CN1283852C - Method for growing gadolinium orthosilicate scintillation crystal - Google Patents
Method for growing gadolinium orthosilicate scintillation crystal Download PDFInfo
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- CN1283852C CN1283852C CN 200310108610 CN200310108610A CN1283852C CN 1283852 C CN1283852 C CN 1283852C CN 200310108610 CN200310108610 CN 200310108610 CN 200310108610 A CN200310108610 A CN 200310108610A CN 1283852 C CN1283852 C CN 1283852C
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Abstract
The present invention relates to a growing method for gadolinium silicate scintillation crystals. Lutetium silicate crystals, yttrium silicate crystals and lutetium yttrium silicate crystals, which have the structure approximate to the structure of gadolinium silicate crystals, are mainly used, seed crystals have the general chemical formula of (Lu[1-x]Y[x])2SiO5 when x is greater than or equal to zero and is smaller than or equal to one, an appropriate temperature for sowing seeds is selected, and gadolinium silicate crystals which do not crack can be grown generally within the temperature range of 1980 to 2200 DEG C. The growing method solves the cracking problem existing when the seed crystals are processed and also preferably solves the cracking or fracture problem existing at seed crystal points during crystal growth; consequently, the finished product rate for the growth of gadolinium silicate scintillation crystals is greatly increased.
Description
Technical field
The present invention relates to the gadolinium siliate scintillation crystal, (chemical general formula is (Lu particularly to adopt silicic acid lutetium, yttrium silicate or silicic acid lutetium yttrium
1-xY
x)
2SiO
5(0≤x≤1)) seeded growth mixes the growth method of cerium gadolinium siliate scintillation crystal.The Ce:GSO crystal of being grown can be widely used in fields such as high energy physics, nuclear physics, nuclear medicine, oil well detection and safety detection.
Background technology
Gadolinium siliate (Gd
2SiO
5, or GSO) be a kind of good luminous host crystalline material, rare earth ion doped GSO monocrystalline has luminescent properties preferably.For example the adulterated GSO crystal of rare-earth cerium ion (Ce) (Ce:GSO) is exactly a kind of new type high temperature scintillation crystal of excellent property, and this crystal has high light output (8000Ph/MeV), fast time decay (60ns), big effective atomic number (Z=59) and high-density (ρ=6.71g/cm
3) etc. characteristic, simultaneously the anti-irradiation ability of Ce:GSO crystalline is strong, also is difficult for deliquescence.Therefore, Ce:GSO has a wide range of applications in fields such as high energy nuclear physics, image nuclear medicine (PET), oil well exploration, industrial online detection and safety inspections.
Gadolinium orthosilicate belongs to congruent melting compound, and fusing point is about 1950 ℃, therefore adopts induction heating iridium crucible Czochralski grown doping GSO single crystal usually.Because gadolinium orthosilicate belongs to P2
1/ c structure, along (100) face cleavage, and gadolinium siliate has very serious anisotropy (coefficient of thermal expansion b axle is the twice of a and c axle) (referring to 109 (1991) the 386th pages of Journal of Cryst à l Growth).So, in Czochralski grown GSO crystal process and in the follow-up crystal course of processing, be easy to occur crystal cleavage, cleavage etc., thereby increased the difficulty of crystal growth and processing, reduced the rate that manufactures a finished product (referring to the United States Patent (USP) of people such as Kurata application, the patent No. 5,667,583).
Formerly in the technology,, usually adopt the GSO crystal of different directions to carry out crystal growth as seed crystal in order to overcome GSO crystalline cleavatge of crystals.For example, adopt with [010] axle to become 60 degree angles, become 30 to spend angles, and can grow no rimose GSO crystal (referring to the Japanese Patent that people such as Kurata apply for, the patent No.: 07-267782) with (100) the parallel seed crystal of face that dissociates with [001] axle.But, formerly still adopt the GSO crystal as seed crystal in the technology, have following shortcoming:
On the one hand the processing disalignment to the process of GSO seed crystal in because mechanical vibration etc. are easy to cause the cleavatge of crystals even the pulverizing of seed crystal, processing seed crystal difficulty is big;
On the other hand, in adopting GSO seeded growth crystalline process, the small thermal shocking that the temperature fluctuation in solid-liquid interface and the burner hearth forms all easily causes the cracking and the fracture of crystal seed crystal, so that crystal and the seed crystal of the GSO of growth come off.In addition, when crystal growth finished to be cooled to room temperature, the temperature fluctuation in the burner hearth also can cause the cleavage, cracking of seed crystal and influence the GSO crystalline quality that links to each other with seed crystal.Above-mentioned shortcoming all can make growth GSO crystalline yield rate low, and the crystal production cost is high.
