CN114133141A - Perovskite quantum dot glass ceramic and preparation method thereof - Google Patents
Perovskite quantum dot glass ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN114133141A CN114133141A CN202111629668.9A CN202111629668A CN114133141A CN 114133141 A CN114133141 A CN 114133141A CN 202111629668 A CN202111629668 A CN 202111629668A CN 114133141 A CN114133141 A CN 114133141A
- Authority
- CN
- China
- Prior art keywords
- glass
- perovskite quantum
- quantum dot
- cooling
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of microcrystalline glass, in particular to perovskite quantum dot microcrystalline glass and a preparation method thereof. The preparation method comprises the following steps: A) melting the glass raw material, cooling and forming, and then annealing to obtain perovskite quantum dot base glass; the glass raw material comprises B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr; b is2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr in a molar ratio of 30-60: 29-59: 9: 2-10: 4-12: 0-12: 3-9; B) and performing thermoelectric treatment on the base glass at 480-550 ℃, 100-1500V of voltage and 20-500 Hz of voltage in a nitrogen atmosphere to obtain the perovskite quantum dot glass ceramics, wherein the quantum conversion efficiency is high, and the size of the perovskite quantum dots is controllable.
Description
Technical Field
The invention relates to the technical field of microcrystalline glass, in particular to perovskite quantum dot microcrystalline glass and a preparation method thereof.
Background
The perovskite quantum dot glass is mainly applied to the optical field and the energy field. The perovskite quantum dot glass is a luminescent material with excellent performance, and can emit light with different wavelengths through light excitation when being coupled with a device, and has high photoluminescence quantum yield and narrow emission wavelength, so that the perovskite quantum dot glass has huge application potential on diodes, lasers and photodetectors. Meanwhile, the perovskite quantum dot glass is widely applied to the field of energy. The perovskite quantum dot glass can be used for manufacturing solar cells, has high energy conversion efficiency, and is expected to replace single crystal silicon solar cells.
The traditional perovskite quantum belongs to inorganic-organic hybrid perovskite, and compared with inorganic perovskite quantum dot glass, the energy band structure of the traditional perovskite quantum is easy to adjust, and higher quantum yield can be realized. However, the inorganic-organic hybrid perovskite has the defects of unstable structure and easy influence of moisture and oxygen in the environment. And the perovskite quantum dot glass can effectively protect the perovskite quantum dots from environmental influence because the exterior of the perovskite quantum dots is wrapped by the glass phase. At present, the perovskite quantum dot glass adopts a borate glass system. Phase separation can occur during heat treatment of the borate glass, boron-oxygen triangles and boron-oxygen tetrahedrons inside the glass are mutually converted at the moment, the structure inside the borate glass is changed, and perovskite quantum dots grow in the gap between the boron-oxygen triangles and the boron-oxygen tetrahedrons. Therefore, the ratio of boron-oxygen trigones to boron-oxygen tetrahedra is particularly important for perovskite quantum dot deposition. In addition, the perovskite quantum dots deposited in the borate glass need to be solved that the glass components and the elements consisting of perovskite need to be mutually soluble, and only the glass with specific components can precipitate the perovskite quantum dots. Meanwhile, when the perovskite quantum dots are separated out from the perovskite quantum dot glass, Cs, Pb and Br elements are distributed and differentiated in the glass, so that the perovskite quantum dots are distributed and differentiated, and meanwhile, the perovskite is low in crystallinity, and the performance of the perovskite is affected.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a perovskite quantum dot glass ceramic and a preparation method thereof, and the perovskite quantum dot glass ceramic prepared by the present invention has high quantum conversion efficiency.
The invention provides a preparation method of perovskite quantum dot glass ceramics, which comprises the following steps:
A) melting the glass raw material, cooling and forming, and then annealing to obtain perovskite quantum dot base glass;
the glass raw material comprises B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr; b is2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr in a molar ratio of 30-60: 29-59: 8-9: 2-10: 4-12: 0-12: 3-9;
B) performing thermoelectric treatment on the perovskite quantum dot base glass in a nitrogen atmosphere to obtain perovskite quantum dot microcrystalline glass;
the temperature of the thermoelectric treatment is 480-550 ℃, the voltage is 100-1500V, and the frequency of the voltage is 20-500 Hz.
