CN108359461B - Deep red double-peak emitting titanium germanate nano fluorescent powder and preparation method thereof - Google Patents
Deep red double-peak emitting titanium germanate nano fluorescent powder and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a deep red double-peak emitting titanium germanate nano fluorescent powder. TheThe chemical formula of the phosphor is M2wMg2‑ wTi1‑x‑yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<0.7, 0-1, M is alkali metal element, or NzMg2‑zTi1‑x‑ yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<Z is more than 0.7 and less than or equal to 0.2, and N is an alkaline earth metal element. The fluorescent powder has the advantages of high red color gamut, high luminous efficiency, low color temperature, low cost and the like.
Description
Technical Field
The invention relates to a luminescent material, in particular to a deep red double-peak emitting titanium germanate nano fluorescent powder and a preparation method thereof.
Background
At present, white light LED is used as a novel green environment-friendly solid illumination light source, and has the advantages of energy conservation, environmental protection, small volume, low heat productivity, low power consumption, long service life, quick response and the like, so that the white light LED is widely used for backlight sources of mobile phones and liquid crystal displays, indicator lamps, outdoor illumination, indoor illumination, landscape illumination, billboards, traffic indicator lamps and the like, and a white light LED heat tide is raised in the field of global semiconductors and illumination. Existing white LEDs achieve white light emission mainly by using light emitted from a Light Emitting Diode (LED) to excite a phosphor. There are three main approaches to realizing white LEDs: the white light LED is formed by combining a blue light chip and yellow fluorescent powder which can be effectively excited by blue light, which is a mainstream technical scheme for realizing the white light LED at present, but the white light LED lacks red light components; secondly, an ultraviolet chip and fluorescent powder which can be effectively excited by ultraviolet light to emit red, green and blue tricolor light are combined into a white light LED; and thirdly, assembling the red, green and blue three-base LED chips to realize white light. However, the fluorescent powder which can be effectively excited by near ultraviolet light and blue light is relatively lack, especially the high-efficiency red fluorescent powder is deficient, so that the color rendering index of the white light LED is relatively low, the color temperature is relatively high, and the popularization and application of the LED are influenced.
In recent years, people try to realize a white light LED by using a blue light LED chip and a green and red fluorescent powder or a near ultraviolet-ultraviolet (350-410 nm) emitting InGaN tube core to excite a three-primary-color fluorescent powder, so as to obtain a white light LED with high color rendering and low color temperature. The japanese sub-company has an innovative invention in the field (US5998925A) to obtain white light by exciting YAG yellow phosphor with a blue GaN chip, which has high luminous efficiency, but has high color temperature and poor color rendering due to lack of red light in the spectral components. Chinese patent 201110157772.2 discloses an oxynitride phosphor for manufacturing a white LED with high color rendering and low color temperature. However, the luminous efficiency of the nitrogen oxide fluorescent powder is low, and the preparation method needs to adopt a high-temperature and high-pressure method, so that the nitrogen oxide fluorescent powder has a great limitation as a white light LED material at present. In addition, most of red light emitted by the existing red fluorescent powder has poor color rendering property, is not close to real red and is yellow. Therefore, it is very important to research a novel red phosphor for LEDs.
Disclosure of Invention
The first purpose of the invention is to provide a deep red double-peak emission titanium germanate nano fluorescent powder which has the advantages of high red color gamut, high luminous efficiency, low color temperature, low cost and the like.
The invention also aims to provide a preparation method of the deep red double-peak emitting titanium germanate nano fluorescent powder.
The purpose of the invention is realized by the following technical scheme:
a deep red double-peak emitting titanium germanate nano fluorescent powder is characterized in that: the chemical formula of the fluorescent powder is M2wMg2-wTi1-x-yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<0.7, 0-1, M is alkali metal element, or NzMg2-zTi1-x-yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<Z is more than 0.7 and less than or equal to 0.2, and N is an alkaline earth metal element.
When the alkali metal element M or the alkaline earth metal element N in the chemical formula of the fluorescent powder is selected as different metal elements, the prepared final product fluorescent powder has no difference in appearance and luminous effect, the difference is only that the luminous range is adjusted differently, but the double emission peaks are respectively within two numerical ranges of 630nm +/-10 nm and 660nm +/-10 nm.
