CN109928640A - Inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material and preparation method thereof - Google Patents
Inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material and preparation method thereof Download PDFInfo
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Abstract
A mole composition for inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material disclosed by the invention is indicated by chemical formula are as follows: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3, wherein x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I, CsPbX3It is compound in the chalcogenide glass ceramic material with the nanometer crystalline form of precipitation.The material is transparent in 2~10 micrometer spectrums, 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 and relevant quantum dot light emitting material.The preparation method of the material is with GeS2‑Sb2S3‑Ga2S3For glass matrix, the CsPbX close to saturation is introduced3Ingredient prepares basic chalcogenide glass using melt quenching method, is then heat-treated by crystallization, can control and CsPbX is precipitated3It is nanocrystalline.The preparation method of the material can need to design and select suitable glass to form according to function, and CsPbX is precipitated in control3Crystallite dimension and distribution.
Description
Technical field
The invention belongs to functional glass ceramic material fields, and in particular to a kind of inorganic halide lead caesium nanocomposite sulphur system
Glass ceramic material and preparation method thereof can be applied to infrared optics and photonics.
Background technique
Inorganic perovskite CsPbX3(X=Cl, Br, I) is nanocrystalline to possess unique optical universal, high luminous quantum efficiency
And the advantages that easily prepared, cause the extensive concern of researcher.However, CsPbX3Material is in oxidation and moist atmosphere
It is in environment and unstable, it is greatly limited in the application of all kinds of photoelectric fields, such as solar battery, laser and display
Deng.It therefore, is raising CsPbX3Nanocrystalline stability, a kind of effective method are that it is with organic polymer or inorganic
The inert bases such as glass are mutually compound.
It is well known that the light function nano obtained in oxide glass by crystallization heat treatment is brilliant or quanta point material has
There is excellent both thermally and chemically stability.In recent years, a variety of CsPbX are had reported3The oxide glass-ceramics of nanocomposite,
And its novel photonic nature and application is studied, such as unique luminous and Random Laser characteristic (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).).But the preparation strategy taken in the thesis work reported at present be all directly will be relevant
Halide is mixed with oxide raw material, the melting under open atmosphere.This preparation strategy inevitably will cause halide
Volatilization, leads to sample preparation poor repeatability.Therefore, it is necessary to redesign glass composition and preparation method, repeatably obtain each
Class CsPbX3The glass ceramic material of nanocomposite.
Different from oxide glass, chalcogenide glass is to carry out melting-quenching acquisition in vacuum-tight quartz glass tube
's.Chalcogenide glass possesses good halide solubility, and does not have the loss of halide during glass preparation.Especially
It is that chalcogenide glass has unique low phonon energy, the wide attributes such as infrared transparent window and good rare earth solubility, various
Photon field possesses good application prospect.In addition, although having CsCl, RbI and Cs in chalcogenide glass3LaCl6Equal halide are received
Rice partial crystallization crystalline substance research report, but never obtained CsPbX3The chalcogenide glass ceramic of perovskite nanocomposite.By careful
Composition design and Crystallizing treatment, prepare CsPbX3The chalcogenide glass ceramic of nanocomposite have good researching value with
Application value.
Summary of the invention
The technical problems to be solved by the present invention are: in view of the deficiencies of the prior art, a kind of inorganic halide lead caesium is provided and is received
Brilliant compound chalcogenide glass ceramic material of rice and preparation method thereof, the chalcogenide glass ceramic material is in 2~10 micrometer spectrums
It is transparent, there is preferable both thermally and chemically stability, good fracture toughness, be adapted for rare earth ion doped research and develop in novel
Infraluminescence or laser material and relevant quantum dot light emitting material.The preparation method of the chalcogenide glass ceramic material being capable of root
It needs to design and select suitable glass to form according to function, CsPbX is precipitated in control3Crystallite dimension and distribution.
The technical scheme of the invention to solve the technical problem is: inorganic halide lead caesium nanocomposite sulphur system glass
A mole composition for glass ceramic material, the chalcogenide glass ceramic material is indicated by chemical formula are as follows: (1-x-y-z) GeS2·xSb2S3·
yGa2S3·zCsPbX3, wherein x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I,
CsPbX3It is compound in the chalcogenide glass ceramic material with the nanometer crystalline form of precipitation.
