CN116574511A - Europium-samarium co-doped borate red light conversion agent and preparation method thereof - Google Patents
Europium-samarium co-doped borate red light conversion agent and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QMABZEWAQYHYST-UHFFFAOYSA-N europium samarium Chemical compound [Sm][Eu] QMABZEWAQYHYST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 38
- -1 europium ions Chemical class 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 34
- 238000000227 grinding Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 230000005284 excitation Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229930002875 chlorophyll Natural products 0.000 description 3
- 235000019804 chlorophyll Nutrition 0.000 description 3
- 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 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7797—Borates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of rare earth luminescent materials, in particular to a europium-samarium co-doped borate red light conversion agent and a preparation method thereof. The europium samarium co-doped borate red light conversion agent has a chemical general formula as follows: k (K) 7 MY (2‑x‑y) (B 5 O 10 ) 3 :xEu 3+ ,ySm 3+ The method comprises the steps of carrying out a first treatment on the surface of the x represents the mole number of doping trivalent europium ions, and x is more than 0 and less than or equal to 2.0; y represents the mole number of doped trivalent samarium ions, and y is more than 0 and less than or equal to 0.8; m is one of the elements Mg, ca, sr and Ba. The invention adopts a high-temperature solid phase method, has simple preparation process, easily obtained synthetic raw materials, easy operation and low preparation cost; the borate is adopted as a matrix material, and the borate is simple in preparation process, low in synthesis temperature, good in light transmittance, high in optical damage threshold, good in thermal stability, rich and various in structure and wide in selectable range, and is an excellent luminous matrix material.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a europium-samarium co-doped borate red light conversion agent and a preparation method thereof.
Background
The rare earth luminescent material has important research significance in light conversion luminescent materials, has outstanding physical and chemical properties, and can be widely applied to the fields of light conversion agricultural films, illumination, display, detection and the like. Rare earth has spectral properties incomparable with common elements due to the special electronic layer structure, and rare earth luminescence almost covers the whole solid luminescence category.
In order to adapt to the development of technological and ecological agriculture, the preparation of the light conversion agent is developed towards the directions of high light efficiency, high matching, high stability, low cost and low pollution. Most studied are a series of inorganic compounds with europium as a central ion, but the characteristic emission peak position of europium has insufficient matching with the maximum absorption peak position of plant chlorophyll, so that the europium has a large rising space in agriculture. And Sm 3+ The ion has rich energy level transition and high luminous efficiency, can absorb light in the range of 362-402nm, and Sm 3+ The energy level transition of the ion belongs to the f-f electric dipole transition in the configuration, and the spectral line is a line spectrum with strong intensity. When excited by ultraviolet light, the fluorescent dye can emit red orange light, and the maximum emission wavelength of the fluorescent dye is 647nm and is basically matched with the absorption peak position of chlorophyll. Thus, sm can be 3+ Ion co-doping with Eu 3+ The light conversion agent serving as the center ion has great application potential in the field of agricultural light conversion by increasing the matching property of the emission peak of the light conversion agent and the chlorophyll absorption peak.
Therefore, how to obtain the europium-samarium co-doped borate red light conversion agent with high luminous efficiency is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to provide a europium-samarium co-doped borate red light conversion agent and a preparation method thereof, which are used for solving the technical problem of low luminous efficiency of the light conversion agent in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a europium-samarium co-doped borate red light conversion agent, the chemical general formula of which is K 7 MY (2-x-y) (B 5 O 10 ) 3 :xEu 3+ ,ySm 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein x represents the mole number of doping trivalent europium ions, and x is more than 0 and less than or equal to 2.0; y represents the mole number of doped trivalent samarium ions, and y is more than 0 and less than or equal to 0.8; m is the element Mg, ca, sr or Ba.
The invention also provides a preparation method of the europium-samarium co-doped borate red light conversion agent, which comprises the following steps:
(1) Will contain K + Compounds of (C) containing M 2+ Compound (C) containing Y 3+ Eu-containing compounds of (A) 3+ Compound (c) containing Sm 3+ Compounds of (A) and BO-containing 3 3- Mixing and grinding the compound of (C) with absolute ethyl alcohol to obtain a mixture;
(2) And (3) calcining and grinding the mixture obtained in the step (1) in sequence in an air atmosphere to obtain the europium-samarium co-doped borate red light conversion agent.
Preferably, the K-containing + The compound of (2) comprises K 2 CO 3 KOH and KNO 3 One or more of them.
