CN108193271A - Preparation Method is melted in a kind of area that moves horizontally of bromine lead caesium monocrystalline - Google Patents
Preparation Method is melted in a kind of area that moves horizontally of bromine lead caesium monocrystalline Download PDFInfo
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- CN108193271A CN108193271A CN201711466810.6A CN201711466810A CN108193271A CN 108193271 A CN108193271 A CN 108193271A CN 201711466810 A CN201711466810 A CN 201711466810A CN 108193271 A CN108193271 A CN 108193271A
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- ampoule
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/14—Crucibles or vessels
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
- C30B13/28—Controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of areas that moves horizontally of bromine lead caesium monocrystalline to be melted Preparation Method, specifically includes following steps：(1) quartz ampoule is placed in reacting furnace intracavitary, is passed through methane and carries out plating carbon film and handle to obtain plating carbon ampoule；(2) bromine lead caesium powder is packed into the plating carbon ampoule, is evacuated and hermetically sealed, being placed in heat-treatment furnace makes bromine lead caesium powder first melt is cooled and solidified to form polycrystalline charge bar afterwards；(3) sealed ampoule equipped with polycrystalline charge bar is placed in and moved horizontally in zone melting furnace, heater is warming up to 620 650 DEG C, heater is made to be moved to the tail end of sealed ampoule since the tip of sealed ampoule, the growth of bromine lead caesium crystal is thus completed, obtains bromine lead caesium crystal.The present invention is improved by the reaction condition and parameter to its crucial overall flow technological design and each step, be can effectively solve the problem that mechanical shock is big in crystal growing process, crystals thermal stress are high compared with prior art, is difficult to the problems such as growing large-size bromine lead caesium monocrystalline.
Description
Technical field
The invention belongs to field of crystal growth, more particularly, to a kind of bromine lead caesium (CsPbBr3) monocrystalline moves horizontally
Area is melted Preparation Method, and bromine lead caesium monocrystalline obtained can be widely applied to high-energy ray sensing, the energy, LED and the multiple fields such as show.
Background technology
High energy nuclear radiation detector material and its Detection Techniques are widely used, such as day in many fields
Body physics, security, military affairs, medical treatment, nuclear industry and environmental monitoring etc..As application scenarios are to accuracy of detection and sensitivity requirement
It is continuously improved, higher requirement also proposed with material to nuclear radiation detector.
Following feature will generally be had by preparing the material used in high energy nuclear radiation detector：Energy gap is big, former
Sub- ordinal number is high, density is big and the higher carrier mobility service life is accumulated etc..CsPbBr3Possess big energy gap (Eg=
2.25eV), better than existing commercialization nuclear radiation detector material C dZnTe (Eg=1.57eV), larger density (4.86g/
cm3), product of higher carrier mobility service life (10-3cm2/ V), therefore be highly suitable for preparing indoor temperature nucleus radiation detector.
In addition, CsPbBr3With relatively low fusing point (567 DEG C) and solidification point (514 DEG C), it is suitble to prepare bromine lead caesium list using melt method
It is brilliant.
Current existing CsPbBr3Method for preparing single crystal mainly includes melt method (such as Bridgman method, vertical temperature gradient
Growth method) and two major class of solwution method.Traditional melt method crystal growth generally use Bridgman method, this is because Bridgman
Method has constant thermal field, this is significant to crystal growth, but since Bridgman method growth course is to lean on crystal in itself
Movement complete, this just inevitably brings mechanical shock, thus has researcher to devise Vertical Temperature ladder again later
Spend growth method, it is motionless that this method fixes crystal, and crystal growth is completed by the variation of temperature gradient, but this method according to
Rely the stability of thermal field variation, while want the monocrystalline of growing large-size that must increase warm area quantity, production cost is higher.For molten
Liquid method, growth Centimeter Level even larger sized monocrystalline inefficiency, additionally, due to the nucleation rate under liquid environment and growth
The more difficult accurate control of rate, and inclusion enclave is easily generated, crystal quality is seriously affected, therefore, it is difficult to produce large-size high-quality in batches
The monocrystalline of amount.
