Aluminate red fluorescent material as well as preparation method and application thereof

Abstract

The invention discloses an aluminate red fluorescent material as well as a preparation method and application thereof. The aluminate red fluorescent material has a chemical composition as shown in a formula (1): Zn < 1 + 1.5 a > M < II > Al < 2-a-b-c-d-y > M < III > < c > M < IV > < d > O < 4-x > F < 2x >: yCr < 3 + > (1), M < II > is a divalent element and is selected from at least one of Be, Mg, Cu and Cd; m III is a trivalent element and is selected from at least one of B, Ga, Sc, Y, La, Sm, Eu, Gd, Lu and Bi; mIV is a tetravalent element and is selected from at least one of Si, Mn, Ge, Zr and Hf; 0 < = a < = 0.2, 0 < = b < = 0.8, 0 < = c < = 1, 0 < = d < = 0.8, 0 < = x < = 2, and 0.005 < = y < = 0.5. The red fluorescent material can be excited by ultraviolet light or yellow-green light, emits crimson fluorescence with the wave band of 650-850 nm, and has a very ideal application prospect in the aspect of light conversion agricultural greenhouse films.

Description

Technical Field

[0001] The invention relates to an aluminate red fluorescent material and a preparation method and application thereof. Background Art

[0002] The growth and development of plants are closely related to the photosynthesis process. Photosynthesis is the process of photosynthetic pigment molecules in chloroplasts absorbing sunlight, and then undergoing a series of photochemical reactions to convert light energy into chemical energy, thereby providing energy for the growth and development of plants. The solar spectrum is a continuously distributed spectrum that includes spectra in the ultraviolet, visible and infrared bands. However, photosynthetic pigment molecules only absorb the blue and red light components in sunlight, while ultraviolet and yellow-green light cannot be absorbed and utilized by plants, resulting in a waste of some light energy. Therefore, the development of new ultraviolet / yellow-green light-excited fluorescent materials, based on the principles of light conversion and supplementary light, can convert ultraviolet and yellow-green light that plants do not need into red light required for photosynthesis, which can significantly enhance photosynthesis, shorten the growth cycle of plants, and improve the quality and yield of crops.

[0003] Agricultural greenhouse films have good heat preservation and moisture retention functions and have been widely used in the agricultural field. At present, the agricultural film products on the market are mainly PE / PO films, and the agricultural greenhouse films with light conversion function have a relatively low market share. The main reason is that there are few light conversion material systems suitable for plant growth, especially red phosphor materials with yellow-green light excitation characteristics are extremely scarce, and the existing light conversion materials have low spectral matching and low luminous efficiency, which seriously limits the promotion and application of light conversion agricultural films.

[0004] CN115261018A discloses a red inorganic fluorescent powder capable of promoting the growth of greenhouse plants and a preparation method thereof. The chemical formula of the fluorescent powder is CaAl 12-x-y O 19 :xMn 4+ ,yGd 3+ , wherein 0<x<0.5, 0<y<0.5. The excitation wavelength of the aluminate-based manganese-doped red phosphor is 250-500nm, and the emission wavelength is 630nm-680nm. The phosphor does not have yellow-green light excitation characteristics.

[0005] CN116103039A discloses a Li and Mn co-doped aluminate matrix red phosphor and its preparation method. The chemical composition of the phosphor is: Sr4Al 14-a-b O 25 :aMn 4+ , bLi + , cH3BO3, where Mn 4+ From one or a combination of MnCO3, MnO2, Li +It is composed of one or a combination of two of LiF and Li2CO3, with H3BO3 as a cosolvent, where 0 < a < 0.05, 0 < b ≤ 1.5, and 0 < c ≤ 15 wt.% (percentage relative to the total mass). This aluminate matrix red phosphor has the characteristic of being effectively excited by blue light to emit red light.

[0006] CN117431059A discloses a deep red light-emitting phosphor for plant supplementary lighting doped with metal ions and its preparation method. The phosphor is Zn 1-x M x Al2O4:Cr 3+ (M = 2Li + , Ca 2+ , Sr 2+ , Ba 2+ , Mg 2+ ), the excitation spectrum of this phosphor is the characteristic excitation peaks of transition metal ion Cr 3+ , with two broadband peaks located at 394 nm and 534 nm respectively, and its emission spectrum is a series of sharp peaks of Cr 3+ located at 650 nm - 750 nm, with the strongest peak at 687 nm; this phosphor can be effectively excited by ultraviolet light (394 nm) or green light (534 nm) to emit deep red light. The intensities of both the excitation spectrum and the emission spectrum of this phosphor need to be further improved. Summary of the Invention

[0007] In view of this, an object of the present invention is to provide an aluminate red fluorescent material that can be excited by ultraviolet light in the 330 - 460 nm band or yellow-green light in the 460 nm - 650 nm band to emit deep red fluorescence in the 650 - 850 nm band, and has higher intensities of its excitation spectrum and emission spectrum. Another object of the present invention is to provide a preparation method of the above-mentioned aluminate red fluorescent material.

