CN113355095A - Near-infrared fluorescent powder, preparation method thereof and light-emitting device for supplementing light to pitaya - Google Patents
Near-infrared fluorescent powder, preparation method thereof and light-emitting device for supplementing light to pitaya Download PDFInfo
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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
- 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
- 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
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- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
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Abstract
本发明公开了一种近红外荧光粉，其化学通式为(Lu,Gd)3(Ga,Al)5O12:xCr3+,yH3BO3，0.01≤x≤0.2，0≤y≤0.04，其中Cr3+为发光中心。本发明还公开了上述近红外荧光粉的制备方法以及用于火龙果补光的发光装置。本发明的近红外荧光粉的量子效率高、热猝灭性质良好、化学物理稳定性好、发射光谱半峰宽完美复合植物光敏色素的吸收带，用于发光器件中可以给予植物远红光照明，能够加速火龙果在弱光阶段的光合作用，可以缩短火龙果营养生长周期，对火龙果有很好的催花效果，同时还可用于激光照明等领域中。
The invention discloses a near-infrared fluorescent powder whose chemical formula is (Lu, Gd) 3 (Ga, Al) 5 O 12 : xCr 3+ , yH 3 BO 3 , 0.01≤x≤0.2, 0≤y≤ 0.04, in which Cr 3+ is the luminescent center. The invention also discloses a preparation method of the above-mentioned near-infrared fluorescent powder and a light-emitting device used for light supplement of dragon fruit. The near-infrared fluorescent powder of the present invention has high quantum efficiency, good thermal quenching properties, good chemical and physical stability, and the half-peak width of the emission spectrum is perfectly combined with the absorption band of plant phytochromes, and can be used in light-emitting devices to give plants far-red illumination. , can accelerate the photosynthesis of dragon fruit in the low light stage, can shorten the vegetative growth cycle of dragon fruit, has a good flower-inducing effect on dragon fruit, and can also be used in fields such as laser lighting.
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 pitaya.
Background
The light is energy which is not needed in the plant growth process, the vegetative growth cycle of the plant can be shortened through light supplement, the flowering phase and the fruit phase are regulated and controlled, the fruit quality is improved, and the yield of agricultural products is improved. Therefore, the plant light supplement technology is widely applied to the production fields of flowers, fruits, vegetables and the like. In order to meet the requirement of high-efficiency and high-quality production of crops, various artificial light sources are developed and utilized. Incandescent lamps, high-pressure sodium lamps, fluorescent lamps, metal halide lamps, etc. are more common. These several plant factory lamps are applied to various fields due to their respective characteristics, such as indoor flower and vegetable planting, in which a high pressure sodium lamp and a metal halide lamp are generally used. However, the light source of the traditional optical device is a continuous composite spectrum, parameters such as light-quality ratio and the like cannot be regulated, so that a considerable part of spectral energy is wasted, part of light quantity escapes in the using process, and the environmental factors for accurately regulating and controlling the growth of plants are not facilitated.
The dragon fruit is a fruit industry with high economic benefit, and the artificial supplementary lighting is applied to the commercial planting of the dragon fruit on a large scale, so that the method has great promotion effect on promoting the flower formation, the fruit quality and the annual production of the dragon fruit. However, in the prior art, the light-supplementing cost of the dragon fruit is higher due to the defects of few types of light-emitting devices for supplementing light to the dragon fruit, short service life of the traditional fluorescent lamp and incandescent lamp, non-adjustable spectrum, high energy consumption and the like. Therefore, there is a need for a light conversion material and a light emitting device that can promote the formation of flowers and improve the quality of fruits of pitaya.
In the prior art, Cr is already used3+The infrared fluorescent powder as the luminous center is used for plant illumination. For example, chinese patent application No. 201910022825.6 discloses a light emitting device for plant lighting. 201910022825.6, the half-peak width of the Chinese patent is narrow, and the absorption efficiency of the plant far-red light absorption type photosensitive pigment needs to be further improved; but other existing Cr3+The infrared phosphor for the luminescence center generally strives for maximum half-peak width, which results in lower luminescence efficiency. Most importantly, Cr3+Calcination in a reducing atmosphere is almost required to maintain the trivalent chromium ions Cr3+Is stable, but part of the trivalent chromium ions Cr3+Is still reduced into tetravalent chromium ion Cr4+The luminous efficiency in the range of 700-800nm will be further reduced.
