CN108034423B - A kind of Mn2+ ion-doped silicate red phosphor, preparation method and application - Google Patents
A kind of Mn2+ ion-doped silicate red phosphor, preparation method and application Download PDFInfo
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- CN108034423B CN108034423B CN201711493112.5A CN201711493112A CN108034423B CN 108034423 B CN108034423 B CN 108034423B CN 201711493112 A CN201711493112 A CN 201711493112A CN 108034423 B CN108034423 B CN 108034423B
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims description 30
- 239000000843 powder Substances 0.000 claims abstract description 34
- 230000005284 excitation Effects 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims description 52
- 238000001354 calcination Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011656 manganese carbonate Substances 0.000 claims description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- -1 silicon ion Chemical class 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000004020 luminiscence type Methods 0.000 abstract description 11
- 238000000695 excitation spectrum Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 44
- 239000004570 mortar (masonry) Substances 0.000 description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 235000006748 manganese carbonate Nutrition 0.000 description 3
- 229940093474 manganese carbonate Drugs 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/85—Packages
- H10H20/851—Wavelength conversion means
- H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
- H10H20/8512—Wavelength conversion materials
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- Engineering & Computer Science (AREA)
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- Luminescent Compositions (AREA)
Abstract
本发明公开了一种Mn2+离子掺杂的硅酸盐红色荧光粉、制备方法及应用。荧光粉的化学通式为Na2Mg5(1‑x)Si12O30:5xMn2+，其中，x为Mn2+掺杂的摩尔比，0.001≤x≤0.2，采用高温固相合成法制得。本发明制备得到的荧光材料在紫外、近紫外或蓝光等激发光源激发时，能发射波长范围在520～750纳米的红色荧光，激发光谱范围较宽，且在355纳米及420纳米处有强吸收，与商业紫外‑蓝光芯片完美吻合。本发明提供的Mn2+离子掺杂的硅酸盐红色荧光粉，生产成本低，是一种发光性能好的红色荧光材料，可应用于制造紫外‑蓝光激发的白光LED荧光粉。
The invention discloses a silicate red fluorescent powder doped with Mn 2+ ions, a preparation method and an application. The general chemical formula of the phosphor is Na 2 Mg 5(1‑ x ) Si 12 O 30 : 5 x Mn 2+ , where x is the molar ratio of Mn 2+ doping, 0.001≤x≤0.2 , using a high temperature solid phase Synthetically obtained. When excited by an excitation light source such as ultraviolet, near-ultraviolet or blue light, the fluorescent material prepared by the invention can emit red fluorescence with a wavelength range of 520-750 nanometers, has a wide excitation spectrum, and has strong absorption at 355 nanometers and 420 nanometers. , which fits perfectly with commercial UV-Blu-ray chips. The Mn 2+ ion-doped silicate red fluorescent powder provided by the invention has low production cost, is a red fluorescent material with good luminescence performance, and can be applied to manufacture ultraviolet-blue light excited white LED fluorescent powder.
Description
Technical Field
The invention relates to Mn2+A doped silicate red fluorescent powder material, a preparation method and application thereof belong to the technical field of solid fluorescent materials.
Background
Light Emitting Diodes (LEDs) have been recognized as one of the highly efficient technologies with high performance and long-term stability due to their advantages of long lifetime, high energy conversion efficiency, good stability, low price, etc. At present, a commercial white LED is composed of a blue InGaN chip and a yellow phosphor YAG: ce3+The composition is prepared by mixing the following components in percentage by weight: ce3+After absorbing part of blue light (440-460 nm) emitted by the chip, yellow fluorescence (490-550 nm) is emitted and mixed with the unabsorbed blue light to form white light. However, in practical applications, due to the lack of red light component, the Color Rendering Index (CRI) of the device is low, the Correlated Color Temperature (CCT) is high, and it is difficult to meet the requirements of indoor lighting and wide color gamut Liquid Crystal Display (LCD) backlight. In order to avoid the above disadvantages, development of a novel red phosphor having good emission properties is urgently required.
