CN107722972B - Green long-afterglow luminescent material and preparation method thereof - Google Patents
Green long-afterglow luminescent material and preparation method thereof Download PDFInfo
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- CN107722972B CN107722972B CN201711033678.XA CN201711033678A CN107722972B CN 107722972 B CN107722972 B CN 107722972B CN 201711033678 A CN201711033678 A CN 201711033678A CN 107722972 B CN107722972 B CN 107722972B
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Abstract
The invention discloses a green long-afterglow luminescent material and a preparation method thereof. The chemical expression of the luminescent material is Ca2Zn1‑y‑0.5zMzSi2‑0.75xAlxO7‑yWherein x = 0.05-0.15, y = 0.01-0.10, and z = 0.01-0.10, M is Li, Na or K. According to the invention, zinc calcium silicate is used as a matrix material, Al and alkali metal ions are introduced to modify the material, and the preparation process is adjusted by a sectional calcination method, so that the luminescent material with stable chemical properties and excellent luminescent properties can be obtained. The prepared material has the advantages that the luminescent center is completely defective, rare earth ions or transition metal ions are not needed, the stability is good, the cost is low, the luminescent performance is good, and green light can be continuously emitted for more than 10 hours in the dark after the material is irradiated by lamplight for 15 minutes.
Description
Technical Field
The invention belongs to the field of preparation of inorganic functional materials, and particularly relates to a green long-afterglow luminescent material and a preparation method thereof.
Background
The long-afterglow luminescent material, i.e. light-storing material, is a kind of functional ceramic material, can absorb visible light and ultraviolet light, store them and can continuously give out light in the dark. The long afterglow luminescent material is widely applied to the fields of safety illumination indicating equipment, display devices, luminescent ceramics, luminescent paint, photoelectric information and the like. In addition to the above applications, the long afterglow materials can also be applied to solar cells; the near-infrared long-afterglow material can be applied to medical biomarkers to realize the visualization of cancer cell diffusion. The long afterglow material consists of mainly matrix material, activator and auxiliary activator. The matrix material is the main component of the luminescent material and has important influence on the luminescence and afterglow performance of the material. Rare earth ions and transition metal ions are commonly used activators. The co-activator is generally considered to be a substance which does not emit light or emits light weakly in the matrix itself, but which efficiently absorbs excitation energy and transfers it to the luminescence center, thereby making the material ofThe afterglow performance is enhanced. Such as LiSr4(BO3)3: Eu2+，Dy3+In (III) LiSr4(BO3)3As a matrix material, Eu2+Dy as a luminescent center3+As an auxiliary activator, the afterglow time of the material can be prolonged. The invention patent "orange-yellow long afterglow material (application number: 201410791393.2)" discloses Li2Sr1-x-ySiO4：xEu2+，yR3+Preparation of orange-yellow long afterglow material, wherein Li2Sr1-x-ySiO4Is a matrix material, Eu2+Is a luminescent center, R3+As a co-activator; the invention patent of 'long persistence phosphor material (application No. 98124888.8)' discloses a europium (Eu)2+) Dysprosium (Dy)3+) And cerium (Ce)3+) Preparing an alkaline earth phosphoaluminate long afterglow phosphorescent material as an additional activator; the invention patent 'a method for rapidly synthesizing long-afterglow luminescent material (application number: 201010243006.3)' discloses a method for rapidly synthesizing long-afterglow luminescent material Ca(0.8-2x)Zn0.2TiO3:xPr3+，xNa+The preparation process of (1), wherein Pr3+Is a luminescent center, Na+The introduction is favorable for improving the defect concentration of the material so as to improve the luminous performance of the material; the invention discloses a red long afterglow luminescent material and a preparation method thereof (application number: 200910112064. X)2+Ion-activated red long-afterglow luminescent material (Zn)1-α-βMnαLnβ)3（P1-0.8γSiγO4）2The preparation method of (1), wherein Mn2+The ions are luminous centers, and Ln is an auxiliary activator; the invention discloses a red long-afterglow luminescent material and a preparation method thereof (application number: 201310089863.6), and discloses a luminescent material prepared from Cr3+Red long afterglow luminescent material ZnGa as luminescent center2O4：aCr3+,bDy3+And (4) preparing. These luminescent materials all use rare earth ions or some transition metal ions as luminescent centers. The invention takes calcium zinc silicate as a matrix material, and simultaneously modifies the material by introducing Al and alkali metal ionsAnd the preparation process is adjusted by a sectional calcination method, so that the luminescent material with stable chemical property and excellent luminescent property can be obtained. Properly doped with Al and adopting a sectional calcination method is beneficial to improving the stability and the crystallization property of the material, the doping of alkali metal ions and the final high-temperature calcination adopt a reducing atmosphere to effectively manufacture internal defects of the material and utilize the defects to capture photons for light storage, the defects with electrons and holes can migrate in the material and meet in the migration process to be extinguished and emit light, the light-emitting center of the material is completely a defect without rare earth ions or transition metal ions, and the prepared material has the advantages of excellent light-emitting property, low raw material cost and the like.