Preferably, the M-containing 2+ The compound of (2) is MCO 3 、M(OH) 2 Or M (NO) 3 ) 2 Wherein M is the element Mg, ca, sr or Ba.
Preferably, the Y-containing 3+ The compound of (2) is Y 2 O 3 、Y(NO 3 ) 3 And Y (OH) 3 One or more of them.
Preferably, the Eu-containing material 3+ The compound of (a) is Eu 2 O 3 、Eu(NO 3 ) 2 And Eu (OH) 3 One or more of them.
Preferably, the Sm-containing agent 3+ Is Sm 2 O 3 、Sm(NO 3 ) 2 And Sm (OH) 3 One or more of them.
Preferably, the BO-containing agent 3 3- The compound of (2) is H 3 BO 3 And/or K 2 B 4 O 7 ·10H 2 O。
Preferably, the addition amount of the absolute ethyl alcohol in the step (1) is 20-70% of the total mass of the raw materials.
Preferably, the calcination temperature in the step (2) is 600-900 ℃ and the calcination time is 6-12 h.
The invention has the beneficial effects that:
the invention adopts a high-temperature solid phase method, has simple preparation process, easily obtained synthetic raw materials, easy operation and low preparation cost; in addition, the pollution problem of toxic organic solvents and waste liquid can be avoided, and the method is environment-friendly and low in cost. The invention adopts borate as matrix material, and has simple preparation process, low synthesis temperature, good light transmittance, high optical damage threshold, good thermal stability, rich and various structures and wide selectable range, thereby being an excellent luminous matrix material.
The borate red light conversion agent prepared by the invention is co-doped with Sm 3+ The spectrum is widened, the ultraviolet light-emitting diode is used in the field of light-converting agricultural films, can be effectively excited by short-wave ultraviolet light and long-wave ultraviolet light, and shows strong emission in the range of 580-630 nm, and the strongest red light emission peak-to-peak value is located at 610 nm.
Drawings
FIG. 1 is an SEM image of a borate red light converter prepared in comparative example 3;
FIG. 2 is an X-ray diffraction pattern of the borate red light converter prepared in example 2;
FIG. 3 is a graph showing the excitation spectra obtained at an emission wavelength of 610nm of the borate red light converting agents prepared in comparative examples 1 to 4;
FIG. 4 is a graph showing the emission spectra of the borate red light conversion agents prepared in comparative examples 1 to 4 at 393nm excitation wavelength;
FIG. 5 is a graph showing the excitation spectra obtained at an emission wavelength of 600nm for the borate red light converting agents prepared in comparative example 3 and examples 1 to 4;
FIG. 6 is a graph showing the emission spectra obtained at an excitation wavelength of 346nm of the borate red light converting agents prepared in comparative example 3 and examples 1 to 4.
Detailed Description
The invention provides a europium-samarium co-doped borate red light conversion agent, the chemical general formula of which is K 7 MY (2-x-y) (B 5 O 10 ) 3 :xEu 3+ ,ySm 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein x represents the mole number of doping trivalent europium ions, and x is more than 0 and less than or equal to 2.0; y represents the mole number of doped trivalent samarium ions, and y is more than 0 and less than or equal to 0.8; m is the element Mg, ca, sr or Ba.
In the invention, x represents the mole number of doping trivalent europium ions, and x is more than 0 and less than or equal to 2.0, preferably 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7 and 1.8; y represents the mole number of the trivalent samarium ion doping, and y is more than 0 and less than or equal to 0.8, preferably 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 and 0.8.
The invention also provides a preparation method of the europium-samarium co-doped borate red light conversion agent, which comprises the following steps:
(1) Will contain K + Compounds of (C) containing M 2+ Compound (C) containing Y 3+ Eu-containing compounds of (A) 3+ Compound (c) containing Sm 3+ Compounds of (A) and BO-containing 3 3- Mixing and grinding the compound of (C) with absolute ethyl alcohol to obtain a mixture;
(2) And (3) calcining and grinding the mixture obtained in the step (1) in sequence in an air atmosphere to obtain the europium-samarium co-doped borate red light conversion agent.
In the present invention, the K-containing + The compound of (2) comprises K 2 CO 3 KOH and KNO 3 One or more of them, preferably K 2 CO 3 KOH and KNO 3 More preferably KOH, K 2 CO 3 。
In the present invention, the M-containing 2+ The compound of (2) is MCO 3 、M(OH) 2 Or M (NO) 3 ) 2 Preferably MCO 3 Or M (NO) 3 ) 2 Further preferred is MCO 3 Wherein M is an element of Mg, ca, sr or Ba, and M is preferably Mg, ca or Ba, and more preferably Ca or Ba.
