1. The cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission is characterized in that the structural general formula is RLu_{2-x- y}Ce_xMn_yAl_4-ySi_1+yO₁₂(ii) a R is Ca²⁺，Sr²⁺，Ba²⁺One or more combinations thereof.

2. The cerium-manganese activated single matrix phosphor with ultra-wideband emission according to claim 1, wherein x, y are stoichiometric numbers, 0< x ≦ 0.2, 0< y ≦ 0.4.

3. The ultra-wideband emission cerium-manganese activated single matrix phosphor of claim 1, wherein Ce³⁺Is a blue-green luminescent center, Mn²⁺Is the center of red and near infrared light emission.

4. The preparation method of the cerium manganese activated single-matrix fluorescent powder with ultra-wideband emission is characterized by comprising the following steps of:

(1) according to the general chemical formula RLu_2-x-yCe_xMn_yAl_4-ySi_1+yO₁₂Weighing each component; wherein x, y are stoichiometric numbers, 0<x≤0.2，0<y≤0.4；

(2) Fully synthesizing according to the stoichiometric ratio to obtain the fluorescent powder.

5. The method for preparing the ultra-wideband emission cerium-manganese activated single matrix phosphor according to claim 3, comprising the steps of:

(1) according to the general chemical formula RLu_2-x-yCe_xMn_yAl_4-ySi_1+yO₁₂Weighing each component; wherein x, y are stoichiometric numbers 0<x≤0.2，0<y≤0.4；

(2) Grinding and uniformly mixing the weighed components in an agate mortar to obtain a mixture;

(3) placing the mixture in a high-temperature muffle furnace, and sintering for 2-10 h at 1350-1450 ℃ in a reducing gas atmosphere to obtain a sintered block;

(4) crushing the obtained sintered block, and fully grinding the obtained powder;

(5) and further washing, filtering and drying the obtained powder to obtain a finished product of the fluorescent powder.

6. The method of claim 3, wherein R is Ca²⁺，Sr²⁺，Ba²⁺An oxide, carbonate or nitrate of one or more of (a); lu (Lu)³⁺，Ce³⁺，Mn²⁺，Al³⁺，Si⁴⁺The raw material is selected from one of oxide, carbonate or nitrate.

7. The method of claim 3, wherein the reducing gas is CO or H₂。

8. The multifunctional 1-pc-LED light-emitting device with ultra-wideband emission application of the cerium-manganese activated single-matrix fluorescent powder is characterized in that the cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission as claimed in any one of claims 1 to 7 is arranged in the multifunctional 1-pc-LED light-emitting device.

9. The ultra-wideband cerium manganese activated single matrix phosphor as claimed in claims 1-7, wherein the method used in a multifunctional 1-pc-LED lighting device is as follows:

(1) uniformly mixing the cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission with glue; obtaining a mixture;

(2) covering the mixture in the step (1) on an LED chip;

(3) and (3) curing the LED chip covered in the step (2).

10. The cerium manganese activated single matrix phosphor with ultra-wideband emission according to claim 9, wherein the LED chip is one of an InGaN or GaN semiconductor chip; the glue is preferably one of epoxy resin or silica gel.

Background

Phosphor-converted LED technology (pc-LED) phosphor materials are a crucial part. The broader the band of the phosphor, the greater the potential utility. The continuous emission of the visible light region can realize high color rendering and low color temperature white light output; the emission of far-red light and near-infrared region can be applied to the fields of plant illumination, biological monitoring, etc. At present, the main approach for realizing ultra-wideband emission by converting fluorescent powder into LED (pc-LED) is to combine two kinds of fluorescent powder (2-pc-LED) and even multiple kinds of fluorescent powder (Multi-pc-LED) by an LED chip. However, compared with the 1-pc-LED scheme, the scheme has the advantages that the manufacturing cost is increased, clustering phenomena are easily formed among different fluorescent powders, and meanwhile, a reabsorption phenomenon often exists among the different fluorescent powders, so that energy loss is caused. Therefore, the development of a broad-band emission phosphor with excellent performance, and thus the development of a high-performance 1-pc-LED light emitting device, has been the direction of efforts in science and industry.

