CN1225572C - Integrated melt method for crystal growth - Google Patents
Integrated melt method for crystal growth Download PDFInfo
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- CN1225572C CN1225572C CN 200310112171 CN200310112171A CN1225572C CN 1225572 C CN1225572 C CN 1225572C CN 200310112171 CN200310112171 CN 200310112171 CN 200310112171 A CN200310112171 A CN 200310112171A CN 1225572 C CN1225572 C CN 1225572C
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- 239000013078 crystal Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 86
- 230000012010 growth Effects 0.000 title claims abstract description 61
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 11
- 239000010980 sapphire Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 230000006698 induction Effects 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 5
- ZPDRQAVGXHVGTB-UHFFFAOYSA-N gallium;gadolinium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Gd+3] ZPDRQAVGXHVGTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000010899 nucleation Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000002223 garnet Substances 0.000 abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 150000004645 aluminates Chemical class 0.000 abstract 1
- 230000008602 contraction Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010437 gem Substances 0.000 description 3
- 229910001751 gemstone Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010979 ruby Substances 0.000 description 2
- 229910001750 ruby Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- -1 CaAs Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910006295 Si—Mo Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000000339 bright-field microscopy Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- MNKMDLVKGZBOEW-UHFFFAOYSA-M lithium;3,4,5-trihydroxybenzoate Chemical compound [Li+].OC1=CC(C([O-])=O)=CC(O)=C1O MNKMDLVKGZBOEW-UHFFFAOYSA-M 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- FPSFKBGHBCHTOE-UHFFFAOYSA-M sodium 1-[(3-methyl-5-oxo-1-phenyl-4H-pyrazol-4-yl)diazenyl]-4-sulfonaphthalen-2-olate Chemical compound [Na+].O=C1C(N=NC=2C3=CC=CC=C3C(=CC=2O)S([O-])(=O)=O)C(C)=NN1C1=CC=CC=C1 FPSFKBGHBCHTOE-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- CMJCEVKJYRZMIA-UHFFFAOYSA-M thallium(i) iodide Chemical compound [Tl]I CMJCEVKJYRZMIA-UHFFFAOYSA-M 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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Abstract
The present invention provides a comprehensive fusant method for crystal growth, wherein seeding, neck contraction and shouldering are carried out by a pulling method, and a soaking growth method and/or a temperature gradient method is adopted in isometric growth. The method can produce various high-quality crystals with large size and especially oxide crystals, such as sapphire substrate crystals, doped or undoped aluminum oxide, aluminate crystals, garnet crystals (YAG, GGG and GsGG), niobate crystals, etc. The method has the advantages of growth of crystals with large size, little pollution, observation of the conditions of liquid levels and crystal growth and use of original pulling devices of the pulling method, the soaking growth method and the temperature gradient method. Meanwhile, the technology overcomes the defects of high color center rate and high dislocation rate of crystal growth of the pulling method and the temperature gradient method. The present invention also has the advantages of good quality of crystals, little stress, no defects of slip bands and twin crystals, low dislocation density, good crystal perfection, good optical uniformity and easy industrialization.
Description
Technical field
The present invention relates to crystal growth, be specifically related to melt growth, particularly in conjunction with a kind of comprehensive melt growth method that lifts, steeps multiple growth patterns such as living and warm ladder.
Technical background
At present, from melt growing crystal be the preparation crystal the most frequently used with most important a kind of method.Needed monocrystal material during modern technologies such as electronics, optics are used, major part prepares with the melt growth method.For example: Si, Ge, CaAs, GaP, LiNbO
3, Nd:YAG, Nd:Cr:GSGG, Al
2O
3And Ti:Al
2O
3Crystal etc., and the halogen compound of some basic metal and alkaline-earth metal etc.Many crystal enter the suitability for industrialized production of different scales already.
