CN117431059A - Preparation and application of deep red luminescent material for metal ion doped zinc aluminate plant light filling - Google Patents
Preparation and application of deep red luminescent material for metal ion doped zinc aluminate plant light filling Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 title claims description 11
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 title abstract description 9
- 239000011701 zinc Substances 0.000 title description 60
- 239000000463 material Substances 0.000 title description 9
- 229910052725 zinc Inorganic materials 0.000 title description 8
- -1 zinc aluminate Chemical class 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 52
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 238000000295 emission spectrum Methods 0.000 abstract description 23
- 238000000695 excitation spectrum Methods 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 28
- 239000011777 magnesium Substances 0.000 description 20
- 239000011575 calcium Substances 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910000423 chromium oxide Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005090 crystal field Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229930002868 chlorophyll a Natural products 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229930002869 chlorophyll b Natural products 0.000 description 1
- NSMUHPMZFPKNMZ-VBYMZDBQSA-M chlorophyll b Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C=O)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 NSMUHPMZFPKNMZ-VBYMZDBQSA-M 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000008636 plant growth process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/685—Aluminates; Silicates
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G7/00—Botany in general
- A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
- A01G7/045—Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Botany (AREA)
- Ecology (AREA)
- Forests & Forestry (AREA)
- Environmental Sciences (AREA)
- Luminescent Compositions (AREA)
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
Technical Field
The invention relates to the technical field of artificial light sources, in particular to a metal ion (Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ,Li + ) Doped ZnAl 2 O 4 :Cr 3+ Preparation and application of dark red luminescent material for plant light filling.
Background
In the process of plant growth, the photosensitive pigment promotes seed germination, removes yellowing, expands leaf and other stepsSegments have a very important role. The photosensitizing pigment exists in two forms, one is red light absorption (Pr), and the absorption spectrum is two bands of 350 nm-400 nm and 600 nm-700 nm; the other is far-red light absorption type (Pfr), and the absorption spectrum is a broadband which is positioned between 380 nm and 420 nm and between 650nm and 780 nm; these two different forms of presence promote plant growth by absorbing light; in addition, photosynthesis is the basis for plant growth, and its absorption of light is mainly dependent on three plant pigments: chlorophyll a, which has an absorption spectrum of 350 nm-450 nm and 600 nm-700 nm, another chlorophyll b, which has an absorption spectrum of 380 nm-470 nm and 610 nm-650 nm, and finally a β -carotenoid, which has an absorption spectrum of 400 nm-500 nm. In modern agriculture, facility agriculture is an important sign of agricultural modernization, is also a necessary trend of realizing the development of agricultural modernization in China, is mostly one year old due to the limitation of natural conditions in northern areas of China, and in order to meet the demands of people on vegetables and fruits, out-of-season fruits and vegetables are planted in many areas by utilizing greenhouses, so that good economic benefits are achieved, light supplementing is needed to be carried out on plants in greenhouse planting, and LEDs are used as a new generation solid state lighting system, and have the advantages of high luminous efficiency, environmental protection, long service life and the like, and are usually used as plant growth lamps to supplement illumination. The existing fluorescent powder has less dark red fluorescent powder, and has important significance in developing dark red fluorescent powder excited by near ultraviolet or green light. Cr (Cr) 3+ Ions may exhibit near ultraviolet or green excitation to emit deep red light in many matrices.
Disclosure of Invention
The invention uses ZnAl 2 O 4 Cr as a matrix material for fluorescent powder 3+ As the luminescence center, alkaline earth metal ions (Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) Doped matrix, reduced lattice symmetry and modified Cr 3+ The surrounding local crystal field environment thereby alters the luminescence properties of the sample. The fluorescent powder prepared by the invention can be effectively excited by near ultraviolet light and green light, and is used for solving the problem of dark red fluorescent powder for plant light supplementing.