A mole composition for inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material of the present invention is indicated by chemical formula are as follows:
(1-x-y-z)GeS2·xSb2S3·yGa2S3·zCsPbX3, wherein x=0.15~0.75, y=0.05~0.2, z=0.05
~0.1, X Cl, Br or I, this mole composition connect halide (the i.e. caesium halide and lead halide) content introduced in parent glass
Nearly degree of super saturation, it can be ensured that in the crystallization heat treatment process in later period, CsPbX3Crystal can be precipitated, and effectively control CsPbX3
The crystallite dimension of crystal is 5~50 nanometers, crystallinity about 20%.It should be noted that being suitably introduced into Ga2S3Glass can be improved
Halogen complex state in network improves metal halide solubility, guarantees the volume of caesium halide and lead halide.By CsPbX3It receives
The brilliant microcrystal grain of the rice of the present invention chalcogenide glass ceramic material compound with parent glass is transparent in 2~10 micrometer spectrums,
With preferably both thermally and chemically stability, good fracture toughness, be adapted for rare earth ion doped research and development it is novel in it is infrared
Luminous or laser material and relevant quantum dot light emitting material.
The preparation method of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material, comprising the following steps:
(1) raw material is chosen: according to mole constitutional chemistry formula (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3, choosing
Take Ge, Ga, Sb, S, CsX and PbX2Shared equivalents ratio weighs Ge, Ga, Sb, S simple substance and CsX, PbX2Raw materials of compound is spare,
Wherein, x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I；
(2) in the dry environment full of inert gas, by Ge, Sb, S, CsX and PbX2After raw material mixing, it is placed in quartz
In ampoule and vacuum degree is evacuated to less than 10-3Pa, then seal quartz ampoule and be placed in heating equipment；
(3) prepared by parent glass: heating equipment is warming up to 830~950 DEG C, it is cooling after being melted 8~18 hours, and it obtains not
Annealed glass measures the glass transformation temperature T of the unannealed glass by differential scanning calorimetry instrumentg, then this is not moved back
Flint glass is placed in fine annealing furnace and anneals, and annealing temperature is than glass transformation temperature TgAfter low 30 DEG C, cycle annealing 2~5 hours
50 DEG C are cooled to the furnace hereinafter, obtaining parent glass；
(4) parent glass is put into progress crystallization heat treatment, heat of crystallization in the crystallization furnace with inert atmosphere protection device
Treatment temperature is than glass transformation temperature Tg10~40 DEG C high, crystallization is heat-treated 3~100 hours at a temperature of this, makes inside glass
The CsPbX being largely evenly distributed is precipitated3It is nanocrystalline；Finally cool to room temperature with the furnace, i.e. acquisition inorganic halide lead caesium is nanocrystalline multiple
Close chalcogenide glass ceramic material.
Preferably, the specific preparation process of parent glass is as follows in step (3): making heating equipment lower than 2 DEG C/min
Heating rate be to slowly warm up to 340 DEG C, and at this temperature keep the temperature 1~3 hour；Make heating equipment lower than 5 DEG C/min again
Heating rate be to slowly warm up to 750 DEG C, and at this temperature keep the temperature 1~2 hour；Then make heating equipment with 1~2 DEG C/min
Heating rate be to slowly warm up to 830~950 DEG C, and at this temperature keep the temperature 8~10 hours, glass metal will be filled during heat preservation
Quartz ampoule shaken or vibrated；Hereafter 780~900 DEG C are cooled to the rate of temperature fall of 2~3 DEG C/min；Make quartzy peace
After small jar is erect and stands 0.5~2 hour, the quenching in air or mixture of ice and water；Than Glass Transition in fine annealing furnace
Temperature TgLow 30 DEG C of thermostatic is annealed 2~5 hours, cools to 50 DEG C with the furnace later hereinafter, obtaining parent glass.
