CN110760308B - High-thermal-stability fluorescent powder - Google Patents

High-thermal-stability fluorescent powder Download PDF

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CN110760308B
CN110760308B CN201910821265.0A CN201910821265A CN110760308B CN 110760308 B CN110760308 B CN 110760308B CN 201910821265 A CN201910821265 A CN 201910821265A CN 110760308 B CN110760308 B CN 110760308B
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temperature
fluorescent powder
purity
phosphor
room temperature
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CN110760308A (en
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苟婧
陈雅利
俞斌勋
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Shaanxi Normal University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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    • C09K11/7778—Phosphates with alkaline earth metals

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Abstract

The invention discloses a high-thermal stability fluorescent powder, the molecular formula of which is Sr8Zn0.88‑xSc(PO4)7:12％Tb3+Wherein x is more than or equal to 0.4 and less than or equal to 0.8. The invention changes Zn in the matrix2+Ratio at Tb3+At constant concentration, the increase in x will be more V "ZnAnd V·· ODefects are introduced into the phosphor. Excited by 370nm near ultraviolet light, due to V "Zn+V·· OShallow traps and Tb in defective clusters3+Energy transfer between energy levels, Tb3+Is/are as follows5D3→7FJAnd5D4→7FJthe emission peak increases with the increase of x, and when x is 0.4, the luminous intensity of the fluorescent powder can reach 1.4 times of x 0. Since during the temperature rise V "Zn+V·· OElectrons captured by traps at different depths can be released in the defect clusters, and the thermal quenching behavior of the fluorescent powder at high temperature is compensated. When the temperature reaches 200 ℃, the luminous intensity of the phosphor with x being 0.8 can reach 1.22 times of the room temperature, and the luminous intensity of the phosphor with x being 0 is 1.03 times of the room temperature.

