CN1834311A - Method and appts. of using molten lead iodide to grow monocrystal - Google Patents
Method and appts. of using molten lead iodide to grow monocrystal Download PDFInfo
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- CN1834311A CN1834311A CNA2006100203938A CN200610020393A CN1834311A CN 1834311 A CN1834311 A CN 1834311A CN A2006100203938 A CNA2006100203938 A CN A2006100203938A CN 200610020393 A CN200610020393 A CN 200610020393A CN 1834311 A CN1834311 A CN 1834311A
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- lead iodide
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Abstract
This invention discloses method and equipment for preparing lead iodide single crystals from lead iodide melt, which comprises the steps of: cleaning an ampule, filling it with lead iodide powders, degassing and sealing the ampule, growing the single crystals and cooling. The method can effectively suppress the decomposition of lead iodide melt and the vaporization of iodine, and can remove segregated lead. The ampule is made of a quartz tube, and comprises a seed crystal bag, a growth chamber, a connecting vessel, a lead tube, a loading bag anb a hook. After filling, the ampule is placed into a two-stage temperature range vertical tubular furnace to finish the growth of the single crystals. The as-grown single crystals are orange and semi-transparent with sizes up to Phi (15-20)X30 mm. The electrical resistivity of as-grown single crystals can reach 1012-1013 ohm .cm, thus the single crystals have wide applications, especially as room temperature nuclear radiation detector.
Description
Technical field:
The invention belongs to the single crystal preparation field, particularly a kind of method with lead iodide melt growth single crystal.
Technical background:
Lead iodide (PbI
2) single crystal belongs to hexagonal system, is the translucent wide bandgap semiconductor materials of orange, PbI under the room temperature
2The crystalline energy gap is about 2.3～2.5eV, has very high resistivity, and very big application potential is arranged in optical information record recording system, nonlinear optical system, can be used for making photocell, the scintillation crystal photo-detector of hot operation etc.; PbI
2Big (the Z of ordination number
Pb=82, Z
I=53), energetic ray being had higher stopping power, is one of the most promising material of making by room temperature x-ray (or gamma-rays) detector.With HgI of the same type
2Crystal is compared, PbI
2Crystal has bigger energy gap, and vapour pressure is also much lower, and not volatile, chemical stability is better, does not have phase transformation from the fusing point to the room temperature, therefore uses PbI
2The device that crystal is made can be worked in room temperature even higher temperature range.Because above characteristics, the lead iodide crystal has become one of novel material of primary study in recent years.
Growth PbI
2The method of single crystal mainly contains vapor phase process, gel method, melting method three classes, and when adopting the vapor phase process growth, the iodine atom is easy to be diffused into PbI
2Go in the lattice, cause lattice distortion, with the PbI of this rich iodine
2The detector energy resolving power that crystal is made is relatively poor.As T.Shoji, K.Sakamoto, K.Ohba, IEEETrans.Nucl.Sci., 44 (2), 1997, p451-452 report.Single crystal size with gel growth is less, is generally several millimeters, and the crystal more than the growth centimetre-sized is very difficult, thereby application is restricted.Melting method mainly contains three kinds, i.e. vertical bridgman method, horizontal zone melting method and moving area smelting process.
T.Shoji, K.Ohba, T.Suehiro, IEEE Trans.Nucl.Sci., 41 (4), 1994, p694-697 is with the vertical bridgman method PbI that grows
2Single crystal, growth temperature and growth velocity are respectively 410 ℃ and 4mm/h, make the PbI that is of a size of Φ 8 * 30mm
2Crystal ingot.Because the crystal purity that made at that time is not high, so the detector energy resolving power of making is relatively poor.I.B.Oliveira, F.E.Costa, M.J.Armelin, IEEE Trans.Nucl.Sci., 49 (4), 2002, p1968-1973 adopts the raw material of purifying through 500 sub-region meltings, utilize vertical bridgman method growing crystal (not charging into rare gas element in the ampoule), also do not obtain good effect, with the detector that this crystal is made, energy resolution is relatively poor.
