CN1313650C - Method for growing rare earth thio-oxide crystal - Google Patents
Method for growing rare earth thio-oxide crystal Download PDFInfo
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- CN1313650C CN1313650C CNB2004100533036A CN200410053303A CN1313650C CN 1313650 C CN1313650 C CN 1313650C CN B2004100533036 A CNB2004100533036 A CN B2004100533036A CN 200410053303 A CN200410053303 A CN 200410053303A CN 1313650 C CN1313650 C CN 1313650C
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- 239000013078 crystal Substances 0.000 title claims abstract description 111
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000010792 warming Methods 0.000 claims description 46
- 238000009792 diffusion process Methods 0.000 claims description 26
- 238000007789 sealing Methods 0.000 claims description 26
- -1 rare-earth sulfide Chemical class 0.000 claims description 25
- 230000012010 growth Effects 0.000 claims description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- MYZAXBZLEILEBR-RVFOSREFSA-N (2S)-1-[(2S,3R)-2-[[(2R)-2-[[2-[[(2S)-2-[(2-aminoacetyl)amino]-5-(diaminomethylideneamino)pentanoyl]amino]acetyl]amino]-3-sulfopropanoyl]amino]-3-hydroxybutanoyl]pyrrolidine-2-carboxylic acid Chemical compound C[C@@H](O)[C@H](NC(=O)[C@H](CS(O)(=O)=O)NC(=O)CNC(=O)[C@H](CCCN=C(N)N)NC(=O)CN)C(=O)N1CCC[C@H]1C(O)=O MYZAXBZLEILEBR-RVFOSREFSA-N 0.000 claims description 2
- 108700002400 risuteganib Proteins 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract 1
- 238000012856 packing Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 238000005303 weighing Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 12
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ICEQPULPQCSMOJ-UHFFFAOYSA-N OS([Gd])(=O)=O Chemical compound OS([Gd])(=O)=O ICEQPULPQCSMOJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A method for growing rare-earth thio-oxide crystal by using flux and a temperature gradient furnace includes the steps of preparing seed crystal, pressing material block and growing crystal by temperature gradient method. The method can obtain centimeter-level high-quality rare earth thio-oxide 2O2S) and rare earth element-doped rare earth thio oxide (Re: re2O2S) single crystal blanks.
Description
Technical field
The invention relates to rare earth thio-oxide (Re
2O
2S) and rare earth doped rare earth thio-oxide (Re ': Re
2O
2S) crystalline growth method.
Background technology
Rare earth thio-oxide (Re
2O
2S) being the Industrial materials that a class haves a great attraction, also is simultaneously very unique in scientific basic research.They are broadband semiconductors, as phosphor material, have used nearly 30 years on the various modern engineering.For example, Nd activated La
2O
2S crystal (Nd:LOS) is the laserable material of very promising low threshold value, high-luminous-efficiency, see J.Appl.Phys., 1971,42 (8): 3043-3048, under pulse and continuous two kinds of laser work modes, the pumping threshold power of Nd:LOS all is lower than Nd:YAG, if can prepare the Nd:LOS crystal that optical quality can be mentioned in the same breath with YAG, its continuous laser slope efficiency estimate will be Nd:YAG 8-12 doubly.Adulterated Gd
2O
2S is section's scintillation material, can be used for X ray video intensifying screen.Eu activated Y
2O
2S crystal (Eu:YOS) is the storage phosphor and the very high cathode-luminescence material of luminous efficiency of multiple infrared excitation, referring to J.Electrochem.Soc., and 1969,116:1047.
