CN109928640B - Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof - Google Patents

Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof Download PDF

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CN109928640B
CN109928640B CN201910264958.4A CN201910264958A CN109928640B CN 109928640 B CN109928640 B CN 109928640B CN 201910264958 A CN201910264958 A CN 201910264958A CN 109928640 B CN109928640 B CN 109928640B
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林常规
王景松
赵旭浩
刘雪云
焦清
张培晴
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Ningbo University
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Abstract

本发明公开的无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料的摩尔组成按化学式表示为:(1‑x‑y‑z)GeS2·xSb2S3·yGa2S3·zCsPbX3,其中,x=0.15~0.75,y=0.05~0.2,z=0.05~0.1,X为Cl、Br或I,CsPbX3以析出的纳米晶形式复合于该硫系玻璃陶瓷材料中。该材料在2~10微米光谱范围内透明,具有较好的热学和化学稳定性、良好的断裂韧性,适于进行稀土离子掺杂研发新型中红外发光或激光材料以及相关的量子点发光材料。该材料的制备方法以GeS2‑Sb2S3‑Ga2S3为玻璃基质,引入接近饱和的CsPbX3成分,使用熔融淬冷法制备出基础硫系玻璃,然后通过析晶热处理,可控制析出CsPbX3纳米晶。该材料的制备方法能够根据功能需要设计和选择合适的玻璃组成,控制析出CsPbX3晶粒尺寸与分布。

Figure 201910264958

The molar composition of the inorganic lead halide cesium nanocrystalline composite chalcogenide glass-ceramic material disclosed in the present invention is represented by the chemical formula as: (1-x-y-z)GeS 2 ·xSb 2 S 3 ·yGa 2 S 3 · zCsPbX 3 , wherein , x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X is Cl, Br or I, CsPbX 3 is compounded in the chalcogenide glass ceramic material in the form of precipitated nanocrystals. The material is transparent in the spectral range of 2-10 microns, has good thermal and chemical stability, and good fracture toughness, and is suitable for rare earth ion doping to develop new mid-infrared light-emitting or laser materials and related quantum dot light-emitting materials. The preparation method of the material uses GeS 2 ‑Sb 2 S 3 ‑Ga 2 S 3 as a glass matrix, introduces a nearly saturated CsPbX 3 component, uses a melting quenching method to prepare a basic chalcogenide glass, and then undergoes crystallization heat treatment, which can be controlled CsPbX3 nanocrystals were precipitated. The preparation method of the material can design and select an appropriate glass composition according to functional requirements, and control the size and distribution of the precipitated CsPbX 3 grains.

Figure 201910264958

Description

Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof
Technical Field
The invention belongs to the field of functional glass ceramic materials, and particularly relates to an inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and a preparation method thereof, which can be applied to the fields of infrared optics and photonics.
Background
Inorganic perovskite CsPbX3The (X ═ Cl, Br, I) nanocrystals have the advantages of unique optical versatility, high luminescence quantum efficiency, and easy preparation, and have attracted extensive attention of researchers. However, CsPbX3The material is unstable in oxidative and humid atmospheric environments, which greatly limits the application of the material in various photoelectric fields, such as solar cells, lasers, displays and the like. Therefore, to increase CsPbX3The stability of nanocrystals is an effective method of complexing them with inert matrices such as organic polymers or inorganic glasses.
It is well known that optically functional nanocrystalline or quantum dot materials obtained by devitrification heat treatment in oxide glasses have excellent thermal and chemical stability. In recent years, various CsPbX have been reported3The nano crystal composite oxide glass ceramic and its novel photon characteristics and application, such as unique luminescence and random laser characteristics (J.Am.Ceram.Soc.,102[ 3)]1090-100(2019).;ACS Appl.Mater.Int.,10[22]18918-26(2018).;J.Mater.Chem.C,6[25]6832-39(2018).). However, the preparation strategy adopted in the work of the reported papers is to mix the relevant halide directly with the oxide raw material and to smelt under an open atmosphere. This preparation strategy inevitably leads to volatilization of the halide, resulting in poor reproducibility of sample preparation. Therefore, the glass composition and preparation method need to be redesigned, and various CsPbX types can be obtained repeatedly3A glass ceramic material compounded by nano crystals.
