CN114958352B - A kind of red phosphor and preparation method and application thereof - Google Patents

Abstract

The invention discloses a Ca ₁₄ (Zn, Mg) ₆ (Al, B) ₁₀ O ₃₅ matrix red phosphor and its preparation method and application. Its general chemical formula is: Ca ₁₄ Zn _6‑a Mg _a+c Al _10‑b‑2c B _b Mn _c O ₃₅ , 0≤a≤1.5, 0≤b≤0.5, 0≤c≤0.5, and a, b and c are not 0 at the same time. In this invention, Mg partially replaces Zn and B partially replaces Al, thereby effectively improving the absorption of blue light. The quantum efficiency of the prepared phosphor is as high as over 85%, which is environmentally friendly and can be excited by ultraviolet to blue light (280-460nm). Obtain red emission at 660-780nm, and the thermal quenching temperature is as high as 300°C. Its fluorescence intensity only drops to 50% of room temperature at a high temperature of 580K. It has high thermal stability and luminescence performance, and has good economic benefits. and development prospects.

Description

A kind of red phosphor and preparation method and application thereof

Technical field

The invention relates to the technical field of fluorescent material preparation, and relates to a red phosphor of Ca ₁₄ (Zn, Mg) ₆ (Al, B) ₁₀ O ₃₅ matrix and its preparation method and application. Specifically, it relates to a Ca ₁₄ with high luminous efficiency. (Zn,Mg) ₆ (Al,B) ₁₀ O ₃₅ matrix red phosphor and its preparation method and application.

Background technique

Commercial white-light LEDs mainly achieve white light emission through "blue LED chip + yellow phosphor". They are widely used in various fields because of their excellent characteristics such as high luminous brightness, low energy consumption and environmental friendliness. However, the above-mentioned white light LEDs lack red luminescent components, so it is difficult to emit warm white light, and have defects such as low color rendering index and high color temperature. In order to make up for the luminescence defects of existing white light LEDs, the synthesis of red phosphors that can efficiently absorb blue light and produce red light emission has become a research hotspot.

Currently, in red phosphors that can efficiently absorb blue light and produce red light emission, the cost of rare earth elements is high and the synthesis of nitrides requires high temperature and high pressure, and the reaction conditions are relatively harsh, which limits its application development. Mn ⁴⁺ doped fluoride is toxic, environmentally unfriendly and has poor stability. Synthetic oxides have low cost, simple synthesis process, non-toxic and pollution-free raw materials, and good chemical and thermal stability. At the same time, the excitation spectrum of Mn ⁴⁺ is located in the blue-violet region, and its emission spectrum is a strong narrow red emission. , but its quantum efficiency is generally below 80%. Therefore, how to develop a high quantum efficiency Mn ⁴⁺ doped oxide red phosphor system will have high economic benefits and application prospects.

Based on the high luminous efficiency of LED light sources, the use of LED light sources to promote plant growth has been widely used in agricultural production. For example, the patent document with application number CN201810554012.7 discloses Ca ₁₄ Al ₁₀ Zn ₆ O ₃₅ :Mn ⁴⁺ phosphor, which involves a method of using LED plant growth light source to promote the growth and development of Pleurotus eryngii. However, the phosphor in this patent document is prepared by a hydrothermal method, which still has shortcomings such as low yield and high preparation cost. Therefore, it is not suitable for the industrial development of phosphors, and the phosphors prepared by this method still have the defect of low quantum efficiency. Therefore, how to prepare phosphors with high quantum efficiency, high yield, low preparation cost, and suitable for industrial development has become an urgent technical problem to be solved.

Contents of the invention

In order to improve the above technical problems, the present invention provides a red phosphor, which has the following general chemical 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 Mn ⁴⁺ is co-doped to balance the Al ³⁺ position in the octahedral center by co-doping Mg ²⁺ ;

0≤a≤1.5, 0≤b≤0.5, 0≤c≤0.5, and a, b and c are not 0 at the same time;

Preferably, 0.1≤a≤0.9, for example, a=0, 0.1, 0.2, 0.5, 0.7, 0.9, 1.0;

Preferably, 0.01≤b≤0.4, for example, 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 is composed of Ca source, Zn source, Mg source, Al source, B source and The raw materials of Mn source are prepared by solid phase sintering method.