Preferably, in the step A), the melting temperature is 1150-1250 ℃ and the time is 8-12 min.
Preferably, in the step A), the temperature for cooling and forming is 290-310 ℃.
Preferably, in the step A), the annealing temperature is 330-370 ℃ and the annealing time is 18-22 h.
Preferably, step B) further includes, before the thermoelectric treatment:
and cutting the perovskite quantum dot base glass, and then polishing the surface of the cut glass.
Preferably, the step B) of subjecting the perovskite quantum dot base glass to thermoelectric treatment in a nitrogen atmosphere comprises:
in the nitrogen atmosphere, heating the perovskite quantum dot base glass to 480-550 ℃, preserving heat for 5-8 hours, applying an electric field, and processing for 5-8 hours at 480-550 ℃, 100-1500V voltage and 20-500 Hz voltage frequency.
Preferably, the heating rate is 8-12 ℃/min.
Preferably, the step B) further comprises, after the thermoelectric treatment: cooling;
the cooling rate is 0.5-1.5 ℃/min;
the temperature after cooling is 130-170 ℃.
Preferably, after the temperature reduction, the method further comprises: cooling to room temperature along with the furnace.
The invention also provides the perovskite quantum dot glass ceramics prepared by the preparation method.
The invention adopts specific components with specific proportion, can be quickly melted at lower melting temperature, and avoids the volatilization of halogen elements. Meanwhile, the perovskite quantum dot base glass prepared from the specific components in specific proportions can be subjected to phase splitting at about 500 ℃, so that perovskite quantum dots are separated out, a borosilicate glass phase can be formed at the periphery of the quantum dots in an in-situ crystallization mode, and the perovskite quantum dots are protected from being influenced by the environment by the spherical shell structure. Furthermore, the introduction of an electric field can reduce the perovskite CsPbBr3The crystallization activation energy of (a) is required to be shorter, and meanwhile, the thermoelectric treatment can improve the quantum conversion efficiency. Therefore, the obtained perovskite quantum dot glass ceramics have high quantum conversion efficiency and controllable size of perovskite quantum dots.
Drawings
Fig. 1 is a TEM image of the perovskite quantum dot glass ceramics of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 provides a preparation method of perovskite quantum dot glass ceramics, which comprises the following steps:
A) melting the glass raw material, cooling and forming, and then annealing to obtain perovskite quantum dot base glass;
the glass raw material comprises B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr; what is needed isB above2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr in a molar ratio of 30-60: 29-59: 9: 2-10: 4-12: 0-12: 3-9;
B) performing thermoelectric treatment on the perovskite quantum dot base glass in a nitrogen atmosphere to obtain perovskite quantum dot microcrystalline glass;
the temperature of the thermoelectric treatment is 480-550 ℃, the voltage is 100-1500V, and the frequency of the voltage is 20-500 Hz.
The invention firstly melts the raw material of the glass, then cools and shapes the glass, and then carries out annealing to prepare the perovskite quantum dot base glass.
In the present invention, the glass raw material includes B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr; b is2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr in a molar ratio of 30-60: 29-59: 8-9: 2-10: 4-12: 0-12: 3 to 9. In certain embodiments of the invention, B is2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr at a molar ratio of 30: 49: 9: 2: 4: 2: 3. 50: 25: 9: 10: 12: 2: 9. 35: 30: 9: 10: 12: 2: 4. 33: 30: 9: 10: 8: 2: 7. 38: 34: 8: 9: 6: 12: 5 or 36: 32: 9: 10: 10: 0: 9.
in some embodiments of the present invention, before melting the glass raw materials, the method further comprises: and ball-milling and uniformly mixing the glass raw materials. The method for ball milling and blending is not particularly limited in the present invention, and a method for ball milling and blending known to those skilled in the art may be used.
In some embodiments of the present invention, the melting temperature is 1150-1250 ℃ and the time is 8-12 min. In certain embodiments, the temperature of the melting is 1200 ℃. In certain embodiments, the time for the melting is 10 min. In certain embodiments of the invention, the melting is performed in a silicon carbide rod furnace.
