CN117431059A - Preparation and application of deep red luminescent material for metal ion doped zinc aluminate plant light filling - Google Patents

Abstract

The invention discloses dark red fluorescent powder Zn for plant light filling _1‑x M _x Al ₂ O ₄ :Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ ,Mg ²⁺ ) Is prepared by the preparation method of the catalyst. The fluorescent powder is Zn _1‑x M _x Al ₂ O ₄ :Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ ,Mg ²⁺ ) The excitation spectrum of the fluorescent powder is transition metal ion Cr ³⁺ Is characterized by two broadband with peak at 394nm and 534nm respectively, and has an emission spectrum of Cr ³⁺ A series of sharp peaks at 650nm-750 nm, the strongest peak at 687 nm; the fluorescent powder can be effectively excited by ultraviolet light (394 nm) or green light (534 nm) to emit deep red light, and the optimal doping concentration is 0.6 mol%.

Description

Preparation and preparation of deep red luminescent materials doped with metal ions doped zinc aluminate for plant light supplementation application

Technical field

The invention relates to the technical field of artificial light sources, and in particular to metal ions (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mg ²⁺ , Li ⁺ )-doped ZnAl ₂ O ₄ :Cr ³⁺ for deep red plant lighting. Preparation and application of luminescent materials.

Background technique

In the process of plant growth, phytochromes play a very important role in promoting seed germination, de-etiolation, and leaf expansion. Phytochrome exists in two forms, one is the red light absorbing type (Pr), the absorption spectrum is two bands of 350 nm-400nm and 600 nm - 700 nm; the other is the far red light absorbing type (Pfr) , the absorption spectrum is a broad band located at 380 nm-420 nm and 650 nm - 780 nm; these two different forms of existence promote plant growth by absorbing light; in addition, photosynthesis is the basis of plant growth, and its absorption of light mainly depends on Based on three plant pigments: one chlorophyll a, whose absorption spectrum is a broad band of 350 nm-450 nm and 600 nm-700 nm, and another chlorophyll b, whose absorption spectrum is 380 nm-470 nm and 610 nm-650 nm Broadband, the last beta-carotenoid, has an absorption spectrum of 400 nm-500 nm. In modern agriculture, facility agriculture is an important symbol of agricultural modernization and an inevitable trend in the development of agricultural modernization in my country. Due to limitations of natural conditions in northern my country, crops are mostly cooked once a year. In order to meet people's demand for vegetables and fruits, According to demand, many areas use greenhouses to grow off-season fruits and vegetables, which has good economic benefits. Greenhouse planting requires supplementary light for plants. As a new generation of solid-state lighting system, LED has the advantages of high luminous efficiency, environmental protection, and long service life. Often used as grow lights to supplement lighting. There are relatively few deep red phosphors among existing phosphors, so it is of great significance to develop deep red phosphors excited by near-ultraviolet or green light. Cr ³⁺ ions can exhibit near-ultraviolet or green light excitation and emit deep red light in many matrices.

Contents of the invention

The present invention uses ZnAl ₂ O ₄ as the matrix material of the phosphor, Cr ³⁺ as the luminescence center, and uses a matrix doped with alkaline earth metal ions (Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mg ²⁺ ) to reduce the crystal The symmetry of the lattice and modification of the local crystal field environment around Cr ³⁺ change the luminescence properties of the sample. The phosphor prepared in this invention can be effectively excited by near-ultraviolet light and green light, and is used to solve the problem of deep red phosphor for plant supplementary light.

The invention first provides a deep red phosphor doped with transition metal ion Cr ³⁺ . The structural formula of the luminescent material is: ZnAl _2(1-y) O ₄ :2yCr ³⁺ (0.002 ≤ y ≤ 0.02).

The invention also provides a deep red phosphor doped with alkali metal ions Li ⁺ . The structural formula of the luminescent material is: Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (0 ≤ x ≤ 0.3).