The preparation method of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material of the present invention, with GeS2-Sb2S3-
Ga2S3For glass matrix, the CsPbX close to saturation is introduced3Ingredient prepares basic chalcogenide glass using melt quenching method, then
It is heat-treated by crystallization, can control and CsPbX is precipitated3It is nanocrystalline, obtain chalcogenide glass ceramic material.The method of the present invention being capable of basis
Function needs to design and select suitable glass to form, and CsPbX is precipitated in control3Crystallite dimension and distribution.With basic chalcogenide glass
It compares, inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material prepared by the present invention has the thermodynamics significantly improved steady
Qualitative and environment resistant impact property, has been provided simultaneously with rare earth ion doped luminescence enhancement performance and quantum dot light emitting characteristic.With with
It is compared toward the preparation method of chalcogenide glass ceramic material, controllable method for preparing proposed by the present invention can be simply by by halogenation
Caesium, lead halide and chalcogenide glass matrix carry out consolute and again Crystallizing treatment, and CsPbX is precipitated in control3Crystal obtains performance difference
Saturating infrared function chalcogenide glass ceramic.
Preferably, the CsPbX being precipitated in step (4)3Nanocrystalline crystallite dimension is 5~50 nanometers.
Compared with the prior art, the advantages of the present invention are as follows: inorganic halide lead caesium nanocomposite chalcogenide glass of the present invention
A mole composition for ceramic material is indicated by chemical formula are as follows: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3, wherein x
=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I, this mole composition make to introduce in parent glass
Halide content close to degree of super saturation, it can be ensured that in the crystallization heat treatment process in later period, CsPbX3Crystal can be precipitated, and
Effectively control CsPbX3The crystallite dimension of crystal is 5~50 nanometers, crystallinity about 20%.By CsPbX3Nanocrystalline microcrystal grain with
The compound chalcogenide glass ceramic material of the present invention of parent glass is transparent in 2~10 micrometer spectrums, has preferable calorifics
With chemical stability, good fracture toughness, it is adapted for the novel middle infraluminescence of rare earth ion doped research and development or laser material
And relevant quantum dot light emitting material.The preparation side of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material of the present invention
Method can need to design and select suitable glass to form according to function, and CsPbX is precipitated in control3Crystallite dimension and distribution.With base
Plinth chalcogenide glass is compared, and inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material prepared by the present invention, which has, to be significantly improved
Thermodynamic stability and environment resistant impact property, be provided simultaneously with and sent out suitable for rare earth ion doped luminescence enhancement performance and quantum dot
Light characteristic.Compared with the preparation method of previous chalcogenide glass ceramic material, controllable method for preparing proposed by the present invention can be simple
By the way that caesium halide, lead halide and chalcogenide glass matrix are carried out consolute and again Crystallizing treatment, CsPbX is precipitated in control on ground3Crystal obtains
Obtain the saturating infrared function chalcogenide glass ceramic of performance difference.
Detailed description of the invention
Fig. 1 is the X ray diffracting spectrum of 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 3；
Fig. 4 is the scanning electron micrograph of chalcogenide glass ceramic material in embodiment 3.
Specific embodiment
Below in conjunction with attached Example, present invention is further described in detail.
Embodiment 1: taking X is Cl, x=0.3, y=0.1, z=0.06, and mole composition of chalcogenide glass ceramic material is by change
Formula indicates are as follows: 54GeS2·30Sb2S3·10Ga2S3·6CsPbCl3, according to this mole composition calculate raw material Ge, Ga, Sb,
S, CsCl and PbCl2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by be uniformly mixed
Raw material is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then is taken out true
Sky, when the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated,
After being first warming up to 340 DEG C, heat preservation 3 hours with the rate of 2 DEG C/min, then with the rate of 4 DEG C/min 750 DEG C are warming up to, heat preservation 2 is small
When；Then 920 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 10 hours；Then with 3 DEG C/min of rate
It is cooled to 850 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；Finally it is placed in 240 DEG C of precision
It anneals in annealing furnace, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 5 hours；Obtained parent glass is put
Enter to be heat-treated in the crystallization furnace that temperature is 270 DEG C 20 hours, finally furnace cooling is nanocrystalline multiple to get inorganic halide lead caesium is arrived again
Close chalcogenide glass ceramic material.