Unlike oxide glass, chalcogenide glass is obtained by melt-quenching in a vacuum-tight quartz glass tube. Chalcogenide glasses possess good halide solubility and do not suffer halide loss during the glass making process. In particular, chalcogenide glasses have unique low phonon energies, wide infrared transparent windows and good propertiesThe solubility of rare earth and other properties, and has good application prospect in various photon fields. In addition, although CsCl, RbI and Cs are present in chalcogenide glasses3LaCl6Isohalide nanocrystalline research reports, but CsPbX has never been obtained3Perovskite nanocrystalline composite chalcogenide glass ceramics. The CsPbX is prepared and obtained by careful composition design and crystallization treatment3The nanocrystalline composite chalcogenide glass ceramic has good research value and application significance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects of the prior art, the chalcogenide glass ceramic material is transparent in a spectral range of 2-10 microns, has good thermal and chemical stability and good fracture toughness, and is suitable for rare earth ion doping research and development of novel mid-infrared luminescent or laser materials and related quantum dot luminescent materials. The preparation method of the chalcogenide glass ceramic material can design and select proper glass composition according to functional requirements, and control precipitation of CsPbX3Grain size and distribution.
The technical scheme adopted by the invention for solving the technical problems is as follows: the molar composition of the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material is represented by the chemical formula: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3Wherein X is 0.15-0.75, y is 0.05-0.2, z is 0.05-0.1, X is Cl, Br or I, CsPbX3Is compounded in the chalcogenide glass ceramic material in the form of precipitated nano crystals.
The molar composition of the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material is represented by the chemical formula: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3Wherein X is 0.15-0.75, y is 0.05-0.2, z is 0.05-0.1, X is Cl, Br or I, the molar composition makes the content of the halide (namely cesium halide and lead halide) introduced into the base glass close to the supersaturation degree, and the later crystallization heat treatment process can be ensuredMiddle, CsPbX3The crystal can be separated out and CsPbX can be effectively controlled3The crystal grain size of the crystal is 5-50 nm, and the crystallinity is about 20%. Ga is appropriately introduced2S3Can improve the halogen coordination state in the glass network, improve the solubility of metal halide and ensure the doping amount of cesium halide and lead halide. From CsPbX3The chalcogenide glass ceramic material compounded by the nanocrystalline microcrystalline particles and the base glass is transparent in a spectral range of 2-10 micrometers, has good thermal and chemical stability and good fracture toughness, and is suitable for rare earth ion doping research and development of novel mid-infrared luminescent or laser materials and related quantum dot luminescent materials.
The preparation method of the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material comprises the following steps:
(1) selecting raw materials: according to the molar composition formula (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3Selecting Ge, Ga, Sb, S, CsX and PbX2Weighing simple substances Ge, Ga, Sb and S, CsX and PbX2The compound is prepared from raw materials, wherein X is 0.15-0.75, y is 0.05-0.2, z is 0.05-0.1, and X is Cl, Br or I;
(2) ge, Sb, S, CsX and PbX are mixed in dry atmosphere filled with inert gas2Mixing the raw materials, placing in a quartz ampoule, and vacuumizing to a vacuum degree of less than 10-3Pa, sealing the quartz ampoule by melting and placing the quartz ampoule in heating equipment;
(3) preparing base glass: heating equipment to 830-950 ℃, melting for 8-18 hours, cooling to obtain non-annealed glass, and measuring the glass transition temperature T of the non-annealed glass by a differential scanning calorimetry analyzergThen placing the unannealed glass in a precision annealing furnace for annealing, wherein the annealing temperature is higher than the glass transition temperature TgAnnealing at the constant temperature of 30 ℃ for 2-5 hours, and cooling to below 50 ℃ along with the furnace to obtain base glass;
(4) putting the base glass into a crystallization furnace with an inert atmosphere protection device for crystallization heat treatment, wherein the temperature of the crystallization heat treatment is higher than the glass transition temperature TgThe temperature is 10-40 ℃, and crystallization heat treatment is carried out for 3-100 hours at the temperature, so that a large amount of uniformly distributed CsPbX is precipitated in the glass3A nanocrystal; and finally, cooling to room temperature along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material.