The invention firstly provides a method for manufacturing the LED display panelDoped with transition metal ion Cr 3+ The structural formula of the dark red fluorescent powder of the luminescent material is as follows: znAl (ZnAl) 2(1-y) O 4 :2yCr 3+ （0.002 ≤ y ≤ 0.02）。
The invention also provides a doped alkali metal ion Li + The structural formula of the dark red fluorescent powder of the luminescent material is as follows: zn (zinc) 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ （0 ≤ x ≤ 0.3）。
The invention also provides a doped alkaline earth metal ion Ca 2+ The structural formula of the dark red fluorescent powder of the luminescent material is as follows: zn (zinc) 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ （0 ≤ x ≤ 0.25）。
The invention also provides a doped alkaline earth metal ion Sr 2+ The structural formula of the dark red fluorescent powder of the luminescent material is as follows: zn (zinc) 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ （0 ≤ x ≤ 0.25）。
The invention also provides a doped alkaline earth metal ion Ba 2+ The structural formula of the dark red fluorescent powder of the luminescent material is as follows: zn (zinc) 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ （0 ≤ x ≤ 0.25）。
The invention also provides a doped alkaline earth metal ion Mg 2+ The structural formula of the dark red fluorescent powder of the luminescent material is as follows: zn (zinc) 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ （0 ≤ x ≤ 1）。
The preparation method of the aluminate dark red fluorescent powder comprises the following steps: according to chemical formula ZnAl 2(1-y) O 4 :2yCr 3 + Weighing Zn-containing compound, al-containing compound and Cr-containing compound 3+ Fully grinding the compound to obtain a mixture;
step two, the preparation method of the aluminate dark red fluorescent powder comprises the following steps: according to 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+ ) Weighing Zn-containing compound, al-containing compound and Cr-containing compound 3+ The compound of (2) and the metal ion-containing compound Li-containing compound + Compound (c) containing Ca 2+ Compound (c) containing Sr 2+ Compounds of (1) contain Ba 2+ Is a compound of formula (II) and Mg-containing 2+ Fully grinding the compound to obtain a mixture;
and thirdly, roasting the mixture obtained in the first step and the second step at a high temperature, and grinding the sample uniformly after cooling to room temperature to obtain the metal ion doped fluorescent powder with different types and different concentrations.
Preferably, the source of the metal ionic compound in the mixture of the above steps is a 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, or a Zn-containing halide.
Preferably, the Al-containing compound is an Al-containing oxide, an Al-containing carbide, an Al-containing chloride, or an Al-containing oxyacid 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 roasting temperature is 1200-1500 ℃ and the roasting time is 1-15 h.
The principle of the invention is as follows: in ZnAl 2 O 4 :Cr 3+ Metal ions are introduced into(Li + ,Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) Can reduce symmetry of crystal lattice and modify Cr 3+ The surrounding local crystal field environment thereby enhances the luminescence properties of the sample. In Zn 1- x M x Al 1.988 O 4 :0.012Cr 3+ (M=2Li + ,Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) Cr in the deep red fluorescent powder 3+ A series of sharp peaks with an emission spectrum of ions ranging from 650nm to 750 nm, 687 ofThe nm peak is the strongest. Zn (zinc) 1-x M x Al 1.988 O 4 :0.012Cr 3+ (M=2Li + ,Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) There are two stronger wideband in the range of 350 nm to 600 nm, the strongest peaks being at 394nm and 534nm respectively, ascribed to Cr 3+ A kind of electronic device 4 A 2 ( 4 F)→ 4 T 1 ( 4 F) And 4 A 2 ( 4 F)→ 4 T 2 ( 4 f) The fluorescent powder can be effectively excited by near ultraviolet light and green light to emit deep red light, so that the conversion from ultraviolet light or green light to deep red light is realized, and the fluorescent powder can be used as a plant light supplementing light source.
Compared with the prior art, the invention has the beneficial effects that:
the invention is characterized in that ZnAl 1.988 O 4 :0.012Cr 3+ Is based on the incorporation of metal ions (Li + ,Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) Can reduce symmetry of crystal lattice and modify Cr 3+ The surrounding local crystal field environment achieves the purpose of changing the luminous performance of the sample.
Drawings
For a more concise and clear description of the technical solutions of the present invention, the drawings that are required for the embodiments of the present invention will be briefly described below, and of course, the drawings in the following description are only for some embodiments of the present invention, and one skilled in the art may obtain other drawings according to the following drawings without inventive effort.
