CN109320092A - A kind of compound chalcogenide glass ceramic material of lead halide crystallite and preparation method thereof - Google Patents
A kind of compound chalcogenide glass ceramic material of lead halide crystallite and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses compound chalcogenide glass ceramic material of a kind of lead halide crystallite and preparation method thereof, a mole composition for the chalcogenide glass ceramic material is indicated by chemical formula are as follows: (1-x-y) GeS2·xSb2S3·yPbX2, wherein x=0.1 ~ 0.85, y=0.1 ~ 0.25, X Cl, Br or I, PbX2It is compound in the chalcogenide glass ceramic material with the microcrystalline form of precipitation.The ceramic material is a kind of compound infrared permeation sulfur series glass ceramic material of the novel metal halide crystallite that can be applied to infrared optics and photonics, it has preferable both thermally and chemically stability, good fracture toughness, is adapted for the novel middle infraluminescence of rare earth ion doped research and development or laser material；The preparation method of the ceramic material can need to design and select suitable glass to form according to rare earth ion, simply by lead halide and chalcogenide glass matrix are carried out consolute and again Crystallizing treatment, different lead halide crystal phases is precipitated in control, obtains the saturating infrared function chalcogenide glass ceramic of performance difference.
Description
Technical field
The invention belongs to functional glass technical field of ceramic material, specifically a kind of compound chalcogenide glass pottery of lead halide crystallite
Ceramic material and preparation method thereof.
Background technique
Halogenation leading crystal has the characteristics that wide visible-infrared transparent window, low phonon energy, always extremely important
Light functional crystal material.But halogenation leading crystal is easy to deliquesce in air, more demanding to use environment.This intrinsic defect
Constrain the application of halogenation leading crystal.In recent years, researcher has attempted various methods and carrys out stabilisation of halogenated leading crystal, develops perhaps
More novel functions and application.One of preferable method is heat-treated by crystallization, and lead halide is precipitated in glass matrix
Crystallite.Inert glass matrix can be effectively protected halide crystallite from environmental injury, and be conducive to make flakiness,
The photonic device of the various forms such as film, optical fiber.A kind of typical successful case is rear earth doping oxygen-fluorine glass ceramic material,
It is heat-treated by crystallization, PbF is precipitated in oxide glass matrix2Crystal, rare earth ion are enriched in the lower fluorine of phonon energy
In atomic lattice, the luminescent properties enhancing such as visible, near-infrared and upper conversion is realized.It can by electron transition mechanism in rare earth ion
Know, PbX2(X=Cl, Br or I) etc. there is the metal halide crystal of more low phonon energy can be more advantageous to rare earth luminescence.
However, so far in addition to CsPbX3Outside the compound only a few oxide glass-ceramics material of quantum dot, other metal halogen are seldom seen
The report of compound crystal composite glass-ceramic material.The reason of causing this phenomenon has: lead halide is easy to deliquesce, and mixes in raw material
Shi Rongyi deliquesces adhesion, causes mixing uneven, to be difficult to realize uniformly be melted；In addition, PbX2Raw material is in high temperature melting
It more easily volatilizees, is difficult to fuse into oxide glass matrix.
Chalcogenide glass is one kind based on the chalcogens such as sulphur, selenium, tellurium, is bound up with other metals or nonmetalloid
Amorphous solid.Chalcogenide glass is usually that raw material is placed in vitreosil ampoule, is melted and is obtained by rocking furnace.Sulphur system glass
Glass has high halide solubility, compares oxide glass, is more suitable for doing lead halide introducing and crystallization research.In addition, sulphur system
Glass has wide infrared transparent window, is the ideal host material for studying infraluminescence in rare earth ion.Therefore, phonon is obtained
The compound chalcogenide glass ceramic material of the metal halides crystal such as the extremely low chloride of energy, bromide, iodide, will be expected in
It realizes and breaks through in terms of infraluminescence even mid-infrared laser material.In consideration of it, the present invention proposes a kind of lead halide crystallite composite sulfur
Series vitro-ceramic material and preparation method thereof.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, it is compound provide a kind of lead halide crystallite
Chalcogenide glass ceramic material and preparation method thereof, it is red that the compound chalcogenide glass ceramic material of the lead halide crystallite is that one kind can be applied to
The compound infrared permeation sulfur series glass ceramic material of the novel metal halide crystallite of outer optics and photonics has preferable
Both thermally and chemically stability, good fracture toughness are adapted for the novel middle infraluminescence of rare earth ion doped research and development or laser
Material；The preparation method of the compound chalcogenide glass ceramic material of the lead halide crystallite can need to design and select according to rare earth ion
Suitable glass composition, simply by lead halide and chalcogenide glass matrix are carried out consolute and again Crystallizing treatment, control is precipitated
Different lead halide crystal phases obtains the saturating infrared function chalcogenide glass ceramic of performance difference.