The method of growing crystal is varied in the melt, for example crystal pulling method at first is to introduce seed crystal to form a monocrystalline nuclear in melt, then, constantly carry out rearranging of atom or molecule on the boundary of nucleus melt, the array of being piled up directly changes oldered array into and forms crystal.This is the most general the most frequently used method.Also have warm terraced method, that is the Bridgman method, utilize thermograde that melt in the crucible is solidified into crystal gradually, wherein can be with or without seed crystal, also can keep temperature-resistant and make degradation under the crucible.Kyropoulos (Kyropoul method) seed crystals that use are immersed in melt inner control temperature with it and grow, wherein slowly rotary pulling or not rotary pulling more.The top-seeded solution growth that also has flux method and improvement thereof, zone melting method, melting zone method (float-zone method), flame melt method or the like.
Crystal pulling method has been realized industrialization at first, for example semiconductor crystal such as silicon single crystal; Also have oxide crystal such as garnet class, sapphire and ruby, niobium, tantalic acid salt and nonlinear optics borate family crystal.The patent documentation of this respect piece is unequal to poly-.But this method defectiveness at first is that crystal diameter is limited by crucible diameter, and both ratios generally are 1: 3, only about 1: 2 of elemental crystal such as silicon single-crystal maximum, and therefore many improvement flowers are at continuous charging (for example continuous growth of silicon single-crystal); Next is to have concentration gradient when the material that mixes than the heavy ion radius, has a strong impact on use.
With regard to sapphire and garnet, the patent of crystal pulling method such as KR2001017991, RU2164267, JP11121855sls, JP10338594, US5866092 etc.
The patent such as the CN85100534 of the terraced method of temperature, RU2049832 etc.Its shortcoming is to contain defectives such as bubble in the crystal, is difficult to obtain high quality crystal.Also have CN97106255 and JP7010672 etc., vertical warm terraced method growing lithium aluminate and lithium gallate crystal.
The patent of kyropoulos such as CS8801546 and CS264935.Its shortcoming is that the speed of growth is slow, is unfavorable for industrialization.
In a word, different methods has different separately relative merits.Up to now, also there is not a kind of comprehensive several different methods and a growth method of maximizing favourable factors and minimizing unfavourable ones.
Summary of the invention
The purpose of this invention is to provide a kind of comprehensive melt method for growing crystal, wherein use crystal pulling method to sow, receive neck, shouldering, when isodiametric growth, adopt kyropoulos and/or warm terraced method.
Another object of the present invention provides a kind of comprehensive melt method for growing sapphire crystal.
Further object of the present invention provides a kind of comprehensive melt method for growing garnet crystal.
Another object of the present invention provides a kind of comprehensive melt method for growing niobate crystal.
A further object of the invention provides a kind of comprehensive melting method of crystal growth, and wherein crystalline pulling rate and rotating speed change.
Other purposes of the present invention and advantage will be more clear hereinafter.
Purpose of the present invention is intended to overcome above-mentioned the deficiencies in the prior art, and a kind of comprehensive melting method is provided, can growing large-size high-quality Sapphire Substrate crystal and LiNbO
3, Nd:YAG, Nd:Cr:GSGG mixes or undopes Al
2O
3Wait each crystalloid, particularly oxide crystal.This method uses crystal pulling method to sow, receive neck, shouldering, adopts kyropoulos and/or warm terraced method when isodiametric growth.
At first introduce seed crystal in melt, carry out seeding and shouldering with general crystal pulling method, wherein seed crystal is fallen in the crucible in the raw-material melt, it is molten that seed crystal and melt are soaked mutually.Induce by seed crystal that molecule is rearranged for oldered array on solid-liquid body interface, form crystal.Utilize crystal growing and pulling device rotation, vertical operation to control crystalline growth velocity, until reaching the diameter that needs.The general technology parameter of crystal pulling method all is known, and certainly, different its parameters of raw material are different; But can obtain by conventional optimization test fully, need not to give unnecessary details.Generally speaking, rotating speed is between 5～200rpm, and is preferred 20～100, more preferably 10～50rpm.Between the general 0.1～5.0mm/hr of pulling rate, preferred 1.0～2.5, more preferably 0.5～1.5mm/hr.And the niobate of difficult growth specifically is a lithium niobate crystals, and its rotating speed is relative with pulling rate smaller, generally between 10～25rpm and 0.5～1.2mm/hr.For silicon single crystal, bigger undoubtedly.Pulling rate can reach several even tens millimeters of per minute.