FIG. 1 shows the phosphor ZnAl obtained in example 1 2(1-y) O 4 :2yCr 3+ XRD pattern of (y= 0.002,0.004,0.006,0.008,0.001,0.015,0.02).
FIG. 2 shows the phosphor ZnAl obtained in example 1 2(1-y) O 4 :2yCr 3+ Excitation spectrum (a) and emission spectrum (b) of (y= 0.002,0.004,0.006,0.008,0.001,0.015,0.02).
FIG. 3 shows the phosphor Zn obtained in example 2 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ XRD pattern of (x= 0.05,0.1,0.15,0.2,0.25,0.3).
FIG. 4 shows the phosphor Zn obtained in example 2 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ Excitation spectrum (a) and emission spectrum (b) of (x= 0,0.05,0.1,0.15,0.2,0.25,0.3).
FIG. 5 shows the phosphor Zn obtained in example 3 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25).
FIG. 6 shows the phosphor Zn obtained in example 3 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ Excitation spectrum (a) and emission spectrum (b) of (x= 0,0.1,0.25).
FIG. 7 shows the phosphor Zn obtained in example 4 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25).
FIG. 8 shows the phosphor Zn obtained in example 4 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ Excitation spectrum (a) and emission spectrum (b) of (x= 0,0.1,0.25).
FIG. 9 shows the phosphor Zn obtained in example 5 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25).
FIG. 10 shows the phosphor Zn obtained in example 5 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ Excitation spectrum (a) and emission spectrum (b) of (x= 0,0.1,0.25).
FIG. 11 shows the phosphor Zn obtained in example 6 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ XRD pattern of (x= 0.1,0.25,0.5,0.75,0.9,1).
FIG. 12 shows the phosphor Zn obtained in example 6 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ Excitation spectrum (a) and emission spectrum (b) of (x= 0,0.1,0.25,0.5,0.75,0.9,1).
Description of the embodiments
The invention will be described in detail with reference to specific embodiments thereof for further understanding of the invention, but the following description is merely illustrative of the nature and advantages of the invention and is not intended to limit the invention to the specific forms set forth in the claims.
Examples
Takes zinc oxide, aluminum oxide and chromium oxide as initial raw materials according to chemical formula ZnAl 2(1-y) O 4 :2yCr 3+ The stoichiometric ratio of (y= 0.002,0.004,0.006,0.008,0.001,0.015,0.02) is respectively weighted three raw materials, fully grinding in an agate mortar, placing a sample into a corundum crucible after grinding uniformly, transferring to high temperature, roasting for 6 hours in air at 1400 ℃, cooling to room temperature, taking out and grinding uniformly to obtain a series of Cr 3+ Doped dark red fluorescent powder with the composition of ZnAl 2(1-y) O 4 :2yCr 3+ （y=0.002,0.004,0.006,0.008,0.001,0.015,0.02）。
FIG. 1 shows the phosphor ZnAl obtained in example 1 2(1-y) O 4 :2yCr 3+ From the XRD pattern of (C), it can be seen that the spectrum and ZnAl 2 O 4 Consistent, prove successful preparation of ZnAl 2(1-y) O 4 :2yCr 3+ Fluorescent powder. FIG. 2 shows the phosphor ZnAl obtained in example 1 2(1-y) O 4 :2yCr 3+ As can be seen from the figure, znAl has an excitation spectrum (a) and an emission spectrum (b) 2(1-y) O 4 :2yCr 3+ Two stronger broad bands with excitation spectra in the range of 350 nm to 600 nm, the strongest peaks being at 394nm and 534nm respectively, ascribed to Cr 3+ A kind of electronic device 4 A 2 ( 4 F)→ 4 T 1 ( 4 F) And 4 A 2 ( 4 F)→ 4 T 2 ( 4 f) Is a transition of (2); the fluorescent powder has a series of sharp peaks with the emission spectrum ranging from 650nm to 750 nm, wherein the peak value of 687 nm is strongest; in the fluorescent powder ZnAl 2(1-y) O 4 :2yCr 3+ (y= 0.002,0.004,0.006,0.008,0.001,0.015,0.02) with Cr 3+ The intensity of the excitation and emission spectra increases and decreases, the spectral intensity being strongest when y=0.006, i.e. the optimum doping concentration is 0.6 at%. From the above, fluorescence was foundPowder ZnAl 2(1-y) O 4 :2yCr 3+ Can be effectively excited by near ultraviolet light and green light to emit deep red light, realizes the conversion from ultraviolet light or green light to deep red light, and can be used as a plant light supplementing light source.