Preferably, the specific preparation process of the base glass in the step (3) is as follows: heating the heating equipment to 340 ℃ slowly at a heating rate of less than 2 ℃/min, and keeping the temperature for 1-3 hours at the temperature; slowly heating the heating equipment to 750 ℃ at the heating rate of less than 5 ℃/min, and preserving the heat for 1-2 hours at the temperature; then slowly heating the heating equipment to 830-950 ℃ at the heating rate of 1-2 ℃/min, and preserving the temperature for 8-10 hours, wherein the quartz ampoule filled with the glass liquid is shaken or oscillated during the heat preservation; then, cooling to 780-900 ℃ at a cooling rate of 2-3 ℃/min; standing the quartz ampoule for 0.5-2 hours, and quenching in air or ice water mixture; in a precision annealing furnace at a specific glass transition temperature TgAnnealing at constant temperature of 30 ℃ for 2-5 hours, and then cooling to below 50 ℃ along with the furnace to obtain the base glass.
The invention relates to a method for preparing an inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material, which uses GeS2-Sb2S3-Ga2S3For glass matrix, CsPbX is introduced to approach saturation3The components are prepared into basic chalcogenide glass by a melting quenching method, and then CsPbX can be controllably precipitated by crystallization heat treatment3Nanocrystalline to obtain the chalcogenide glass ceramic material. The method can design and select proper glass composition according to functional requirements, and control and precipitate CsPbX3Grain size and distribution. Compared with basic chalcogenide glass, the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material prepared by the method has the advantages of obviously improved thermodynamic stability and environmental impact resistance, and simultaneously has the rare earth ion doped luminescence enhancement performance and the quantum dot luminescence characteristic. Compared with the prior preparation method of the chalcogenide glass ceramic material, the controllable preparation method provided by the invention can be used for simply mixing and melting cesium halide, lead halide and chalcogenide glass matrix and recrystallizing the mixtureControl and precipitate CsPbX3And crystallizing to obtain the infrared transmitting chalcogenide glass ceramic with different properties.
Preferably, the CsPbX precipitated in the step (4)3The grain size of the nanocrystal is 5-50 nanometers.
Compared with the prior art, the invention has the advantages that: the molar composition of the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material is represented by the chemical formula: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3Wherein X is 0.15-0.75, y is 0.05-0.2, z is 0.05-0.1, and X is Cl, Br or I, the molar composition enables the content of halide introduced into the base glass to be close to the supersaturation degree, and the CsPbX can be ensured in the later crystallization heat treatment process3The crystal can be separated out and CsPbX can be effectively controlled3The crystal grain size of the crystal is 5-50 nm, and the crystallinity is about 20%. From CsPbX3The chalcogenide glass ceramic material compounded by the nanocrystalline microcrystalline particles and the base glass is transparent in a spectral range of 2-10 micrometers, has good thermal and chemical stability and good fracture toughness, and is suitable for rare earth ion doping research and development of novel mid-infrared luminescent or laser materials and related quantum dot luminescent materials. The preparation method of the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material can design and select proper glass composition according to functional requirements, and control the precipitation of CsPbX3Grain size and distribution. Compared with basic chalcogenide glass, the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material prepared by the method has the advantages of obviously improved thermodynamic stability and environmental impact resistance, and has the characteristics of being suitable for rare earth ion doped luminescence enhancement and quantum dot luminescence. Compared with the prior preparation method of the chalcogenide glass ceramic material, the controllable preparation method provided by the invention can simply carry out the mixed melting and recrystallization treatment on cesium halide, lead halide and chalcogenide glass matrix to control the precipitation of CsPbX3And crystallizing to obtain the infrared transmitting chalcogenide glass ceramic with different properties.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sulfur-based glass ceramic material of example 1;
FIG. 2 is a scanning electron micrograph of a chalcogenide glass ceramic material according to example 1;
FIG. 3 is an X-ray diffraction pattern of the sulfur-based glass ceramic material of example 3;
FIG. 4 is a scanning electron micrograph of a chalcogenide glass ceramic material from example 3.