Disclosure of Invention
The invention aims to provide a novel green long-afterglow luminescent material taking defects as luminescent centers and modified calcium zinc silicate as a matrix material and a preparation method thereof, the long-afterglow luminescent material takes the defects as the luminescent centers, has simple preparation process, low cost and excellent luminescent performance compared with the traditional long-afterglow luminescent material taking rare earth ions or transition metal ions as the luminescent centers, and can continuously emit green light for more than 10 hours in the dark after being irradiated by lamplight for 15 minutes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a green long-afterglow luminescent material with defect as luminescent center and Ca as chemical expression2Zn1-y- 0.5zMzSi2-0.75xAlxO7-yWherein x = 0.05-0.15, y = 0.01-0.10, z = 0.01-0.10, and M is Li, Na or K.
The preparation method of the green long-afterglow luminescent material comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、M2CO3、Al(NO3)3·9H2O, and weighing boric acid accounting for 5-20% of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 4 to 8 hours at the rotating speed of 600 revolutions per minute, taking out the mixture, and putting the mixture into a drying oven to be air-dried for 6 hours at the temperature of 120 ℃ to obtain white powder;
3) placing the white powder in a crucible, pre-calcining the white powder in air at the temperature of 800-900 ℃ for 1-5 hours, and then calcining the white powder in H2/N2Mixed gas (H)2、N2The volume ratio of (2-8) to (92-98)) or a CO reducing atmosphere, and calcining at 900-1200 ℃ for 2-6 hours to obtain the luminescent material.
The invention has the beneficial effects that:
according to the invention, zinc calcium silicate is used as a matrix material, Al and alkali metal ions are introduced to modify the material, and the preparation process is adjusted by a sectional calcination method, so that the luminescent material with stable chemical properties and excellent luminescent properties can be obtained. The prepared material has the advantages that the luminescent center is completely defective, rare earth ions or transition metal ions are not needed, the stability is good, the cost is low, the luminescent performance is good, bright green light can be observed in a dark place after 15 minutes of light irradiation, and the visual inspection afterglow time can be as long as more than 10 hours.
Drawings
FIG. 1 shows a green long-afterglow luminescent material Ca obtained in example 12Zn0.92K0.06Si1.925Al0.1O6.95X-ray diffraction pattern of (a);
FIG. 2 shows a green long-afterglow luminescent material Ca obtained in example 12Zn0.92K0.06Si1.925Al0.1O6.95Excitation and emission spectra of (a);
FIG. 3 shows a green long-lasting phosphor Ca obtained in example 12Zn0.92K0.06Si1.925Al0.1O6.95Pyroelectric spectrum diagram.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
A green long-afterglow luminescent material with Ca as chemical expression2Zn0.92K0.06Si1.925Al0.1O6.95The preparation method comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、K2CO3、Al(NO3)3·9H2O, weighing boric acid accounting for 10 percent of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 6 hours at the rotating speed of 600 revolutions per minute, taking out the mixture, and putting the mixture into a drying box to carry out air drying for 6 hours at 120 ℃ to obtain white powder;
3) the white powder was placed in a crucible, pre-calcined in air at 850 ℃ for 3 hours, then calcined in H2/N2Mixed gas (H)2、N2At a volume ratio of 4: 96), at 1050 ℃ for 4 hours, to obtain a light-emitting material.
XRD tests show that the prepared material is classified into an XRD standard pattern PDF35-0745, as shown in figure 1.
As can be seen from FIG. 2, the material synthesized by the present technology has 2 strong excitation peaks between 300-400 nm, and the emission peak is located between 521 nm and falls into the green light band range.