Because the thio-oxide fusing point is generally higher, as the LOS fusing point be 2070 ± ℃, about 2200 ℃ of YOS, in air, be heated to more than 600 ℃ with regard to oxidized formation subsulphate, generation is decomposed and the loss of sulphur and understand under the temperature of fusion in vacuum or inert atmosphere, and thermal expansivity anisotropy difference is big, //the c axle, 6 * 10
-6/ K; ⊥ c axle, 3 * 10
-6/ K), the crystal of growing from melt is the substantial deviation chemical dosage ratio often, and always there is the rimose problem inevitably in the growth of large-size crystals simultaneously.For avoiding the melt pyrolytic decomposition to produce the loss of sulphur, adopt the electrons leaves welding sealed crucible, see J.Appl.Phys., 1971,42 (8): 3049-3053, but the crystal of being grown forms polycrystalline easily, the sulphur content skewness, easily produce bubble, crystals generally contains blackstreak, and specific refractory power is seriously inhomogeneous.In addition, adopt Ar atmosphere or the Ar and the H of overvoltage
2The mixed atmosphere of S can be avoided the oxidation of oxysulfide, but can not reduce the decomposition and the S loss of melt, the crystal formation heterogeneous structure of growth, and cracking is seen Mater.Res.Bull. easily, 1973,8:1421-1426.The transparent YOS monocrystalline size that for example, can access only is 0.5 * 0.5 * 0.3mm
3, (Phys.Rev.B, 2002,65:094302; 2003,68:035107), can't carry out orientation cutting or polishing.
Summary of the invention
The technical problem to be solved in the present invention is to overcome above-mentioned prior art problems, and a kind of rare earth thio-oxide crystalline growth method is provided, and this method can obtain a centimetre magnitude, high-quality rare earth thio-oxide (Re
2O
2S) and rare earth doped rare earth thio-oxide (Re ': Re
2O
2S) single crystal blank.
Technical solution of the present invention is as follows:
A kind of rare earth thio-oxide crystalline growth method is the method that adopts fusing assistant and utilize the temperature gradient furnace growing crystal, comprises seed crystal preparation, the compacting of material piece and temperature gradient method growing crystal step.
Described seed crystal preparation adopts the lanthanuma luminate single crystal body of the directed cutting of C axle to make seed crystal for the first time, adopts the crystal bar of the directed cutting of rare earth thio-oxide single crystal to make seed crystal later on.
This rare earth thio-oxide crystalline growth method comprises the following steps:
1. system is expected piece: adopt sodium sulphite Na
2S presses Na as fusing assistant
2S: Re
2O
2S=(20～40): the weight percent batching of (80～60) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 800～1000 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing single-crystal, to obtain rare earth thio-oxide Re
2O
2The S crystal.
The described the 1. system material piece adopts Na
2S presses Na as fusing assistant
2S: (Re ': Re
2O
2S)=(20～40): the weight percent batching of (80～60) is pressed into the material piece after abundant ground and mixed is even, at last to obtain rare rare earth thio-oxide Re ' that goes up element doping: Re
2O
2The S crystal.
With rare-earth sulfide Re
2S
3As fusing assistant, rare earth thio-oxide crystalline growth method is characterized in that this method comprises the following steps:
1. system is expected piece: adopt rare-earth sulfide Re
2S
3As fusing assistant, press Re
2S
3: Re
2O
2S=(25～50): the weight percent batching of (75～50) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 1000～1200 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing crystal, to obtain Re
2O
2The S crystal.
With rare-earth sulfide Re
2S
3As the rare earth doped rare earth thio-oxide Re ' of fluxing agent growth: Re
2O
2S crystalline key is the described the 1. system material piece, adopts rare-earth sulfide Re
2S
3As fusing assistant, press Re
2S
3: Re ': Re
2O
2S=(25～50): the weight percent batching of (75～50), be pressed into the material piece after abundant ground and mixed is even, last to obtain rare earth doped rare earth thio-oxide Re ': Re
2O
2The S crystal.
The temperature gradient method technology of described growing single-crystal is: keep more than 2 hours in top temperature, lower the temperature 200～400 ℃ with the speed less than 2 ℃/hour, then to reduce to room temperature less than 30 ℃/hour speed.
The vertically-guided temperature gradient furnace (TGT) of graphite resistance heating is adopted in crystal growth, and crucible material is tungsten (a W crucible), and the crucible top is auxiliary adds a cover, and suppresses the melt volatilization, thereby reduces the S loss.