[0008] The present invention adopts the following technical solutions to achieve the above objects.

[0009] On the one hand, the present invention provides an aluminate red fluorescent material having a chemical composition as shown in formula (1):

[0010] Zn 1+1.5a M Ⅱ b Al 2-a-b-c-d-y M Ⅲ c M Ⅳ d O 4-x F 2x :yCr 3+ (1),

[0011] wherein, MⅡ M is a divalent element. Ⅱ At least one selected from Be, Mg, Cu, Cd; M Ⅲ For trivalent elements, M Ⅲ At least one selected from B, Ga, Sc, Y, La, Sm, Eu, Gd, Lu, and Bi; M Ⅳ M is a tetravalent element. Ⅳ At least one selected from Si, Mn, Ge, Zr, and Hf;

[0012] Among them, 1+1.5a represents the molar coefficient of Zn, b represents M Ⅱ The molar coefficient of Al is 2-abcdy, and c represents the molar coefficient of M Ⅲ The molar coefficient, d represents M Ⅳ , 4-x represents the molar coefficient of O, 2x represents the molar coefficient of F, and y represents the molar coefficient of Cr;

[0013] Among them, 0≤a≤0.2, 0≤b≤0.8, 0≤c≤1, 0≤d≤0.8, 0≤x≤2, 0.005≤y≤0.5.

[0014] According to the aluminate red fluorescent material of the present invention, preferably, M Ⅱ One selected from Be, Mg, Cu and Cd.

[0015] According to the aluminate red fluorescent material of the present invention, preferably, M Ⅲ One selected from B, Ga, Sc, Y, La, Sm, Eu, Gd, Lu and Bi.

[0016] According to the aluminate red fluorescent material of the present invention, preferably, M Ⅳ One selected from Si, Mn, Ge, Zr and Hf.

[0017] According to the aluminate red fluorescent material of the present invention, preferably, 0≤a≤0.1, 0≤b≤0.5, 0≤c≤0.6, and 0≤d≤0.6.

[0018] According to the aluminate red fluorescent material of the present invention, preferably, 0≤x≤1, 0.008≤y≤0.2.

[0019] According to the aluminate red fluorescent material of the present invention, preferably, the aluminate red fluorescent material has any one of the following compositions:

[0020] Zn 1.12 Al 1.906 O4:0.014Cr 3+ ;

[0021] ZnAl 1.986 O 3.7 F 0.6 :0.014Cr 3+ ;

[0022] Zn 1.12 Al 1.906 O 3.9 F 0.2 :0.014Cr 3+ ;

[0023] Zn 1.12 Al 1.506 Ga 0.4 O 3.9 F 0.2 :0.014Cr 3+ ;

[0024] Zn 1.12 Al 1.886 La 0.02 O 3.9 F 0.2 :0.014Cr 3+ ;

[0025] Zn 1.12 Mg 0.2 Al 1.506 Ge 0.2 O 3.9 F 0.2 :0.014Cr 3+ ;

[0026] Zn 1.12 Mg 0.2 Al 1.506 Si 0.2 O 3.9 F 0.2 :0.014Cr 3+ ;

[0027] Zn 1.12 Mg 0.4 Al 0.706 Ga 0.4 Ge 0.4 O 3.9 F 0.2 :0.014Cr 3+ 。

[0028] On the other hand, the present invention also provides a method for preparing the aluminate red fluorescent material as described above, comprising the following steps:

[0029] According to the composition of the aluminate red fluorescent material, the aluminate red fluorescent material containing Zn, M Ⅱ , Al, MⅢ 、M Ⅳ The raw materials of inorganic compounds of F and Cr elements are mixed and sintered to obtain the aluminate red fluorescent material; wherein the sintering includes pre-sintering and high-temperature sintering, the pre-sintering temperature is 900-1100°C, the pre-sintering time is 2-4h, the high-temperature sintering temperature is 1200-1600°C, and the high-temperature sintering time is 4-8h.

[0030] According to the preparation method of the present invention, preferably, the inorganic compound containing Zn element is zinc oxide and zinc fluoride; Ⅱ The inorganic compound of element is M Ⅱ Oxides or carbonates; inorganic compounds containing Al are aluminum oxides; inorganic compounds containing M Ⅲ The inorganic compound of element is M Ⅲ Oxides of elements; containing M Ⅳ The inorganic compound of element is M Ⅳ Oxide; the inorganic compound containing F element is zinc fluoride; the inorganic compound containing Cr element is chromium trioxide or chromium carbonate.