The X ray diffracting spectrum of chalcogenide glass ceramic material is shown in that Fig. 1, scanning electron micrograph are shown in Fig. 2 in embodiment 1.
From Fig. 1 and Fig. 2 as it can be seen that CsPbCl has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 20nm.In addition, phase
Than parent glass, CsPbCl obtained3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 8 DEG C, breaks
It splits toughness and improves 2 times, hardness enhances 10%, does not observe crack propagation under micro indentation effect, has preferable heat
Learn stability and environment resistant impact property.
Embodiment 2: taking X is Cl, x=0.5, y=0.12, z=0.08, and mole composition of chalcogenide glass ceramic material is by change
Formula indicates are as follows: 30GeS2·50Sb2S3·12Ga2S3·8CsPbCl3, according to this mole composition calculate raw material Ge, Ga, Sb,
S, CsCl and PbCl2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by be uniformly mixed
Raw material is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then is taken out true
Sky, when the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated,
After being first warming up to 340 DEG C, heat preservation 3 hours with the rate of 2 DEG C/min, then with the rate of 5 DEG C/min 750 DEG C are warming up to, heat preservation 2 is small
When；Then 850 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 10 hours；Then with 2 DEG C/min of rate
It is cooled to 800 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；Finally it is placed in 220 DEG C of precision
It anneals in annealing furnace, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 3 hours；Obtained parent glass is put
Enter to be heat-treated in the crystallization furnace that temperature is 240 DEG C 20 hours, finally furnace cooling is nanocrystalline multiple to get inorganic halide lead caesium is arrived again
Close chalcogenide glass ceramic material.CsPbCl has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 30nm.This
Outside, parent glass, CsPbCl obtained are compared3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 10
DEG C, hardness enhances 15%, does not observe crack propagation under micro indentation effect, has preferably thermal stability and anti-ring
Border impact property.
Embodiment 3: taking X is Br, x=0.4, y=0.2, z=0.07, and mole composition of chalcogenide glass ceramic material is by change
Formula indicates are as follows: 33GeS2·40Sb2S3·20Ga2S3·7CsPbBr3, according to this mole composition calculate raw material Ge, Ga, Sb,
S, CsBr and PbBr2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by be uniformly mixed
Raw material is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then is taken out true
Sky, when the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated,
After being first warming up to 340 DEG C, heat preservation 3 hours with the rate of 2 DEG C/min, then with the rate of 3 DEG C/min 750 DEG C are warming up to, heat preservation 2 is small
When；Then 900 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 8 hours；Then dropped with 2 DEG C/min of rate
Temperature is to 840 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；240 DEG C of precision is finally placed in move back
It anneals in stove, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 3 hours；Obtained parent glass is put into
Temperature is be heat-treated 10 hours in 270 DEG C of crystallization furnace, finally again furnace cooling to get to inorganic halide lead caesium nanocomposite
Chalcogenide glass ceramic material.
The X ray diffracting spectrum of chalcogenide glass ceramic material is shown in that Fig. 3, scanning electron micrograph are shown in Fig. 4 in embodiment 3.
From Fig. 3 and Fig. 4 as it can be seen that CsPbBr has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 40nm.In addition, phase
Than parent glass, CsPbBr obtained3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 10 DEG C, breaks
It splits toughness and improves 2 times, hardness enhances 8%, does not observe crack propagation under micro indentation effect, has preferable calorifics
Stability and environment resistant impact property.