The technical scheme of the invention to solve the technical problem is: a kind of compound chalcogenide glass pottery of lead halide crystallite
A mole composition for ceramic material, the chalcogenide glass ceramic material is indicated by chemical formula are as follows: (1-x-y) GeS2·xSb2S3·yPbX2,
Wherein x=0.1~0.85, y=0.1~0.25, X Cl, Br or I, PbX2The sulphur system glass is compound in the microcrystalline form of precipitation
In glass ceramic material.
Preferably, x=0.15~0.85, y=0.1~0.15.
Alternatively, preferably, x=0.1~0.8, y=0.15~0.2.
Alternatively, preferably, x=0.1~0.75, y=0.2~0.25.
Preferably, the PbX2The crystallite dimension of crystallite is 50~2000 nanometers.
A kind of preparation method of the compound chalcogenide glass ceramic material of lead halide crystallite, comprising the following steps:
(1) according to mole constitutional chemistry formula (1-x-y) GeS2·xSb2S3·yPbX2, wherein x=0.1~0.85, y=
0.1~0.25, X Cl, Br or I, with Ge, Sb, S and PbX2For raw material, calculates and each raw material is weighed；
(2) in the dry environment full of inert gas, by Ge, Sb, S and PbX2After raw material mixing, it is placed in quartz ampoule
In and be evacuated to vacuum degree less than 10-3Pa, then seal quartz ampoule and be placed in heating equipment；
(3) heating equipment is warming up to 800~900 DEG C, quenching after being melted 6~18 hours obtains unannealed glass, measures
The glass transformation temperature T of this is unannealed glassg, then the unannealed glass is placed in fine annealing furnace, than Glass Transition
Temperature TgCycle annealing 2~5 hours at a temperature of low 10~30 DEG C cools to 50 DEG C with the furnace hereinafter, obtaining basic glass later
Glass；
(4) parent glass is put into the crystallization furnace with inert atmosphere protection device, than glass transformation temperature TgIt is high
Crystallization is heat-treated 3~100 hours at a temperature of 10~40 DEG C, is largely evenly distributed in crystallization process in inside glass precipitation
PbX2Crystallite finally cools to room temperature with the furnace, i.e. the acquisition compound chalcogenide glass ceramic material of lead halide crystallite.
Preferably, detailed process is as follows for step (3): making heating equipment slow with the heating rate of 1~2 DEG C/min first
Slowly 340 DEG C are warming up to, and keep the temperature 1~3 hour at this temperature；Make heating equipment slow with the heating rate of 2~5 DEG C/min again
750 DEG C are warming up to, and keeps the temperature 1~2 hour at this temperature；Then 800 are to slowly warm up to the heating rate of 1~2 DEG C/min
~950 DEG C, and 8~10 hours are kept the temperature at this temperature, quartz ampoule is shaken or is vibrated by heat preservation while；Later with 2
The rate of temperature fall of~3 DEG C/min is cooled to 780~900 DEG C；Hereafter after erectting quartz ampoule and standing 0.5~2 hour, in sky
Quenching in gas or mixture of ice and water；Finally than glass transformation temperature T in fine annealing furnacegLow 10~30 thermostatic moves back
Fire 2~5 hours cools to 50 DEG C with the furnace hereinafter, obtaining parent glass later.
Preferably, in step (4), the PbX that is precipitated in crystallization process2The crystallite dimension of crystallite is 50~2000 nanometers.
Compared with the prior art, the advantages of the present invention are as follows:
1, a mole composition for the compound chalcogenide glass ceramic material of lead halide crystallite disclosed by the invention is indicated by chemical formula are as follows:
(1-x-y)GeS2·xSb2S3·yPbX2, wherein x=0.1~0.85, y=0.1~0.25, X Cl, Br or I, PbX2To be precipitated
Microcrystalline form be compound in the chalcogenide glass ceramic material.This mole, which forms, can guarantee that the content of lead halide in parent glass connects
Nearly degree of super saturation, so that it is guaranteed that in the heat treatment process in chalcogenide glass ceramic material preparation later period, halogenation leading crystal energy
Enough a large amount of uniformly precipitations.