In the present invention, the Y-containing 3+ The compound of (2) is Y 2 O 3 、Y(NO 3 ) 3 And Y (OH) 3 One or more of them, preferablySelected as Y 2 O 3 And/or Y (NO) 3 ) 3 Further preferably Y 2 O 3 。
In the present invention, the Eu-containing material 3+ The compound of (a) is Eu 2 O 3 、Eu(NO 3 ) 2 And Eu (OH) 3 One or more of them, preferably Eu 2 O 3 、Eu(NO 3 ) 2 、Eu(OH) 3 Further preferably Eu 2 O 3 、Eu(NO 3 ) 2 。
In the invention, the Sm-containing alloy contains 3+ Is Sm 2 O 3 、Sm(NO 3 ) 2 And Sm (OH) 3 One or more of them, preferably Sm 2 O 3 、Sm(NO 3 ) 2 、Sm(OH) 3 Further preferably Sm 2 O 3 、Sm(NO 3 ) 2 。
In the present invention, the BO-containing agent 3 3- The compound of (2) is H 3 BO 3 And/or K 2 B 4 O 7 ·10H 2 O, preferably H 3 BO 3 。
In the present invention, the amount of the absolute ethyl alcohol added in the step (1) is 20 to 70% by weight, preferably 30 to 60% by weight, and more preferably 40 to 50% by weight of the total mass of the raw materials.
In the present invention, the polishing time in the step (1) is 20 to 40 minutes, preferably 25 to 35 minutes, and more preferably 28 to 33 minutes.
In the present invention, the calcining temperature in the step (2) is 600 to 900 ℃, preferably 650 to 850 ℃, and more preferably 700 to 800 ℃; the calcination time is 6 to 12 hours, preferably 7 to 11 hours, and more preferably 8 to 10 hours.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
K 7 CaY 0.39 (B 5 O 10 ) 3 :1.6Eu 3+ ,0.01Sm 3+
In K 2 CO 3 、CaCO 3 、Y 2 O 3 、Eu 2 O 3 、Sm(NO 3 ) 2 H and H 3 BO 3 The preparation method comprises the steps of weighing raw materials according to the molar quantity expressed by a chemical formula, grinding, adding absolute ethanol accounting for 40% of the total mass of the raw materials, and grinding for 30 minutes to fully mix the raw materials. The well-mixed reactants were calcined at 750 ℃ for 10 hours in an air atmosphere. And cooling to room temperature, and grinding the blocky sample obtained by calcination into powder to obtain the required fluorescent powder.
Example 2
K 7 CaY 0.38 (B 5 O 10 ) 3 :1.6Eu 3+ ,0.02Sm 3+
With KOH, ca (OH) 2 、Y(NO 3 ) 3 、Eu(NO 3 ) 2 、Sm 2 O 3 H and H 3 BO 3 The preparation method comprises the steps of weighing raw materials according to the molar quantity expressed by a chemical formula, putting the raw materials into an agate mortar, adding absolute ethanol accounting for 45% of the total mass of the raw materials, and grinding for 25 minutes to fully mix the raw materials. The well-mixed reactants were calcined at 800 ℃ for 10 hours in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Example 3
K 7 CaY 0.36 (B 5 O 10 ) 3 :1.6Eu 3+ ,0.04Sm 3+
By KNO 3 、Ca(NO 3 ) 2 、Y(OH) 3 、Eu 2 O 3 、Sm(OH) 3 H and H 3 BO 3 The preparation method comprises the steps of weighing raw materials according to the molar quantity expressed by a chemical formula, putting the raw materials into an agate mortar, adding absolute ethanol accounting for 45% of the total mass of the raw materials, and grinding for 35 minutes to fully mix the raw materials. The well-mixed reactants were calcined at 800 ℃ for 11h in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Example 4
K 7 CaY 0.32 (B 5 O 10 ) 3 :1.6Eu 3+ ,0.08Sm 3+
In K 2 CO 3 、CaCO 3 、Y 2 O 3 、Eu(OH) 3 、Sm 2 O 3 K is as follows 2 B 4 O 7 ·10H 2 O is used as a raw material, the raw material is weighed according to the mol weight expressed by a chemical formula and put into an agate mortar, absolute ethanol with the total mass of 50% of the raw material is added, and the raw material is ground for 40 minutes, so that the raw material is fully mixed. The well-mixed reactants were calcined at 850 ℃ for 11h in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Comparative example 1
K 7 CaY 1.4 (B 5 O 10 ) 3 :0.6Eu 3+
