CN110283589B - Rare earth ion double-doped strontium hydrogen phosphate luminescent material and preparation method thereof - Google Patents

Rare earth ion double-doped strontium hydrogen phosphate luminescent material and preparation method thereof Download PDF

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CN110283589B
CN110283589B CN201910625584.4A CN201910625584A CN110283589B CN 110283589 B CN110283589 B CN 110283589B CN 201910625584 A CN201910625584 A CN 201910625584A CN 110283589 B CN110283589 B CN 110283589B
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srhpo
rare earth
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CN110283589A (en
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刘丁菡
何振波
刘运
朱毅
欧立杨
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Chengdu yuhuanfeng Culture Communication Co.,Ltd.
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • 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
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Abstract

The invention relates to a rare earth ion double-doped strontium hydrogen phosphate luminescent material and a preparation method thereof, wherein the method comprises the step 1 of adding Sr (NO)3)2、(NH4)2HPO4、Dy(NO3)3.6H2O and Eu (NO)3)3Dissolving the mixed solution in deionized water to obtain a mixed solution, and adjusting the pH of the mixed solution to 4-8 to obtain a reaction precursor solution; step 2, reacting the reaction precursor solution at the temperature of 150-300 ℃ for 20-28 h, and cooling to room temperature to obtain a mixed system containing a product; step 3, removing impurities from the product in the mixed system, and drying the obtained product to obtain the rare earth ion double-doped SrHPO4Luminescent material SrHPO4:x％Eu3+/y％Dy3+Wherein x is 2-8 and y is 0.5-7; change Eu3+/Dy3+ double-doped SrHPO4The luminescent property of the rear material and the function of adjusting the light color are realized.

Description

Rare earth ion double-doped strontium hydrogen phosphate luminescent material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparing luminescent materials by double-doping rare earth ions with double ions, and particularly relates to a rare earth ion double-doping strontium hydrogen phosphate luminescent material and a preparation method thereof.
Background
Electrons of rare earth ions in the 4f electron layer can jump between different energy levels, and a large amount of absorption and fluorescence emission spectrum information is generated. The rare earth luminescent material has the characteristics of narrow luminescent band, high color purity and bright color; the light absorption capacity is strong, and the conversion efficiency is high; the emission wavelength distribution area is wide; fluorescence lifetimes range widely, spanning from nanoseconds to milliseconds to 6 orders of magnitude. In addition, the rare earth luminescent material has stable physical and chemical properties, is high temperature resistant, can bear high-power electron beams, high-energy radiation, strong light and the like, has incomparable excellent properties compared with other luminescent materials due to various advantages, and is widely applied to the fields of illumination display, information storage amplification, medical diagnosis, biological fluorescent probes and the like.
The double doping of double rare earth ions in a proper matrix material can generate a better energy transfer effect, so that not only can the fluorescence of the material be influenced by luminescence, but also the effect of adjustable light color can be achieved, and the application field and range of the luminescent material can be further expanded. Due to SrHPO4Has a crystal structure similar to that of phosphate with good physical and chemical stability, Sr2+The radius is similar to that of rare earth ions, so SrHPO4Can be used as an important fluorescent powder matrix material. Eu adopting rare earth ion characteristic luminescence3+Dy with excellent luminous brightness and afterglow time3+Double doped in a host material SrHPO4In the method, the energy transfer effect between rare earth ions and the rare earth ions and SrHPO are utilized4The synergistic effect between the SrHPO and the4The photochromic adjustment is achieved after doping, but currently Eu is concerned3+And Dy3+Double doped SrHPO4Matrix materials have not been reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the rare earth ion double-doped strontium hydrogen phosphate luminescent material and the preparation method thereof, the operation is convenient, the synthesis process is simple, the product granularity is uniform, the synthesis granularity is controllable, no pollution is caused, the cost is low, and SrHPO is enabled4Realizes the adjustable light color after doping, expands SrHPO4In the application field after doping.