2, the crystal grain of lead halide crystallite compound in the compound chalcogenide glass ceramic material of lead halide crystallite disclosed by the invention
Size can be distributed in 50~2000 nanometers, and crystallinity is transparent in 3~10 micrometer spectrums greater than 20%.The lead halide is micro-
Brilliant compound chalcogenide glass ceramic material is a kind of novel metal halide crystallite that can be applied to infrared optics and photonics
Compound infrared permeation sulfur series glass ceramic material has preferable both thermally and chemically stability, good fracture toughness, be suitable for into
The novel middle infraluminescence of the rare earth ion doped research and development of row or laser material.
3, the preparation method of the compound chalcogenide glass ceramic material of lead halide crystallite disclosed by the invention, is a kind of crystalline controlling
The controllable preparation method being precipitated.The preparation method selects GeS first2-Sb2S3For glass matrix, the halogenation close to saturation is introduced
Lead composition prepares parent glass using melt quenching method, then by accurate crystallization heat treatment, controls the PbX of precipitation2It is micro-
Crystalline substance finally obtains the compound chalcogenide glass ceramic material of lead halide crystallite.Compared with basic chalcogenide glass, halogenation prepared by the present invention
The compound chalcogenide glass ceramic material of lead crystallite has the thermodynamic stability and environment resistant impact property significantly improved, is provided simultaneously with
Rare earth ion doped luminescence enhancement performance.It is proposed by the present invention controllable compared with previous chalcogenide glass ceramic preparation method
The preparation process of preparation method can need to design and select suitable glass to form according to rare earth ion, simply by by halogen
Change lead and chalcogenide glass matrix carries out consolute and again Crystallizing treatment, different lead halide crystal phases is precipitated in control, obtains performance difference
Saturating infrared function chalcogenide glass ceramic.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of parent glass and chalcogenide glass ceramic material in embodiment 1；
Fig. 2 is the scanning electron micrograph of chalcogenide glass ceramic material in embodiment 1；
Fig. 3 is the X ray diffracting spectrum of chalcogenide glass ceramic material in embodiment 5.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Embodiment 1: taking X is Cl, and when x=0.2, y=0.15, a mole composition for chalcogenide glass ceramic material presses chemical formula table
It is shown as 65GeS2·20Sb2S3·15PbCl2, raw material Ge, Sb, S and PbCl are calculated according to this mole composition2Weight,
It weighs and is uniformly mixed in the glove box of drying full of inert gas；Then uniformly mixed raw material is packed into advance in chloroazotic acid
It in the middle quartz ampoule for impregnating 2 hours and being dried after being washed with deionized water, then vacuumizes, when the vacuum degree in quartz ampoule is less than
10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to the rate of 2 DEG C/min
It after 340 DEG C, heat preservation 3 hours, then with the rate of 4 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating of 1 DEG C/min
Rate is slowly increased to 850 DEG C, waves melted 10 hours；Then 800 DEG C are cooled to the rate of 3 DEG C/min；Hereafter make quartz ampoule
After erectting and standing 0.5 hour in mixture of ice and water quenching；Finally quartz ampoule is placed in 240 DEG C of fine annealing furnace and is moved back
Fire, cycle annealing cool to 50 DEG C with the furnace hereinafter, obtaining parent glass after 5 hours；Parent glass is put into indifferent gas
In the crystallization furnace of atmosphere protective device, crystallization is heat-treated 20 hours at 300 DEG C, is precipitated a large amount of points in inside glass in crystallization process
The uniform PbCl of cloth2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbCl of embodiment 12The compound chalcogenide glass ceramic of crystallite
Material.
The X ray diffracting spectrum of parent glass and chalcogenide glass ceramic material is shown in Fig. 1 in embodiment 1.It can be seen from figure 1 that analysis
PbCl has been precipitated in sample after crystalline substance heat treatment2Crystal.The scanning electron micrograph of chalcogenide glass ceramic material in embodiment 1
See Fig. 2.As it is clear from fig. 2 that PbCl in the chalcogenide glass ceramic material2The crystallite dimension of crystallite is 100nm or so.