T.Shoji, K.Ohba, T.Suehiro, IEEE Trans.Nucl.Sci., 42 (4), 1995, p659-661 adopts horizontal zone melting method (ZM) growth PbI
2Crystal.Through 60 times the growth of purification repeatedly, having obtained resistivity is 10
10The crystal of Ω cm.1977, Japanese clear 51-60011 patent just was based on that this principle proposes.The ZM method has only been considered the purification problem of material, does not suppress the evaporation of iodine, thereby can not effectively control the crystalline stoicheiometry, is difficult to obtain high-quality crystal.
T.Shoji, K.Hitomi, T.Tiba, IEEE Trans.Nucl.Sci., 45 (3), 1998, p581-584 has grown quality PbI preferably with mobile melting zone method (TMZ)
2Single crystal.In this experiment, PbI
2Raw material not as with the growth of ZM method through repeatedly purifying, and be the PbI of 4N directly with purity
2Powder-tight and charges into 1.5 atmospheric Ar gas in quartz crucible, to prevent the evaporation of iodine, growth temperature is 500 ℃, and the crucible rate travel is 5cm/h, has obtained resistivity with this method and has reached 10
12The single crystal of Ω cm.In the TMZ method, though the pressure of rare gas element can effectively be controlled, the steam pressure difference of iodine is still remarkable in the temperature field heterogeneous, and the evaporation of iodine is not effectively controlled, and is difficult to obtain stay-in-grade single crystal.
During with melt method for growing lead iodide crystal, always there is the part remaining space top of ampoule, and by chemical equilibrium theory as can be known, can set up chemical equilibrium as follows this moment:
Wherein L and G represent liquid phase and gas phase respectively.Because plumbous vapour pressure is more much lower than the vapour pressure of iodine, omitted the influence of gas phase lead and liquid phase iodine at this.This shows in the crystal growing process that lead iodide can part decompose.
The iodine that decompose to produce mainly is stored in the remaining space on ampoule top (being the evaporation of iodine) with the form of steam, has broken away from melt, has upset the stoicheiometry of melt, is unfavorable for obtaining the fine single crystal, must be controlled in crystal growing process.
A plumbous part of decomposing generation is deposited on the bottom of lead iodide melt, and another part is dissolved in the lead iodide melt.At the initial stage with the vertical bridgman method growing crystal, the lead of these fusions can fractional condensation come out to be deposited in the seed crystal bag, and in the later stage of crystal growth, the lead that fractional condensation is come out becomes second phase in the lead iodide crystal ingot, reduces the crystalline quality.
Melting method has two shortcomings: first melt directly contacts with the remaining space of ampoule top, this provides condition for the decomposition of lead iodide and the evaporation of iodine, even above ampoule, charge into rare gas element in the remaining space, can not suppress the decomposition of lead iodide and the evaporation of iodine fully; Its two are melt solidifying directions (crystal growth direction) with melt in the precipitation direction of fractional condensation lead inconsistent, in vertical bridgman method, crystal growth direction is opposite with the precipitation direction of fractional condensation lead, in horizontal zone melting method and mobile melting zone method, crystal growth direction is vertical with the precipitation direction of fractional condensation lead, the discharge that this is unfavorable for fractional condensation lead is difficult to obtain fine pbi 2 single crystal body.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, provide a kind of method and specific equipment, so that stably prepare the high-quality pbi 2 single crystal body of large size, high resistivity with lead iodide melt growth single crystal.
The present invention is a kind of improvement to melting method, and with respect to traditional melt growth method, the present invention innovates the processing condition and the method for crystal growth suppressing the decomposition of lead iodide, stoping the evaporation of iodine and discharge in melt aspect fractional condensation plumbous.
