Near-infrared light fluorescent ceramic, method for manufacturing the same, and light source device

Abstract

This application belongs to the field of light source technology and provides a near-infrared fluorescent ceramic. When excited by excitation light with a wavelength of 440nm-470nm, the near-infrared fluorescent ceramic generates near-infrared light with a wavelength of 690nm-890nm. The near-infrared fluorescent ceramic provided in this application provides a lower-cost near-infrared light generation method, achieving near-infrared light generation in the 690-890nm range, with a wide emission range and broad application prospects. Furthermore, this application also provides a method for preparing the near-infrared fluorescent ceramic and a light source device.

Description

Technical Field

[0001] This application relates to the field of light source technology, specifically to a near-infrared fluorescent ceramic, its preparation method, and a light source device. Background Technology

[0002] Near-infrared (NIR, 780–2500 nm) light possesses advantages such as strong penetration, high resolution, and high signal-to-noise ratio. It has broad application prospects in modern agriculture and security monitoring, information detection in food safety testing, and light conversion films in the photovoltaic field. Currently, the main technologies for generating near-infrared light are electroluminescent LED chips and photoluminescent fluorescence conversion. Existing mainstream commercial gallium arsenide-based LED chips emit near-infrared light with narrow spectrum and poor tunability. Furthermore, their device fabrication is complex, and their cost is more than 10 times that of blue LED chips, limiting their application and promotion. Currently, near-infrared fluorescence conversion technology based on rare-earth luminescent materials shows great application potential, and research and exploration of near-infrared luminescent materials, device fabrication, and related applications have begun both domestically and internationally.

[0003] Currently, near-infrared light is mainly fabricated using chips, which suffers from problems such as narrow spectrum, poor tunability, and high cost, and these issues urgently need to be addressed. Summary of the Invention

[0004] This application provides a near-infrared fluorescent ceramic, its preparation method, and a light source device to at least partially improve the above-mentioned technical problems.

[0005] In a first aspect, embodiments of this application provide a near-infrared fluorescent ceramic with the general chemical formula Y0. 3-x Lu x Cr y A(Al 1-z, Ga z ) 3-y BO 12 , where 0.01≤x≤3, 0.0005≤y≤0.1, and 0.005≤z≤0.5.

[0006] In some implementations, 0.3 ≤ x ≤ 1.5, 0.005 ≤ y ≤ 0.09, and 0.01 ≤ z ≤ 0.33.

[0007] In some embodiments, the excitation wavelength of the near-infrared fluorescent ceramic is 440nm-470nm, and the emission wavelength of the near-infrared fluorescent ceramic is near-infrared light with a wavelength of 690nm-890nm.

[0008] In some embodiments, its chemical formula is Y 2.5 Lu 0.5 Cr 0.015 A(A l 0.8,Ga 0.2 ) 2.985 BO 12 .

[0009] In some embodiments, its chemical formula is Y 1.5 Lu 1.5 Cr 0.02 A(Al 0.8, Ga 0.2 ) 2.98 BO 12 .

[0010] In some embodiments, its chemical formula is Y 0.5 Lu 1.5 Cr 0.015 A(A l 0.7, Ga 0.3 ) 2.985 BO 12 .

[0011] In some embodiments, A is selected from at least one of Mg, Ga, Sr, and Zn.

[0012] In some implementations, B is selected from at least one of the elements Si, Ge, In, and Zr.

[0013] Secondly, embodiments of this application also provide a light source device, including a light source and a wavelength conversion device, wherein the wavelength conversion device includes the aforementioned near-infrared fluorescent ceramic.

[0014] Thirdly, the embodiments of this application also provide a method for preparing the above-mentioned near-infrared fluorescent ceramic, including: weighing and mixing raw materials according to a metering ratio to form powder, calcining the powder, grinding and sieving it, loading it into a mold to form it, sintering it and then annealing it to form the near-infrared fluorescent ceramic.