[0031] In another aspect, the present invention further provides a use of the aluminate red fluorescent material as described above in the preparation of light-converting agricultural greenhouse film.

[0032] The aluminate red fluorescent material provided by the present invention can be excited by ultraviolet light in the 330-460nm band or yellow-green light in the 460nm-650nm band, and emits deep red fluorescence in the 650-850nm band, and its excitation spectrum and emission spectrum have higher intensities and better luminescence characteristics. The aluminate red fluorescent material can be used for light-converting agricultural greenhouse film, and can absorb ultraviolet light and yellow-green light that are not needed by plants in the solar spectrum, and convert them into red light required by plants, which has a good promoting effect on the growth and development of plants and early maturity. The preparation method of the present invention is relatively simple, and the obtained aluminate red fluorescent material has stable performance.

[0033] Instruction Manual

[0034] Figure 1 1 and 2 are XRD diagrams of the aluminate red fluorescent material of Example 1 and the aluminate red fluorescent material of Comparative Example 1.

[0035] Figure 2 1 and 2 are the excitation spectra and emission spectra of the aluminate red fluorescent material of Example 1 and the aluminate red fluorescent material of Comparative Example 1. Figure 2 (a) is the excitation spectrum, Figure 2 (b) is the emission spectrum.

[0036] Figure 3The excitation spectrum and emission spectrum of the aluminate red fluorescent material of Example 2 and the aluminate red fluorescent material of Comparative Example 1 are shown. Figure 3 (a) is the excitation spectrum, Figure 3 (b) is the emission spectrum.

[0037] Figure 4 The excitation spectrum and emission spectrum of the aluminate red fluorescent material of Example 3 and the aluminate red fluorescent material of Comparative Example 1 are shown. Figure 4 (a) is the excitation spectrum, Figure 4 (b) is the emission spectrum.

[0038] Figure 5 The excitation spectrum and emission spectrum of the aluminate red fluorescent material of Example 4 and the aluminate red fluorescent material of Comparative Example 1 are shown. Figure 5 (a) is the excitation spectrum, Figure 5 (b) is the emission spectrum.

[0039] Figure 6 1 and 2 are the excitation spectra and emission spectra of the aluminate red fluorescent material of Example 5 and the aluminate red fluorescent material of Comparative Example 1. Figure 6 (a) is the excitation spectrum, Figure 6 (b) is the emission spectrum.

[0040] Figure 7 The excitation spectrum and emission spectrum of the aluminate red fluorescent material of Example 6 and the aluminate red fluorescent material of Comparative Example 1 are shown. Figure 7 (a) is the excitation spectrum, Figure 7 (b) is the emission spectrum.

[0041] Figure 8 1 and 2 are the excitation spectra and emission spectra of the aluminate red fluorescent material of Example 7 and the aluminate red fluorescent material of Comparative Example 1. Figure 8 (a) is the excitation spectrum, Figure 8 (b) is the emission spectrum.

[0042] Fig. 9 ] are the excitation spectrum and emission spectrum of the aluminate red fluorescent material of Example 8 and the aluminate red fluorescent material of Comparative Example 1. Fig. 9 (a) is the excitation spectrum, Fig. 9 (b) is the emission spectrum.

[0043] Fig.10 These are the excitation spectrum and emission spectrum of the aluminate red fluorescent material of Comparative Example 2. Fig.10 (a) is the excitation spectrum, Fig.10 (b) is the emission spectrum.

[0044] Fig.11This is the transmittance result of the light conversion film prepared from the aluminate red fluorescent material of Example 6. DETAILED DESCRIPTION

[0045] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0046] <Aluminate red fluorescent material>

[0047] The invention provides an aluminate red fluorescent material, which can be effectively excited by ultraviolet light or yellow-green light, and emits deep red light in the 650-850nm band, and the intensities of the excitation spectrum and the emission spectrum are both higher.

[0048] The aluminate red fluorescent material of the present invention has a chemical composition as shown in formula (1):

[0049] Zn 1+1.5a M Ⅱ b Al 2-a-b-c-d-y M Ⅲ c M Ⅳ d O 4-x F 2x :yCr 3+ (1)

[0050] In the present invention, Zn is zinc element. 1+1.5a represents the molar coefficient of Zn element. 0≤a≤0.2, preferably, 0≤a≤0.1, more preferably, 0≤a≤0.08.

[0051] In the present invention, M Ⅱ M is a divalent element. Ⅱ At least one element selected from Be (beryllium), Mg (magnesium), Cu (copper), and Cd (cadmium), preferably at least one element selected from Mg, Cu, and Cd, and more preferably Mg. b represents M Ⅱ The molar coefficient of the element is 0≤b≤0.8, preferably, 0≤b≤0.5, more preferably, 0≤b≤0.4, and even more preferably, 0≤b≤0.2.

