission spectrum is between 530-550nm; preferably, the general chemical formula of the fluorescent emitting layer Among them, a=4.5, b=0.04.

The second object of the present invention is to provide a method for preparing a fluorescent emission layer based on metal aluminum-based mesoporous alumina. The preparation method includes: 1) preparing the Y precursor and the Ce precursor into an aqueous solution with a mass concentration of 50%; the molar ratio of Y and Ce in the Y precursor and the Ce precursor is 2:b, wherein, 0.01<b <0.1; 2) Put the metal aluminum-based mesoporous alumina into the solution obtained in step 1) and soak for 24-48 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution , vacuum-dried at 80°C for 24h; 4) put the aluminum-based mesoporous alumina dried in step 3) into a high-temperature furnace, and put it in a hydrogen or nitrogen-hydrogen mixed gas atmosphere at a temperature of 600-625°C After reacting for 24-48 hours, a fluorescent emission layer prepared based on aluminum-based mesoporous alumina and having the general chemical formula Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ was obtained, where 3≤a≤6, 0.01<b<0.1. Preferably, the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%.

The present invention also provides a reflective structural laser lighting device, which includes a blue laser diode and a fluorescent emission layer prepared on the basis of metal aluminum-based mesoporous alumina placed opposite to it.

The specific plan is as follows:

A fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina, the general chemical formula of the fluorescent emission layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , wherein, 3≤a≤6, 0.01<b <0.1; further, in the general chemical formula of the fluorescent emitting layer, a=4.5, b=0.04. The fluorescent emission layer is prepared based on aluminum-based mesoporous alumina, which is a metal aluminum plate containing mesoporous alumina on one side; the pore size of the mesoporous alumina is 2-50 nm, and the thickness is 20-200μm.

Further, under the excitation of blue light of 450nm, the wavelength range of the emission spectrum produced by the fluorescent emitting layer is between 460nm and 760nm, and the main peak of the emission spectrum is between 530nm and 550nm.

The present invention also provides the preparation method of the fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina comprising: 1) preparing the Y precursor and the Ce precursor so that the mass concentration is 40% to 60% (more preferably 50%) 2) putting the metal aluminum-based mesoporous alumina into the solution obtained in step 1) and soaking for a certain period of time; 3) taking out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, Put it into a vacuum oven for drying; 4) put the aluminum-based mesoporous alumina dried in step 3) into a high-temperature furnace, and perform a high-temperature reaction under a reducing atmosphere to obtain a kind of aluminum-based mesoporous alumina The prepared fluorescent emission layer has a general chemical formula of Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , where 3≤a≤6, 0.01<b<0.1.

Further, the Y precursor is selected from the nitrate of Y;

Optionally, the Ce precursor is selected from Ce nitrates;

Optionally, the purity of both the Y precursor and the Ce precursor is not lower than 99.5wt%.

Further, the molar ratio of Y and Ce in the Y precursor and Ce precursor is 2:b, wherein, 0.01<b<0.1.

Optionally, the aluminum-based mesoporous alumina is a metal aluminum plate containing mesoporous alumina on one side; the pore size of the mesoporous alumina is 2-50 nm; the thickness of the mesoporous alumina is 20-20 nm. 200μm;

Optionally, the soaking time is 24 to 48 hours;

Optionally, drying at 70-90° C. for 18-30 hours, more preferably, the temperature of vacuum drying is 80° C., and the drying time is 24 hours.

Further, the temperature of the high-temperature solid phase reaction is 600-625°C, and the time of the high-temperature reaction is 24-48 hours;

Optionally, the reducing atmosphere is hydrogen or nitrogen-hydrogen mixed gas; preferably, the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%.

The present invention also provides a laser lighting device, which includes a blue laser diode and the fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina. The laser lighting device is a reflective structure, and the light outlet of the blue laser diode is placed opposite to the fluorescent emitting layer.