The invention also provides a deep red phosphor doped with alkaline earth metal ions Ca ²⁺ . The structural formula of the luminescent material is: Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (0 ≤ x ≤ 0.25).

The invention also provides a deep red phosphor doped with alkaline earth metal ions Sr ²⁺ . The structural formula of the luminescent material is: Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (0 ≤ x ≤ 0.25).

The invention also provides a deep red phosphor doped with alkaline earth metal ions Ba ²⁺ . The structural formula of the luminescent material is: Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (0 ≤ x ≤ 0.25).

The invention also provides a deep red phosphor doped with alkaline earth metal ions Mg ²⁺ . The structural formula of the luminescent material is: Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (0 ≤ x ≤ 1).

Step 1. The preparation method of the above-mentioned deep red aluminate phosphor is as follows: according to the stoichiometric ratio of the chemical formula ZnAl _2(1-y) O ₄ :2yCr ^{3 +} , weigh the Zn-containing compound, the Al-containing compound, and the Cr-containing compound. ³⁺ compound, after sufficient grinding, a mixture is obtained;

Step 2. The preparation method of the above-mentioned deep red aluminate phosphor is as follows: according to the chemical formula Zn _1-x M _x Al _1.988 O ₄ :0.012Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ , Mg ²⁺ ), weigh Zn-containing compounds, Al-containing compounds, Cr ³⁺ -containing compounds and metal ion-containing compounds, Li ⁺ -containing compounds, Ca ²⁺ -containing compounds, Sr ²⁺ -containing compounds Compounds containing Ba ²⁺ and compounds containing Mg ²⁺ are fully ground to obtain a mixture;

Step 3: Calculate the mixture obtained in Steps 1 and 2 at high temperature, then grind the sample evenly after cooling to room temperature to obtain phosphors doped with metal ions of different types and concentrations.

Preferably, the source of the metal ion compound in the mixture of the above steps is metal oxide, metal carbonate, metal fluoride or metal chloride.

Preferably, the Zn-containing compound is a Zn-containing oxide, a Zn-containing nitride, a Zn-containing hydride, a Zn-containing hydroxide, a Zn-containing chloride, and a Zn-containing halide.

Preferably, the Al-containing compound is an Al-containing oxide, an Al-containing carbide, an Al-containing chloride, and an Al-containing oxo acid salt.

Preferably, the Cr-containing compound is a Cr-containing oxide, a Cr-containing sulfate, a Cr-containing carbonate, a Cr-containing fluoride or a Cr-containing hydroxide.

Preferably, in the second step, the calcination temperature is 1200~1500°C and the calcination time is 1~15h.

Principle of the invention: introducing metal ions (Li ⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mg ²⁺ ) into ZnAl ₂ O ₄ :Cr ³⁺ can reduce the symmetry of the crystal lattice and modify Cr ³⁺ The surrounding local crystal field environment enhances the luminescence performance of the sample. Emission of Cr ³⁺ ions in Zn _{1- x} M _x Al _1.988 O ₄ :0.012Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ ,Mg ²⁺ ) deep red phosphor A series of sharp peaks with a spectral range from 650 nm to 750 nm, with the strongest peak at 687 nm. Zn _1-x M _x Al _1.988 O ₄ :0.012Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ ,Mg ²⁺ ) has two stronger ones in the range of 350 nm to 600 nm Broadband, the strongest peaks are located at 394 nm and 534 nm respectively, belonging to ⁴ A ₂ ( ⁴ F) → ⁴ T ₁ ( ⁴ F) and ⁴ A ₂ ( ⁴ F) → ⁴ T ₂ ( ⁴ F) ^of Cr 3+ ) transition, it can be seen from the above that the phosphor can be effectively excited by near-ultraviolet light and green light to emit deep red light, realizing the conversion of ultraviolet light or green light to deep red light, and can be used as a supplementary light source for plants.