According to an embodiment of the present invention, the Ca source is provided by a compound containing Ca element; for example, provided by at least one of carbonate, oxide, chloride, fluoride, nitrate and sulfate containing Ca element. ; Preferably provided by carbonate containing Ca element.

According to an embodiment of the present invention, the Zn source is provided by a compound containing Zn element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate and sulfate containing Zn element; preferably by Provided by oxides containing Zn element.

According to an embodiment of the present invention, the Mg source is provided by a compound containing Mg element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate and sulfate containing Mg element; preferably by Provided by oxides containing Mg element.

According to an embodiment of the present invention, the Al source is provided by a compound containing Al element; for example, provided by at least one of an oxide, carbonate, chloride, nitrate and sulfate containing Al element; preferably by Oxides containing Al elements are provided.

According to an embodiment of the present invention, the B source is provided by a compound containing B element; for example, the compound containing B element is at least one of H ₃ BO ₃ , B ₂ O ₃ and B ₂ H ₆ ; preferably is H ₃ BO ₃ .

According to an embodiment of the present invention, the Mn source is provided by a compound containing Mn element; for example, provided by at least one of carbonate, oxide, chloride, nitrate and sulfate containing Mn element; preferably by Carbonate containing Mn element is provided.

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 _{1 4} 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 an embodiment of the present invention, the phosphor can be excited by ultraviolet/near ultraviolet/violet/blue light with a wavelength of 280-480 nm. Preferably, the phosphor can emit red light with a wavelength range of 660-780 nm after being excited, and the strongest peak of its emission spectrum is located in the range of 710-720 nm, preferably around 713 nm.

The invention also provides a method for preparing the phosphor, which includes the following steps:

The phosphor powder is obtained by using Ca source, Zn source, Mg source, Al source, B source and Mn source as raw materials through solid phase sintering method.

According to an embodiment of the present invention, the Ca source, Zn source, Mg source, Al source, B source and Mn source have the meanings as described above.

According to an embodiment of the present invention, before the solid phase sintering, the step of ball milling the mixed raw materials is further included. Preferably, the rotation speed of the ball mill is 190-210r/min, and the time is 10-30h.

According to an embodiment of the present invention, the preparation method further includes adding ball milling media 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 to 1%, preferably 0.2 to 0.8%, and examples are 0.1%, 0.5%, 0.8%, and 1%.

According to the embodiment of the present invention, the solid-liquid ratio of the ethanol solution of oleic acid and 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.

According to an embodiment of the present invention, the preparation method further includes the step of drying the mixed raw materials after ball milling. For example, the drying temperature is 40°C to 80°C, and examples are 40°C, 60°C, and 80°C.

According to an embodiment of the present invention, the solid phase sintering temperature is 1200-1300°C, preferably 1230-1280°C, and is exemplified by 1200°C, 1230°C, 1250°C, 1280°C, and 1300°C.

According to the embodiment of the present invention, the solid phase sintering time is 1 to 12 hours, preferably 2 to 10 hours, preferably 2 hours, 5 hours, 8 hours, or 10 hours.

According to an embodiment of the present invention, the preparation method of the red phosphor includes the following steps:

①Weigh the Ca source, Zn source, Mg source, Al source, B source and Mn source, and add 12 mL of ethanol solution containing 0.5% oleic acid;

② Keep the mixture prepared in step ① at a rotation speed of 190-210r/min for 10-30h;

③Dry the uniformly mixed slurry in step ② to obtain precursor powder;

④ Calculate the precursor powder obtained in step ③ at 1230-1280°C for 2-10h to obtain a phosphor with the chemical formula Ca ₁₄ Zn _6-a Mg _a+c Al _10-b-2c B _b Mn _c O ₃₅ (0 ≤a≤1.5, 0≤b≤0.5, 0≤c≤0.5).

The present invention also provides the application of the above-mentioned phosphor in a light-emitting device. Wherein, the light-emitting device is used in agricultural production and other fields.

Preferably, the light emitting device is a white light LED device. Further, the white light LED device is used in agricultural production and other fields. For example, the white LED light source is used to promote plant growth.

The present invention also provides a light-emitting device, which includes 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 light emitting device is a white light LED device.

According to an embodiment of the present invention, the light-emitting device further includes an LED chip, and the LED chip is used to carry 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/violet/blue LED chip with a wavelength of 280-480 nm. Preferably it is a blue LED chip.

According to an embodiment of the present invention, the blue LED chip is a blue LED chip with a peak value between 420-480 nm.