In K 2 CO 3 、CaCO 3 、Y 2 O 3 、Eu 2 O 3 H and H 3 BO 3 Raw materials are weighed according to the molar quantity expressed by a chemical formula, absolute ethyl alcohol accounting for 50% of the total mass of the raw materials is added, and the raw materials are ground for 20 minutes, so that the raw materials are fully mixed. The well-mixed reactants were calcined at 750 ℃ for 7h in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Comparative example 2
K 7 CaY 0.8 (B 5 O 10 ) 3 :1.2Eu 3+
By KNO 3 、CaCO 3 、Y 2 O 3 、Eu 2 O 3 H and H 3 BO 3 The preparation method comprises the steps of weighing raw materials according to the molar quantity expressed by a chemical formula, putting the raw materials into an agate mortar, adding absolute ethyl alcohol accounting for 40% of the total mass of the raw materials, and grinding for 25 minutes to fully mix the raw materials. The well-mixed reactants were calcined at 800 ℃ for 8h under an air atmosphere. Cooling to room temperature in a high-temperature tube furnaceGrinding the block sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Comparative example 3
K 7 CaY 0.4 (B 5 O 10 ) 3 :1.6Eu 3+
In K 2 CO 3 、CaCO 3 、Y 2 O 3 、Eu 2 O 3 H and H 3 BO 3 The preparation method comprises the steps of weighing raw materials according to the molar quantity expressed by a chemical formula, putting the raw materials into an agate mortar, adding absolute ethyl alcohol accounting for 40% of the total mass of the raw materials, and grinding for 30 minutes to fully mix the raw materials. The well-mixed reactants were calcined at 800 ℃ for 9h in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Comparative example 4
K 7 CaEu 2 (B 5 O 10 ) 3
In K 2 CO 3 、CaCO 3 、Eu 2 O 3 K is as follows 2 B 4 O 7 ·10H 2 O is used as a raw material, the raw material is weighed according to the mol weight expressed by a chemical formula and put into an agate mortar, absolute ethanol accounting for 45% of the total mass of the raw material is added, and the raw material is ground for 30 minutes, so that the raw material is fully mixed. The well-mixed reactants were calcined at 850 ℃ for 9h in an air atmosphere. And (3) cooling to room temperature in a high-temperature tube furnace, and grinding the blocky sample obtained by calcination into powder in an agate mortar to obtain the required fluorescent powder.
Performance tests were performed on the above examples 1 to 4 and comparative examples 1 to 4: as can be seen from FIG. 1, SEM test of the borate red light converting agent prepared in comparative example 3 shows that the obtained light converting agent has irregularly shaped particles which are gathered together, and the distance between the particles is good, which indicates that the crystal growth is good. As can be seen from FIG. 2, the co-doped borate red light conversion agent prepared in example 2 was subjected to an X-ray diffraction test, and the diffraction peak of the obtained co-doped borate red light conversion agent was well matched with that of a standard card, and no impurity peak was present. Indicating the synthesized Eu 3+ And Sm 3+ Ion doping K 7 CaY 0.38 (B 5 O 10 ) 3 :1.6Eu 3+ ,0.02Sm 3+ The light conversion agent is in a pure phase.
As can be seen from FIG. 3 and FIG. 4, the rare earth borate red light conversion agents prepared in comparative examples 1-4 respectively measure the excitation spectrum at the monitoring wavelength of 610nm, and measure the emission spectrum at the excitation wavelength of 393nm, and the rare earth borate red light conversion agents prepared in comparative examples 1-4 have a relatively strong excitation peak in the ultraviolet region, so that the near ultraviolet light which is extremely weak in plant absorption can be well converted into the red light which is relatively strong in plant absorption; the emission spectrum of the rare earth borate red light conversion agent prepared in the comparative example shows some line peaks in the range of 580 to 750nm, along with Eu 3+ The emission intensity of the (c) tends to rise and then fall, and the emission peak is strongest at the doping concentration of x=1.6.
