CN111849480A - Infrared phosphor, phosphor composite material and light-emitting device comprising same, and preparation method of phosphor composite material - Google Patents

Infrared phosphor, phosphor composite material and light-emitting device comprising same, and preparation method of phosphor composite material Download PDF

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CN111849480A
CN111849480A CN202010040247.1A CN202010040247A CN111849480A CN 111849480 A CN111849480 A CN 111849480A CN 202010040247 A CN202010040247 A CN 202010040247A CN 111849480 A CN111849480 A CN 111849480A
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phosphor
light
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李恬音
黄文泽
郑巧翎
包真
刘如熹
杨佳伟
吕侊懋
康桀侑
林治民
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Everlight Electronics Co Ltd
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Abstract

The invention provides a fluorescent powder, which is represented by the following general formula (I): ga2‑x‑yO3:xCr3+,ySn4+General formula (I), wherein 0<x is less than or equal to 0.1 and y is less than or equal to 0.1. The invention also provides a fluorescent powder composite material containing the fluorescent powder, a light-emitting device and a method for preparing the fluorescent powder composite material.

Description

Infrared phosphor, phosphor composite material and light-emitting device comprising same, and preparation method of phosphor composite material
Technical Field
The invention relates to a fluorescent powder, in particular to a fluorescent powder taking Ga2O3 as a main body. The invention also relates to an infrared phosphor, a phosphor composite material containing the phosphor, a light-emitting device containing the phosphor composite material, and a preparation method of the phosphor composite material.
Background
With the development of semiconductor technology, light-emitting diodes (LEDs) have been researched into micro-LEDs and sub-millimeter-LEDs (mini-LEDs). The micro-LED is characterized in that the unit size of a chip of a traditional LED is reduced to be smaller than 100 micrometers, the unit size of a chip of a mini-LED is between 100 micrometers and 200 micrometers, and the micro-LED and the mini-LED have the characteristics of high efficiency, high brightness, high reliability, fast reaction time and the like, and have the characteristics of small size, light weight, thinness, energy conservation and the like. However, with the development of micro-LEDs and mini-LEDs, the size of the chip unit is continuously reduced, so that the size of the phosphor material of an LED (pc-LED) using phosphor as a light emitting center faces a bottleneck, because most phosphor particles sintered at high temperature are in the micrometer scale and have the problem of uneven size, easily deriving high scattering effect and poor dispersibility.
Disclosure of Invention
In view of the foregoing technical problems, the present invention provides a phosphor and a phosphor composite material prepared by using the same, wherein the phosphor has excellent light emitting efficiency, and can be loaded on a nano-sized carrier to form the phosphor composite material, so that the particle size of the phosphor composite material reaches a nano-scale, and thus the phosphor can be applied to micro-light emitting devices such as micro-LEDs and mini-LEDs, and can provide excellent light emitting efficiency, and solve the problems of too large size and poor dispersibility of the phosphor.
Accordingly, an object of the present invention is to provide a phosphor represented by the following general formula (I):
Ga2-x-yO3:xCr3+,ySn4+the general formula (I),
wherein x is more than 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1.
In some embodiments of the invention, 0< y ≦ 0.1 in formula (I).
Another objective of the present invention is to provide a phosphor composite material, which comprises a carrier and the phosphor on the surface of the carrier, wherein the carrier is mesoporous oxide nanoparticles (mesoporus oxide nanoparticles).
In some embodiments of the present invention, wherein the vector is selected from the group consisting of: mesoporous Silica Nanoparticles (MSNs), mesoporous titania nanoparticles, mesoporous zinc oxide nanoparticles, and combinations thereof.
In some embodiments of the invention, the particle diameter of the phosphor composite is less than 200 nanometers.
It is still another object of the present invention to provide a method for preparing the phosphor composite material, which comprises the following steps:
based on the element proportion of the general formula (I), weighing precursors for providing elements of the fluorescent powder according to the stoichiometric proportion, and preparing a precursor solution;
mixing the precursor solution with a carrier, and drying to obtain powder; and
and sintering the obtained powder to obtain the fluorescent powder composite material.
