CN113355095B - Near infrared fluorescent powder, preparation method thereof and light-emitting device for supplementing light to dragon fruits - Google Patents
Near infrared fluorescent powder, preparation method thereof and light-emitting device for supplementing light to dragon fruits Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The invention discloses near infrared fluorescent powder, which has a chemical general formula of (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 X is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.04, wherein Cr 3+ Is the luminescence center. The invention also discloses a preparation method of the near infrared fluorescent powder and a light-emitting device for supplementing light to the dragon fruits. The near infrared fluorescent powder has high quantum efficiency, good thermal quenching property, good chemical physical stability and perfect half-peak width of an emission spectrum, and can be used for providing far-red illumination for plants in a light-emitting device, accelerating photosynthesis of the dragon fruits in a weak light stage, shortening the nutrition growth period of the dragon fruits, having good flower forcing effect on the dragon fruits, and being also used in the fields of laser illumination and the like.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to near infrared fluorescent powder, a preparation method thereof and a luminescent device for supplementing light to dragon fruits.
Background
The light is the energy which is necessary to be absent in the plant growth process, the nutrient growth period of the plant can be shortened through light supplementing, the flowering phase and the fruit phase are regulated and controlled, the quality of fruits is improved, and the yield of agricultural products is improved. Therefore, the plant light supplementing technology has been widely applied in the production fields of flowers, fruits, vegetables and the like. In order to meet the high-efficiency and high-quality production of crops, various artificial light sources are developed and utilized. Conventional, more common are incandescent, high pressure sodium, fluorescent, metal halide, etc. These plant lamps are used in various fields such as indoor flower and vegetable planting, and generally use high-pressure sodium lamps and metal halide lamps due to their respective characteristics. However, the traditional light sources of the optical device are all continuous composite spectrums, parameters such as light quality proportion and the like cannot be regulated, so that a considerable part of spectrum energy is wasted, and part of light quantity escapes in the using process, so that the environment factors for accurately regulating and controlling plant growth are not facilitated.
The dragon fruit is a fruit industry with high economic benefit, and the artificial light supplementing has been applied to the commercial planting of the dragon fruit on a large scale, and has great promotion effects on promoting the flower formation, the fruit quality and the annual production of the dragon fruit. However, the types of light emitting devices for supplementing light to the dragon fruit in the prior art are few, and the defects of short service life, non-adjustable spectrum, high energy consumption and the like of the traditional fluorescent lamp and the incandescent lamp lead to higher light supplementing cost of the present dragon fruit. Therefore, the commercial planting industry of dragon fruits is in urgent need for light conversion materials and light emitting devices capable of promoting the flower formation of dragon fruits and improving the quality of the fruits.
In the prior art, cr is used as 3+ Infrared phosphors, which are luminescent centers, are used in plant illumination. For example, application number 201910022825.6 the chinese patent application discloses a lighting device for plant illumination. While 201910022825.6 has a narrow half-peak width, the absorption efficiency of the plant far-red light absorption type photosensitive pigment needs to be further improved; but other existing Cr 3+ The half-width of the infrared fluorescent powder serving as a luminescence center is generally pursued to be maximized, which leads to lower luminous efficiency. Most importantly, cr 3+ Almost to be calcined in a reducing atmosphere to maintain trivalent chromium ions Cr 3+ Is stable in valence state, but part of trivalent chromium ion Cr 3+ Is still reduced to tetravalent chromium ion Cr 4+ The luminous efficiency in the range of 700-800nm will be further reduced.
Disclosure of Invention
The invention aims to provide a light conversion material, namely near infrared fluorescent powder, which can be used for shortening the nutrition growth period of the dragon fruit and promoting flower and protecting fruit in the planting of the dragon fruit, wherein a laser band of the light conversion material extends from 350nm to 720nm, and an emission range of the light conversion material covers from 620nm to 1200nm.
In order to achieve the above purpose, the invention adopts the following technical scheme:
near infrared fluorescent powder with chemical general formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 X is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.04, wherein Cr 3+ Is the luminescence center.
Preferably, x in the chemical formula is 0.01.ltoreq.x.ltoreq.0.2.