According to an embodiment of the present invention, the light-emitting device includes a luminescent material layer coated on the LED chip, and the luminescent material layer contains 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 can be epoxy resin, polycarbonate or silica gel; silica gel is preferred. The amount of glue is not particularly limited, as long as it can be evenly coated on the LED chip according to operations known in the art.

According to an embodiment of the present invention, the light emitting device is a white light LED device. Further, the white light LED device is used in agricultural production and other fields. For example, the white LED light source is used to promote plant growth.

The present invention also provides a method for preparing the above-mentioned light-emitting device, which includes the following steps: uniformly mixing the above-mentioned phosphor material and glue, and then coating the mixture on the LED chip.

The present invention also provides a light-emitting device containing the above-mentioned light-emitting material for use in agricultural production and other fields. For example, the white LED light source is used to promote plant growth.

Beneficial effects of the present invention:

In the present invention, Ca ₁₄ Al ₁₀ Zn ₆ O ₃₅ :Mn ⁴⁺ phosphor is co-doped with Mg ²⁺ /Mn ⁴⁺ , in which Al ³⁺ is replaced by Mn ⁴⁺ , resulting in charge imbalance and aggravating the resulting crystal defects. In order to eliminate the non-radiative transition, the present invention effectively improves the absorption of blue light by partially replacing Zn with Mg and replacing Al with B partially, so that the quantum efficiency of the phosphor reaches more than 85%, and at the same time, the prepared phosphor has good thermal properties. Stability, its fluorescence intensity only drops to 50% of room temperature at a high temperature of 580K; when the temperature is lower than 500K, the CIE chromaticity coordinates remain almost unchanged, and the relative intensity at temperatures of 460K and 540K remains at room temperature (300K ) 99% and 82%. The thermal stability of the Mg ²⁺ /Mn ⁴⁺ co-doped Ca ₁₄ Al ₁₀ Zn ₆ O ₃₅ :Mn ⁴⁺ phosphor prepared by the present invention is significantly higher than the currently commercialized red phosphor YAG:Ce ³⁺ . The thermal stability of K ₂ TiF ₆ :Mn ⁴⁺ and Sr ₂ Si ₅ N ₈ :Eu ²⁺ is the most outstanding Mn ⁴⁺ activated oxide phosphor to date.

Description of the drawings

Figure 1 is a graph showing changes in fluorescence intensity and quantum efficiency of red phosphors prepared in Examples 1-3 as a function of Mn doping concentration.

Figure 2 shows the excitation and emission spectra of the red phosphor prepared in Examples 4-7.

Figure 3 shows the excitation and emission spectra of the red phosphor prepared in Example 5.

Figure 4 is a graph showing changes in quantum efficiency of red phosphors prepared in Examples 8-12 as B concentration changes.

Figure 5 shows the thermal quenching performance and color coordinates of the red phosphor prepared in Example 13.

Figure 6 shows an LED device prepared from the red phosphor prepared in Example 2.

Figure 7 is a fluorescence spectrum of an LED device prepared from the red phosphor prepared in Example 2.

Detailed ways

The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following examples are only illustrative and explain the present invention and should not be construed as limiting the scope of the present invention. All technologies implemented based on the above contents of the present invention are covered by the scope of protection intended by the present invention.

Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

Example 1-3

A kind of Mn ⁴⁺ activated red phosphor of Ca ₁₄ Zn ₆ Al ₁₀ O _35. The general chemical formula of the phosphor is Ca ₁₄ Zn _6-a Mg _{a+ c} Al _10-b-2c B _b Mn _c O ₃₅ , as shown in the table 1 gives the Mn doping concentration of the prepared phosphor and the ratio of the raw materials. By changing the amount of _MnCO3 in the raw materials, samples with different Mn doping concentrations can be prepared while other synthesis conditions remain unchanged (Examples 1-3).

Raw materials used: CaCO ₃ , Al ₂ O ₃ , ZnO, MgO, MnCO ₃

①The mass (g) of each raw material component in Examples 1-3 is as shown in Table 1. Weigh the raw materials and put them into the ball mill tank, and add 12 mL of 0.5% oleic acid ethanol solution;

Table 1

Example number chemical formula Number of Mn atoms CaCO ₃ Al ₂ O ₃ ZnO MnCO ₃ MgO total amount 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

②Place the ball mill jar from step ① in the ball mill and maintain it at a speed of 210r/min for 10h;

③ Take out the uniformly mixed slurry in step ②, put it into a petri dish, and dry it in an oven at 60°C to obtain precursor powder;

④ Calculate the precursor powder obtained in step ③ in a muffle furnace at 1280°C for 2 hours to finally obtain the red phosphor powder of Example 1-3.