The invention is realized by the following technical scheme:
a preparation method of a rare earth ion double-doped strontium hydrogen phosphate luminescent material comprises the following steps,
step 1, Sr (NO)3)2、(NH4)2HPO4、Dy(NO3)3.6H2O and Eu (NO)3)3Dissolved in deionized waterObtaining a mixed solution, and adjusting the pH of the mixed solution to 4-8 to obtain a reaction precursor solution;
wherein, Sr (NO)3)2、Dy(NO3)3.6H2O and Eu (NO)3)3Sum of moles and (NH)4)2HPO4Is the same in mole number, Eu (NO)3)3Is Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mol percentage of the total mole number of O is 2 to 8 percent, and Dy (NO)3)3.6H2O represents Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mol percentage of the total mole number of O is 0.5 to 7 percent;
step 2, reacting the reaction precursor solution at the temperature of 150-300 ℃ for 20-28 h, and cooling to room temperature to obtain a mixed system containing a product;
step 3, removing impurities from the product in the mixed system, and drying the obtained product to obtain the rare earth ion double-doped SrHPO4Luminescent material SrHPO4:x％Eu3+/y％Dy3+Wherein x is 2-8 and y is 0.5-7.
Preferably, Sr (NO) is added in step 13)2、(NH4)2HPO4、Dy(NO3)3.6H2O and Eu (NO)3)3Uniformly dissolving in deionized water to obtain a mixed solution.
Preferably, the pH of the mixed solution is adjusted by nitric acid or aqueous ammonia in step 1.
Preferably, the mixed system containing the product is washed with absolute ethanol and deionized water in sequence in step 3, the resulting washing solution is centrifuged, and the process is repeated until the centrifuged product is free of impurities.
Further, the time for washing each time by absolute ethyl alcohol and dehydrated deionized water is 5-15 min, the obtained washing liquid is centrifuged under the conditions that the rotating speed is 5000-10000 r/min and the time is 3-8 min, and the process is repeated for 2-4 times.
Preferably, the product obtained in the step 3 is dried for 12-24 hours at 80-100 ℃.
Preferably, the method also comprises a step 4 of carrying out double doping on the rare earth ions obtained in the step 3 with SrHPO4Luminescent material SrHPO4:x％Eu3+/y％Dy3+Grinding for 0.2-0.5 h to obtain uniform powder.
Preferably, Eu (NO) in step 13)3Is Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mole percentage of the total mole number of O is 5 percent, and Dy (NO)3)3.6H2O represents Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mole percentage of the sum of the moles of O is 0.5%, 1%, 3%, 5% or 7%.
Preferably, the temperature in the step 2 is increased to the reaction temperature at the rate of 5 ℃/min, and after the reaction, the temperature is reduced to 60 ℃ at the rate of 3 ℃/min, and then the reaction product is naturally cooled to the room temperature.
Rare earth ion double-doped SrHPO prepared by any one of the methods4Luminescent material SrHPO4:x％Eu3+/y％Dy3+。
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts SrHPO with stable physicochemical property4The crystal is used as a matrix material doped with rare earth ions, and Sr (NO) is prepared under the low-temperature condition by using a low-temperature hydrothermal method3)2、Eu(NO3)3、Dy(NO3)3.6H2O and (NH)4)2HPO4Removing impurities in the product after reaction, and then drying to obtain the rare earth ion double-doped SrHPO4SrHPO (strontium lead oxide) fluorescent powder4:x％Eu3+/y％Dy3+Not only utilize Eu3+And Dy3+The mutual influence between the Eu and the Eu is also utilized3+/Dy3+With a matrix material SrHPO4Through the energy transfer mechanism between rare earth ions and SrHPO4The combined action of the crystal field environment mainly based on the matrix, thereby changing Eu3 +/Dy3+Double doped SrHPO4The luminescent property of the rear material and the function of adjusting the light color are realized.
Drawings
FIG. 1 is a graph showing SrHPO prepared in comparative examples 1 to 54:x％Eu3+The XRD pattern of the fluorescent powder is that x is 2, 4, 5, 6 and 8 respectively.
FIG. 2 shows SrHPO prepared in comparative examples 1 to 54:x％Eu3+The excitation spectrum of the fluorescent powder at the monitoring wavelength of 617nm is shown, wherein x is 2, 4, 5, 6 and 8 respectively.