Because Re
2O
2S thermal expansivity anisotropy difference is big, the C direction of principal axis growing crystal of artificial control thermal expansivity maximum, can reduce radially thermal stresses of crystal, and avoid in the process of cooling that crystal growth finishes crucible, thereby reduce the probability of crystal cleavage widely crystalline pressure.Just secondary growth adopts along the lanthanum aluminate (LaAlO of the directed cutting of C axle
3) single crystal is as the seed product.LaAlO
3Belong to hexagonal system, the similar Re of its crystalline structure
2O
2S has close with it lattice constant and fusing point.Seed crystal is positioned over the conical lower portion of W crucible, guiding growth Re
2O
2The S single crystal.Promptly adopt Re later on
2O
2Seed crystal rod growth Re after the directed cutting of S single crystal
2O
2S and Re ': Re
2O
2The S crystal.
The present invention adopts temperature gradient method (TGT) growth rare earth thio-oxide (Re
2O
2S) sharp other rare earth doped rare earth thio-oxide (Re:Re
2O
2S) single crystal blank.Carry out along C axle orientation by introducing seed crystal control crystal growth, reduced the crystal cleavage probability greatly.Simultaneously, add Na in the raw material in proportion
2S or Re
2S
3, reduced crystal growth temperature widely, avoided Re
2O
2The S pyrolytic decomposition causes the S loss, can obtain being of a size of the high quality single crystal of Ф 5～7 * 6～10cm.Can be used for distinctive physics of such material and optical property are carried out scientific research, wide application prospect is arranged in fields such as laser and flickers.
Embodiment
The invention will be further described below by embodiment:
Embodiment 1: sulfo-lanthanum trioxide (La
2O
2S) single crystal
Take by weighing 1 kilogram of La
2O
2S powder and 200 gram Na
2S, abundant ground and mixed is the back briquetting evenly, and the bottom of packing into then is placed with the LaAlO of C axle orientation
3In the tungsten crucible of seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 1 * 10
-3Pa is warming up to 1000 ℃, is incubated 4 hours rear hearth vacuum tightness and reaches 4 * 10
-3Pa, charging into high-purity Ar to malleation is 0.1Mpa.Be warming up to 1680 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1320 ℃, reduce to room temperature with 30 ℃/hour speed then.
Embodiment 2: sulfo-yttrium oxide (Y
2O
2S) single crystal
Take by weighing 1 kilogram of Y
2O
2S powder and 400 gram Na
2S, abundant ground and mixed is the back briquetting evenly, and the bottom of packing into then is placed with the La of C axle orientation
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 800 ℃, is incubated 5 hours rear hearth vacuum tightness and reaches 8 * 10
-3Pa, charging into high-purity Ar to malleation is 0.01Mpa.Be warming up to 1780 ℃ then, constant temperature after 3 hours the speed with 1 ℃/hour be cooled to 1520 ℃, reduce to room temperature with 10 ℃/hour speed then.
Embodiment 3: sulfo-gadolinium sesquioxide (Gd
2O
2S) single crystal
Take by weighing 1 kilogram of Gd
2O
2S powder and 300 gram Na
2S, abundant ground and mixed is the back briquetting evenly, and the bottom of packing into then is placed with the Y of C axle orientation
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2 * 10
-3Pa is warming up to 900 ℃, is incubated 5 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.04Mpa.Be warming up to 1760 ℃ then, constant temperature after 5 hours the speed with 2 ℃/hour be cooled to 1460 ℃, reduce to room temperature with 25 ℃/hour speed then.
Embodiment 4: sulfo-cerium oxide (Ce
2O
2S) single crystal
Take by weighing 1 kilogram of Ce
2O
2S powder and 250 gram Na
2S, abundant ground and mixed is the back briquetting evenly, and the bottom of packing into then is placed with the LaAlO of C axle orientation
3In the W crucible of seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2 * 10
-3Pa is warming up to 1200 ℃, is incubated 4 hours rear hearth vacuum tightness and reaches 4 * 10
-3Pa, charging into high-purity Ar to malleation is 0.04Mpa.Be warming up to 1660 ℃ then, constant temperature after 5 hours the speed with 2 ℃/hour be cooled to 1300 ℃, reduce to room temperature with 30 ℃/hour speed then.