At present, the development and application of the single-matrix fluorescent powder with ultra-wideband emission have the following bottlenecks that (1) the ultra-wideband emission fluorescent powder which has low luminous efficiency and can be effectively excited by an LED chip (450 nm) is rare; (2) ultra-wideband phosphors with emissions from blue to near-infrared are rare. For example, single matrix phosphor Sr₂AlSi₂O₆N:Eu²⁺The broadband emission from 400nm to 800nm is realized, but the broadband emission cannot be effectively excited by an LED chip (450 nm), and the quantum efficiency is about 10 percent; single matrix phosphor Ba₃ScB₃O₉:Eu²⁺The emission range covers 580-1000nm, the LED chip (450 nm) cannot be effectively excited, and the luminous efficiency in the near infrared region is low; although the cerium-manganese co-activated garnet-structured phosphor provided in chinese patent 201910934049.7 has strong absorption in the wavelength range of 400-500nm, it does not emit light in the far-red and near-infrared regions, and the emission range only covers the visible light region of 500nm-700 nm.

Disclosure of Invention

In view of the above research and development status, the present invention provides cerium (Ce) with ultra-wideband emission³⁺) Manganese (Mn)²⁺) Activating single-matrix fluorescent powder and a multifunctional 1-pc-LED device using the same. The ultra-wideband emission fluorescent powder developed by the invention can be effectively excited by a blue light LED chip,the emission range is 460-880nm, the quantum efficiency is higher, and the physicochemical property is stable. The 1-pc-LED light-emitting device based on the ultra-wideband emission fluorescent powder not only realizes warm white light output with higher color rendering property and low color temperature, but also can be applied to the fields of plant illumination, biological detection and the like.

The invention achieves the above object by at least one of the following technical means.

The cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission has a structural general formula of RLu_2-x-yCe_xMn_yAl_{4- y}Si_1+yO₁₂(ii) a x, y are stoichiometric numbers, 0<x≤0.2，0<y≤0.4。

Further, R is Ca²⁺，Sr²⁺，Ba²One or more combinations of (a);

further, Ce in the cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission³⁺Is a blue-green luminescent center, Mn²⁺Is the center of red and near infrared light emission.

The preparation method of the cerium manganese activated single-matrix fluorescent powder with ultra-wideband emission comprises the following steps:

(1) according to the general chemical formula RLu_2-x-yCe_xMn_yAl_4-ySi_1+yO₁₂Weighing each component; wherein x, y are stoichiometric numbers, 0<x≤0.2，0<y≤0.4；

(2) Fully synthesizing according to the stoichiometric ratio to obtain the fluorescent powder.

Further, the preparation method of the cerium manganese activated single-matrix fluorescent powder with ultra-wideband emission comprises the following steps:

(1) according to the general chemical formula RLu_2-x-yCe_xMn_yAl_4-ySi_1+yO₁₂Weighing each component; wherein x, y are stoichiometric numbers 0<x≤0.2，0<y≤0.4；

(2) Grinding and uniformly mixing the weighed components in an agate mortar to obtain a mixture;

(3) placing the mixture in a high-temperature muffle furnace, and sintering for 2-10 h at 1350-1450 ℃ in a reducing gas atmosphere to obtain a sintered block;

(4) crushing the obtained sintered block, and fully grinding the obtained powder;

(5) and further washing, filtering and drying the obtained powder to obtain a finished product of the fluorescent powder.

Further, R is Ca²⁺，Sr²⁺，Ba²⁺An oxide, carbonate or nitrate of one or more of (a).

Further, Lu³⁺，Ce³⁺，Mn²⁺，Al³⁺，Si⁴⁺The raw material is selected from one of oxide, carbonate or nitrate.

Further, the reducing gas is CO or H₂。

The multifunctional 1-pc-LED light-emitting device with the ultra-wideband emission function and the application of the cerium-manganese activated single-matrix fluorescent powder comprises a packaging substrate, an LED chip and the ultra-wideband emission function.

The cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission is used in a multifunctional 1-pc-LED light-emitting device in the following method:

(1) uniformly mixing the cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission with glue; obtaining a mixture;

(2) covering the mixture in the step (1) on an LED chip;

(3) and (3) curing the LED chip covered in the step (2).

Further, the LED chip is one of InGaN or GaN semiconductor chips, preferably a blue InGaN semiconductor chip; the glue is preferably one of epoxy resin or silica gel.

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

1) the method is easy to operate from the preparation of the fluorescent powder to the encapsulation of the pc-LED device, has no pollution and low manufacturing cost, and can be industrially popularized.

2) The ultra-wideband single-matrix fluorescent powder can be effectively excited by an LED chip (440nm-460 nm).

3) The emission range of the fluorescent powder is 460-880nm, and the fluorescent powder still has high-efficiency emission particularly in the far-red and near-infrared regions (700-880 nm).

4) The 1-pc-LED light-emitting device prepared by the single-matrix fluorescent powder can realize the output of warm white light, and can also be applied to the fields of plant illumination, biological monitoring and the like to realize the multifunctional application of the 1-pc-LED light-emitting device.