[0052] In the present invention, M Ⅲ For trivalent elements, M Ⅲ At least one element selected from B (boron), Ga (gallium), Sc (scandium), Y (yttrium), La (lanthanum), Sm (samarium), Eu (europium), Gd (gadolinium), Lu (lutetium), Bi (bismuth), preferably at least one element selected from Ga, La, Sm, Eu, Gd, Bi, more preferably one element selected from Ga and La. c represents M ⅢThe molar coefficient of the element is 0≤c≤1, preferably, 0≤c≤0.6, more preferably, 0≤c≤0.5, for example, c can be 0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, or 0.5.

[0053] In the present invention, M Ⅳ M is a tetravalent element. Ⅳ At least one element selected from Si (silicon), Mn (manganese), Ge (germanium), Zr (zirconium), Hf (hafnium), preferably at least one selected from Si, Ge and Zr, more preferably one of Si and Ge. d represents M Ⅳ The molar coefficient of the element is 0≤d≤0.8, preferably, 0≤d≤0.6, more preferably, 0≤d≤0.4, and even more preferably, 0≤d≤0.2.

[0054] In the present invention, Al is an aluminum element, and 2-abcdy represents the molar coefficient of the Al element.

[0055] In the present invention, O is an oxygen element. 4-x represents the molar coefficient of the O element. F is a fluorine element, and 2x represents the molar coefficient of the F element. Cr is a chromium element, and y represents the molar coefficient of the Cr element. Wherein, 0≤x≤2, preferably, 0≤x≤1, more preferably, 0≤x≤0.5, and more preferably, 0≤x≤0.3. Wherein, 0.005≤y≤0.5, preferably, 0.008≤y≤0.2, more preferably, 0.010≤y≤0.1, and more preferably, 0.012≤y≤0.05, and further preferably, 0.012≤y≤0.02, for example, y can be 0.005, 0.012, 0.014, 0.02, 0.04, 0.06, 0.08.

[0056] According to a specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Al 1.906 O4:0.014Cr 3+ .

[0057] According to another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: ZnAl 1.986 O 3.7 F 0.6 :0.014Cr 3+ .

[0058] According to another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Al 1.906 O 3.9 F 0.2 :0.014Cr 3+ .

[0059] According to another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Al 1.506 Ga 0.4 O 3.9 F 0.2 :0.014Cr 3+ .

[0060] According to another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Al 1.886 La 0.02 O 3.9 F 0.2 :0.014Cr 3+ .

[0061] According to yet another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Mg 0.2 Al 1.506 Ge 0.2 O 3.9 F 0.2 :0.014Cr 3+ .

[0062] According to yet another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Mg 0.2 Al 1.506 Si 0.2 O 3.9 F 0.2 :0.014Cr 3+ .

[0063] According to yet another specific embodiment of the present invention, the composition of the aluminate red fluorescent material is: Zn 1.12 Mg 0. 4Al 0.706 Ga 0.4 Ge 0.4 O 3.9 F 0.2 :0.014Cr 3+ .

[0064] Compared with ZnAl 1.986 O4:0.014Cr 3+ The fluorescent material of the present invention has significantly improved intensities of the excitation spectrum and emission spectrum of the aluminate red fluorescent material, has excellent luminescence characteristics, an excitation spectrum range of 300 to 650 nm, and can emit deep red light in the 650 to 850 nm band under the excitation of ultraviolet light or yellow-green light.

[0065] <Preparation method>

[0066] The preparation method of the aluminate red fluorescent material of the present invention may include the following steps: a raw material mixing step and a sintering step. Optionally, it also includes a grinding and screening step. The following is a detailed description.

[0067] Raw material mixing steps

[0068] According to the composition of the aluminate red fluorescent material, the aluminate red fluorescent material containing Zn, M Ⅱ , Al, M Ⅲ 、M Ⅳ The raw materials of inorganic compounds of the elements F and Cr are mixed to obtain a raw material mixture.

[0069] In the present invention, the inorganic compound containing Zn element is zinc oxide and zinc fluoride. In some specific embodiments, the inorganic compound containing Zn element is zinc oxide. In other specific embodiments, the inorganic compound containing Zn element is zinc oxide and zinc fluoride.

[0070] In the present invention, M Ⅱ The inorganic compound of element is M Ⅱ According to one embodiment of the present invention, the compound contains M Ⅱ The inorganic compound of the element is magnesium oxide. According to another specific embodiment of the present invention, the inorganic compound containing M Ⅱ The inorganic compound of the element is copper oxide.

[0071] In the present invention, the inorganic compound containing the Al element is aluminum oxide.