[0015] The raw materials include oxides or corresponding salts containing Y, oxides or corresponding salts containing Lu, oxides or corresponding salts containing Cr, oxides or corresponding salts containing Al, oxides or corresponding salts containing Ga, oxides or corresponding salts containing A, oxides or corresponding salts containing B, or tetraethyl orthosilicate.

[0016] The near-infrared fluorescent ceramic, its preparation method, and the light source device provided in this application embodiment can achieve a lower-cost near-infrared light generation method, realize near-infrared light generation in the range of 690-890nm, have a wide emission range, and have broad application prospects. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0018] Figure 1 This is a morphology diagram of a near-infrared fluorescent ceramic proposed in an embodiment of this application.

[0019] Figure 2 This is the emission spectrum of a near-infrared fluorescent ceramic proposed in an embodiment of this application.

[0020] Figure 3 This is a schematic diagram of the structure of a light source device proposed in an embodiment of this application. Detailed Implementation

[0021] To enable those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present application without inventive effort are within the scope of protection of the present application.

[0022] In this application, unless otherwise expressly specified or limited, the terms "installation," "connection," "fixation," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components; they can refer to mere surface contact; or they can refer to surface contact connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0023] Furthermore, the terms "first," "second," etc., are used only for distinguishing descriptions and should not be construed as referring to specific or particular structures. The terms "some embodiments," "other embodiments," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this application, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. Furthermore, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this application, as well as the features of different embodiments or examples.

[0024] like Figure 1 As shown, this application provides a near-infrared fluorescent ceramic with the general chemical formula Y. 3-x Lu x Cr y A(Al 1-z, Ga z ) 3-y BO 12 Where 0.01≤x≤3, 0.0005≤y≤0.1, and 0.005≤z≤0.5. This near-infrared fluorescent ceramic has a garnet structure, an excitation spectrum wavelength of 440nm-470nm, and an emission spectrum wavelength of 690nm-890nm.

[0025] In some embodiments of this application, A is selected from at least one of Mg, Ga, Sr, and Zn. For example, in one embodiment of this application, A is selected from Mg, but other elements may also be used. B is selected from at least one of Si, Ge, In, and Zr. For example, in one embodiment of this application, B is selected from Si, but other elements may also be used.

[0026] The near-infrared fluorescent ceramic provided in this application is based on classic systems such as gallate / aluminate, and incorporates an AB (e.g., Mg-Si) system to obtain a novel fluorescent ceramic material with stable structure and a wide range of near-infrared light emission capabilities. By controlling the x / y and z ratios, the anisotropic parameters of the near-infrared fluorescent ceramic, such as the wavelength range of the emitted near-infrared light, can be precisely controlled.

[0027] In some implementations, the values ​​of 0.3 ≤ x ≤ 1.5, 0.005 ≤ y ≤ 0.09, and 0.01 ≤ z ≤ 0.33 can be controlled. Within this range, near-infrared fluorescent ceramics can generate near-infrared light of 700 nm to 830 nm when excited by excitation light with wavelengths of 440 nm to 470 nm, exhibiting better tunability.

[0028] The aforementioned near-infrared fluorescent ceramics can be prepared in the following manner:

[0029] Raw materials are weighed and mixed according to a specified ratio to form a powder. The raw materials include oxides or corresponding salts containing Y, oxides or corresponding salts containing Lu, oxides or corresponding salts containing Cr, oxides or corresponding salts containing Al, oxides or corresponding salts containing Ga, oxides or corresponding salts containing A, and oxides containing B. For example, when B is Si, tetraethyl orthosilicate (TEOS) can be used. Mixing can be performed using methods such as wet ball milling, chemical co-precipitation mixing, sol-gel mixing, and dry grinding. This embodiment does not limit the specific methods used.

