CN114958352A - Red fluorescent powder and preparation method and application thereof - Google Patents
Red fluorescent powder and preparation method and application thereof Download PDFInfo
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- C09K11/647—Borates
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention discloses Ca 14 (Zn,Mg) 6 (Al,B) 10 O 35 The red fluorescent powder of the substrate, the preparation method and the application thereof have the chemical general formula: ca 14 Zn 6‑a Mg a+c Al 10‑b‑2c B b Mn c O 35 A is more than or equal to 0 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, and a, b and c are not 0 at the same time. The invention effectively improves the absorption of blue light by partially replacing Zn with Mg and partially replacing Al with B, the quantum efficiency of the prepared fluorescent powder is up to more than 85 percent, the fluorescent powder is environment-friendly, can be excited by ultraviolet to blue light (280 plus 460nm) to obtain 660 plus 780nm red emission, the thermal quenching temperature is up to more than 300 ℃, and the fluorescence intensity is 580K at high temperatureThe temperature is reduced to 50% of the room temperature, and the fluorescent powder has high thermal stability and luminescent property, and has good economic benefit and development prospect.
Description
Technical Field
The invention relates to the technical field of fluorescent material preparation, and relates to Ca 14 (Zn,Mg) 6 (Al,B) 10 O 35 A red fluorescent powder of a substrate, a preparation method and an application thereof, in particular to Ca with high luminous efficiency 14 (Zn,Mg) 6 (Al,B) 10 O 35 Red fluorescent powder of matrix and its preparation method and application.
Background
Commercial white LEDs mainly emit white light through a blue LED chip and yellow phosphor, and are widely used in various fields due to their excellent characteristics of high luminance, low energy consumption, and environmental friendliness. However, the white LEDs lack red light emitting components, so that warm white light is difficult to emit, and have disadvantages of low color rendering index and high color temperature. In order to make up for the light emitting defects of the existing white light LEDs, the synthesis of red fluorescent powder capable of efficiently absorbing blue light and generating red light emission becomes a research hotspot.
At present, in red fluorescent powder capable of efficiently absorbing blue light and generating red light emission, the rare earth element has high cost, the synthesis of nitride needs high temperature and high pressure, and the reaction conditions are harsh, so that the application development of the red fluorescent powder is limited. Mn 4+ Doped fluorides are toxic, environmentally unfriendly and have poor stability. Low cost of synthesized oxide, simple synthesis process, nontoxic and pollution-free raw materials, good chemical stability and thermal stability, and Mn 4+ The excitation spectrum of (2) is in the blue-violet region, and the emission spectrum is intense narrow red emission, but the quantum efficiency is generally below 80%. Therefore, the temperature of the molten metal is controlled,how to develop Mn with high quantum efficiency 4+ The doped oxide red fluorescent powder system has high economic benefit and application prospect.
Based on the higher luminous efficiency of the LED light source, the promotion of plant growth by the LED light source is widely applied in the aspect of agricultural production. For example, patent document CN201810554012.7 discloses Ca 14 Al 10 Zn 6 O 35 :Mn 4+ Fluorescent powder, which relates to a method for promoting the growth and development of pleurotus eryngii by using an LED plant growth light source. However, the phosphor in the patent document is prepared by a hydrothermal method, and the method still has the defects of low yield, high preparation cost and the like. Therefore, the method is not suitable for the industrialized development of the fluorescent powder, and the fluorescent powder prepared by the method still has the defect of low quantum efficiency. Therefore, how to prepare the fluorescent powder which has high quantum efficiency, high yield and low preparation cost and can be suitable for industrial development becomes a technical problem to be solved urgently.
Disclosure of Invention
In order to improve the technical problem, the invention provides a red phosphor which has the following chemical general formula Ca 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 Wherein:
the matrix is Ca 14 (Zn,Mg) 6 (Al,B) 10 O 35 The activator is Mn 4+ And by co-doping with Mg 2+ To balance Mn 4+ Substituted octahedral centre Al 3+ A location;
a is more than or equal to 0 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, and a, b and c are not 0 at the same time;
preferably 0.1 ≦ a ≦ 0.9, illustratively 0, 0.1, 0.2, 0.5, 0.7, 0.9, 1.0;
preferably 0.01 ≦ b ≦ 0.4, illustratively b ≦ 0.01, 0.05, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5;
preferably, 0.05 ≦ c ≦ 0.4, c ≦ 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5.