In some embodiments of the invention, the sintering process is ramped up to 1000 ℃ to 1500 ℃ at a rate of 2 ℃/minute to 7 ℃/minute and sintering for 1 hour to 10 hours.
Another object of the present invention is to provide a light emitting device, comprising:
a light source capable of emitting light having a wavelength in the range of 350 nm to 650 nm; and
an encapsulation layer comprising the phosphor composite material as described above dispersed therein and disposed such that the phosphor composite material is excitable by light emitted by the light source.
In some embodiments of the present invention, the phosphor composite is excited by light emitted from a light source, emitting light having a wavelength of 650 nm to 1000 nm.
In some embodiments of the invention, the light source may be selected from the group: micro-light emitting diode chip (micro-LED chip), micro-laser diode chip (micro-LD chip), sub-millimeter light emitting diode chip (mini-LED chip), sub-millimeter laser diode chip (mini-LD chip), and combinations thereof.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, some embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a high-resolution transmission electron microscope (HRTEM) image of MSNs;
FIG. 2 is an X-ray diffraction (XRD) pattern of MSNs;
FIG. 3 is an XRD pattern of phosphor composites (GOCS @ MSNs);
FIG. 4 is Ga2O3A schematic diagram of the crystal structure of (a);
FIG. 5 is a HRTEM image of a phosphor composite (GOCS @ MSNs);
FIG. 6 is a Photoluminescence (PL) spectrum and a photoluminescence excitation (PLE) spectrum of the phosphor composite;
FIG. 7 is a PL spectrum of phosphor composites (GOCS @ MSNs) encapsulated in a light emitting device.
Detailed Description
Some embodiments according to the present invention will be described below in detail; as the present invention may be embodied in many different forms without departing from the spirit thereof, the scope of the invention should not be construed as being limited to the specific embodiments set forth herein.
As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the content clearly dictates otherwise.
Unless otherwise indicated, in the present specification and claims, for numerical ranges, between the endpoints of each range and the individual points, and between the individual points may be combined with each other to give one or more new numerical ranges, and such numerical ranges should be considered as being specifically recited in the present specification and claims.
Unless otherwise stated, in the present specification and claims, the wavelength or emission wavelength of the emitted light refers to the peak wavelength (peak wavelength).
Compared with the prior art, the invention has the advantages that the fluorescent powder with the specific composition is provided, and the fluorescent powder with the specific composition and the carrier with the specific size are combined to provide the fluorescent powder composite material which can be applied to micro-devices such as micro-LEDs and mini-LEDs. The following provides a description of the phosphor and phosphor composite material of the present invention and its related applications.
1. Fluorescent powder
The fluorescent powder of the invention is an infrared fluorescent powder, namely, the fluorescent powder which can emit infrared light by being excited by light. The composition of the phosphor of the present invention is represented by the following general formula (I):
Ga2-x-yO3:xCr3+,ySn4+General formula (I).
In the general formula (I), 0< x.ltoreq.0.1, and x may be, for example, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.03, 0.031, 0.032, 0.033, 0.034, 0.035, 0.036, 0.037, 0.038, 0.039, 0.04, 0.041, 0.042, 0.043, 0.044, 0.046, 0.048, 0.049, 0.05, 0.060.060.060, 0.060.043, 0.043, 0.044, 0.045, 0.046, 0.047, 0.084, 0.080.084, 0.080, 0.084, 0.085, 0.080.084, 0.080.080, 0.080.085, 0.080, 0.080.088, 0.080.080, 0.080, 0.080.080, 0.080.088, 0.080, 0.080.080, 0, 0.080.080.080, 0, 0.080.084, 0, 0.087, 0.080.080, 0.088, 0, 0.080, 0.080.080.080.080.080.080.088, 0, 0.080, 0, 0.080.080.080.080.080.087, 0..