[0072] In the present invention, M Ⅲ The inorganic compound of element is M Ⅲ According to a specific embodiment of the present invention, the oxide containing M Ⅲ The inorganic compound of the element is gallium oxide. According to another specific embodiment of the present invention, the inorganic compound containing M Ⅲ The inorganic compound of the element is lanthanum oxide.

[0073] In the present invention, M Ⅳ The inorganic compound of element is M Ⅳ According to a specific embodiment of the present invention, the oxide containing M Ⅳ The inorganic compound of the element is silicon dioxide. According to another specific embodiment of the present invention, the inorganic compound containing M Ⅳ The inorganic compound of the element is germanium dioxide.

[0074] In the present invention, the inorganic compound containing the F element is zinc fluoride.

[0075] In the present invention, the inorganic compound containing Cr element is chromium oxide or chromium carbonate.

[0076] Sintering steps

[0077] The raw material mixture is sintered to obtain the aluminate red fluorescent material, which is conducive to obtaining the aluminate red fluorescent material with better luminescence performance of the present invention.

[0078] Sintering includes pre-sintering and high-temperature sintering. Pre-sintering is performed first, and then high-temperature sintering is performed. The temperature of pre-sintering can be 900-1100°C, preferably 950-1050°C, and more preferably 980-1000°C. The time of pre-sintering can be 2-4h, preferably 2-3.5h, and more preferably 2-3h. The temperature of high-temperature sintering can be 1200-1600°C, preferably 1350-1550°C, and more preferably 1400-1500°C. The time of high-temperature sintering can be 4-8h, preferably 4.5-5.5h, and more preferably 5-6h.

[0079] In the present invention, the temperature may be raised to the sintering temperature at a heating rate of 3 to 10°C / min, preferably 4 to 9°C / min, more preferably 5 to 8°C / min, and even more preferably 5 to 7°C / min.

[0080] Grinding and sieving steps

[0081] After sintering is completed, the temperature is lowered, and then the sintered product is ground and sieved to obtain the aluminate red fluorescent material.

[0082] The grinding may be performed using an agate mortar. The mesh size of the sieve used during sieving may be 300 meshes or more, preferably 400 meshes or more.

[0083] <Application>

[0084] The present invention also provides an application of an aluminate red fluorescent material in the preparation of a light-converting agricultural greenhouse film. The aluminate red fluorescent material can be used for a light-converting agricultural greenhouse film, and can absorb ultraviolet light and yellow-green light in the solar spectrum that are not needed by plants, and convert them into red light required by plants, which has a good promoting effect on the growth and development and early maturity of plants.

[0085] Here is the test method:

[0086] XRD test: The test was carried out using PANalytical (X`Pert PRO) X-ray diffractometer.

[0087] Excitation spectrum and emission spectrum: tested using Edinburgh (FL1000) fluorescence spectrometer.

[0088] Transmittance test: tested using UH4150 spectrophotometer.

[0089] Example 1

[0090] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Al 1.906 O4:0.014Cr 3+ .

[0091] According to the above chemical composition, a certain amount of zinc oxide, aluminum oxide and chromium trioxide were weighed and added to an agate mortar, and fully ground for 30 minutes to obtain a raw material mixture. The raw material mixture was then transferred to a corundum crucible, heated to 1000°C at a heating rate of 5°C / min, and pre-sintered at 1000°C for 2 hours. After pre-sintering, the temperature was continued to rise to 1400°C at a heating rate of 5°C / min, and sintered at a high temperature of 1400°C for 6 hours. The sintered product was ground and sieved to obtain an aluminate red fluorescent material.

[0092] Example 2

[0093] The chemical composition of the aluminate red fluorescent material in this embodiment is ZnAl 1.986 O 3.7 F 0.6 :0.014Cr 3+ .

[0094] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, aluminum oxide and chromium trioxide are weighed. The remaining operations are the same as those in embodiment 1.

[0095] Example 3

[0096] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Al 1.906 O 3.9 F 0.2 :0.014Cr 3+ .

[0097] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, aluminum oxide and chromium trioxide are weighed. The remaining operations are the same as those in embodiment 1.

[0098] Example 4

[0099] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Al 1.506 Ga 0.4 O 3.9 F0.2 :0.014Cr 3+ .

[0100] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, aluminum oxide, gallium oxide and chromium trioxide are weighed. The remaining operations are the same as those in embodiment 1.

[0101] Example 5

[0102] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Al 1.886 La 0.02 O 3.9 F 0.2 :0.014Cr 3+ .

[0103] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, aluminum oxide, lanthanum oxide and chromium trioxide are weighed. The remaining operations are the same as those in Embodiment 1.

[0104] Example 6

[0105] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Mg 0.2 Al 1.506 Ge 0.2 O 3.9 F 0.2 :0.014Cr 3+ .

[0106] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, magnesium oxide, aluminum oxide, germanium dioxide and chromium trioxide are weighed. The remaining operations are the same as those in Embodiment 1.

