CN114804623A - Cesium-lead-halide nanocrystalline dispersion glass and heat treatment method thereof - Google Patents

Cesium-lead-halide nanocrystalline dispersion glass and heat treatment method thereof Download PDF

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CN114804623A
CN114804623A CN202210469441.0A CN202210469441A CN114804623A CN 114804623 A CN114804623 A CN 114804623A CN 202210469441 A CN202210469441 A CN 202210469441A CN 114804623 A CN114804623 A CN 114804623A
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CN114804623B (en
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刘超
郭云岚
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

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Abstract

The invention relates to cesium-lead halide nanocrystalline dispersion glass and a heat treatment method thereof, and the cesium-lead halide nanocrystalline dispersion glass comprises the following steps: providing precursor glass capable of precipitating cesium-lead halide nanocrystals, and carrying out initial heat treatment on the precursor glass; cooling the precursor glass subjected to the initial heat treatment to room temperature, then heating to T2 for secondary heat treatment for time T2, then cooling at a cooling speed V in a temperature range from T2 to T4, and then cooling from T4 to room temperature; or the precursor glass after the initial heat treatment is firstly cooled to T3, then cooled at a cooling speed V in the temperature range from T3 to T4, and then cooled to the room temperature from T4. In the heat treatment method, the glass is slowly cooled at a low temperature, so that CsPbX in the glass is led to be in the glass 3 The crystal phase quality of the nano crystal is stable, and the prepared CsPbX is 3 Luminous efficiency of nano crystal dispersion glass and itsThe stability is improved.

Description

Cesium-lead-halide nanocrystalline dispersion glass and heat treatment method thereof
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to cesium-lead halide nanocrystalline dispersion glass and a heat treatment method thereof.
Background
Cesium-lead halide perovskite CsPbX 3 The (X ═ Cl, Br, I) nanocrystal has excellent photoelectric properties and has important application values in the fields of information display, illumination, imaging and the like. But due to CsPbX 3 Nanocrystals are less chemically and thermally stable, and usually need to be dispersed in a certain medium,to improve its stability. The glass material has good stability and is widely applied in the fields of information display, illumination, imaging and the like. Mixing CsPbX 3 The nanocrystals combine with glass to form CsPbX 3 The nano-crystal dispersed glass can improve CsPbX 3 Nanocrystal stability, expansion of CsPbX 3 The application field of the nanocrystalline dispersion glass.
Semiconductor nanocrystals or other functional nanocrystals are prepared in glass, which is typically heat treated at a temperature range near or above the glass transition point; the temperature and time of glass heat treatment are key influencing factors of the performance of the nanocrystal. Preparation of CsPbX in glass 3 And (4) nano-crystalline, and a heat treatment method is also adopted. In practice, however, CsPbX is prepared in a glass of given composition 3 Nanocrystalline, CsPbX prepared by heat treatment with same heat treatment temperature and time 3 The luminous quantum efficiency of the nanocrystalline dispersion glass fluctuates greatly, and stable device performance is difficult to obtain. Therefore, the problem of preparing CsPbX by heat treatment is solved 3 Poor stability of luminous efficiency of nano-crystal dispersion glass, for CsPbX 3 The development of the nanocrystalline dispersion glass photoelectric functional device has a positive effect.
Disclosure of Invention
The invention provides cesium-lead halide nanocrystalline dispersion glass capable of improving the stability of luminous efficiency and a heat treatment method thereof for solving the technical problems.
The technical scheme of the invention is as follows:
a heat treatment method of cesium-lead halogen perovskite nanocrystalline dispersion glass comprises the following steps:
providing precursor glass capable of precipitating cesium-lead halogen nanocrystals, and carrying out initial heat treatment on the precursor glass;
cooling the precursor glass subjected to the initial heat treatment to room temperature, then heating to T2 for secondary heat treatment, wherein the time is T2, then cooling at a cooling speed V in a temperature range from T2 to T4, and then cooling from T4 to room temperature (called scheme one below); or
The precursor glass after the initial heat treatment is firstly cooled to T3, then cooled at a cooling speed V in a temperature range from T3 to T4, and then cooled to room temperature from T4 (referred to as scheme II below).