In the general formula (I), 0. ltoreq. y.ltoreq.0.1, and preferably 0< y.ltoreq.0.1, and y may be, for example, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.03, 0.031, 0.032, 0.033, 0.034, 0.035, 0.036, 0.037, 0.038, 0.039, 0.04, 0.041, 0.042, 0.043, 0.044, 0.045, 0.046, 0.047, 0.068, 0.069, 0.040.049, 0.041, 0.040.043, 0.080.084, 0.080.080, 0.080, 0.084, 0.080.080.080.084, 0.080.085, 0.080.080.080, 0.080.080.080.080, 0.080, 0.080.080.080, 0, 0.080.080.080.080, 0.080, 0.080.080, 0, 0.080.080.080.088, 0, 0.080.080.080, 0.080.080.080.080, 0.080, 0, 0.080.080.080.080.080.080.080, 0, 0.080, 0.080.080.080.080, 0.080, 0, 0.080.08.
In the phosphor of the present invention, Ga2O3Is a main crystal, and Cr3+And Sn4+Is an activator. Due to Cr3+And Sn4+Has an ionic radius close to Ga3+Ionic radius of (2), thus Cr as an activator3+Or Sn4+Can enter Ga3+In place of Ga3+. In the phosphor of the present invention, the content of the activator is preferably such that the values of x and y in the general formula (I) are within the aforementioned ranges to obtain a preferable light emission intensity.
The phosphor of the present invention can be excited by light having a wavelength of at least 350 nm to 650 nm and can emit light having a wavelength of 650 nm to 1000 nm, such as 651 nm, 655 nm, 660 nm, 665 nm, 670 nm, 675 nm, 680 nm, 685 nm, 690 nm, 695 nm, 700 nm, 705 nm, 710 nm, 715 nm, 720 nm, 725 nm, 730 nm, 735 nm, 740 nm, 745 nm, 750 nm, 755 nm, 760 nm, 765 nm, 770 nm, 775 nm, 780 nm, 785 nm, 790 nm, 795 nm, 800 nm, 805 nm, 810 nm, 815 nm, 820 nm, 825 nm, 830 nm, 915 nm, 840 nm, 845 nm, 850 nm, 855 nm, 860 nm, 865 nm, 870 nm, 875 nm, 880 nm, 885 nm, 890 nm, 895 nm, 900 nm, 905 nm, 910 nm, 915 nm, 920 nm, 925 nm, 930 nm, 935 nm, 940 nm, 945 nm, 950 nm, 955 nm, 960 nm, 965 nm, 970 nm, 975 nm, 980 nm, 985 nm, 990 nm, 995 nm, or 1000 nm.
The method for preparing the phosphor of the present invention is not particularly limited, and can be prepared by any conventional method for preparing a phosphor. The existing methods for preparing phosphor powder include, but are not limited to, solid-state reaction synthesis (solid-state reaction), co-precipitation (co-precipitation method), spray pyrolysis (spray pyrolysis), and sol-gel (sol-gel). In some embodiments of the present invention, the solid state reaction synthesis is exemplified.
2. Phosphor composite material
The fluorescent powder can be formed on a nano-scale carrier, and provides a nano-scale fluorescent powder composite material which can be applied to a micro device. Therefore, the present invention also provides a phosphor composite material comprising the phosphor, the phosphor composite material comprising a carrier and the phosphor on the surface of the carrier, wherein the carrier is mesoporous oxide nanoparticles.
Herein, mesoporous oxide nanoparticles refer to nanoscale oxide particles having a mesoporous structure, and mesoporous refers to pores having a diameter of 2 to 50 nm. Examples of mesoporous oxide nanoparticles include, but are not limited to, Mesoporous Silica Nanoparticles (MSNs), mesoporous titania nanoparticles, and mesoporous zinc oxide nanoparticles. The mesoporous oxide nanoparticles may be used alone or in combination. In the accompanying examples, Mesoporous Silica Nanoparticles (MSNs) were used.
In the present invention, mesoporous oxide nanoparticles may use commercially available mesoporous oxide nanoparticles, or may be prepared by an existing nanomaterial preparation method. The nanomaterial preparation method includes, but is not limited to, an electrochemical deposition method, an electroless plating method, a chemical polymerization method, a sol-gel method, and a chemical vapor deposition method. Taking the preparation of MSNs as an example, firstly, an ammonium compound is dissolved in a solvent to form a solution, a silane compound is dropped into the solution under an oil bath to perform a reaction, to obtain a mixed solution containing nano silica, then the mixed solution is centrifuged, and the obtained solid is dried, ground and calcined, to obtain MSNs.