The preparation method of the deep red bimodal emission titanium germanate nano fluorescent powder comprises the following steps:
(1) weighing corresponding titanium oxide, germanium oxide, manganese carbonate, magnesium oxide or magnesium carbonate and metal salt containing M element or N element according to the stoichiometric ratio of each element in the chemical formula;
2) mixing titanium oxide, germanium oxide, manganese carbonate, magnesium oxide or magnesium carbonate and metal salt containing M element or N element, grinding, adding a lubricant in the grinding process, wherein the adding amount of the lubricant is limited by the fact that the ground system keeps dispersing until reactants and ligands completely react to obtain precursor powder;
3) and calcining the precursor powder in an air atmosphere to obtain the target product.
It is further clear that the calcination temperature in the step 3) is 1300 ℃ to 1500 ℃, and the calcination time is 3 to 6 hours.
As a further specific example, the metal salt containing the M element or the N element may be selected from carbonates, nitrates, and chlorides of alkali metal elements or alkaline earth metal elements.
More specifically, the lubricant is ethanol or ethylene glycol.
As a further definition, the above polishing is performed at room temperature.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a deep red double-peak emission titanium germanate nano fluorescent powder which has double emission peaks (the double emission peaks are respectively 630nm +/-10 nm and 660nm +/-1)0 nm), the luminescence is more diversified; the substrate is titanium germanate, and the luminescent center is Mn4+The raw materials do not contain rare earth ions, so the cost is low; the crystallinity is good, the particles are fine, the particle surfaces are smooth, and the distribution is uniform; the red light-emitting diode has good light-emitting characteristics, high red color gamut, high color display degree and real color development, the color coordinate value is (0.7147, 0.2853), and the red light-emitting diode is close to standard red light; the fluorescent powder can effectively absorb excitation wavelength within the range of 200-500 nm, is suitable for being used as red fluorescent powder for vacuum ultraviolet and ultraviolet excitation, and has high luminous efficiency and good stability, the thermal quenching temperature (the temperature when the emission spectrum intensity is 50% of the normal temperature) is higher than 200 ℃, the emission spectrum intensity is higher than 85% of the normal temperature at 150 ℃, and the luminous efficiency is 80% of the normal temperature at 250 ℃; the color temperature of the deep red light emitted by the eye care lamp is low, and the eye care lamp has little damage to eyes. In addition, the method adopts a calcination method to prepare the fluorescent powder, has the advantages of simple process, easy operation, low cost, good repeatability and the like, and is easy to industrialize.
Drawings
FIG. 1 is an XRD spectrum of a deep red double-peak emitting titanium germanate nano-phosphor in example 1 of the present invention;
FIG. 2 is an SEM image of a deep red bimodal emitting TiGermate NanoFluorogenic powder described in example 1 of the present invention;
FIG. 3 is an excitation spectrum of the deep red double-peak emitting titanium germanate nano-phosphor in example 1 with a monitoring wavelength of 661nm and an emission spectrum with an excitation wavelength of 300 nm;
fig. 4 is a color coordinate diagram of the deep red bi-peak emitting titanium germanate nano-phosphor in embodiment 1 of the present invention.
FIG. 5 is a thermal stability test chart of the deep red dual-peak emitting titanium germanate nano-phosphor in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
A preparation method of a deep red double-peak emission titanium germanate nano fluorescent powder comprises the following steps:
(1) according to Mg2Ti0.699Ge0.3O4:0.001Mn4+Weighing corresponding magnesium carbonate, titanium oxide, germanium oxide and manganese carbonate according to the stoichiometric ratio of each element in the chemical formula;
2) grinding magnesium carbonate, titanium oxide, germanium oxide and manganese carbonate at room temperature, adding ethanol during grinding, wherein the adding amount of the ethanol is limited by keeping the dispersion of a ground system until reactants and ligands completely react to obtain precursor powder;
3) and calcining the precursor powder in an air atmosphere at 1400 ℃ for 6 hours to obtain the target product.
The XRD spectrogram, SEM image, color coordinate image, thermal stability test image, and the excitation spectrum with monitoring wavelength of 661nm and the emission spectrum with excitation wavelength of 300nm of the deep red double-peak emitting titanium germanate nano-phosphor prepared in the example are respectively shown in figures 1, 2, 4, 5 and 3; therefore, the fluorescent powder has double emission peak values of 630nm and 660nm, so that the luminescence is more diversified; the particles are fine, the surfaces of the particles are smooth, and the particles are uniformly distributed; the luminous efficiency is high, the stability is good, the luminous efficiency at 250 ℃ is 80% at normal temperature, and the emission spectrum intensity at 150 ℃ is more than 85% of that at normal temperature; the red light-emitting diode has good light-emitting characteristics, high red color gamut, high color display degree and real color development, the color coordinate value is (0.7147, 0.2853), and the color is close to the standard red light.