Compared with the prior art, the present invention has the following beneficial effects:

The invention provides a fluorescent emitting layer prepared on the basis of metal aluminum-based mesoporous alumina, a preparation method and application of the fluorescent emitting layer. The general chemical formula of the fluorescent emitting layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , where 3≤a≤6, 0.01<b<0.1; under the excitation of blue light at 450nm, the emission spectrum wavelength of the fluorescent emitting layer is The range is between 460-760nm, and the main peak of the emission spectrum is between 530-550nm. Compared with the prior art, the fluorescent emitting layer prepared by the present invention based on aluminum-based mesoporous alumina has a simple overall structure and is easy to synthesize; the fluorescent emitting layer is directly grown on the aluminum plate, and after the laser excites the fluorescent emitting layer , With the good thermal conductivity of the aluminum plate, the heat generated by the fluorescent emitting layer is quickly conducted away, without heat accumulation and obvious temperature rise of the fluorescent emitting layer, so it can be used for laser lighting.

Description of drawings

Fig. 1 is the emission spectrogram of the fluorescent emission layer that obtains in comparative example 1 of the present invention;

Fig. 2 is the emission spectrogram of the fluorescence emitting layer obtained in comparative example 2 of the present invention;

Fig. 3 is the emission spectrogram of the fluorescence emitting layer obtained in the embodiment of the present invention 1;

Fig. 4 is the emission spectrum diagram of the laser lighting device obtained in Example 17 of the present invention;

Figure 5 is a structural diagram of the laser lighting device obtained in Example 17 of the present invention

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. Those skilled in the art should understand that the examples are only used to help understand the present invention, and should not be regarded as specific limitations on the present invention.

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below in conjunction with examples.

The general chemical formula of the fluorescent emitting layer prepared based on metal aluminum-based mesoporous alumina is as follows:

Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂

Among them, 3≤a≤6, 0.01<b<0.1. In some embodiments provided by the present invention, said a is preferably 3, and b is preferably 0.015; in some embodiments provided by the present invention, said a is preferably 3, and b is preferably 0.02; in some provided by the present invention In an embodiment, the a is preferably 3, and b is preferably 0.04; in some embodiments provided by the present invention, a is preferably 3, and b is preferably 0.08; in some embodiments provided by the present invention, the a is preferably 3, and b is preferably 0.09; in some embodiments provided by the present invention, said a is preferably 3, and b is preferably 0.095; in some embodiments provided by the present invention, said a is preferably 3.5, b It is preferably 0.04; in some embodiments provided by the present invention, said a is preferably 4, and b is preferably 0.04; in some embodiments provided by the present invention, said a is preferably 4.5, and b is preferably 0.04; in this invention In some embodiments provided by the invention, the a is preferably 5, and b is preferably 0.04; in some embodiments provided by the invention, a is preferably 5.5, and b is preferably 0.04; in some embodiments provided by the invention Among them, a is preferably 5.9, and b is preferably 0.04; in some embodiments provided by the present invention, a is preferably 6, and b is preferably 0.04; in some embodiments provided by the present invention, a is preferably is 4.5, and b is preferably 0.02; in some embodiments provided by the present invention, the a is preferably 4.5, and b is preferably 0.03; in other embodiments provided by the present invention, the a is preferably 4.5, and b is preferably is 0.05.

The specific steps of the preparation method of the fluorescent emitting layer prepared based on metal aluminum-based mesoporous alumina are as follows:

1) Prepare the Y precursor and the Ce precursor into an aqueous solution with a mass concentration of 50%; 2) Put the metal aluminum-based mesoporous alumina into the solution obtained in step 1) and soak for a certain period of time; 3) Put the ) the aluminum-based mesoporous alumina soaked in the solution is taken out from the solution, and put into a vacuum oven for drying; 4) the aluminum-based mesoporous alumina dried in step 3) is put into a high-temperature furnace, Under high temperature reaction, a fluorescent emitting layer based on metal aluminum-based mesoporous alumina is obtained. The general chemical formula of the fluorescent emitting layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ , where 3≤ a≤6, 0.01<b<0.1.

In the step, the Y precursor is selected from Y nitrates; the Ce precursor is selected from Ce nitrates. The molar ratio of Y and Ce in the Y precursor and the Ce precursor is 2:b, wherein, 0.01<b<0.1.