According to an embodiment of the present invention, the phosphor Ca 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 The material is prepared from a Ca source, a Zn source, an Mg source, an Al source, a B source and a Mn source by a solid-phase sintering method.
According to an embodiment of the invention, the Ca source is provided by a compound containing an element Ca; for example, provided by at least one of a carbonate, an oxide, a chloride, a fluoride, a nitrate, and a sulfate of a Ca-containing element; preferably provided by a carbonate containing Ca element.
According to an embodiment of the invention, the Zn source is provided by a compound containing the element Zn; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of a Zn-containing element; preferably provided by an oxide containing a Zn element.
According to an embodiment of the invention, the Mg source is provided by a compound containing the Mg element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of an Mg-containing element; preferably provided by an oxide containing Mg element.
According to an embodiment of the present invention, the Al source is provided by a compound containing an Al element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of an Al-containing element; preferably provided by an oxide containing an Al element.
According to an embodiment of the invention, the B source is provided by a compound containing the B element; for example, the B element-containing compound is H 3 BO 3 、B 2 O 3 And B 2 H 6 At least one of (a); preferably H 3 BO 3 。
According to an embodiment of the invention, the Mn source is provided by a compound containing the Mn element; for example, provided by at least one of carbonates, oxides, chlorides, nitrates, and sulfates of the Mn-containing element; preferably provided by a carbonate containing Mn element.
According to an embodiment of the present invention, the phosphor may be Ca 14 Al 9.9 Zn 6 Mn 0.05 Mg 0.05 O 35 、Ca 14 Al 9.6 Zn 6 Mn 0.2 Mg 0.2 O 35 、Ca 14 Al 9.4 Zn 6 Mn 0.3 Mg 0.3 O 35 、Ca 14 Al 9.75 B 0.05 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.7 B 0.1 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.65 B 0.15 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.6 B 0.2 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.75 B 0.05 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.8 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.6 B 0.2 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.5 B 0.3 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.4 B 0.4 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.3 B 0.5 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.79 B 0.01 Zn 6 Mn 0.1 Mg 0.1 O 35 。
According to the embodiment of the invention, the fluorescent powder can be excited by ultraviolet/near ultraviolet/purple light/blue light with the wavelength of 280-480 nm. Preferably, the phosphor powder can emit red light with the wavelength range of 660-780nm after being excited, and the strongest peak of the emission spectrum is located in the range of 710-720nm, and preferably around 713 nm.
The invention also provides a preparation method of the fluorescent powder, which comprises the following steps:
and (2) taking a Ca source, a Zn source, an Mg source, an Al source, a B source and a Mn source as raw materials, and obtaining the fluorescent powder by a solid-phase sintering method.
According to an embodiment of the invention, the Ca source, Zn source, Mg source, Al source, B source and Mn source have the meaning as described above.
According to an embodiment of the present invention, before the solid phase sintering, the method further comprises the step of performing ball milling on the mixed raw materials. Preferably, the rotation speed of the ball milling is 190-.
According to an embodiment of the present invention, the preparation method further comprises adding a ball milling medium to the mixed raw materials. For example, the ball milling medium may be an ethanol solution of oleic acid. Further, the concentration of the ethanol solution of oleic acid is 0.1-1%, preferably 0.2-0.8%, exemplary 0.1%, 0.5%, 0.8%, 1%.
According to the embodiment of the invention, the solid-to-liquid ratio of the ethanol solution of the oleic acid to the total weight of the mixed raw materials is 12mL (9.0-11.0) g, preferably 12mL (9.5-10.5) g, and more preferably 12mL (9.8-10.2) g.
According to the embodiment of the invention, the preparation method further comprises the step of drying the mixed raw materials after ball milling. For example, the drying temperature is 40 to 80 ℃, and exemplary temperatures are 40 ℃, 60 ℃ and 80 ℃.
According to an embodiment of the invention, the temperature of the solid phase sintering is 1200-1300 ℃, preferably 1230-1280 ℃, exemplary 1200 ℃, 1230 ℃, 1250 ℃, 1280 ℃, 1300 ℃.
According to the embodiment of the invention, the solid phase sintering time is 1-12 h, preferably 2-10h, preferably 2h, 5h, 8h and 10 h.