Preferably, the room temperature is. ltoreq.T 4 < 180 ℃, preferably 100. ltoreq. T4 < 180 ℃.
Preferably, the temperature T1 of the initial heat treatment is > Tg-50, where Tg is the glass transition temperature of the precursor glass; the time t1 of the initial heat treatment is more than or equal to 30 min.
Preferably, T2 is more than or equal to 200 ℃ and less than T1, and T2 is more than or equal to 30min and less than 5 h.
Preferably, T2 is more than or equal to 200 ℃ and less than T1-50.
Preferably, 200 ℃ T2 < 450 ℃.
Preferably, V.ltoreq.3 ℃/min.
Preferably, V is less than or equal to 1 ℃/min and less than or equal to 2 ℃/min.
Preferably, 300 ℃ T3 < 450 ℃.
The cesium-lead-halide perovskite nanocrystalline dispersion glass is obtained after the heat treatment method of the cesium-lead-halide perovskite nanocrystalline dispersion glass.
The invention has the beneficial effects that: CsPbX prepared by conventional heat treatment 3 The luminous efficiency of the nano-crystal dispersion glass is greatly different, and CsPbX is difficult to ensure 3 The stability of the luminous efficiency of the nanocrystalline dispersion glass. In the first scheme, after the initial heat treatment of the glass is finished, the glass can be cooled to the room temperature at any speed (including water cooling, air cooling and the like), then the glass is heated to the temperature range of the secondary heat treatment, the temperature is kept for a certain time, and then the glass is slowly cooled to the room temperature to obtain CsPbX 3 Nanocrystalline dispersed glass. By using the scheme, CsPbX in glass can be obviously improved 3 Crystal quality of nano crystal, reducing CsPbX 3 The luminescent quantum efficiency of the nano-crystal is improved due to the defects in the nano-crystal. In the second scheme, after the glass is subjected to the initial heat treatment, the glass is cooled to a low-temperature range at any speed, and then the glass is slowly cooled to the room temperature to obtain CsPbX 3 Nanocrystalline dispersed glass. By using the second scheme, CsPbX prepared in glass can be improved 3 Crystal quality of nano crystal, reducing CsPbX 3 The luminescent quantum efficiency of the nano-crystal is improved due to the defects in the nano-crystal. In both schemes, the glass isUndergoes a slow cooling process in a low temperature period, so that CsPbX in the glass is generated 3 The crystal phase quality of the nano crystal is stable, and the prepared CsPbX is 3 The luminous efficiency and the stability of the nanocrystalline dispersion glass are improved.
Drawings
FIG. 1 contains CsPbCl 3-x Br x Nanocrystalline, CsPbBr 3 Nanocrystalline, CsPbBr 3-x I x Nanocrystalline, CsPbI 3 The X-ray diffraction pattern of the nanocrystalline glass. In the figure, CBG represents a CsPbCl-containing material 3-x Br x Glass of nanocrystalline, BG stands for CsPbBr-containing glass 3 Glass of nanocrystalline, BIG for CsPbBr-containing 3-x I x Glass of nanocrystalline, IG stands for CsPbI-containing glass 3 A nanocrystalline glass.
Detailed Description
The invention provides a heat treatment method of cesium-lead halogen perovskite nanocrystalline dispersion glass, which comprises the following steps:
providing precursor glass capable of precipitating cesium-lead halide nanocrystals, and carrying out initial heat treatment on the precursor glass;
cooling the precursor glass subjected to the initial heat treatment to room temperature, then heating to T2 for secondary heat treatment, wherein the time is T2, then cooling at a cooling speed V in a temperature range from T2 to T4, and then cooling from T4 to room temperature; or
The precursor glass after the initial heat treatment is firstly cooled to T3, then cooled at a cooling speed V in a temperature range from T3 to T4, and then cooled to room temperature from T4.
The precursor glass provided by the invention is glass with a certain composition, the glass contains a certain amount of cesium, lead and halogen elements, and CsPbX can be precipitated in the glass through conventional heat treatment 3 And (4) nanocrystals. The precursor glass specifically means: the raw materials of each component are fully mixed according to the proportion, and the glass raw material obtained after melting, forming and annealing is called precursor glass. CsPbX 3 In the formula, X is one or a mixture of more than two of Cl, Br or I. The CsPbCl can be prepared by conventional heat treatment 3-x Br x Nanocrystalline glass, CsPbBr 3 Nanocrystalline glass, CsPbBr 3-x I x Nanocrystalline glass, CsPbI 3 Nanocrystalline glass (see fig. 1).