[0030] Among them, ball milling wet mixing refers to the process of mixing various raw materials by adding grinding balls and solvents, and then grinding them in a ball mill. The impact, shearing and grinding effects generated during the rotation of the grinding balls, as well as the grinding-aiding effect of solvents (such as water, alcohol, etc.) in the wet process, are used to mix and grind the materials.

[0031] Chemical coprecipitation mixing refers to adding a precipitant to a mixed metal salt solution, causing two or more cations in the solution to precipitate together, forming a precipitate mixture or a solid solution precursor. This method is based on the chemical reaction between different metal ions and the precipitant in solution, forming insoluble compounds that co-precipitate, and then drying them to form a powder.

[0032] Sol-gel mixing refers to the reaction of easily hydrolyzed metal compounds (inorganic salts or metal alkoxides) with water in a certain solvent. After hydrolysis and condensation, the compounds gradually gel, and then undergo post-processing such as drying and sintering to obtain the desired powder.

[0033] After the powder is formed, it can be dried. Drying methods include microwave drying, spray drying, and oven drying, which are not limited in this embodiment. After drying, the powder is calcined, preferably at 800℃-1100℃. After calcination, the powder is ground and sieved, then placed into a mold for shaping. The shaping method can be dry pressing, cold isostatic pressing, etc. In some embodiments, the shaping operation may be omitted, and pressure sintering can be used in the subsequent sintering process.

[0034] The shaped powder is then sintered. Various sintering methods are possible, such as vacuum sintering, sintering with a H2 mixture or other reducing atmospheres, hot isostatic pressing, spark plasma sintering, and hot pressing. This embodiment does not limit the specific method. As a more specific implementation, sintering is performed as follows: the shaped powder is heated to 1000℃-1400℃ and held for 0.5h-4h, then further heated to 1600℃-1900℃, and sintered at 1*10... -3 Heating at 300 MPa for 2-50 hours. After high temperature and high pressure, followed by heat and pressure holding, dense fluorescent ceramics are obtained.

[0035] The obtained fluorescent ceramic is annealed to form the near-infrared fluorescent ceramic. The annealing method is not limited, and annealing can be carried out in air, a reducing atmosphere, or an oxygen atmosphere. Preferably, the annealing temperature can be 900℃-1400℃, and the annealing holding time can be, for example, 2h-50h. After that, the ceramic is cooled to room temperature to complete the annealing and obtain the near-infrared fluorescent ceramic.

[0036] The above-mentioned method for preparing near-infrared fluorescent ceramics has the advantage of low cost, and the prepared near-infrared fluorescent ceramics are low in cost and high in purity.

[0037] The present application will be described in detail below with reference to specific embodiments:

[0038] Example 1

[0039] This embodiment provides a near-infrared fluorescent ceramic. Figure 1 Its morphology diagram is shown, and its chemical formula is Y. 2.5 Lu 0.5 Cr 0.015 Mg(Al) 0.8, Ga 0.2 ) 2.985 S iO 12 The fluorescent ceramic material has a garnet structure. The excitation wavelength of the fluorescent ceramic material is 440-470 nm, and it can be effectively excited by blue light. Figure 2 As shown, the fluorescent ceramic material emits near-infrared light with a wavelength range of 690nm-890nm under blue light excitation. The spectrum of the fluorescent ceramic material covers near-infrared light emission in the range of 780-830nm.

[0040] The aforementioned near-infrared fluorescent ceramics are prepared in the following manner:

[0041] Based on the chemical formula Y of near-infrared fluorescent ceramics 2.5 Lu 0.5 Cr 0.015 Mg(Al) 0.8, Ga 0.2 ) 2.985 SiO12 Calculate the stoichiometric ratio of each element, and based on the stoichiometric ratio, weigh out the oxides containing Y, Lu, Cr, Al, Ga, A (Mg), and B (Si) as raw materials.