According to an embodiment of the present invention, the method for preparing the red phosphor comprises the following steps:
firstly, weighing a Ca source, a Zn source, an Mg source, an Al source, a B source and a Mn source, and adding 12mL of ethanol solution containing 0.5% of oleic acid;
keeping the mixture prepared in the step I for 10-30h at the rotating speed of 190-210 r/min;
thirdly, drying the slurry uniformly mixed in the second step to obtain precursor powder;
fourthly, calcining the precursor powder obtained in the third step at the temperature of 1230- 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 Phosphor of(0≤a≤1.5，0≤b≤0.5，0≤c≤0.5)。
The invention also provides the application of the fluorescent powder in a light-emitting device. Wherein the light-emitting device is used in the fields of agricultural production and the like.
Preferably, the light emitting device is a white LED device. Further, the white light LED device is used in the fields of agricultural production and the like. For example, plant growth is promoted using the white LED light source.
The invention also provides a light-emitting device which comprises the fluorescent powder material Ca 14 Zn 6-a Mg a+ c Al 10-b-2c B b Mn c O 35 . Preferably, the light emitting device is a white LED device.
According to the embodiment of the invention, the light-emitting device further comprises an LED chip for carrying the above-mentioned phosphor material Ca 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 . Preferably, the LED chip is an ultraviolet/near ultraviolet/purple light/blue light LED chip with the wavelength of 280-480 nm. Preferably a blue LED chip.
According to the embodiment of the invention, the blue LED chip is a blue LED chip with the peak value between 420-480 nm.
According to the embodiment of the invention, the light-emitting device comprises a luminescent material layer coated on the LED chip, and the luminescent material layer contains the uniformly dispersed fluorescent powder material Ca 14 Zn 6-a Mg a+c Al 10-b- 2c B b Mn c O 35 . Further, the luminescent material layer also contains glue. For example, the glue may be epoxy, polycarbonate or silicone; silica gel is preferred. The amount of the glue used is not particularly limited, and it may be uniformly applied to the LED chip according to a known operation in the art.
According to an embodiment of the present invention, the light emitting device is a white LED device. Further, the white light LED device is used in the fields of agricultural production and the like. For example, plant growth is promoted using the white LED light source.
The invention also provides a preparation method of the light-emitting device, which comprises the following steps: and uniformly mixing the fluorescent powder material and the glue, and coating the mixture on an LED chip.
The invention also provides a luminescent device containing the luminescent material, which is used in the fields of agricultural production and the like. For example, plant growth is promoted using the white LED light source.
The invention has the beneficial effects that:
the invention passes through Mg 2+ /Mn 4+ Codoped with Ca 14 Al 10 Zn 6 O 35 :Mn 4+ A phosphor, wherein: al (Al) 3+ Quilt Mn 4+ The invention replaces the defects which cause charge unbalance and aggravate non-radiative transition of the generated crystal defects, and the invention replaces Zn and B by Mg partially, thereby effectively improving the absorption of blue light, so that the quantum efficiency of the fluorescent powder reaches more than 85 percent, and simultaneously the prepared fluorescent powder has good thermal stability, and the fluorescence intensity is reduced to 50 percent of the room temperature at the high temperature of 580K; when the temperature is below 500K, the CIE chromaticity coordinates remain almost unchanged, and the relative intensities at temperatures of 460K and 540K remain 99% and 82% of those at room temperature (300K), respectively. Mg prepared by the invention 2+ /Mn 4+ Codoped with Ca 14 Al 10 Zn 6 O 35 :Mn 4+ The thermal stability of the fluorescent powder is obviously higher than that of the current commercial red fluorescent powder YAG Ce 3+ ,K 2 TiF 6 :Mn 4+ And Sr 2 Si 5 N 8 :Eu 2+ Is Mn, which has been the most excellent so far 4+ And activating the oxide fluorescent powder.
Drawings
FIG. 1 is a graph showing the change of the fluorescence intensity and quantum efficiency of red phosphors prepared in examples 1 to 3 with Mn doping concentration.
FIG. 2 shows the excitation and emission spectra of the red phosphors prepared in examples 4-7.
FIG. 3 shows the excitation and emission spectra of the red phosphor prepared in example 5.
FIG. 4 is a graph showing the change in quantum efficiency of the red phosphors prepared in examples 8-12 with the change in B concentration.
FIG. 5 shows the thermal quenching performance and color coordinates of the red phosphor prepared in example 13.
Fig. 6 is an LED device prepared from the red phosphor prepared in example 2.
Fig. 7 is a fluorescence spectrum of an LED device prepared from the red phosphor prepared in example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Examples 1 to 3
Mn (manganese) 4+ Activated Ca 14 Zn 6 Al 10 O 35 The red phosphor has a chemical general formula of Ca 14 Zn 6-a Mg a+ c Al 10-b-2c B b Mn c O 35 The doping concentration of Mn and the ratio of the raw materials for the phosphor are shown in Table 1. By changing MnCO in the raw material 3 The amount of (c) can be adjusted to prepare samples with different Mn doping concentrations (examples 1-3) without changing other synthesis conditions.