The initial heat treatment temperature T1> Tg-50, wherein Tg is the glass transition temperature of the precursor glass containing cesium, lead and halogen elements; the heat treatment time t1 is more than or equal to 30 min. The glass transition temperature is determined by testing using conventional thermal analysis.
The temperature of the secondary heat treatment is more than or equal to 200 ℃ and less than T2 and less than T1, preferably, more than or equal to 200 ℃ and less than T2 and less than T1-50, and further preferably, more than or equal to 200 ℃ and less than T2 and less than 450 ℃; the heat treatment time is more than or equal to 30min and less than or equal to t2 and less than or equal to 5h, preferably, more than or equal to 30min and less than or equal to t2 and less than or equal to 2 h. The room temperature is less than or equal to T4 and less than 180 ℃, and the temperature is preferably less than or equal to 100 ℃ and less than or equal to T4 and less than 180 ℃.
The cooling speed V is less than or equal to 3 ℃/min, preferably, the cooling speed V is less than or equal to 1 ℃/min and less than or equal to 2 ℃/min.
Several specific examples are described below. In the following examples, CsPbBr 3 The glass comprises the following components: 35SiO 2 -35B 2 O 3 -5CaO-5ZnO-2PbO-3Cs 2 O-15NaBr；CsPbBr 1-x I x The glass comprises the following components: 30SiO 2 -39B 2 O 3 -5CaO-5ZnO-2PbO-4Cs 2 O-5KBr-10KI；CsPbI 3 The glass comprises the following components: 30SiO 2 -39B 2 O 3 -5CaO-5ZnO-2PbO-4Cs 2 O-15KI；CsPbCl 3- x Br x The glass comprises the following components: 40SiO 2 2 -35B 2 O 3 -5CaO-5ZnO-2PbO-3Cs 2 O-5NaCl-5NaBr (all in mole percent). It is to be understood that the heat treatment method of the present invention is not limited to the specific mole percent content of each glass composition in the present example, and that the effects can be achieved with the heat treatment method of the present invention for the remaining glass compositions, which are merely one example.
Example 1
This example provides a cesium-lead halide perovskite nanocrystal CsPbBr 3 A heat treatment method of dispersed glass comprises the following steps:
provide a method capable of precipitating CsPbBr 3 Testing the precursor glass of the nanocrystalline by adopting a comprehensive thermal analyzer, wherein the transition temperature of the glass is 505 ℃;
carrying out initial heat treatment on the precursor glass in a muffle furnace, wherein the heat treatment temperature is 540 ℃, and the heat preservation time is 2 h;
after the initial heat treatment is finished, keeping the glass in a muffle furnace, turning off a power supply of the muffle furnace, and slowly cooling the glass to room temperature along with the muffle furnace, wherein the average cooling speed is-5 ℃/min;
after cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 350 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the temperature range of 350 ℃ to 150 ℃ at the speed of 3 ℃/min.
After the temperature is reduced from 150 ℃ to room temperature, the luminous quantum efficiency of the glass is measured to be 81.0 percent by using an absolute fluorescence quantum efficiency tester.
Comparative example 1
This comparative example differs from example 1 in that after the initial heat treatment was completed, the glass was removed from the muffle furnace and allowed to cool naturally in air to room temperature at an average cooling rate of-20 ℃/min. After cooling to room temperature, the luminescent quantum efficiency of the glass was measured to be 52.1% using an absolute fluorescent quantum efficiency tester.
Comparative example 2
The difference between this comparative example and example 1 is that after the initial heat treatment was completed, the glass was kept in the muffle furnace, the power supply to the muffle furnace was turned off, the glass was slowly cooled down with the muffle furnace, and the average cooling rate was-5 ℃/min. After cooling to room temperature, the luminescent quantum efficiency of the glass was measured to be 65.1% using an absolute fluorescent quantum efficiency tester.
