CN112795381B - Perovskite structure fluorescent powder for agricultural illumination and preparation method thereof - Google Patents
Perovskite structure fluorescent powder for agricultural illumination and preparation method thereof Download PDFInfo
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- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
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- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier 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
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- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
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Abstract
The invention relates to perovskite structure fluorescent powder for agricultural illumination and a preparation method thereof, wherein the general formula of the perovskite structure fluorescent powder is as follows: CaLa4‑ xTi4O15:xEu3+Wherein x is more than or equal to 0 and less than or equal to 0.60. CaLa prepared by citric acid-ethylene glycol sol combustion method4Ti4O15The material, the complex obtained by the mixed complexing agent sol combustion method has higher stability than a single coordination system. CaLa4Ti4O15As a phosphor body, which is an excitation center Eu3+Provides good crystal field and physical and chemical stability. The transfer efficiency between the charge transfer zone of the fluorescent powder and the rare earth ions is higher, and the luminous intensity can be greatly improved. After being excited, the fluorescent powder emits strong red light which can be absorbed by plants, and can be applied to agricultural LED illumination. The fluorescent powder prepared by using the sol combustion method has the advantages of simple synthesis process, low synthesis temperature, short synthesis period, uniform size distribution of the obtained fluorescent powder, good luminous performance and the like.
Description
Technical Field
AgricultureCaLa for lighting LED4-xTi4O15:xEu3+A fluorescent powder material and a preparation method thereof belong to the technical field of rare earth luminescent materials.
Background
Compared with the traditional incandescent lamp and fluorescent light source, the semiconductor LED has the advantages of high energy efficiency, long service life, quick response time, environmental friendliness and the like, is called as a fourth-generation green lighting mode, and is widely applied to various industries.
With the rapid development of the global facility agriculture and gardening industry, the light environment control technology for plant growth is more and more emphasized. The plant growth conditions are proper temperature, nutrition, moisture, illumination and the like. Among them, light irradiation is an extremely important influence factor. In areas with high latitude, insufficient illumination time and low air temperature, artificial auxiliary illumination becomes one of key technologies for ensuring high quality and stable yield of horticultural plants, flowers, crops and the like. The environment-friendly LED light source has the advantages of high light energy utilization rate, low energy consumption, long service life, small volume, less heat generation and the like. Therefore, the development of agricultural lighting LEDs for promoting plant growth is a very urgent task.
Eu3+Rich in energy level transition (5D0→7F0,7F1,7F2,7F3,7F4). Generally, Eu3+Doped phosphor with orange light5D0→7F1) And red light (5D0→7F2) The transmission is dominant. Except for typical Eu3+Besides the doped red fluorescent powder, the red fluorescent powder has high intensity5D0→7F4Transition Eu3+The doped far-red phosphor enters the human vision. The fluorescent powder has high-intensity far-red light emission capability and is a luminescent material for plant growth illumination.
Rare earth Eu reported in the prior art3+The phosphor material with perovskite structure is disclosed in, for example, Chinese patent publication No. CN110982526A, Eu3+Ion-doped SrLaMgTaO6Red fluorescencePowder, and a high-temperature solid-phase sintering process is adopted in the implementation process. It is worth noting that the fluorescent powder has the defects of secondary calcination, high calcination temperature, long preparation period, high energy consumption and the like. Some preparation of ALa4Ti4O15(A ═ Ca, Ba, Sr) (Colloids and Surfaces A-physical and Engineering applications 481 (2015)) 125-4Ti4O15The ceramic material needs to be calcined at 1200-1600 ℃ for several hours, and compared with the preparation method of the invention, the energy consumption and the time consumption are high, and the appearance and the performance of the prepared sample are not as good as those of the material prepared by the preparation method of the invention.