Examples
Taking zinc oxide, aluminum oxide, chromium oxide and lithium carbonate as starting materials according to a chemical formula Zn 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ The stoichiometric ratio of (x= 0,0.05,0.1,0.15,0.2,0.25,0.3) is respectively measured, four raw materials are fully ground in an agate mortar, after grinding uniformly, a sample is put into a corundum crucible and is transferred to high temperature, roasting is carried out for 6 hours in air at 1400 ℃, cooling is carried out to room temperature, and then the mixture is taken out and ground uniformly, thus obtaining a series of Cr 3+ Doped dark red fluorescent powder with Zn composition 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）。
FIG. 3 shows the phosphor Zn obtained in example 2 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), from which it can be seen that the spectrum and ZnAl 2 O 4 Consistent with each other, the successful preparation of the fluorescent powder Zn is proved 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ . FIG. 4 shows the phosphor Zn obtained in example 2 1-x Li 2x Al 1.988 O 4 :0.012Cr 3+ The excitation spectrum (a) and the emission spectrum (b) of (x= 0,0.05,0.1,0.15,0.2,0.25,0.3), and the peak positions of the shapes of the excitation spectrum and the emission spectrum of the fluorescent powder and ZnAl can be seen from the figure 1.988 O 4 :0.012Cr 3+ Consistent with Li in strength + The intensity of the excitation and emission spectra increases and decreases, the spectral intensity being the strongest when x=0.25, i.e. the optimal doping concentration is 0.25 at%.
Examples
Zinc oxide, aluminum oxide, chromium oxide and calcium carbonate are taken as starting materials, and Zn is adopted according to the chemical formula 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ The stoichiometric ratio of (x=0.1, 0.25) respectively weighing four raw materials, fully grinding in an agate mortar, placing a sample into a corundum crucible after grinding uniformly, transferring to high temperature, roasting in air for 6 hours at 1400 ℃, cooling to room temperature, taking out and grinding uniformly to obtain a series of Cr 3+ Doped dark red fluorescent powder with Zn composition 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ （x=0.1,0.25）。
FIG. 5 shows Zn obtained in example 3 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25), from which it can be seen that the spectrum and ZnAl when x=0.1 2 O 4 Consistent with each other, the successful preparation of the fluorescent powder Zn is proved 0.9 Ca 0.1 Al 1.988 O 4 :0.012Cr 3+ The method comprises the steps of carrying out a first treatment on the surface of the Whereas when x=0.25, a hetero-phase has occurred. FIG. 6 shows the phosphor Zn obtained in example 3 1-x Ca x Al 1.988 O 4 :0.012Cr 3+ The excitation spectrum (a) and the emission spectrum (b) of (x= 0,0.1,0.25), and the peak positions of the shapes of the excitation spectrum and the emission spectrum of the fluorescent powder and ZnAl can be seen from the figure 1.988 O 4 :0.012Cr 3+ In agreement, its strength has been reduced due to Ca 2 + (r=1.06 a) and Zn 2+ The ionic radii of (r=0.6 a) differ significantly.