Technical scheme of the present invention is: the method with lead iodide melt growth single crystal is that the lead iodide powder of purifying with process is a raw material, it is characterized in that it comprises following processing step:
1, cleaning ampoule
The cleaning ampoule is the processing of ampoule being removed impurity, uses the washed with de-ionized water ampoule, dries, to reduce the foreign matter content in the crystal;
2, charging and remove the sealing gland small jar
Volume be filled with water method metering ampoule growth room, seed crystal bag, communicating vessels and plumbous liquid pipe, the lead iodide polycrystal raw material of purifying and the quality of lead powder to determine to pack into, load weighted lead iodide polycrystal raw material and lead powder are encased in the ampoule after the cleaning successively, after charging is finished, at room temperature vacuumize, the air pressure in ampoule reduces to 10
-3Pa～10
-4The charging tube of hermetically enclosed ampoule during Pa;
3, crystal growth and cooling
It is two sections temperature province vertical tube type growth furnace that the ampoule that lead iodide polycrystal raw material and lead powder are housed is put into crystal growing furnace, vertical tube type growth furnace upper temp is set to 330～380 ℃, temperature of lower is set to 420～500 ℃, crystallization zone of transition thermograde is set to 8～12 ℃/centimetre, at first make ampoule growth room and seed crystal bag in temperature is 420～500 ℃ vertical tube type growth furnace, insulation was left standstill 10～15 hours, promote ampoule with 0.2～0.8 millimeter/hour speed then, until the growth room of ampoule till to enter vertical tube type growth furnace upper temp fully be 330～380 ℃ temperature province, stop to promote and heating, allow ampoule in the vertical tube type growth furnace, naturally cool to room temperature, can obtain required pbi 2 single crystal body.
The enforcement of aforesaid method need to be equipped with corresponding apparatus, except that clean room, vacuum drying oven, vacuum diffusion pump, two sections existing devices such as temperature province vertical tube type growth furnace, also needs the ampoule of design specialized.
Ampoule provided by the invention, make of silica tube, ampoule becomes molectron by seed crystal bag, growth room, communicating vessels, plumbous liquid pipe, charging tube, the hook groups that blind end is jujube shape, the seed crystal bag is above the growth room, coaxial with the growth room, be used for eliminating nucleus, form seed crystal, seed crystal grows into single crystal in the growth room; The bottom, growth room is communicated with plumbous liquid pipe with communicating vessels, and plumbous liquid pipe is identical with seed crystal bag orientation with the growth room, and opening upwards constitutes U type structure; The length of plumbous liquid pipe is than long 20～30 millimeters of the total length of seed crystal bag and growth room, and the opening of plumbous liquid pipe promptly constitutes charging tube, after lead iodide and lead powder are packed into, vacuumizes the sealing charging tube, and makes hook at sealing part.
The present invention has following beneficial effect:
1, the prepared pbi 2 single crystal body structure of the present invention complete, present uniform orange translucent, hardness is even, stress is little, size can reach Φ (15～20) * 30 millimeter, the resistivity of the harsh single crystal that grows can reach 10
12Ω cm～10
13Ω cm, thereby wide application are specially adapted to make indoor temperature nucleus radiation detector.
2, the present invention is pressed into the lead iodide melt in growth room and the seed crystal bag with the liquid lead melt, when making lead iodide fill up ampoule growth room and seed crystal bag, lead iodide melt and ampoule top remaining space are isolated, suppressed the decomposition of lead iodide, thoroughly stoped the evaporation of iodine.
3, because the density of liquid lead is bigger than the density of lead iodide melt, in the process of setting of lead iodide melt, the plumbous melt that fractional condensation is come out can under action of gravity, deposit to gradually melt below, so adopting, the present invention gets sequence of crystallization from top to bottom, make crystal growth direction identical, can fully get rid of the lead of fractional condensation with plumbous precipitation direction.
4, in the process of setting of lead iodide melt, may be attended by the variation of volume, adopt liquid lead in the plumbous liquid pipe to be pressed into and isolate, have automatic compensation function.
5, the pbi 2 single crystal ingot of the present invention's growth can be used blade cuts and cleavage easily, and crystal mass is even, the raw material availability height.
Description of drawings:
Fig. 1 U type ampoule.