Comparative example 3
The present comparative example differs from example 1 in that after the initial heat treatment was completed, the glass was quickly transferred from the muffle furnace to water at normal temperature and cooled to room temperature at an average cooling rate of-200 ℃/min. The luminous quantum efficiency of the glass measured by an absolute fluorescent quantum efficiency tester is 45.3%.
Comparative example 4
To provide a method capable of precipitating CsPbCl 3-x Br x Precursor glass of nanocrystals (see fig. 1). Measured by an integrated thermal analyzer, the glass has a transition temperature of489 deg.C. The glass is subjected to initial heat treatment in a muffle furnace, the heat treatment temperature is 500 ℃, and the heat preservation time is 10 h. After the initial heat treatment is completed, the glass is removed from the muffle furnace and naturally cooled in the air, and the average cooling speed is 20 ℃/min. After cooling to room temperature, the luminescent quantum efficiency of the glass was measured to be 18.1% using an absolute fluorescent quantum efficiency tester.
Comparative example 5
Provide a method capable of precipitating CsPbBr 3-x I x Precursor glass of nanocrystals (see fig. 1). The glass transition temperature was 493 ℃ as measured by a comprehensive thermal analyzer. The glass is subjected to initial heat treatment in a muffle furnace, wherein the heat treatment temperature is 500 ℃, and the heat preservation time is 10 hours. After the initial heat treatment is completed, the glass is quickly moved to water at normal temperature from the muffle furnace and cooled to room temperature, and the average cooling speed is 200 ℃/min. After cooling to room temperature, the luminescent quantum efficiency of the glass was measured to be 33.4% using an absolute fluorescent quantum efficiency tester.
Comparative example 6
To provide a method capable of precipitating CsPbI 3 Nanocrystalline glass (see fig. 1). The glass transition temperature was 490 ℃ as measured by a comprehensive thermal analyzer. The glass is subjected to initial heat treatment in a muffle furnace, wherein the heat treatment temperature is 520 ℃, and the heat preservation time is 10 hours. After the initial heat treatment is finished, the glass is kept in a muffle furnace, the power supply of the muffle furnace is closed, the glass is slowly cooled along with the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the luminescent quantum efficiency of the glass was measured to be 23.7% using an absolute fluorescent quantum efficiency tester.
Example 2
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 300 ℃, the temperature is kept for 1 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min within the temperature range of 300 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.8%.
Example 3
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 250 ℃, the temperature is kept for 1.5 hours, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min within the temperature range of 250 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.8%.
Example 4
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 200 ℃, the temperature is kept for 2 hours, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min within the temperature range of 200 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.7%.
Comparative example 7
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 190 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at 3 ℃/min within the temperature range of 190 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescence quantum efficiency tester was 67.2%.
Example 5
This example differs from example 1 in that after the initial heat treatment was completed, the glass was kept in a muffle furnace and cooled down to 350 ℃ with the furnace, and then slowly cooled down to 150 ℃ at a rate of 1 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.2%.
Example 6
This example differs from example 1 in that after the initial heat treatment was completed, the glass was kept in a muffle furnace and cooled down to 300 ℃ with the furnace, and then slowly cooled down to 150 ℃ at a rate of 2 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.2%.
Example 7
This example differs from example 1 in that after the completion of the initial heat treatment, the glass was rapidly moved from the muffle furnace to water at normal temperature for cooling. Then placing the glass in a muffle furnace, heating to 350 ℃, preserving the temperature for 0.5 hour, and then slowly reducing the temperature of the muffle furnace at the temperature range of 350-150 ℃ at the cooling speed of 1 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.2%.
Example 8
This example differs from example 1 in that after the completion of the initial heat treatment, the glass was rapidly moved from the muffle furnace to water at normal temperature for cooling. Then placing the glass in a muffle furnace, heating to 300 ℃, preserving the temperature for 1 hour, then slowly reducing the temperature of the muffle furnace, and cooling at the speed of 1 ℃/min within the temperature range of 300-150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.2%.
Example 9
This example differs from example 1 in that after the completion of the initial heat treatment, the glass was rapidly moved from the muffle furnace to water at normal temperature for cooling. Then the glass is put into a muffle furnace, the temperature is raised to 250 ℃, the temperature is kept for 1.5 hours, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 1 ℃/min within the temperature range of 250 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.0%.