Embodiment 5: doping content be 1.0at% mix ytterbium sulfo-lanthanum trioxide (Yb:La
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 1.0at%Yb:La
2O
2S powder and 300 gram La
2S
3, abundant ground and mixed is the back briquetting evenly, the La of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2.5 * 10
-3Pa is warming up to 850 ℃, is incubated 4.5 hours rear hearth vacuum tightness and reaches 4.0 * 10
-3Pa, charging into high-purity Ar to malleation is 0.03Mpa.Be warming up to 1680 ℃ then, constant temperature after 4 hours the speed with 2 ℃/hour be cooled to 1300 ℃, reduce to room temperature with 18 ℃/hour speed then.
Embodiment 6: doping content is the neodymium-doped sulfo-lanthanum trioxide (Nd:La of 10.0at%
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 10.0at%Nd:La
2O
2S powder and 500 gram La
2S
3, abundant ground and mixed is the back briquetting evenly, the La of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1660 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1260 ℃, reduce to room temperature with 25 ℃/hour speed then.
Embodiment 7: doping content be 2.0at% mix europium sulfo-lanthanum trioxide (Eu:La
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 2.0at%Eu:La
2O
2S powder and 400 gram La
2S
3, abundant ground and mixed is the back briquetting evenly, the La of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1700 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1330 ℃, reduce to room temperature with 15 ℃/hour speed then.
Embodiment 8: doping content be 20.0at% mix terbium sulfo-lanthanum trioxide (Tb:La
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 20.0at%Tb:La
2O
2S powder and 250 gram La
2S
3, abundant ground and mixed is the back briquetting evenly, the La of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1660 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1260 ℃, reduce to room temperature with 30 ℃/hour speed then.
Embodiment 9: doping content be 0.5at% mix ytterbium sulfo-yttrium oxide (Yb:Y
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 0.5at%Yb:Y
2O
2S powder and 300 gram Y
2S
3, abundant ground and mixed is the back briquetting evenly, the Y of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2.5 * 10
-3Pa is warming up to 1000 ℃, is incubated 4.5 hours rear hearth vacuum tightness and reaches 4.0 * 10
-3Pa, charging into high-purity Ar to malleation is 0.03Mpa.Be warming up to 1780 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1380 ℃, reduce to room temperature with 18 ℃/hour speed then.
Embodiment 10: doping content is the neodymium-doped sulfo-yttrium oxide (Nd:Y of 15.0at%
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 15.0at%Nd:Y
2O
2S powder and 500 gram Y
2S
3, abundant ground and mixed is the back briquetting evenly, the Y of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.025Mpa.Be warming up to 1740 ℃ then, constant temperature after 6 hours the speed with 2 ℃/hour be cooled to 1360 ℃, reduce to room temperature with 20 ℃/hour speed then.
Embodiment 11: doping content be 5.0at% mix europium sulfo-yttrium oxide (Eu:Y
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 5.0at%Eu:Y
2O
2S powder and 400 gram Y
2S
3, abundant ground and mixed is the back briquetting evenly, the Y of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1760 ℃ then, constant temperature after 5 hours the speed with 1.5C/ hour be cooled to 1400 ℃, reduce to room temperature with 25 ℃/hour speed then.
Embodiment 12: doping content be 20.0at% mix terbium sulfo-yttrium oxide (Tb:Y
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 20.0at%Tb:Y
2O
2S powder and 250 gram Y
2S
3, abundant ground and mixed is the back briquetting evenly, the Y of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1200 ℃, is incubated 6 hours rear hearth vacuum tightness and reaches 6 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1760 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1360 ℃, reduce to room temperature with 30 ℃/hour speed then.
Embodiment 13: doping content be 2.5at% mix ytterbium sulfo-gadolinium sesquioxide (Yb:Gd
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 2.5at%Yb:Gd
2O
2S powder and 300 gram Gd
2S
3, abundant ground and mixed is the back briquetting evenly, the Gd of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2.5 * 10
-3Pa is warming up to 1000 ℃, is incubated 4.5 hours rear hearth vacuum tightness and reaches 4.0 * 10
-3Pa, charging into high-purity Ar to malleation is 0.03Mpa.Be warming up to 1760 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1380 ℃, reduce to room temperature with 18 ℃/hour speed then.