During isodiametric growth, can stop to lift or lifting with low speed, cooling simultaneously is so that all carry out the growth of crystalline major portion under melt liquid level.Can be that kyropoulos also can be warm terraced method or both combinations.So, growing environment is stable, is easy to obtain the crystal of good quality.Meanwhile, broken through the diameter restrictions of crystal pulling method, can growth diameter greater than the crystal of crystal pulling method.In other words, use the general technology parameter of kyropoulos and/or warm terraced method during isodiametric growth.Some simple crystal, for example symmetry good cube or hexagonal and elemental crystal, can use warm terraced method to become crystal fully up to melt.And difficult growth or doping are then adopted kyropoulos, particularly niobate crystal than long radius ionic crystal; Give full play to the advantage of kyropoulos this moment, can obtain the crystal of good quality.Equally, these processing parameters are different and variant according to raw material, can obtain by conventional optimization test equally.With sapphire or garnet is example, and the disclosed parameter of above-mentioned reference all can be used for reference.Cooling rate is generally between 0.1～5 ℃/hr when using warm terraced method; The big cooling rate of crystalline size is slow, otherwise fast slightly.And niobate crystal is generally between 0.1～2 ℃/hr.When grow doping sapphire or yttrium aluminium or gadolinium gallium garnet, use kyropoulos, can lift also and can not lift, rotate or do not rotate.Cooling rate is faster a little than the terraced method of temperature.Rotating speed is generally 0～50, preferred 5～20rpm; Pulling rate is generally 0～5, and is preferred 0.2～1.0, more preferably between 0.05～0.5mm/hr.
When crystal growth finishes, crystal is proposed the liquid level of melt.If have the rotation and lift, can stop in good time, controlled temperature is slowly reduced to room temperature then.This moment, cooling rate can be used for reference the cooling rate of kyropoulos, generally between 10～100 ℃/hr.Or between 1～100 ℃/hr of warm terraced method.Certainly, the later stage can be strengthened cooling rate, and not ftractureing with crystal is as the criterion.
Equipment that present method is used and type of heating do not have strict restriction, use the general equipment that lifts usually; No matter induction heating still is a resistive heating can both be used.In conjunction with sophisticated equipment and computer control present method is attained a yet higher goal.And use a computer control and going up or LOAD CELLS and optics or infrared sensor etc. down of the crystal growth equipment of China at present finishes that employed equipment is exactly computer control and last LOAD CELLS when of the present invention more.In other words, although the temperature field of kyropoulos and/or warm terraced method and crystal pulling method is slightly variant, there is no particular requirement in the method.In general, the lower limit of the common temperature of a use crystal pulling method scope gets final product or is lower.Because in melt growth, the temperature field of the whole bag of tricks is similar.When thermograde is excessive,, easily produce defective though can make fast growth crystal thermal stresses big.Temperature is terraced when too small, though it is slow to make crystal mass improve the speed of growth, is unfavorable for industrialization.The warm ladder of crystal pulling method can be bigger, and bubble is living relative less with the warm ladder of warm terraced method.From the crystal growth principle, guaranteeing that warm ladder is the bigger the better under the crystalline quality situation, the big output height of temperature ladder.Certainly, different crystal equality of temperature ladder not.During the good crystal growth of thermal conductivity, warm ladder can be greatly; The crystal temperature ladder of poor heat conductivity is then smaller.As long as by simple optimization test, be not difficult to obtain suitable temperature field.In addition, need be aspect insulation need suitably to strengthen, because present method crystalline size big than simple crystal pulling method sometimes.