Detailed Description
The invention is described in further detail below with reference to the examples of the drawings.
Example 1: taking X as Cl, X as 0.3, y as 0.1 and z as 0.06, the molar composition of the chalcogenide glass ceramic material is represented by the chemical formula: 54GeS2·30Sb2S3·10Ga2S3·6CsPbCl3Calculating the raw materials Ge, Ga, Sb, S, CsCl and PbCl according to the molar composition2Weighing in a glove box filled with inert gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; putting the sealed quartz tube into a swinging furnace for heating, firstly heating to 340 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, then heating to 750 ℃ at the speed of 4 ℃/min, and preserving heat for 2 hours; slowly raising the temperature to 920 ℃ at the heating rate of 1 ℃/minute, and melting for 10 hours in a swinging manner; then the temperature is reduced to 850 ℃ at the speed of 3 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precision annealing furnace at 240 ℃ for annealing, keeping the temperature for 5 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; and putting the obtained base glass into a crystallization furnace at the temperature of 270 ℃ for heat treatment for 20 hours, and finally cooling along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material.
The X-ray diffraction pattern of the sulfur-based glass ceramic material in example 1 is shown in FIG. 1, and the scanning electron micrograph is shown in FIG. 2. As can be seen from FIGS. 1 and 2, CsPbCl was precipitated from the sample after the crystallization heat treatment3Crystalline, with a grain size of about 20 nm. In addition, compare basic glassGlass, CsPbCl obtained3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 8 ℃, the fracture toughness is increased by 2 times, the hardness is enhanced by 10%, crack propagation is not observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has better thermal stability and environmental impact resistance.
Example 2: taking X as Cl, X as 0.5, y as 0.12 and z as 0.08, and the molar composition of the chalcogenide glass ceramic material is represented by the chemical formula: 30GeS2·50Sb2S3·12Ga2S3·8CsPbCl3Calculating the raw materials Ge, Ga, Sb, S, CsCl and PbCl according to the molar composition2Weighing in a glove box filled with inert gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; putting the sealed quartz tube into a swinging furnace for heating, firstly heating to 340 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, then heating to 750 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours; then slowly raising the temperature to 850 ℃ at the heating rate of 1 ℃/minute, and melting for 10 hours in a swinging manner; then cooling to 800 ℃ at the speed of 2 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precision annealing furnace at 220 ℃ for annealing, keeping the temperature for 3 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; and putting the obtained base glass into a crystallization furnace at the temperature of 240 ℃ for heat treatment for 20 hours, and finally cooling along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material. CsPbCl is precipitated from the sample after crystallization heat treatment3Crystalline, with a grain size of about 30 nm. In addition, CsPbCl was obtained as compared with the base glass3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 10 ℃, the hardness is enhanced by 15%, no crack propagation is observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has excellent thermal stability and environmental impact resistance.
Example 3: taking the molar composition of the chalcogenide glass ceramic material as chemical formula, wherein X is Br, X is 0.4, y is 0.2 and z is 0.07The formula is shown as: 33GeS2·40Sb2S3·20Ga2S3·7CsPbBr3Calculating the raw materials Ge, Ga, Sb, S, CsBr and PbBr according to the molar composition2Weighing in a glove box filled with inert gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; putting the sealed quartz tube into a swinging furnace for heating, firstly heating to 340 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, then heating to 750 ℃ at the speed of 3 ℃/min, and preserving heat for 2 hours; slowly raising the temperature to 900 ℃ at the heating rate of 1 ℃/minute, and melting for 8 hours in a swinging manner; then cooling to 840 ℃ at the speed of 2 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precision annealing furnace at 240 ℃ for annealing, keeping the temperature for 3 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; and (3) putting the obtained base glass into a crystallization furnace at the temperature of 270 ℃ for heat treatment for 10 hours, and finally cooling along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material.