Description

High-thermal-stability fluorescent powder
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to a fluorescent powder with high thermal stability.
Background
When the high-power LED is used, the working temperature is very high, and the fluorescent powder can generate thermal quenching when emitting light, namely, the fluorescent powder is reduced along with the temperature rise. Therefore, for high-power WLEDs (white-light-emitting diodes), the development of phosphors with excellent thermal stability at high operating temperatures is the bottleneck of the current commercial high-power WLEDs. At present, commercial fluorescent powder can generate a quenching phenomenon of fluorescence at a high working temperature, and the working temperature of 120 ℃ is a temperature limit at which high-efficiency output efficiency can be realized by high-power WLED. Therefore, how to design and develop new phosphors with high luminous intensity and high thermal stability is a great challenge to realize commercialization of high-power WLEDs.
The invention patent with publication number CN 108893113A discloses a chromaticity-adjustable high-thermal-stability fluorescent powder, wherein the molecular formula is Sr8Zn0.88Sc(PO4)7:12％Tb3+The phosphor of (1) exhibits the most excellent thermal stability, which is measured at 75 ℃ and 175 ℃,5D3→7FJthe emission intensity of the emission peak was increased to 1.28 and 1.19 times at room temperature,5D4→7FJthe emission intensity of the emission peak was increased to 1.19 and 1.18 times at room temperature, respectively. However, when the temperature exceeds 175 ℃, the luminous intensity begins to decrease, and particularly when the temperature reaches 250 ℃, the luminous intensity already decreases below the room-temperature luminous intensity. For high power LEDs, this drawback still remains to be improved.
Disclosure of Invention
The invention aims to provide a fluorescent powder with higher luminous intensity and high thermal stability under the excitation of near ultraviolet light.
In view of the above, the molecular formula of the phosphor with high thermal stability of the present invention is Sr8Zn0.88-xSc(PO4)7:12％Tb3+Wherein x is 0.4. ltoreq. x.ltoreq.0.8, preferably 0.8.
The preparation method of the fluorescent powder with high thermal stability comprises the following steps: according to Sr8Zn0.88-xSc(PO4)7:12％Tb3+The Sr (NO) with the purity of more than 98 percent3)2、ZnO、(NH4)2HPO4、Sc2O3And Tb4O7Uniformly mixing, firstly preserving heat for 3-5 hours at 850-950 ℃, then preserving heat for 10-12 hours at 1200-1300 ℃, and naturally cooling to room temperature.
In the above method for producing a phosphor having high thermal stability, Sr is preferable8Zn0.88-xSc(PO4)7:12％Tb3+The stoichiometric ratio of (A) is that Sr (NO) with the purity of 99.9 percent is added3)2ZnO with purity of 99.99 percent and NH with purity of 98.5 percent4)2HPO4Sc of 99.99% purity2O3And Tb with a purity of 99.99%4O7Mixing, maintaining at 900 deg.C for 4 hr, maintaining at 1250 deg.C for 11 hr, and naturally cooling to room temperature.
The invention is realized by adding Sr8Zn0.88-xSc(PO4)7:12％Tb3+Changing Zn in phosphor2+Ion ratio, more V "ZnAnd V··ODefects are introduced into the fluorescent powder, under the excitation of near ultraviolet light 370nm, defect clusters are used as traps to capture electrons, and the electrons are transferred to Tb under certain thermal disturbance3+Of ions5D3Energy level, further through5D3Energy level transfer to5D4Energy level, thereby realizing thermal stability of the fluorescent powder at high working temperature.
At room temperature when Sr is8Zn0.88-xSc(PO4)7:12％Tb3+The fluorescent powder is excited by 370nm near ultraviolet light, Tb3+Is/are as follows5D3→7FJAnd5D4→7FJthe emission of (a) increases with increasing x. Thus, Tb is enhanced3+It is not the intrinsic nature of the f-f transition that is emitted, which should be associated with increased V "ZnThe defect is relevant. Except for Tb3+Is/are as follows5D3→7FJAnd5D4→7FJbesides the emission, the 400-405 nm emission area is also affected by the increase of x. V'ZnThe defect increase can enhance the emission between 400-405 nm. Therefore, the emission band between 400-405 nm is due toIn V "Zn+V¨OAnd releasing carriers captured by the defective clusters. Therefore, Tb3+Is/are as follows5D3→7FJAnd5D4→7FJthe enhancement of emission should be due to shallow V "Zn+V¨ODefect cluster trap and Tb3+Energy transfer between energy levels.
When the working temperature is increased, the Sr is excited by the near ultraviolet light8Zn0.88-xSc(PO4)7:12％Tb3+During fluorescent powder, the trap with deeper energy level transfers the captured electrons to Tb under thermal disturbance3+Of ions5D3Energy level, thereby making up for high temperature5D3→7FJAnd5D4→7FJthe thermal quenching phenomenon of an emission peak realizes the zero thermal quenching behavior of the fluorescent powder at high temperature.
Drawings
FIG. 1 shows emission spectra of samples prepared in examples 1 to 3 and comparative example 1 under excitation of 370nm near ultraviolet light at room temperature.
FIG. 2 is a schematic diagram showing the relationship between the integrated intensity of the emission spectrum and the doping concentration x under the excitation of 370nm near ultraviolet light at room temperature for samples prepared in examples 1 to 3 and comparative example 1.