Alternatively, y is more than or equal to 0.02 and less than or equal to 0.04 in the chemical formula.
Further, the excitation wavelength is 350nm to 720nm, the emission wavelength is 620nm to 1200nm, the emission peak position is 728nm, and the emission half-width is 107nm.
Another object of the present invention is to provide a method for preparing the near infrared fluorescent powder, which comprises the following steps:
s1: according to the general chemical formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 Weighing raw materials according to the stoichiometric ratio, and grinding and mixing to obtain a raw material mixture;
s2: calcining the raw material mixture in air or reducing atmosphere to obtain a calcined body;
s3: grinding the calcined body into powder to obtain the near infrared fluorescent powder.
In the preparation method, the raw materials comprise a lutetium simple substance or a lutetium-containing compound, a gadolinium simple substance or a gadolinium-containing compound, a gallium simple substance or a gallium-containing compound, an aluminum simple substance or an aluminum-containing compound, a chromium simple substance or a chromium-containing compound.
In the preparation method, in the calcination, the reducing atmosphere can be CO gas or H 2 And N 2 The calcination temperature is 1250-1450 ℃, and the calcination time is 3-7 hours.
It is still another object of the present invention to provide a light emitting device for supplementing light to a dragon fruit, comprising an excitation source and a luminescent material, wherein the luminescent material comprises the near infrared fluorescent powder.
Further, the excitation source is a blue light LED chip or a near ultraviolet light LED chip, and the luminescent material comprises a green light fluorescent powder layer, a red light fluorescent powder layer and a near infrared fluorescent powder layer which are sequentially fixed on the excitation source.
Further, the peak position of the red light fluorescent powder layer is 714-740 nm, and the wavelength of the blue light LED chip is 420-475 nm.
Compared with the prior art, the invention has the beneficial effects that:
the chemical general formula of the invention is (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 The near infrared fluorescent powder has high quantum efficiency, good thermal quenching property, good chemical and physical stability, and half-peak width of an emission spectrum reaching 107nm, can perfectly compound an absorption band of plant photosensitive pigment, is used for supplementing fruits of the dragon fruits, can prolong photosynthesis time of the dragon fruits, can shorten nutrition growth period of the dragon fruits, has good flower forcing effect on the dragon fruits, and finally improves fruit bearing rate.
The chemical general formula of the invention is (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 The near infrared fluorescent powder of (2) can be sintered in air or in reducing atmosphereThe chromium-retaining ion is trivalent and cannot be reduced to tetravalent chromium ion, so that the near infrared fluorescent powder has high quantum efficiency.
The chemical general formula of the invention is (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 The near infrared fluorescent powder has high luminous efficiency and good thermal stability, can be used for far-red illumination of plants in a luminous device, is used for the fields of laser illumination and the like, and can also be used for the fields of nondestructive detection of foods, health monitoring, night vision monitoring and the like.
Comprises the compound of the invention with the chemical general formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 The emission peak position of the near infrared fluorescent powder after encapsulation is red shifted to the vicinity of 732nm from 728nm, and the half-peak width is about 80nm, so that the light-emitting device is perfectly matched with the far-red light absorption band of the plant photosensitive pigment. Therefore, the near infrared fluorescent powder can efficiently convert blue light into far red light to provide far red light illumination for plants.
Drawings
FIG. 1 is an XRD pattern of the near infrared phosphor of example 1 of the present invention;
FIG. 2 is an XRD pattern of the near infrared phosphor of example 2 of the present invention;
FIG. 3 is a graph showing the emission spectrum of the near infrared fluorescent powder of example 1 of the present invention;
fig. 4 is a schematic structural diagram of a light emitting device according to embodiment 10 of the present invention;
FIG. 5 is a graph showing the comparison of the emission spectrum of the near infrared phosphor layer of the light emitting device of embodiment 10 of the present invention with the absorbance spectrum of the phytochrome of the plant;
fig. 6 is a light-emitting effect diagram of the light-emitting device according to embodiment 10 of the present invention;
FIG. 7 is an X-ray photoelectron spectrum of the near infrared phosphor of the present invention;
fig. 8 is a peak splitting process diagram of fig. 7.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Near infrared fluorescent powder with chemical general formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 X is more than or equal to 0.01 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.04, wherein Cr 3+ Is the luminescence center.