Embodiment 2: taking X is Cl, and when x=0.5, y=0.1, a mole composition for chalcogenide glass ceramic material presses chemical formula table
It is shown as 40GeS2·50Sb2S3·10PbCl2, raw material Ge, Sb, S and PbCl are calculated according to this mole composition2Weight,
It weighs and is uniformly mixed in the glove box of drying full of inert gas；Then uniformly mixed raw material is packed into advance in chloroazotic acid
It in the middle quartz ampoule for impregnating 2 hours and being dried after being washed with deionized water, then vacuumizes, when the vacuum degree in quartz ampoule is less than
10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to the rate of 2 DEG C/min
It after 340 DEG C, heat preservation 3 hours, then with the rate of 5 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating of 1 DEG C/min
Rate is slowly increased to 800 DEG C, waves melted 10 hours；Then 780 DEG C are cooled to the rate of 2 DEG C/min；Hereafter make quartz ampoule
After erectting and standing 0.5 hour in mixture of ice and water quenching；Finally quartz ampoule is placed in 220 DEG C of fine annealing furnace and is moved back
Fire, cycle annealing cool to 50 DEG C with the furnace hereinafter, obtaining parent glass after 3 hours；Parent glass is put into indifferent gas
In the crystallization furnace of atmosphere protective device, crystallization is heat-treated 20 hours at 290 DEG C, is precipitated a large amount of points in inside glass in crystallization process
The uniform crystallite dimension of cloth is the PbCl of 150nm or so2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbCl of embodiment 22
The compound chalcogenide glass ceramic material of crystallite.
Embodiment 3: taking X is Br, and when x=0.1, y=0.15, a mole composition for chalcogenide glass ceramic material presses chemical formula table
It is shown as 75GeS2·10Sb2S3·15PbBr2, raw material Ge, Sb, S and PbBr are calculated according to this mole composition2Weight,
It weighs and is uniformly mixed in the glove box of drying full of inert gas；Then uniformly mixed raw material is packed into advance in chloroazotic acid
It in the middle quartz ampoule for impregnating 2 hours and being dried after being washed with deionized water, then vacuumizes, when the vacuum degree in quartz ampoule is less than
10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to the rate of 2 DEG C/min
It after 340 DEG C, heat preservation 3 hours, then with the rate of 3 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating of 1 DEG C/min
Rate is slowly increased to 950 DEG C, waves melted 8 hours；Then 850 DEG C are cooled to the rate of 2 DEG C/min；Hereafter make quartz ampoule perpendicular
After standing and standing 0.5 hour in mixture of ice and water quenching；Finally quartz ampoule is placed in 260 DEG C of fine annealing furnace and is annealed,
Cycle annealing cools to 50 DEG C with the furnace hereinafter, obtaining parent glass after 3 hours；Parent glass is put into and is protected with inert atmosphere
In the crystallization furnace of protection unit, crystallization is heat-treated 20 hours at 310 DEG C, and a large amount of distributions are precipitated in inside glass in crystallization process
Even crystallite dimension is the PbBr of 300nm or so2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbBr of embodiment 32Crystallite
Compound chalcogenide glass ceramic material.
Embodiment 4: taking X is Br, and when x=0.6, y=0.2, a mole composition for chalcogenide glass ceramic material presses chemical formula table
It is shown as 20GeS2·60Sb2S3·20PbBr2, raw material Ge, Sb, S and PbBr are calculated according to this mole composition2Weight,
It weighs and is uniformly mixed in the glove box of drying full of inert gas；Then uniformly mixed raw material is packed into advance in chloroazotic acid
It in the middle quartz ampoule for impregnating 2 hours and being dried after being washed with deionized water, then vacuumizes, when the vacuum degree in quartz ampoule is less than
10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to the rate of 1 DEG C/min
It after 340 DEG C, heat preservation 3 hours, then with the rate of 4 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating of 1 DEG C/min
Rate is slowly increased to 880 DEG C, waves melted 8 hours；Then 820 DEG C are cooled to the rate of 2 DEG C/min；Hereafter make quartz ampoule perpendicular
After standing and standing 0.5 hour in mixture of ice and water quenching；Finally quartz ampoule is placed in 180 DEG C of fine annealing furnace and is annealed,
Cycle annealing cools to 50 DEG C with the furnace hereinafter, obtaining parent glass after 3 hours；Parent glass is put into and is protected with inert atmosphere
In the crystallization furnace of protection unit, crystallization is heat-treated 20 hours at 250 DEG C, and a large amount of distributions are precipitated in inside glass in crystallization process
Even crystallite dimension is the PbBr of 500nm or so2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbBr of embodiment 42Crystallite
Compound chalcogenide glass ceramic material.