One kind that zone-melting process belongs to melt method is moved horizontally, growth process is in the constant item of the set temperature of heater
Under part, rod-like polycrystal ingot is melted by a narrow area by heater, rest part keeps solid-state, and then heater is transported in the horizontal direction
It is dynamic, melting zone is made to be moved along the length direction of polycrystalline ingot, the rest part of crystal ingot entire in this way crystallizes again after melting successively, that is, passes through
Drive the solid liquid interface of material is mobile in the horizontal direction to complete crystal growth.
Due to CsPbBr3Monocrystalline is more crisp, the spy during easily broken and melt method for growing Jing Guo phase transformation twice
Point, therefore it is an important research topic to overcome the internal stress generated during growth, in general can be given birth to by reducing
Long speed and temperature gradient reduce internal stress, but the excessively slow speed of growth can reduce production efficiency, and too small temperature gradient is cut
Weak crystal growth power, in addition, traditional vertical-growth mode is since crystal gravity in itself is in growth course
Internal stress can be introduced, and by the way of horizontal growth, the influence of crystal gravity itself is eliminated, cooperation is coated with the quartz of carbon film
Container can greatly reduce this internal stress, therefore can obtain the monocrystalline of high quality.Move horizontally zone-melting process growth CsPbBr3
There are following advantages for crystal：
1) be conducive to CsPbBr3Transformation stress is from the release of ampoule wall in crystal growing process.Due to CsPbBr3Crystal is given birth to
There is phase transformation twice, i.e., with the reduction of temperature, the CsPbBr at 130 DEG C in growth process3Crystal structure is from high temperature cubic phase (Pm-
3m, a=b=c=0.5874nm) it is changed into tetragonal phase (P4/mbm, a=b=0.5859nm, c=0.5895nm), it is down to 88 DEG C
When, but from tetragonal phase converting be orthorhombic phase (Pbnm, a=0.8207nm, b=0.8255nm, c=1.1759nm).In phase transformation
Cheng Zhong due to the variation of lattice parameter, generates larger stress in crystal.Horizontal zone-melting technique is by moving horizontally heater
Realize CsPbBr3Crystal growth, horizontal positioned rod-like polycrystal ingot top area are in open free state, are conducive in this way
CsPbBr3Transformation stress is from the release of ampoule wall in crystal growing process, so as to greatly reduce caused by transformation stress
Crystal cleavage.
2) since crystal growth is carried out along horizontal direction, stress and unevenness caused by avoiding crystal self gravitation effect
Even problem is suitble to prepare the large size single crystal that integrality is good, uniformity is good.
3) since zone-melting process can purify crystalline material while crystal growth, segregation coefficient can be made smaller
Impurity enriched thus can obtain the higher crystal of purity in the tail end of crystal.
4) in addition this method growth crystal also has plurality of advantages, for example equipment is simple, mechanical shock is small.Visible horizon moves
Zone-melting process, which has, prepares the large scale CsPbBr that crackle is few, purity is high, integrality is good, crystalline phase is single3The advantage of crystal.It is and current
Domestic and international researcher moves horizontally zone-melting process growth CsPbBr without use3The successful case of monocrystalline.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the purpose of the present invention is to provide a kind of bromine lead caesium monocrystalline
It moves horizontally area and Preparation Method is melted, for CsPbBr3Monocrystalline is more crisp, passes through during easily broken and melt method for growing
Twice the characteristics of phase transformation, wherein by (being handled including ampoule, the preparation of polycrystalline charge bar its crucial overall flow technological design
And horizontal zone melting crystal growth) and each step reaction condition and parameter (such as gas flow, movement speed, treatment temperature
With the time etc.) it is improved, it can effectively solve the problem that problems with compared with prior art：
1) CsPbBr is solved3The problem of transformation stress is big in crystal growing process and easily cracks.Due to CsPbBr3Crystal
There is phase transformation twice, i.e., with the reduction of temperature, the CsPbBr at 130 DEG C in growth course3Crystal structure turns from high temperature cubic phase
Become tetragonal phase, when being down to 88 DEG C, and from tetragonal phase converting be orthorhombic phase.In phase transition process, due to the variation of lattice parameter,
Larger stress is generated in crystal.Horizontal zone-melting technique is to realize CsPbBr by moving horizontally heater3Crystal growth, it is horizontal
The rod-like polycrystal ingot top area of placement is in open free state, is conducive to CsPbBr in this way3Phase in crystal growing process
Varying stress is from the release of ampoule wall, so as to greatly reduce the crystal cleavage problem caused by transformation stress.
2) large scale CsPbBr is solved3The problem of crystal growth is difficult.Bridgman method is growth widely used at present
The method of large size single crystal, but since this method is the mobile realization crystal growth by ampoule, caused by the movement of ampoule
Mechanical oscillation easily generate fault of construction in crystal.And vertical gradient freeze technique growing large-size monocrystalline, it needs mostly warm
The growth furnace in area, equipment is complicated and thermal field stability is difficult to ensure that.Solution growth CsPbBr3Crystal can be at a lower temperature
It carries out, stress problem caused by phase transformation can be avoided, but solution growth easily generates inclusion enclave, seriously affects crystal quality,
In addition solution growth Centimeter Level even larger sized monocrystalline inefficiency.And zone-melting process crystal growth is moved horizontally, pacify
Small jar is motionless, and heater is moved along horizontal direction progress, and equipment is simple, mechanical shock is small etc., avoids due to gravity
Caused stress and problem of non-uniform are suitble to prepare the large scale CsPbBr that integrality is good, uniformity is good3Monocrystalline.
3) CsPbBr is solved3Crystal purity and monocrystalline quality problems.Detector is to material purity and monocrystalline quality requirement pole
The presence of height, trace impurity and defect can all cause detection efficient to reduce.Since zone-melting process can be to crystalline substance while crystal growth
Body material is further purified, and can make the smaller impurity enriched of segregation coefficient in the tail end of crystal, thus can be obtained pure
The higher CsPbBr of degree3Crystal.
The present invention provides a kind of areas that moves horizontally of bromine lead caesium monocrystalline to be melted Preparation Method, which is characterized in that including following
Step：
(1) the cylindrical quartz ampoule with conical tip of clean dried is placed in reacting furnace intracavitary and is evacuated to vacuum,
Then furnace chamber is warming up to 1000-1150 DEG C, methane is passed through into the quartz ampoule while carrier gas is passed through, so as to the stone
English ampoule interior wall carries out plating carbon film and handles to obtain plating carbon ampoule；
(2) it is packed into CsPbBr in the plating carbon ampoule obtained to the step (1)3Powder is evacuated and hermetically sealed to obtain
Then sealed ampoule will be equipped with the CsPbBr3The sealed ampoule of powder is placed in heat-treatment furnace, and heat-treatment furnace heating is made
CsPbBr3Powder melts, and then cooling makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar, obtains equipped with polycrystalline charge bar
Sealed ampoule；
(3) sealed ampoule equipped with polycrystalline charge bar that the step (2) obtains is placed in and moves horizontally zone melting furnace
In quartz ampoule, the heater for moving horizontally zone melting furnace is moved to the tip of the sealed ampoule, and the heater is warming up to
620-650 DEG C, the heater is then moved with the speed of 5-20 μm/min, the heater is made to be opened from the tip of the sealed ampoule
Beginning is moved to the other end of the sealed ampoule, thus completes the growth course of bromine lead caesium crystal, obtains bromine lead caesium crystal.
As present invention further optimization, in the step (1), the carrier gas that the plating carbon film processing uses is that purity is
The nitrogen of 99.9-99.999%, the flow of the carrier gas is 70-110mL/s；The flow of the methane be 20-60mL/s, the methane
Preferably purity is the methane of 99.9-99.999%；The plating carbon film processing preferred process 20-60min.
As present invention further optimization, in the step (1), the circle with conical tip of the clean dried
Cylindricality quartz ampoule is obtained by will be dried after the cylindrical cleaning for carrying conical tip；
Preferably, described clean is specifically：With mass fraction it is 65-68wt%'s by the cylinder with conical tip
Concentrated nitric acid impregnates, and is then cleaned with deionized water；Then, then by the quartz ampoule with acetone soln impregnate, and then spend from
Sub- water cleaning；Finally, which is cleaned by ultrasonic with deionized water.
As present invention further optimization, in the step (2), the polycrystalline charge bar is by first by the heat treatment
Stove is warming up to 570-600 DEG C by 6-12h, and then keeping the temperature 1-4h makes CsPbBr3Powder fully melts, and is finally dropped by 12-24h
It is obtained after warming to room temperature.
The present invention is first to carry out preferred cleaning to quartz ampoule, then carry out carbon coating processing；Specifically plated
During carbon process, it is that plating carbon furnace chamber first is evacuated to vacuum to be warming up to 1000-1150 DEG C again, 70- is first pressed when ventilating after stablizing
110mL/s speed is passed through nitrogen of the purity for 99.9-99.999% as carrier gas, then is passed through purity by 20-60mL/s speed and is
The methane of 99.9-99.999% continues 20-60min, thus forms carbon film on quartz ampoule inner wall, so as to be pacified using the plating carbon
Small jar carries out crystal growth.Plating carbon ampoule has many benefits for moving horizontally zone-melting process growth, is that carbon film can be to avoid crystalline substance first
Body and quartz wall adhesion reduce parasitic nucleation；Next alleviates crystal and the quartz container inner wall coefficient of expansion is unequal causes
Stress；Simultaneously for CsPbBr3Monocrystalline is more crisp, the spy during easily broken and melt method for growing Jing Guo phase transformation twice
Point moves horizontally melting zone method using plating carbon ampoule and combination and realizes CsPbBr by moving horizontally heater3Crystal growth, in this way
Horizontal positioned polycrystalline charge bar top area is in open free state, so as to be conducive to CsPbBr3In crystal growing process
Transformation stress greatly reduces the crystal cleavage problem caused by transformation stress from the release of plating carbon ampoule wall.
In crystal growth, the present invention is using the growth for moving horizontally zone-melting process progress bromine lead caesium monocrystalline, specifically will
Heter temperature is warming up to 620-650 DEG C, then moves melting zone center with the speed of 5-20 μm/min, makes melting zone from sealed ampoule
Tip start to be moved to the tail end of the sealed ampoule (even if the solid liquid interface of growth raw material is moved from the tip of ampoule in ampoule
To the tail end of ampoule), the growth course of bromine lead caesium crystal is thus completed, obtains bromine lead caesium crystal.As it can be seen that the present invention is by each
The overall co-ordination of step can obtain the CsPbBr for having many advantages, such as that crackle is few, purity is high, integrality is good, crystalline phase is single3It is single
It is brilliant.
Zone-melting process growth bromine lead caesium monocrystalline is moved horizontally in the present invention, is with CsPbBr3Polycrystalline charge bar is object；This is more
Brilliant charge bar is by first by CsPbBr3Powder fully melts, then slow cooling to room temperature makes the CsPbBr of molten state3Solidify shape
Into；The present invention is also by preferably controlling CsPbBr3The preparation process of polycrystalline charge bar, that is, first by CsPbBr3Powder passes through 6-12h
570-600 DEG C is warming up to, then keeping the temperature 1-4h makes CsPbBr3Powder fully melts, and is finally cooled to room temperature by 12-24h, by
Ingredient uniform polycrystalline charge bar is made in this, can further improve the subsequently bromine lead caesium crystal through moving horizontally zone-melting process acquisition
Quality.
Have the characteristics that by the above technical scheme conceived by the present invention as described below：It uses with conical tip
Ampoule is conducive in crystal growing process eliminating for extra nucleus at tip as the container for loading bromine lead caesium powder, passes through ampoule
Plating carbon and control heater slowly move horizontally the various stress releases be conducive in crystal growing process.With it is existing
CsPbBr3Growing technology is compared, due to using the fusing and crystallization for moving horizontally heater realization crystal ingot, polycrystalline charge bar top region
Domain is in open free state, is conducive to CsPbBr3Since stress caused by phase transformation twice is from ampoule wall in crystal growing process
Upper release.This method is opposite with mechanical shock compared with conventional crystal growing method such as Bridgman method, vertical zone-melting technique
Thermal stress smaller, inside crystal growing process is smaller, suitable for growing large-size CsPbBr3The advantages such as monocrystalline, while pass through water
The bromine lead caesium monocrystalline of flat zone-melting process growth has many advantages, such as that crackle is few, purity is high, integrality is good, crystalline phase is single, to prepare big ruler
Very little high-performance bromine lead caesium monocrystalline provides a kind of approach.
Description of the drawings
Fig. 1 is the structure diagram that zone melting furnace is moved horizontally in the embodiment of the present invention.
Fig. 2 is the CsPbBr grown in the embodiment of the present invention3Monocrystalline pictorial diagram.
Fig. 3 is CsPbBr in the embodiment of the present invention3The X ray diffracting spectrum of monocrystalline.
The meaning of each reference numeral is as follows in figure：1 is quartz ampoule；2 be heater；3 be stent；4 be guide rail；5 be pedestal；
6 be movable base.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Embodiment 1
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 110mL/s speed at 1150 DEG C, and former speed continuation is kept after stablizing
Carrier gas is passed through, and is passed through the methane that purity is 99.999% by 60mL/s speed and continues 20min, it then will plating carbon unit temp drop
To room temperature, plating carbon ampoule is obtained.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 620 DEG C, setting heater is with the speed of 5 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 2
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 110mL/s speed at 1150 DEG C, and former speed continuation is kept after stablizing
Carrier gas is passed through, and is passed through the methane that purity is 99.999% by 60mL/s speed and continues 20min, it then will plating carbon unit temp drop
To room temperature, plating carbon ampoule is obtained.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, its tip is made to place vertically downward, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes
CsPbBr3Powder fully melts, and last set heat-treatment furnace is cooled to room temperature by 16h, makes the CsPbBr of molten state3Solidification
Form polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 620 DEG C, setting heater is with the speed of 10 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 3
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 80mL/s speed at 1150 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 40mL/s speed and continue 20min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 620 DEG C, setting heater is with the speed of 20 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 4
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 80mL/s speed at 1100 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 40mL/s speed and continue 30min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, its tip is made to place vertically downward, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes
CsPbBr3Powder fully melts, and last set heat-treatment furnace is cooled to room temperature by 16h, makes the CsPbBr of molten state3Solidification
Form polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved into ampoule tip, it will
The heater for moving horizontally zone melting furnace is warming up to 635 DEG C, and setting heater is moved with the speed of 5 μm/min since ampoule tip
To the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and room temperature is down to by 48h, it completes
Entire crystal growing process.
Embodiment 5
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 80mL/s speed at 1100 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 40mL/s speed and continue 30min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 635 DEG C, setting heater is with the speed of 10 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 6
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 70mL/s speed at 1100 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 20mL/s speed and continue 30min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, its tip is made to place vertically downward, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes
CsPbBr3Powder fully melts, and last set heat-treatment furnace is cooled to room temperature by 16h, makes the CsPbBr of molten state3Solidification
Form polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 635 DEG C, setting heater is with the speed of 20 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 7
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 70mL/s speed at 1000 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 20mL/s speed and continue 60min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 650 DEG C, setting heater is with the speed of 5 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 8
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 70mL/s speed at 1000 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 20mL/s speed and continue 60min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 650 DEG C, setting heater is with the speed of 10 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
Embodiment 9
(1) ampoule prepares
Ampoule cleans.
(a) concentrated nitric acid for being 68wt% with mass fraction impregnates 48h, then the deionized water cleaning and dipping with more than 10M Ω
The ampoule finished；
(b) 48h, then the ampoule finished with the deionized water cleaning and dipping of more than 10M Ω are impregnated with acetone soln；
(c) it is cleaned by ultrasonic ampoule with the deionized water of more than 10M Ω.
Ampoule plates carbon.Ampoule after cleaning is dried, one layer of carbon film is plated in inner wall.Its carbon coating uses
Nitrogen that purity is 99.999% first is passed through as carrier gas by 70mL/s speed at 1000 DEG C, and original speed is kept to continue to lead to after stablizing
Enter carrier gas, and be passed through the methane that purity is 99.999% by 20mL/s speed and continue 60min, be then down to plating carbon unit temp
Room temperature obtains plating carbon ampoule.After plating carbon, plating carbon ampoule is taken out, and rinse plating carbon with the deionized water of more than 10M Ω and pacify
Small jar, drying.
(2) preparation of polycrystalline charge bar
By CsPbBr3Powder is packed into plating carbon ampoule, is evacuated and hermetically sealed.CsPbBr will be housed3The sealing quartz ampoule of powder
It is placed in heat-treatment furnace, heat-treatment furnace is warming up to 580 DEG C by 10h, and then keeping the temperature 2h makes CsPbBr3Powder fully melts, most
Setting heat-treatment furnace is cooled to room temperature by 16h afterwards, makes the CsPbBr of molten state3Solidification forms polycrystalline charge bar.
(3) crystal growth
Then the sealed ampoule equipped with the polycrystalline charge bar is placed in the quartz ampoule for moving horizontally zone melting furnace, heater is moved
To ampoule tip, the heater for moving horizontally zone melting furnace is warming up to 650 DEG C, setting heater is with the speed of 20 μm/min from peace
Small jar tip starts to be moved to the tail end of ampoule, after device stabilization to be heated is by whole section of crystal, heater stop motion, and pass through
48h is down to room temperature, completes entire crystal growing process.
As it can be seen that the present invention (is melted in the area that moves horizontally of structure especially as shown in Figure 1 by using moving horizontally zone melting furnace
Stove), it creatively proposes for perovskite-like material C sPbBr3Method for monocrystal growth, specifically included ampoule prepare and
Two committed steps of crystal growth, can obtain high quality, be suitble to prepare the CsPbBr of high energy nuclear radiation detector3It is single
It is brilliant.
The volumetric flow of gas (such as flow of methane, nitrogen) occurred in the present invention, unless otherwise indicated, corresponds to standard
Volumetric flow of gas under state.Room temperature in the present invention refers to 10 DEG C~40 DEG C of temperature.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made all within the spirits and principles of the present invention etc., should all include
Within protection scope of the present invention.
Claims (4)
1. Preparation Method is melted in a kind of area that moves horizontally of bromine lead caesium monocrystalline, which is characterized in that includes the following steps：
(1) the cylindrical quartz ampoule with conical tip of clean dried is placed in reacting furnace intracavitary and is evacuated to vacuum, then
Furnace chamber is warming up to 1000-1150 DEG C, methane is passed through into the quartz ampoule while carrier gas is passed through, so as to pacify to the quartz
Small jar inner wall carries out plating carbon film and handles to obtain plating carbon ampoule；
(2) bromine lead caesium powder is packed into the plating carbon ampoule obtained to the step (1), is evacuated and hermetically sealed to obtain sealing peace
Then sealed ampoule equipped with the bromine lead caesium powder is placed in heat-treatment furnace by small jar, heat-treatment furnace heating is made bromine lead caesium powder
Material fusing, then cooling make the bromine lead caesium of molten state solidify to form polycrystalline charge bar, obtain the sealed ampoule equipped with polycrystalline charge bar；
(3) sealed ampoule equipped with polycrystalline charge bar that the step (2) obtains is placed in the quartz for moving horizontally zone melting furnace
The heater for moving horizontally zone melting furnace is moved to the tip of the sealed ampoule, and the heater is warming up to 620- by Guan Zhong
650 DEG C, the heater is then moved with the speed of 5-20 μm/min, the heater is made to be moved since the tip of the sealed ampoule
It moves to the other end of the sealed ampoule, thus completes the growth course of bromine lead caesium crystal, obtain bromine lead caesium crystal.
2. Preparation Method is melted in the area that moves horizontally of bromine lead caesium monocrystalline as described in claim 1, which is characterized in that the step (1)
In, the carrier gas that the plating carbon film processing uses is the nitrogen that purity is 99.9-99.999%, and the flow of the carrier gas is 70-
110mL/s；The flow of the methane is 20-60mL/s, which is preferably the methane that purity is 99.9-99.999%；It is described
Plate carbon film processing preferred process 20-60min.
3. Preparation Method is melted in the area that moves horizontally of bromine lead caesium monocrystalline as described in claim 1, which is characterized in that the step (1)
In, the cylindrical quartz ampoule with conical tip of the clean dried is the cylinder by that will carry conical tip
Drying obtains after quartz ampoule cleaning；
Preferably, described clean is specifically：With mass fraction it is 65- by the cylindrical quartz ampoule with conical tip
The concentrated nitric acid of 68wt% impregnates, and is then cleaned with deionized water；Then it, then by the quartz ampoule with acetone soln impregnates, and connect
It and is cleaned with deionized water；Finally, which is cleaned by ultrasonic with deionized water.
4. Preparation Method is melted in the area that moves horizontally of bromine lead caesium monocrystalline as described in claim 1, which is characterized in that the step (2)
In, the polycrystalline charge bar is by the way that the heat-treatment furnace first is warming up to 570-600 DEG C by 6-12h, and then keeping the temperature 1-4h makes
Bromine lead caesium powder fully melts, and is finally obtained after 12-24h is cooled to room temperature.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112627A (en) * | 2018-09-30 | 2019-01-01 | 华中科技大学 | A method of improving bromine lead caesium monocrystalline resistivity |
| CN110512273A (en) * | 2019-08-07 | 2019-11-29 | 华中科技大学 | A method of improving monocrystalline crystalline quality |
| CN111379025A (en) * | 2020-04-22 | 2020-07-07 | 上海应用技术大学 | Growth method of cesium-lead halide crystal |
| CN113957523A (en) * | 2021-10-26 | 2022-01-21 | 中国电子科技集团公司第四十六研究所 | Multi-element crystal purification device and method |
| CN114197031A (en) * | 2021-11-23 | 2022-03-18 | 上海应用技术大学 | Preparation method of bromine lead copper single crystal |
| CN114645327A (en) * | 2022-02-11 | 2022-06-21 | 上海大学 | Perovskite single crystal and growth method thereof |
| CN115196656A (en) * | 2022-08-26 | 2022-10-18 | 华中科技大学鄂州工业技术研究院 | CsBr purification method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483825A (en) * | 2015-12-11 | 2016-04-13 | 华中科技大学 | Preparation method of bromine-lead-cesium single crystals |
| WO2016151535A1 (en) * | 2015-03-24 | 2016-09-29 | King Abdullah University Of Science And Technology | Methods of preparation of organometallic halide structures |
| WO2017195191A1 (en) * | 2016-05-08 | 2017-11-16 | Yeda Research And Development Co. Ltd. | Process for the preparation of halide perovskite and perovskite-related materials |
-
2017
- 2017-12-29 CN CN201711466810.6A patent/CN108193271B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016151535A1 (en) * | 2015-03-24 | 2016-09-29 | King Abdullah University Of Science And Technology | Methods of preparation of organometallic halide structures |
| CN105483825A (en) * | 2015-12-11 | 2016-04-13 | 华中科技大学 | Preparation method of bromine-lead-cesium single crystals |
| WO2017195191A1 (en) * | 2016-05-08 | 2017-11-16 | Yeda Research And Development Co. Ltd. | Process for the preparation of halide perovskite and perovskite-related materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112627A (en) * | 2018-09-30 | 2019-01-01 | 华中科技大学 | A method of improving bromine lead caesium monocrystalline resistivity |
| CN109112627B (en) * | 2018-09-30 | 2020-05-19 | 华中科技大学 | Method for improving resistivity of cesium lead bromide single crystal |
| CN110512273A (en) * | 2019-08-07 | 2019-11-29 | 华中科技大学 | A method of improving monocrystalline crystalline quality |
| CN111379025A (en) * | 2020-04-22 | 2020-07-07 | 上海应用技术大学 | Growth method of cesium-lead halide crystal |
| CN113957523A (en) * | 2021-10-26 | 2022-01-21 | 中国电子科技集团公司第四十六研究所 | Multi-element crystal purification device and method |
| CN114197031A (en) * | 2021-11-23 | 2022-03-18 | 上海应用技术大学 | Preparation method of bromine lead copper single crystal |
| CN114645327A (en) * | 2022-02-11 | 2022-06-21 | 上海大学 | Perovskite single crystal and growth method thereof |
| CN114645327B (en) * | 2022-02-11 | 2023-11-07 | 上海大学 | Perovskite single crystal and growth method thereof |
| CN115196656A (en) * | 2022-08-26 | 2022-10-18 | 华中科技大学鄂州工业技术研究院 | CsBr purification method |
| CN115196656B (en) * | 2022-08-26 | 2023-09-19 | 华中科技大学鄂州工业技术研究院 | CsBr purifying method |
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