Example 10
This example differs from example 1 in that after the completion of the initial heat treatment, the glass was rapidly moved from the muffle furnace to water at normal temperature for cooling. Then placing the glass in a muffle furnace, heating to 200 ℃, preserving the temperature for 2 hours, then slowly reducing the temperature of the muffle furnace, and cooling at the speed of 1 ℃/min within the temperature range of 200-150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.8%.
Example 11
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 300 ℃, the temperature is kept for 1 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 1.5 ℃/min within the temperature range of 300 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.0%.
Example 12
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 300 ℃, the temperature is kept for 1 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 1 ℃/min within the temperature range of 300 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 81.1%.
Example 13
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 300 ℃, the temperature is kept for 1 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 0.5 ℃/min within the temperature range of 300 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.6%.
Example 14
The difference between this example and example 1 is that after the initial heat treatment is completed, the glass is kept in the muffle furnace, the power supply of the muffle furnace is turned off, and the glass is cooled to room temperature along with the slow cooling of the muffle furnace, and the average cooling speed is 5 ℃/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 350 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min in the temperature range of 350 ℃ to 100 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 80.2%.
Example 15
This example differs from comparative example 4 in that after the initial heat treatment was completed, the glass was removed from the muffle furnace and allowed to cool naturally in air at an average cooling rate of-20 deg.C/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 420 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at 3 ℃/min in a temperature range from 420 ℃ to 150 ℃. After the temperature is reduced to room temperature, the luminous quantum efficiency of the glass is measured to be 25.2% by adopting an absolute fluorescence quantum efficiency tester.
Example 16
This example differs from comparative example 4 in that after the initial heat treatment was completed, the glass was removed from the muffle furnace and allowed to cool naturally in air at an average cooling rate of-20 deg.C/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 420 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min within the temperature range of 420 ℃ to 150 ℃. After the temperature is reduced to room temperature, the luminous quantum efficiency of the glass is measured to be 25.7% by adopting an absolute fluorescence quantum efficiency tester.
Example 17
This example differs from comparative example 4 in that after the initial heat treatment was completed, the glass was removed from the muffle furnace and allowed to cool naturally in air at an average cooling rate of-20 deg.C/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 420 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 1 ℃/min within the temperature range of 420 ℃ to 150 ℃. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 25.7%.
Example 18
This example differs from comparative example 4 in that after the initial heat treatment was completed, the glass was removed from the muffle furnace and allowed to cool naturally in air at an average cooling rate of-20 deg.C/min. After cooling to room temperature, the glass is placed in a muffle furnace, the temperature is raised to 420 ℃, the temperature is kept for 0.5 hour, then the temperature of the muffle furnace is slowly reduced, and the temperature is reduced at the speed of 2 ℃/min within the temperature range of 380 ℃ to 150 ℃. After the temperature is reduced to room temperature, the luminous quantum efficiency of the glass is measured to be 25.3% by adopting an absolute fluorescence quantum efficiency tester.
Example 19
This example differs from comparative example 5 in that after the initial heat treatment was completed, the glass was quickly transferred from the muffle furnace to water at normal temperature and cooled to room temperature at an average cooling rate of-200 deg.C/min. And then placing the glass in a muffle furnace, heating to 350 ℃, preserving the heat for 0.5 hour, and then slowly reducing the temperature of the muffle furnace at the temperature range of 350-150 ℃ at the cooling speed of 2 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 54.7%.
Example 20
This example differs from comparative example 5 in that after the initial heat treatment was completed, the glass was quickly transferred from the muffle furnace to water at normal temperature and cooled to room temperature at an average cooling rate of-200 deg.C/min. And then placing the glass in a muffle furnace, heating to 300 ℃, preserving the heat for 1 hour, and then slowly reducing the temperature of the muffle furnace at the temperature range of 300-150 ℃ at the cooling speed of 2 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescent quantum efficiency tester was 54.6%.
Example 21
This example differs from comparative example 6 in that after the initial heat treatment was completed, the glass was retained in a muffle furnace and cooled down to 375 ℃ with the furnace, followed by slow cooling down to 150 ℃ at a rate of 2 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescence quantum efficiency tester was 48.6%.