Embodiment 5: taking X is I, and when x=0.4, y=0.2, a mole composition for chalcogenide glass ceramic material is indicated by chemical formula
For 40GeS2·40Sb2S3·20PbI2, raw material Ge, Sb, S and PbI are calculated according to this mole composition2Weight, be full of
It weighs and is uniformly mixed in the glove box of the drying of inert gas；Then uniformly mixed raw material is fitted into and is soaked in chloroazotic acid in advance
It steeped 2 hours and in the quartz ampoule dried after being washed with deionized water, then vacuumized, when the vacuum degree in quartz ampoule is less than 10- 3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to 340 with the rate of 2 DEG C/min
DEG C, it after heat preservation 3 hours, then with the rate of 2 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating rate of 1 DEG C/min
900 DEG C are slowly increased to, is waved melted 10 hours；Then 860 DEG C are cooled to the rate of 2 DEG C/min；Hereafter erect quartz ampoule
And stand 0.5 hour after in mixture of ice and water quenching；Finally quartz ampoule is placed in 220 DEG C of fine annealing furnace and is annealed, it is permanent
Temperature annealing cools to 50 DEG C with the furnace hereinafter, obtaining parent glass after 3 hours；Parent glass is put into inert atmosphere protection
In the crystallization furnace of device, crystallization is heat-treated 10 hours at 290 DEG C, is largely evenly distributed in crystallization process in inside glass precipitation
Crystallite dimension be 2000nm or so PbI2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbI of embodiment 52Crystallite is multiple
Close chalcogenide glass ceramic material.
The X ray diffracting spectrum of chalcogenide glass ceramic material is shown in Fig. 3 in embodiment 5.It can be seen from figure 3 that after crystallization heat treatment
Sample in PbI has been precipitated2Crystal.
Embodiment 6: taking X is I, and when x=0.1, y=0.25, a mole composition for chalcogenide glass ceramic material presses chemical formula table
It is shown as 65GeS2·10Sb2S3·25PbI2, raw material Ge, Sb, S and PbI are calculated according to this mole composition2Weight, filling
It weighs and is uniformly mixed in the glove box of the drying of full inert gas；Then uniformly mixed raw material is fitted into advance in chloroazotic acid
It impregnated 2 hours and in the quartz ampoule dried after being washed with deionized water, then vacuumized, when the vacuum degree in quartz ampoule is less than
10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, is first warming up to the rate of 2 DEG C/min
It after 340 DEG C, heat preservation 3 hours, then with the rate of 2 DEG C/min is warming up to 750 DEG C, keeps the temperature 2 hours；Then with the heating of 1 DEG C/min
Rate is slowly increased to 950 DEG C, waves melted 10 hours；Then 880 DEG C are cooled to the rate of 2 DEG C/min；Hereafter make quartz ampoule
After erectting and standing 0.5 hour in mixture of ice and water quenching；Finally quartz ampoule is placed in 240 DEG C of fine annealing furnace and is moved back
Fire, cycle annealing cool to 50 DEG C with the furnace hereinafter, obtaining parent glass after 5 hours；Parent glass is put into indifferent gas
In the crystallization furnace of atmosphere protective device, crystallization is heat-treated 20 hours at 300 DEG C, is precipitated a large amount of points in inside glass in crystallization process
The uniform crystallite dimension of cloth is the PbI of 1600nm or so2Crystallite finally cools to room temperature with the furnace, that is, obtains the PbI of embodiment 62
The compound chalcogenide glass ceramic material of crystallite.
Claims (8)
1. a kind of compound chalcogenide glass ceramic material of lead halide crystallite, it is characterised in that mole group of the chalcogenide glass ceramic material
It is indicated at by chemical formula are as follows: (1-x-y) GeS2·xSb2S3·yPbX2, wherein x=0.1 ~ 0.85, y=0.1 ~ 0.25, X Cl, Br
Or I, PbX2It is compound in the chalcogenide glass ceramic material with the microcrystalline form of precipitation.