In some embodiments of the present invention, the temperature of the cooling forming is 290-310 ℃. In certain embodiments, the temperature of the cold forming is 300 ℃.
In certain embodiments of the present invention, the method of cold forming comprises:
and pouring the molten glass raw material on an iron plate at 290-310 ℃ for cooling and forming.
In some embodiments of the invention, the annealing temperature is 330-370 ℃ and the annealing time is 18-22 h. In certain embodiments, the annealing is at a temperature of 350 ℃ for a period of 20 hours.
In certain embodiments of the invention, the annealing is performed in a precision annealing furnace.
In some embodiments of the present invention, after the annealing, further comprising: cooling to room temperature along with the furnace.
And after obtaining the perovskite quantum dot base glass, performing thermoelectric treatment on the perovskite quantum dot base glass in a nitrogen atmosphere to obtain the perovskite quantum dot microcrystalline glass.
In some embodiments of the present invention, before the thermoelectric treatment, the method further comprises:
and cutting the perovskite quantum dot base glass, and then polishing the surface of the cut glass.
In certain embodiments of the invention, the cut glass is a glass wafer having a diameter of 1cm and a thickness of 0.5 cm. In certain embodiments of the invention, the cutting employs a laser cutter.
In some embodiments of the invention, the polishing is performed by polishing the upper and lower surfaces of the cut glass using a polishing machine. The upper and lower surfaces of the glass after cutting and polishing are mutually attached to the electrode device in the thermocouple device, and the shape of the glass wafer is used for better illuminating the coupling device.
In the invention, the thermoelectric treatment is carried out in a nitrogen atmosphere, and the nitrogen atmosphere can avoid the adhesion of electrode oxidation and glass.
In certain embodiments of the invention, the thermoelectric treatment of the perovskite quantum dot base glass under a nitrogen atmosphere comprises:
in the nitrogen atmosphere, heating the perovskite quantum dot base glass to 480-550 ℃, preserving heat for 5-8 hours, applying an electric field, and processing for 5-8 hours at 480-550 ℃, 100-1500V voltage and 20-500 Hz voltage frequency.
In certain embodiments of the invention, the post-ramp temperature is 500 ℃, 530 ℃, 510 ℃, or 540 ℃. In certain embodiments of the invention, the incubation time is 5 hours, 6 hours, or 7 hours.
In certain embodiments of the invention, the treatment temperature after application of the electric field is 500 ℃, 530 ℃, 510 ℃, or 540 ℃. In certain embodiments of the present invention, the voltage is 1500V, 1000V, 500V, or 100V. In certain embodiments of the invention, the voltage frequency is 500Hz, 250Hz, 20Hz or 100 Hz. In certain embodiments of the invention, the time of the treatment is 5 h.
In some embodiments of the present invention, the temperature raising rate is 8-12 ℃/min. In certain embodiments, the rate of temperature increase is 10 ℃/min.
Initiation of thermoelectric treatment, CsPbBr3The quantum dots begin to deposit in the glass and the electric field to CsPbBr over the heat treatment time3The distribution of quantum dots has influence, Pb ions are particularly obvious to express and migrate along the direction of an electric field in the glass, and therefore, the perovskite quantum dots which are not uniformly distributed in the glass due to component difference are homogenized. The voltage magnitude and voltage frequency parameters are changed, so that the migration activation of Cs, Pb and Br elements forming the perovskite is changed, and the size and the number of quantum dots deposited in the glass are changed.
In some embodiments of the present invention, after the thermoelectric treatment, the method further comprises: and (5) cooling.
In some embodiments of the present invention, the cooling rate is 0.5-1.5 ℃/min. In certain embodiments, the rate of cooling is 1 ℃/min.
In some embodiments of the present invention, the temperature after the temperature reduction is 130 to 170 ℃. In certain embodiments, the reduced temperature is 150 ℃.
In some embodiments of the present invention, after the cooling, the method further includes: cooling to room temperature along with the furnace.