Examples
Taking zinc oxide, aluminum oxide, chromium oxide and strontium carbonate as starting raw materials according to a chemical formula Zn 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ The stoichiometric ratio of (x=0.1, 0.25) respectively weighing four raw materials, fully grinding in an agate mortar, placing a sample into a corundum crucible after grinding uniformly, transferring to high temperature, roasting in air for 6 hours at 1400 ℃, cooling to room temperature, taking out and grinding uniformly to obtain a series of Cr 3+ Doped dark red fluorescent powder with Zn composition 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ （x=0.1,0.25）。
FIG. 7 shows Zn obtained in example 4 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25), from which it can be seen that the spectrum and ZnAl when x=0.1 2 O 4 Consistent with each other, the successful preparation of the fluorescent powder Zn is proved 0.9 Sr 0.1 Al 1.988 O 4 :0.012Cr 3+ The method comprises the steps of carrying out a first treatment on the surface of the Whereas when x=0.25, a hetero-phase has occurred. FIG. 8 shows the phosphor Zn obtained in example 4 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ The excitation spectrum (a) and the emission spectrum (b) of (x= 0,0,0.1,0.25), and the peak positions of the shapes of the excitation spectrum and the emission spectrum of the fluorescent powder and ZnAl can be seen from the figure 1.988 O 4 :0.012Cr 3+ In agreement, its strength has been reduced due to Sr 2+ (r=1.27 a) and Zn 2+ The ionic radii of (r=0.6 a) differ significantly.
Examples
Zinc oxide, aluminum oxide, chromium oxide and barium carbonate are taken as initial raw materials, and Zn is adopted according to a chemical formula 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ The stoichiometric ratio of (x=0.1, 0.25) respectively weighing four raw materials, fully grinding in an agate mortar, placing a sample into a corundum crucible after grinding uniformly, transferring to high temperature, roasting in air for 6 hours at 1400 ℃, cooling to room temperature, taking out and grinding uniformly to obtain a series of Cr 3+ Doped dark red fluorescent powder with Zn composition 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ （x=0.1,0.25）。
FIG. 9 shows Zn obtained in example 5 1-x Ba x Al 1.988 O 4 :0.012Cr 3+ (x=0.1, 0.25), from which it can be seen that the spectrum and ZnAl when x=0.1 2 O 4 Consistent with each other, the successful preparation of the fluorescent powder Zn is proved 0.9 Bar 0.1 Al 1.988 O 4 :0.012Cr 3+ The method comprises the steps of carrying out a first treatment on the surface of the Whereas when x=0.25, a hetero-phase has occurred. FIG. 10 shows the phosphor Zn obtained in example 5 1-x Sr x Al 1.988 O 4 :0.012Cr 3+ An excitation spectrum (a) and an emission spectrum (b) of (x= 0,0.1,0.25),as can be seen from the graph, the peak positions of the shapes of the excitation spectrum and the emission spectrum of the fluorescent powder and ZnAl 1.988 O 4 :0.012Cr 3+ Consistently, its strength has been reduced due to Ba 2 + (r=1.34 a) and Zn 2+ The ionic radii of (r=0.6 a) differ significantly.
Examples
Takes zinc oxide, aluminum oxide, chromium oxide and magnesium carbonate as initial raw materials according to the chemical formula Zn 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ The stoichiometric ratio of (x= 0.1,0.25,0.5,0.75,0.9,1) is respectively measured, four raw materials are fully ground in an agate mortar, after grinding uniformly, a sample is put into a corundum crucible and is transferred to high temperature, roasting is carried out for 6 hours in air at 1400 ℃, cooling is carried out to room temperature, and then the mixture is taken out and ground uniformly, thus obtaining a series of Cr 3+ Doped dark red fluorescent powder with Zn composition 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ （x=0.1,0.25,0.5,0.75,0.9,1）。
FIG. 11 shows the Zn concentration obtained in example 6 1-x Mg x Al 1.988 O 4 :0.012Cr 3+ (x= 0.1,0.25,0.5,0.75,0.9,1), from which it can be seen that the spectrum and ZnAl 2 O 4 Consistent with each other, the successful preparation of the fluorescent powder Zn is proved 1- x Mg x Al 1.988 O 4 :0.012Cr 3+ (x= 0.1,0.25,0.5,0.75,0.9,1); this is due to Mg 2+ (r=0.57 a) and Zn 2+ (r=0.6 a) the difference in ionic radii is small. FIG. 12 shows the phosphor Zn obtained in example 6 1-x Mg x Al 1.988 O 4 :0.012Cr 3 + As can be seen from the graph, the excitation spectrum (a) and the emission spectrum (b) of (x= 0,0.1,0.25,0.5,0.75,0.9,1) of the fluorescent powder are two stronger broadband with the excitation spectrum ranging from 350 nm to 600 nm, and the strongest peaks are respectively positioned at 394nm and 534nm and belong to Cr 3+ A kind of electronic device 4 A 2 ( 4 F)→ 4 T 1 ( 4 F) And 4 A 2 ( 4 F)→ 4 T 2 ( 4 f) Is a transition of (2); the fluorescent powder has a series of sharp peaks with the emission spectrum ranging from 650nm to 750 nm, wherein the peak value of 686 nm is strongest; in fluorescent powder 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+ The intensity of the excitation and emission spectra increases and decreases, the spectral intensity being the strongest when x=0.5, i.e. the optimum doping concentration is 50 at%.