The purity of the Y precursor and the Ce precursor is not lower than 99.5%, and the higher the purity, the less impurities the obtained luminescent material has.

The aluminum-based mesoporous alumina is a metal aluminum plate containing mesoporous alumina on one side. The pore size of the aluminum-based mesoporous alumina is 2-50 nm, and the thickness of the mesoporous alumina is preferably 20-200 μm. In some embodiments provided by the present invention, the pore size of the mesoporous alumina is preferably 3 nm, and the thickness of the mesoporous alumina is preferably 25 μm; in some embodiments provided by the present invention, the mesoporous alumina The pore size of aluminum is preferably 20nm, and the thickness of mesoporous alumina is preferably 100 μm; in some embodiments provided by the present invention, the pore size of the mesoporous alumina is preferably 45nm, and the thickness of mesoporous alumina is preferably 150 μm; in other embodiments provided by the present invention, the pore size of the mesoporous alumina is preferably 40 nm, and the thickness of the mesoporous alumina is preferably 180 μm.

The soaking time is 24-48 hours, and in some embodiments provided by the present invention, the soaking time is preferably 36 hours.

The temperature of the vacuum drying is 80° C., and the drying time is 24 hours.

The reducing atmosphere in the step is hydrogen or nitrogen-hydrogen mixed gas, preferably, the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%; in the present invention, it is preferably nitrogen-hydrogen mixed gas.

In the step, the temperature of the high-temperature solid phase is preferably 600-625° C., and the atmosphere is a mixture of nitrogen and hydrogen. In some embodiments provided by the present invention, the temperature of the high-temperature solid phase is preferably 600° C.; In other embodiments, the temperature of the high-temperature solid phase is preferably 625°C.

The high-temperature solid-phase time in the step is preferably 24-48 hours, more preferably 36-48 hours; in some embodiments provided by the present invention, the high-temperature solid-phase time is preferably 36 hours.

The high-temperature solid reaction phase is preferably carried out in a high-temperature furnace. After the reaction is carried out, the furnace is cooled to room temperature to obtain a fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina.

The invention adopts high-temperature solid-state reaction to successfully prepare a fluorescent emission layer based on metal aluminum-based mesoporous alumina.

The laser lighting device with a reflective structure at least consists of a blue laser diode and a fluorescent emission layer prepared based on metal aluminum-based mesoporous alumina. The general chemical formula of the fluorescent emitting layer prepared based on metal aluminum-based mesoporous alumina is: Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ (wherein, 3≤a≤6, 0.01<b<0.1).

In order to further illustrate the present invention, a fluorescent emitting layer prepared based on metal aluminum-based mesoporous alumina, a preparation method and a device provided by the present invention are described in detail below in conjunction with examples.

The reagents used in the following comparative examples and examples are all commercially available.

In the mixed atmosphere of nitrogen and hydrogen adopted in the following comparative examples and examples, the volume content of hydrogen is 20%.

The Y precursor and Ce precursor used in the comparative examples and examples are only examples, and do not constitute a limitation on the raw materials of the precursors. The purity of the precursors is not less than 99.5 wt%.

Comparative example 1

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·1.667Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 40nm and a thickness of 180μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 1.667Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·1.667Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. Using a fluorescence spectrometer to measure the emission spectrum of the obtained fluorescent emitting layer, it was found that the obtained fluorescent emitting layer emitted light relatively weakly and hardly emitted light (see FIG. 1 ).

Comparative example 2

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·2Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 40nm and a thickness of 180μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 2Al ₂ O ₃ 0.04CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in a _{nitrogen -} hydrogen gas mixture atmosphere at a temperature of ₆₂₅ °C to obtain _a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer, and it was found that the obtained fluorescent emission layer emitted light very weakly and hardly emitted light (see FIG. 2 ).

Comparative example 3

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·2.9Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 40nm and a thickness of 180μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 2.9Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·2.9Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emitting layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescent emitting layer emits extremely weak light.

Comparative example 4

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·6.5Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 40nm and a thickness of 180μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 6.5Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·6.5Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emitting layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescent emitting layer emits extremely weak light.