It can be seen from fig. 3 that the unmodified modified material synthesized in air has no heat release peak at low temperature (below 420K) indicating a low trap concentration suitable for the trap depth, while the modified material calcined in a reducing atmosphere has a strong heat release peak (360K) at low temperature (below 420K) indicating a high trap concentration suitable for the trap depth.
The prepared luminescent material can observe bright green light in dark after being irradiated by light for 15 minutes, and the visual afterglow time can reach more than 10 hours.
Example 2
A green long-afterglow luminescent material with Ca as chemical expression2Zn0.985Na0.01Si1.9625Al0.05O6.99The preparation method comprisesThe method comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、Na2CO3、Al(NO3)3·9H2O, weighing boric acid accounting for 5 percent of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 4 hours at the rotating speed of 600 revolutions per minute, taking out the mixture, putting the mixture into a drying box, and carrying out air drying for 6 hours at 120 ℃ to obtain white powder;
3) the white powder was placed in a crucible, pre-calcined at 800 ℃ in air for 5 hours, then calcined in H2/N2Mixed gas (H)2、N2At a volume ratio of 2: 98), calcining at 900 ℃ for 6 hours to obtain the luminescent material.
The prepared luminescent material can observe bright green light in dark after being irradiated by light for 15 minutes, and the visual afterglow time can reach more than 10 hours.
Example 3
A green long-afterglow luminescent material with Ca as chemical expression2Zn0.85Li0.1Si1.8875Al0.15O6.9The preparation method comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、Li2CO3、Al(NO3)3·9H2O, and weighing boric acid accounting for 5-20% of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 8 hours at the rotating speed of 600 revolutions per minute, taking out the tank, and putting the tank into a drying oven to carry out air drying for 6 hours at 120 ℃ to obtain white powder;
3) the white powder was placed in a crucible, pre-calcined in air at 900 ℃ for 1 hour, and then calcined in a CO reducing atmosphere at 1200 ℃ for 2 hours to obtain a light-emitting material.
The prepared luminescent material can observe bright green light in dark after being irradiated by light for 15 minutes, and the visual afterglow time can reach more than 10 hours.
Example 4
A green long-afterglow luminescent material with Ca as chemical expression2Zn0.94K0.04Si1.94Al0.08O6.96The preparation method comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、K2CO3、Al(NO3)3·9H2O, and weighing boric acid accounting for 5-20% of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 5 hours at the rotating speed of 600 revolutions per minute, taking out the mixture, putting the mixture into a drying box, and carrying out air drying for 6 hours at 120 ℃ to obtain white powder;
3) the white powder was placed in a crucible, pre-calcined in air at 880 ℃ for 4 hours, and then calcined in H2/N2Mixed gas (H)2、N2At a volume ratio of 8: 92), calcining at 1100 ℃ for 3 hours to obtain the luminescent material.
The prepared luminescent material can observe bright green light in dark after being irradiated by light for 15 minutes, and the visual afterglow time can reach more than 10 hours.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A green long afterglow luminescent material is characterized in that: the chemical expression of the luminescent material is Ca2Zn1-y- 0.5zMzSi2-0.75xAlxO7-yWherein x = 0.05-0.15, y = 0.01-0.10, z = 0.01-0.10, and M is Li, Na or K.
2. A method for preparing the green long afterglow luminescent material as claimed in claim 1, characterized in that: the method comprises the following steps:
1) weighing CaCO according to stoichiometric ratio3、ZnO、SiO2、M2CO3、Al(NO3)3·9H2O, weighing boron oxide accounting for 5-20% of the total mass of the raw materials;
2) mixing the weighed substances, putting the mixture into a ball milling tank, adding absolute ethyl alcohol until the volume of the tank is three quarters of the volume of the tank, covering a cover tightly, putting the tank into the ball milling machine, carrying out ball milling for 4 to 8 hours at the rotating speed of 600 revolutions per minute, taking out the mixture, and putting the mixture into a drying oven to be air-dried for 6 hours at the temperature of 120 ℃ to obtain white powder;
3) placing the white powder in a crucible, calcining the white powder in air at the temperature of 800-900 ℃ for 1-5 hours, and then calcining the white powder in H2/N2Calcining for 2-6 hours at 900-1200 ℃ in a mixed gas or CO reducing atmosphere to obtain the luminescent material.
3. The preparation method of the green long-afterglow luminescent material as claimed in claim 2, wherein: said H2/N2H in the mixed gas2、N2The volume ratio of (2-8) to (92-98).
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