As shown in Figure 1, as the Mn concentration increases, the emission peak shapes of Examples 1-3 are consistent, and the fluorescence intensity shows a trend of first weakening and then increasing. Similarly, the quantum efficiency of the sample also first decreases and then increases.

Referring to Figure 6, a light-emitting device is formed by mixing the phosphor material prepared in Example 2 and silica gel evenly, then coating it on the light-emitting surface of the blue LED chip, and heating and drying it to form a phosphor light-emitting layer. After the positive and negative electrodes are energized, the LED chip emits blue light. The red phosphor luminescent layer emits light after absorbing the blue light. The fluorescence spectrum is shown in Figure 7. The results in Figure 7 show that the red phosphor prepared by the present invention can be excited by blue light with a wavelength of 420-480nm to emit red light with a wavelength range of 660-780nm, and the strongest peak of its emission spectrum is located in the range of 710-720nm. Inside.

Example 4-7:

A kind of Mn ⁴⁺ activated red phosphor of Ca ₁₄ Zn ₆ Al ₁₀ O _35. The general chemical formula of the phosphor is Ca ₁₄ Zn _6-a Mg _{a+ c} Al _10-b-2c B _b Mn _c O ₃₅ , as shown in the table 2 gives the B doping concentration of the prepared phosphor and the ratio of the raw materials. By changing the amount of H ₃ BO ₃ in the raw materials, samples with different B doping concentrations can be prepared while other synthesis conditions remain unchanged (Examples 4-7).

Raw materials used: CaCO ₃ , Al ₂ O ₃ , ZnO, MgO, MnCO ₃ , H ₃ BO ₃

①The mass (g) of each raw material component in Example 4-7 is as shown in Table 2. Weigh the raw materials and put them into the ball mill tank, and add 12 mL of 0.5% oleic acid ethanol solution;

Table 2

Example number chemical formula Number of B atoms CaCO ₃ Al ₂ O ₃ H ₃ BO ₃ ZnO MnCO ₃ MgO total amount 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

②Place the ball mill jar from step ① in the ball mill and maintain it at a speed of 190r/min for 20h;

③ Take out the uniformly mixed slurry in step ②, put it into a petri dish, and dry it in an oven at 60°C to obtain precursor powder;

④ Calculate the precursor powder obtained in step ③ in a muffle furnace at 1230°C for 8 hours to finally obtain Example 4-7.

Figure 2-3 shows the excitation and emission spectra of samples with different B doping concentrations. The excitation spectrum shows that the phosphor can be effectively excited under ultraviolet/near ultraviolet/violet/blue light of 280-460nm. The emission spectrum shows that the phosphor prepared in Example 4-7 The obtained phosphor can emit far-red light of 660-730nm under 325nm excitation, with a peak at 713nm. As the B doping amount increases, the fluorescence intensity of the phosphor samples first increases and then decreases. The Ca ₁₄ Al _9.7 B _0.1 Zn _5.1 Mn _0.1 MgO ₃₅ phosphor prepared in Example 5 has the highest fluorescence intensity.

Examples 8-12:

A kind of Mn ⁴⁺ activated red phosphor of Ca ₁₄ Zn ₆ Al ₁₀ O _35. The general chemical formula of the phosphor is Ca ₁₄ Zn _6-a Mg _{a+ c} Al _10-b-2c B _b Mn _c O ₃₅ , as shown in the table 3 gives the B doping concentration of the prepared phosphor and the ratio of the raw materials. By changing the amount of H ₃ BO ₃ in the raw materials, samples with different B doping concentrations can be prepared while other synthesis conditions remain unchanged (Examples 8-12).