Embodiment 14: doping content is the neodymium-doped sulfo-gadolinium sesquioxide (Nd:Gd of 10.0at%
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 10.0at%Nd:Gd
2O
2S powder and 500 gram Gd
2S
3, abundant ground and mixed is the back briquetting evenly, the Gd of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.025Mpa.Be warming up to 1740 ℃ then, constant temperature after 6 hours the speed with 2 ℃/hour be cooled to 1460 ℃, reduce to room temperature with 20 ℃/hour speed then.
Embodiment 15: doping content be 25.0at% mix europium sulfo-gadolinium sesquioxide (Eu:Gd
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 25.0at%Eu:Gd
2O
2S powder and 400 gram Gd
2S
3, abundant ground and mixed is the back briquetting evenly, the Gd of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1150 ℃, is incubated 8 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1720 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1400 ℃, reduce to room temperature with 25 ℃/hour speed then.
Embodiment 16: doping content be 30.0at% mix terbium sulfo-gadolinium sesquioxide (Tb:Gd
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 20.0at%Tb:Gd
2O
2S powder and 250 gram Gd
2S
3, abundant ground and mixed is the back briquetting evenly, the Gd of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1200 ℃, is incubated 6 hours rear hearth vacuum tightness and reaches 6 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1740 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1360 ℃, reduce to room temperature with 30 ℃/hour speed then.
Embodiment 17: doping content be 0.5at% mix ytterbium sulfo-cerium oxide (Yb:Ce
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 0.5at%Yb:Ce
2O
2S powder and 250 gram Ce
2S
3, abundant ground and mixed is the back briquetting evenly, the Ce of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 2.5 * 10
-3Pa is warming up to 1000 ℃, is incubated 4.5 hours rear hearth vacuum tightness and reaches 4.0 * 10
-3Pa, charging into high-purity Ar to malleation is 0.03Mpa.Be warming up to 1660 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1380 ℃, reduce to room temperature with 18 ℃/hour speed then.
Embodiment 18: doping content is the neodymium-doped sulfo-cerium oxide (Nd:Ce of 15.0at%
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 15.0at%Nd:Ce
2O
2S powder and 500 gram Ce
2S
3, abundant ground and mixed is the back briquetting evenly, the Ce of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.025Mpa.Be warming up to 1650 ℃ then, constant temperature after 6 hours the speed with 2 ℃/hour be cooled to 1400 ℃, reduce to room temperature with 20 ℃/hour speed then.
Embodiment 19: doping content be 25.0at% mix europium sulfo-cerium oxide (Eu:Ce
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 25.0at%Eu:Ce
2O
2S powder and 400 gram Ce
2S
3, abundant ground and mixed is the back briquetting evenly, the Ce of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1100 ℃, is incubated 7 hours rear hearth vacuum tightness and reaches 5 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1640 ℃ then, constant temperature after 5 hours the speed with 1.5 ℃/hour be cooled to 1240 ℃, reduce to room temperature with 25 ℃/hour speed then.
Embodiment 20: doping content be 40.0at% mix terbium sulfo-cerium oxide (Tb:Ce
2O
2S) single crystal
Taking by weighing 1 kilogram of doping content is 20.0at%Tb:Ce
2O
2S powder and 250 gram Ce
2S
3, abundant ground and mixed is the back briquetting evenly, the Ce of the C axle orientation of packing into then
2O
2In the W crucible of S seed crystal, be placed on the ZrO in the TGT stove behind the crucible cover that closes
2On the seat.After the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump is evacuated to 3 * 10
-3Pa is warming up to 1200 ℃, is incubated 6 hours rear hearth vacuum tightness and reaches 6 * 10
-3Pa, charging into high-purity Ar to malleation is 0.015Mpa.Be warming up to 1660 ℃ then, constant temperature after 4 hours the speed with 1.5 ℃/hour be cooled to 1300 ℃, reduce to room temperature with 30 ℃/hour speed then.