FIG. 3 is a graph of SrHPO prepared in comparative examples 1 to 54:x％Eu3+The emission spectrum of the fluorescent powder at an excitation wavelength of 394nm, wherein x is 2, 4, 5, 6 and 8 respectively.
FIG. 4 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+The XRD spectrum of the fluorescent powder is that x is 0, 0.5, 1, 3, 5 and 7 respectively.
FIG. 5 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+The excitation spectrum of the fluorescent powder at the monitoring wavelength of 617nm is shown, wherein x is 0, 0.5, 1, 3, 5 and 7 respectively.
FIG. 6 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+The emission spectrum of the fluorescent powder under the excitation of a wavelength of 394nm, wherein x is 0, 0.5, 1, 3, 5 and 7 respectively.
FIG. 7 is a chromaticity coordinate diagram of the phosphor samples prepared in comparative example 2, examples 1 to 2, and examples 4 to 7.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to rare earth ion double-doped SrHPO4A luminescent material and a preparation method thereof, wherein the preparation method specifically comprises the following steps,
step 1, Sr (NO) with a certain stoichiometric ratio3)2、(NH4)2HPO4、Dy(NO3)3.6H2O is dissolved by the deionized water and then is mixed with Eu (NO)3)3Uniformly mixing, and adjusting the pH to 4-8 by nitric acid and ammonia water to obtain the rare earth ion double-doped SrHPO4A reaction precursor liquid of a light-emitting material;
wherein, Sr (NO)3)2、Dy(NO3)3.6H2O and Eu (NO)3)3Sum of moles and (NH)4)2HPO4Is the same in mole number, Eu (NO)3)3Is Sr (NO)3)2、Dy(NO3)3.6H2O and Eu (NO)3)3The mole percentage of the total mole number is 2 to 8 percent, and Dy (NO)3)3.6H2O represents Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mol percentage of the total mole number of O is 0.5 to 7 percent;
step 2, placing the reaction precursor solution obtained in the step 1 in a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the stainless steel reaction kettle in an electric heating blowing drying oven to react for 20-28 h at the temperature of 150-300 ℃, cooling to room temperature after the reaction is finished, wherein the temperature is increased to the reaction temperature at the speed of 5 ℃/min, and after the reaction is finished, the temperature is reduced to 60 ℃ at the cooling speed of 3 ℃/min, and then naturally cooling to the room temperature;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 5-15 min, centrifuging the obtained washing liquid under the conditions that the rotating speed is 5000-10000 r/min and the time is 3-8 min, repeating the process for 2-4 times, and removing impurities in the product;
step 4, drying the obtained product at 80-100 ℃ for 12-24 h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.2-0.5 h by using a crucible and a grinding rod to obtain uniform powdery SrHPO4:x％Eu3+/y％Dy3+The luminescent material, wherein x is 2-8 and y is 0.5-7.
In the hydrothermal reaction, the particle size of the powder is mostlyOn the nanometer level, reactants are hydrolyzed and contacted with each other in ion mode, and bond breaking, bond formation and interatomic rearrangement generate a new substance SrHPO under the heating condition4:x％Eu3+/y％Dy3+(ii) a The reaction utilizes Eu3+/Dy3+With a matrix material SrHPO4By synergistic interaction of rare earth ions Eu3+/Dy3+Mechanism of energy transfer between and with SrHPO4The combined action of the crystal field environment mainly based on the matrix, thereby improving Eu3+/Dy3+Double doped SrHPO4The luminescent property of the rear material and the function of adjusting the light color are realized.
Rare earth ion double-doped SrHPO prepared by using preparation method4Luminescent material SrHPO4:x％Eu3+/y％Dy3+。
The present invention is further illustrated by the following specific examples.