As a preferred embodiment of the present invention, x in the chemical formula is 0.01.ltoreq.x.ltoreq.0.2.
As an alternative embodiment of the invention, y is more than or equal to 0.02 and less than or equal to 0.04 in the chemical formula.
The general formula of the invention is (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 The excitation wavelength of the near infrared fluorescent powder with x being more than or equal to 0.01 and less than or equal to 0.2 and y being more than or equal to 0 and less than or equal to 0.04 is 350nm to 720nm. Wherein the excitation peak is mainly 450nm to 618nm. The near infrared fluorescent powder has an emission wavelength of 620nm to 1200nm, an emission peak position of 728nm and an emission half-peak width of 107nm.
The preparation method of the near infrared fluorescent powder comprises the following steps:
s1: according to the general chemical formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 Weighing raw materials according to the stoichiometric ratio, and grinding and mixing to obtain a raw material mixture;
s2: calcining the raw material mixture in air or reducing atmosphere to obtain a calcined body;
s3: grinding the calcined body into powder to obtain the near infrared fluorescent powder.
In the preparation method, the raw materials comprise a lutetium simple substance or a lutetium-containing compound, a gadolinium simple substance or a gadolinium-containing compound, a gallium simple substance or a gallium-containing compound, an aluminum simple substance or an aluminum-containing compound, a chromium simple substance or a chromium-containing compound.
In particular, the lutetium-containing compound can be a lutetium-containing oxide, hydroxide, carbonate, nitrate, halide. The gadolinium-containing compound may be an oxide, hydroxide, carbonate, nitrate, halide containing gadolinium. The gallium-containing compound may be a gallium-containing oxide, hydroxide, carbonate, nitrate, halide. The aluminum-containing compound may be an aluminum-containing oxide, hydroxide, carbonate, nitrate, halide. The chromium-containing compound may be a chromium-containing oxide, hydroxide, carbonate, nitrate, or halide.
In the preparation method, the reducing atmosphere in the calcining gas can be CO gas or H 2 And N 2 The calcination temperature is 1250-1450 ℃, and the calcination time is 3-7 hours.
In a preferred embodiment of the present invention, the raw material or the calcination stage is milled before and after calcination, so that the problems of irregular shape and uneven particle size distribution of the raw material/calcined body can be improved, and the particle size and uniformity of the particle size distribution can be improved. The milling time may be 3min to 1h, preferably 15min-20minn.
At present, the plant lighting device is widely assembled by using semiconductor lamp beads, and cannot be popularized and applied in a large area due to cost limitation. Furthermore, the luminous efficiency of chips of other colors, except for blue chips, is far from proportional to the production cost. In this connection, technical optimization of the plant lighting device is required.
The near infrared fluorescent powder has the characteristic advantages of high quantum efficiency, good temperature quenching property, good chemical and physical stability and perfect half-peak width of an emission spectrum for the absorption of the composite plant photosensitive pigment, and can realize broadband near infrared emission by using light conversion materials of a near blue light chip, a green light chip and a red light chip, thereby being suitable for devices for plant illumination, in particular for a dragon fruit light supplementing device. The near infrared fluorescent powder is used in a light-emitting device, and concretely comprises the following steps:
a light-emitting device for supplementing light to dragon fruits comprises an excitation source and a light-emitting material, wherein the light-emitting material comprises the near infrared fluorescent powder.
As a preferred embodiment of the invention, the excitation source is a blue light LED chip or a near ultraviolet light LED chip, and the luminescent material comprises a green light fluorescent powder layer, a red light fluorescent powder layer and a near infrared fluorescent powder layer which are sequentially fixed on the excitation source.
In the light-emitting device, the peak position of the red light fluorescent powder layer is 714-740 nm, and the wavelength of the blue light LED chip is 420-475 nm.