According to the preparation method of the perovskite quantum dot glass ceramic, the borate glass is prepared firstly, then the borate glass is subjected to in-situ crystallization, and due to the charge difference carried by the boron-oxygen triangle and the boron-oxygen tetrahedron in the borate glass, the boron-containing phase and the glass phase are subjected to the action difference of an electric field, so that the boron-containing phase and the glass phase are separated in an accelerated manner in the electric field, and CsPbBr3Accelerating the precipitation from the glass phase and reducing the deposition time of the perovskite quantum dots. Because the borosilicate ratio between the regions is different inevitably in the glass melting process, the proportion of the boron-oxygen triangle and the boron-oxygen tetrahedron fluctuates in different regions, and after an electric field is introduced, the distribution of perovskite quantum dots is more uniform than that of a thermal field under the unified action of the electric field, the size and the number of the perovskite quantum dots can be adjusted, and the electric field parameters can be realized.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention also provides the perovskite quantum dot glass ceramics prepared by the preparation method.
In certain embodiments of the present invention, the perovskite quantum dot glass ceramics have the size of perovskite quantum dots within 3-25 nm. In some embodiments, the perovskite quantum dot glass ceramics have the size of perovskite quantum dots within the range of 10-15 nm, 15-25 nm, 3-7 nm, 5-10 nm or 8-12 nm.
In certain embodiments of the present invention, the perovskite quantum dot glass ceramics have a quantum conversion efficiency of 35% to 52%.
The invention adopts specific components with specific proportion, can be quickly melted at lower melting temperature, and avoids the volatilization of halogen elements. Meanwhile, the perovskite quantum dot base glass prepared from the specific components in specific proportions can be subjected to phase splitting at about 500 ℃, so that perovskite quantum dots are separated out, a borosilicate glass phase can be formed at the periphery of the quantum dots in an in-situ crystallization mode, and the perovskite quantum dots are protected from being influenced by the environment by the spherical shell structure. Furthermore, introduction of an electric field can reduce perovskiteMine CsPbBr3The crystallization activation energy of (a) is required to be shorter, and meanwhile, the thermoelectric treatment can improve the quantum conversion efficiency.
In order to further illustrate the present invention, the following detailed description of the perovskite quantum dot glass ceramics and the preparation method thereof provided by the present invention is made in conjunction with the examples, but the present invention should not be construed as limiting the scope of the present invention.
In the following examples, the starting materials were all used in analytical purity.
Example 1
The glass raw materials comprise the following components in a molar ratio of 30: 49: 9: 2: 4: 2: 3B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 500 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 5h, applying an electric field, processing for 5h at a temperature of 500 ℃, a voltage of 1500V and a voltage frequency of 500Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) performing transmission electron microscope analysis on the perovskite quantum dot glass ceramics to obtain a TEM image of the perovskite quantum dot glass ceramics, as shown in FIG. 1. Fig. 1 is a TEM image of the perovskite quantum dot glass ceramics of example 1 of the present invention. As can be seen from FIG. 1, the perovskite quantum dot size of the perovskite quantum dot glass ceramics is 10-15 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 35 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and experimental results show that the fluorescence lifetime is 23.13 ns.
Example 2
The glass raw materials comprise the following components in a molar ratio of 50: 25: 9: 10: 12: 2: 9B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 530 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 7h, applying an electric field, processing for 5h at a temperature of 530 ℃, a voltage of 1000V and a voltage frequency of 250Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) carrying out transmission electron microscope analysis on the perovskite quantum dot glass ceramics, wherein experimental results show that the size of the perovskite quantum dots of the perovskite quantum dot glass ceramics is 15-25 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 50 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and the experimental result shows that the fluorescence lifetime is 34.21 ns.
Example 3
The glass raw materials comprise the following components in a molar ratio of 35: 30: 9: 10: 12: 2: 4B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 530 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 6h, applying an electric field, processing for 5h at a temperature of 530 ℃, a voltage of 1500V and a voltage frequency of 20Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) carrying out transmission electron microscope analysis on the perovskite quantum dot glass ceramics, wherein experimental results show that the size of the perovskite quantum dots of the perovskite quantum dot glass ceramics is 10-15 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 52 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and the experimental result shows that the fluorescence lifetime is 40.21 ns.