Example 1
Rare earth ion double-doped SrHPO4The preparation method of the luminescent material specifically comprises the following steps,
step 1, 1.610g of Sr (NO)3)21.069g of (NH)4)2HPO40.018g Dy (NO)3)3.6H2O is dissolved in deionized water and 4ml of Eu (NO)3)3Mixing, adjusting pH to 4 with nitric acid, wherein Sr (NO) is added3)2Is 7.572mmol, (NH)4)2HPO4The mole number of (2) is 8.012mmol, Dy (NO)3)3.6H2The mole number of O is 0.04mmol, Eu (NO)3)3Is 0.4mmol, so that Eu3+Has a doping concentration of 5% and Dy3+The doping concentration of (a) is 0.5%;
step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in an electrothermal blowing dry oven at the temperature of 180 ℃, cooling to room temperature after the reaction is finished, wherein the temperature is increased to the reaction temperature at the speed of 5 ℃/min, and after the reaction is finished, cooling to 60 ℃ at the cooling speed of 3 ℃/min, and naturally cooling to the room temperature;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 0.1h, centrifuging the obtained washing liquid under the conditions that the rotating speed is 10000r/min and the time is 3min, repeating the process for 4 times, and removing impurities in the product;
step 4, drying the obtained product at 80 ℃ for 12h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.5h by using a crucible and a grinding rod to obtain uniform powdery SrHPO4:5％Eu3+/0.5％Dy3+A luminescent material.
Rare earth ion double-doped SrHPO prepared by using preparation method4Luminescent material SrHPO4:5％Eu3+/0.5％Dy3+。
Example 2
Rare earth ion double-doped SrHPO4The preparation method of the luminescent material specifically comprises the following steps,
step 1, 1.60g of Sr (NO)3)21.067 of (NH)4)2HPO40.037g of Dy (NO)3)3.6H2O is dissolved in deionized water and 4ml of Eu (NO)3)3Mixing, adjusting pH to 6 with nitric acid, and adjusting pH to obtain Sr (NO)3)2Is 7.517mmol, (NH)4)2HPO4The mole number of (2) is 7.997mmol, Dy (NO)3)3.6H2The mole number of O is 0.08mmol, Eu (NO)3)3Is 0.4mmol, so that Eu3+Has a doping concentration of 5% and Dy3+The doping concentration of (a) is 1%;
step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in an electrothermal blowing dry oven at the temperature of 180 ℃, cooling to room temperature after the reaction is finished, wherein the temperature is increased to the reaction temperature at the speed of 5 ℃/min, and after the reaction is finished, cooling to 60 ℃ at the cooling speed of 3 ℃/min, and naturally cooling to the room temperature;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 5min, centrifuging the obtained washing liquid under the conditions that the rotating speed is 5000r/min and the time is 8min, repeating the process for 3 times, and removing impurities in the product;
step 4, drying the obtained product at 100 ℃ for 18h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.2h by using a crucible and a grinding rod to obtain uniform powdery SrHPO4:5％Eu3+/1％Dy3+A luminescent material.
Rare earth ion double-doped SrHPO prepared by using preparation method4Luminescent material SrHPO4:5％Eu3+/1％Dy3+。
Example 3
Rare earth ion double-doped SrHPO4The preparation method of the luminescent material specifically comprises the following steps,
step 1, 1.610g of Sr (NO)3)21.069g of (NH)4)2HPO40.018g Dy (NO)3)3.6H2O is dissolved in deionized water and 4ml of Eu (NO)3)3Mixing, adjusting pH to 8 with ammonia water, wherein Sr (NO) is added3)2Is 7.572mmol, (NH)4)2HPO4The mole number of (2) is 8.012mmol, Dy (NO)3)3.6H2The mole number of O is 0.04mmol, Eu (NO)3)3Is 0.4mmol, so that Eu3+Has a doping concentration of 5% and Dy3+The doping concentration of (a) is 0.5%;
step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 28 hours in an electrothermal blowing dry oven at the temperature of 150 ℃, cooling to room temperature after the reaction is finished, wherein the temperature is increased to the reaction temperature at the speed of 5 ℃/min, and after the reaction is finished, cooling to 60 ℃ at the cooling speed of 3 ℃/min, and naturally cooling to the room temperature;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 15min, centrifuging the obtained washing liquid under the conditions that the rotating speed is 8000r/min and the time is 5min, repeating the process for 2 times, and removing impurities in the product;
step 4, drying the obtained product at 90 ℃ for 24h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.3h by using a crucible and a grinding rod to obtain uniform powdery SrHPO4:5％Eu3+/0.5％Dy3+A luminescent material.