The used raw materials are as follows: CaCO 3 、Al 2 O 3 、ZnO、MgO、MnCO 3
The mass (g) of each raw material component in examples 1-3 is as shown in table 1 below, the raw materials are weighed and placed in a ball mill tank, and 12mL of 0.5% oleic acid ethanol solution is added;
TABLE 1
| Example numbering | Chemical formula (II) | Number of Mn atoms | CaCO 3 | Al 2 O 3 | ZnO | MnCO 3 | MgO | Total amount of |
| Example 1 | Ca 14 Al 9.9 Zn 6 Mn 0.05 Mg 0.05 O 35 | 0.05 | 5.88529 | 2.11975 | 2.05078 | 0.02414 | 0.00846 | 10.07996 |
| Example 2 | Ca 14 Al 9.6 Zn 6 Mn 0.2 Mg 0.2 O 35 | 0.2 | 5.88529 | 2.05551 | 2.05078 | 0.09656 | 0.03385 | 10.08814 |
| Example 3 | Ca 14 Al 9.4 Zn 6 Mn 0.3 Mg 0.3 O 35 | 0.3 | 5.88529 | 2.01269 | 2.05078 | 0.14484 | 0.05078 | 10.09360 |
Secondly, placing the ball milling tank in the first step in a ball mill, and keeping the ball milling tank at a rotating speed of 210r/min for 10 hours;
taking out the evenly mixed slurry obtained in the step two, putting the slurry into a culture dish, and drying the slurry in a drying oven at the temperature of 60 ℃ to obtain precursor powder;
and fourthly, calcining the precursor powder obtained in the third step in a muffle furnace at 1280 ℃ for 2 hours to finally obtain the red fluorescent powder of the embodiment 1-3.
As shown in FIG. 1, the emission peak patterns of examples 1 to 3 are consistent with each other with the increase of Mn concentration, and the fluorescence intensity tends to decrease first and then increase, and the quantum efficiency of the sample also decreases first and then increases.
Referring to fig. 6, a light emitting device was fabricated by mixing the phosphor material prepared in example 2 with silica gel uniformly, and then coating it on the light emitting surface of a blue LED chip, and heating and drying it to form a phosphor light emitting layer. And then the LED chip emits blue light after the positive electrode and the negative electrode are electrified, the red fluorescent powder luminescent layer can emit light after absorbing the blue light, and the fluorescent spectrogram is shown in figure 7. The results in fig. 7 show that: the red fluorescent powder prepared by the invention can be excited by blue light with the wavelength of 420-480nm to emit red light with the wavelength range of 660-780nm, and the strongest peak of the emission spectrum is positioned in the range of 710-720 nm.
Examples 4 to 7:
mn (manganese) 4+ Activated Ca 14 Zn 6 Al 10 O 35 The red phosphor has a chemical general formula of Ca 14 Zn 6-a Mg a+ c Al 10-b-2c B b Mn c O 35 The doping concentration of B in the prepared phosphor and the ratio of the preparation raw materials are shown in Table 2. By changing H in the raw material 3 BO 3 In other synthesis conditions, samples with different B doping concentrations can be prepared (examples 4-7).
The used raw materials are as follows: CaCO 3 、Al 2 O 3 、ZnO、MgO、MnCO 3 、H 3 BO 3
The mass (g) of each raw material component in examples 4 to 7 is as shown in table 2 below, and the raw materials are weighed and placed in a ball mill tank, and 12mL of 0.5% oleic acid ethanol solution is added;
TABLE 2
| Example numbering | Chemical formula (II) | B atomNumber of | CaCO 3 | Al 2 O 3 | H 3 BO 3 | ZnO | MnCO 3 | MgO | Total amount of |
| Example 4 | Ca 14 Al 9.75 B 0.05 Zn 5.1 Mn 0.1 MgO 35 | 0.05 | 5.852 | 2.076 | 0.078 | 1.733 | 0.048 | 0.168 | 9.88116 |
| Example 5 | Ca 14 Al 9.7 B 0.1 Zn 5.1 Mn 0.1 MgO 35 | 0.1 | 5.852 | 2.065 | 0.083 | 1.733 | 0.048 | 0.168 | 9.87482 |
| Example 6 | Ca 14 Al 9.65 B 0.15 Zn 5.1 Mn 0.1 MgO 35 | 0.15 | 5.852 | 2.054 | 0.087 | 1.733 | 0.048 | 0.168 | 9.86847 |
| Example 7 | Ca 14 Al 9.6 B 0.2 Zn 5.1 Mn 0.1 MgO 35 | 0.2 | 5.852 | 2.044 | 0.091 | 1.733 | 0.048 | 0.168 | 9.86213 |
Secondly, placing the ball milling tank in the first step in a ball mill, and keeping the ball milling tank at the rotating speed of 190r/min for 20 hours;
taking out the slurry uniformly mixed in the step two, putting the slurry into a culture dish, and drying the slurry in a drying oven at the temperature of 60 ℃ to obtain precursor powder;
and fourthly, calcining the precursor powder obtained in the third step in a muffle furnace for 8 hours at 1230 ℃, and finally obtaining the embodiment 4-7.