Example 4
The glass raw materials comprise the following components in a molar ratio of 33: 30: 9: 10: 8: 2: 7B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 500 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 7h, applying an electric field, processing for 5h at a temperature of 500 ℃, a voltage of 500V and a voltage frequency of 100Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) carrying out transmission electron microscope analysis on the perovskite quantum dot glass ceramics, wherein experimental results show that the size of the perovskite quantum dots of the perovskite quantum dot glass ceramics is 3-7 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 46 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and the experimental result shows that the fluorescence lifetime is 32.56 ns.
Example 5
The glass raw materials comprise a raw material with a molar ratio of 38: 34: 8: 9: 6: 12: 5B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 510 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 7h, applying an electric field, processing for 5h at the temperature of 510 ℃, the voltage of 100V and the voltage frequency of 20Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) carrying out transmission electron microscope analysis on the perovskite quantum dot glass ceramics, wherein experimental results show that the size of the perovskite quantum dots of the perovskite quantum dot glass ceramics is 5-10 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 39 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and the experimental result shows that the fluorescence lifetime is 26.67 ns.
Example 6
The glass raw materials comprise the following components in a molar ratio of 36: 32: 9: 10: 10: 0: 9B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr, the total mass of the glass raw material is 100 g;
1. ball-milling and uniformly mixing the glass raw materials by using a ball mill, putting the mixture into a silicon-carbon rod furnace, melting the mixture at the furnace temperature of 1200 ℃, pouring the mixture on a 300-DEG C iron plate after 10min, cooling the mixture for forming, putting the mixture into a 350-DEG C precision annealing furnace for annealing for 20h, and cooling the mixture to room temperature along with the furnace to obtain perovskite quantum dot base glass;
2. cutting the perovskite quantum dot base glass into glass wafers with the diameter of 1cm and the thickness of 0.5cm by using a laser cutter, polishing the upper and lower surfaces of the glass wafers by using a polishing machine, and after polishing, mutually attaching the upper and lower surfaces of the glass wafers to an electrode device in a thermocouple device;
heating the glass wafer to 540 ℃ at a speed of 10 ℃/min under the nitrogen atmosphere, preserving heat for 5h, applying an electric field, processing for 5h at a temperature of 540 ℃, a voltage of 1500V and a voltage frequency of 20Hz, stopping heating after the electric field is finished, cooling the furnace temperature to 150 ℃ at a speed of 1 ℃/min, and cooling to the room temperature along with the furnace to obtain the perovskite quantum dot glass ceramics.
And (3) carrying out transmission electron microscope analysis on the perovskite quantum dot glass ceramics, wherein experimental results show that the size of the perovskite quantum dots of the perovskite quantum dot glass ceramics is 8-12 nm.
The perovskite quantum dot glass ceramics measured by an Edinburgh FLS1000 fluorescence spectrometer have the quantum conversion efficiency of 37 percent.
The perovskite quantum dot glass ceramics are subjected to fluorescence lifetime test by adopting a steady-state transient fluorescence spectrum analyzer, and the experimental result shows that the fluorescence lifetime is 34.21 ns.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of perovskite quantum dot glass ceramics comprises the following steps:
A) melting the glass raw material, cooling and forming, and then annealing to obtain perovskite quantum dot base glass;
the glass raw material comprises B2O3、SiO2、ZnO、Na2CO3、Cs2CO3、PbBr2And NaBr; b is2O3、SiO2、ZnO、Na2CO3、Cs2CO3And NaBr in a molar ratio of 30-60: 29-59: 8-9: 2-10: 4-12: 0-12: 3-9;
B) performing thermoelectric treatment on the perovskite quantum dot base glass in a nitrogen atmosphere to obtain perovskite quantum dot microcrystalline glass;
the temperature of the thermoelectric treatment is 480-550 ℃, the voltage is 100-1500V, and the frequency of the voltage is 20-500 Hz.
2. The method according to claim 1, wherein the melting temperature in step A) is 1150-1250 ℃ for 8-12 min.
3. The method according to claim 1, wherein the temperature of the cooling molding in step A) is 290 to 310 ℃.
4. The preparation method according to claim 1, wherein in the step A), the annealing temperature is 330-370 ℃ and the annealing time is 18-22 h.
5. The method according to claim 1, wherein the step B) further comprises, before the thermoelectric treatment:
and cutting the perovskite quantum dot base glass, and then polishing the surface of the cut glass.