Rare earth ion double-doped SrHPO prepared by using preparation method4Luminescent material SrHPO4:5％Eu3+/0.5％Dy3+。
Example 4
Rare earth ion double-doped SrHPO4The preparation method of the luminescent material specifically comprises the following steps,
step 1, 1.60g of Sr (NO)3)21.067 of (NH)4)2HPO40.037g of Dy (NO)3)3.6H2O is dissolved in deionized water and 4ml of Eu (NO)3)3Mixing, adjusting pH to 6 with nitric acid, and adjusting pH to obtain Sr (NO)3)2Is 7.517mmol, (NH)4)2HPO4The mole number of (2) is 7.997mmol, Dy (NO)3)3.6H2The mole number of O is 0.08mmol, Eu (NO)3)3Is 0.4mmol, so that Eu3+Has a doping concentration of 5% and Dy3+The doping concentration of (a) is 1%;
step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 20 hours in an electrothermal blowing dry oven at the temperature of 300 ℃, cooling to room temperature after the reaction is finished, wherein the temperature is increased to the reaction temperature at the speed of 5 ℃/min, and after the reaction is finished, cooling to 60 ℃ at the cooling speed of 3 ℃/min, and naturally cooling to the room temperature;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 5min, centrifuging the obtained washing liquid under the conditions that the rotating speed is 5000r/min and the time is 8min, repeating the process for 3 times, and removing impurities in the product;
step 4, drying the obtained product at 100 ℃ for 18h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.2h by using a crucible and a grinding rod to obtain uniform powdery SrHPO4:5％Eu3+/1％Dy3+A luminescent material.
Rare earth ion double-doped SrHPO prepared by using preparation method4Luminescent material SrHPO4:5％Eu3+/1％Dy3+。
To fully explain Eu3+And Dy3+Double doped SrHPO4The characteristics of the luminescent material, now mixing it with singly doped Eu3+SrHPO of4Light emitting material and single doped Dy3+SrHPO of4The luminescent materials were compared, the comparative examples are as follows,
comparative example 1
Rare earth ion Eu3+Single doped SrHPO4The preparation method of the luminescent material specifically comprises the following steps,
step 1, 1.731g of Sr (NO)3)2And 1.09g of (NH)4)2HPO4Respectively dissolving with deionized water and 1.7ml of Eu (NO)3)3Mixing, adjusting pH to 6 with nitric acid, and adjusting pH to obtain Sr (NO)3)2Is 8.141mmol, (NH)4)2HPO4Is 8.307mmol, Eu (NO)3)3Is 0.166mmol, so that Eu3+The doping concentration of (2%); (ii) a
Step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in an electrothermal blowing dry oven at the temperature of 180 ℃, and cooling to room temperature after the reaction is finished;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 0.1h, centrifuging the obtained washing liquid under the conditions that the rotating speed is 10000r/min and the time is 3min, repeating the process for 4 times, and removing impurities in the product;
step 4, drying the obtained product at 80 ℃ for 12h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.5h by using a crucible and a grinding rod to obtain SrHPO4:2％Eu3+A luminescent material.
Comparative example 2
Rare earth ion Eu3+Single doped SrHPO4A method for preparing a luminescent material comprises the following steps,
step 1, 1.622g of Sr (NO)3)2And 1.071g of (NH)4)2HPO4Respectively dissolved in deionized water and 4ml of Eu (NO)3)3Mixing, adjusting pH to 6 with nitric acid, and adjusting pH to obtain Sr (NO)3)2Is 7.628mmol, (NH)4)2HPO4Is 8.029mmol, Eu (NO)3)3Is 0.401mmol, so that Eu3+The doping concentration of (a) is 5%; (ii) a
Step 2, placing the reaction precursor solution obtained in the step 1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours in an electrothermal blowing dry oven at the temperature of 180 ℃, and cooling to room temperature after the reaction is finished;
step 3, washing the mixed system containing the product obtained in the step 2 by using absolute ethyl alcohol and dehydrated deionized water for 0.1h, centrifuging the obtained washing liquid under the conditions that the rotating speed is 10000r/min and the time is 3min, repeating the process for 4 times, and removing impurities in the product;
step 4, drying the obtained product at 80 ℃ for 12h, and taking out the sample after cooling to room temperature;
step 5, grinding the taken sample for 0.5h by using a crucible and a grinding rod to obtain SrHPO4:5％Eu3+A luminescent material.
