CN114634312A - Doped Al3+CsPbBr of3Quantum dot glass ceramic and preparation method thereof - Google Patents

Doped Al3+CsPbBr of3Quantum dot glass ceramic and preparation method thereof Download PDF

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CN114634312A
CN114634312A CN202210226434.8A CN202210226434A CN114634312A CN 114634312 A CN114634312 A CN 114634312A CN 202210226434 A CN202210226434 A CN 202210226434A CN 114634312 A CN114634312 A CN 114634312A
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glass
cspbbr
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quantum dot
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杜英
陈丹平
陶依婷
王盼挺
吴婷
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • 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 provides a doped Al3+CsPbBr of3Quantum dot glass ceramic and a preparation method thereof, belonging to the technical field of functional glass. The glass consists of the following raw materials in percentage by mole: p2O58‑23mol％，Na2O 2‑11mol％，K2O 0‑10mol％，ZnO 7‑16mol％，Al2O31‑30mol％，B2O320‑65mol％，Cs2O 3‑14mol％，PbBr21-8 mol% of NaBr, 1-10 mol% of NaBr. The invention dopes Al3+CsPbBr of3The quantum dot glass ceramic has high light yield, short decay life and high stability, and the CsPbBr is added3The quantum dot glass ceramic is used for preparing white light emitting diodes, illumination and other fields and becomes a new generation of scintillating material.

Description

Doped Al3+CsPbBr of3Quantum dot glass ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of functional glass, in particular to Al-doped glass3+CsPbBr of3Quantum dot glass ceramic and a preparation method thereof.
Background
Inorganic cesium lead halide CsPbX3The perovskite quantum dots (X ═ Cl, Br, I) are of great interest due to their excellent optical properties, such as broad wavelength tunability with controllable band gap, full width at half maximum of emission band, and high photoluminescence quantum efficiency, which indicates their great potential application in the field of white Light Emitting Diodes (LEDs). Recently, lead cesium halide perovskites have become a new type of scintillating material for applications in ultrasensitive X-ray detectors and low dose radiography. When they are scaled down to the size range of quantum dots, excellent scintillation performance comparable to commercial single crystals (e.g., LuAG: Ce) has been achieved due to exciton confinement effects. Only the anion component is needed to be adjusted, and the attractive twinkling luminescence which cannot be imagined by the traditional scintillation crystal and can be adjusted in color can be obtained. Thus, CsPbX3The perovskite quantum dot is expected to be applied to the fields of medical diagnosis, safety inspection, basic scientific research, dosimetry and the like. However, although perovskite quantum dots have excellent photoluminescence and scintillation properties, they have poor stability, limiting their practical applications. Research reports, inorganic CsPbX3Perovskite quantum dots can be precipitated in different oxide glass systems by melt quenching methods, such as borosilicate, germanoborate, phosphoborate, phosphosilicate, and tellurite borate glasses. Since the oxide glass matrix can effectively prevent the degradation of the metal halide quantum dots, the stability of these glass-embedded quantum dots is significantly improved and they still show good optical properties inside the glass. However, quantum dot glasses have a problem that the scintillation efficiency is generally low among the above glasses. This is due to the fact that the quantum dots in the glass are too small in size and have too many surface defects. In addition, there are a large number of non-bridging oxygen defects in the glass, and the various defects will act as recombination centers for electron-hole pairs generated by high energy rays, thereby terminating the energy transfer of the electron-hole pairs to the quantum dots. Therefore, how to greatly improve CsPbX3The scintillating luminous efficiency of quantum dots in glass is a serious challenge for developing new scintillating glass ceramics.
Adding Al to glass3+Is the most common and effective method for eliminating non-bridging oxygen defects. Our previous studies reported the reduction of Na+And increase of Al3+Content of (1), Ce3+The photoluminescence and scintillation efficiency of the doped glass is greatly improved because of the Al3+Can be converted to a bridging oxygen in combination with a non-bridging oxygen. Al (Al)3+The addition of the compound can not only improve the chemical stability of the glass, but also is important for the development of photoluminescence and scintillation properties of the glass. Therefore, the present invention is to introduce Al into the glass3+And the CsPbBr is obviously enhanced by controlling the doping amount thereof3Photoluminescence and scintillation of quantum dot glass ceramics, especially quantum efficiency is improved, which is CsPbBr3The development of quantum dot glass ceramics in the field of scintillating materials provides a new path.