Disclosure of Invention
One of the purposes of the invention is to provide a light conversion material, namely near-infrared fluorescent powder, which can be used for shortening the vegetative growth cycle of the dragon fruits and promoting flower and fruit retention in the planting of the dragon fruits, wherein the laser band extends from 350nm to 720nm, and the emission range covers from 620nm to 1200 nm.
In order to achieve the purpose, the invention adopts the following technical scheme:
a near infrared fluorescent powder with chemical formula of (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3X 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 is3+Is a luminescent center.
Preferably, x in the chemical formula is 0.01 ≦ x ≦ 0.2.
Alternatively, y is 0.02 ≦ y ≦ 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-peak width is 107 nm.
The invention also aims to provide a preparation method of the near-infrared fluorescent powder, which comprises the following steps:
s1: according to the general chemical formula (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3Weighing the 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: and grinding the calcined body into powder to obtain the near-infrared fluorescent powder.
In the preparation method, the raw materials comprise lutetium elementary substance or lutetium-containing compound, gadolinium elementary substance or gadolinium-containing compound, gallium elementary substance or gallium-containing compound, aluminum elementary substance or aluminum-containing compound, chromium elementary substance or chromium-containing compound.
In the preparation method, in the calcination, the reducing atmosphere can be CO gas or H2And N2The calcining temperature is 1250-1450 ℃, and the calcining time is 3-7 hours.
The invention further aims to provide a light-emitting device for supplementing light to pitaya, which comprises an excitation source and a light-emitting material, wherein the light-emitting material comprises the near-infrared fluorescent powder.
Further, the excitation source is a blue light LED chip or a near ultraviolet 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.
Furthermore, 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)5O12:xCr3+,yH3BO3The near-infrared fluorescent powder has the advantages of high quantum efficiency, good thermal quenching property, good chemical and physical stability, emission spectrum half-peak width of 107nm, perfect composite of absorption bands of plant phytochrome, fruit supplementation for pitaya, prolongation of the photosynthesis time of the pitaya, shortening of the vegetative growth period of the pitaya, good flower forcing effect on the pitaya and finally improvement of the fruit bearing rate.
The chemical general formula of the invention is (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3The near-infrared fluorescent powder can ensure that chromium ions are trivalent and cannot be reduced into tetravalent chromium ions no matter the near-infrared fluorescent powder is sintered in air or reducing atmosphere, so that the near-infrared fluorescent powder has high quantum efficiency.
The chemical general formula of the invention is (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3The near-infrared fluorescent powder has high luminous efficiency and good thermal stability, can be used for illuminating plants with far-red light in a luminescent device, is used in the fields of laser illumination and the like, and can also be used in the fields of food nondestructive testing, health monitoring, night vision monitoring and the like.
Comprises the chemical formula of (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3The emission peak position of the near-infrared fluorescent powder is red shifted to be near 732nm from 728nm after the near-infrared fluorescent powder is packaged, the half-peak width is about 80nm, and the emission peak position 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 for plants.
Drawings
FIG. 1 is an XRD pattern of a 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 an emission spectrum of a near-infrared phosphor according to example 1 of the present invention;
fig. 4 is a schematic structural view of a light-emitting device according to embodiment 10 of the present invention;
fig. 5 is a graph showing the emission spectrum of the near-infrared phosphor layer of the light-emitting device according to embodiment 10 of the present invention and the absorption spectrum of the phytochrome of the plant;
fig. 6 is a graph showing the light emitting effect 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 graph of the peak separation process of fig. 7.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in 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 obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
A near infrared fluorescent powder with chemical formula of (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3X 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 is3+Is a luminescent 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 0.02. ltoreq. y.ltoreq.0.04 in the chemical formula.
The general formula of the invention is (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3X is more than or equal to 0.01 and less than or equal to 0.2, and y is more than or equal to 0 and less than or equal to 0.04, and the excitation wavelength of the near-infrared fluorescent powder is 350nm to 720 nm. Wherein the excitation peak is mainly 450nm to 618 nm. The emission wavelength of the near-infrared fluorescent powder is 620nm to 1200nm, the emission peak position is 728nm, and the emission half-peak width is 107 nm.
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)5O12:xCr3+,yH3BO3Weighing the 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: and grinding the calcined body into powder to obtain the near-infrared fluorescent powder.
In the preparation method, the raw materials comprise lutetium elementary substance or lutetium-containing compound, gadolinium elementary substance or gadolinium-containing compound, gallium elementary substance or gallium-containing compound, aluminum elementary substance or aluminum-containing compound, chromium elementary substance or chromium-containing compound.
Specifically, 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 an oxide, hydroxide, carbonate, nitrate, halide, of gallium. 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, halide.
In the preparation method, in the calcining gas, the reducing atmosphere can be CO gas or H gas2And N2The calcining temperature is 1250-1450 ℃, and the calcining time is 3-7 hours.
In a preferred embodiment of the present invention, the raw material or the calcination stage is ground before and after calcination in the production method, whereby the problems of irregular shape and uneven particle size distribution of the raw material/calcined body can be solved, and the particle size and uniformity of the particle size distribution can be improved. The milling time may be 3min to 1h, preferably 15min to 20 minn.
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. Moreover, the light emitting efficiency of the chips of other colors besides the blue light chip is far from being proportional to the production cost. For this, technical optimization of the plant lighting device is required.
The near-infrared fluorescent powder has the characteristics of high quantum efficiency, good temperature quenching property, good chemical and physical stability and perfect absorption of the composite plant photosensitive pigment with perfect half-peak width of an emission spectrum, can use light conversion materials of a near-blue light chip, a green light chip and a red light chip to realize broadband near-infrared emission, and is suitable for devices for plant illumination, particularly dragon fruit light supplementing devices. The near-infrared fluorescent powder is used in a light-emitting device, and specifically comprises the following components:
a light-emitting device for supplementing light to pitaya 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 present invention, the excitation source is a blue light LED chip or a near ultraviolet light LED chip, and the luminescent material includes a green phosphor layer, a red phosphor layer, and a near infrared phosphor 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:
the substrate is sequentially provided with 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 along the light emitting direction. The green light fluorescent powder layer is formed by mixing existing green light fluorescent powder and glue and then coating the mixture on a blue light LED chip (or a near ultraviolet light LED chip). The red light fluorescent powder layer is formed by mixing existing red light fluorescent powder with glue and then coating the mixture on the green light 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-light fluorescent powder layer. Wherein, the glue is preferably epoxy resin or silica gel.
Example 1
A near infrared fluorescent powder with chemical formula of (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3Wherein x is 0.13 and y is 0.
The preparation method of the near-infrared fluorescent powder comprises the following steps:
according to the stoichiometric ratio of each element in the chemical formula, accurately weighing Lu2O3，Gd2O3，Ga2O3，Al2O3，Cr2O3，H3BO3And (3) putting the high-purity powder raw material into an agate mortar for grinding for about 20min, and fully and uniformly mixing the raw materials. Transferring the mixed raw materials into a corundum crucible, placing the corundum crucible into an air high-temperature muffle furnace, calcining for 5h at 1350 ℃, naturally cooling, taking out, grinding again for about 10 minutes to obtain (Lu, Gd)3(Ga,Al)5O12:0.13Cr3+The XRD pattern of the phosphor is shown in figure 1, and the near-infrared phosphor is a single pure phase as can be seen from figure 1. The emission spectrum of the phosphor is shown in fig. 3.
Example 2
A near infrared fluorescent powder with chemical formula of (Lu, Gd)3(Ga,Al)5O12:xCr3+,yH3BO3Wherein x is 0.13 and y is 0.03.
The preparation method of the near-infrared fluorescent powder comprises the following steps:
according to the stoichiometric ratio of each element in the chemical formula, accurately weighing Lu2O3，Gd2O3，Ga2O3，Al2O3，Cr2O3，H3BO3And (3) putting the high-purity powder raw material into an agate mortar for grinding for about 20min, and fully and uniformly mixing the raw materials. Transferring the mixed raw materials into a corundum crucible, placing the corundum crucible into a high-temperature tube furnace of air, calcining for 5h at 1350 ℃, naturally cooling, taking out, grinding again for about 10 minutes to obtain (Lu, Gd)3(Ga,Al)5O12:0.13Cr3+,0.03H3BO3The XRD pattern of the phosphor is shown in FIG. 2, which shows that the near infrared phosphor has a hetero-phase Gd in addition to the original garnet main phase3BO3。
Examples 3 to 9
The preparation procedure was the same as in example 1, and the chemical formula, calcination temperature, atmosphere and calcination time were as shown in Table 1 below.
TABLE 1 chemical formulas and preparation parameters of the NIR phosphors 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 no H is added3BO3XRD of examples consistent with FIG. 1 with addition of H3BO3Example XRD consistent with figure 2.
Example 10
Referring to fig. 4, a light emitting device for supplementing light to dragon fruit includes 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; or a near ultraviolet LED chip, such as an InGaN semiconductor chip. In the embodiment, a blue LED chip with a wavelength of 420-475 nm is selected.
The luminescent material comprises a green phosphor layer 21, a red phosphor layer 22 and a near-infrared phosphor layer 23 which are sequentially fixed on the LED chip 11. The green phosphor layer 21 can be efficiently excited by a blue chip, and can be one selected from sulfide green phosphor, silicate green phosphor, aluminate green phosphor and silicon-based nitride (oxide). In particular MN2S4:Eu2+(M＝Ba,Sr,Ca),(N＝Al,Ga,In)；(Ba,Sr)2SiO4:Eu2+With Ca2MgSi2O7 Eu2+；MSrAl3O7:Eu2+(M＝Y,La,Gd)；β-SiAlON:Eu2+、SrSi2O2N2:Eu2+、SiAlON:Yb2+. The red phosphor layer 22 can be efficiently excited by a blue chip and can be selected from borate phosphor, YVO4 Eu system red phosphor, nitride red phosphor, and molybdate red phosphor. In particular Ca2BO3Cl:Eu2+；YVO4:Eu；M2Si5N8:Eu2+(M ═ Ca, Sr, Ba). The peak position of the near-red fluorescent powder layer 22 is 714-740 nm.
The preparation method of the light-emitting device comprises the following steps:
the blue LED chip, the green fluorescent powder layer, the red fluorescent powder layer and the near-infrared fluorescent powder layer are sequentially arranged on the substrate along the light emitting direction. The green light fluorescent powder layer is formed by mixing existing green light fluorescent powder and glue and then coating the mixture on a blue light LED chip. The red light fluorescent powder layer is formed by mixing existing red light fluorescent powder with glue and then coating the mixture on the green light 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-light fluorescent powder layer. Wherein, the glue is preferably epoxy resin or silica gel.
Example 3
To verify Cr3+Whether or not the valence of (A) is oxidized to Cr4+The sample powder was subjected to X-ray photoelectron spectroscopy as shown in fig. 7. As is clear from fig. 7, the characteristic binding energy of Cr ions at 575.88eV is shown, and the peak separation processing is performed in the characteristic binding energy range, thereby obtaining fig. 8. From FIG. 8, it can be seen that the peaks of 580.9eV and 576.4eV belong to Cr 2P3/2, and Cr 2P3/2 belongs to Cr3+Nuclear-level electrons. Therefore, the Cr in the preparation process of the near-infrared fluorescent powder3+Sintering in air does not oxidize.
The above description is only for the preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, and therefore, all equivalent or modifications that do not depart from the spirit of the present invention are intended to fall within the scope of the present invention.
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