FIG. 2-3 shows the excitation and emission spectra of samples with different B-doping concentrations, the excitation spectra show that the phosphor can be effectively excited under the conditions of 280-460nm UV/near UV/purple/blue light, and the emission spectra show that the phosphor prepared in examples 4-7 can be excited at 325nmAll can emit 660-730nm far-red light, and the peak value is positioned at 713 nm. As the amount of B doping increased, the fluorescence intensity of the phosphor sample showed a tendency to increase and then decrease, wherein Ca was prepared in example 5 14 Al 9.7 B 0.1 Zn 5.1 Mn 0.1 MgO 35 The fluorescent intensity of the phosphor is maximized.
Examples 8 to 12:
mn (manganese) 4+ Activated Ca 14 Zn 6 Al 10 O 35 The red phosphor has a chemical general formula of Ca 14 Zn 6-a Mg a+ c Al 10-b-2c B b Mn c O 35 The doping concentration of B in the prepared phosphor and the ratio of the preparation raw materials are shown in Table 3. By changing H in the raw material 3 BO 3 In other cases, samples with different B doping concentrations (examples 8-12) were prepared.
The used raw materials are as follows: CaCO 3 、Al 2 O 3 、ZnO、MgO、MnCO 3 、H 3 BO 3
The mass (g) of each raw material component in examples 8 to 12 is as shown in table 3 below, and the raw materials were weighed and placed in a ball mill jar, and 12mL of a 0.5% oleic acid ethanol solution was added;
TABLE 3
| Example numbering | Chemical formula (II) | Number of B atoms | CaCO 3 | Al 2 O 3 | H 3 BO 3 | ZnO | MnCO 3 | MgO | Total amount of |
| Example 8 | Ca 14 Al 9.8 Zn 5.5 Mn 0.1 Mg 0.6 O 35 | / | 5.899 | 2.103 | / | 1.987 | 0.048 | 0.051 | 10.038 |
| Example 9 | Ca 14 Al 9.6 B 0.2 Zn 5.5 Mn 0.1 Mg 0.6 O 35 | 0.2 | 5.852 | 2.044 | 0.052 | 1.869 | 0.048 | 0.101 | 9.965 |
| Example 10 | Ca 14 Al 9.5 B 0.3 Zn 5.5 Mn 0.1 Mg 0.6 O 35 | 0.3 | 5.852 | 2.022 | 0.077 | 1.869 | 0.048 | 0.101 | 9.970 |
| Example 11 | Ca 14 Al 9.4 B 0.4 Zn 5.5 Mn 0.1 Mg 0.6 O 35 | 0.4 | 5.852 | 2.001 | 0.103 | 1.869 | 0.048 | 0.101 | 9.974 |
| Example 12 | Ca 14 Al 9.3 B 0.5 Zn 5.5 Mn 0.1 Mg 0.6 O 35 | 0.5 | 5.852 | 1.980 | 0.129 | 1.869 | 0.048 | 0.101 | 9.979 |
Placing the ball milling tank in the step I in a ball mill, and keeping the ball milling tank in the ball mill for 30 hours at a rotating speed of 200 r/min;
taking out the slurry uniformly mixed in the step two, putting the slurry into a culture dish, and drying the slurry in a drying oven at the temperature of 60 ℃ to obtain precursor powder;
and fourthly, calcining the precursor powder obtained in the third step in a muffle furnace at 1250 ℃ for 5 hours to finally obtain the embodiment 8-12.