[0042] The raw materials were ball-milled and mixed, and dried to obtain a powder with a particle size distribution of approximately 100 μm. The powder was then calcined at 800℃-1100℃ to remove organic matter and residual media or solvents. The calcined powder was then ground and sieved. The calcined powder was placed into a mold for molding, and the molded powder was heated to 1000℃-1400℃ and held for 0.5h-4h, then further heated to 1600℃-1900℃ at a temperature of 1*10. -3 Sintering was carried out under Pa-300Mpa conditions for 2h-50h. After high temperature and high pressure, and holding at temperature and pressure, dense fluorescent ceramics were obtained. The high temperature sintered samples were then annealed to obtain completely dense pure phase near-infrared fluorescent ceramics.

[0043] Example 2

[0044] This embodiment provides a near-infrared fluorescent ceramic with the chemical formula Y. 1.5 Lu 1.5 Cr 0.02 Mg(Al 0.8, Ga 0.2 ) 2.98 SiO 12 The fluorescent ceramic material has a garnet structure. Its excitation wavelength is 440-470 nm, and it can be effectively excited by blue light, emitting near-infrared light with a wavelength range of 690 nm-890 nm under blue light excitation. The spectrum of the fluorescent ceramic material covers near-infrared light emission in the range of 780-830 nm.

[0045] The aforementioned near-infrared fluorescent ceramics are prepared in the following manner:

[0046] Based on the chemical formula Y of near-infrared fluorescent ceramics 1.5 Lu 1.5 Cr 0.02 Mg(Al) 0.8, Ga 0.2 ) 2.98 S iO 12 Calculate the stoichiometric ratio of each element, and based on the stoichiometric ratio, weigh out the oxides containing Y, Lu, Cr, Al, Ga, A (Mg), and B (Si) as raw materials.

[0047] The raw materials were ball-milled and mixed, and dried to obtain a powder with a particle size distribution of approximately 100 μm. The powder was then calcined at 800℃-1100℃ to remove organic matter and residual media or solvents. The calcined powder was then ground and sieved. The calcined powder was placed into a mold for molding, and the molded powder was heated to 1000℃-1400℃ and held for 0.5h-4h, then further heated to 1600℃-1900℃ at a temperature of 1*10. -3 Sintering was carried out under Pa-300Mpa conditions for 2h-50h. After high temperature and high pressure, and holding at temperature and pressure, dense fluorescent ceramics were obtained. The high temperature sintered samples were then annealed to obtain completely dense pure phase near-infrared fluorescent ceramics.

[0048] Example 3

[0049] This embodiment provides a near-infrared fluorescent ceramic with the chemical formula Y. 0.5 Lu 1.5 Cr 0.015 Mg(Al 0.7, Ga 0.3 ) 2.985 S iO 12 The fluorescent ceramic material has a garnet structure. Its excitation wavelength is 440-470 nm, and it can be effectively excited by blue light, emitting near-infrared light with a wavelength range of 690 nm-890 nm under blue light excitation. The spectrum of the fluorescent ceramic material covers near-infrared light emission in the range of 780-830 nm.

[0050] The aforementioned near-infrared fluorescent ceramics are prepared in the following manner:

[0051] Based on the chemical formula Y of near-infrared fluorescent ceramics 0.5 Lu 1.5 Cr 0.015 Mg(Al 0.7, Ga 0.3 ) 2.985 SiO 12 Calculate the stoichiometric ratio of each element, and based on the stoichiometric ratio, weigh out the oxides containing Y, Lu, Cr, Al, Ga, and A (Mg) and TEOS as raw materials.

[0052] The raw materials were ball-milled and mixed, and dried to obtain a powder with a particle size distribution of approximately 100 μm. The powder was then calcined at 800℃-1100℃ to remove organic matter and residual media or solvents. The calcined powder was then ground and sieved. The calcined powder was placed into a mold for molding, and the molded powder was heated to 1000℃-1400℃ and held for 0.5h-4h, then further heated to 1600℃-1900℃ at a temperature of 1*10. -3 Sintering was carried out under Pa-300Mpa conditions for 2h-50h. After high temperature and high pressure, and holding at temperature and pressure, dense fluorescent ceramics were obtained. The high temperature sintered samples were then annealed to obtain completely dense pure phase near-infrared fluorescent ceramics.