Summary of the invention
The technical problem to be solved in the present invention is:
Solve the difficult processing of gadolinium siliate GSO seed crystal of different directions;
The seed crystal cracking that the growth interface temperature fluctuation causes during crystal growth;
The seed crystal cracking that temperature fluctuation causes in the crystal growing process, crystal comes off;
The excessive seed crystal fracture that causes of thermograde in the temperature-fall period;
Thereby provide a kind of growth method of gadolinium siliate scintillation crystal, with the no rimose gadolinium siliate scintillation crystal of growth
Technical solution of the present invention is: silicic acid lutetium, yttrium silicate and the silicic acid lutetium yttrium crystal of usefulness and the close structure of GSO crystal, chemical general formula is (Lu
1-xY
x)
2SiO
5(0≤x≤1) does seed crystal, and the temperature of sowing by adjusting generally in 2200-1980 ℃ of scope, reduces with the increase of x in the following formula, seed crystal is contacted with melt, with indehiscent cerium GSO crystal of mixing of growing.
Silicic acid lutetium, yttrium silicate and silicic acid lutetium yttrium crystal all belong to C
2/ c structure and GSO crystal belong to oblique system, and cleavage is not easy to crack, are processed into the seed crystal of any direction arbitrary shape easily.On the other hand, silicic acid lutetium yttrium crystalline fusing point and GSO are comparatively close, and (the former is in 2200 ℃ of-1980 ℃ of scopes, the latter is about 1950 ℃), simultaneously, crystal such as GSO and silicic acid lutetium (LSO), yttrium silicate (YSO) and silicic acid lutetium yttrium can form the congruent melting compound crystal, and just silicic acid lutetium yttrium crystal can serve as GSO crystalline seed crystal.So, adopt above-mentioned silicic acid lutetium yttrium seed crystal to carry out welding preferably with GSO, through crystal seed eliminate can growing high-quality the GSO single crystal.And silicic acid lutetium, yttrium silicate and silicic acid lutetium yttrium crystalline thermal shock resistance are better, above-mentioned seed crystal (Lu in the GSO crystal growing process and behind the growth ending
1-xY
x)
2SiO
5(0≤x≤1) is the energy heat shock resistance all, so crystal is difficult for producing problems such as cracking fracture.
Be that example is set forth employing silicic acid lutetium yttrium seeded growth Ce:GSO crystalline concrete steps below with the crystal pulling method:
(1) makes silicic acid lutetium yttrium (Lu
1-xY
x)
2SiO
5(0≤x≤1) seed crystal, the seed crystal direction can be [010], [100] or [001] etc., and shape can be cylindrical or long strip shape, and size is processed according to seed holder, and the above-mentioned seed crystal that will process is packed in the seed chuck;
The Ce:GSO polycrystal raw material that (2) will prepare is in advance packed in iridium crucible or the molybdenum crucible, and in the lifting furnace of packing into, adopts frequency induction heating in neutral atmosphere or reducing atmosphere the raw material in the crucible to be melted fully;
(3) according to seed crystal (Lu
1-xY
x)
2SiO
5The size of x in (0≤x≤1) selects to sow temperature in 2200 ℃ of-1980 ℃ of scopes, along with the increase of the x content temperature of sowing reduces.The suitable temperature of sowing is not grown up fast with seed crystal and unhappy fast thawing turns to standard;
(4) under the suitable temperature of sowing, seed crystal is contacted with melt, soaked 0.5-2 hour, after the balance, set cooling process 5-100 ℃/hour slowly, beginning pulling growth Ce:GSO crystal, by eliminating the crystal seed method, final crystallization goes out monophasic Ce:GSO single crystal;
(5) after crystal reached predetermined size by shouldering, isodiametric growth, crystal growth finished.Slowly be cooled to room temperature, can obtain indehiscent Ce:GSO scintillation crystal.