Compared with the prior art, the beneficial effects of the present invention are:

The present invention incorporates metal ions (Li ⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mg ²⁺ ) on the basis of ZnAl _1.988 O ₄ :0.012Cr ³⁺ to reduce the symmetry of the crystal lattice and modify Cr ^{3 +} The surrounding local crystal field environment achieves the purpose of changing the luminescence properties of the sample.

Description of the drawings

In order to explain the technical solutions of the present invention more concisely and clearly, the drawings required for the embodiments of the present invention will be briefly described below. Of course, the drawings in the following description are only for some embodiments of the present invention. Ordinary technicians can obtain other drawings based on the following drawings without exerting creative efforts.

Figure 1 is the XRD pattern of the phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ (y=0.002, 0.004, 0.006, 0.008, 0.001, 0.015, 0.02) obtained in Example 1.

Figure ₂ shows the excitation spectrum (a ₎ and the emission spectrum ⁽ b).

Figure 3 is an XRD pattern of the phosphor Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.05, 0.1, 0.15, 0.2, 0.25, 0.3) obtained in Example 2.

Figure 4 shows the excitation spectrum (a) and emission of the phosphor Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.05,0.1,0.15,0.2,0.25,0.3) obtained in Example 2 Spectrum (b).

Figure 5 is an XRD pattern of the phosphor Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1, 0.25) obtained in Example 3.

Figure 6 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25) obtained in Example 3.

Figure 7 is an XRD pattern of the phosphor Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) obtained in Example 4.

Figure 8 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25) obtained in Example 4.

Figure 9 is an XRD pattern of the phosphor Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1, 0.25) obtained in Example 5.

Figure 10 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25) obtained in Example 5.

Figure 11 is an XRD pattern of the phosphor Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1, 0.25, 0.5, 0.75, 0.9, 1) obtained in Example 6.

Figure 12 shows the excitation spectrum (a) and emission of the phosphor Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25,0.5,0.75,0.9,1) obtained in Example 6 Spectrum (b).

Implementation

In order to further understand the present invention, the present invention will be described in detail below with reference to specific embodiments. However, it should be noted here that the following description is only for further illustrating the features and advantages of the present invention and is not intended to limit the patent requirements of the present invention.

Example

Using zinc oxide, aluminum oxide, and chromium oxide as starting materials, according to the stoichiometric ratio of the chemical formula ZnAl _2(1-y) O ₄ :2yCr ³⁺ (y=0.002,0.004,0.006,0.008,0.001,0.015,0.02) Weigh the three raw materials respectively and grind them fully in an agate mortar. After grinding evenly, put the sample into a corundum crucible and transfer it to a high temperature. Roast it in the air at 1400°C for 6 hours. After cooling to room temperature, take it out and grind it evenly. , a series of Cr ³⁺ doped deep red phosphors were obtained, whose composition is ZnAl _2(1-y) O ₄ :2yCr ³⁺ (y=0.002,0.004,0.006,0.008,0.001,0.015,0.02).

Figure 1 is the XRD pattern of the phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ obtained in Example 1. It can be seen from the figure that the spectrum is consistent with ZnAl ₂ O ₄ , proving that ZnAl was successfully prepared. _2(1-y) O ₄ :2yCr ³⁺ phosphor. Figure 2 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ obtained in Example 1. It can be seen from the figure that ZnAl _2(1-y) The excitation spectrum of O ₄ :2yCr ³⁺ is two strong broadbands in the range of 350 nm to 600 nm. The strongest peaks are located at 394 nm and 534 nm respectively, which belong to ⁴ A ₂ ( ⁴ F) → ⁴ of Cr ³⁺ T ₁ ( ⁴ F) and ⁴ A ₂ ( ⁴ F) → ⁴ T ₂ ( ⁴ F) transition; the emission spectrum range of this phosphor is a series of sharp peaks from 650 nm to 750 nm, of which the 687 nm peak is the strongest; In the phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ (y=0.002,0.004,0.006,0.008,0.001,0.015,0.02), as the concentration of Cr ³⁺ increases, the intensity of the excitation and emission spectra first It increases and then decreases. When y=0.006, the spectral intensity is the strongest, that is, the optimal doping concentration is 0.6 at%. It can be seen from the above that the phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ can be effectively excited by near-ultraviolet light and green light to emit deep red light, realizing the conversion of ultraviolet or green light to deep red light, and can be used as Plant supplementary light source.