The particle diameter of the phosphor composite material of the present invention is less than 200 nm, such as 195 nm, 190 nm, 185 nm, 180 nm, 175 nm, 170 nm, 165 nm, 160 nm, 155 nm, 150 nm, 145 nm, 140 nm, 135 nm, 130 nm, 125 nm, 120 nm, 115 nm, 110 nm, 105 nm, 100 nm, 95 nm, 90 nm, 85 nm, 80 nm, 75 nm, 70 nm, 65 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 5 nm, or 1 nm, so that the phosphor composite material is particularly suitable for micro light emitting devices such as micro-LEDs and mini-LEDs.
3. Preparation method of fluorescent powder composite material
The invention also provides a method for preparing the fluorescent powder composite material, which comprises the following steps: based on the element proportion of the general formula (I), weighing precursors for providing elements of the fluorescent powder according to the stoichiometric proportion, and preparing a precursor solution; mixing the precursor solution with a carrier, and drying to obtain powder; and carrying out high-temperature sintering treatment on the obtained powder to obtain the fluorescent powder composite material.
The precursors of the elements of the phosphor comprise a compound containing gallium (Ga), a compound containing chromium (Cr), and optionally a compound containing tin (Sn). Gallium (Ga) -containing compounds include, but are not limited to, compounds containingOxides of gallium (Ga) (e.g. Ga)2O3) Carbonates (e.g. Ga)2(CO3)3) Nitrate (e.g. Ga (NO))3)3) And halides (e.g., GaCl)3). Compounds containing chromium (Cr) include, but are not limited to, oxides containing chromium (Cr) (e.g., Cr)2O3) Carbonates (e.g. Cr)2(CO3)3) Nitrate (e.g. Cr (NO))3)3) And halides (e.g., CrCl)3). Tin (Sn) -containing compounds include, but are not limited to, tin (Sn) -containing oxides (e.g., SnO2) Carbonates (e.g. Sn (CO))3)2) Nitrate (e.g. Sn (NO))3)4) And halides (e.g., SnCl) 2). The compounds of the foregoing elements may be used alone or in combination of two or more thereof as precursors of the respective elements. In the examples that follow, gallium nitrate (Ga (NO) is used3)3) Chromium nitrate (Cr (NO)3)3) And stannous chloride (SnCl)2) Used as the precursor of each element of the fluorescent powder.
Generally, the molar concentration of the precursor solution is proportional to the amount of the phosphor finally formed on the carrier, and thus, increasing the molar concentration of the precursor solution increases the intensity of the light emitted from the phosphor composite material. In a preferred embodiment of the method of the present invention, the molar concentration of the precursor solution is 0.1M to 5M. In addition, when the precursor solution and the carrier are mixed, the mixing ratio of the carrier to the precursor solution is preferably 100 mg: 1 ml to 100 mg: 10 ml.
After the precursor solution is mixed with the carrier, the obtained mixed solution can be dried into powder by any existing mode, and further sintered at high temperature to form the fluorescent powder composite material. In some embodiments of the present invention, the mixed solution obtained after mixing the precursor solution and the carrier is dried in an oven at a temperature of 60 ℃ to 100 ℃, further ground into powder, and finally placed in a crucible for sintering, wherein the sintering condition is that the temperature is raised to 1000 ℃ to 1500 ℃ at a rate of 2 ℃/min to 7 ℃/min, and the sintering is performed for 1 hour to 10 hours.
4. Light emitting device
The fluorescent powder composite material can be applied to a light-emitting device. Accordingly, the present invention also provides a light emitting device comprising a light source and an encapsulation layer in which the phosphor composite as described above is dispersed, wherein the light source can emit light having a wavelength in the range of 350 nm to 650 nm, and the encapsulation layer is disposed such that the phosphor composite can be excited by the light emitted by the light source. In some embodiments of the present invention, the phosphor composite material may be excited by light emitted from a light source to emit light having a wavelength of 650 nm to 1000 nm.