Disclosure of Invention
The invention aims to provide an Al-doped alloy3+CsPbBr of3The quantum dot glass ceramic has high light yield, short attenuation life and high stability, and the CsPbBr is increased3The quantum dot glass ceramic is used for preparing white light emitting diodes, illumination and other fields and becomes a new generation of scintillating material.
The technical scheme of the invention is realized as follows:
the invention provides a doped Al3+CsPbBr of3The quantum dot glass ceramic is prepared from the following raw materials in percentage by mole: p2O5 8-23mol％，Na2O 2-11mol％，K2O 0-10mol％，ZnO 7-16mol％，Al2O3 1-30mol％，B2O3 20-65mol％，Cs2O 3-14mol％，PbBr2 1-8mol％，NaBr 1-10mol％。
As a further improvement of the invention, the glass consists of the following raw materials in percentage by mole: the glass consists of the following raw materials in percentage by mole: p is2O5 15mol％，Na2O 5mol％，K2O 5mol％，ZnO 10mol％，Al2O3 1-26mol％，B2O3 24-50mol％，Cs2O 7mol％，PbBr2 3mol％，NaBr 5mol％。
The invention further protects the doped Al3+CsPbBr of3The preparation method of the quantum dot glass ceramic comprises the following steps:
calculating the mass of each corresponding glass composition according to the composition and the mole percentage of the raw materials, and accurately weighing each raw material;
secondly, grinding the weighed raw materials in a corundum mortar, and uniformly mixing to form a mixture;
thirdly, putting the mixture into a covered alumina crucible to melt in a high-temperature furnace, taking out the crucible after the mixture is completely melted, and pouring clear molten glass on a preheated stainless steel mold to obtain transparent glass;
quickly transferring the glass to a muffle furnace for annealing treatment, preserving heat, then cooling along with the furnace, taking out the glass, and cutting and polishing to form polished glass;
fifthly, the polished glass is further subjected to heat treatment and naturally cooled to obtain the doped Al3+CsPbBr of3Quantum dot glass-ceramics.
As a further improvement of the invention, said P2O5From NaPO3、KPO3And Al (PO)3)3Introduction of the Na2O and K2O is respectively prepared from NaPO3And KPO3Introduction of the Al2O3From Al (PO)3)3Introduction of B2O3From H3BO3Introduction of said Cs2O is formed by Cs2CO3And (4) introducing.
As a further development of the invention, the annealing temperature is 30 to 50 ℃ below the Tg temperature.
As a further improvement of the invention, the heat preservation time is 4-8 h.
As a further improvement of the invention, the heat treatment temperature is 400-490 ℃.
As a further improvement of the invention, the heat treatment time is 1-48 h.
The invention has the following beneficial effects: doped Al prepared by the invention3+CsPbBr of3The quantum dot glass ceramic confirms that the glass contains CsPbBr through X-ray diffraction test analysis, Raman test and TEM image3And (4) quantum dots. Undoped Al3+CsPbBr of3The photoluminescence and scintillation intensity of the quantum dot glass ceramic is very weak, the quantum efficiency is low, and Al is doped3+CsPbBr of3The photoluminescence intensity and the scintillation intensity of the quantum dot glass ceramic are respectively enhanced by 8 times and 6 times, the quantum efficiency is increased from 43% to 76%, and particularly, the scintillation intensity is 1.7 times of BGO. This is because of Al3+Eliminates the non-bridge oxygen defect in the glass and promotes CsPbBr3And (5) growing the quantum dots.
The invention dopes Al3+CsPbBr of3The quantum dot glass ceramic has high light yield, short decay life and high stability, and the CsPbBr is added3The quantum dot glass ceramic is used for preparing white light emitting diodes, illumination and other fields and becomes a new generation of scintillating material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows the Al doping of the present invention3+CsPbBr of3Photoluminescence spectra of comparative example 1, example 3, example 5 and example 7 of quantum dot glass ceramics are compared;
FIG. 2 shows Al doping of the present invention3+CsPbBr of3Comparative scintillation luminescence spectra of comparative example 1, example 3, example 5 and example 7 of quantum dot glass ceramics.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is prepared by doping Al3+Enhanced CsPbBr3The glass compositions of 1 comparative example and 14 specific examples of quantum dot glass-ceramics are shown in table 1:
TABLE 1
Figure BDA0003539357470000051
Comparative example 1:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing schemes are as shown in table 2:
TABLE 2
Figure BDA0003539357470000061
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 430 ℃ for 3 hours and naturally cooled to obtain Al-free glass3+CsPbBr of3The quantum dot glass has a transparent sample and a yellowish green color. The photoluminescence spectrum of a sample measured by an FLS920 instrument of Edinburgh company in England is shown in figure 1, and an X-ray source with tube voltage of 100KV and tube current of 1mA is adopted to be matched with Zulihan light SBP-300 lightThe spectrometer instrument measures the scintillation luminescence spectrum of the sample as shown in figure 2.