Example

Using zinc oxide, aluminum oxide, chromium oxide and lithium carbonate as starting materials, according to the chemical formula Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.05,0.1,0.15,0.2,0.25,0.3 ) of the stoichiometric ratio. Weigh the four raw materials and grind them fully in an agate mortar. After grinding evenly, put the sample into a corundum crucible and transfer it to a high temperature. Roast in the air at 1400°C for 6 hours and cool to room temperature. Then take it out and grind it evenly to obtain a series of Cr ³⁺ doped deep red phosphors whose composition is Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.05,0.1,0.15,0.2 ,0.25,0.3).

Figure 3 is the XRD pattern of the phosphor Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.05,0.1,0.15,0.2,0.25,0.3) obtained in Example 2. It can be seen from the figure It can be seen that the spectrum is consistent with ZnAl ₂ O ₄ , proving that the phosphor Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ was successfully prepared. Figure 4 shows the excitation spectrum (a) and emission of the phosphor Zn _1-x Li _2x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.05,0.1,0.15,0.2,0.25,0.3) obtained in Example 2 Spectrum (b), it can be seen from the figure that the shape peak position of the excitation spectrum and emission spectrum of this phosphor is consistent with ZnAl _1.988 O ₄ :0.012Cr ³⁺ , and its intensity increases with the concentration of Li ⁺ excitation and emission The intensity of the spectrum first increases and then decreases. When x=0.25, the spectrum intensity is the strongest, that is, the optimal doping concentration is 0.25 at%.

Example

Using zinc oxide, aluminum oxide, chromium oxide, and calcium carbonate as starting materials, four types were weighed according to the stoichiometric ratio of the chemical formula Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) The raw materials are fully ground in an agate mortar. After grinding evenly, the sample is placed in a corundum crucible and transferred to a high temperature. It is roasted in the air at 1400°C for 6 hours. After cooling to room temperature, it is taken out and ground evenly to obtain a series of Cr. ³⁺ doped deep red phosphor, its composition is Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25).

Figure 5 is the XRD pattern of Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) obtained in Example 3. It can be seen from the figure that when x=0.1, the spectrum is consistent with ZnAl ₂ O ₄ phase is consistent, proving that the phosphor Zn _0.9 Ca _0.1 Al _1.988 O ₄ :0.012Cr ³⁺ was successfully prepared; when x=0.25, a heterogeneous phase has been produced. Figure 6 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Ca _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25) obtained in Example 3. From the figure It can be seen that the shape peak position of the excitation spectrum and emission spectrum of the phosphor is consistent with that of ZnAl _1.988 O ₄ :0.012Cr ³⁺ , and its intensity has been decreasing. This is due to the interaction between Ca ^{2 +} (r = 1.06 Å) and Zn ² The ionic radii of ⁺ (r = 0.6 Å) are quite different.

Example

Using zinc oxide, aluminum oxide, chromium oxide, and strontium carbonate as starting materials, four types were weighed according to the stoichiometric ratio of the chemical formula Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) The raw materials are fully ground in an agate mortar. After grinding evenly, the sample is placed in a corundum crucible and transferred to a high temperature. It is roasted in the air at 1400°C for 6 hours. After cooling to room temperature, it is taken out and ground evenly to obtain a series of Cr. ³⁺ doped deep red phosphor, its composition is Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25).