Embodiment 4: taking X is Br, x=0.5, y=0.1, z=0.1, and mole composition of chalcogenide glass ceramic material is by chemistry
Formula indicates are as follows: 30GeS2·50Sb2S3·10Ga2S3·10CsPbBr3, according to this mole composition calculate raw material Ge, Ga, Sb,
S, CsBr and PbBr2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by be uniformly mixed
Raw material is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then is taken out true
Sky, when the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated,
After being first warming up to 340 DEG C, heat preservation 3 hours with the rate of 1 DEG C/min, then with the rate of 4 DEG C/min 750 DEG C are warming up to, heat preservation 2 is small
When；Then 880 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 8 hours；Then dropped with 2 DEG C/min of rate
Temperature is to 780 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；180 DEG C of precision is finally placed in move back
It anneals in stove, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 3 hours；Obtained parent glass is put into
Temperature is be heat-treated 20 hours in 230 DEG C of crystallization furnace, finally again furnace cooling to get to inorganic halide lead caesium nanocomposite
Chalcogenide glass ceramic material.CsPbBr has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 50nm.In addition,
Compared to parent glass, CsPbBr obtained3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 12 DEG C,
Hardness enhances 18%, does not observe crack propagation under micro indentation effect, has preferable thermal stability and environment resistant
Impact property.
Embodiment 5: taking X is I, x=0.2, y=0.05, z=0.05, and mole composition of chalcogenide glass ceramic material is by change
Formula indicates are as follows: 70GeS2·20Sb2S3·5Ga2S3·5CsPbI3, according to this mole composition calculate raw material Ge, Ga, Sb, S,
CsI and PbI2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by uniformly mixed raw material
It is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then vacuumized,
When the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated, first with
The rate of 2 DEG C/min is warming up to 340 DEG C, 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 950 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 10 hours；Then cooled down with 2 DEG C/min of rate
To 860 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；Finally it is placed in 260 DEG C of fine annealing
It anneals in furnace, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 3 hours；Obtained parent glass is put into temperature
Degree be heat-treated 5 hours in 290 DEG C of crystallization furnace, finally again furnace cooling to get to inorganic halide lead caesium nanocomposite sulphur
Series vitro-ceramic material.CsPbI has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 5nm.In addition, comparing
Parent glass, CsPbI obtained3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 5 DEG C, and hardness increases
Strong by 8%, fracture toughness improves 1.5 times, does not observe crack propagation under micro indentation effect, has preferable calorifics steady
Qualitative and environment resistant impact property.
Embodiment 6: taking X is I, x=0.15, y=0.15, z=0.1, and mole composition of chalcogenide glass ceramic material is by change
Formula indicates are as follows: 60GeS2·15Sb2S3·15Ga2S3·10CsPbI3, according to this mole composition calculate raw material Ge, Ga, Sb,
S, CsI and PbI2Weight, weigh and be uniformly mixed in the glove box full of inert gas；Then by uniformly mixed original
Material is fitted into quartz ampoule, which impregnated 2 hours in chloroazotic acid in advance and dried after being washed with deionized water, then is taken out true
Sky, when the vacuum degree in quartz ampoule is 10-3It is sealed when Pa with oxy arc；The quartz ampoule sealed is put into rocking furnace and is heated,
After being first warming up to 340 DEG C, heat preservation 3 hours with the rate of 2 DEG C/min, then with the rate of 2 DEG C/min 750 DEG C are warming up to, heat preservation 2 is small
When；Then 930 DEG C are slowly increased to 1 DEG C/min of heating rate, waved melted 10 hours；Then with 2 DEG C/min of rate
It is cooled to 850 DEG C；Erect quartz ampoule, standing quenching in mixture of ice and water after 0.5 hour；Finally it is placed in 250 DEG C of precision
It anneals in annealing furnace, constant temperature cools to 50 DEG C with the furnace hereinafter, both obtaining parent glass after 3 hours；Obtained parent glass is put
Enter to be heat-treated in the crystallization furnace that temperature is 280 DEG C 5 hours, finally furnace cooling is nanocrystalline multiple to get inorganic halide lead caesium is arrived again
Close chalcogenide glass ceramic material.CsPbI has been precipitated in heat of crystallization treated sample3Crystal, crystallite dimension are about 30nm.This
Outside, parent glass, CsPbI obtained are compared3The glass transformation temperature of the chalcogenide glass ceramic of nanocomposite improves 12
DEG C, hardness enhances 15%, and fracture toughness improves 2 times, does not observe crack propagation under micro indentation effect, has preferable
Thermal stability and environment resistant impact property.