The X-ray diffraction pattern of the chalcogenide glass-ceramic material in example 3 is shown in FIG. 3, and the scanning electron micrograph is shown in FIG. 4. As can be seen from FIGS. 3 and 4, CsPbBr was precipitated from the samples after the crystallization heat treatment3Crystalline, with a grain size of about 40 nm. In addition, CsPbBr obtained compared to the base glass3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 10 ℃, the fracture toughness is increased by 2 times, the hardness is enhanced by 8%, crack propagation is not observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has better thermal stability and environmental impact resistance.
Example 4: taking X as Br, X as 0.5, y as 0.1 and z as 0.1, the molar composition of the chalcogenide glass ceramic material is expressed by the chemical formula: 30GeS2·50Sb2S3·10Ga2S3·10CsPbBr3Calculating the raw materials Ge, Ga, Sb, S, CsBr and PbBr according to the molar composition2Is filled withWeighing in a glove box of sexual gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; putting the sealed quartz tube into a swinging furnace for heating, firstly heating to 340 ℃ at the speed of 1 ℃/min, preserving heat for 3 hours, then heating to 750 ℃ at the speed of 4 ℃/min, and preserving heat for 2 hours; slowly raising the temperature to 880 ℃ at the heating rate of 1 ℃/minute, and melting for 8 hours in a swinging manner; then the temperature is reduced to 780 ℃ at the speed of 2 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precision annealing furnace at 180 ℃ for annealing, keeping the temperature for 3 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; and putting the obtained base glass into a crystallization furnace at the temperature of 230 ℃ for heat treatment for 20 hours, and finally cooling along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material. CsPbBr is precipitated from the sample after crystallization heat treatment3Crystalline, with a grain size of about 50 nm. In addition, CsPbBr obtained compared to the base glass3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 12 ℃, the hardness is enhanced by 18%, no crack propagation is observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has better thermal stability and environmental impact resistance.
Example 5: taking X as I, X ═ 0.2, y as 0.05 and z as 0.05, the molar composition of the chalcogenide glass ceramic material is expressed by the chemical formula: 70GeS2·20Sb2S3·5Ga2S3·5CsPbI3Calculating the raw materials Ge, Ga, Sb, S, CsI and PbI according to the molar composition2Weighing in a glove box filled with inert gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; heating the sealed quartz tube in a rocking furnace at 2 deg.C/min to 340 deg.C for 3 hr, and heating to 750 deg.C at 2 deg.C/minKeeping the temperature for 2 hours; slowly raising the temperature to 950 ℃ at the heating rate of 1 ℃/minute, and melting for 10 hours in a swinging manner; then the temperature is reduced to 860 ℃ at the speed of 2 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precise annealing furnace at 260 ℃ for annealing, keeping the temperature for 3 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; and (3) putting the obtained base glass into a crystallization furnace with the temperature of 290 ℃ for heat treatment for 5 hours, and finally cooling along with the furnace to obtain the inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material. CsPbI is precipitated from the sample after crystallization heat treatment3Crystalline, with a grain size of about 5 nm. In addition, the CsPbI obtained compared to the base glass3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 5 ℃, the hardness is enhanced by 8%, the fracture toughness is increased by 1.5 times, no crack propagation is observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has better thermal stability and environmental impact resistance.