FIG. 3 is a luminescence thermal quenching spectrum with increasing temperature under 370nm near UV excitation for the sample prepared in comparative example 1.
FIG. 4 is a luminescence thermal quenching spectrum with increasing temperature under 370nm near UV excitation for samples prepared in example 1.
FIG. 5 is a luminescence thermal quenching spectrum with increasing temperature under 370nm near UV excitation for samples prepared in example 3.
FIG. 6 is a graph showing the integrated area of the emission peak at 400 to 650nm as the temperature rises for the sample prepared in example 3, as a function of temperature.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
According to Sr8Zn0.48Sc(PO4)7:12％Tb3+In stoichiometric ratio, 1.6930g (8mmol) of Sr (NO) with the purity of 99.9 percent3)20.0391g (0.48mmol) ZnO with a purity of 99.99%, 0.9244g (7mmol) NH with a purity of 98.5%4)2HPO40.0690g (0.5mmol) of Sc with a purity of 99.99%2O3And 0.0022g (0.03mmol) Tb 99.99% pure4O7Uniformly mixing, keeping the temperature at 900 ℃ for 4 hours, keeping the temperature at 1250 ℃ for 11 hours, and naturally cooling to room temperature to obtain Sr8Zn0.48Sc(PO4)7:12％Tb3+And (3) fluorescent powder.
Example 2
According to Sr8Zn0.28Sc(PO4)7:12％Tb3+In stoichiometric ratio, 1.6930g (8mmol) of Sr (NO) with the purity of 99.9 percent3)20.0228g (0.28mmol) of ZnO having a purity of 99.99%, 0.9244g (7mmol) of (NH) having a purity of 98.5%4)2HPO40.0690g (0.5mmol) of Sc with a purity of 99.99%2O3And 0.0022g (0.03mmol) Tb 99.99% pure4O7Uniformly mixing, keeping the temperature at 900 ℃ for 4 hours, keeping the temperature at 1250 ℃ for 11 hours, and naturally cooling to room temperature to obtain Sr8Zn0.28Sc(PO4)7:12％Tb3+And (3) fluorescent powder.
Example 3
According to Sr8Zn0.08Sc(PO4)7:12％Tb3+1.6930g (8mmol) of Sr (NO) with a purity of 99.9%3)20.0065g (0.08mmol) ZnO with 99.99% purity, 0.9244g (7mmol) NH with 98.5% purity4)2HPO40.0690g (0.5mmol) of Sc with a purity of 99.99%2O3And 0.0022g (0.03mmol) Tb 99.99% pure4O7Uniformly mixing, keeping the temperature at 900 ℃ for 4 hours, keeping the temperature at 1250 ℃ for 11 hours, and naturally cooling to room temperature to obtain Sr8Zn0.08Sc(PO4)7:12％Tb3+And (3) fluorescent powder.
Comparative example 1
According to Sr8Zn0.88Sc(PO4)7:12％Tb3+1.6930g (8mmol) of Sr (NO) with a purity of 99.9%3)20.0716g (0.88mmol) ZnO of 99.99% purity, 0.9244g (7mmol) NH of 98.5% purity4)2HPO40.0690g (0.5mmol) of Sc with a purity of 99.99%2O3And 0.0022g (0.03mmol) Tb 99.99% pure4O7Uniformly mixing, keeping the temperature at 900 ℃ for 4 hours, keeping the temperature at 1250 ℃ for 11 hours, and naturally cooling to room temperature to obtain Sr8Zn0.88Sc(PO4)7:12％Tb3+And (3) fluorescent powder.
The inventors carried out tests on the luminescent properties at room temperature and the luminescent thermal stability after temperature rise on the samples prepared in examples 1 to 3 and comparative example 1, and the results are shown in fig. 1 to 6.
As can be seen from FIG. 1, at Tb3+Tb in the sample under the condition of constant concentration3+Increases with increasing x until x is 0.4 and then decreases gradually. Due to the luminous center Tb3+Constant concentration, the increase in emission intensity should be associated with an increase in V "ZnThe defect is relevant. Except for Tb3+Is/are as follows5D3→7FJAnd5D4→7FJin addition to the emission, the emission intensity of 400-405 nm is also influenced by the increase of x, and the monotonic increase of the emission peak intensity of 400-405 nm along with the increase of x obviously shows that V'ZnThe increased defects can increase the luminous intensity between 400 nm and 405 nm. Thus, the enhancement of emission between 400-405 nm is due to V "Zn+V¨OAnd releasing carriers captured by the defective clusters. In addition, Tb3+Is/are as follows5D3→7FJAnd5D4→7FJshould the emission enhancement be due to shallow V "Zn+V¨ODefect cluster trap and Tb3+Energy transfer between energy levels.
FIG. 2 shows Sr8Zn0.88-x(PO4)7:12％Tb3+The curve of the variation relationship between the integrated luminous intensity and the value of x of the phosphor under the room temperature condition shows that the luminous intensity of the phosphor is increased along with the increase of x until x is 0.4, and then is gradually reduced. When x is 0.4, the luminous intensity can be 1.4 times that of x being 0.
Fig. 3 to 5 show the thermal quenching luminescence spectra of the samples prepared in comparative example 1 and examples 1 and 3, and it can be seen that the luminescence intensity can be enhanced with the increase of temperature, wherein the sample of example 3(x ═ 0.8) has the best thermal stability, so the integral luminescence intensity with the change of temperature is shown in fig. 6, and it can be seen from the figure that the integral luminescence intensity is gradually enhanced with the increase of temperature, and the luminescence intensity can reach 1.22 times of the room temperature when 200 ℃. This is because increasing the temperature can release electrons trapped in traps of different depths. Increase in temperature makes V "Zn+V··OThe energy released by the defect cluster trap is preferentially transferred to Tb3+Of ions5D3Energy level, then transferred to5D4Energy level, thereby realizing the property that the intensity of the fluorescent powder is gradually enhanced along with the increase of temperature.