Equally, crucible is not had strict restriction yet, only otherwise with fusant reaction and can be just in the operation of crystal pulling temperature.For example precious metal crucible, oxide compound crucible or quartz crucible etc., different crystal different heating mode is used different crucibles, and this is well known to those skilled in the art.During the growth high temperature crystal, resistive heating can be used graphite, tungsten or molybdenum or the heating of its alloy.In this case, generally adopt inert atmosphere or reducing atmosphere; Use tungsten, molybdenum or its alloy radiation shield and crucible simultaneously.The crystal growth of lesser temps is fairly simple, uses precious metal or its alloy crucible, oxide compound crucible such as alumina crucible or quartz crucible etc., and resistance wire or rod heating get final product.According to the kind of crystalline material, selectable heating material also has globars, Si-Mo rod, nichrome wire, nickel aluminium wire or its alloy or the like.Induction heating uses the precious metal crucible more, as platinum, iridium or its alloy crucible.Adopt inert atmosphere or air atmosphere (platinum crucible etc.) this moment; Oxide compound lagging material such as aluminum oxide, magnesium oxide, zirconium white or its composition etc.
Description of drawings
Fig. 1 is the warm field device structural representation of the inventive method growing crystal;
Fig. 2 is the synoptic diagram of the inventive method growing crystal.
Wherein 1 is the Medium frequency induction coil, the 2nd, and die casting mica base, the 3rd, zirconium white collet, the 4th, zirconium white insulation sand, the 5th, zirconium white insulation base, the 6th, zirconium white ring, the 7th, stay-warm case on the zirconium white, the 8th, refractory brick cover (1), the 9th, refractory brick cover (2), the 10th, quartz socket tube, the 11st, molybdenum crucible lid, the 12nd, molybdenum crucible, the 13rd, ceramic lifting rod, the 14th, molybdenum matter seed chuck, the 15th, seed crystal, the 16th, liquid level, the 17th, melt, the 18th, crystal.
Hereinafter with reference to accompanying drawing in detail the present invention is described in detail in conjunction with specific embodiments, same numbers is represented same parts in the accompanying drawing.Certainly, embodiment is only for explanation restriction absolutely not.
Embodiment
Use homemade single crystal growing furnace (for example factory of Xi'an University of Technology makes, and has computer control, last LOAD CELLS), molybdenum crucible, Frequency Induction Heating, the zirconium white lagging material, specific configuration is as shown in Figure 1.
Aluminum oxide 2500 grams that sintering is crossed are put into the crucible of Φ 100mm, vacuumize to charge into hydrogen to 0.8atm after reaching 10-2Pa.Heat up and melt, reduce seed rod preheating seed crystal, seed crystal rotating speed 30rpm allows seed crystal contact melt liquid level, lifts with 3mm/hr after the thermal equilibrium; Receive neck and shouldering.Gradual slow reduces pulling rate and rotating speed behind the about 15mm of crystal diameter, branch is clipped to 1.5mm/hr and 15rpm is 30mm until crystal diameter, reduce pulling rate and rotating speed according to the further gradual slow of the amplification of crystal diameter, when diameter is 60mm left and right sides Shi Tingla, rotating speed is 8rpm.Thermal equilibrium 40 minutes, this moment, diameter still can strengthen a little.With the speed cooling of 0.2 ℃/hr, the cooling rate gradual slow is until 0.5 ℃/hr two days later.What of clout the reduction of observing melt liquid level judge, slowly pulling crystal leaves melt then, and beginning is accelerated cooling rate gradually with the cooling of 20 ℃/hr speed, and until reducing to room temperature, blank is taken out in blow-on.
Cut blank end to end, directed (0001) cuts the 2mm thin slice, and polishing both surfaces is carried out optical detection, and the result is as follows:
X ray twin crystal curve FWHM=10 " (second, angular unit),
Dislocation desity D＜3 * 10
3/ cm
2,
Optical transmittance: ultraviolet 0.3 mu m waveband T＞80%; 0.4～4 mu m waveband T＞87%;
Optical homogeneity Δ n=2 * 10
-5
The chrome red jewel is mixed in embodiment 2 growths
With step and the equipment of embodiment 1,, put into the molybdenum crucible growth with 2500 gram aluminum oxide with according to the chromic oxide of total amount 3.0wt%.Seeding shouldering speed that different is is 2.5 to change to 1.0mm/hr gradually, and rotating speed remains on 10rpm always.Obtain the ruby of good quality, light extraction efficiency reaches more than 1.0%.