The invention prepares the CaLa with a layered perovskite structure by a low-temperature and rapid citric acid-ethylene glycol sol combustion method process for the first time4Ti4O15Materials, also first studied in CaLa4Ti4O15Middle doped rare earth Eu3+And (3) ions are added to prepare the luminescent material which can effectively absorb near ultraviolet light or blue light and efficiently emit red light. The preparation method adopts a citric acid-glycol sol combustion method, and adopts a sol precursor formed by mixing citric acid and glycol to complex metal ions: citric acid as Ca2+、La3+And Ti4+The complexing agents of the three metal cation coordination have strong coordination and esterification capacity, and the glycol can play the role of a second ligand and a dispersing agent. The complexation of metal ions is enhanced through the combined action of two ligands, and a larger stable network structure is obtained by utilizing the esterification between functional groups of the two ligands and the hydrogen bond between complexing molecules, so that cations are more uniformly distributed in a precursor. The adopted raw materials are metal acetate instead of traditional nitrate, the pollution of nitric oxide generated by the reaction of the nitrate is avoided, meanwhile, a network chain structure is easier to form with a complexing agent, the use of urea is avoided, the generation of air pollutants is reduced, the production cost is reduced, and the obtained sol precursor is calcined at a certain temperature to obtain CaLa which has smaller particles, is uniformly distributed and has good luminous performance4-xTi4O15:xEu3+And (3) fluorescent powder. The precursor is ignited and combusted in the temperature rise process, the temperature is raised to the heat preservation temperature after combustion, and the crystal growth is further promoted, so that the luminous performance is improved, the influence of multiple times of high-temperature calcination on the luminous performance of the fluorescent powder is avoided, and the method is environment-friendly, economical and efficient. By utilizing the red light-emitting characteristic of the prepared fluorescent powder and matching with an ultraviolet LED chip or a blue LED chip, a novel agricultural lighting LED can be prepared.
Disclosure of Invention
The invention solves the first technical problem of providing a plant lighting fluorescent powder material with low cost and good luminous performance.
The technical scheme of the invention is as follows: agricultural lighting fluorescent powder material with a layered perovskite structure: has a chemical formula of CaLa4- xTi4O15:xEu3+(0<x is less than or equal to 0.60) the phosphor for the agricultural lighting LED, the main phase structure of the phosphor is a hexagonal system, and the space point group is p-3m1 (164). The invention provides a method for preparing Eu3+The red phosphor is a luminescence center, has strong absorption at 394nm and 465nm, and has better matching property with near ultraviolet LED chips and blue LED chips.
The second problem to be solved by the invention is to provide a preparation method of the layered perovskite type red fluorescent powder, which reduces the production energy consumption, is synthesized quickly and greatly shortens the synthesis period, and comprises the following steps:
a. according to CaLa4-xTi4O15:xEu3+(0<x is less than or equal to 0.60) and the stoichiometric ratio of calcium acetate (C)4H6CaO4·4H2O), lanthanum acetate (C)6H11LaO7) And europium acetate (C)6H14EuO7) Dissolving the raw materials in deionized water and stirring until all the raw materials are completely dissolved to form a solution 1; weighing butyl titanate (Ti (OC) according to stoichiometric ratio4H9)4) Citric acid (C)6H8O7) And ethylene glycol (CH)2OH)2Dissolving in glacial acetic acid solution to form solution 2, slowly dropping solution 2 into solution 1, stirring, mixing with ammonia waterThe pH value of the solution;
b. b, placing the mixed solution obtained in the step a in a water bath pot, heating and continuously stirring until sol appears;
c. d, transferring the sol obtained in the step b to a corundum crucible, placing the corundum crucible in a muffle furnace at 300 ℃ and preserving heat for 20min, wherein the water in the sol disappears rapidly under the state, and citric acid and ethylene glycol are used as combustion agents to combust to generate flame; raising the temperature of the furnace, keeping the temperature for a period of time, and then cooling the furnace to room temperature to obtain a fluffy fluorescent powder sample;
d. c, fully grinding the perovskite fluorescent powder obtained in the step c to obtain CaLa4-xTi4O15:xEu3+And (3) fluorescent powder.
The technical scheme of the invention is also characterized in that:
the invention is characterized in that the complex obtained by the sol combustion method of the mixed complexing agent has higher stability than a single coordination system, is outstanding in property, and has the advantages of low synthesis cost, simple operation, short preparation period, mass production and the like.
Perovskite CaLa prepared by the invention4-xTi4O15:xEu3+(0<x is less than or equal to 0.60), the value of x in the invention should be within the above-mentioned range, and when the value of x exceeds 0.44, Eu3+The ions will cause a substantial decrease in luminescence intensity due to concentration quenching.
In one embodiment, in step a, citric acid-ethylene glycol is used as both a metal ion complexing agent and a combustion agent, and the molar ratio of citric acid to metal cations is 1: 1-2: 1, and the molar ratio of ethylene glycol to citric acid is 3: 1-4: 1.
In one embodiment, in step a, the pH value of the mixed solution is 4-6.
In one embodiment, in step b, the set temperature for heating the water bath in step b is 50 ℃ to 90 ℃.
In one embodiment, in the step b, the sol is formed by heating and stirring in a water bath at a stirring speed of 300 to 1000 rad/min.
In one embodiment, in step c, the muffle furnace calcination time is 0.5-2 h.