In the light emitting device of the present invention, the light source may be one or more selected from the following group: a micro light emitting diode chip, a micro laser diode chip, a sub-millimeter light emitting diode chip, and a sub-millimeter laser diode chip. The microchip is a chip with a chip unit size of less than 100 micrometers, and the submillimeter chip is a chip with a chip unit size of 100 micrometers to 200 micrometers. The types of the chips may be, for example, horizontal chips, vertical chips or flip-chip (flip-chip-type) chips, but the invention is not limited thereto, and those skilled in the art can select the appropriate chip type according to the needs. Specific examples of light sources include, but are not limited to, GaN as a micro-LED chip, GaN as a micro-laser diode chip, GaN as a sub-millimeter LED chip, GaN as a sub-millimeter laser diode chip, InGaN as a micro-LED chip, InGaN as a sub-millimeter laser diode chip, InAlGaN as a micro-LED chip, InAlGaN as a micro-laser diode chip, InAlGaN as a sub-millimeter laser diode chip, SiC as a micro-LED chip, SiC as a sub-millimeter LED chip, ZnSe as a micro-laser diode chip, ZnSe as a sub-millimeter LED chip, ZnSe as a sub-millimeter laser diode chip, BN as a micro-laser diode chip, BN is a sub-millimeter light emitting diode chip, BN is a sub-millimeter laser diode chip, BAlGaN is a micro light emitting diode chip, BAlGaN is a micro laser diode chip, BAlGaN is a sub-millimeter light emitting diode chip, and BAlGaN is a sub-millimeter laser diode chip.
In the light emitting device of the present invention, the encapsulating layer covers the light source to provide an encapsulating function, and the phosphor composite material is dispersed therein. The material of the encapsulating layer is not particularly limited, and may be any optical encapsulating material existing in the technical field of the present invention, such as epoxy resin, silicone resin (silicone), etc., but the present invention is not limited thereto. In the following examples, silicone is used as the material of the encapsulation layer.
The ratio of the optical packaging material to the phosphor composite material in the packaging layer is not particularly limited, and may be generally 3: 1 to 1: 3, e.g. 2.5: 1. 2: 1. 1.5: 1. 1: 1. 1: 1.5, 1: 2. or 1: 2.5, when the content ratio of the encapsulating material to the phosphor composite material is within the above range, the light emitting device can have favorable light emitting intensity and light emitting efficiency.
In addition, the distribution of the phosphor composite material in the encapsulating layer may be uniform or non-uniform, for example, it may exhibit a gradient change or a continuous change with increasing or decreasing content along the thickness direction of the encapsulating layer. Generally speaking, the higher the content of the phosphor composite material in the encapsulation layer is, the thinner the thickness of the formed encapsulation layer can be and the higher the density is, which is beneficial to the heat dissipation of the light-emitting device and reduces the occurrence probability of cracks of the encapsulation layer, thereby improving the light-emitting efficiency of the light-emitting device. The lower the content of the fluorescent powder composite material in the packaging layer is, the more transparent the formed packaging layer is, the larger distance between adjacent light sources in later-stage processing is facilitated, the precision requirement of cutting and separating the light source covered with the packaging layer is reduced, and therefore the reliability and the uniformity of the device are improved. Therefore, by making the phosphor composite material in the encapsulation layer present gradient concentration, for example, the phosphor composite material in the encapsulation layer portion close to the light source has higher concentration, and the phosphor composite material in the encapsulation layer portion far from the light source has lower concentration, which not only can improve the light emitting efficiency, but also is beneficial to the later process.
The preparation method of the light emitting device of the present invention is not particularly limited, and the following embodiments are specifically illustrated and not described herein.
The light emitting device of the present invention can be applied to a remote controller, an automobile sensor, iris recognition, face detection, a medical detection device, a biomedical image device, and the like, but the present invention is not limited thereto.
The invention is further illustrated by the following specific embodiments.