6. The method of manufacturing according to claim 1, wherein the step B) of subjecting the perovskite quantum dot base glass to thermoelectric treatment under a nitrogen atmosphere comprises:
in the nitrogen atmosphere, heating the perovskite quantum dot base glass to 480-550 ℃, preserving heat for 5-8 hours, applying an electric field, and processing for 5-8 hours at 480-550 ℃, 100-1500V voltage and 20-500 Hz voltage frequency.
7. The method according to claim 6, wherein the temperature rise rate is 8 to 12 ℃/min.
8. The method according to claim 1, wherein the step B) further comprises, after the thermoelectric treatment: cooling;
the cooling rate is 0.5-1.5 ℃/min;
the temperature after cooling is 130-170 ℃.
9. The method of claim 8, further comprising, after the cooling: cooling to room temperature along with the furnace.
10. The perovskite quantum dot glass ceramics prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111629668.9A CN114133141B (en) | 2021-12-28 | 2021-12-28 | Perovskite quantum dot glass ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111629668.9A CN114133141B (en) | 2021-12-28 | 2021-12-28 | Perovskite quantum dot glass ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114133141A true CN114133141A (en) | 2022-03-04 |
| CN114133141B CN114133141B (en) | 2022-12-06 |
Family
ID=80383779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111629668.9A Active CN114133141B (en) | 2021-12-28 | 2021-12-28 | Perovskite quantum dot glass ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114133141B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650591A (en) * | 2022-10-28 | 2023-01-31 | 福建师范大学 | Perovskite quantum dot glass material and preparation method of film thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556053A (en) * | 2004-01-12 | 2004-12-22 | 同济大学 | Preparaton method of distribution controllable nano-crystal and micro crystal glass |
| US20170233645A1 (en) * | 2014-11-04 | 2017-08-17 | Shenzhen Tcl New Technology Co., Ltd | Perovskite quantum dot material and preparation method thereof |
| CN109761498A (en) * | 2018-12-31 | 2019-05-17 | 温州大学 | A kind of KxCs1-xPbBr3Devitrified glass and preparation method thereof |
| CN109987848A (en) * | 2019-03-22 | 2019-07-09 | 昆明理工大学 | One kind containing CsPbBr3Quantum-dot superlattice structure glass and preparation method thereof |
| CN110194593A (en) * | 2019-05-08 | 2019-09-03 | 杭州电子科技大学 | A method of full-inorganic perovskite quantum dot crystallization in glass is promoted by addition fluoride |
| CN110294597A (en) * | 2019-05-28 | 2019-10-01 | 华南农业大学 | A kind of width colour gamut, which show, uses caesium lead bromine perovskite quantum dot fluorescence glass and its preparation method and application |
| CN111233337A (en) * | 2020-03-03 | 2020-06-05 | 五邑大学 | Green light emitting microcrystalline glass for wide color gamut backlight display and preparation method thereof |
| CN112047635A (en) * | 2020-09-17 | 2020-12-08 | 昆明理工大学 | Preparation method and application of efficient all-inorganic perovskite quantum dot glass |
| CN112159110A (en) * | 2020-10-10 | 2021-01-01 | 陕西科技大学 | Energy storage glass ceramic capable of adjusting ferroelectricity by controlling crystallization power, preparation method and application |
| CN112876084A (en) * | 2020-12-25 | 2021-06-01 | 温州大学 | Quantum dot glass ceramics and preparation method thereof and method for preparing quantum dot glass ceramics product by applying 3D printing technology |
| 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 |
-
2021
- 2021-12-28 CN CN202111629668.9A patent/CN114133141B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556053A (en) * | 2004-01-12 | 2004-12-22 | 同济大学 | Preparaton method of distribution controllable nano-crystal and micro crystal glass |
| US20170233645A1 (en) * | 2014-11-04 | 2017-08-17 | Shenzhen Tcl New Technology Co., Ltd | Perovskite quantum dot material and preparation method thereof |
| CN109761498A (en) * | 2018-12-31 | 2019-05-17 | 温州大学 | A kind of KxCs1-xPbBr3Devitrified glass and preparation method thereof |
| CN109987848A (en) * | 2019-03-22 | 2019-07-09 | 昆明理工大学 | One kind containing CsPbBr3Quantum-dot superlattice structure glass and preparation method thereof |