Adopt silicic acid lutetium yttrium seeded growth Ce:GSO crystal, be not only applicable to above-mentioned Czochralski grown and be suitable for other growth method, resemble especially in the technology of growing crystal from melt such as temperature gradient method, falling crucible method.
The advantage that the present invention compares with technology formerly is: the seed crystal with silicic acid lutetium yttrium crystal during as the growth gadolinium siliate, avoided seed crystal to add the cracking problem in man-hour on the one hand, the seed crystal place that all temps fluctuation causes when having solved crystal growth well again ftractures or breakage problem, has greatly improved the yield rate of growing crystal.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1: with silicic acid lutetium Lu
2SiO
5Seeded growth gadolinium siliate Ce:GSO crystal
By above-mentioned Czochralski grown
Step (1) is made Lu
2SiO
5Seed crystal, seed crystal direction are b axle ([010] direction), are of a size of φ 4 * 60mm, and seed crystal is packed in the seed chuck;
Step (2) adopts Frequency Induction Heating iridium crucible Czochralski grown gadolinium orthosilicate, and the Ir crucible size is Φ 80 * 60mm.Pack into the Ce:GSO polycrystal that sinters in advance in the Ir crucible and place lifting furnace, at N
2Being warming up to melt in the gas shiled atmosphere melts fully;
Step (3): about the temperature regulation to 2200 of will sowing ℃;
Step (4): with Lu
2SiO
5Seed crystal contacts with melt, soaks 0.5 hour, by the cooling of 100 ℃/H speed, carries out necking down growth (pulling rate 1-5mm/h, rotating speed 15-50RPM);
(5) carry out crystal shouldering, isodiametric growth set by step, reach predetermined size Φ 30 * 60mm after, crystal growth finishes.Slowly be cooled to room temperature, take out the Ce:GSO crystal, crystal is transparent, complete, do not ftracture.
Embodiment 2: with silicic acid lutetium yttrium (Lu
0.5Y
0.5)
2SiO
5Seeded growth gadolinium siliate Ce:GSO crystal
Press step in the foregoing description 1 (1) processing (Lu
0.5Y
0.5)
2SiO
5Seed crystal, and in the seed chuck of packing into; Press step in the foregoing description 1 (2) at Ar gas and 1vol%H
2The mixing reducing atmosphere in, with the fusing fully in the Mo crucible fully of the Ce:GSO polycrystal that sinters in advance; Regulate the temperature of sowing by step (3) among the embodiment 1 and be about 2000 ℃; Press step among the embodiment 1 (4) with (Lu
0.5Y
0.5)
2SiO
5Seed crystal contacts with melt, soaks 1 hour, adopts 50 ℃/H speed cooling beginning pulling growth; After step (5) crystal growth reached predetermined size Φ 30 * 60mm among the embodiment 1, crystal growth finished.Slowly be cooled to room temperature, take out the Ce:GSO crystal, crystal is transparent, complete, do not ftracture.
Embodiment 3: use yttrium silicate Y
2SiO
5Crystal seeded growth gadolinium siliate Ce:GSO crystal
Step (1) processing Y
2SiO
5Seed crystal, and in the seed chuck of packing into;
Step (2) is placed on the Ce:GSO polycrystal that sinters in advance in the Ir crucible and melts in Ar gas atmosphere;
Step (3) is regulated the temperature of sowing and is about 1980 ℃;
Step (4) is with Y
2SiO
5Seed crystal contacts with melt, soaks 1 hour, adopts 100 ℃/H speed cooling beginning pulling growth;
After step (5) crystal growth reached predetermined size Φ 30 * 60mm, crystal growth finished, and slowly is cooled to room temperature, took out the Ce:GSO crystal, and crystal is transparent, complete, do not ftracture.