[0107] Example 7

[0108] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Mg 0.2 Al 1.506 Si 0.2 O 3.9 F 0.2 :0.014Cr 3+ .

[0109] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, magnesium oxide, aluminum oxide, silicon dioxide and chromium trioxide are weighed. The remaining operations are the same as those in Embodiment 1.

[0110] Example 8

[0111] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Mg 0.4 Al 0.706 Ga 0.4 Ge 0.4 O 3. 9F 0.2 :0.014Cr 3+ .

[0112] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, magnesium oxide, aluminum oxide, gallium oxide, germanium dioxide and chromium trioxide are weighed. The remaining operations are the same as those in Embodiment 1.

[0113] Comparative Example 1

[0114] The chemical composition of the aluminate red fluorescent material in this comparative example is ZnAl 1.986 O4:0.014Cr 3+ .

[0115] According to the above chemical composition, a certain amount of zinc oxide, aluminum oxide and chromium trioxide were weighed and added to an agate mortar, and fully ground for 30 minutes to obtain a mixed raw material. The mixed raw material was then transferred to a corundum crucible, heated to 1000°C at a heating rate of 5°C / min, and pre-sintered at 1000°C for 2h. After pre-sintering, the temperature was continued to rise to 1400°C at a heating rate of 5°C / min, and sintered at a high temperature of 1400°C for 6h. The sintered product was ground and sieved to obtain an aluminate red fluorescent material.

[0116] Comparative Example 2

[0117] The chemical composition of the aluminate red fluorescent material in this embodiment is Zn 1.12 Mg 0.2 Al 1.506 Ti 0.2 O 3.9 F 0.2 :0.014Cr 3+ .

[0118] In this embodiment, according to the above chemical composition, a certain amount of zinc oxide, zinc fluoride, magnesium oxide, aluminum oxide, titanium dioxide and chromium trioxide are weighed. The remaining operations are the same as those in Embodiment 1.

[0119] Table 1

[0120] serial number Chemical composition serial number Chemical composition Comparative Example 1 <![CDATA[ZnAl 1.986 O4:0.014Cr 3+ ]]> Example 5 <![CDATA[Zn 1.12 To 1.886 The 0.02 Oh 3.9 F 0.2 :0.014Cr 3+ ]]> Example 1 <![CDATA[Zn 1.12 Al 1.906 O4:0.014Cr 3+ ]]> Example 6 <![CDATA[Zn 1.12 Mg 0.2 Al 1.506 Ge 0.2 O 3.9 F 0.2 :0.014Cr 3+ ]]> Example 2 <![CDATA[ZnAl 1.986 O 3.7 F 0.6 :0.014Cr 3+ ]]> Example 7 <![CDATA[Zn 1.12 Mg 0.2 Al 1.506 Si 0.2 O 3.9 F 0.2 :0.014Cr 3+ ]]> Example 3 <![CDATA[Zn 1.12 Al 1.906 Oh 3.9 F 0.2 :0.014Cr 3+ ]]> Example 8 <![CDATA[Zn 1.12 Mg 0.4 Al 0.706 Ga 0.4 Ge 0.4 O 3.9 F 0.2 :0.014Cr 3+ ]]> Example 4 <![CDATA[Zn 1.12 Al 1.506 Yes 0.4 Oh 3.9 F 0.2 :0.014Cr 3+ ]]> Comparative Example 2 <![CDATA[Zn 1.12 Mg 0.2 Al 1.506 Of 0.2 SHE 3.9 F 0.2 :0.014Cr 3+ ]]>

[0121] Characterization and testing

[0122] (I) XRD test

[0123] The aluminate red fluorescent materials obtained in Example 1 and Comparative Example 1 were subjected to XRD test. The results are shown in Figure 1 .Depend on Figure 1 It can be seen that the diffraction peaks of the aluminate red fluorescent material obtained in the present invention and the diffraction peaks of the fluorescent material obtained in the comparative example are consistent with the standard PDF card, indicating that the use of Zn 2+ For Al 3+ Non-equivalent substitution will not cause changes in the original crystal structure.

[0124] (II) Testing of excitation spectrum and emission spectrum

[0125] The aluminate red fluorescent materials obtained in Examples 1 to 8, Comparative Example 1 and Comparative Example 2 were tested for excitation spectra and emission spectra.

[0126] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 1 and Comparative Example 1 are shown in Figure 2 . Figure 2 (a) is the excitation spectrum; Figure 2 (b) is the emission spectrum. Figure 2 It can be seen that the aluminate red fluorescent material provided in Example 1 has significantly improved intensities of the excitation spectrum and the emission spectrum compared to the sample provided in Comparative Example 1. The excitation spectrum ranges from 300 to 650 nm, and it can emit deep red light in the 650 to 800 nm band under the excitation of ultraviolet light and yellow-green light.