Example 2
A preparation method of a deep red double-peak emission titanium germanate nano fluorescent powder comprises the following steps:
(1) according to Mg1.99Ba0.01Ti0.699Ge0.3O4:0.001Mn4+Weighing corresponding barium carbonate, magnesium oxide, titanium oxide, germanium oxide and manganese carbonate according to the stoichiometric ratio of each element in the chemical formula;
2) grinding barium carbonate, magnesium oxide, titanium oxide, germanium oxide and manganese carbonate at room temperature, adding ethylene glycol during grinding, wherein the adding amount of the ethylene glycol is limited by keeping the dispersion of a ground system until reactants and ligands completely react to obtain precursor powder;
3) and calcining the precursor powder in an air atmosphere at 1300 ℃ for 5.5 hours to obtain the target product.
Example 3
A preparation method of a deep red double-peak emission titanium germanate nano fluorescent powder comprises the following steps:
(1) according to Na0.04Mg1.98Ti0.799Ge0.2O4:0.001Mn4+Weighing corresponding sodium carbonate, magnesium carbonate, titanium oxide, germanium oxide and manganese carbonate according to the stoichiometric ratio of each element in the chemical formula;
2) grinding sodium carbonate, magnesium carbonate, titanium oxide, germanium oxide and manganese carbonate at room temperature, adding ethylene glycol during grinding, wherein the adding amount of the ethylene glycol is limited by keeping the dispersion of a ground system until reactants and ligands completely react to obtain precursor powder;
3) and calcining the precursor powder in an air atmosphere at 1500 ℃ for 3 hours to obtain the target product.
Claims (7)
1. A deep red double-peak emitting titanium germanate nano fluorescent powder is characterized in that: the chemical formula of the fluorescent powder is M2wMg2-wTi1-x-yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<0.7, 0-1, M is alkali metal element, or NzMg2- zTi1-x-yGeyO4：xMn4+Wherein 0 is<x<0.05，0<y<Z is more than 0 and less than or equal to 0.7 and more than 0 and less than or equal to 0.2, and N is an alkaline earth metal element;
the dual emission peak values of the fluorescent powder are respectively within the ranges of 630nm +/-10 nm and 660nm +/-10 nm.
2. The method for preparing the deep red double-peak emitting titanium germanate nano fluorescent powder according to claim 1, which is characterized by comprising the following steps:
(1) weighing corresponding titanium oxide, germanium oxide, manganese carbonate, magnesium oxide or magnesium carbonate and metal salt containing M element or N element according to the stoichiometric ratio of each element in the chemical formula;
(2) mixing titanium oxide, germanium oxide, manganese carbonate, magnesium oxide or magnesium carbonate and metal salt containing M element or N element, grinding, adding a lubricant in the grinding process, wherein the adding amount of the lubricant is limited by the fact that the ground system keeps dispersing until reactants and ligands completely react to obtain precursor powder;
(3) the precursor powder is calcined under an air atmosphere.
3. The method for preparing the deep red bimodal emission titanium germanate nano fluorescent powder as claimed in claim 2, wherein the method comprises the following steps: the calcination temperature in the step (3) is 1300-1500 ℃, and the calcination time is 3-6 hours.
4. The method for preparing the deep red bimodal emission titanium germanate nano fluorescent powder as claimed in claim 2, wherein the method comprises the following steps: the metal salt containing M element or N element is selected from carbonate, nitrate and chloride of alkali metal element or alkaline earth metal element.
5. The method for preparing the deep red bimodal emission titanium germanate nano fluorescent powder as claimed in claim 2, wherein the method comprises the following steps: the lubricant is ethanol or glycol.
6. The method for preparing the deep red double-peak emitting titanium germanate nano fluorescent powder according to claim 4, wherein the method comprises the following steps: the lubricant is ethanol or glycol.
7. The method for preparing the deep red bimodal emission titanium germanate nano fluorescent powder as claimed in any one of claims 2 to 6, wherein the method comprises the following steps: the milling is carried out at room temperature.
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| CN105524614A (en) * | 2015-12-16 | 2016-04-27 | 华南理工大学 | Red germanate long-afterglow luminescent material and preparation method thereof |
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| CN105524614A (en) * | 2015-12-16 | 2016-04-27 | 华南理工大学 | Red germanate long-afterglow luminescent material and preparation method thereof |
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| Effects of Al- and Sn-substitution on photoluminescence properties of Mn4+-doped spinel-type Mg2TiO4 phosphor;Sasaki, Takuya等;《JOURNAL OF LUMINESCENCE》;20170318;540-545 * |
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