Drawings

FIG. 1 is an X-ray diffraction pattern and a standard pattern of example 3;

FIG. 2 is an excitation spectrum of example 3;

FIG. 3 is an emission spectrum of example 3;

FIG. 4 is a map of a 1-pc-LED light emitting device prepared by combining the phosphor with an LED chip of example 5.

The specific implementation mode is as follows:

the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings and the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The method for synthesizing the fluorescent powder in the embodiment of the invention adopts a high-temperature solid-phase method. However, the synthesis method of the phosphor is not limited to the high temperature solid phase method. Any conventional method known to those skilled in the art for synthesizing the fluorescent powder by using the prior known technical means (such as a sol-gel method, a combustion method and an emulsion method) is within the protection scope of the present invention.

In the examples, analytically pure BaCO was used₃，SrCO₃，CaCO₃High purity Lu₂O₃，CeO₂，MnCO₃，SiO₂，Al₂O₃As raw materials, the phosphors of the various embodiments of the present invention were prepared.

Example 1:

in this embodiment, pressAccording to CaLu_1.56Ce_0.04Mn_0.40Al_3.60Si_1.40O₁₂Weighing CaCO according to the stoichiometric ratio of the chemical elements₃0.0500 g, Lu₂O₃0.1522 g of CeO₂0.0034 g of MnCO₃0.0230 g of Al₂O₃0.0918 g of SiO₂0.0421 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 2 hours at 1450 ℃ in a CO reducing atmosphere, taking out after natural cooling, fully grinding, further washing, filtering and drying to obtain the fluorescent powder CaLu_1.56Ce_0.04Mn_0.40Al_3.60Si_1.40O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission intensity of the phosphor in the near infrared region is stronger than that in the visible light region.

Example 2:

in this example, according to SrLu_1.60Ce_0.04Mn_0.36Al_3.64Si_1.36O₁₂The SrCO is weighed according to the stoichiometric ratio of the chemical elements₃0.0738 g Lu₂O₃0.1592 g of CeO₂0.0034 g of MnCO₃0.0207 g, Al₂O₃0.0928 g of SiO₂0.0409 g, grinding in agate mortar, mixing homogeneously, setting inside corundum crucible, covering, sintering in high temperature furnace in CO reducing atmosphere at 1350 deg.c for 6 hr, cooling naturally, taking out and grinding to obtain SrLu as fluorescent powder_1.60Ce_0.04Mn_0.36Al_3.64Si_1.36O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission of the phosphor in the near infrared region is slightly stronger than that in the visible region.

Example 3:

in this example, according to BaLu_1.56Ce_0.12Mn_0.32Al_3.68Si_1.32O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0987 g，Lu₂O₃0.1552 g of CeO₂0.0103 g of MnCO₃0.0184 g of Al₂O₃0.0938 g of SiO₂0.0397 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 6 hours at 1400 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding, further washing, filtering and drying to obtain the fluorescent powder BaLu_1.56Ce_0.12Mn_0.32Al_3.68Si_1.32O₁₂。

FIG. 1 is an XRD diffraction pattern and a standard pattern for this example;

FIG. 2 is an excitation spectrum of the present embodiment, which shows that the phosphor can be effectively excited by the LED chip (440nm-460 nm);

FIG. 3 shows the emission spectrum of the present example, which extends from 460nm (blue light) to 880nm (near infrared light emission).

Example 4:

in this example, according to Ba_0.75Sr_0.25Lu_1.64Ce_0.04Mn_0.32Al_3.68Si_1.32O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0740 g of SrCO₃0.0185 g, Lu₂O₃0.1632 g of CeO₂0.0034 g of MnCO₃0.0184 g of Al₂O₃0.0938 g of SiO₂0.0397 g of fluorescent powder Ba is put into an agate mortar to be ground and mixed evenly, put into a corundum crucible, covered, put into a high-temperature furnace, sintered for 6 hours at 1420 ℃ in a CO reducing atmosphere, naturally cooled, taken out and fully ground to obtain the fluorescent powder Ba_0.75Sr_0.25Lu_1.64Ce_0.04Mn_0.32Al_3.68Si_1.32O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission of the phosphor in the near infrared region is slightly stronger than that in the visible region.

Example 5:

in this example, according to BaLu_1.68Ce_0.04Mn_0.28Al_3.72Si_1.28O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0987 g Lu₂O₃0.1671 g of CeO₂0.0034 g of MnCO₃0.0161 g of Al₂O₃0.0948 g of SiO₂0.0385 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 8 hours at 1450 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding, further washing, filtering and drying to obtain the fluorescent powder BaLu_1.68Ce_0.04Mn_0.28Al_3.72Si_1.28O₁₂。

Uniformly mixing the cerium-manganese activated single-matrix fluorescent powder with ultra-wideband emission with glue to obtain a mixture;

covering the mixture on the LED chip;

and curing the covered LED chip.