5. Examples of the embodiments
5.1. Preparation of Mesoporous Silica Nanoparticles (MSNs)
5.728 g of cetyltrimethylammonium bromide (CTAB) is dissolved in 280 ml of deionized water and 80 ml of alcohol, and then 0.5 ml of ammonia (NH) is added4OH) aqueous solution, and uniformly stirred for 30 minutes to obtain a mixed solution. The mixed solution was stirred for 30 minutes under an oil bath at 60 ℃ and 14.6 ml of Tetraethoxysilane (TEOS) was slowly dropped thereto, followed by uniform stirring to effect a reaction for 2 hours. Then, the mixed solution is placed in a centrifuge tube, absolute methanol and deionized water (volume ratio is 1: 1) are used for washing and centrifuging for three times, and white solid obtained after centrifugation is placed in an oven at 80 ℃ for drying for 12 hours. And grinding the dried white solid into powder, placing the powder in a boat-shaped crucible, raising the temperature to 550 ℃ at the rate of 5 ℃ per minute, calcining the powder for 5 hours, and naturally cooling the powder to room temperature to obtain the MSNs.
The MSNs were analyzed using XRD and HRTEM, and the results are shown in fig. 1 and 2, where fig. 1 is a graph of HRTEM of MSNs, and fig. 2 is a graph of XRD of MSNs. As shown in fig. 1, it can be seen that MSNs are spherical in appearance and have a particle size of 75 nm. As shown in FIG. 2, it can be seen that the crystal structure of MSNs is SiO2The crystal structures of the MSNs are consistent, so that the crystal structure of the MSNs can be judged to be SiO2。
5.2. Preparation of phosphor composite material
0.5 ml of 1M gallium nitrate (Ga (NO)3)3) Solution, 0.2 ml of 0.05M chromium nitrate (Cr (NO)3)3) Solution, 0.05 ml of 0.05M stannous chloride (SnCl)2) The solution is mixed evenly to prepare precursor solution.The precursor solution was mixed with 100 mg of MSNs and dried in an oven at 80 ℃ to give a white solid. Grinding the white solid into powder, placing the powder in a small crucible, raising the temperature to 1200 ℃ at a heating rate of 5 ℃ per minute, sintering the powder for 5 hours, and naturally cooling the temperature to room temperature to obtain the phosphor composite material (GOCS @ MSNs), wherein the chemical structure of the phosphor can be represented by the following formula: ga1.95O3:0.04Cr3+,0.01Sn4+。
The phosphor composite was analyzed using XRD and HRTEM, and the results are shown in fig. 3 and 5, where fig. 3 is a graph of XRD of the phosphor composite (GOCS @ MSNs), and fig. 5 is a graph of HRTEM of the phosphor composite (GOCS @ MSNs). As can be seen from FIG. 3, the phosphor composite has Ga 2O3The crystal structure of (2) is a triclinic system (triclinic crystal system) as illustrated in fig. 4. As can be seen from FIG. 5, the phosphor composite material has a cylindrical appearance and a particle size of 40 nm.
In addition, PL/PLE spectra (instrument model: FluoroMax-3, available from HORIBA) of the phosphor composite were measured, and the results are shown in FIG. 6. As shown in FIG. 6, a light source with a wavelength of 460 nm is used to excite the phosphor composite material, the light emission range of the phosphor composite material is 650 nm to 850 nm, and the peak of the emitted light is 700 nm (2E→4A2) And a full width at half maximum (FWHM) of 85 nm. In addition, the excitation wave band of 700 nm of the phosphor composite material is measured to obtain an excitation range of 350 nm to 650 nm and an excitation wave peak of 440 nm (S) ((S))4A2→4T1) And 605 nm (4A2→4T2)。
5.3. Preparation of light-emitting devices
The prepared phosphor composite material and the mini-LED chip are used for preparing a light-emitting device, and the preparation method is as follows. First, a blue GaN chip having a size of 9 × 5 mils (mil) and an emission peak of 473 nm was prepared as a light source. And bonding the light source on the substrate. Then, the prepared fluorescent powder composite material and silicone resin are mixed in a proportion of 1: 1, and covering the mixture on a light source in a dispensing manner. The light source covered with the mixture is dried to harden the mixture into an encapsulation layer, resulting in a light emitting device. The drying is started from normal temperature, the temperature is raised to 60 ℃ at the temperature rising rate of 10 ℃ per minute and is kept for 1 hour, then the temperature is raised to 150 ℃ at the temperature rising rate of 10 ℃ per minute and is kept for 3 hours, and then furnace cooling is carried out.