In one embodiment, in step c, after the sol undergoes a combustion reaction, the temperature is raised to 1000-1200 ℃ again and the temperature is maintained.
In one embodiment, in step d, the obtained phosphor sample after cooling is ground by an agate mortar for 1-10 min.
The third technical problem to be solved by the invention is to use the CaLa4-xTi4O15:xEu3+The agricultural lighting fluorescent powder is matched with an ultraviolet LED chip or a blue LED chip to be applied to the preparation of plant lighting LED devices.
The invention has the beneficial effects that: compared with the prior art, the invention has the following remarkable characteristics:
1. the invention creatively uses a simple sol combustion method to form CaLa4Ti4O15The material solves the problems of high calcination temperature and long preparation period of the traditional solid phase method.
2. The invention highlights the use of a citric acid-ethylene glycol sol combustion method, with citric acid as Ca2+、La3+And Ti4+The complexing agents of the three metal cation coordination have strong coordination and esterification capacity, and the glycol can play the role of a second ligand and a dispersing agent. The complexation of metal ions is enhanced through the combined action of two ligands, and a larger stable network structure is obtained by utilizing the esterification between functional groups of the two ligands and the hydrogen bond between complexing molecules, so that cations are more uniformly distributed in a precursor. The citric acid-glycol system can form a stable structure and realize the uniform distribution of ions, and the occurrence of esterification in the system highlights the dispersion effect of glycol on sol in the multi-ligand system. Meanwhile, the metal acetate replaces the traditional nitrate to serve as a starting raw material, the pollution of nitrogen oxides generated by the reaction of the nitrate is avoided, a network chain structure is formed with a complexing agent more easily, the use of urea is avoided, and the generation of air pollutants is reduced.
3. Eu is adopted in the invention3+Ion-doped CaLa4Ti4O15The agricultural illuminating fluorescent powder is obtained from the substrate. The matrix is chemically and physically stable and can be used as a luminescence center Eu3+The ions provide a good crystal field environment.
4. The prepared fluorescent powder has strong absorption at 394nm and 465nm, and is a layered perovskite red fluorescent powder which has better matching property with a near ultraviolet LED chip and a blue LED chip.
5. The invention adopts a sol combustion method to synthesize CaLa4-xTi4O15:xEu3+And (3) fluorescent powder. The preparation method has the advantages of simple synthesis process, low synthesis temperature, short synthesis period, uniform size distribution of the obtained fluorescent powder and good luminescence property.
Drawings
FIG. 1 shows the CaLa obtained in example 14Ti4O15And CaLa3.56Ti4O15:0.44Eu3+XRD of the phosphor powder is compared with a standard PDF card.
FIG. 2 shows that CaLa is obtained in example 13.56Ti4O15:0.44Eu3+Emission and excitation profiles of the phosphors at monitoring wavelengths of 394nm and 622 nm.
FIG. 3 shows the CaLa synthesized in example 2 at different temperatures3.56Ti4O15:0.44Eu3+Emission spectrum of the sample.
FIG. 4 shows the CaLa obtained in example 24-xTi4O15:xEu3+(x-0-0.60).
FIG. 5 shows CaLa prepared by using the citric acid monodentate system and the citric acid-ethylene glycol mixed system obtained in example 3 as the complexing agent3.56Ti4O15:0.44Eu3+An emission spectrum.
FIG. 6 shows the CaLa obtained in example 33.56Ti4O15:0.44Eu3+And a full spectrum chart of the packaged 395nm near ultraviolet LED chip.
Detailed Description
The invention is described in more detail below with reference to specific examples, which are given as reference to a part of the test results.
Example 1
A preparation method of red fluorescent powder with a layered perovskite structure comprises the following steps:
step one, when x is 0.20, according to CaLa4-xTi4O15:xEu3+(0<x is less than or equal to 0.60) stoichiometric ratio weighing C4H6CaO4·4H2O、C6H11LaO7And C6H14EuO7Dissolving in 3ml deionized water, heating at 30 deg.C with stirring in water bath, and weighing butyl titanate (Ti (OC) according to stoichiometric ratio4H9)4) Citric acid (ratio to metal cation 2: 1) mixing with glacial acetic acid (inhibiting hydrolysis reaction) in deionized water, stirring, mixing and stirring the above two solutions at 40 deg.C in a water bath, and slowly adding dropwise ammonia water to adjust pH to 4;
step two, slowly heating the water bath pot in which the mixed transparent solution is placed in the step one to 70 ℃, and continuously stirring at the rotating speed of 700rad/min until transparent sol is obtained;
step three, transferring the sol obtained in the step two to a corundum crucible, putting the corundum crucible in a muffle furnace at 300 ℃ and preserving heat for 0.5h, wherein the moisture in the sol can quickly disappear in the state, and citric acid is used as a combustion agent to combust to generate flame; the muffle furnace is heated to 1000 ℃ again at a speed of 5 ℃/min and the temperature is kept for 1 h. Taking out the sample after the sample is cooled to room temperature along with the furnace to obtain a fluffy white powder sample;
step four, grinding the white powder obtained in the step three for 5min to obtain CaLa3.8Ti4O15:0.20Eu3+Red phosphor powder.
The powder samples obtained were subjected to powder diffraction (Ultima iv, Rigaku, Japan) and fluorescence spectrum (Hitachi F-4600, Japan) tests, the excitation spectrum was measured at a monitoring wavelength of 622nm, and the test results are shown in fig. 1 and 2, and it can be seen that the resulting material was mixed with CaLa4Ti4O15The standard PDF card has good matching; the fluorescent powder has a plurality of excitation peaks in the range of 300-500nm, and an ultraviolet LED chipHas better matching property with blue light.
Example 2
A preparation method of red fluorescent powder with a layered perovskite structure comprises the following steps:
step one, when x is 0.44, according to CaLa4-xTi4O15:xEu3+(0<x is less than or equal to 0.60) stoichiometric ratio weighing C4H6CaO4·4H2O、C6H11LaO7And C6H14EuO7Dissolving in 5ml deionized water, heating at 30 deg.C with stirring in water bath, and weighing butyl titanate (Ti (OC) according to stoichiometric ratio4H9)4) Citric acid (ratio to metal cation 2: 1) mixing with glacial acetic acid (inhibiting hydrolysis reaction) in deionized water, stirring, mixing and stirring the two solutions at 40 deg.C in a water bath, and slowly adding dropwise ammonia water to adjust pH to 4;
step two, slowly heating the water bath pot in which the mixed transparent solution is placed in the step one to 80 ℃, and continuously stirring at the rotating speed of 700rad/min until obtaining transparent sol;
step three, transferring the sol obtained in the step two to a corundum crucible, and putting the corundum crucible in a muffle furnace at 300 ℃ for heat preservation for 20min, wherein the water in the sol can quickly disappear in the state, and citric acid is used as a combustion agent to combust to generate flame; the muffle furnace is heated to 1100 ℃ again at the speed of 5 ℃/min and the temperature is kept for 1 h. Taking out the sample after the sample is cooled to room temperature along with the furnace to obtain a fluffy white powder sample;
step four, grinding the white powder obtained in the step three for 5min to obtain CaLa3.56Ti4O15:0.44Eu3+Red phosphor powder.
The obtained powder sample was subjected to a fluorescence spectrum (Hitachi F-4600, Japan) test, and the emission spectrum was measured at 394nm as a monitoring wavelength, and the test results are shown in FIGS. 3 and 4, and it can be seen that CaLa synthesized at 1100 ℃ is present3.56Ti4O15:0.44Eu3 +The phosphor has a strong red emission at 622 nm.
Example 3
A preparation method of red fluorescent powder with a layered perovskite structure comprises the following steps:
step one, when x is 0.44, according to CaLa4-xTi4O15:xEu3+(0<x is less than or equal to 0.60) stoichiometric ratio weighing C4H6CaO4·4H2O、C6H11LaO7And C6H14EuO7Dissolving in 5ml deionized water, heating at 30 deg.C with stirring in water bath, and weighing butyl titanate (Ti (OC) according to stoichiometric ratio4H9)4) Citric acid (1.2 to metal cation ratio: 1) ethylene glycol (3.5 to citric acid: 1) mixing with glacial acetic acid (inhibiting hydrolysis reaction) in deionized water, stirring, mixing and stirring the two solutions at 40 deg.C in a water bath, and slowly adding dropwise ammonia water to adjust pH to 5;
step two, slowly heating the water bath pot in which the mixed transparent solution is placed in the step one to 80 ℃, and continuously stirring at the rotating speed of 700rad/min until obtaining transparent sol;
step three, transferring the sol obtained in the step two to a corundum crucible, placing the corundum crucible in a muffle furnace at 300 ℃ and preserving heat for 20min, wherein the water in the sol can quickly disappear in the state, and citric acid and ethylene glycol are used as combustion agents to combust to generate flame; the muffle furnace is heated to 1100 ℃ again at the speed of 5 ℃/min and the temperature is kept for 1 h. Taking out the sample after the sample is cooled to room temperature along with the furnace to obtain a fluffy white powder sample;
step four, grinding the white powder obtained in the step three for 5min to obtain CaLa3.56Ti4O15:0.44Eu3+Red phosphor powder.