Fig. 4 shows the effect of B concentration on the quantum efficiency of phosphor samples. Examples 9-12 increased B at different concentrations based on example 8, and it can be seen that the quantum efficiency of examples 9-12 is significantly higher than that of example 8, and as the concentration of B increased, the quantum efficiency of the sample tended to increase first and then decrease, with the quantum efficiency of example 11 being the highest.
Example 13
Mn (manganese) 4+ Activated Ca 14 Zn 6 Al 10 O 35 The red phosphor has a chemical general formula of Ca 14 Zn 6-a Mg a+ c Al 10-b-2c B b Mn c O 35 Table 4 shows the doping concentration and the compounding ratio of the preparation raw material of B of example 13.
The used raw materials are as follows: CaCO 3 、Al 2 O 3 、ZnO、MgO、MnCO 3 、H 3 BO 3
The mass (g) of each raw material component in example 13 is as shown in table 4 below, the raw materials are weighed and placed in a ball milling tank, and 12mL of 0.5% oleic acid ethanol solution is added;
TABLE 4
| Example numbering | Chemical formula (II) | Number of B atoms | CaCO 3 | Al 2 O 3 | H 3 BO 3 | ZnO | MnCO 3 | MgO | Total amount of |
| Example 13 | Ca 14 Al 9.79 B 0.01 Zn 6 Mn 0.1 O 35 | 0.01 | 5.852 | 2.084 | 0.003 | 2.039 | 0.048 | 0.017 | 10.042 |
Secondly, placing the ball milling tank in the first step in a ball mill, and keeping the ball milling tank for 20 hours at a rotating speed of 210 r/min;
taking out the slurry uniformly mixed in the step two, putting the slurry into a culture dish, and drying the slurry in a drying oven at the temperature of 60 ℃ to obtain precursor powder;
and fourthly, calcining the precursor powder obtained in the third step in a muffle furnace at 1250 ℃ for 5 hours to finally obtain the embodiment 13.
FIG. 5 shows the quenching performance and color coordinates of the red phosphor prepared in this example. (wherein: the thermal quenching performance is measured by a fluorescence spectrometer for the emission spectrum of the red phosphor prepared in this example from room temperature (300K) to high temperature (573K), and the thermal quenching curve is obtained by using the integral area ratio of the fluorescence intensity at each temperature), as shown in the figure: the temperature at which the fluorescence intensity of the red phosphor prepared in example 13 was reduced to 50% of the original value was 573K, thus indicating that the phosphor prepared in the present invention has good thermal stability.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A red phosphor is characterized in that the phosphor has the following chemical general formula Ca 14 Zn 6-a Mg a+c Al 10-b- 2c B b Mn c O 35 Wherein:
the matrix is Ca 14 (Zn,Mg) 6 (Al,B) 10 O 35 The activator is Mn 4+ And by co-doping with Mg 2+ To balance Mn 4+ Substituted octahedral centre Al 3+ A location;
a is more than or equal to 0 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, and a, b and c are not 0 at the same time;
preferably, 0.1. ltoreq. a. ltoreq.0.9;
preferably, 0.01. ltoreq. b.ltoreq.0.4;
preferably, 0.05. ltoreq. c.ltoreq.0.4.
2. The red phosphor of claim 1, wherein the phosphor Ca is 14 Zn 6-a Mg a+c Al 10-b- 2c B b Mn c O 35 The material is prepared from a Ca source, a Zn source, an Mg source, an Al source, a B source and a Mn source by a solid-phase sintering method.
Preferably, the Ca source is provided by a compound containing Ca element; for example, provided by at least one of a carbonate, an oxide, a chloride, a fluoride, a nitrate, and a sulfate of a Ca-containing element; preferably provided by a carbonate containing Ca element.
Preferably, the Zn source is provided by a Zn-containing compound; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of a Zn-containing element; preferably provided by an oxide containing a Zn element.
Preferably, the Mg source is provided by a compound containing an Mg element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of an Mg-containing element; preferably provided by an oxide containing Mg element.
Preferably, the Al source is provided by a compound containing an Al element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate, and sulfate of an Al-containing element; preferably provided by an oxide containing an Al element.
Preferably, the source of B is provided by a compound containing an element B; for example, the B element-containing compound is H 3 BO 3 、B 2 O 3 And B 2 H 6 At least one of; preferably H 3 BO 3 。
Preferably, the Mn source is provided by a Mn element-containing compound; for example, provided by at least one of carbonates, oxides, chlorides, nitrates, and sulfates of the Mn-containing element; preferably provided by a carbonate containing Mn element.