[0127] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 2 are shown in Figure 3 . Figure 3 (a) is the excitation spectrum; Figure 3 (b) is the emission spectrum. Figure 3 It can be seen that the intensity of the excitation spectrum and emission spectrum of the aluminate red fluorescent material in Example 2 is improved to a certain extent compared with the aluminate red fluorescent material in Comparative Example 1, indicating that the aluminate red fluorescent material in Example 2 has a certain intensity. - For O 2- Non-equivalent substitution can eliminate oxygen vacancy defects inside the crystal to a certain extent, thereby improving the luminescence performance of the material.

[0128] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 3 are shown in Figure 4 . Figure 4 (a) is the excitation spectrum; Figure 4 (b) is the emission spectrum. Figure 4 It can be seen that the intensity of the excitation spectrum and emission spectrum of the aluminate red fluorescent material in Example 3 is significantly improved compared with the aluminate red fluorescent material in Comparative Example 1, indicating that the use of Zn 2+ and F -The doping strategy can greatly improve the luminescence performance of the obtained fluorescent material.

[0129] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 4 are shown in Figure 5 . Figure 5 (a) is the excitation spectrum; Figure 5 (b) is the emission spectrum. Figure 5 It can be seen that the aluminate red fluorescent material of Example 4 has significantly higher intensities of excitation spectrum and emission spectrum than the aluminate red fluorescent material of Comparative Example 1, indicating that Ga 3+ For Al 3+ Equivalent substitution can significantly improve the luminescent properties of fluorescent materials.

[0130] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 5 are shown in Figure 6 . Figure 6 (a) is the excitation spectrum; Figure 6 (b) is the emission spectrum. Figure 6 It can be seen that the aluminate red fluorescent material of Example 5 has significantly higher intensities of excitation spectrum and emission spectrum than the aluminate red fluorescent material of Comparative Example 1, indicating that La 3+ For Al 3+ Equivalent substitution can improve the luminescent properties of fluorescent materials.

[0131] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 6 are shown in Figure 7 . Figure 7 (a) is the excitation spectrum; Figure 7 (b) is the emission spectrum. Figure 7 It can be seen that the aluminate red fluorescent material of Example 6 has significantly enhanced intensities of the excitation spectrum and emission spectrum compared with the aluminate red fluorescent material of Comparative Example 1, and the band of the emission spectrum is wider, indicating that Mg 2+ and Ge 4+ For Al 3+ Non-equivalent substitution can effectively regulate the luminescent properties of fluorescent materials and significantly improve the luminescent performance of fluorescent materials.

[0132] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 7 are shown in Figure 8 . Figure 8 (a) is the excitation spectrum; Figure 8 (b) is the emission spectrum. Figure 8 It can be seen that the intensity of the excitation spectrum and emission spectrum of the aluminate red fluorescent material in Example 7 is significantly improved compared with the aluminate red fluorescent material in Comparative Example 1, indicating that Mg 2+ and Si 4+ For Al3+ Non-equivalent substitution can significantly improve the luminescent properties of fluorescent materials.

[0133] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Example 8 are shown in Fig. 9 . Fig. 9 (a) is the excitation spectrum; Fig. 9 (b) is the emission spectrum. Fig. 9 It can be seen that the aluminate red fluorescent material of Example 8 has significantly enhanced intensities of the excitation spectrum and emission spectrum compared with the aluminate red fluorescent material of Comparative Example 1, and the band of the emission spectrum is wider, indicating that Mg 2+ , Ga 3+ and Ge 4+ For Al 3+ Atomic substitution can optimize and improve the luminescence properties of fluorescent materials.

[0134] The excitation spectrum ranges of the aluminate red fluorescent materials of Examples 2 to 8 are 300 to 650 nm respectively, and they can emit deep red light in the 650 to 850 nm band under the excitation of ultraviolet light or yellow-green light.

[0135] The excitation spectrum and emission spectrum of the aluminate red fluorescent material obtained in Comparative Example 2 are shown in Fig.10 . Fig.10 (a) is the excitation spectrum; Fig.10 (b) is the emission spectrum. Fig.10 and Figure 7 By comparison, it can be seen that the intensities of the excitation spectrum and the emission spectrum of the aluminate red fluorescent material of Comparative Example 2 are both less than the spectral intensity of the aluminate red fluorescent material of Example 6.

[0136] (III) Application test in light-converting agricultural greenhouse film

[0137] The aluminate red fluorescent material obtained in Example 6 was coated on a PET film by screen printing to prepare a light-converting film, and the transmittance of the obtained light-converting film was tested. Fig.11 .Depend on Fig.11 It can be seen that the light-converting film has good transmittance in the visible light region, but the transmittance of yellow-green light in the 500-600nm band decreases, indicating that the fluorescent material provided in this embodiment has good absorption characteristics for yellow-green light and can be used in light-converting agricultural greenhouse films.