Example 6: taking X as I, X ═ 0.15, y as 0.15 and z as 0.1, the molar composition of the chalcogenide glass ceramic material is expressed by the chemical formula: 60GeS2·15Sb2S3·15Ga2S3·10CsPbI3Calculating the raw materials Ge, Ga, Sb, S, CsI and PbI according to the molar composition2Weighing in a glove box filled with inert gas and mixing uniformly; then putting the uniformly mixed raw materials into a quartz tube, soaking the quartz tube in king water for 2 hours in advance, washing the quartz tube with deionized water, drying the quartz tube, vacuumizing the quartz tube when the vacuum degree in the quartz tube is 10-3Sealing by melting with oxygen acetylene flame under Pa; putting the sealed quartz tube into a swinging furnace for heating, firstly heating to 340 ℃ at the speed of 2 ℃/min, preserving heat for 3 hours, then heating to 750 ℃ at the speed of 2 ℃/min, and preserving heat for 2 hours; slowly raising the temperature to 930 ℃ at the heating rate of 1 ℃/minute, and melting for 10 hours in a swinging manner; then the temperature is reduced to 850 ℃ at the speed of 2 ℃/min; standing a quartz ampoule, and quenching in an ice-water mixture after standing for 0.5 hour; finally, placing the glass in a precision annealing furnace at 250 ℃ for annealing, keeping the temperature for 3 hours, and then cooling the glass to below 50 ℃ along with the furnace to obtain base glass; putting the obtained base glass into a crystallization furnace with the temperature of 280 DEG CAnd carrying out heat treatment for 5 hours, and finally cooling along with a furnace to obtain the inorganic lead and cesium halide nanocrystalline composite chalcogenide glass ceramic material. CsPbI is precipitated from the sample after crystallization heat treatment3Crystalline, with a grain size of about 30 nm. In addition, the CsPbI obtained compared to the base glass3The glass transition temperature of the nanocrystalline composite chalcogenide glass ceramic is increased by 12 ℃, the hardness is enhanced by 15%, the fracture toughness is improved by 2 times, no crack propagation is observed under the action of micro-indentation, and the nanocrystalline composite chalcogenide glass ceramic has better thermal stability and environmental impact resistance.

Claims (4)

1.无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料,其特征在于,该硫系玻璃陶瓷材料的摩尔组成按化学式表示为:(1-x-y-z)GeS2·xSb2S3·yGa2S3·zCsPbX3,其中,x=0.15~0.75,y=0.05~0.2,z=0.05~0.1,X为Cl、Br或I,CsPbX3以析出的纳米晶形式复合于该硫系玻璃陶瓷材料中。1. Inorganic lead halide cesium nanocrystalline composite chalcogenide glass-ceramic material, is characterized in that, the molar composition of this chalcogenide glass-ceramic material is represented by chemical formula as: (1-xyz)GeS 2 ·xSb 2 S 3 ·yGa 2 S 3 zCsPbX 3 , wherein x=0.15-0.75, y=0.05-0.2, z=0.05-0.1, X is Cl, Br or I, and CsPbX 3 is compounded in the chalcogenide glass-ceramic material in the form of precipitated nanocrystals. 2.无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料的制备方法,其特征在于,包括以下步骤:2. the preparation method of inorganic lead halide cesium nanocrystalline composite chalcogenide glass ceramic material, is characterized in that, comprises the following steps: (1)选取原料:按照摩尔组成化学式(1-x-y-z)GeS2·xSb2S3·yGa2S3·zCsPbX3,选取Ge、Ga、Sb、S、CsX和PbX2所占当量比例,称取Ge、Ga、Sb、S单质和CsX、PbX2化合物原料备用,其中,x=0.15~0.75,y=0.05~0.2,z=0.05~0.1,X为Cl、Br或I;(1) Selection of raw materials: according to the molar chemical formula (1-xyz)GeS 2 ·xSb 2 S 3 ·yGa 2 S 3 ·zCsPbX 3 , select the equivalent proportions of Ge, Ga, Sb, S, CsX and PbX 2 , called Get Ge, Ga, Sb, S elemental substance and CsX, PbX 2 compound raw materials for use, wherein, x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X is Cl, Br or