The modes of emplacement in Fig. 2 U type ampoule when cooling and in U type ampoule mobile lead iodide raw material synoptic diagram.Wherein:
1 seed crystal bag, 2 growth rooms, 3 communicating vesselss
4 plumbous liquid pipe 5 charging tubes 6 hooks
Embodiment:
The present embodiment preparation size is the pbi 2 single crystal body of 15 millimeters * 30 millimeters of Φ, and best scheme is that the silica tube with 15 millimeters * 500 millimeters of internal diameter Φ is made into U type ampoule as shown in Figure 1.
The processing step of present embodiment is as follows:
1, cleaning ampoule
Use the washed with de-ionized water ampoule, dry, remove impurity.
2, charging and remove the sealing gland small jar
With the volume of be filled with water method metering ampoule seed crystal bag 1, growth room 2, communicating vessels 3 and plumbous liquid pipe 4, with the quality of definite need pack into lead iodide polycrystal raw material and lead powder; Load weighted lead iodide polycrystal raw material and lead powder are encased in the ampoule after the cleaning successively, in the charging process, for guaranteeing the lead iodide melt to be pressed into growth room 2 and to fill up under the condition of seed crystal bag 1, also need suitably to increase the consumption of lead powder, because in the actually operating, the lead iodide that adds can not enter the growth room 2 of ampoule fully, and need more lead powder and replenish this moment; In the process of lead iodide of packing into, constantly rotate ampoule, so that lead iodide as much as possible is packed in the growth room 2; At room temperature vacuumize after charging is finished, the air pressure in ampoule reduces to 10
-3During Pa the charging tube 5 of hermetically enclosed ampoule and with charging tube 5 be made into the hook 6, then ampoule is placed on temperature is to heat in 480 ℃ the box-type furnace by shown in Figure 2, allow plumbous and the lead iodide fusing, insulation was left standstill 1 hour, make lead iodide melt and liquid lead layering, rotate ampoule gradually by the diagram direction of arrow shown in Figure 2 again, make lead iodide fully enter growth room 2 and seed crystal bag 1, get back to behind the naturally cooling of position shown in Figure 2 standby then.
3, crystal growth and cooling
Charging and the U type ampoule that removes the sealing gland small jar are hung in two sections temperature province vertical tube type growth furnace by position shown in Figure 1, heat up with 95 ℃/hour speed, the high-temperature zone is warmed up to 480 ℃, cold zone is warmed up to 350 ℃, insulation 12h, promote ampoule, the pulling speed of ampoule is controlled at 0.5 millimeter/hour, allow the crystallization gradually from top to bottom of lead iodide melt under these conditions, until the growth room of ampoule till to enter vertical tube type growth furnace upper temp fully be 350 ℃ temperature province, stop to promote and heating, allow ampoule in the vertical tube type growth furnace, naturally cool to room temperature, can obtain required pbi 2 single crystal body.After testing, the resistivity of the harsh pbi 2 single crystal body that grows is 3 * 10
12Ω cm belongs to high resistant fine pbi 2 single crystal body.
In crystal growing process, as run into emergency situation such as power failure, should immediately ampoule be taken out from the vertical tube type growth furnace, place cooling by position shown in Figure 2, otherwise ampoule can break.
Claims (4)
1, the present invention relates to a kind of growth method and equipment of pbi 2 single crystal body, is that the lead iodide powder of purifying with process is a raw material, it is characterized in that it comprises following processing step:
(1), cleaning ampoule
Use the washed with de-ionized water ampoule, dry, remove impurity;
(2), charging and remove the sealing gland small jar
Ampoule after cleaning dried is with the volume of be filled with water method metering ampoule growth room, seed crystal bag, communicating vessels and plumbous liquid pipe, the lead iodide polycrystal raw material of purifying and the quality of lead powder to determine to pack into, load weighted lead iodide polycrystal raw material and lead powder are encased in the ampoule after the cleaning successively, after charging is finished, at room temperature vacuumize, the air pressure in ampoule reduces to 10
-3Pa～10
-4The charging tube of hermetically enclosed ampoule during Pa;
(3), crystal growth and cooling
It is two sections temperature province vertical tube type growth furnace that the ampoule that lead iodide polycrystal raw material and lead powder are housed is put into crystal growing furnace, vertical tube type growth furnace upper temp is set to 330～380 ℃, temperature of lower is set to 420～500 ℃, crystallization zone of transition thermograde is set to 8～12 ℃/centimetre, at first make ampoule growth room and seed crystal bag in temperature is 420～500 ℃ vertical tube type growth furnace, insulation was left standstill 10～15 hours, promote ampoule with 0.2～0.8 millimeter/hour speed then, until the growth room of ampoule till to enter vertical tube type growth furnace upper temp fully be 330～380 ℃ temperature province, stop to promote and heating, allow ampoule in the vertical tube type growth furnace, naturally cool to room temperature, can obtain required pbi 2 single crystal body.