Comparative example 5

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.015CeO ₂ . Select a single-sided metal aluminum-based macroporous alumina with a pore size of 70nm and a thickness of 180μm. According to the pore size and thickness of the macroporous alumina and the external dimensions of the metal aluminum-based macroporous alumina, first calculate the metal aluminum-based macroporous alumina. The number of moles of alumina in alumina, and then take Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, and accurately weigh it according to the stoichiometric ratio of chemical formula Y ₂ O ₃ 3Al ₂ O ₃ 0.015CeO ₂ The raw materials, and then 1) Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ are formulated into an aqueous solution with a mass concentration of 50%; 2) metal aluminum-based macroporous alumina is placed in the solution obtained in step 1) 3) take out the metal aluminum-based macroporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based macroporous alumina in step 3) Alumina was placed in a high-temperature furnace, and _reacted for 36 hours in a nitrogen _{- hydrogen} mixed gas atmosphere at a temperature of 625°C _to obtain a metal-aluminum _- based Fluorescent emission layer made of macroporous alumina. The emission spectrum of the obtained fluorescent emitting layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescent emitting layer emits extremely weak light.

Comparative example 6

The chemical formula of the material described in this comparative example is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.015CeO ₂ . Select a single-sided metal aluminum-based microporous alumina with a pore size of 1.8nm and a thickness of 180 μm. According to the pore size and thickness of the microporous alumina and the external dimensions of the metal aluminum-based microporous alumina, the metal aluminum-based microporous alumina The number of moles of alumina in porous alumina, and then use Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.015CeO ₂ to be accurately weighed Take the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based microporous alumina into the obtained Soak in the solution for 36 hours; 3) Take out the metal aluminum-based microporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) Dry the metal aluminum-based microporous alumina in step 3) Porous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a metal-based aluminum alloy with the general chemical formula Y ₂ O ₃ ·3Al ₂ O ₃ ·0.015CeO ₂ Fluorescent emission layer prepared on the basis of microporous alumina. The emission spectrum of the obtained fluorescent emitting layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescent emitting layer emits extremely weak light.

Comparative example 7

In this comparative example, a ceramic sheet with a chemical composition of Y ₃ Al ₅ O ₁₂ 0.06Ce and a thickness of 300 μm was selected, and the ceramic sheet was fixed on an aluminum plate with thermally conductive silica gel with a thermal conductivity of 1.5W/(m·K). The thickness of the silica gel is 100 μm. After the heat-conducting silica gel is cured, use a 450nm blue laser with a power density of 5W/ ^mm2 to irradiate the ceramic sheet. After 10 minutes, the temperature rise of the ceramic sheet is relatively high (see Table 1). Obviously, limited by the obvious interface layer between the ceramic sheet and the aluminum plate, the thermal resistance is relatively large. Therefore, after laser irradiation, the ceramic sheet produces an obvious temperature rise, and the temperature rise will inevitably lead to obvious thermal quenching of the fluorescent material. .

Example 1

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.015CeO ₂ . Select a single-sided aluminum-based mesoporous alumina with a pore size of 3 nm and a thickness of 25 μm, and calculate the aluminum-based The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.015CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in _a nitrogen _{- hydrogen} gas mixture atmosphere at a temperature of ₆₀₀ °C to obtain a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. Using a fluorescence spectrometer to measure the emission spectrum of the obtained fluorescent emitting layer, it was found that the obtained fluorescent emitting layer luminesced strongly, the wavelength range of the emission spectrum was between 460-760nm, and the main peak of the emission spectrum was located at 531nm (see Figure 3). After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 2

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.02CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 20nm and a thickness of 100μm. According to the size and thickness of the mesopores and the external dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.02CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in a _{nitrogen -} hydrogen mixture atmosphere at a temperature of ₆₂₅ °C to _obtain a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 3

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.04CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in a _{nitrogen -} hydrogen mixture atmosphere at a temperature of ₆₂₅ °C to obtain _a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 4

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.08CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 40nm and a thickness of 180μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.08CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in a _{nitrogen -} hydrogen mixture atmosphere at a temperature of ₆₂₅ °C to _obtain a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 5