Examples 5 to 11 and comparative examples 3 to 5
Examples 5 to 11 differ from example 1 only in Sr (NO)3)2Mass of, Eu3+Doping concentration of (1) andDy3+the doping concentrations of comparative examples 2 to 4 are different from those of comparative example 1 only in Sr (NO)3)2Mass of, Eu3+Doping concentration and Dy of3+The doping concentrations of (A) are different, and thus the parameters of examples 5 to 11 different from example 1 and the parameters of comparative examples 2 to 4 different from comparative example 1 are tabulated, specifically as shown in Table 1, wherein Sr (NO)3)2And Dy (NO)3)3.6H2The unit of O is g, Eu (NO)3)3Unit is ml, Eu3+And Dy3+The doping concentrations in mol are% in all.
TABLE 1 specific parameters in examples 5 to 11 and comparative examples 2 to 4
Examples of the present invention Sr(NO3)2 Eu(NO3)3 Dy(NO3)3.6H2O Eu3+ Dy3+
Comparative example 3 1.714 3.2 0 4 0
Comparative example 4 1.702 4.8 0 6 0
Comparative example 5 1.690 6.4 0 8 0
Example 5 1.553 4 0.109 5 3
Example 6 1.507 4 0.180 5 5
Example 7 1.461 4 0.249 5 7
Example 8 1.643 1.6 0.073 2 2
Example 9 1.556 3.2 0.145 4 4
Example 10 1.488 4 0.216 5 6
Example 11 1.413 6.2 0.231 8 6.5
FIG. 1 is a graph of SrHPO prepared in comparative examples 1 to 54:x％Eu3+An XRD (X-ray diffraction) spectrum of the fluorescent powder, wherein x is 2, 4, 5, 6 and 8 respectively; the comparison analysis shows that when Eu is used3+When the concentration is less than 8 percent, the prepared SrHPO4:x％Eu3+The diffraction peak of the fluorescent powder sample is matched with that of the JCPDS 12-0368 standard card, no impurity peak appears, and the prepared sample is pure SrHPO4And (4) crystals. When Eu is used3+When the concentration exceeds 8%, the diffraction image of the prepared sample is changed, and a mixed peak appears, which indicates that the doping with too high concentration can cause the change of the phase structure of the matrix.
FIG. 2 is a graph of SrHPO prepared in comparative examples 1 to 54:x％Eu3+An excitation spectrum of the fluorescent powder at a monitoring wavelength of 617nm, wherein x is 2, 4, 5, 6 and 8 respectively; excitation peaks appear at 361nm, 380nm, 394nm, 415nm and 464nm, respectively corresponding to Eu3+Is/are as follows7F0→5D4、7F0→5G2、7F0→5L6、7F0→5D3And7F0→5D2transition; at the position of 394nm7F0→5L6The visible light absorption peak is also obviously stronger than other absorption peaks, belonging to Eu3+Characteristic excitation peak of (1), the two excitation lines are Eu3+Intrinsic 4f-4f transition absorption peak, which indicates that the wavelength of the excitation source can be extended to the visible region.
FIG. 3 is a graph of SrHPO prepared in comparative examples 1 to 54:x％Eu3+An emission spectrum of the fluorescent powder under excitation of an excitation wavelength of 394nm, wherein x is 2, 4, 5, 6 and 8 respectively; four peaks at 592nm, 617nm, 653nm, 701nm were seen, corresponding to Eu3+5D0→7F1、5D0→7F2、5D0→7F3And5D0→7F4and (4) electron transition. In Eu3+When the doping concentration is 5%, the peak value of the emission peak of the fluorescent powder is maximum, and the luminous intensity of the sample is strongest. Emission peak intensity with Eu3+The doping concentration rises first and then falls, and when the concentration is 5%, the strongest peak appears, which indicates that the quenching concentration is 5%.