The above examples are only intended to illustrate the method of the invention. It is noted that those skilled in the art can make appropriate improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications are also within the scope of the claims of the present invention.
Claims (8)
1. Preparation of transition metal ion Cr 3+ Doped dark red fluorescent powder ZnAl 2(1-y) O 4 :2yCr 3+ Wherein y is more than or equal to 0.002 and less than or equal to 0.02.
2. Preparation of metal ions (Li) + ,Ca 2+ ,Sr 2+ ,Ba 2+ ,Mg 2+ ) Doped dark red phosphor Zn 1-x M x Al 1.988 O 4 :0.012Cr 3+ Wherein x is more than or equal to 0 and less than or equal to 1.
3. The dark red phosphor Zn according to claims 1 and 2 1-x M x Al 2（1-y） O 4 :2yCr 3+ （M = 2Li + ,Ca 2+ ,Sr 2+ ,Ba 2 + ,Mg 2+ ) Is characterized by comprising the following steps:
the preparation method of the aluminate dark red fluorescent powder comprises the following steps: according to chemical formula ZnAl 2(1-y) O 4 :2yCr 3+ Weighing Zn-containing compound, al-containing compound and Cr-containing compound 3+ Fully grinding the compound to obtain a mixture;
step two, the aboveThe preparation method of the aluminate dark red fluorescent powder comprises the following steps: according to 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+ ) Weighing Zn-containing compound, al-containing compound and Cr-containing compound 3+ The compound of (2) and the metal ion-containing compound Li-containing compound + Compound (c) containing Ca 2+ Compound (c) containing Sr 2+ Compounds of (1) contain Ba 2+ Is a compound of formula (II) and Mg-containing 2+ Fully grinding the compound to obtain a mixture;
and thirdly, roasting the mixture obtained in the first step and the second step at a high temperature, and grinding the sample uniformly after cooling to room temperature to obtain the metal ion doped fluorescent powder with different types and different concentrations.
4. The Cr according to claim 3 3+ The preparation method of the doped dark red fluorescent powder is characterized in that the metal ion compound in the mixture of the steps is from metal oxide, metal carbonate, metal fluoride or metal chloride.
5. The Cr according to claim 3 3+ The preparation method of the doped dark red fluorescent powder is characterized in that the Zn-containing compound is Zn-containing oxide, zn-containing nitride, zn-containing hydride, zn-containing hydroxide, zn-containing chloride and Zn-containing halide.
6. The Cr according to claim 3 3+ The preparation method of the doped dark red fluorescent powder is characterized in that the compound containing Al is an oxide containing Al, a carbide containing Al, a chloride containing Al and an oxysalt containing Al.
7. The Cr according to claim 3 3+ The preparation method of the doped dark red fluorescent powder is characterized in that the Cr-containing compound is an oxide containing Cr, a sulfate containing Cr and a carbonate containing CrCr-containing fluorides or Cr-containing hydroxides.
8. The Cr according to claim 3 3+ The preparation method of the doped dark red fluorescent powder is characterized in that in the third step, the roasting temperature is 1200-1500 ℃ and the roasting time is 1-15 h.
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