I; (2)在充满惰性气体的干燥环境中,将Ge、Ga、Sb、S、CsX和PbX2原料混合后,置于石英安瓿中并抽真空至真空度小于10-3Pa,再熔封石英安瓿并置于加热设备中;(2) In a dry environment full of inert gas, after mixing the raw materials of Ge, Ga, Sb, S, CsX and PbX 2 , place them in a quartz ampoule and evacuate to a degree of vacuum less than 10 -3 Pa, and then seal the quartz Ampoules and placed in a heating device; (3)基础玻璃制备:将加热设备升温至830~950℃,熔制8~18小时后冷却,得到未退火玻璃,通过示差扫描量热分析仪测定该未退火玻璃的玻璃转变温度Tg,然后将该未退火玻璃置于精密退火炉中退火,退火温度比玻璃转变温度Tg低30℃,恒温退火2~5小时后随炉冷却至50℃以下,即获得基础玻璃;(3) Preparation of base glass: heating the heating equipment to 830-950° C., melting for 8-18 hours, and then cooling to obtain unannealed glass, and measuring the glass transition temperature T g of the unannealed glass by differential scanning calorimetry, The unannealed glass is then placed in a precision annealing furnace for annealing, the annealing temperature is 30°C lower than the glass transition temperature T g , and the base glass is obtained after constant temperature annealing for 2 to 5 hours and then cooling to below 50°C with the furnace; (4)将基础玻璃放入具有惰性气氛保护装置的晶化炉中进行析晶热处理,析晶热处理温度比玻璃转变温度Tg高10~40℃,于此温度下析晶热处理3~100小时,使玻璃内部析出大量分布均匀的CsPbX3纳米晶;最后随炉冷却至室温,即获得无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料。(4) Put the base glass into a crystallization furnace with an inert atmosphere protection device for crystallization heat treatment, the crystallization heat treatment temperature is 10-40°C higher than the glass transition temperature T g , and the crystallization heat treatment is performed at this temperature for 3-100 hours , so that a large number of CsPbX 3 nanocrystals with uniform distribution are precipitated inside the glass; finally, the inorganic lead halide cesium nanocrystal composite chalcogenide glass-ceramic material is obtained by cooling to room temperature with the furnace. 3.根据权利要求2所述的无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料的制备方法,其特征在于,步骤(3)中基础玻璃的具体制备过程如下:使加热设备以低于2℃/min的升温速率缓慢升温至340℃,并在此温度下保温1~3小时;再使加热设备以低于5℃/min的升温速率缓慢升温至750℃,并在此温度下保温1~2小时;然后使加热设备以1~2℃/min的升温速率缓慢升温至830~950℃,并在此温度下保温8~10小时,保温期间将盛有玻璃液的石英安瓿进行晃动或振荡;此后以2~3℃/min的降温速率降温至780~900℃;使石英安瓿竖立并静置0.5~2小时后,在空气或冰水混合物中淬冷;在精密退火炉中以比玻璃转变温度Tg低30℃的温度恒温退火2~5小时,之后随炉冷却至50℃以下,即获得基础玻璃。3. the preparation method of inorganic lead halide cesium nanocrystalline composite chalcogenide glass-ceramic material according to claim 2, is characterized in that, in step (3), the concrete preparation process of base glass is as follows: make heating equipment be lower than 2 ℃ The heating rate of /min is slowly raised to 340°C, and kept at this temperature for 1-3 hours; then the heating equipment is slowly raised to 750°C at a heating rate lower than 5°C/min, and kept at this temperature for 1~3 hours 2 hours; then the heating equipment is slowly heated to 830-950°C at a heating rate of 1-2°C/min, and kept at this temperature for 8-10 hours, during which the quartz ampoule filled with the glass liquid is shaken or shaken. After that, the temperature is lowered to 780-900°C at a cooling rate of 2-3°C/min; the quartz ampoule is erected and allowed to stand for 0.5-2 hours, then quenched in air or ice-water mixture; The temperature at which the transition temperature T g is 30°C lower is constant temperature annealing for 2 to 5 hours, and then cooled to below 50°C with the furnace to obtain the base glass. 4.根据权利要求2所述的无机卤化铅铯纳米晶复合硫系玻璃陶瓷材料的制备方法,其特征在于,步骤(4)中析出的CsPbX3纳米晶的晶粒尺寸为5~50纳米。4 . The method for preparing an inorganic lead halide cesium nanocrystal composite chalcogenide glass ceramic material according to claim 2 , wherein the CsPbX 3 nanocrystals precipitated in step (4) have a grain size of 5 to 50 nanometers. 5 .
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