Example 22
This example differs from comparative example 6 in that after the initial heat treatment was completed, the glass was kept in a muffle furnace and cooled down to 350 ℃ with the furnace, and then slowly cooled down to 150 ℃ at a rate of 1 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescence quantum efficiency tester was 48.6%.
Example 23
This example differs from comparative example 6 in that after the initial heat treatment was completed, the glass was kept in a muffle furnace and cooled down to 300 ℃ with the furnace, and then slowly cooled down to 150 ℃ at a rate of 1 ℃/min. After the temperature was decreased to room temperature, the luminescent quantum efficiency of the glass measured with an absolute fluorescence quantum efficiency tester was 48.4%.
It should be understood that the same and similar parts in the various embodiments of the present invention are referred to each other, and the above embodiments should not be construed as limiting the scope of the present invention. Also, the invention relates to cesium lead halide perovskites (CsPbX) 3 ) Nanocrystalline dispersed glass is not limited to borosilicate glass, for CsPbX 3 The nano-crystal dispersion silicate glass, germanate glass, boron germanate glass, phosphate glass, boron phosphate glass, tellurate glass, boron tellurate glass and the combination of the above glasses have the same effect. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A heat treatment method of cesium-lead halide nanocrystalline dispersion glass is characterized by comprising the following steps:
providing precursor glass capable of precipitating cesium-lead halide nanocrystals, and carrying out initial heat treatment on the precursor glass; cooling the precursor glass subjected to the initial heat treatment to room temperature, then heating to T2 for secondary heat treatment, wherein the time is T2, then cooling at a cooling speed V in a temperature range from T2 to T4, and then cooling from T4 to room temperature; or the precursor glass after the initial heat treatment is firstly cooled to T3, then cooled at a cooling speed V in the temperature range from T3 to T4, and then cooled to the room temperature from T4.
2. The method for heat-treating a cesium lead halide nanocrystalline dispersion glass according to claim 1, wherein said room temperature is ≦ T4 < 180 ℃.
3. The method for the thermal treatment of a cesium lead halide nanocrystalline dispersion glass according to claim 1, wherein the temperature T1 of the initial thermal treatment is > Tg-50, where Tg is the glass transition temperature of the precursor glass; the time t1 of the initial heat treatment is more than or equal to 30 min.
4. The method for heat-treating cesium lead halide nanocrystalline dispersion glass according to claim 3, wherein T2 < T1 is not lower than 200 ℃ and T2 < 5 hours is not lower than 30 min.
5. The method for heat-treating cesium lead halide nanocrystalline dispersion glass according to claim 4, wherein T2 is not less than 200 ℃ but not more than T1-50.
6. The method for heat-treating a cesium lead halide nanocrystalline dispersion glass according to claim 4, wherein T2 is 200 ℃ or more and 450 ℃ or less.
7. The method for heat-treating cesium lead halide nanocrystalline dispersion glass according to claim 1, wherein V is 3 ℃/min or less.
8. The method for heat-treating cesium lead halide nanocrystalline dispersed glass according to claim 1, wherein V is 1 ℃/min or less and 2 ℃/min or less.
9. The method for heat-treating a cesium lead halide nanocrystalline dispersion glass according to claim 1, wherein T3 is 300 ℃ or more and less than 450 ℃ or less.
10. Cesium lead halide nanocrystalline dispersion glass obtained after the thermal treatment method of cesium lead halide nanocrystalline dispersion glass according to claims 1 to 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110395910A (en) * 2019-07-04 2019-11-01 华中科技大学 A kind of fluorescent glass and preparation method thereof for laser lighting
CN111777334A (en) * 2020-07-17 2020-10-16 湘潭大学 CsPbBr with high fluorescence intensity3Preparation method of quantum dot glass
CN112010562A (en) * 2020-08-31 2020-12-01 陕西科技大学 Lithium disilicate glass-ceramic and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110395910A (en) * 2019-07-04 2019-11-01 华中科技大学 A kind of fluorescent glass and preparation method thereof for laser lighting
CN111777334A (en) * 2020-07-17 2020-10-16 湘潭大学 CsPbBr with high fluorescence intensity3Preparation method of quantum dot glass
CN112010562A (en) * 2020-08-31 2020-12-01 陕西科技大学 Lithium disilicate glass-ceramic and preparation method thereof

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