FIG. 4 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+Comparing XRD spectrograms of the fluorescent powder and a standard card JCPDS 12-0368, wherein x is 0, 0.5, 1, 3, 5 and 7 respectively; the X-ray diffraction peak intensity and peak position of the samples are well matched with that of the standard card JCPDS NO.12-0368, no other miscellaneous peaks appear, and the samples are pure-phase SrHPO4And (4) crystals. The diffraction pattern being sharp line patternThe half-height width ratio is narrow, the relative intensity of diffraction peak is large, and the sample has high crystallinity because Eu3+And Dy3+Low concentration doping does not cause SrHPO4Change of phase structure of matrix.
FIG. 5 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+The excitation spectrum of the fluorescent powder at the monitoring wavelength of 617nm is shown, wherein x is 0, 0.5, 1, 3, 5 and 7 respectively, and the positions of several excitation peaks are located at 357nm, 380nm, 394nm, 415nm and 465nm, and the excitation peaks are caused by Eu3+Caused by transition of internal 4f-4f electron shells, and Eu corresponds to several excitation peaks in the figure3+Internal of7F0—5D4、7F0—5G2、7F0—5L6、7F0—5D3And7F0—5D2and (4) electron transition. The peak is highest at 394nm, so 394nm is selected as the excitation wavelength when measuring the emission spectrum.
FIG. 6 shows SrHPO prepared in comparative example 2, examples 1 to 2 and examples 4 to 74:5％Eu3+/x％Dy3+The emission spectrum of the fluorescent powder under the excitation of 394nm wavelength, wherein x is 0, 0.5, 1, 3, 5, 7 respectively, three main emission peaks can be seen in the spectrum, and belong to Eu3+Respectively located at 594nm, 617nm and 701nm, and three main emission peaks respectively corresponding to Eu3+Is/are as follows5D0—7F1、5D0—7F2And5D0—7F4transition, and the peak intensity at 617nm is higher than that at 594nm, which proves that more Eu is present3+Occupying the positions of the lower symmetry lattice sites in the system. With Dy3+The concentration of (2) is increased continuously, the position where the emission peak appears and the shape of the emission peak are not changed, but the intensity of the emission peak is reduced continuously, namely the light-emitting performance of the material is reduced continuously.
Intensity of emission peak of sample with Dy3+Increase in concentration ofAnd is continuously decreased due to one reason that Eu3+And Dy3+Charged ratio Sr2+When Dy is excessive3+When the doping amount is too large, the positive charge vacancies in the crystal are too much, so that the charge imbalance is increased, the lattice stress is increased, the non-radiative transition is increased, and the emission peak intensity of the fluorescent powder is reduced; another reason is that Eu3+Because of Dy3 +Increase and decrease of doping amount, Eu in the system3+Directed Dy3+Phenomenon of transferring energy, but transferring to Dy3+Energy of (2) is converted into Dy3+I.e. Dy, of3+From Eu to Eu3+The energy obtained by the resonance transfer between the two is released in the form of non-radiative transition, namely phonon radiation, and the luminescence property of the material is reduced.
FIG. 7 is a chromaticity coordinate diagram of the phosphor samples prepared in comparative example 2, examples 1 to 2, and examples 4 to 7, in which the color coordinates of the two samples are overlapped, and it is known that Dy is not doped3+，Eu3+The color coordinates of the sample at 5% doping concentration were (0.581,0.418) in the red region. When Eu is used3+While the concentration is kept constant, the Dy is followed3+The color coordinate of the sample is shifted to the upper left, i.e., the orange red region, specifically, when Dy is added3+When the doping concentration is 0.5%, the chromaticity coordinate of the sample falls in a red light region, namely a position B in the figure; when Dy3+When the doping concentration is increased to 1%, the chromaticity coordinate of the doped with the chromaticity coordinate gradually shifted towards the orange-red light region, namely at the position C in the graph; when Dy3+When the doping concentration is continuously increased to 3%, the chromaticity coordinate of the doping concentration is further shifted towards the orange-red light region, namely D in the figure; when Dy3+When the doping concentration is increased to 5%, the chromaticity coordinate of the doping concentration falls at E in the graph; when Dy3+At a doping concentration of 7%, the shift from the orange-red region to the orange region is started, i.e., at F in the figure. The fluorescent powder can effectively make up the deficiency of the red light part. By changing Dy3+The doping concentration of the fluorescent powder can change the luminescent color of the fluorescent powder, which shows that the fluorescent powder has greater application value in the field of luminescent of the color-adjustable fluorescent powder.