At present, the commercial red fluorescent powder is mainly Eu2+Doped nitrides, e.g. Sr2Si5N8:Eu2+(see the literature: Van Duong Luong et al, Preparation of Sr2Si5N8:Eu2+for white light-emitting diodes by multi-step heat stream, Journal of Alloys and Compounds, 509, 7525-3:Eu2+(see literature: Hyo Sung Kim et al, Luminescence properties of CaAlSiN3:Eu2+phosphorus prepared by direct-lubricating method using fine metal hydride powders, Journal of Alloys and Compounds, 633, 97-103), and the like. Eu (Eu)2+The doped nitride red fluorescent powder has the advantages of stable physical and chemical properties, good thermal stability, high luminous efficiency and the like. But the emission spectrum is too wide, the phenomenon of reabsorption is easy to occur when the nitride fluorescent powder is mixed with green and yellow fluorescent powder, and the peak emission part exceeds a human eye sensitive area, so that the radiant lumen efficiency of a device is reduced. In recent years, rare earth ion doped red phosphor has been widely reported, such as Eu3+，Sm3+. However, rare earth ions are in short supply, expensive and greatly limited in use.
At present, the divalent manganese ion Mn is concerned2+Many reports have been made on doped red fluorescent powder, which has higher luminous intensity and thermal stability. Divalent manganese holds promise as a replacement for rare earth ion activators and can also minimize device manufacturing costs. For example, the Chinese invention patent CN105131954A reports a red phosphor Ba which can be used for a white light LED or an energy-saving lamp x(3-)Mn x3Y(PO4)3And a method for the preparation thereof; chinese invention patent CN102719243A reports a manganese ion activated red long afterglow luminescent material AlN Mn2+And a method for preparing the same. However, non-rare earth Mn2+At present, the ion-doped silicate red fluorescent powder is not reported.
Disclosure of Invention
The invention aims at the product type of the red fluorescent powder for the existing white light LEDProviding a non-rare earth Mn2+The ion-doped silicate red fluorescent powder can emit red fluorescent Mn when excited by excitation light sources such as ultraviolet, near-ultraviolet or blue light2+An ion-doped silicate red fluorescent powder, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: providing a Mn2+The ion-doped silicate red fluorescent powder has a chemical formula as follows: na (Na)2Mg x5(1-)Mn x5Si12O30Wherein, in the step (A),xis Mn2+The mol ratio of doping is more than or equal to 0.001x≤0.2。
Under the excitation of ultraviolet, near ultraviolet or blue light, the fluorescent powder provided by the invention emits red fluorescence with the wavelength of 520-750 nanometers.
The technical scheme of the invention also comprises Mn2+The preparation method of the ion-doped silicate red fluorescent powder adopts a high-temperature solid phase method and comprises the following steps:
(1) according to the formula Na2Mg x5(1-)Mn x5Si12O30Weighing the following raw materials in corresponding stoichiometric ratio: containing sodium ions Na+Compound of (2), Mg ion-containing Mg2+Compound of (2), silicon ion-containing Si4+Compound of (5) and manganese ion containing Mn2+The compound of (1), wherein,xis Mn2+The mol ratio of doping is more than or equal to 0.001x≤0.2；
(2) Weighing sodium ion Na+Compound of (2), magnesium ion Mg2+Compound of (2), silicon ion Si4+Compound of (2) and manganese ion Mn2+Adding a proper amount of ethanol solution into the compound, and fully grinding to obtain a precursor;
(3) placing the precursor in an alumina crucible, carrying out primary calcination in a muffle furnace in an air atmosphere at the calcination temperature of 600-900 ℃ for 2-8 hours, and cooling to room temperature;
(4) adding appropriate amount of ethanol solution, grinding, placing in alumina crucible, calcining in air muffle furnace for the second timeThe temperature is 900-1200 ℃, the calcination time is 2-8 hours, the mixture is cooled to room temperature and then ground to obtain Mn2+Ion-doped silicate red phosphor.