Figure 7 is the XRD pattern of Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) obtained in Example 4. It can be seen from the figure that when x=0.1, the spectrum is consistent with ZnAl ₂ O ₄ phase is consistent, proving that the phosphor Zn _0.9 Sr _0.1 Al _1.988 O ₄ :0.012Cr ³⁺ was successfully prepared; when x=0.25, a heterogeneous phase has been produced. Figure 8 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0,0.1,0.25) obtained in Example 4. From It can be seen from the figure that the shape peak position of the excitation spectrum and emission spectrum of the phosphor is consistent with that of ZnAl _1.988 O ₄ :0.012Cr ³⁺ , and its intensity has been decreasing. This is due to the difference between Sr ²⁺ (r = 1.27 Å) and The ionic radii of Zn ²⁺ (r = 0.6 Å) are quite different.

Example

Using zinc oxide, aluminum oxide, chromium oxide, and barium carbonate as starting materials, four types were weighed according to the stoichiometric ratio of the chemical formula Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) The raw materials are fully ground in an agate mortar. After grinding evenly, the sample is placed in a corundum crucible and transferred to a high temperature. It is roasted in the air at 1400°C for 6 hours. After cooling to room temperature, it is taken out and ground evenly to obtain a series of Cr. ³⁺ doped deep red phosphor, its composition is Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25).

Figure 9 is the XRD pattern of Zn _1-x Ba _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25) obtained in Example 5. It can be seen from the figure that when ₂ O ₄ phase is consistent, proving that the phosphor Zn _0.9 Bar _0.1 Al _1.988 O ₄ :0.012Cr ³⁺ was successfully prepared; when x=0.25, a heterogeneous phase has been produced. Figure 10 shows the excitation spectrum (a) and emission spectrum (b) of the phosphor Zn _1-x Sr _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25) obtained in Example 5. From the figure It can be seen that the shape peak position of the excitation spectrum and emission spectrum of the phosphor is consistent with that of ZnAl _1.988 O ₄ :0.012Cr ³⁺ , and its intensity has been decreasing. This is due to the interaction between Ba ^{2 +} (r = 1.34 Å) and Zn ² The ionic radii of ⁺ (r = 0.6 Å) are quite different.

Example

Using zinc oxide, aluminum oxide, chromium oxide, and magnesium carbonate as starting materials, according to the chemical formula Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25,0.5,0.75,0.9,1) Stoichiometric ratio: Weigh the four raw materials and grind them fully in an agate mortar. After grinding evenly, put the sample into a corundum crucible and transfer it to a high temperature. Roast it in the air at 1400°C for 6 hours. Cool it to room temperature and take it out. And grind it evenly to obtain a series of Cr ³⁺ doped deep red phosphors, whose composition is Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25,0.5,0.75,0.9,1 ).

Figure 11 is the XRD pattern of Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0.1,0.25,0.5,0.75,0.9,1) obtained in Example 6. It can be seen from the figure that the spectrum _The figure is consistent with _{ZnAl 2} O _{4 , proving} that the ^phosphor Zn _1- There is a small difference in the ionic radii of Mg ²⁺ (r = 0.57 Å) and Zn ²⁺ (r = 0.6 Å). Figure 12 shows the excitation spectrum (a) and emission of the phosphor Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ^{3 +} (x=0,0.1,0.25,0.5,0.75,0.9,1) obtained in Example 6 Spectrum (b), it can be seen from the figure that the excitation spectrum of the phosphor is two strong broadbands in the range of 350 nm to 600 nm, with the strongest peaks at 394 nm and 534 nm respectively, belonging to Cr ³⁺ The transitions of ⁴ A ₂ ( ⁴ F) → ⁴ T ₁ ( ⁴ F) and ⁴ A ₂ ( ⁴ F) → ⁴ T ₂ ( ⁴ F); the emission spectrum range of this phosphor is in the series from 650 nm to 750 nm Sharp edge, with the 686 nm peak being the strongest; in the phosphor Zn _1-x Mg _x Al _1.988 O ₄ :0.012Cr ³⁺ (x=0,0.1,0.25,0.5,0.75,0.9,1) with Mg ² As the concentration of ⁺ increases, the intensity of the excitation and emission spectra first increases and then decreases. When x=0.5, the spectral intensity is the strongest, that is, the optimal doping concentration is 50 at%.