The obtained powder sample was subjected to a fluorescence spectrum (Hitachi F-4600, Japan) test, an emission spectrum was measured with 394nm as a monitoring wavelength, and the test result is shown in FIG. 5, which shows that CaLa synthesized by adding a single complexing agent and a citric acid-ethylene glycol mixed complexing agent3.56Ti4O15:0.44Eu3+The fluorescent powder has strong red light emission at 622nm, and the fluorescent powder obtained after the mixed complexing agent is burnt has higher emission intensity. Using powder samples and 395nmAfter the ultraviolet LED chip is packaged, a photochromic test is carried out, the measured full spectrum is shown in figure 6, and it can be seen that the intensity of the emitted light of the chip at 395nm is far less than the intensity of the emitted red light of the fluorescent powder excited by the ultraviolet LED chip at 622 nm. The result shows that the fluorescent powder can be applied to white LEDs and agricultural lighting LEDs after being packaged with ultraviolet LED chips or blue LED chips.
Claims (8)
1. A preparation method of a low-cost red-light fluorescent powder material applied to agricultural lighting LEDs is characterized in that the chemical formula of the fluorescent powder is CaLa4-xTi4O15:xEu3+Wherein 0 is<x is less than or equal to 0.60, the main phase structure is a hexagonal system, and the space point group is p-3m1(No. 164); CaLa4-xTi4O15:xEu3+The preparation method of the red light fluorescent powder material comprises the following steps:
a. according to CaLa4-xTi4O15:xEu3+(0<x is less than or equal to 0.60) and the stoichiometric ratio of calcium acetate (C)4H6CaO4·4H2O), lanthanum acetate (C)6H11LaO7) And europium acetate (C)6H14EuO7) Dissolving the raw materials in deionized water and stirring until all the raw materials are completely dissolved to form a solution 1; weighing butyl titanate (Ti (OC) according to stoichiometric ratio4H9)4) Citric acid (C)6H8O7) And ethylene glycol (CH)2OH)2Dissolving the mixed solution in a glacial acetic acid solution to form a solution 2, slowly dropping the solution 2 into the solution 1, stirring and mixing uniformly, and adjusting the pH value of the mixed solution by ammonia water;
b. b, placing the mixed solution obtained in the step a in a water bath kettle, heating and continuously stirring until sol appears;
c. d, transferring the sol obtained in the step b to a corundum crucible, placing the corundum crucible in a muffle furnace at 300 ℃ and preserving heat for 20min, wherein the water in the sol disappears rapidly under the state, and citric acid and ethylene glycol are used as combustion agents to combust to generate flame; raising the temperature of the furnace, preserving the temperature for a period of time, and then cooling the furnace to room temperature to obtain a fluffy fluorescent powder sample;
d. c, fully grinding the perovskite fluorescent powder obtained in the step c to obtain CaLa4-xTi4O15:xEu3+And (3) fluorescent powder.
2. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED according to claim 1, characterized in that: when the value of x exceeds 0.44, Eu3+The ions will cause a large reduction in luminescence intensity due to concentration quenching.
3. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED as claimed in claim 2, wherein the preparation method comprises the following steps: in the step a, citric acid-ethylene glycol is used as a metal ion complexing agent and a combustion agent, the molar ratio of citric acid to metal cations is 1: 1-2: 1, and the molar ratio of ethylene glycol to citric acid is 3: 1-4: 1.
4. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED according to claim 3, wherein the preparation method comprises the following steps: in the step a, the pH value of the mixed solution is 4-6.
5. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED according to claim 4, wherein the preparation method comprises the following steps: in the step b, the set temperature for heating the water bath in the step b is 50-90 ℃.
6. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED according to claim 5, wherein the preparation method comprises the following steps: in the step b, a water bath heating and stirring mode is adopted to form the sol, and the stirring speed is 300-1000 rad/min.
7. The preparation method of the low-cost red-light fluorescent powder material applied to the agricultural lighting LED according to claim 6, wherein the preparation method comprises the following steps: in the step c, the muffle furnace is used for calcining for 0.5-2 hours.
8. The preparation method of the LED low-cost red-light fluorescent powder material applied to agricultural illumination according to claim 7, characterized in that: in the step c, after the sol is subjected to combustion reaction, the temperature is raised to 1000-1200 ℃ again for heat preservation.
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