The Na containing sodium ions of the invention+The compound of (A) is sodium nitrate NaNO3Sodium carbonate Na2CO3One of sodium hydroxide NaOH and NaCl chloride. The magnesium ion Mg2+The compound of (A) is magnesium oxide MgO and magnesium nitrate Mg (NO)3)2·6H2O, magnesium hydroxide Mg (OH)2MgCl, magnesium chloride2·6H2O, basic magnesium carbonate 4MgCO3·Mg(OH)2·5H2And O is one of the compounds. The Si containing silicon ions4+The compound of (A) is silicon dioxide SiO2. The manganese ion Mn2+The compound of (A) is manganese acetate Mn (CH)3COO)2Manganese carbonate MnCO3MnCl, manganese chloride2And manganese oxide MnO.
The primary calcination temperature in the step (3) is 700-850 ℃. And (4) the temperature of the second calcination is 1050-1150 ℃.
Mn provided by the technical scheme of the invention2+The application of the ion-doped silicate red fluorescent powder is to prepare ultraviolet-blue light excited white light LED fluorescent powder.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1. the prepared fluorescent powder can be excited by ultraviolet light, near ultraviolet light and blue light to emit red light with the dominant wavelength of 600 nanometers in the range of 520-750 nanometers, and the synthesis method is simple, high in preparation efficiency and low in energy consumption.
2. The prepared fluorescent powder has small particle size, uniform distribution and good stability and color rendering property, and the emitted red light can improve the color rendering index and the color temperature of the white light emitting diode.
3. The invention has no waste gas and waste liquid discharge, and is an environment-friendly inorganic luminescent material.
Drawings
FIG. 1 is a schematic representation of a solution prepared according to example 1 of the present inventionNa2Mg4.995Mn0.005Si12O30X-ray powder diffraction pattern of (a);
FIG. 2 shows Na prepared according to the technical scheme of example 1 of the invention2Mg4.995Mn0.005Si12O30An excitation spectrogram obtained under the monitoring of 600 nm wavelength;
FIG. 3 shows Na prepared according to the technical scheme of example 1 of the invention2Mg4.995Mn0.005Si12O30Luminescence spectrum under 355 nm excitation;
FIG. 4 shows Na prepared according to the technical scheme of example 1 of the invention2Mg4.995Mn0.005Si12O30Attenuation profile at 355 nm excitation, 600 nm wavelength monitoring;
FIG. 5 shows Na prepared according to the embodiment of the present invention2Mg4.8Mn0.2Si12O30X-ray powder diffraction pattern of (a);
FIG. 6 shows Na prepared according to example 3 of the present invention2Mg4.8Mn0.2Si12O30Luminescence spectrum under 355 nm excitation;
FIG. 7 shows Na prepared according to the embodiment of the present invention2Mg4.8Mn0.2Si12O30Attenuation profile at 355 nm excitation, 600 nm wavelength monitoring;
FIG. 8 shows Na prepared according to example 5 of the present invention2Mg4.5Mn0.5Si12O30X-ray powder diffraction pattern of (a);
FIG. 9 shows Na prepared according to example 5 of the present invention2Mg4.5Mn0.5Si12O30Luminescence spectrum under 355 nm excitation;
FIG. 10 shows Na prepared according to example 5 of the present invention2Mg4.5Mn0.5Si12O30Attenuation profile at 355 nm excitation, 600 nm wavelength monitoring.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Example 1
This example prepares sample Na2Mg4.995Mn0.005Si12O30
According to the chemical formula Na2Mg4.995Mn0.005Si12O30The stoichiometric ratio of each element in the raw materials is measured by weighing sodium nitrate NaNO3: 0.85 g, magnesium oxide MgO: 1 g of manganese acetate Mn (CH)3COO)2: 0.0036 g of SiO, silicon oxide2: 3.6 g of the Mn-Mn composite material is placed into an agate mortar, an appropriate amount of ethanol solution is added, the mixture is fully ground, the mixture is placed into an alumina crucible, the first calcination is carried out in a muffle furnace under the air atmosphere, the calcination temperature is 700 ℃ and the calcination time is 6 hours, the mixture is cooled to room temperature, the mixture is placed into the mortar again, a small amount of ethanol solution is added, the mixture is fully ground, the mixture is placed into the alumina crucible, the second calcination is carried out in the2+Ion-doped silicate red phosphor.