PL spectra (instrument type: FluoroMax-3, available from HORIBA) of the light-emitting device were measured, and the results are shown in FIG. 7. As shown in fig. 7, the peak of the light emitted from the light emitting device was 740 nm and the full width at half maximum was 145 nm.
The above embodiments are merely illustrative of the principles and effects of the present invention, and illustrate the technical features of the present invention, but do not limit the scope of the present invention. Any changes or arrangements which can be easily made by those skilled in the art without departing from the technical principle and spirit of the present invention shall fall within the scope of the present invention. Accordingly, the scope of the invention is as set forth in the following claims.

Claims (10)

1. A phosphor represented by the following general formula (I):
Ga2-x-yO3:xCr3+,ySn4+the general formula (I),
wherein x is more than 0 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1.
2. The phosphor of claim 1, wherein 0< y ≦ 0.1.
3. A phosphor composite material comprising a support and the phosphor of claim 1 on the surface of said support, wherein said support is a mesoporous oxide nanoparticle.
4. The phosphor composite of claim 3, wherein the carrier is selected from the group of: mesoporous silica nanoparticles, mesoporous titania nanoparticles, mesoporous zinc oxide nanoparticles, and combinations thereof.
5. The phosphor composite of claim 3, wherein the particle diameter of the phosphor composite is less than 200 nanometers.
6. A method of making the phosphor composite of any of claims 3 to 5, comprising the steps of:
based on the element proportion of the general formula (I), weighing precursors for providing elements of the fluorescent powder according to the stoichiometric proportion, and preparing a precursor solution;
mixing the precursor solution with a carrier, and drying to obtain powder; and
and sintering the obtained powder to obtain the fluorescent powder composite material.
7. The production method according to claim 6, wherein the sintering treatment is heating up to 1000 ℃ to 1500 ℃ at a rate of 2 ℃/min to 7 ℃/min, and sintering for 1 hour to 10 hours.
8. A light emitting device, comprising:
a light source that can emit light having a wavelength in a range of 350 to 650 nanometers; and
an encapsulation layer comprising the phosphor composite of any of claims 3 to 5 dispersed therein and disposed such that the phosphor composite is excitable by light emitted by the light source.
9. The light emitting device of claim 8, wherein the phosphor composite is excitable by light emitted by the light source, emitting light at a wavelength of 650 nanometers to 1000 nanometers.
10. The light emitting device of claim 8, wherein the light source is selected from the group of: a micro light emitting diode chip, a micro laser diode chip, a sub-millimeter light emitting diode chip, a sub-millimeter laser diode chip, and combinations thereof.
CN202010040247.1A 2019-04-26 2020-01-15 Infrared phosphor, phosphor composite material and light-emitting device comprising same, and preparation method of phosphor composite material Pending CN111849480A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115595152A (en) * 2022-10-20 2023-01-13 杭州电子科技大学（Cn） Near-infrared emission enhanced Ga 2 O 3 ：Cr 3+ Luminescent material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1500367A (en) * 2001-03-29 2004-05-26 ��ʿ��Ƭ��ʽ���� Electrolumine scence device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1500367A (en) * 2001-03-29 2004-05-26 ��ʿ��Ƭ��ʽ���� Electrolumine scence device

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
S. HARINATH BABU等: "Microstructure,ferromagnetic and photoluminescence properties of ITO and Cr doped ITO nanoparticles using solid state reaction", 《PHYSICA B》 *
TOSHIHIRO MIYATA等: "Gallium oxide as host material for multicolor emitting phosphors", 《JOURNAL OF LUMINESCENCE》 *
ZHANJUN LI等: "In Vivo Repeatedly Charging Near-Infrared-Emitting Mesoporous SiO2/ZnGa2O4 :Cr3+ Persistent Luminescence Nanocomposites", 《ADV. SCI》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115595152A (en) * 2022-10-20 2023-01-13 杭州电子科技大学（Cn） Near-infrared emission enhanced Ga 2 O 3 ：Cr 3+ Luminescent material and preparation method thereof
CN115595152B (en) * 2022-10-20 2023-09-12 杭州电子科技大学 Ga with near infrared emission enhancement 2 O 3 ：Cr 3+ Luminescent material and preparation method thereof

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