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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- glass
- temperature
- ceramic material
- hours
- chalcogenide glass
- 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.)
- Active
Links
- 239000005387 chalcogenide glass Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 37
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 19
- 150000004820 halides Chemical class 0.000 claims abstract description 16
- 239000002159 nanocrystal Substances 0.000 claims abstract description 14
- 239000006112 glass ceramic composition Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract 6
- 229910005839 GeS 2 Inorganic materials 0.000 claims abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000010453 quartz Substances 0.000 claims description 57
- 239000006121 base glass Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000003708 ampul Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000010791 quenching Methods 0.000 abstract description 9
- 230000000171 quenching effect Effects 0.000 abstract description 9
- 239000002096 quantum dot Substances 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000007613 environmental effect Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007373 indentation Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- -1 cesium halide Chemical class 0.000 description 5
- 229910005842 GeS2 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000000075 oxide glass Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000005347 annealed glass Substances 0.000 description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Inorganic materials [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 2
- 239000005283 halide glass Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910005228 Ga2S3 Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
Images
Landscapes
- Glass Compositions (AREA)
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。
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.
Description
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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910264958.4A CN109928640B (en) | 2019-04-03 | 2019-04-03 | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910264958.4A CN109928640B (en) | 2019-04-03 | 2019-04-03 | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109928640A CN109928640A (en) | 2019-06-25 |
| CN109928640B true CN109928640B (en) | 2021-08-27 |
Family
ID=66989150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910264958.4A Active CN109928640B (en) | 2019-04-03 | 2019-04-03 | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109928640B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592227B (en) * | 2020-04-28 | 2022-05-17 | 宁波大学 | Cs3Sb2Br9 perovskite nanocrystalline composite chalcogenide glass-ceramic material and preparation method thereof |
| CN111517641A (en) * | 2020-04-28 | 2020-08-11 | 宁波大学 | CsSnX3 nanocrystalline composite chalcogenide glass ceramic material and preparation method |
| CN112174534B (en) * | 2020-10-16 | 2022-03-11 | 江苏师范大学 | Ni-containing alloy2+Doped CsPbI3Chalcogenide glass ceramic of perovskite nanocrystalline and preparation method thereof |
| CN116903027B (en) * | 2023-07-13 | 2025-05-27 | 中国科学院新疆理化技术研究所 | Compound cesium gallium chloride and cesium gallium chloride infrared nonlinear optical crystal, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232161A (en) * | 2013-05-03 | 2013-08-07 | 中国建筑材料科学研究总院 | Preparation method and equipment of Ge-Sb-Se systematic infrared glass |
| US9340446B1 (en) * | 2013-02-04 | 2016-05-17 | Lockheed Martin Corporation | Optical apparatus and method of forming a gradient index device |
| CN107162429A (en) * | 2017-07-17 | 2017-09-15 | 宁波大学 | A kind of infrared chalcogenide glass ceramic of graded index and preparation method thereof |
| CN109320092A (en) * | 2018-10-24 | 2019-02-12 | 宁波大学 | A kind of lead halide microcrystalline composite chalcogenide glass ceramic material and preparation method thereof |
-
2019
- 2019-04-03 CN CN201910264958.4A patent/CN109928640B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9340446B1 (en) * | 2013-02-04 | 2016-05-17 | Lockheed Martin Corporation | Optical apparatus and method of forming a gradient index device |
| CN103232161A (en) * | 2013-05-03 | 2013-08-07 | 中国建筑材料科学研究总院 | Preparation method and equipment of Ge-Sb-Se systematic infrared glass |
| CN107162429A (en) * | 2017-07-17 | 2017-09-15 | 宁波大学 | A kind of infrared chalcogenide glass ceramic of graded index and preparation method thereof |
| CN109320092A (en) * | 2018-10-24 | 2019-02-12 | 宁波大学 | A kind of lead halide microcrystalline composite chalcogenide glass ceramic material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| GeS_2-Ga_2S_3-CsI硫系玻璃的析晶行为及其组成依赖研究;林常规等;《物理学报》;20120808;第61卷(第15期);第1-6页 * |
| 双卤化物共掺新型硫系多光谱玻璃的制备及性能;张腾宇等;《光子学报》;20161015;第45卷(第10期);第2页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109928640A (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109928640B (en) | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof | |
| CN109987848B (en) | CsPbBr-containing material3Quantum dot superlattice structure glass and preparation method thereof | |
| CN109354059B (en) | A solid-phase synthesis method of inorganic perovskite quantum dots | |
| Yu et al. | Sol–gel deposition and luminescent properties of oxyapatite Ca 2 (Y, Gd) 8 (SiO 4) 6 O 2 phosphor films doped with rare earth and lead ions | |
| CN109320092A (en) | A kind of lead halide microcrystalline composite chalcogenide glass ceramic material and preparation method thereof | |
| CN101209898A (en) | Erbium-doped transparent oxyfluoride glass ceramic containing yttrium-barium fluoride nanocrystals and preparation method thereof | |
| CN103046137A (en) | Sapphire crystal with high mechanical property and fabrication method thereof | |
| CN101088946A (en) | A kind of transparent glass ceramics containing yttrium sodium fluoride nanocrystals doped with erbium and its preparation and application | |
| CN101265026B (en) | Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof | |
| CN111517641A (en) | CsSnX3 nanocrystalline composite chalcogenide glass ceramic material and preparation method | |
| CN111592227B (en) | Cs3Sb2Br9 perovskite nanocrystalline composite chalcogenide glass-ceramic material and preparation method thereof | |
| CN114477775B (en) | Divalent europium ion doped microcrystalline glass scintillator and preparation method thereof | |
| CN103382089B (en) | Containing Cs3LaCl6Nanocrystalline transparent sulfur-halogen glass ceramics and its preparation | |
| Lin et al. | Second-order optical nonlinearity and ionic conductivity of nanocrystalline GeS 2–Ga 2 S 3–LiI glass-ceramics with improved thermo-mechanical properties | |
| CN113149432A (en) | Anti-radiation boron tellurate luminescent glass and preparation method thereof | |
| CN106835262A (en) | A kind of method for growing aluminium tetraborate salt crystal | |
| JP5728618B2 (en) | Titanium-doped ternary silicate thin film, method for producing the same, and application thereof | |
| CN114455837A (en) | Perovskite quantum dot glass and preparation method and application thereof | |
| CN1544369A (en) | Oxyfluoride glass ceramics doped with rare earth ions and preparation method thereof | |
| CN112174534B (en) | Ni-containing alloy2+Doped CsPbI3Chalcogenide glass ceramic of perovskite nanocrystalline and preparation method thereof | |
| CN101215092A (en) | Infrared-transmitting chalcogenide halide glass-ceramic with frequency doubling function and preparation method thereof | |
| CN110204209A (en) | A kind of upper conversion glass ceramic composite material of the rear-earth-doped scandium base fluorinated nano crystalline substance of selectivity | |
| CN109868502B (en) | Rare earth doped niobate single crystal up-conversion luminescent material and preparation method thereof | |
| Chen et al. | Growth of lead molybdate crystals by vertical Bridgman method | |
| CN114835403A (en) | Zinc fluoride-aluminum fluoride based microcrystalline 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 |