3. The red phosphor of claim 1 or 2, wherein the phosphor is Ca 14 Al 9.9 Zn 6 Mn 0.05 Mg 0.05 O 35 、Ca 14 Al 9.6 Zn 6 Mn 0.2 Mg 0.2 O 35 、Ca 14 Al 9.4 Zn 6 Mn 0.3 Mg 0.3 O 35 、Ca 14 Al 9.75 B 0.05 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.7 B 0.1 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.65 B 0.15 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.6 B 0.2 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.75 B 0.05 Zn 5.1 Mn 0.1 MgO 35 、Ca 14 Al 9.8 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.6 B 0.2 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.5 B 0.3 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.4 B 0.4 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.3 B 0.5 Zn 5.5 Mn 0.1 Mg 0.6 O 35 、Ca 14 Al 9.79 B 0.01 Zn 6 Mn 0.1 Mg 0.1 O 35 。
Preferably, the phosphor is capable of being excited by ultraviolet/near ultraviolet/violet/blue light with a wavelength of 280-480 nm.
Preferably, the phosphor powder can emit red light with the wavelength range of 660-780nm after being excited, and the strongest peak of the emission spectrum is located in the range of 710-720nm, and preferably around 713 nm.
4. The method of any one of claims 1-3, wherein the method comprises the steps of:
and (2) taking a Ca source, a Zn source, an Mg source, an Al source, a B source and a Mn source as raw materials, and obtaining the fluorescent powder by a solid-phase sintering method.
Preferably, the Ca source, Zn source, Mg source, Al source, B source and Mn source have the meaning as defined in claim 2.
Preferably, the method further comprises the step of ball milling the mixed raw materials before the solid phase sintering. Preferably, the rotation speed of the ball milling is 190-.
Preferably, the preparation method further comprises adding a ball milling medium to the mixed raw materials. For example, the ball milling medium may be an ethanol solution of oleic acid. Further, the concentration of the ethanol solution of the oleic acid is 0.1-1%, and preferably 0.2-0.8%.
5. The preparation method according to claim 4, wherein the solid-to-liquid ratio of the ethanol solution of oleic acid to the total weight of the mixed raw materials is 12mL (9.0-11.0) g, preferably 12mL (9.5-10.5) g, more preferably 12mL (9.8-10.2) g.
Preferably, the preparation method further comprises the step of drying the mixed raw materials after ball milling. For example, the drying temperature is 40-80 ℃.
Preferably, the temperature of the solid phase sintering is 1200-1300 ℃, preferably 1230-1280 ℃.
Preferably, the solid phase sintering time is 1-12 h, preferably 2-10h, preferably 2h, 5h, 8h and 10 h.
6. The method of claim 4 or 5, comprising the steps of:
firstly, weighing a Ca source, a Zn source, a Mg source, an Al source, a B source and a Mn source, and adding 12mL of ethanol solution containing 0.5% of oleic acid;
secondly, keeping the mixture prepared in the step I for 10-30h at the rotating speed of 190-210 r/min;
thirdly, drying the slurry uniformly mixed in the second step to obtain precursor powder;
fourthly, calcining the precursor powder obtained in the third step at the temperature of 1230- 14 Zn 6- a Mg a+c Al 10-b-2c B b Mn c O 35 The phosphor (a is more than or equal to 0 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 0.5, and c is more than or equal to 0 and less than or equal to 0.5).
7. Use of the phosphor according to any one of claims 1 to 3 and/or the phosphor produced by the production method according to any one of claims 4 to 6 in a light-emitting device. Wherein the light-emitting device is used in the fields of agricultural production and the like.
Preferably, the light emitting device is a white LED device. Further, the white light LED device is used in the fields of agricultural production and the like. For example, plant growth is promoted using the white LED light source.
8. A light-emitting device comprising the phosphor according to any one of claims 1 to 3 and/or the phosphor material Ca prepared by the preparation method according to any one of claims 4 to 6 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 . Preferably, the light emitting device is a white LED device.
Preferably, the light emitting device further comprises an LED chip for carrying the phosphor material Ca 14 Zn 6- a Mg a+c Al 10-b-2c B b Mn c O 35 。
Preferably, the LED chip is an ultraviolet/near ultraviolet/purple light/blue light LED chip with the wavelength of 280-480 nm. Preferably a blue LED chip.
Preferably, the blue LED chip is a blue LED chip with a peak value between 420 and 480 nm.