Referring to the attached figure 1, which is an X-ray powder diffraction pattern of a sample prepared according to the technical scheme of the embodiment, the test result shows that the prepared sample has no impurity peak and is a single-phase material.
Referring to fig. 2, which shows the excitation spectrum of the sample prepared according to the technical scheme of the embodiment at the monitoring wavelength of 600 nm, it can be seen that the excitation spectrum of the prepared sample is wide in range and has strong absorption at 355 nm.
Refer to FIG. 3, which is a graph of the emission spectrum of a sample prepared according to the embodiment under 355 nm excitation. As can be seen from the figure, the main central light-emitting wavelength of the material is a red light-emitting waveband of 600 nanometers.
Referring to FIG. 4, which is a luminescence decay curve of a sample prepared according to the embodiment of the present invention, the calculated decay time is 4.4 ms.
Example 2
Preparation ofSample Na2Mg4.995Mn0.005Si12O30
According to the chemical formula Na2Mg4.995Mn0.005Si12O30The stoichiometric ratio of each element in the raw materials is measured by weighing sodium carbonate Na2CO3: 0.53 g magnesium nitrate hexahydrate Mg (OH)2-6H2O: 6.4 g of manganese carbonate MnCO3: 0.0057 g, silica SiO2: 3.6 g of the Mn-Mn composite material is put into an agate mortar, a small amount of ethanol solution is added, the mixture is fully ground and then put into an alumina crucible, the mixture is calcined for the first time in a muffle furnace in the air atmosphere, the calcination temperature is 720 ℃, the calcination time is 6 hours, the mixture is cooled to room temperature, the mixture is put into the mortar again, a small amount of ethanol solution is added, the mixture is fully ground and then put into the alumina crucible, the mixture is calcined for the second time in the muffle furnace in the air atmosphere, the calcination temperature is 1070 ℃, the calcination time is 6 hours, and the mixture is ground to obtain Mn2+Ion-doped silicate red phosphor.
The XRD, excitation spectrogram, luminescence spectrogram and luminescence attenuation curve of the sample prepared in the technical scheme of this example are the same as those of the sample prepared in example 1.
Example 3
Preparation of sample Na2Mg4.8Mn0.2Si12O30
According to the chemical formula Na2Mg4.8Mn0.2Si12O30Weighing sodium hydroxide NaOH: 0.4 g, magnesium hydroxide MgOH: 1.4 g, manganese oxide MnO: 0.071 g of SiO 22: 3.6 g of the Mn-Mn composite material is put into an agate mortar, a small amount of ethanol solution is added, the mixture is fully ground and then put into an alumina crucible, the mixture is calcined for the first time in a muffle furnace in the air atmosphere, the calcination temperature is 750 ℃, the calcination time is 6 hours, the mixture is cooled to room temperature, the mixture is put into the mortar again, a small amount of ethanol solution is added, the mixture is fully ground and then put into the alumina crucible, the mixture is calcined for the second time in the muffle furnace in the air atmosphere, the calcination temperature is 1090 ℃, the calcination time is 6 hours, and the mixture is ground to obtain Mn2+Red color of ion-doped silicateAnd (3) fluorescent powder.
Referring to the attached figure 5, which is an X-ray powder diffraction pattern of a sample prepared according to the technical scheme of the embodiment, the test result shows that the prepared sample has no impurity peak and is a single-phase material.
Refer to FIG. 6, which is a graph of the emission spectrum of a sample prepared according to the embodiment under 355 nm excitation. As can be seen from the figure, the main central light-emitting wavelength of the material is a red light-emitting waveband of 600 nanometers.
Referring to FIG. 7, which is a luminescence decay curve of a sample prepared according to the embodiment of the present invention, the calculated decay time is 3.7 ms.