Claims (4)
1. inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material, which is characterized in that the chalcogenide glass ceramic material
Mole composition by chemical formula indicate are as follows: (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3, wherein x=0.15~
0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I, CsPbX3The sulphur is compound in the nanometer crystalline form of precipitation
In series vitro-ceramic material.
2. the preparation method of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material, which is characterized in that including following step
It is rapid:
(1) raw material is chosen: according to mole constitutional chemistry formula (1-x-y-z) GeS2·xSb2S3·yGa2S3·zCsPbX3, choose
Ge, Ga, Sb, S, CsX and PbX2Shared equivalents ratio weighs Ge, Ga, Sb, S simple substance and CsX, PbX2Raw materials of compound is spare,
In, x=0.15~0.75, y=0.05~0.2, z=0.05~0.1, X Cl, Br or I；
(2) in the dry environment full of inert gas, by Ge, Ga, Sb, S, CsX and PbX2After raw material mixing, it is placed in quartzy peace
In small jar and vacuum degree is evacuated to less than 10-3Pa, then seal quartz ampoule and be placed in heating equipment；
(3) prepared by parent glass: heating equipment is warming up to 830~950 DEG C, it is cooling after being melted 8~18 hours, and it obtains unannealed
Glass measures the glass transformation temperature T of the unannealed glass by differential scanning calorimetry instrumentg, then by the unannealed glass
Glass is placed in fine annealing furnace and anneals, and annealing temperature is than glass transformation temperature TgWith furnace after low 30 DEG C, cycle annealing 2~5 hours
50 DEG C are cooled to hereinafter, obtaining parent glass；
(4) parent glass is put into progress crystallization heat treatment in the crystallization furnace with inert atmosphere protection device, crystallization heat treatment
Temperature is than glass transformation temperature Tg10~40 DEG C high, crystallization is heat-treated 3~100 hours at a temperature of this, and inside glass is precipitated
The CsPbX being largely evenly distributed3It is nanocrystalline；Finally cool to room temperature with the furnace, i.e. acquisition inorganic halide lead caesium nanocomposite sulphur
Series vitro-ceramic material.
3. the preparation method of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material according to claim 2,
It is characterized in that, the specific preparation process of parent glass is as follows in step (3): making heating equipment with the heating speed lower than 2 DEG C/min
Rate is to slowly warm up to 340 DEG C, and keeps the temperature 1~3 hour at this temperature；Make heating equipment with the heating speed lower than 5 DEG C/min again
Rate is to slowly warm up to 750 DEG C, and keeps the temperature 1~2 hour at this temperature；Then make heating equipment with the heating speed of 1~2 DEG C/min
Rate is to slowly warm up to 830~950 DEG C, and keeps the temperature 8~10 hours at this temperature, pacifies the quartz for filling glass metal during heat preservation
Small jar is shaken or is vibrated；Hereafter 780~900 DEG C are cooled to the rate of temperature fall of 2~3 DEG C/min；Erect quartz ampoule simultaneously
After standing 0.5~2 hour, the quenching in air or mixture of ice and water；Than glass transformation temperature T in fine annealing furnacegIt is low
30 DEG C of thermostatic is annealed 2~5 hours, cools to 50 DEG C with the furnace later hereinafter, obtaining parent glass.
4. the preparation method of inorganic halide lead caesium nanocomposite chalcogenide glass ceramic material according to claim 2,
It is characterized in that, the CsPbX being precipitated in step (4)3Nanocrystalline crystallite dimension is 5~50 nanometers.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910264958.4A CN109928640B (en) | 2019-04-03 | 2019-04-03 | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
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| CN201910264958.4A CN109928640B (en) | 2019-04-03 | 2019-04-03 | Inorganic lead-cesium halide nanocrystalline composite chalcogenide glass ceramic material and preparation method thereof |
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| CN109928640A true CN109928640A (en) | 2019-06-25 |
| CN109928640B CN109928640B (en) | 2021-08-27 |
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