2, the growth method of pbi 2 single crystal body according to claim 1 and custom-designed special-purpose ampoule, make of silica tube, it is characterized in that ampoule forms molectron by seed crystal bag (1), growth room (2), communicating vessels (3), plumbous liquid pipe (4), charging tube (5), hook (6) that blind end is " jujube shape ", seed crystal bag (1) is the top of (2) in the growth room, coaxial with growth room (2), be used for eliminating nucleus, form seed crystal, seed crystal grows into single crystal in growth room (2).
3, special-purpose ampoule according to claim 2 is characterized in that bottom, growth room (2) is communicated with plumbous liquid pipe (4) with communicating vessels (3), and plumbous liquid pipe (4) is identical with seed crystal bag (1) orientation with growth room (2), and opening upwards constitutes U type structure.
4, special-purpose ampoule according to claim 2, the length that it is characterized in that plumbous liquid pipe (4) is grown 20～30 millimeters than the total length of seed crystal bag (1) and growth room (2), the opening of plumbous liquid pipe (4) promptly constitutes charging tube (5), after lead iodide and lead powder are packed into, vacuumize sealing charging tube (5), and be made into hook (6) at sealing part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100203938A CN100408731C (en) | 2006-03-02 | 2006-03-02 | Method and appts. of using molten lead iodide to grow monocrystal |
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|---|---|---|---|
| CNB2006100203938A CN100408731C (en) | 2006-03-02 | 2006-03-02 | Method and appts. of using molten lead iodide to grow monocrystal |
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| CN1834311A true CN1834311A (en) | 2006-09-20 |
| CN100408731C CN100408731C (en) | 2008-08-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912418A (en) * | 2012-10-18 | 2013-02-06 | 西华大学 | Method and system for growing lead iodide single crystals |
| CN102912434A (en) * | 2012-10-31 | 2013-02-06 | 西华大学 | Method and system for regulating and controlling chemical ratio of lead iodide |
| CN112831842A (en) * | 2020-12-26 | 2021-05-25 | 云南农业大学 | Seed crystal growth device convenient for seed crystal transplantation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225572C (en) * | 2003-11-18 | 2005-11-02 | 深圳市淼浩高新科技开发有限公司 | Integrated melt method for crystal growth |
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2006
- 2006-03-02 CN CNB2006100203938A patent/CN100408731C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912418A (en) * | 2012-10-18 | 2013-02-06 | 西华大学 | Method and system for growing lead iodide single crystals |
| CN102912418B (en) * | 2012-10-18 | 2015-03-04 | 西华大学 | Method and system for growing lead iodide single crystals |
| CN102912434A (en) * | 2012-10-31 | 2013-02-06 | 西华大学 | Method and system for regulating and controlling chemical ratio of lead iodide |
| CN102912434B (en) * | 2012-10-31 | 2014-12-31 | 西华大学 | Method and system for regulating and controlling chemical ratio of lead iodide |
| CN112831842A (en) * | 2020-12-26 | 2021-05-25 | 云南农业大学 | Seed crystal growth device convenient for seed crystal transplantation |
| CN112831842B (en) * | 2020-12-26 | 2021-11-19 | 云南农业大学 | Seed crystal growth device convenient for seed crystal transplantation |
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| CN100408731C (en) | 2008-08-06 |
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