Raw materials used: CaCO ₃ , Al ₂ O ₃ , ZnO, MgO, MnCO ₃ , H ₃ BO ₃

①The mass (g) of each raw material component in Examples 8-12 is as shown in Table 3. Weigh the raw materials and put them into the ball mill tank, and add 12 mL of 0.5% oleic acid ethanol solution;

table 3

Example number chemical formula Number of B atoms CaCO ₃ Al ₂ O ₃ H ₃ BO ₃ ZnO MnCO ₃ MgO total amount 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

②Place the ball mill jar from step ① in the ball mill and keep it at a speed of 200r/min for 30h;

③ Take out the uniformly mixed slurry in step ②, put it into a petri dish, and dry it in an oven at 60°C to obtain precursor powder;

④ Calculate the precursor powder obtained in step ③ in a muffle furnace at 1250°C for 5 hours to finally obtain Examples 8-12.

Figure 4 shows the effect of B concentration on the quantum efficiency of phosphor samples. Examples 9-12 add B at different concentrations based on Example 8. It can be seen that the quantum efficiency of Example 9-12 is significantly higher than that of Example 8. As the concentration of B increases, the quantum efficiency of the sample has The tendency is to increase first and then decrease, among which the quantum efficiency of Example 11 is the highest.

Example 13

A kind of Mn ⁴⁺ activated red phosphor of Ca ₁₄ Zn ₆ Al ₁₀ O _35. The general chemical formula of the phosphor is Ca ₁₄ Zn _6-a Mg _{a+ c} Al _10-b-2c B _b Mn _c O ₃₅ , as shown in the table 4 gives the doping concentration of B and the ratio of preparation raw materials in Example 13.

Raw materials used: CaCO ₃ , Al ₂ O ₃ , ZnO, MgO, MnCO ₃ , H ₃ BO ₃

①The mass (g) of each raw material component in Example 13 is as shown in Table 4. Weigh the raw materials and put them into the ball mill tank, and add 12 mL of 0.5% oleic acid ethanol solution;

Table 4

Example number chemical formula Number of B atoms CaCO ₃ Al ₂ O ₃ H ₃ BO ₃ ZnO MnCO ₃ MgO total amount 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

②Place the ball mill jar from step ① in the ball mill and maintain it at a speed of 210r/min for 20h;

③ Take out the uniformly mixed slurry in step ②, put it into a petri dish, and dry it in an oven at 60°C to obtain precursor powder;

④ Calculate the precursor powder obtained in step ③ in a muffle furnace at 1250°C for 5 hours to finally obtain Example 13.

Figure 5 shows the thermal quenching performance and color coordinates of the red phosphor prepared in this embodiment. (Among them: Thermal quenching performance uses a fluorescence spectrometer to test the emission spectrum of the red phosphor prepared in this example from room temperature (300K) to high temperature (573K), and uses the integrated area ratio of the fluorescence intensity at each temperature to obtain the thermal quenching curve ), it can be seen from the figure that the fluorescence intensity of the red phosphor prepared in Example 13 drops to 50% of the original temperature at 573K, which shows that the phosphor prepared by 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-described embodiment. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (37)