[0138] The present invention is not limited to the above-mentioned embodiments. Without departing from the essential content of the present invention, any deformation, improvement and substitution that can be conceived by those skilled in the art shall fall within the scope of the present invention.

Claims

1. An aluminate red fluorescent material, characterized in that: It has a chemical composition as shown in formula (1): Zn 1+1.5a M Ⅱ b Al 2-a-b-c-d-y M Ⅲ c M Ⅳ d O 4-x F 2x :yCr 3+ (1), Among them, M Ⅱ M is a divalent element. Ⅱ At least one selected from Be, Mg, Cu, Cd; M Ⅲ For trivalent elements, M Ⅲ At least one selected from B, Ga, Sc, Y, La, Sm, Eu, Gd, Lu, and Bi; M Ⅳ M is a tetravalent element. Ⅳ At least one selected from Si, Mn, Ge, Zr, and Hf; Among them, 1+1.5a represents the molar coefficient of Zn, b represents M Ⅱ The molar coefficient of Al, 2-abcdy represents the molar coefficient of Al, and c represents M Ⅲ The molar coefficient, d represents M Ⅳ , 4-x represents the molar coefficient of O, 2x represents the molar coefficient of F, and y represents the molar coefficient of Cr; Among them, 0≤a≤0.2, 0≤b≤0.8, 0≤c≤1, 0≤d≤0.8, 0≤x≤2, 0.005≤y≤0.

5.

2. The aluminate red fluorescent material according to claim 1, characterized in that: M Ⅱ Selected from one of Be, Mg, Cu and Cd.

3. The aluminate red fluorescent material according to claim 1, characterized in that: M Ⅲ Selected from one of B, Ga, Sc, Y, La, Sm, Eu, Gd, Lu, and Bi.

4. The aluminate red fluorescent material according to claim 1, characterized in that: M Ⅳ Selected from one of Si, Mn, Ge, Zr and Hf.

5. The aluminate red fluorescent material according to claim 1, characterized in that: 0≤a≤0.1, 0≤b≤0.5, 0≤c≤0.6, 0≤d≤0.

6.

6. The aluminate red fluorescent material according to claim 1, characterized in that: 0≤x≤1, 0.008≤y≤0.

2.

7. The aluminate red fluorescent material according to claim 1, characterized in that: The aluminate red fluorescent material has any one of the following compositions: Zn 1.12 Al 1.906 O4:0.014Cr 3+ ; ZnAl 1.986 About 3.7 F 0.6 :0.014Cr 3+ ; Zn 1.12 Al 1.906 O 3.9 F 0.2 :0.014Cr 3+ ; Zn 1.12 Al 1.506 Ga 0.4 O 3.9 F 0.2 :0.014Cr 3+ ; Zn 1.12 To 1.886 The 0.02 Oh 3.9 F 0.2 :0.014Cr 3+ ; Zn 1.12 Mg 0.2 Al 1.506 Ge 0.2 O 3.9 F 0.2 :0.014Cr 3+ ; Zn 1.12 Mg 0.2 Al 1.506 Si 0.2 O 3.9 F 0.2 :0.014Cr 3+ ; Zn 1.12 Mg 0.4 Al 0.706 Ga 0.4 Ge 0.4 O 3.9 F 0.2 :0.014Cr 3+ 。 8. A method for preparing the aluminate red fluorescent material according to any one of claims 1 to 6, characterized in that: The steps include: According to the chemical composition of the aluminate red fluorescent material, the Ⅱ , Al, M Ⅲ 、M Ⅳ The raw materials of inorganic compounds of F and Cr elements are mixed and sintered to obtain the aluminate red fluorescent material; wherein the sintering includes pre-sintering and high-temperature sintering, the pre-sintering temperature is 900-1100°C, the pre-sintering time is 2-4h, the high-temperature sintering temperature is 1200-1600°C, and the high-temperature sintering time is 4-8h.

9. The preparation method according to claim 8, characterized in that: Inorganic compounds containing Zn are zinc oxide and zinc fluoride; Ⅱ The inorganic compound of element is M Ⅱ Oxides or carbonates; inorganic compounds containing Al are aluminum oxides; inorganic compounds containing M Ⅲ The inorganic compound of element is M Ⅲ Oxides of elements; containing M Ⅳ The inorganic compound of element is M Ⅳ Oxide; the inorganic compound containing F element is zinc fluoride; the inorganic compound containing Cr element is chromium trioxide or chromium carbonate.

10. Use of the aluminate red fluorescent material according to any one of claims 1 to 7 in preparing light-converting agricultural greenhouse film.

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