Preferably, the light emitting device comprises a luminescent material layer coated on the LED chip, wherein the luminescent material layer contains the uniformly dispersed phosphor material Ca 14 Zn 6-a Mg a+c Al 10-b-2c B b Mn c O 35 . Further, the luminescent material layer also contains glue. For example, the glue may be epoxy, polycarbonate or silicone; silica gel is preferred.
Preferably, the light emitting device is a white LED device. Further, the white light LED device is used in the fields of agricultural production and the like. For example, the white LED light source is used to promote plant growth.
9. A method for producing the light-emitting device according to claim 8, comprising the steps of: the fluorescent powder material and the glue are uniformly mixed and then coated on the LED chip.
10. A light-emitting device comprising the phosphor according to any one of claims 1 to 3 and/or the luminescent material obtained by the production method according to any one of claims 4 to 6 is used in the fields of agricultural production and the like. For example, plant growth is promoted using the white LED light source.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531144A (en) * | 2014-12-14 | 2015-04-22 | 中国科学院福建物质结构研究所 | CaMg<2>Al<16>O<27>:Mn <4+> red fluorescent powder and preparation technology thereof |
| CN105154080A (en) * | 2015-09-18 | 2015-12-16 | 湖南爱德光电新材料有限公司 | Dark red phosphor and application thereof |
| CN106701073A (en) * | 2017-01-06 | 2017-05-24 | 江苏师范大学 | Mn4+ ion doped titanate-based red fluorescent powder and preparation method thereof |
| CN107118764A (en) * | 2016-12-21 | 2017-09-01 | 广东工业大学 | A kind of red fluorescence powder and preparation method thereof |
| CN108384542A (en) * | 2018-02-02 | 2018-08-10 | 上海应用技术大学 | A kind of red fluorescence material and preparation method thereof |
| CN108834742A (en) * | 2018-06-01 | 2018-11-20 | 深圳市昀晨光电有限公司 | A method of promote Growth of Pleurotus eryngii to develop using LED plant growth light source |
| CN110205120A (en) * | 2019-06-24 | 2019-09-06 | 福建农林大学 | A kind of near ultraviolet excitated mixture red fluorescence powder, preparation method and application |
| CN112094645A (en) * | 2020-09-30 | 2020-12-18 | 华南理工大学 | Eu doped2+Blue light fluorescent material, preparation method thereof and white light LED light-emitting device |
-
2021
- 2021-02-25 CN CN202110211683.5A patent/CN114958352B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531144A (en) * | 2014-12-14 | 2015-04-22 | 中国科学院福建物质结构研究所 | CaMg<2>Al<16>O<27>:Mn <4+> red fluorescent powder and preparation technology thereof |
| CN105154080A (en) * | 2015-09-18 | 2015-12-16 | 湖南爱德光电新材料有限公司 | Dark red phosphor and application thereof |
| CN107118764A (en) * | 2016-12-21 | 2017-09-01 | 广东工业大学 | A kind of red fluorescence powder and preparation method thereof |
| CN106701073A (en) * | 2017-01-06 | 2017-05-24 | 江苏师范大学 | Mn4+ ion doped titanate-based red fluorescent powder and preparation method thereof |
| CN108384542A (en) * | 2018-02-02 | 2018-08-10 | 上海应用技术大学 | A kind of red fluorescence material and preparation method thereof |
| CN108834742A (en) * | 2018-06-01 | 2018-11-20 | 深圳市昀晨光电有限公司 | A method of promote Growth of Pleurotus eryngii to develop using LED plant growth light source |
| CN110205120A (en) * | 2019-06-24 | 2019-09-06 | 福建农林大学 | A kind of near ultraviolet excitated mixture red fluorescence powder, preparation method and application |
| CN112094645A (en) * | 2020-09-30 | 2020-12-18 | 华南理工大学 | Eu doped2+Blue light fluorescent material, preparation method thereof and white light LED light-emitting device |
Non-Patent Citations (3)
| Title |
|---|
| YIBING WU等: "A high-performance non-rare-earth deep-red-emitting Ca14-xSrxZn6Al10O35:Mn4+ phosphor for high-power plant growth LEDs", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| YIYANG ZHOU等: "Synthesis and luminescence properties of Mn4+-dopant Ca14Zn6Ga10-xAlxO35 solid solution", 《PROGRESS IN NATURAL SCIENCE: MATERIALS INTERNATIONAL》 * |
| 祁康成主编: "《发光原理与发光材料》", 29 February 2012, 电子科技大学出版社 * |
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