The LED chip adopted in the embodiment is an InGaN semiconductor chip, and the selling enterprise, Shenzhen Shenwanglong technology Limited company with the model number of 450nm blue-light chip; the glue used in this embodiment is mixed glue, and LED package silica gel a/B glue, where glue a and glue B are used in a 1:4 ratio, and a selling enterprise of LED package silica gel a/B glue is shenzhen exwanglong science and technology limited.

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission in the near infrared region of the phosphor of this example is slightly weaker than that in the visible region.

FIG. 4 shows a 1-pc-LED device prepared by combining the fluorescent powder with an LED chip according to the present embodiment, which realizes a light source with high color rendering and low color temperature, and has strong emission in the far-red and near-infrared regions (700-. The LED light source can be used in the fields of indoor illumination, plant illumination, biological monitoring and the like.

Example 6:

in this example, according to Ba_0.75Ca_0.25Lu_1.68Ce_0.08Mn_0.24Al_3.76Si_1.24O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃:0.0740 g of CaCO₃0.0125 g of Lu₂O₃0.1671 g of CeO₂0.0069 g of MnCO₃0.0138 g of Al₂O₃0.0958 g of SiO₂0.0372 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 6 hours at 1380 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding to obtain the fluorescent powder Ba_0.75Ca_0.25Lu_1.68Ce_0.08Mn_0.24Al_3.76Si_1.24O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission in the near infrared region of the phosphor of this example is slightly weaker than that in the visible region.

Example 7:

in this example, according to Ba_0.75Sr_0.20Ca_0.05Lu_1.72Ce_0.04Mn_0.24Al_3.76Si_1.24O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0740 g of SrCO₃0.0148 g of CaCO₃0.0025 g Lu₂O₃0.1711 g of CeO₂0.0034 g of MnCO₃0.0138 g of Al₂O₃0.0958 g of SiO₂0.0372 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 10 hours at 1380 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding to obtain the fluorescent powder Ba_0.75Sr_0.20Ca_0.05Lu_1.72Ce_0.04Mn_0.24Al_3.76Si_1.24O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission in the near infrared region of the phosphor of this example is slightly weaker than that in the visible region.

Example 8:

in this example, according to BaLu_1.76Ce_0.2Mn_0.20Al_3.80Si_1.20O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0987 g Lu₂O₃0.1751 g of CeO₂0.0172 g of MnCO₃0.0115 g, Al₂O₃0.0969 g of SiO₂0.0360 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 6 hours at 1380 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding to obtain the fluorescent powder BaLu_1.76Ce_0.04Mn_0.20Al_3.80Si_1.20O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission in the near infrared region of the phosphor of this example is slightly weaker than that in the visible region.

Example 9:

in this example, according to BaLu_1.72Ce_0.08Mn_0.20Al_3.80Si_1.20O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0987 g Lu₂O₃0.1711 g of CeO₂0.0069 g of MnCO₃0.0115 g, Al₂O₃0.0969 g of SiO₂0.0360 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 6 hours at 1380 ℃ in CO reducing atmosphere, naturally cooling, taking out and fully grinding, further washing, filtering and drying to obtain the fluorescent powder BaLu_1.72Ce_0.08Mn_0.20Al_3.80Si_1.20O₁₂。

The crystal structure of this example is similar to that of example 3, the light emission intensity is slightly weaker than that of example 3, and the light emission of the phosphor in the near infrared region is weaker than that in the visible region.

Example 10:

in this example, according to BaLu_1.80Ce_0.04Mn_0.16Al_3.84Si_1.16O₁₂Weighing BaCO according to the stoichiometric ratio of the chemical elements₃0.0987 g Lu₂O₃0.1791 g of CeO₂0.0034 g of MnCO₃0.0092 g, Al₂O₃0.0979 g of SiO₂0.0348 g, grinding and mixing evenly in an agate mortar, putting into a corundum crucible, covering, putting into a high-temperature furnace, sintering for 6 hours at 1380 ℃ in a CO reducing atmosphere, naturally cooling, taking out and fully grinding to obtain the fluorescent powder BaLu_1.80Ce_0.04Mn_0.16Al_3.84Si_1.16O₁₂。

It is obvious that the above embodiments are only intended to illustrate the way of implementing ultra-wideband emission and multifunctional 1-pc-LEDs of the present invention, and that other variations and modifications are possible on the basis of the above description. Thus, obvious variations and modifications of the invention as herein set forth are intended to be within the scope of the present invention.