As can be seen from FIGS. 5 and 6, the rare earth borate red light conversion agents prepared in comparative example 3 and examples 1 to 4 were measured for their excitation spectra at a monitoring wavelength of 600nm, and for their emission spectra at an excitation wavelength of 346nm, respectively, and the rare earth co-doped borate red light conversion agents prepared in examples 1 to 4 had Eu existing in the excitation spectra 3+ Characteristic excitation peaks of (2), also Sm 3+ Characteristic excitation peaks of (2). An excitation peak exists around 346nm, and the intensity of the excitation peak is along with Sm 3+ The doping amount increases due to Sm 3+ A kind of electronic device 6 H 5/2 → 4 K 17/2 A transition; the two emission peaks of the co-doped sample with an emission spectrum between 560 and 575nm are attributed to Sm 3+ A kind of electronic device 4 G 5/2 → 6 H 5/2 Transition, emission peaks around 580nm, 591nm and 700nm are respectively attributed to Eu 3+ A kind of electronic device 5 D 0 → 7 F 0 、 5 D 0 → 7 F 1 And 5 D 0 → 7 F 4 the transition, peaks at 600-630nm and 650nm are due to Sm 3+ And Eu 3+ And (3) the combined action. Along with Sm 3+ An increase in the doping level in Sm 3+ Eu under characteristic excitation of (E) 3+ The emission intensity shows a tendency to riseThere is a hydrogen sulfide compound from Sm 3+ To Eu 3+ Is provided.
As can be seen from the above examples, the present invention provides a europium-samarium co-doped borate red light conversion agent and a preparation method thereof. And only dope Eu 3+ Co-doped Sm compared to the sample of (C) 3+ The spectrum is broadened afterwards. The red light conversion agent can be effectively excited by short wave ultraviolet and long wave ultraviolet, and shows strong emission in the range of 580-630 nm, wherein the strongest red light emission peak value is positioned at 610nm, and can be used in the field of light conversion agricultural films.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A europium-samarium co-doped borate red light conversion agent is characterized in that the chemical general formula is K 7 MY (2-x-y) (B 5 O 10 ) 3 :xEu 3+ ,ySm 3+ The method comprises the steps of carrying out a first treatment on the surface of the Wherein x represents the mole number of doping trivalent europium ions, and x is more than 0 and less than or equal to 2.0; y represents the mole number of doped trivalent samarium ions, and y is more than 0 and less than or equal to 0.8; m is the element Mg, ca, sr or Ba.
2. The method for preparing the europium-samarium co-doped borate red light conversion agent according to claim 1, which is characterized by comprising the following steps:
(1) Will contain K + Compounds of (C) containing M 2+ Compound (C) containing Y 3+ Eu-containing compounds of (A) 3+ Compound (c) containing Sm 3+ Compounds of (A) and BO-containing 3 3- Mixing and grinding the compound of (C) with absolute ethyl alcohol to obtain a mixture;
(2) And (3) calcining and grinding the mixture obtained in the step (1) in sequence in an air atmosphere to obtain the europium-samarium co-doped borate red light conversion agent.
3. According to claim 2The preparation method is characterized in that the K-containing material + The compound of (2) comprises K 2 CO 3 KOH and KNO 3 One or more of them.
4. A method according to claim 2 or 3, wherein the M-containing substance is 2+ The compound of (2) is MCO 3 、M(OH) 2 Or M (NO) 3 ) 2 Wherein M is the element Mg, ca, sr or Ba.
5. The method according to claim 4, wherein the Y-containing component is 3+ The compound of (2) is Y 2 O 3 、Y(NO 3 ) 3 And Y (OH) 3 One or more of them.
6. The method according to claim 5, wherein the Eu-containing material is a Eu-containing material 3+ The compound of (a) is Eu 2 O 3 、Eu(NO 3 ) 2 And Eu (OH) 3 One or more of them.
7. The process according to claim 2, 3, 5 or 6, wherein said Sm-containing compound is selected from the group consisting of 3+ Is Sm 2 O 3 、Sm(NO 3 ) 2 And Sm (OH) 3 One or more of them.
8. The method of claim 7, wherein the BO-containing material comprises 3 3- The compound of (2) is H 3 BO 3 And/or K 2 B 4 O 7 ·10H 2 O。
9. The preparation method according to claim 8, wherein the absolute ethyl alcohol in the step (1) is added in an amount of 20 to 70% of the total mass of the raw materials.
10. The method according to claim 8 or 9, wherein the calcination in the step (2) is performed at 600 to 900 ℃ for 6 to 12 hours.
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