| CN110194593A (en) * | 2019-05-08 | 2019-09-03 | 杭州电子科技大学 | A method of full-inorganic perovskite quantum dot crystallization in glass is promoted by addition fluoride |
| CN110294597A (en) * | 2019-05-28 | 2019-10-01 | 华南农业大学 | A kind of width colour gamut, which show, uses caesium lead bromine perovskite quantum dot fluorescence glass and its preparation method and application |
| CN111233337A (en) * | 2020-03-03 | 2020-06-05 | 五邑大学 | Green light emitting microcrystalline glass for wide color gamut backlight display and preparation method thereof |
| CN112047635A (en) * | 2020-09-17 | 2020-12-08 | 昆明理工大学 | Preparation method and application of efficient all-inorganic perovskite quantum dot glass |
| CN112159110A (en) * | 2020-10-10 | 2021-01-01 | 陕西科技大学 | Energy storage glass ceramic capable of adjusting ferroelectricity by controlling crystallization power, preparation method and application |
| CN112876084A (en) * | 2020-12-25 | 2021-06-01 | 温州大学 | Quantum dot glass ceramics and preparation method thereof and method for preparing quantum dot glass ceramics product by applying 3D printing technology |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650591A (en) * | 2022-10-28 | 2023-01-31 | 福建师范大学 | Perovskite quantum dot glass material and preparation method of film thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114133141B (en) | 2022-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5786179B2 (en) | Gallium oxide single crystal and manufacturing method thereof | |
| CN104529166B (en) | A kind of Ce：YAG devitrified glasses and its application in white light LEDs | |
| CN114133141B (en) | Perovskite quantum dot glass ceramic and preparation method thereof | |
| CN102765883B (en) | Preparation method of YAG microcrystalline glass | |
| CN112281213A (en) | Rare earth doping (Lu)aScbYc)2O3(a + b + c = 1) single crystal optical fiber, and preparation method and application thereof | |
| CN104692658A (en) | Method for fixing CdS and Se in borosilicate glass | |
| CN106007385B (en) | The preparation method of Surface Crystallization devitrified glass | |
| CN102368502A (en) | Zinc oxide film doped with Al and preparation method thereof | |
| US10577278B2 (en) | Glass ceramic for excitation of high-power semiconductor light source and preparation method and use thereof | |
| CN104909741B (en) | Preparation method of garnet type aluminate fluorescent ceramic and prepared fluorescent ceramic | |
| KR20120097832A (en) | Fabrication method of silicate glass including lead sulfide quantum dots containing rare earth metal | |
| CN1955130A (en) | Glass ceramic and its preparation method | |
| JP4158926B2 (en) | Method for producing β-FeSi2 using laser annealing | |
| CN105948511A (en) | Near-infrared luminescence transparent glass ceramic and preparation method thereof | |
| CN103304142B (en) | Manufacturing method of spontaneous crystallization type up-conversion luminescence transparent glass ceramics | |
| CN109180011B (en) | PbTe/CdTe double quantum dot co-doped borosilicate glass and preparation process thereof | |
| CN1331791C (en) | Neodymium doped borate glass with high luminous quantum efficiency and its preparing method | |
| Shyu et al. | ZrO2-nucleated calcium aluminate glass-ceramics with mid-infrared transparency | |
| Singh et al. | Intense photoluminescence from erbium-doped tantalum oxide thin films deposited by sputtering | |
| CN111362580B (en) | Glass ceramic and preparation method thereof | |
| JP2007063048A (en) | Semiconductor ingot and method for producing solar cell element | |
| CN101205116A (en) | Nd-doped Li2O-Al2O3-SiO2 series transparent laser glass ceramics and method for making same | |
| CN112499974B (en) | Precipitation of Mg 3 (BO 3 )F 3 Nanocrystalline glass ceramics and preparation method thereof | |
| CN116768466B (en) | Method for reducing core crystal segregation in single crystal glass composite optical fiber | |
| CN116282928B (en) | Gallium/zinc aluminate doped near-infrared tellurium germanate nanocrystalline glass and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |