CN108004591A - The preparation of elpasolite type scintillator material - Google Patents
The preparation of elpasolite type scintillator material Download PDFInfo
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- CN108004591A CN108004591A CN201711310654.4A CN201711310654A CN108004591A CN 108004591 A CN108004591 A CN 108004591A CN 201711310654 A CN201711310654 A CN 201711310654A CN 108004591 A CN108004591 A CN 108004591A
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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Abstract
The present invention relates to the method for the scintillation crystal material for being used to prepare the elpasolite type structure with theoretical composition A2BC (1 y) MyX (6 y), wherein：A is selected from Cs, Rb, K, Na；B is selected from Li, K, Na；C is selected from rare earth element, Al, Ga；M is selected from alkaline-earth metal；X is selected from F, Cl, Br, I, and y is to substitute the atomic fraction of C and in 0 to 0.05 scope with M, and this method includes the crystallization that it begins through cooling from the liquid-bath comprising r moles of A and s moles of B, which causes 2s/r to be more than 1 with the material comprising A and B.This method has what is improved to prepare yield.Moreover, the crystal obtained can be with the composition closer to stoichiometry and with improved scintillation properties.
Description
Technical field
The present invention relates to the elpasolite phase (especially monocrystalline) that rare earth or metal halide are prepared with excellent yield
Method.
Background technology
Scintillator material is widely used for detecting γ or X-ray and high energy particle, such as alpha particle, neutron.
Flicker based on by photon, incidence X either the energy of gamma-rays or high energy particle be converted into visible region or
The physical principle of the light near visible area.Especially, inorganic scintillator be preferably monocrystalline or polycrystalline.Monocrystalline since there is no
Across the interior scattering of granule boundary, inhomogeneities and other it are present in the defects of polycrystalline material and allow easily to extract light.
Excellent crystalline state is necessary, because its most effective decision scintillation mechanisms.The light of the extraction and then the skill for passing through this area
Device, photodiode, SiPM (silicon photoelectric multiplier), APD (avalanche optoelectronics two known to art personnel as photomultiplier
Pole pipe) etc. be collected.Polycrystalline scintillator can be by being compacted or sintering or prepared with the powder that adhesive coats
Always to allow to extract light.In general, it is excessively opaque that these non-single-crystal materials, which exceed certain thickness, and it is insufficient to allow foot
Enough incident high energy particles or photon stop.In general, single crystal scintillator material is preferable.γ photons, α or β particles, band
The detection of charged particle or neutron in nuclear medicine, fundamental physics, for luggage security scanners (detection door frame), on side
Continuous monitoring, geophysics's diagnostic system in mine and the application for oil drilling etc. of border container and lorry
In there is main benefit.In such applications, and neutron and gamma-rays, and flicker detection can desirably usually be distinguished
Device should be able to produce the signal of different fluorescent characteristics according to ray type in this case.WO2005/068585 is taught
This type elpasolite scintillator is led.US8362439 teaches the mixture of elpasolite scintillator.
The content of the invention
The usual method for trying to prepare those skilled in the art of elpasolite monocrystalline is the crystallization implemented since liquid-bath,
Stoichiometry of the composition of the liquid-bath corresponding to target crystal.What the growing method no matter used is, for many multiple
Miscellaneous composition (three components are even more complicated), there are the phenomenon of incompatible fusing.The crystallization of the main phase of elpasolite is adjoint
There is the secondary phase of precipitation either formerly there occurs secondary phase to go out by field trash or in the form of being not intended to the monophase field of phase
It is existing.Have been noted that the crystalline material obtained from these liquid-baths with complicated composition includes a high proportion of field trash now, or
Person is even only by parasitic secondary phase composition.The monocrystalline of acquisition or the crystalline material of polycrystalline type are also referred to as crystallizing
Block (ingot).In the case of the monocrystalline made of incompatible fusing, secondary phase be usually located at the monocrystal material end or
Person periphery.This secondary phase forms the zone of opacity for the monocrystalline feature for disturbing main phase.It is some it is favourable in the case of, still
The partially recycled portion of monocrystalline of transparent single crystal of these unusable areas and preservation without field trash can be removed by finally cutting
Material.These field trashes correspond to the parasitic phase with the composition different from sought composition.Accord with the present invention it has been found that
It is a kind of to reduce the ratio in these impure regions, or even them are removed in some cases, and in this case providing more preferable
The method for preparing yield.
In addition to obtaining and preferably preparing yield, the present invention also allows to obtain the theoretical chemistry meter closer to elpasolite
The crystal of the composition of amount, or even in some cases it is enriched with it, especially it is enriched with some elements, such as Li.The enrichment of Li is in
The detection of son is favourable.In most cases, it is presented as more preferable light transmission closer to the composition of theoretical stoichiometric
With, in flicker, more preferable energy resolution.Moreover, the present invention allows to use so-called " cutting krousky (Czochralski) "
Growing method, it always thinks (especially most of for incompatible fusing crystal by those skilled in the art so far
Elpasolite crystalloid) it is impossible.In Bridgman (Brigman) growth, the method according to the invention allows to obtain
The material yield of the available crystal of higher, i.e., it, which causes, includes less parasitism for incompatible fusing elpasolite
The ingot of phase.
The present invention relates to the method and the scintillation crystal material for being used to prepare scintillation crystal material in itself.The present invention relates to
And the method for being used to prepare the scintillation crystal material of the elpasolite type structure with following theoretical composition
A2BC(1-y)MyX(6-y)(1)
Wherein
Zero A is selected from Cs, Rb, K, Na
Zero B is selected from Li, K, Na
Zero C is selected from rare earth, Al, Ga
Zero M is selected from alkaline earth element, especially Ca, Mg, Sr, Ba
Zero X is selected from F, Cl, Br, I,
Wherein, y represent with the atomic fraction of M substitutions C (Elements C and M occupy the same loci of the elpasolite) (or mole point
Number) and in 0 to 0.05 scope (this represent y can be zero), this method includes it from comprising the molten of r moles of A and s moles of B
Bath begins through the crystallization of cooling, which causes 2s/r to be more than 1 with the material comprising A and B.
The above does not indicate that the actual scintillation crystal material obtained of the method according to the invention has theoretical chemistry meter
Amount composition.They refer to that it produces the crystal that its formula will be formula (1), if its composition is actually theoretical (changes
Learn metering) words.
The formula of the material actually prepared can be from the elemental analysis of every kind of element (in the case of XRF in addition to Li)
(ICP-inductively coupled plasma-or XRF-x-ray fluorescence) be measured and be about scheduled on the formula middle-jiao yang, function of the spleen and stomach of elpasolite from
The summation of son is 4.
The fact that ratio 2s/r is higher than 1 represents in the liquid-bath " B is excessive " within the scope of this invention.Exactly in this meaning
In justice, wording " B is excessive " can be used in scope of the present application.This is because the elpasolite of the theoretical stoichiometric
So that the ratio of twice of the molal quantity of B and A of molal quantity is equal to 1.It has now been discovered that in the actual crystal prepared, this
Kind of ratio actually, be lower than 1, during by using being worked for 1 2s/r, and be exactly based on improve it is related with the liquid-bath
2s/r ratios, can approach in the elpasolite actually prepared even up to, even more than B and the A atom of stoichiometry
(or mole) ratio.
It is preferred that 2s/r is more preferably higher than 1.25 even above 1.5 higher than 1.05.Especially, 2s/r can be higher than 1.15.It is special
Not, 2s/r can be higher than 1.35.In the case of excessively big B excessive (excessive 2s/r ratios), parasitic phase can be formed,
Also harmful field trash is caused.Preferably, the B molar excess in the bath (and therefore 2s/r ratios) is not enough to start in crystallization
Shi Yinqi forms B3C (1-y) MyX6 phases, bottom line it be sufficiently low to cause the formation as few as possible.Therefore,
2s/r is preferably shorter than 10 more preferably less than 5.Especially, 2s/r can be usually less than 3.
The 2s/r ratios are calculated by the A and the mole of B being introduced into the bath.Elements A and B are drawn with halogenated form
Enter.Consider that these elements can be run on type-A site or B type bits in the case of the wherein bath includes K either Na
On point, the ratio for the element that can be determined by experiment on these operation to A sites and on B sites, then 2s/ can be calculated
R ratios.In order to determine the ratio in Na and K present on any site, X-ray diffraction can be used to implement structural research.For
This, using sealed sample bag, prevents that aquation occurs when powder from contacting with surrounding air and therefore is destroyed.Because these
Material is strongly moisture absorption.The excessive therefore posteriority of according to the present invention Na or K (as B types of elements) by finally making
The accurate formula of standby elpasolite is by determining the relative percentage in the type-A site either Na on B types site or K
And it is determined.In general, Na will be mainly run to B types site.For example, if from including 1.7 moles
CsCl, 1.5 moles of LiCl, NaCl and 2 of 0.5 mole mole of YCl3 bath in crystallized, and in actual crystallization
Elpasolite in the Na that includes be 80% and be 20% on type-A site on B types site, at this moment 0.5 mole in bath
Na can almost be decomposed into 0.1 mole of ACl types NaCl and 0.4 mole of BCl types NaCl.The bath is therefore comprising 1.8
Mole ACl (1.7 moles of CsCl+0.1 moles of NaCl), 1.9 moles of BCl (1.5 moles of LiCl+0.4 moles of NaCl) and 2 moles
YCl3.Therefore 2s/r ratios are 2.1.
The compound for carrying A, B, C and M exists in liquid-bath with halide mode, its halogen corresponds to the X of formula (1).Number
The different halogen X of kind can reside in liquid-bath, if final crystal must include different halogens.If t is represented
The molal quantity of C in the liquid-bath, if u represents the molal quantity of the M in the liquid-bath, at this moment preferably, ratio 2 (t+u)/r exists
In the range of 0.8-1.2.It is preferred that u/ (t+u) is less than 0.1.Especially, u can be zero.
The crystal elpasolite obtained by the method according to the invention, which can have, is in close proximity to theoretical stoichiometric
True formula.This true formula can be indicated by following formula
AaBbCcMmXx(2)
Wherein A, B, C, M and X have the meaning above provided, and a, b, c, m and x represent the respective atom of A, B, C, M and X atom
Fraction.Atomic ratio 2b/a (therefore end value is included in the range of this) in 0.97 to 1.4 scope, this 2b/a ratios are usual
Less than 1.2.
Crystal according to the present invention is mainly the face-centered cubic elpasolite crystal structure with space group.About
The summation (i.e. a+b+c+m) for determining the atomic fraction of cation is equal to 4, and usual a is in 1.7 to 2.3 scope, and b is 0.8 to 1.2
Scope in, c in 0.85 to 1.1 scope, m in 0 to 0.05 scope and x in 5.05 to 6.9 scope.
In the method according to the invention, the B is excessively preferably enough so that in the elpasolite actually prepared,
Twice of the atomic fraction of B types of elements and the ratio (therefore 2b/a ratios in formula (2)) of the atomic fraction of type-A element
It is at least 0.97.
In formula (1) and (2), A can be the mixture of several elements selected from Cs, Rb, K and Na.Similarly, B can be with
The mixture of several elements selected from Li, K or Na.The present invention relates more particularly to the situation that wherein B includes Li.In many feelings
Under condition, B is only Li.Similarly, C can be it is several be selected from rare earth (it includes Sc and Y), the mixture of the element of Al and Ga.
Similarly, M can be several mixtures selected from alkaline earth element, the mixing of especially several elements selected from Ca, Mg, Sr or Ba
Thing.In addition, X can be the mixture of several elements selected from F, Cl, Br and I.The present invention relates more particularly to wherein X and includes
The situation of Cl, Br and I.
The present invention relates more particularly to wherein A and includes Cs, and B includes the situation that Li and X includes Cl or Br.Particularly pay close attention to
Following two situations：1) A includes Cs, and B includes Li, and C includes Br comprising La and X；2) A includes Cs, and B includes Li, and C includes Y and X bags
Containing Cl.
Rare earth is the element of the group of the lanthanides from La to Lu, either Sc or Y (latter two element is similar to rare earth).The present invention is more
Particularly wherein C is included selected from the lanthanide series or the situation of the rare earth of Y from La to Lu.
The elpasolite is doped with the active element for providing or improving its scintillation properties.Active element is at least
Rare earth selected from Ce, Pr, Eu, Tb and Nd.It can be the mixture of the mixture of activator, especially Ce and Pr.Activation member
Element is a part for C types of elements.In general, in elpasolite, activator C ' ' is with than element another and for C types
Atomic fraction c ' ' lower C ' (especially Y) exists, the Elements C ' exist with atomic fraction c '.If C represents two kinds of Elements Cs '
And the mixture of C ' ' (especially be respectively Y and Ce), at this moment the atomic fraction c of C types of elements cause c=c '+c ' '.Active element
The atomic fraction c ' ' of C ' ' so that c ' '/(c+m) higher than 0.00001 and below or equal to 0.1, c represent Elements C (it includes
All C types of elements, therefore Elements C ') atomic fraction, and m be element M atomic fraction.Elements C and M are in elpasolite
Identical site is occupied in lattice.The elpasolite can also include the mixture of the mixture of activator, especially Ce and Pr.
In this case, elpasolite includes three kinds of C types of elements (all on C types site)：C ', C ' ' and C ' ' ' are (for example, special
It is not respectively Y, Ce and Pr), last surface element exists with atomic fraction c ' ' '.In this case, (c ' '+c ' ' ')/(c+
M) higher than 0.00001 and below or equal to 0.1.
Presence of the M in elpasolite, especially Sr, the viscosity, fusion temperature, the liquid-bath for changing the mixture to be melted exist
The surface tension of emissivity and the liquid-bath in infrared ray.Presence of the M in crystal, special Sr, thus it is possible to vary its glitter
Matter such as its light efficiency (rendementlumineux) and its energy resolution.
The present invention relates more particularly to the scintillator material of formula (1) and (2) above, and wherein B includes Li, X include Cl, Br or
Person I, and C are included selected from the lanthanide series from La to Lu, or the rare earth of Y, the activation of its flicker action of the scintillator material
Element is doped.The material of formula (1) and (2) can especially cause B to be Li above, and X is selected from Cl, Br or I, and C be selected from from
The lanthanide series of La to Lu, or Y, the scintillator material are doped with the active element of its flicker action.Especially, according to this
The material of invention cannot include fluorine.Scintillator material prepared in accordance with the present invention can have bloom efficiency, especially use
The γ excitations of 662keV measure.Especially, light efficiency can be higher than 15000 photons/MeV.Material rich in LaBr3, such as
CLLB can have the light efficiency higher than 25000 photons/MeV.
Scintillator material prepared in accordance with the present invention can be (small high in flicker peak half with excellent energy resolution
Overall with).The measurement of flicker can use gamma ray projector, photoelectric multiplier and the gauge measurement system of 137Cs types to be implemented.
Scintillator material prepared in accordance with the present invention can have the energy resolution less than 6%, even lower than 5%, which uses 137Cs
Gamma ray projector measures.The present invention relates more particularly to the situation that wherein B includes Li in formula (1) and (2).The present invention is more special
It is not related to the A wherein in formula (1) and (2) and includes the situation that Cs and B includes Li.The present invention relates more particularly to wherein in formula
(1) and in (2) A includes the situation that Cs and B includes La comprising Li and C.The present invention relates more particularly to wherein in formula (1) and (2)
Middle A includes Cs, B and includes the situation that Li, C include Br comprising La and X, especially when the X higher than 80% mole is Br (80% mole
X be Br).
The present invention relates more particularly to the A wherein in formula (1) and (2) and includes the situation that Cs, B include Y comprising Li and C.This
Invention relates more particularly to the A wherein in formula (1) and (2) and includes the situation that Cs, B include Cl comprising Li, C comprising Y and X, especially
Ground is when X is the Cl higher than 80% mole (80% mole of X is Cl).
Elpasolite can especially have following theoretical composition:
- doping or undoped Cs2LiYCl6, especially Cs2LiYCl6:Ce, is usually known as by those skilled in the art "
The compound of CLYC "；
- doping or undoped Cs2LiLaBr6, especially Cs2LiLaBr6:Ce, is usually claimed by those skilled in the art
For the compound of " CLLB "；
- doping or undoped Cs2LiLaBr6 (1-z) Cl6z, wherein z are 0 to 1, especially Cs2LiLaBr6 (1-z)
Cl6z:Ce；
- doping or undoped Cs2LiLaCl6, especially Cs2LiLaCl6:Ce, is usually claimed by those skilled in the art
For the compound of " CLLC "；
- doping or undoped Cs2LiYBr6, especially Cs2LiYBr6:Ce, is usually referred to by those skilled in the art as "
The compound of CLYB "；
- doping or undoped Cs2LiYF6, especially Cs2LiYF6:Ce, is usually referred to by those skilled in the art as "
The compound of CLYF "；
- doping or undoped Cs2 (1-z) Rb2zLiTRX6, especially Cs2 (1-z) Rb2zLiTRX6:Ce, wherein z are 0
Rare earth is represented to 1, TR；
- doping or undoped Rb2LiYX6, especially Rb2LiYX6:Ce；
- doping or undoped Cs2 (1-z) Rb2zLiTRI6, wherein z are 0 to 1, especially Cs2 (1-z) Rb2zLiTRI6:
Ce, TR represent rare earth,
- doping or undoped Cs2LiY (1-x) LaxCl6, especially Cs2LiY (1-x) LaxCl6:Ce.
Therefore, theory can forms A2BC (1-y) MyX (6-y) and have by prepared according to the methods of the invention
The scintillator material for having the elpasolite type structure of the AaBbCcMmXx of true formula can correspond to one of situations below：
- A is Cs, and B Li, C are the mixture of Y and Ce, and X is Cl；
- A is Cs, and B Li, C are the mixture of La and Ce, and X is Br；
- A is Cs, and B Li, C are the mixture of Y and Ce, and X is F；
- A is Cs, and B Li, C are the mixture of La and Ce, and X is Cl；
- A is the mixture of Cs and Rb, and B Li, C are the mixture of La and Ce, and X is Br；
- A is Cs, and B Li, C are the mixture of La and Ce, and X is the mixture of Cl and Br；
- A is Cs, and B Li, C are the mixture of Y and Ce, and X is the mixture of Cl and Br；
- A is Cs, and B Li, C are the mixture of La, Y and Ce, and X is Cl；
- A is the mixture of Cs and Na, and B is the mixture of Li and Na, and C is the mixture of Y and Ce, and X is Cl.
According to the present invention, significantly reducing for the formation of parasitic phase even suppresses to pass through from relative to desired final crystal
Form the liquid-bath of the composition (being included at it for the theoretical stoichiometric of crystal for the meaning of molar excess B) of offset
Prepare crystallization and realize.Moreover, (formula (2)) atomic fraction ratio 2b/a is closer to the theoretical stoichiometric ratio for 1, even
Higher than 1.
Trigger the growth since liquid-bath, the composition of the liquid-bath inaccurately corresponds to the stoichiometry group of elpasolite
Into not corresponding to the final composition of desired elpasolite yet.In general, the method according to the invention is " auto-flux " class
Type, i.e. liquid-bath are not included in crystal not existing chemical element.If around crystal or reach around crystal
Liquid is without uniformly composition, and consideration, for the part of the liquid directly contacted with the crystal, there are excessive (the i.e. 2s/r of B
>1).It is in fact possible to using the growing technology for being referred to as " more crucibles ", according to the technology there are at least two crucibles (one
Inside another), to implement the method according to the invention, once in innermost crucible and contact with crystalline material
If fluid composition meets the condition of B excess according to the present invention.
The method according to the invention usually carries out in crucible or the closing even phial of sealing.Crucible especially can be with
It is made of the graphite with pyrolytic coating or is made of vitreous carbon.The phial that the closing even seals is usually by quartz or glass
Glass carbon or platinum are made.
According to the present invention, by container (crucible, phial etc.) that halogenation raw material are placed under nonoxidizing atmosphere
Operated, then heat it until raw material melt, then according to selected technology (Bridgman, cut krousky etc.)
Implement crystal growth and be cooled to environment temperature.
Krousky technology or cloth Ritchie can such as be cut by using one of technology known to those skilled in the art
Graceful technology either Baghdad salol husband technology (horizontal bridgman technology) or triumphant sieve bubble Loews (Kyropoulos) technology or "
VerticalGradientFreeze " technologies (by the crystallization for controlling thermal gradient) or so-called EFG (EdgeFeedingGrowth)
Technology or include the use of " continuous feed " technologies of multiple crucibles, especially in double crucible, (one of crucible is positioned at another
In a) in crystal growth, implement the present invention to produce monocrystalline.
Elpasolite monocrystalline, which can have, is higher than 10cm3, even above the volume of 100cm3.Even if the crystallization of crystal growth
Block includes field trash, and the mono crystalline portion of no field trash, which can have, is higher than 10cm3, even above the volume of 100cm3.
Especially, the method according to the invention can produce such ingot：First the 2/3 of the growth volume of its monocrystal material
Any phase mutually different from elpasolite comprising less than 10% volume, this is significant.Especially, krousky type is being cut
Method for monocrystal growth in the case of, the growth volume of monocrystal material first 2/3 cannot include it is any with the phase of elpasolite not
Same phase, this is also significant.
It can also use the method according to the invention and prepare polycrystalline.For this reason, the mixture of raw material is set to melt and cool down
The melt of the acquisition is enough (without specific careful).Then, can be by crushing or grinding acquisition desired size.
Crystal powder can also be obtained by grinding.
Raw material for producing liquid-bath are incorporated into the element of the composition of the elpasolite.It may, for example, be the halogen of A
Compound, the halide of B, the halide of C and M halide mixture.Then excess B halide is fed (relative to final crystalline substance
The target chemical metering composition of body) it is enough.For the mixture of raw material, it may also is that the mixing of several halide
Thing, at least one of the mixture include elements A, at least two of B, C and M.Still herein, feed and excessive include element
The halide (measure and form relative to target chemical) of B is enough.
Example available for the compound for forming Li excess according to the present invention be LiCl, Li3YCl6, Cs3Li2Cl5,
Cs2Li3Cl5 and Li3LaBr6.
The method according to the invention is presented as crystal growth as the result of the controlled cooling of the bath of melt composition.This
Kind melt composition is used as compound or the change for the raw material for producing the expectation composition that element it is expected in liquid bath by fusing
Polymer mixtures (this compound or compound mixture are referred to as precursor) obtain.It can use with it is expected liquid-bath
Form the single compound of the composition accurately met.It can also use the mixing of the halide into the different elements for it is expected composition
Thing is as raw material.Therefore, if it is desired to CLYC is prepared, the chloride of the chloride of Cs, the chloride of Li, Y can be mixed, and must
When wanting, the chloride of Ce (in the case where Ce is adulterated).
B according to the present invention is excessive incompletely to be entered in final crystalline material, and the B for not entering into the material can
To be recycled after solidification as accessory substance, and especially reused in the scope of the method according to the invention.If
Using krousky method for monocrystal growth is cut, which is present in excess in the liquid phase kept in crucible.If using in cloth
Strange graceful method for monocrystal growth, which is present in excess in the region comprising field trash, wherein the region is mainly in this method
At the end of formed and be than there is no the ratio of smaller during excess under any circumstance.
B according to the present invention can excessively allow to make the composition of final crystalline material closer to perfect stoichiometry group
Into A2BC (1-y) MyX (6-y).When by being tied with the accurate corresponding bath formed that forms with target elpasolite crystal
When brilliant, stoichiometry deficiency is about 2 to 3% moles of B.In order to overcome this shortage, the present invention proposes to use B excessive, preferably extremely
Excessive (the 2s/r of B 5% mole few>1.05).
For given elpasolite, in liquid-bath, (first 2/3 of growth volume for the liquid-bath ingot is fully
(100%) be made of the elpasolite) in there are 2s/r minimum values.If t to be known as to the molal quantity of the C in the bath, this
When, raw material are introduced in the bath (so that 2t/r ratios are even above 1.1, even at least 1.2) even above 1.08 higher than 1
Allow to reduce 2s/r minimum value (in the minimum value, grow first the 2/3 of volume fully (100% volume) by the potassium ice crystal
Stone forms).For available elpasolite volume in first the 2/3 of the identical ingot in preparation, the raising of 2t/r ratios is permitted
Perhaps 2s/r ratios are reduced.The raising of 2t/r ratios can be by introducing compound in liquid-bath, especially B3CX6 type compounds
(B, C and X have the meaning previously provided), realizes such as Li3LaBr6 or Li3YCl6.This C can also excessively pass through bigger
The CX3 of amount and realize.But allow the excess for realizing B and C at the same time using B3CX6 type compounds.High 2t/r ratios are to crystallization
This influence of block quality is especially significant in the case of elpasolite, for elpasolite, the C higher than 80% mole
It is that the La and X higher than 80% mole is the bromine elpasolite of LaBr3 " (" enrichment).If 2t/r is higher, the receipts of perfect cystal
Rate is improved, especially more than first the 2/3 of growth volume.In the case of bridgeman growth, reduced at the end of growth
The amount (the especially grey parts of attached drawing 1c) of inappropriate material.In the case where cutting krousky (Czochralski) growth,
It is left less material in bath at the end of the growth.2t/r is improved to even allow for reducing 2s/r, such as to less than 1.65.
In the case of elpasolite, wherein C includes La, especially if it exceeds 80% mole of C is La and wherein X bags
Containing Br, especially if it exceeds 80% mole of X is bromine, especially in the case of CLLB type elpasolites, at this moment have at the same time
Have higher than 1, even above 1.08, even above 1.1, even at least 1.2 2t/r the fact, concomitantly have higher than 1.05,
The fact that even at least 1.1 2s/r allow obtain at least 1.1, even at least 1.15, even at least 1.2, be especially up to
1.4 2b/a.
The elpasolite of rare earth halide be typically moisture absorption and must be handled in appropriate atmosphere, i.e. drying
And located in neutral either reducing atmosphere (containing hydrogen and nitrogen gas, argon gas, nitrogen, hydrogeneous argon gas) or in a vacuum
Reason.This is also applied for used e measurement technology, it must be implemented in appropriate atmosphere, especially diffractometry.Not
The diffractometry for being adapted to carry out in atmosphere (especially surrounding air) can fully make the measuring error.Bridgman
(Bridgman) method, it can cause crystallization to seal hair in phial (being usually made of quartz or vitreous carbon) under vacuo
It is raw, it is favourable in terms of this angle, because crystallization is easily realized in appropriate atmosphere.
The elevated temperature of the liquid-bath is set to depend on the formula of the bath before crystallization.In general, before crystallization, according to composition
The bath is set to rise to 400 to 1100 DEG C.In the scope of method for monocrystal growth, cooldown rate is usually 0.01 DEG C/h to 5 DEG C/
Hour.In Bridgman method, the translational velocity of crystal is usually 0.01mm/h to 20mm/h.If seek to obtain potassium ice crystal
The polycrystalline of stone phase, cooldown rate can be it is more faster, in particular 5 to 200 DEG C/h.
The ingot taken out in the attached phial Fig. 1 shows after the growth of Bridgman type crystals from them.Situation a)
Corresponding to situation about obtaining in the prior art, i.e., the unavailable ingot of high volume fraction, because ingot is mingled with comprising many
Thing (grey parts), especially in early growth period, it corresponds to the lower part of ingot.When expression of results, the ingot is considered
This narrow and therefore count for according to the present invention growth volume.Situation c) corresponds to has height according to the present invention
Available monocrystalline ratio situation.Grey parts at top correspond to undesirable phase.Situation b) corresponds to intermediate state, makes
B is excessively excessive less than the B used in c), it has caused higher level of inclusions.
Attached drawing 2 represents the ingot after the growth of krousky type crystals is cut.Narrow in upper zone
Corresponding to the single crystal seed for triggering the growth.This part is in expression of results without considering.In a), ingot is
It is fully disabled, because it is by the complete ground contamination of field trash and corresponds to the prior art, that is, lack B excess.In c),
Ingot is perfect, no field trash.It is excessive using B according to the present invention.Situation b) correspond in situation a) and c) it
Between intermediate state, the B that has is excessively excessive less than the B used in c).
Embodiment
Prepare the mixture of powders of the raw material of the halide type for the cation that be embedded in elpasolite.
By preparing monocrystalline from the crystallization of liquid-bath, the composition of liquid-bath is listed in Table 1.Embodiment be it is according to the present invention or
It is comparative example and includes explaining " contrast " in the latter cases.The composition of the bath can carry out overall expression and wherein pass through
To introduce it in the form of the summation of the elpasolite of stoichiometry and excessive one or more compounds (including B).In the table
In, BG represents that having been carried out the growth of Bridgman type and CZ represents to have been carried out cutting the growth of krousky type.In embodiment 8
In the case of, sodium can move to the site of Cs or Li, notice in final crystal posteriority, the Na on Li sites
Ratio be 89% and the Na ratios on Cs sites be 11%.This be why, for the 2 moles of Cs introduced in the bath,
The amount of A is 2 (for Cs)+0.074 (for the 11% of 0.67 mole of Na) or 2.074 moles in the bath.B's in the bath
Amount is 1 (for Li)+0.596 (for the 89% of 0.67 mole of Na) or 1.596 moles.Herein therefore 2s/r ratios are (2
×1.596)/2.074=1.54。
In the case where CZ types are grown, the not all bath used is converted into crystallization block of material, this is for this
Technology is intrinsic.On the contrary, in Bridgman crystallization, all baths used have been solidified as ingot.In the last of table 1
In one column, the percentage of the real available monocrystalline in first the 2/3 of the growth of the ingot of the solidification is given.Therefore given birth in CZ
It is not related to the percentage of the material used in the bath in length.On the contrary, in bridgeman growth, it is further related in the bath
The percentage of the material used.Embodiment 20,21,22,24 shows that in the case of CLLB, high 2s/r ratios are drawn in the bath
Rise be significantly higher than in elpasolite 1 2b/a.
Table 1.
Table 2 gives the scintillation properties of some crystal being had been described above in table 1.It is indicated herein to use 662keV's
The relative luminous efficiency rate (the LO columns for being used for " light efficiency ") of γ excitation measurements, and energy resolution (full width at half maximum at flicker peak).Dodge
Bright measurement is implemented using the gamma ray projector, photoelectric multiplier and gauge measurement system of 137Cs types.The value of acquisition that
This can be compared, because they are measured using definite sample geometry and using identical survey tool.
The value of energy resolution is lower, it is better.Light efficiency is preferably as high as possible.It is opposite for CLYC type crystals, light efficiency
Expressed in the light efficiency (LO for being arbitrarily evaluated as 1) of embodiment 1.For CLLB type crystals, light efficiency relative to
The light efficiency (LO for being arbitrarily evaluated as 1) of embodiment 11 has been carried out expressing.
Table 2.
Fig. 1 a) and 1c) represent the phial according to the embodiment after the crystal growth of Bridgman type.Embodiment 1,
2 and 15 generate in attached drawing 1a) in crystallization block type ingot.Embodiment 5,6,7,8,10,13,14 and 17 generates
Attached drawing 1c) in crystallization block type ingot.For embodiment 5,6,7,8,10,13,14,17, the growth of the monocrystal material
First the 2/3 of volume includes the mutually different phases from elpasolite less than 10% volume.It is impure in the case of these are specific
The volume of phase is 0%.
In the case of embodiment 15 and 16, display：The phases mutually different from elpasolite of first 2/3 volume are by means of this hair
It is bright to be reduced to 8% from 24%.Therefore embodiment 16 is produced in attached drawing 1b) ingot of type or the growth body of monocrystal material
Long-pending first 2/3 includes less than 10% volume but is greater than the 0% mutually different phases from elpasolite.
Fig. 2 a) and 2c) represent the ingot according to the embodiment after the crystal growth of krousky type is cut.Implement
Example 3 and 11 produce in attached drawing 2a) crystallization block type ingot.Embodiment 4,9,12,18 and 19 produce in attached drawing 2c) knot
The ingot of crystal block type.For these embodiments 4,9 and 12,18 and 19, the growth volume of 100% monocrystal material do not include with
The mutually different phases of elpasolite.
It can be clearly seen, according to the present invention using excess B (or 2s/r>1) embodiment causes being mingled with for much less
Thing and therefore more preferable single crystal preparation yield.They also produce more preferable scintillation properties.
In the case of embodiment 5,6,19,20,21,22,24,25,26,27 and 28, the 2t/r in the bath is higher than 1 He
2s/r in the bath is higher than 1.08.In these cases, according to its type, observed in attached drawing 1c or 2c corresponding
Growth, improves perfect cystal yield.In the case of bridgeman growth, the grey parts of exactly attached drawing 1c are reduced.
In the case of cutting krousky growth, exactly the amount of remaining material is reduced in the bath.In the situation of embodiment 7 and 27
Under, the quality (grey parts of attached drawing 1c) of parasitic phase is measured at the end of the growth relative to being introduced in Bridgman phial
In material gross mass percentage.It was observed that this percentage (10%) in the case of embodiment 27 is relative to embodiment 7
Percentage (17.9%) be significantly it is lower.The material yield is much higher compared with Example 7 in the case of embodiment 27
's.
Claims (10)
1. it is used to prepare the scintillation crystal material of the elpasolite type structure with theoretical composition A2BC (1-y) MyX (6-y)
Method, wherein
- A is selected from Cs, Rb, K, Na,
- B is selected from Li, K, Na,
- C is selected from rare earth element, Al, Ga,
- M is selected from alkaline-earth metal,
- X is selected from F, Cl, Br, I,
Y represents the atomic fraction with M substitutions C and in 0 to 0.05 scope, and this method includes it from including r moles of A and s
The liquid-bath of mole B begins through the crystallization of cooling, is characterized in that the active element of its flicker action of the scintillation crystal material
It is doped, and is characterized in that the liquid-bath causes 2s/r to be more than 1 with the material comprising A and B.
2. according to previous item the method for claim, it is characterized in that 2s/r is higher than 1.05.
3. according to previous item the method for claim, it is characterized in that 2s/r is higher than 1.15, preferably above 1.25.
4. according to previous item the method for claim, it is characterized in that 2s/r is higher than 1.35, preferably above 1.5.
5. according to the method for any one of preceding claims, it is characterized in that 2s/r is less than 10, preferably shorter than 5, is preferably lower than 3.
6. according to the method for any one of preceding claims, be characterized in that 2s/r be enough so that in the crystalline material B
Twice of the atomic fraction of types of elements and the ratio of the atomic fraction of type-A element are at least 0.97.
7. according to the method for any one of preceding claims, it is characterized in that M is selected from Ca, Mg, Sr or Ba.
8. according to the method for any one of preceding claims, it is at least one selected from Ce, Pr, Eu, Tb and Nd to be characterized in that C is included
Rare earth element is activated, its atomic fraction causes its atomic fraction and the Elements C and the atomic fraction of M in the crystalline material
The ratio of summation is higher than 0.00001 and below or equal to 0.1.
9. according to the method for any one of preceding claims, it is characterized in that 2s/r is not enough to cause to form B3C when crystallizing and starting
(1-y) MyX6 phases.
10. according to the method for any one of preceding claims, it is characterized in that B includes Li.
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| WO2020136951A1 (en) * | 2018-12-26 | 2020-07-02 | パナソニックＩｐマネジメント株式会社 | Method for producing halides |
| WO2020136954A1 (en) * | 2018-12-26 | 2020-07-02 | パナソニックＩｐマネジメント株式会社 | Method for producing halide |
| WO2020136952A1 (en) * | 2018-12-26 | 2020-07-02 | パナソニックＩｐマネジメント株式会社 | Halide production method |
| WO2020136955A1 (en) * | 2018-12-26 | 2020-07-02 | パナソニックＩｐマネジメント株式会社 | Method for producing halide |
| CN114411251A (en) * | 2022-01-20 | 2022-04-29 | 西北工业大学深圳研究院 | Method for growing high-quality CLLB crystal by using moving heater method |
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| CN105102693A (en) * | 2013-04-12 | 2015-11-25 | 圣戈班晶体及检测公司 | Production of an elpasolite-type scintillator material |
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