Example 4
Preparation of sample Na2Mg4.7Mn0.3Si12O30
According to the chemical formula Na2Mg4.7Mn0.3Si12O30Weighing sodium chloride NaCl according to the stoichiometric ratio of the elements: 0.5844 g of MgCl nitrate hexahydrate2-6H2O: 4.775 g of manganese chloride MnCl2: 0.1886 g of SiO silicon oxide2: 3.6 g of the Mn-Mn composite material is put into an agate mortar, a small amount of ethanol solution is added, the mixture is fully ground and then put into an alumina crucible, the mixture is calcined for the first time in a muffle furnace in the air atmosphere, the calcination temperature is 770 ℃, the calcination time is 6 hours, the mixture is cooled to room temperature, the mixture is put into the mortar again, a small amount of ethanol solution is added, the mixture is fully ground and then put into the alumina crucible, the mixture is calcined for the second time in the muffle furnace in the air atmosphere, the calcination temperature is 1100 ℃, the calcination time is 6 hours, and the mixture is ground to obtain the Mn-Mn composite material2+Ion-doped silicate red phosphor.
The XRD, excitation spectrogram, luminescence spectrogram and luminescence attenuation curve of the sample prepared in the technical scheme of this example are the same as those of the sample prepared in example 3.
Example 5
Preparation of sample Na2Mg4.5Mn0.5Si12O30
According to the chemical formula Na2Mg4.8Mn0.2Si12O30The stoichiometric ratio of each element in the raw materials is measured by weighing sodium carbonate Na2CO3: 0.53 g of basic magnesium carbonate 4MgCO3·Mg(OH)2·5H2O: 2.1861 g of manganese carbonate MnCO3: 0.2874 g of SiO silicon oxide2: 3.6 g of the Mn-Mn composite material is put into an agate mortar, a small amount of ethanol solution is added, the mixture is fully ground and then put into an alumina crucible, the mixture is calcined for the first time in a muffle furnace in the air atmosphere, the calcination temperature is 800 ℃, the calcination time is 6 hours, the mixture is cooled to room temperature, the mixture is put into the mortar again, a small amount of ethanol solution is added, the mixture is fully ground and then put into the alumina crucible, the mixture is calcined for the second time in the muffle furnace in the air atmosphere, the calcination temperature is 1120 ℃, the calcination time is 6 hours, and the mixture is ground to obtain the Mn-Mn composite material2+Ion-doped silicate red phosphor.
Referring to FIG. 8, it is the X-ray powder diffraction pattern of the sample prepared according to the technical scheme of this example, and the test result shows that the prepared sample has no impurity peak and is a single-phase material.
Refer to FIG. 9, which is a graph of the emission spectrum of a sample prepared according to the embodiment under 355 nm excitation. As can be seen from the figure, the main central light-emitting wavelength of the material is a red light-emitting waveband of 600 nanometers.
Referring to FIG. 10, which is a graph of luminescence decay of a sample prepared according to the embodiment of the present invention, the calculated decay time is 3.0 ms.
Example 6
Preparation of sample Na2Mg4MnSi12O30
According to the chemical formula Na2Mg4MnSi12O30The stoichiometric ratio of each element in the raw materials is measured by weighing sodium carbonate Na2CO3: 0.53 g of basic magnesium carbonate 4MgCO3·Mg(OH)2·5H2O: 1.9432 g of manganese carbonate MnCO3: 0.5746 g of SiO silicon oxide2: 3.6 g of the mixture is put into an agate mortar, a small amount of ethanol solution is added, the mixture is fully ground and put into an alumina crucible, and the mixture is calcined for the first time in a muffle furnace in air atmosphere, wherein the calcination temperature is 850 ℃ and the calcination time is 6Cooling to room temperature, putting the mixture into a mortar again, adding a small amount of ethanol solution, grinding the mixture fully, putting the mixture into an alumina crucible, calcining the mixture for the second time in a muffle furnace in air atmosphere at 1150 ℃ for 6 hours, and grinding the mixture to obtain Mn2+Ion-doped silicate red phosphor.
The XRD, excitation spectrogram, luminescence spectrogram and luminescence attenuation curve of the sample prepared in the technical scheme of this example are the same as those of the sample prepared in example 5.
The sample provided by each embodiment of the invention has small particle size, uniform distribution and good stability and color rendering property, and the emitted red light can improve the color rendering index and the color temperature of the white light emitting diode.