With step and the equipment of embodiment 1,, put into the crucible growth with 2500 gram aluminum oxide with according to the titanium oxide of total amount 0.2wt%.Different Iridium Crucible and the iraurite crucibles lids of being to use, the gas that charges into is nitrogen, and seeding shouldering speed is 2.5 to change to 1.0mm/hr gradually, and rotating speed remains on 10rpm always.Obtain the sapphire of good quality equally, low-dislocation-density, low scattering, structural integrity height, optical homogeneity Δ n=9 * 10
-7Having used double light path, light to measure length with the method for brewster angle incidence plane of crystal is the titanium gem crystal of 20mm, and measuring crystalline FOM value is 150.
Embodiment 4 induction heating growth neodymium-doped yttrium-aluminum garnet
Substantially according to embodiment 1 same step and equipment, Iridium Crucible and iraurite crucible lid are used in different being to use, and the gas that charges into is nitrogen, and raw material is by the piece material behind the aluminum oxide of chemical formula proportioning, yttrium oxide and Neodymium trioxide (3wt%) and the sintering; Pull rate during the seeding shouldering is 1mm/h, rotating speed 15rpm; Stop during isodiametric growth lifting, rotating speed 5rpm, cooling rate is 0.5 ℃/hr.Obtain the extraordinary crystal of optical homogeneity, light extraction efficiency reaches 2% continuously.Also use the graphite resistance heating in addition under same parameter condition, grow in molybdenum crucible and radiation shield and the argon gas, the crystal optics homogeneity is better than induction heating, but light extraction efficiency is poor slightly, and annealing time is longer.
With spectrophotometry neodymium ion Nd in the crystal that obtains
3+The axial distribution of concentration.The 0.7wt% of neodymium change in concentration from the 2.3wt% of crystal top edge to the position, germ nucleus.The fluorescence lifetime of having measured crystal top and bottom is respectively 160us and 235us.With the Leltz transmitted light microscopy of wide visual field, Nd in crystal
3+Doping content is up to 2.3wt%, and crystalline crystalline perfection and optical homogeneity are still extremely good.
Substantially according to embodiment 1 same step and equipment, different is that the raw material that crystal growth is used is a gadolinium gallium garnet piece material; Use Iridium Crucible and iraurite crucible lid, the gas that charges into is nitrogen and 2% oxygen, and the pull rate during the seeding shouldering is 5mm/hr, rotating speed 20rpm; Stop during isodiametric growth lifting and rotating, cooling rate changes to 4 ℃/hr by 1 ℃/hr through about two days gradual slows.
Do not have bubble, be mingled with in the crystal of growth, macroscopic defects such as cracking.The monocrystalline dislocation desity is less than 10
2Individual/cm
2In addition, also according to user's needs, the different adulterated gadolinium gallium garnets of growth obtain user's favorable comment as non-functional jewel under similarity condition.
Embodiment 6 induction heating growth Lithium niobium trioxide
Substantially according to embodiment 1 same step and equipment, different is that the raw material that crystal growth is used is a Lithium niobium trioxide piece material; Use platinum crucible and platinum crucible lid, the gas that charges into is nitrogen; Pull rate during the seeding shouldering is 1mm/hr, rotating speed 18rpm; Stop during isodiametric growth lifting, cooling rate is 0.5 ℃/hr, adds two days later near about 2 ℃/hr.
Macroscopic defectss such as the large size a axle optics lithium niobate crystals flawless of growth, white silk, bubble and scattering particles, the crystals residual mechanical stress is evenly distributed.Crystal goes to measure behind the twin farmland, and optical homogeneity is good.Dislocation desity in the crystal is not more than 3 * 10
2Individual/cm
2, be (1.3～1.5) * 10 along the axial variations in refractive index of growth
-5/ cm, the crystal transmittance is not less than 87%.