TABLE 2 color coordinates of the phosphors obtained in comparative example 2, examples 1 to 2 and examples 4 to 7
Figure BDA0002126979710000141
The invention adopts a low-temperature hydrothermal method and utilizes Sr (NO)3)2、(NH4)2HPO4、Dy(NO3)3.6H2O and Eu (NO)3)3Reaction to synthesize SrHPO4:x％Eu3+/y％Dy3+The luminescent material reacts according to a certain mole percentage, the sample powder is obtained after the reaction is finished and the reaction is naturally cooled to room temperature through the processes of washing, centrifuging, drying, grinding and the like, and the luminescent material has great application value in the field of light-color-adjustable fluorescent powder luminescence.
The above description is only for several embodiments, not all embodiments, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the above examples, are all embodiments covered by the specific embodiments of the present invention.

Claims (5)

1. A preparation method of a rare earth ion double-doped strontium hydrogen phosphate luminescent material is characterized by comprising the following steps of,
step 1, Sr (NO)3)2、(NH4)2HPO4、Dy(NO3)3.6H2O and Eu (NO)3)3Uniformly dissolving the mixed solution in deionized water to obtain a mixed solution, and adjusting the pH of the mixed solution to 4-8 by using nitric acid or ammonia water to obtain a reaction precursor solution;
wherein, Sr (NO)3)2、Dy(NO3)3.6H2O and Eu (NO)3)3Sum of moles and (NH)4)2HPO4Is the same in mole number, Eu (NO)3)3Is Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mol percentage of the total mole number of O is 2 to 8 percent, and Dy (NO)3)3.6H2O accounts for Sr(NO3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mol percentage of the total mole number of O is 0.5 to 7 percent;
step 2, raising the temperature of the reaction precursor liquid to 150-300 ℃ at the speed of 5 ℃/min, reacting for 20-28 h, then lowering the temperature to 60 ℃ at the cooling speed of 3 ℃/min, and naturally cooling to room temperature to obtain a mixed system containing a product;
and 3, washing a mixed system containing the product by using absolute ethyl alcohol and dehydrated deionized water in sequence, centrifuging the obtained washing liquid, repeating the process until the centrifuged product does not contain impurities, and drying the obtained product at 80-100 ℃ for 12-24 h to obtain the rare earth ion double-doped SrHPO4Luminescent material SrHPO4:x％Eu3+/y％Dy3+Wherein x is 2-8 and y is 0.5-7.
2. The method for preparing the rare earth ion double-doped strontium hydrogen phosphate luminescent material according to claim 1, wherein the washing time of absolute ethyl alcohol and dehydrated deionized water is 5-15 min each time, the obtained washing liquid is centrifuged at the rotating speed of 5000-10000 r/min for 3-8 min, and the process is repeated for 2-4 times.
3. The method for preparing the rare earth ion double-doped strontium hydrogen phosphate luminescent material according to claim 1, further comprising a step 4 of double-doping the rare earth ions obtained in the step 3 with SrHPO4Luminescent material SrHPO4:x％Eu3+/y％Dy3 +Grinding for 0.2-0.5 h to obtain uniform powder.
4. The method for preparing a rare earth ion double-doped strontium hydrogen phosphate luminescent material according to claim 1, wherein Eu (NO) in step 13)3Is Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mole percentage of the total mole number of O is 5 percent, and Dy (NO)3)3.6H2O represents Sr (NO)3)2、Eu(NO3)3And Dy (NO)3)3.6H2The mole percentage of the sum of the moles of O is 0.5%, 1%, 3%, 5% or 7%.
5. Rare earth ion double-doped SrHPO prepared by the method of any one of claims 1 to 44Luminescent material SrHPO4:x％Eu3+/y％Dy3+。
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