Claims (7)
1, a kind of rare earth thio-oxide crystalline growth method is characterized in that this method is the method that adopts fusing assistant and utilize the temperature gradient furnace growing crystal, comprises seed crystal preparation, the compacting of material piece and temperature gradient method growing crystal step.
2, rare earth thio-oxide crystalline growth method according to claim 1, it is characterized in that described seed crystal preparation, adopt for the first time the lanthanuma luminate single crystal body of the directed cutting of C axle to make seed crystal, adopt the crystal bar of the directed cutting of rare earth thio-oxide single crystal to make seed crystal later on.
3, rare earth thio-oxide crystalline growth method according to claim 2 is characterized in that this method comprises the following steps:
1. system is expected piece: adopt sodium sulphite Na
2S presses Na as fusing assistant
2S: Re
2O
2S=(20～40): the weight percent batching of (80～60) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 800～1000 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing single-crystal, to obtain rare earth thio-oxide Re
2O
2The S crystal.
4, rare earth thio-oxide crystalline growth method according to claim 2 is characterized in that this method comprises the following steps:
1. system material piece adopts Na
2S presses Na as fusing assistant
2S: (Re: Re
2O
2S)=(20～40): the weight percent batching of (80～60) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 800～1000 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing single-crystal, last to obtain rare earth doped rare earth thio-oxide Re: Re
2O
2The S crystal.
5, rare earth thio-oxide crystalline growth method according to claim 2 is characterized in that this method comprises the following steps:
1. system is expected piece: adopt rare-earth sulfide Re
2S
3As fusing assistant, press Re
2S
3: Re
2O
2S=(25～50): the weight percent batching of (75～50) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 1000～1200 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing crystal, to obtain Re
2O
2The S crystal.
6, rare earth thio-oxide crystalline growth method according to claim 2 is characterized in that this method comprises the following steps:
1. system material piece adopts rare-earth sulfide Re
2S
3As fusing assistant, press Re
2S
3: (Re: Re
2O
2S)=(25～50): the weight percent batching of (75～50) is pressed into the material piece after abundant ground and mixed is even;
2. seed crystal is placed in the seed slot of tungsten crucible bottom, will expects packagedly in tungsten crucible, be placed in the temperature gradient furnace after this crucible is added a cover, after the closely knit sealing of burner hearth, successively open mechanical pump and diffusion pump and be evacuated to vacuum tightness and be better than 3 * 10
-3Pa is warming up to 1000～1200 ℃, is incubated burner hearth vacuum tightness and is better than 1 * 10
-2Charge into high-purity Ar behind the Pa to malleation 0～0.2Mpa;
3. press temperature gradient method technology growing crystal, last to obtain rare earth doped rare earth thio-oxide Re: Re
2O
2The S crystal.
7, according to each described rare earth thio-oxide crystalline growth method of claim 1 to 6, the temperature gradient method technology that it is characterized in that described growing single-crystal is: keep more than 2 hours in top temperature, lower the temperature 200～400 ℃ with speed, then to reduce to room temperature less than 30 ℃/hour speed less than 2 ℃/hour.
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5386797A (en) * | 1992-03-27 | 1995-02-07 | Kabushiki Kaisha Toshiba | Single crystal of compound, laser rod, laser oscillator, scintillator, CT scanner, color display and process for preparing the same |
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2004
- 2004-07-30 CN CNB2004100533036A patent/CN1313650C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5386797A (en) * | 1992-03-27 | 1995-02-07 | Kabushiki Kaisha Toshiba | Single crystal of compound, laser rod, laser oscillator, scintillator, CT scanner, color display and process for preparing the same |
Non-Patent Citations (3)
| Title |
|---|
| Czochraksi crystal growth of lanthanum oxysulfide R.J.Baughman,Mat. Res. Bull.,Vol.8 1973 * |
| Growth and properties of Lanthanum oxysulfide crystals L.E.Sobon et. al,Journal of applied Physics,Vol.42 No.8 1971 * |
| Optical properties and electronic structure of yttrium oxysulfide Minoru Itoh,Yoshiyuki Inabe,Physical Review B,Vol.68 No.3 2003 * |
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