1. A red phosphor, characterized in that the phosphor has the following general chemical 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 Mn ⁴⁺ is co-doped to balance the Al ³⁺ position in the octahedral center by co-doping Mg ²⁺ ; 0≤a≤1.5, 0.01≤b≤0.5, 0.05≤c≤0.5, and a, b and c are not 0 at the same time. 2. The red phosphor according to claim 1, characterized in that, 0.1≤a≤0.9. 3. The red phosphor according to claim 1, characterized in that, 0.01≤b≤0.4. 4. The red phosphor according to claim 1, characterized in that, 0.05≤c≤0.4. 5. The red phosphor according to any one of claims 1 to 4, wherein the phosphor Ca ₁₄ Zn _6-a Mg _{a+ c} Al _10-b-2c B _b Mn _c O ₃₅ is composed of Ca The raw materials of source, Zn source, Mg source, Al source, B source and Mn source are prepared by solid phase sintering method. 6. The red phosphor according to claim 5, wherein the Ca source is provided by at least one of carbonate, oxide, chloride, fluoride, nitrate and sulfate containing Ca element. . 7. The red phosphor of claim 5, wherein the Zn source is provided by at least one of oxides, carbonates, chlorides, nitrates and sulfates containing Zn elements. 8. The red phosphor of claim 5, wherein the Mg source is provided by at least one of oxides, carbonates, chlorides, nitrates and sulfates containing Mg elements. 9. The red phosphor of claim 5, wherein the Al source is provided by at least one of oxides, carbonates, chlorides, nitrates and sulfates containing Al elements. 10. The red phosphor of claim 5, wherein the B source is provided by at least one of B element-containing compounds H ₃ BO ₃ , B ₂ O ₃ and B ₂ H ₆ . 11. The red phosphor according to claim 5, wherein the Mn source is provided by at least one of carbonate, oxide, chloride, nitrate and sulfate containing Mn element. 12. The red phosphor according to any one of claims 1 to 4, characterized in that the phosphor is Ca ₁₄ Al _9.9 Zn ₆ Mn _0.05 Mg _0.05 O ₃₅ or 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 _{0.1 5} 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 _9.8 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 _{1 4} 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 Z n _{6 0.1} Mg _0.1 O ₃₅ . 13. The red phosphor according to any one of claims 1 to 4, characterized in that the phosphor can be excited by ultraviolet/near ultraviolet/violet light/blue light with a wavelength of 280-480 nm. 14. The red phosphor according to any one of claims 1 to 4, characterized in that, after being excited, the phosphor can emit red light in the wavelength range of 660-780 nm, with the strongest peak of its emission spectrum located at 710 nm. -720nm range. 15. The preparation method of red phosphor according to any one of claims 1-14, characterized in that the preparation method includes the following steps: Mix Ca source, Zn source, Mg source, Al source, B source and Mn source as raw materials to obtain mixed raw materials, and obtain the phosphor powder through solid phase sintering method. 16. The preparation method according to claim 15, characterized in that the preparation method further includes adding ball milling media to the mixed raw materials. 17. The preparation method according to claim 16, wherein the ball milling medium is an ethanol solution of oleic acid. 18. The preparation method according to claim 17, wherein the concentration of the ethanol solution of oleic acid is 0.1~1%. 19. The preparation method according to claim 18, wherein the concentration of the ethanol solution of oleic acid is 0.2~0.8%. 20. The preparation method according to claim 17, wherein the solid-liquid ratio of the ethanol solution of oleic acid and the total weight of the mixed raw materials is 12 mL: (9.0~11.0) g. 21. The preparation method according to claim 20, characterized in that the solid-liquid ratio of the ethanol solution of oleic acid and the total weight of the mixed raw materials is 12 mL: (9.5~10.5) g. 22. The preparation method according to claim 21, wherein the solid-liquid ratio of the ethanol solution of oleic acid and the total weight of the mixed raw materials is 12 mL: (9.8~10.2) g. 23. The preparation method according to claim 15, wherein the solid phase sintering temperature is 1200-1300°C and the time is 1-12 hours. 24. The preparation method according to claim 23, wherein the solid phase sintering temperature is 1230-1280°C and the time is 2-10 hours. 25. Application of the phosphor according to any one of claims 1 to 14 and/or the phosphor prepared by the preparation method according to any one of claims 15 to 24 in a light-emitting device. 26. The application of claim 25, wherein the light-emitting device is used in the field of agricultural production. 27. The application of claim 25, wherein the light-emitting device is a white light LED device, and the white light LED device is used in the field of agricultural production. 28. The application of claim 27, wherein the white light LED device is used to promote plant growth. 29. A light-emitting device, the light-emitting device comprising the phosphor according to any one of claims 1-14 and/or the phosphor prepared by the preparation method according to any one of claims 15-24. 30. The light-emitting device of claim 29, wherein the light-emitting device further includes an LED chip, and the LED chip is used to carry the phosphor. 31. The light-emitting device of claim 30, wherein the LED chip is an ultraviolet/near ultraviolet/violet/blue LED chip with a wavelength of 280-480 nm. 32. The light-emitting device of claim 31, wherein the blue LED chip is a blue LED chip with a peak value between 420-480 nm. 33. The light-emitting device of claim 30, wherein the light-emitting device includes a luminescent material layer, the luminescent material layer is coated on the LED chip, and the luminescent material layer contains uniformly dispersed The phosphor. 34. The light-emitting device according to claim 33, wherein the light-emitting material layer further contains epoxy resin, polycarbonate or silica gel. 35. The light-emitting device of claim 29, wherein the light-emitting device is a white light LED device, and the white light LED device is used in the field of agricultural production. 36. The light-emitting device of claim 35, wherein the white light LED device is used to promote plant growth. 37. The method for preparing a light-emitting device according to any one of claims 29 to 36, comprising the following steps: uniformly mixing the above-mentioned phosphor with epoxy resin, polycarbonate or silica gel, and then coating the mixture on the LED chip.