The preparation method of the light-emitting device provided by the invention comprises the following steps:
and a blue light LED chip (or a near ultraviolet LED chip), a green light fluorescent powder layer, a red light fluorescent powder layer and a near infrared fluorescent powder layer are sequentially arranged on the substrate along the light emitting direction. The green fluorescent powder layer is formed by mixing the existing green fluorescent powder with glue and then coating the mixed glue on a blue light LED chip (or a near ultraviolet LED chip). The red fluorescent powder layer is prepared by mixing the existing red fluorescent powder with glue and then coating the mixed glue on the green fluorescent powder layer. The near infrared fluorescent powder layer is prepared by mixing the near infrared fluorescent powder and glue, and then coating the mixture on the red fluorescent powder layer. Wherein, the glue is preferably epoxy resin or silica gel.
Example 1
Near infrared fluorescent powder with chemical general formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 Where x=0.13 and y=0.
The preparation method of the near infrared fluorescent powder comprises the following steps:
accurately weighing Lu according to the stoichiometric ratio of each element in the chemical formula 2 O 3 ，Gd 2 O 3 ，Ga 2 O 3 ，Al 2 O 3 ，Cr 2 O 3 ，H 3 BO 3 The high-purity powder raw materials are put into an agate mortar for grinding for about 20min, so that the raw materials are fully and uniformly mixed. Transferring the mixed raw materials into a corundum crucible, placing the corundum crucible in an air high-temperature muffle furnace, calcining for 5 hours at 1350 ℃, naturally cooling, taking out, and grinding again for about 10 minutes to obtain (Lu, gd) 3 (Ga,Al) 5 O 12 :0.13Cr 3+ The XRD pattern of the fluorescent powder is shown in figure 1, and the near infrared fluorescent powder is shown as a single body in figure 1A pure phase. The emission spectrum of the fluorescent powder is shown in figure 3.
Example 2
Near infrared fluorescent powder with chemical general formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 Where x=0.13 and y=0.03.
The preparation method of the near infrared fluorescent powder comprises the following steps:
accurately weighing Lu according to the stoichiometric ratio of each element in the chemical formula 2 O 3 ，Gd 2 O 3 ，Ga 2 O 3 ，Al 2 O 3 ，Cr 2 O 3 ，H 3 BO 3 The high-purity powder raw materials are put into an agate mortar for grinding for about 20min, and the raw materials are fully and uniformly mixed. Transferring the mixed raw materials into a corundum crucible, placing in an air high-temperature tube furnace, calcining at 1350 ℃ for 5h, naturally cooling, taking out, and grinding again for about 10 minutes to obtain (Lu, gd) 3 (Ga,Al) 5 O 12 :0.13Cr 3+ ,0.03H 3 BO 3 As shown in FIG. 2, the XRD pattern of the phosphor shows that the near infrared phosphor has a hetero-phase Gd in addition to the main garnet phase 3 BO 3 。
Examples 3 to 9
The procedure was as in example 1, and the chemical formula, calcination temperature, atmosphere and calcination time are shown in Table 1 below.
Table 1 near infrared phosphor formulas and preparation parameters of examples 3-9
Examples 3 to 7 the raw materials were weighed as compounds containing each metal element, and the results were not affected. In which H is not added 3 BO 3 XRD of the examples is in accordance with FIG. 1, H is added 3 BO 3 The example XRD of (2) is identical to figure 2.
Example 10
Referring to fig. 4, a light emitting device for supplementing light to dragon fruits comprises an excitation source and a luminescent material. Specifically, the laser light source includes a substrate 10, and an LED chip 11 fixed on the substrate 10. The LED chip 11 may be a blue LED chip such as a GaN semiconductor chip; but also near ultraviolet LED chips such as InGaN semiconductor chips. In this embodiment, blue LED chips with wavelengths of 420-475 nm are selected.