Example 1:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 3:
TABLE 3
Figure BDA0003539357470000071
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 400 ℃ for 1 hour and naturally cooled.
Example 2:
the raw materials have the compositions shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 4:
TABLE 4
Figure BDA0003539357470000072
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heatedHeat treatment was carried out at a temperature of 420 c for 6 hours and natural cooling was carried out.
Example 3:
the raw materials have the compositions shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 5:
TABLE 5
Figure BDA0003539357470000081
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, then cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 430 ℃ for 3 hours and naturally cooled. The photoluminescence spectrum of a sample measured by an FLS920 instrument of Edinburgh company in England is shown in figure 1, and the scintillation spectrum of the sample measured by an X-ray source with the tube voltage of 100KV and the tube current of 1mA is shown in figure 2 by matching with an SBP-300 spectrum instrument of Touhahan light.
Example 4:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 6:
TABLE 6
Figure BDA0003539357470000082
Putting the weighed raw materials into a corundum mortar, and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; quickly transferring the glass to a temperature of 350 DEG CAnnealing in an annealing furnace, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 430 ℃ for 11 hours and naturally cooled.
Example 5:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 7:
TABLE 7
Figure BDA0003539357470000091
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (2). Subsequently, the glass sample was heat-treated at 430 ℃ for 3 hours and naturally cooled to obtain Al-containing glass3+CsPbBr of3The quantum dot glass has a transparent sample and a yellow-green color. The photoluminescence spectrum of a sample measured by an FLS920 instrument of Edinburgh company in England is shown in figure 1, and the scintillation spectrum of the sample measured by an X-ray source with the tube voltage of 100KV and the tube current of 1mA is shown in figure 2 by matching with an SBP-300 spectrum instrument of Touhahan light.
There is no known literature that is available for doping Al3+To enhance CsPbBr3Reports of photoluminescence and scintillation of quantum dot glasses compared to Al-free in comparative example 13+CsPbBr of3Quantum dot glass, in this example Al3+CsPbBr3The photoluminescence intensity and the scintillation intensity of the quantum dot glass are respectively enhanced by 8 times and 6 timesThe quantum efficiency increased from 43% to 76%, and in particular, the scintillation luminescence intensity was 1.7 times that of BGO.
Example 6:
the raw materials have the compositions shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 8:
TABLE 8
Figure BDA0003539357470000101
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, then cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 460 ℃ for 9 hours and naturally cooled.
Example 7:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 9:
TABLE 9
Figure BDA0003539357470000111
Putting the weighed raw materials into a corundum mortar, and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3Glass ofAnd (5) blocking. Subsequently, the glass sample was heat-treated at a temperature of 430 ℃ for 3 hours and naturally cooled. The photoluminescence spectrum of a sample measured by an FLS920 instrument of Edinburgh company in England is shown in figure 1, and the scintillation spectrum of the sample measured by an X-ray source with the tube voltage of 100KV and the tube current of 1mA is shown in figure 2 by matching with a Zebra light SBP-300 spectrum instrument.
Example 8:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 10:
watch 10
Figure BDA0003539357470000112
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, then cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 420 ℃ for 3 hours and naturally cooled.
Example 9:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 11:
TABLE 11
Figure BDA0003539357470000121
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; glass to be combinedRapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 410 ℃ for 9 hours and naturally cooled.
Example 10:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing schemes are as in table 12:
TABLE 12
Figure BDA0003539357470000122
Figure BDA0003539357470000131
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 440 ℃ for 12 hours and naturally cooled.
Example 11:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 13:
watch 13
Figure BDA0003539357470000132
Putting the weighed raw materials into a steel frameUniformly mixing in a jade mortar to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 460 ℃ for 18 hours and naturally cooled.
Example 12:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 14:
TABLE 14
Figure BDA0003539357470000141
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, then cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 480 ℃ for 10 hours and naturally cooled.
Example 13:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing protocol is as in table 15:
watch 15
Figure BDA0003539357470000142
The weighed materials are mixedPutting the materials into a corundum mortar, and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving the heat for 4 hours, then cooling the glass to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at a temperature of 450 ℃ for 4 hours and naturally cooled.