[0053] Example 4

[0054] See Figure 3 This embodiment also provides a light source device 1, including a light source 30 and a wavelength conversion device 20. In this embodiment, the wavelength conversion device 20 includes near-infrared fluorescent ceramics of any of the above embodiments. It is understood that the wavelength conversion device 20 may also include fluorescent ceramics of other colors, and this embodiment does not limit this.

[0055] Light source 30 is used to emit excitation light, such as blue light. Wavelength conversion device 20 is used to receive the excitation light and convert it into laser light for emission. The wavelength of the emitted laser light is different from the wavelength of the incident excitation light. More specifically, when the excitation light is incident on the near-infrared fluorescent ceramic, it can be converted into near-infrared light. It can be understood that the wavelength conversion device in this embodiment can be a transmission structure, that is, the excitation light is converted into near-infrared light by the near-infrared fluorescent ceramic and then emitted through the wavelength conversion device, or it can be a reflection structure, that is, the excitation light is converted into near-infrared light by the near-infrared fluorescent ceramic and then reflected in the opposite direction of the excitation light.

[0056] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. A near-infrared fluorescent ceramic, characterized in that, Y 3-x Lu x Cr y A(Al 1-z, Ga z ) 3-y BO 12 wherein 0.01≤x≤3, 0.0005≤y≤0.1, 0.005≤z≤0.

5.

2. The near-infrared fluorescent ceramic according to claim 1, characterized in that, in, 0.3≤x≤1.5, 0.005≤y≤0.09; 0.01≤z≤0.

33.

3. The near-infrared fluorescent ceramic according to claim 1, characterized in that, The near-infrared fluorescent ceramic has an excitation wavelength of 440nm-470nm and an emission wavelength of 690nm-890nm.

4. The near-infrared fluorescent ceramic according to claim 1, characterized in that, Its chemical formula is Y 2.5 Lu 0.5 Cr 0.015 A(Al 0.8, Ga 0.2 ) 2.985 BO 12 .

5. The near-infrared fluorescent ceramic according to claim 1, characterized in that, Its chemical formula is Y 1.5 Lu 1.5 Cr 0.02 A(Al 0.8, Ga 0.2 ) 2.98 BO 12 .

6. The near-infrared fluorescent ceramic according to claim 1, characterized in that, Its chemical formula is Y 0.5 Lu 1.5 Cr 0.015 A(Al 0.7, Ga 0.3 ) 2.985 BO 12 .

7. The near-infrared fluorescent ceramic according to any one of claims 1-6, characterized in that, A is selected from at least one of the elements Mg, Ga, Sr, and Zn.

8. The near-infrared fluorescent ceramic according to any one of claims 1-6, characterized in that, B is selected from at least one of the elements Si, Ge, In, and Zr.

9. A light source device, characterized in that, It includes a light source and a wavelength conversion device, wherein the wavelength conversion device includes near-infrared fluorescent ceramic as described in any one of claims 1-8.

10. The method for preparing near-infrared fluorescent ceramics according to any one of claims 1-8, characterized in that, include: Raw materials are weighed and mixed according to the metering ratio to form powder. The powder is calcined, ground and sieved, then placed into a mold to form a shape. After sintering, it is annealed to form the near-infrared fluorescent ceramic. The raw materials include oxides or corresponding salts containing Y, oxides or corresponding salts containing Lu, oxides or corresponding salts containing Cr, oxides or corresponding salts containing Al, oxides or corresponding salts containing Ga, oxides or corresponding salts containing A, oxides or corresponding salts containing B, or tetraethyl orthosilicate.

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