Claims (3)
1, a kind of growth method of gadolinium siliate scintillation crystal, it is characterized in that with and silicic acid lutetium, yttrium silicate and the silicic acid lutetium yttrium crystal of the close structure of gadolinium orthosilicate, chemical general formula is (Lu
1-xY
x)
2SiO
5Seed crystal is done in 0≤x≤1, by selecting the suitable temperature of sowing, in 2200-1980 ℃ of scope, seed crystal is contacted with melt, and indehiscent cerium gadolinium orthosilicate of mixing begins to grow.
2, the growth method of gadolinium siliate scintillation crystal according to claim 1 is characterized in that concrete steps are as follows:
(1) makes silicic acid lutetium yttrium (Lu
1-xY
x)
2SiO
50≤x≤1 seed crystal: the seed crystal direction can be [010], [100] or [001], and shape can be cylindrical or long strip shape, and the seed crystal that processes is packed in the seed chuck;
The Ce:GSO polycrystal raw material that (2) will prepare is in advance packed in iridium crucible or the molybdenum crucible, reinstalls in the lifting furnace, adopts frequency induction heating in neutral atmosphere or reducing atmosphere the raw material in the crucible to be melted fully;
(3) according to seed crystal (Lu
1-xY
x)
2SiO
5The size of x in 0≤x≤1 is selected the suitable temperature of sowing in 2200 ℃ of-1980 ℃ of scopes;
(4) under suitable temperature, seed crystal is contacted with melt, soaked 0.5-2 hour, after the thermal equilibrium, set cooling process 5-100 ℃/hour slowly, beginning pulling growth Ce:GSO crystal, final crystallization goes out monophasic Ce:GSO single crystal;
(5) crystal is by shouldering, isodiametric growth, reach predetermined size after, crystal growth finishes; Slowly be cooled to room temperature, take out the GSO scintillation crystal.
3, the growth method of gadolinium siliate scintillation crystal according to claim 1 is characterized in that this crystalline growth method is temperature gradient method or falling crucible method.
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|---|---|---|---|
| CN 200310108610 CN1283852C (en) | 2003-11-14 | 2003-11-14 | Method for growing gadolinium orthosilicate scintillation crystal |
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|---|---|---|---|
| CN 200310108610 CN1283852C (en) | 2003-11-14 | 2003-11-14 | Method for growing gadolinium orthosilicate scintillation crystal |
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| CN1283852C true CN1283852C (en) | 2006-11-08 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899711A (en) * | 2010-06-25 | 2010-12-01 | 中国科学院上海光学精密机械研究所 | Thulium-doped gadolinium oxyorthosilicate scintillator and preparation method thereof |
| CN103757708A (en) * | 2014-01-17 | 2014-04-30 | 中国科学院福建物质结构研究所 | High temperature inorganic scintillation crystal growth crucible |
| CN103757702A (en) * | 2014-01-20 | 2014-04-30 | 中国科学院福建物质结构研究所 | Method for preparing high-temperature inorganic scintillation crystal |
| CN104630878B (en) * | 2015-02-05 | 2017-04-12 | 中国电子科技集团公司第二十六研究所 | Method for preparing large-sized slablike Ce3+ ion doped rare-earth orthosilicate-series scintillation crystals through horizontal directional solidification |
| CN105714374B (en) * | 2016-03-01 | 2018-06-01 | 中国科学院长春应用化学研究所 | The growth of low-cost rare earth scintillation crystal |
| CN108560053B (en) * | 2018-04-24 | 2020-01-31 | 安徽晶宸科技有限公司 | lanthanum, dysprosium and cerium codoped yttrium lutetium silicate scintillation material and crystal growth method thereof |
| CN111910254A (en) * | 2020-08-04 | 2020-11-10 | 南昌大学 | Cerium-doped and erbium-doped ytterbium silicate scintillation crystal and preparation method thereof |
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Granted publication date: 20061108 Termination date: 20091214 |