Example 14:
the raw materials are shown in table 1, and the specific preparation process is as follows:
the weighing schemes are as in table 16:
TABLE 16
Figure BDA0003539357470000151
Putting the weighed raw materials into a corundum mortar and uniformly mixing to obtain a mixture; putting the mixture into a covered alumina crucible, melting in a silicon carbide rod electric furnace at 1000 ℃, and pouring molten glass on a stainless steel mold preheated to 350 ℃ after 13 minutes; rapidly transferring the glass to an annealing furnace which is heated to 350 ℃ for annealing, preserving heat for 4 hours, cooling to room temperature along with the furnace, and taking out a glass sample after complete cooling to obtain colorless and transparent glass; cutting, polishing, and processing into 10 × 10 × 2mm3The glass block of (1). Subsequently, the glass sample was heat-treated at 470 ℃ for 8 hours and naturally cooled.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims (8)

1. Doped Al3+CsPbBr of3The quantum dot glass-ceramic is characterized in that the glass comprises the following components in percentage by molThe raw materials by weight ratio are as follows: p2O5 8-23mol％，Na2O 2-11mol％，K2O 0-10mol％，ZnO7-16mol％，Al2O3 1-30mol％，B2O3 20-65mol％，Cs2O 3-14mol％，PbBr2 1-8mol％，NaBr 1-10mol％。
2. Al-doped according to claim 13+CsPbBr of3The quantum dot glass ceramic is characterized in that the glass is composed of the following raw materials in mol percentage: the glass consists of the following raw materials in percentage by mole: p2O5 15mol％，Na2O 5mol％，K2O 5mol％，ZnO 10mol％，Al2O3 1-26mol％，B2O324-50mol％，Cs2O 7mol％，PbBr23mol％，NaBr 5mol％。
3. Al-doped according to claim 1 or 23+CsPbBr of3The preparation method of the quantum dot glass ceramic is characterized by comprising the following steps:
calculating the mass of each corresponding glass composition according to the composition and the mole percentage of the raw materials, and accurately weighing each raw material;
secondly, grinding the weighed raw materials in a corundum mortar, and uniformly mixing to form a mixture;
thirdly, putting the mixture into a covered alumina crucible to melt in a high-temperature furnace, taking out the crucible after the mixture is completely melted, and pouring clear molten glass on a preheated stainless steel mold to obtain transparent glass;
quickly transferring the glass to a muffle furnace for annealing treatment, preserving heat, then cooling along with the furnace, taking out the glass, and cutting and polishing to form polished glass;
fifthly, the polished glass is further subjected to heat treatment and naturally cooled to obtain the doped Al3+CsPbBr of3Quantum dot glass-ceramics.
4. The method according to claim 3Characterized in that said P2O5From NaPO3、KPO3And Al (PO)3)3Introduction of the Na2O and K2O is respectively prepared from NaPO3And KPO3Introduction of the Al2O3From Al (PO)3)3Introduction of B2O3From H3BO3Introduction of said Cs2O from Cs2CO3And (4) introducing.
5. The method of claim 3, wherein the annealing temperature is 30-50 ℃ below the Tg.
6. The method of claim 3, wherein the incubation time is 4-8 hours.
7. The method as claimed in claim 3, wherein the heat treatment temperature is 400-490 ℃.
8. The method of claim 3, wherein the heat treatment time is 1 to 48 hours.
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CN115504673A (en) * 2022-09-27 2022-12-23 中国科学院上海光学精密机械研究所 CsPbBr 3 Quantum dot glass ceramic and preparation method thereof
CN115583799A (en) * 2022-08-30 2023-01-10 昆明理工大学 Photochromic-based anti-counterfeiting glass powder and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113233775A (en) * 2021-06-17 2021-08-10 中国科学院上海光学精密机械研究所 Nano-Ag reinforced CsPbBr3Quantum dot glass and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113233775A (en) * 2021-06-17 2021-08-10 中国科学院上海光学精密机械研究所 Nano-Ag reinforced CsPbBr3Quantum dot glass and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115583799A (en) * 2022-08-30 2023-01-10 昆明理工大学 Photochromic-based anti-counterfeiting glass powder and preparation method thereof
CN115583799B (en) * 2022-08-30 2024-05-31 昆明理工大学 Photochromic-based anti-counterfeiting glass powder and preparation method thereof
CN115504673A (en) * 2022-09-27 2022-12-23 中国科学院上海光学精密机械研究所 CsPbBr 3 Quantum dot glass ceramic and preparation method thereof
CN115504673B (en) * 2022-09-27 2023-08-11 中国科学院上海光学精密机械研究所 CsPbBr 3 Quantum dot glass ceramic and preparation method thereof

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