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.09CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.09CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put the mesoporous alumina into a high-temperature furnace _and react for 36 hours in a nitrogen _{- hydrogen} mixed gas atmosphere at a temperature of ₆₂₅ °C to obtain a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 6

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3Al ₂ O ₃ ·0.095CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3Al ₂ O ₃ 0.095CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put the mesoporous alumina into a high-temperature furnace and react for 36 hours in _a nitrogen _{- hydrogen} gas mixture atmosphere at a temperature of ₆₂₅ °C to obtain a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 7

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·3.5Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 3.5Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 600°C to obtain a chemical formula Y ₂ O ₃ ·3.5Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 8

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·4Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 4Al ₂ O ₃ 0.04CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react _for 36 hours in _a nitrogen _{- hydrogen} mixed gas atmosphere at a temperature of 625°C to obtain _a metal-based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 9

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 4.5Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 10

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·5Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 5Al ₂ O ₃ 0.04CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put the mesoporous alumina into a high-temperature furnace and react for 36 hours in _a nitrogen _{- hydrogen} mixed gas atmosphere at a temperature of 625°C to obtain _a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 11

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·5.5Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 5.5Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·5.5Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 12

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·5.9Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 5.9Al ₂ O ₃ 0.04CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·5.9Al ₂ O ₃ ·0.04CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 13

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·6Al ₂ O ₃ ·0.04CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then using Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 6Al ₂ O ₃ 0.04CeO ₂ is accurate Weigh the raw materials, and then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put the metal aluminum-based mesoporous alumina into the obtained 3) take out the metal aluminum-based mesoporous alumina soaked in step 2) from the solution, and dry it in vacuum at 80°C for 24 hours; 4) dry the metal aluminum-based mesoporous alumina in step 3) Put mesoporous alumina into a high-temperature furnace, and react for 36 hours in a _{nitrogen -} hydrogen gas mixture atmosphere at a temperature of ₆₂₅ °C to obtain _a metal _- based Fluorescent emission layer prepared from aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 14

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.02CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 4.5Al ₂ O ₃ 0.02CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.02CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 15

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.03CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then take Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 4.5Al ₂ O ₃ 0.03CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.03CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Example 16

The chemical formula of the material described in this embodiment is: Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.05CeO ₂ . Select a single-sided metal aluminum-based mesoporous alumina with a pore size of 45nm and a thickness of 150μm. According to the size and thickness of the mesopores and the outer dimensions of the metal aluminum-based mesoporous alumina, first calculate the The number of moles of alumina in mesoporous alumina, then Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ as raw materials, according to the stoichiometric ratio of Y ₂ O ₃ 4.5Al ₂ O ₃ 0.05CeO ₂ Accurately weigh the raw materials, then 1) prepare Y(NO ₃ ) ₃ and Ce(NO ₃ ) ₃ into an aqueous solution with a mass concentration of 50%; 2) put metal aluminum-based mesoporous alumina into the Soak in the obtained solution for 36 hours; 3) Take the metal aluminum-based mesoporous alumina soaked in step 2) out of the solution, and dry it in vacuum at 80°C for 24 hours; 4) Put the dried metal aluminum in step 3) The mesoporous alumina was placed in a high-temperature furnace, and reacted for 36 hours in a nitrogen-hydrogen mixed gas atmosphere at a temperature of 625°C to obtain a chemical formula Y ₂ O ₃ ·4.5Al ₂ O ₃ ·0.05CeO ₂ , Fluorescent emission layer based on aluminum-based mesoporous alumina. The emission spectrum of the obtained fluorescent emission layer was measured by a fluorescence spectrometer. The position and intensity of the main peak of the emission spectrum are shown in Table 1. It can be found that the obtained fluorescence emission layer emits stronger light. After irradiating the fluorescent emitting layer with a 450nm blue laser with a power density of 5W/ ^mm2 for 10 minutes, the temperature rise of the fluorescent emitting layer was low (see Table 1).