The above examples are only used to explain the method of the present invention. It is particularly pointed out that for those skilled in the art, those skilled in the art can make appropriate improvements and modifications to the present invention without violating the principles of the present invention, and these improvements and modifications are also included in the claims of the present invention. within the scope of protection.

Claims (8)

1. The deep red phosphor ZnAl _2(1-y) O ₄ :2yCr ³⁺ doped with transition metal ions Cr ³⁺ was prepared, where 0.002 ≤ y ≤ 0.02. 2. Preparation of deep red phosphor Zn _1-x M _x Al _1.988 O ₄ :0.012Cr ³⁺ doped with metal ions (Li ⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Mg ²⁺ ), formula where 0 ≤ x ≤ 1. 3. Deep red phosphor Zn _1-x M _x Al _{2 (1-y)} O ₄ : 2yCr ³⁺ (M = 2Li ⁺ , Ca ²⁺ , Sr ²⁺ , Ba ^{2 +} , Mg ²⁺ ) chemical preparation method, characterized in that it includes the following steps: Step 1. The preparation method of the above-mentioned deep red aluminate phosphor is as follows: according to the stoichiometric ratio of the chemical formula ZnAl _2(1-y) O ₄ :2yCr ³⁺ , weigh the Zn-containing compound, the Al-containing compound, and the Cr-containing compound. ³⁺ compound, after sufficient grinding, a mixture is obtained; Step 2. The preparation method of the above-mentioned deep red aluminate phosphor is as follows: according to the chemical formula Zn _1-x M _x Al _1.988 O ₄ :0.012Cr ³⁺ (M=2Li ⁺ ,Ca ²⁺ ,Sr ²⁺ ,Ba ²⁺ , Mg ²⁺ ), weigh Zn-containing compounds, Al-containing compounds, Cr ³⁺ -containing compounds and metal ion-containing compounds, Li ⁺ -containing compounds, Ca ²⁺ -containing compounds, Sr ²⁺ -containing compounds Compounds containing Ba ²⁺ and compounds containing Mg ²⁺ are fully ground to obtain a mixture; Step 3: Calculate the mixture obtained in Steps 1 and 2 at high temperature, then grind the sample evenly after cooling to room temperature to obtain phosphors doped with metal ions of different types and concentrations. 4. The preparation method of Cr ³⁺ doped deep red phosphor according to claim 3, characterized in that, in the mixture of the above steps, there are metal ion compounds, and the sources of the metal ion compounds are metal oxides and metal carbonic acids. Salt, metal fluoride or metal chloride. 5. The preparation method of Cr3 ⁺ doped deep red phosphor according to claim 3, characterized in that the Zn-containing compound is a Zn-containing oxide, a Zn-containing nitride, or a Zn-containing hydrogenated compound. substances, Zn-containing hydroxides, Zn-containing chlorides and Zn-containing halides. 6. The preparation method of Cr3 ⁺ doped deep red phosphor according to claim 3, characterized in that the Al-containing compound is an Al-containing oxide, an Al-containing carbide, or an Al-containing chlorine. compounds and Al-containing oxo acid salts. 7. The preparation method of Cr3 ⁺ -doped deep red phosphor according to claim 3, characterized in that the Cr-containing compound is a Cr-containing oxide, a Cr-containing sulfate, or a Cr-containing carbon. acid salt, Cr-containing fluoride or Cr-containing hydroxide. 8. The preparation method of Cr ³⁺ doped deep red phosphor according to claim 3, characterized in that in the step three, the baking temperature is 1200~1500°C and the baking time is 1~15h.