The luminescent material includes a green phosphor layer 21, a red phosphor layer 22, and a near infrared phosphor layer 23 sequentially fixed on the LED chip 11. Wherein the green phosphor layer 21 can be efficiently excited by the blue light chip, and can be selected from one of sulfide green phosphor, silicate green phosphor, aluminate green phosphor and silicon-based oxynitride. In particular MN 2 S 4 :Eu 2+ (M＝Ba,Sr,Ca),(N＝Al,Ga,In)；(Ba,Sr) 2 SiO 4 :Eu 2+ With Ca2MgSi2O7, eu 2+ ；MSrAl 3 O 7 :Eu 2+ (M＝Y,La,Gd)；β-SiAlON:Eu 2+ 、SrSi 2 O 2 N 2 :Eu 2+ 、SiAlON:Yb 2+ . The red phosphor layer 22 can be efficiently excited by a blue light chip and can be selected from borate phosphor, YVO4 Eu system red phosphor, nitride red phosphor and molybdate red phosphor. Specifically Ca 2 BO 3 Cl:Eu 2+ ；YVO4:Eu；M 2 Si 5 N 8 :Eu 2+ (m=ca, sr, ba). The peak position of the near-red light fluorescent powder layer 22 is 714-740 nm.
The preparation method of the light-emitting device comprises the following steps:
and a blue light LED chip, a green light fluorescent powder layer, a red light fluorescent powder layer and a near infrared fluorescent powder layer are sequentially arranged on the substrate along the light emitting direction. The green fluorescent powder layer is formed by mixing the existing green fluorescent powder with glue and then coating the blue LED chip. The red fluorescent powder layer is prepared by mixing the existing red fluorescent powder with glue and then coating the mixed glue on the green fluorescent powder layer. The near infrared fluorescent powder layer is prepared by mixing the near infrared fluorescent powder and glue, and then coating the mixture on the red fluorescent powder layer. Wherein, the glue is preferably epoxy resin or silica gel.
Example 3
To verify Cr 3+ Whether or not the valence state of (C) is oxidized to Cr 4+ The sample powder was subjected to X-ray photoelectron spectroscopy as shown in fig. 7. As can be seen from fig. 7, the characteristic binding energy of Cr ions at 575.88eV was subjected to peak separation treatment within the characteristic binding energy range, and fig. 8 was obtained. As can be seen from FIG. 8, the peak shapes of 580.9eV and 576.4eV are both Cr 2P3/2, and Cr 2P3/2 is Cr 3+ Nuclear level electrons of (a). Therefore, cr in the preparation process of the near infrared fluorescent powder of the invention 3+ Sintering in air does not oxidize.
The foregoing is a preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, so that the equivalents and modifications can be made without departing from the spirit of the disclosure.
Claims (4)
1. A lighting device for dragon fruit light filling, includes excitation source and luminescent material, its characterized in that: the excitation source comprises a blue light LED chip or a near ultraviolet LED chip,
the luminescent material comprises a green light fluorescent powder layer, a red light fluorescent powder layer and a near infrared fluorescent powder layer which are sequentially fixed on the excitation source,
the chemical general formula of the near infrared fluorescent powder is (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 X is more than or equal to 0.01 and less than or equal to 0.2,0.02, y is more than or equal to 0.04, wherein Cr 3+ Is a luminous center;
the preparation method of the near infrared fluorescent powder comprises the following steps:
s1: according to the general chemical formula (Lu, gd) 3 (Ga,Al) 5 O 12 :xCr 3+ ,yH 3 BO 3 Weighing raw materials according to the stoichiometric ratio, and grinding and mixing to obtain a raw material mixture;
s2: calcining the raw material mixture in a reducing atmosphere to obtain a calcined body;
s3: grinding the calcined body into powder to obtain the near infrared fluorescent powder;
the reducing atmosphere is CO gas or H 2 And N 2 The calcination temperature is 1250-1450 ℃, and the calcination time is 3-7 hours.
2. A light-emitting device according to claim 1, wherein: the excitation wavelength of the near infrared fluorescent powder is 350 nm-720 nm, the emission wavelength is 620 nm-1200 nm, the emission peak position is 728nm, and the emission half-peak width is 107nm.
3. A light-emitting device according to claim 1, wherein: the raw materials comprise lutetium-containing compounds, gadolinium-containing compounds, gallium-containing compounds, aluminum-containing compounds, and chromium-containing compounds.
4. A light-emitting device according to claim 1, wherein: the peak position of the near infrared fluorescent powder layer is 714-740 nm, and the wavelength of the blue LED chip is 420-475 nm.
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