According to the same step and the equipment of the resistive heating of embodiment 4, different is that raw material is the magnesium-aluminium spinel powder, and the pull rate during the seeding shouldering is 2mm/hr, rotating speed 30rpm; 0.1mm/hr lifts during isodiametric growth, and cooling rate is 0.2～2 ℃/hr.Obtain high-quality crystal, do not had defectives such as cloud layer, white silk, bubble and scattering particles in the crystal.
According to embodiment 1 same step, the different nickel chromium triangle aluminium resistance wires that are to use heat, and alumina crucible does not vacuumize, and atmosphere is operation down, and raw material is sodium iodide and thallium iodide 2wt%, and the pulling rate when lifting is 5mm/hr, rotating speed 180rpm; Stop the rotation during isodiametric growth and lift, cooling rate changes to 5 ℃/hr by 1 ℃/hr gradual slow.Though crystal grows together with crucible, heating up has a little just melted with regard to lowering the temperature immediately crystal edge after manually slowly lifting out crucible, still obtain the higher scintillation crystal of counting rate.Because this crystal is the simple cubic structure, fusing point is several Baidu, are very easy to growth.
Present method many crystal of can growing are as niobium tantalate crystal LiNbO
3, LiTaO
3, KNbO
3Mix or undope garnet crystal such as Nd:YAG Nd:Cr:GSGG, GGG; Mix or the Al that undopes
2O
3Crystal such as Cr:Al
2O
3And Ti:Al
2O
3Deng; Mix or the halide crystal that undopes; Also has semiconductor crystal such as silicon, germanium, II-IV family or III-V ii vi crystal even Metallic Solids or the like.From growing principle, the advantage of present method is self-evident.It has inherited common crystal pulling method, the advantage of kyropoulos and warm terraced method: but the growing large-size crystal, and pollution is few, can observe liquid level and crystal growth situation in process of growth, can also use the equipment of original Czochralski grown crystal, has reduced investment cost.This technology has overcome the colour center and the high problem of dislocation rate of crystal pulling method and warm terraced method growing crystal simultaneously, can grow the fine large-size crystals, and crystal stress is little, no slip band and twin defective, and dislocation desity is low, and perfection of crystal and optical homogeneity are good; Be easy to industrialization.
Those skilled in the art can do many improvement and conversion after reading specification sheets, but all do not exceed spiritual scope of the present invention.
Claims (9)
1. the comprehensive melting method of a growing crystal is characterized in that using crystal pulling method to sow, receive neck, shouldering, adopts kyropoulos and/or warm terraced method when isodiametric growth.
2. according to the method for claim 1, it is characterized in that described crystal is a sapphire.
3. according to the method for claim 2, it is characterized in that sapphire is chromium-doped.
4. according to the method for claim 1, it is characterized in that described crystal is a yttrium aluminum garnet.
5. according to the method for claim 4, it is characterized in that the crystal doping neodymium.
6. according to the method for claim 1, it is characterized in that described crystal is a gadolinium gallium garnet.
7. according to the process of claim 1 wherein that the speed range when lifting is 5～200rpm, the pulling rate scope is 0.1～5.0mm/hr; Cooling rate scope during isodiametric growth is 0.1～5 ℃/hr; The pulling rate scope is 0～5mm/hr during isodiametric growth, and speed range is 0～50rpm.
8. use induction heating to grow according to the process of claim 1 wherein.
According to the process of claim 1 wherein pulling growth during the stage pulling rate and rotating speed change.
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| CN100408731C (en) * | 2006-03-02 | 2008-08-06 | 西华大学 | Method and appts. of using molten lead iodide to grow monocrystal |
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| CN105624787A (en) * | 2016-02-16 | 2016-06-01 | 中科九曜科技有限公司 | Melt-process crystal growing method of large-size YAG (yttrium aluminum garnet) or sapphire crystals. |
| CN107313109A (en) * | 2017-06-16 | 2017-11-03 | 天通控股股份有限公司 | A kind of manufacture method of piezo-electric crystal |
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