Claims (3)

1. A high thermal stability phosphor, characterized by: the molecular formula of the fluorescent powder is Sr8Zn0.88-xSc(PO4)7:12％Tb3+Wherein x is more than or equal to 0.4 and less than or equal to 0.8; the preparation method comprises the following steps: according to Sr8Zn0.88-xSc(PO4)7:12％Tb3+The Sr (NO) with the purity of more than 98 percent3)2、ZnO、(NH4)2HPO4、Sc2O3And Tb4O7Uniformly mixing, firstly preserving heat for 3-5 hours at 850-950 ℃, then preserving heat for 10-12 hours at 1200-1300 ℃, and naturally cooling to room temperature.
2. A phosphor of claim 1 having high thermal stability, characterized in that: in the formula, x is 0.8.
3. A phosphor with high thermal stability according to claim 1 or 2, characterized in that the phosphor is prepared by the following method: according to Sr8Zn0.88-xSc(PO4)7:12％Tb3+The stoichiometric ratio of (A) is that Sr (NO) with the purity of 99.9 percent is added3)2ZnO with purity of 99.99 percent and (NH) with purity of 98.5 percent4)2HPO4Sc of 99.99% purity2O3And Tb with a purity of 99.99%4O7Mixing, maintaining at 900 deg.C for 4 hr, maintaining at 1250 deg.C for 11 hr, and naturally cooling to room temperature.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893113A (en) * 2018-08-01 2018-11-27 陕西师范大学 A kind of adjustable high thermal stability fluorescent powder of coloration

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893113A (en) * 2018-08-01 2018-11-27 陕西师范大学 A kind of adjustable high thermal stability fluorescent powder of coloration

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Identification of zinc and oxygen vacancy states in nonpolar ZnO single crystal using polarized photoluminescence;J. Liu,et al.;《APPLIED PHYSICS LETTERS》;20101209;第97卷;第231907页 *
Influence of oxygen vacancy on persistent luminescence in ZnGa2O4:Cr3+ and identification of electron carriers;J. SU et al.;《OPTICAL MATERIALS EXPRESS》;20170203;第7卷;第734-743页 *
Investigation of themechanism responsible for the photoluminescence enhancement with Li+ co-doping in highly thermally stable white-emitting Sr8ZnSc(PO4)7:Dy3+ phosphor;Jing Gou et al.;《Journal of Luminescence》;20170308;第187卷;第160-168页 *
Sr8ZnSc(PO4)7:Eu3+,Li+ novel red-emitting phosphors: Synthesis and photoluminescence properties;Jing Gou et al.;《Materials Research Bulletin》;20161025;第86卷;第234-240页 *
Zero-thermal-quenching and photoluminescence tuning with the assistance of carriers from defect cluster traps;Yali Chen et al.;《Journal of Materials Chemistry C》;20180809;第6卷;第10687-10692页 *
白光LED用铈铽激活高效蓝、绿荧光粉发光性能的研究;肖宇;《中国博士学位论文全文数据库》;20190815(第8期);A005-168 *

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