Table 1 Material emission spectrum data table

Example 17

The fluorescent emitting layer obtained in Example 9 with the chemical composition of Y ₂ O ₃ 4.5Al ₂ O ₃ 0.04CeO ₂ based on metal aluminum-based mesoporous alumina is packaged with a blue laser diode with an emission wavelength of 450 nm, The fluorescent emitting layer is placed opposite to the blue laser diode. FIG. 4 shows the emission spectrum of the laser lighting device obtained in Example 17. FIG. 5 shows the structural diagram of the laser lighting device obtained in Example 17.

001: 450nm blue laser; 002: light incident on the fluorescent emitting layer; 003: fluorescent emitting layer based on metal aluminum-based mesoporous alumina; 004: metal aluminum plate; 005: 450nm blue light and fluorescent emitting layer excited by 450nm blue light Mixture of emitted light.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (8)

1. A fluorescence emission layer prepared based on metal aluminum-based mesoporous alumina is characterized by comprising: the fluorescent material comprises metal aluminum-based mesoporous alumina and a fluorescent emission layer arranged on the metal aluminum-based mesoporous alumina;

the metal aluminum-based mesoporous alumina is a metal aluminum plate with a single surface containing mesoporous alumina, the pore size of the mesoporous alumina is 2-50 nm, and the thickness of the mesoporous alumina is 20-200 mu m;

the chemical general formula of the fluorescence emission layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ Wherein a is more than or equal to 3 and less than or equal to 6,0.01<b<0.1。

2. The fluorescence emission layer prepared based on metal aluminum-based mesoporous alumina according to claim 1, wherein in the chemical formula of the fluorescence emission layer, a =4.5, b =0.04.

3. The fluorescence emission layer prepared on the basis of the metal aluminum-based mesoporous alumina as claimed in claim 1 or 2, wherein the wavelength range of an emission spectrum generated by the fluorescence emission layer prepared on the basis of the metal aluminum-based mesoporous alumina is 460-760 nm and the main peak of the emission spectrum is 530-550 nm under the excitation of blue light of 450 nm.

4. The method for preparing a fluorescence emitting layer prepared based on metal aluminum based mesoporous alumina according to any one of claims 1 to 3, comprising the following steps:

1) Preparing a Y precursor and a Ce precursor into an aqueous solution with the mass concentration of 40-60%, wherein the molar ratio of Y to Ce in the Y precursor and the Ce precursor is 2: b, and 0.01-straw-b-0.1;

2) Putting the metal aluminum-based mesoporous alumina into the solution obtained in the step 1), and soaking for 24-48 h;

3) Taking out the metal aluminum-based mesoporous alumina soaked in the step 2) from the solution, putting the solution into a vacuum oven, and drying the solution at the temperature of between 70 and 90 ℃ for 18 to 30 hours;

4) Putting the metal aluminum-based mesoporous alumina dried in the step 3) into a high-temperature furnace, and carrying out high-temperature reaction in a reducing atmosphere to obtain a fluorescence emission layer prepared on the basis of the metal aluminum-based mesoporous alumina, wherein the chemical general formula of the fluorescence emission layer is Y ₂ O ₃ ·aAl ₂ O ₃ ·bCeO ₂ Wherein a is more than or equal to 3 and less than or equal to 6,0.01<b<0.1。

5. The method for preparing a fluorescent emitting layer based on metal aluminum-based mesoporous alumina as claimed in claim 4, wherein the Y precursor is selected from the group consisting of nitrate of Y; the Ce precursor is selected from nitrate of Ce, and the purity of the Y precursor and the purity of the Ce precursor are not lower than 99.5wt%.

6. The preparation method of the fluorescence emission layer prepared based on the metal aluminum based mesoporous alumina as claimed in claim 4 or 5, wherein the temperature of the high-temperature reaction is 600-625 ℃, and the time of the high-temperature reaction is 24-48 h; the reducing atmosphere is hydrogen or a nitrogen-hydrogen mixed gas.

7. A laser illumination device comprising a blue laser diode and a fluorescence emitting layer made of metal aluminum based mesoporous alumina according to claim 1.

8. The laser lighting device according to claim 7, wherein the laser lighting device is a reflective structure, and the light outlet of the blue laser diode is arranged opposite to a fluorescence emission layer made of metal aluminum-based mesoporous alumina.

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