Claims (10)
1. Mn (manganese)2+The ion-doped silicate red fluorescent powder is characterized by having a chemical formula as follows: na (Na)2Mg x5(1-)Mn x5Si12O30Wherein, in the step (A),xis Mn2+The mol ratio of doping is more than or equal to 0.001x≤0.2。
2. A Mn according to claim 12+The ion-doped silicate red fluorescent powder is characterized in that: under the excitation of ultraviolet, near ultraviolet or blue light, the fluorescent powder emits red fluorescence with the wavelength of 520-750 nanometers.
3. An Mn as set forth in claim 12+The preparation method of the ion-doped silicate red fluorescent powder is characterized by adopting a high-temperature solid phase method and comprising the following steps of:
(1) according to the formula Na2Mg x5(1-)Mn x5Si12O30Weighing the following raw materials in corresponding stoichiometric ratio: containing sodium ions Na+Compound of (2), Mg ion-containing Mg2+Compound of (2), silicon ion-containing Si4+Compound of (5) and manganese ion containing Mn2+The compound of (1), wherein,xis Mn2+The mol ratio of doping is more than or equal to 0.001x≤0.2；
(2) Weighing sodium ion Na+Compound of (2), magnesium ion Mg2+Compound of (2), silicon ion Si4+Compound of (2) and manganese ion Mn2+Adding a proper amount of ethanol solution into the compound, and fully grinding to obtain a precursor;
(3) placing the precursor in an alumina crucible, carrying out primary calcination in a muffle furnace in an air atmosphere at the calcination temperature of 600-900 ℃ for 2-8 hours, and cooling to room temperature;
(4) adding a proper amount of ethanol solution, fully grinding, placing in an alumina crucible, carrying out secondary calcination in a muffle furnace in an air atmosphere at the calcination temperature of 900-1200 ℃ for 2-8 hours, cooling to room temperature, and grinding to obtain Mn2+Ion-doped silicate red phosphor.
4. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: the sodium ion Na+The compound of (A) is sodium nitrate NaNO3Sodium carbonate Na2CO3One of sodium hydroxide NaOH and NaCl chloride.
5. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: the magnesium ion Mg2+The compound of (A) is magnesium oxide MgO and magnesium nitrate Mg (NO)3)2·6H2O, magnesium hydroxide Mg (OH)2MgCl, magnesium chloride2·6H2O, basic magnesium carbonate 4MgCO3·Mg(OH)2·5H2And O is one of the compounds.
6. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: the Si containing silicon ions4+The compound of (A) is silicon dioxide SiO2。
7. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: the manganese ion Mn2+The compound of (A) is manganese acetate Mn (CH)3COO)2Manganese carbonate MnCO3MnCl, manganese chloride2And manganese oxide MnO.
8. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: the primary calcination temperature in the step (3) is 700-850 ℃.
9. A Mn according to claim 32+The preparation method of the ion-doped silicate red fluorescent powder is characterized by comprising the following steps of: and (4) the temperature of the second calcination is 1050-1150 ℃.
10. An Mn as set forth in claim 12+The application of the ion-doped silicate red fluorescent powder is characterized in that: the method is used for preparing the ultraviolet-blue light excited white light LED.
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| CN103059838A (en) * | 2012-10-31 | 2013-04-24 | 苏州大学 | A kind of Eu2+ activated silicate yellow phosphor, preparation method and application |
| CN103122244A (en) * | 2013-03-14 | 2013-05-29 | 苏州大学 | A kind of Eu2+ activated silicate white light phosphor and preparation method thereof |
| CN105694870A (en) * | 2016-03-17 | 2016-06-22 | 常州工程职业技术学院 | A kind of Eu3+-activated sodium magnesium orthosilicate red fluorescent powder and its preparation method and application |
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| CN103059838A (en) * | 2012-10-31 | 2013-04-24 | 苏州大学 | A kind of Eu2+ activated silicate yellow phosphor, preparation method and application |
| CN103122244A (en) * | 2013-03-14 | 2013-05-29 | 苏州大学 | A kind of Eu2+ activated silicate white light phosphor and preparation method thereof |
| CN105694870A (en) * | 2016-03-17 | 2016-06-22 | 常州工程职业技术学院 | A kind of Eu3+-activated sodium magnesium orthosilicate red fluorescent powder and its preparation method and application |
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