2. the compound chalcogenide glass ceramic material of a kind of lead halide crystallite according to claim 1, it is characterised in that x=0.15 ~
0.85, y=0.1 ~ 0.15.
3. the compound chalcogenide glass ceramic material of a kind of lead halide crystallite according to claim 1, it is characterised in that x=0.1 ~
0.8, y=0.15 ~ 0.2.
4. the compound chalcogenide glass ceramic material of a kind of lead halide crystallite according to claim 1, it is characterised in that x=0.1 ~
0.75, y=0.2 ~ 0.25.
5. the compound chalcogenide glass ceramic material of a kind of lead halide crystallite according to claim 1, it is characterised in that described
PbX2The crystallite dimension of crystallite is 50~2000 nanometers.
6. a kind of preparation method of the compound chalcogenide glass ceramic material of lead halide crystallite, it is characterised in that the following steps are included:
(1) according to mole constitutional chemistry formula (1-x-y) GeS2·xSb2S3·yPbX2, wherein x=0.1 ~ 0.85, y=0.1 ~ 0.25, X
For Cl, Br or I, with Ge, Sb, S and PbX2For raw material, calculates and each raw material is weighed；
(2) in the dry environment full of inert gas, by Ge, Sb, S and PbX2After raw material mixing, it is placed in quartz ampoule and takes out
Vacuum is to vacuum degree less than 10-3Pa, then seal quartz ampoule and be placed in heating equipment；
(3) heating equipment is warming up to 800~900 DEG C, quenching after being melted 6~18 hours obtains unannealed glass, measures this not
The glass transformation temperature T of annealed glassg, then the unannealed glass is placed in fine annealing furnace, than glass transformation temperature Tg
Cycle annealing 2~5 hours at a temperature of low 10~30 DEG C cools to 50 DEG C with the furnace hereinafter, obtaining parent glass later；
(4) parent glass is put into the crystallization furnace with inert atmosphere protection device, than glass transformation temperature TgIt is high by 10~40
Crystallization is heat-treated 3~100 hours at a temperature of DEG C, and the PbX being largely evenly distributed is precipitated in crystallization process in inside glass2It is micro-
Crystalline substance finally cools to room temperature with the furnace, i.e. the acquisition compound chalcogenide glass ceramic material of lead halide crystallite.
7. a kind of preparation method of the compound chalcogenide glass ceramic material of lead halide crystallite according to claim 6, feature
It is that detailed process is as follows for step (3): heating equipment is made to be to slowly warm up to 340 with the heating rate of 1~2 DEG C/min first
DEG C, and keep the temperature 1~3 hour at this temperature；Heating equipment is set to be to slowly warm up to 750 with the heating rate of 2~5 DEG C/min again
DEG C, and keep the temperature 1~2 hour at this temperature；Then 800~950 DEG C are to slowly warm up to the heating rate of 1~2 DEG C/min, and
8~10 hours are kept the temperature at this temperature, quartz ampoule is shaken or vibrated by heat preservation while；Later with 2~3 DEG C/min's
Rate of temperature fall is cooled to 780~900 DEG C；Hereafter mixed in air or ice water after erectting quartz ampoule and standing 0.5~2 hour
Close quenching in object；Finally than glass transformation temperature T in fine annealing furnacegLow 10~30 thermostatic annealing 2~5 is small
When, 50 DEG C are cooled to the furnace later hereinafter, obtaining parent glass.
8. a kind of preparation method of the compound chalcogenide glass ceramic material of lead halide crystallite according to claim 6, feature
It is in step (4), the PbX being precipitated in crystallization process2The crystallite dimension of crystallite is 50~2000 nanometers.
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| CN109928640A (en) * | 2019-04-03 | 2019-06-25 | 宁波大学 | Inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material and preparation method thereof |
| CN111592227A (en) * | 2020-04-28 | 2020-08-28 | 宁波大学 | Cs3Sb2Br9Perovskite nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
| CN114276023A (en) * | 2021-11-17 | 2022-04-05 | 宁波大学 | Infrared chalcogenide glass ceramic optical fiber and preparation method thereof |
| CN115893478A (en) * | 2022-11-14 | 2023-04-04 | 滨州医学院 | Bromine sulfur germanium lead compound and preparation method and application thereof |
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| CN111592227B (en) * | 2020-04-28 | 2022-05-17 | 宁波大学 | Cs3Sb2Br9Perovskite nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
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