CN1131342C - Method for implementing monocrystal growth control by using paltie effect - Google Patents
Method for implementing monocrystal growth control by using paltie effect Download PDFInfo
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- CN1131342C CN1131342C CN 00132620 CN00132620A CN1131342C CN 1131342 C CN1131342 C CN 1131342C CN 00132620 CN00132620 CN 00132620 CN 00132620 A CN00132620 A CN 00132620A CN 1131342 C CN1131342 C CN 1131342C
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Abstract
The present invention relates to a method for controlling monocrystal growth by Peltier effect. Fusant appropriately contacts the inner surface of a crucible by controlling radio frequency heating powder and selecting charging quantity in the crucible on a monocrystal growth system by a magnetic suspension cold crucible radio frequency heating Czochralski method, and the goal of the realization of the dimension control of monocrystal growth, marking of growth interfaces and modulation doping by reaching the procedures that currents pass through a solid-liquid interface, etc. The present invention can prepare high-quality and superlattice structural monocrystals, and can research the interface state of monocrystal growth. The present invention has the advantages of rapid reaction and accurate control, and can realize finer growth interface marking and modulation doping with complete margins. The present invention is suitable for all conducting materials.
Description
Technical field
The invention belongs to the single crystal growing field, particularly utilize the method for paltie effect control single crystal growing.
Technical background
As everyone knows, paltie effect is the contact interface that electric current passes through the same material of two kinds of different electro-conductive materials or different shape, produces a kind of effect of refrigeration or pyrogenicity on this interface.Utilize electric current to realize that by the solid-liquid growth interface Peltier refrigeration or thermal effect are a kind of effective crystal growth control techniquess with control crystalline growth conditions and composition.On the other types growing system of non-magnetic levitation cold crucible growth apparatus, also can control (document 1 to the size and the doping of single crystal growing with this method, S.Vojdani etc., J.CrystalGrowth, 24/25,374 (1974) and document 2, M.Lichtensteiger etc., J.Electrochem.Soc.118,1013 (1971)).
Magnetic levitation cold crucible radio frequency heating crystal pulling method is that melt, the crystal of a kind of growing metal, alloy and intermetallic compound and material is the effective ways of conductor, semi-conductive material.The heating of melt and the power of magnetic suspension force are provided by a radio-frequency power supply; Energy is coupled on metal cold crucible internal surface and the melt outside surface with the form that exchanges concussion, forms the induced current eddy current; The eddy current melt heating is realized single crystal growing in cooling gradually subsequently; Simultaneously, the magnetic field that eddy current produces produces suspending power, holds up melt, and it is not contacted with the cold crucible surface.This growth pattern is specially adapted to contain the melt of rare earth metal.Melt has effectively prevented rare earth and crucible material intensive chemical reaction at high temperature with not contacting of crucible, has guaranteed the purity of melt and the safety of crucible.But, because the melt that magnetic levitation makes when growth contacting metal cold-crucible internal surface not, make and realize the not path by solid-liquid interface of the necessary electric current of paltie effect.
Summary of the invention
The objective of the invention is to overcome the shortcoming and the deficiency of prior art, in magnetic levitation cold crucible radio frequency heating crystal pulling method single crystal growing system, provide a kind of and realize utilizing peltier effect to carry out the method for single crystal growing size control, growth interface mark and modulation doping.
The objective of the invention is to realize by following technical scheme:
The invention provides a kind of method of utilizing paltie effect to realize single crystal growing control, comprise the steps: that it adopts crystal pulling method, growth apparatus is the metal mechanical lifting gear, two output terminals of a power supply are received respectively on seed rod and the crucible support system, electric current is introduced seed rod through lead, pass through seed crystal, crystal, the solid-liquid interface of crystal and melt, melt, the contact interface of melt and magnetic levitation metal water cold crucible, magnetic levitation metal water cold crucible, the metallic support part of magnetic levitation metal water cold crucible, after lead returns power supply, but this electric current is reversed flow also, and its detailed process comprises the steps:
(1) be protective atmosphere with vacuum, rare gas element or nitrogen, growth material is dropped into magnetic levitation metal water cold crucible, frequency of utilization is that 45～300 kilohertzs and power are that growth material is treated in 4～45 kilowatts radio frequency heating, the Heating temperature scope is the fusing point to 2500 ℃ of growth material, and magnetic levitation metal water cold crucible keeps below 100 ℃ temperature, make the melt of described growth material contact, form solid-liquid interface at contact interface with magnetic levitation metal water cold crucible surface;
(2) when single crystal growing, the galvanic current that adopts 10～25 amperes is by solid-liquid interface, can cause the seed crystal of growing or the variation of crystalline lateral dimensions, thereby control the variation of longitudinal growth speed or to the growth interface mark, obtained monocrystalline at last.
A kind of method of utilizing paltie effect to realize single crystal growing control, also comprise the steps: when the growing crystal starting material be when being selected from two or three element of Fe, Tb, Si, Ti, Ni, Mn, Ga, adopt the alternating current of impulse form, recurrent interval was at 1～10 second, pulse width was at 1～20 second, or the galvanic current of 1～10 ampere of additional galvanic current, the defective that produces in can the control growing process and in the arrangement of crystalline lateral and longitudinal direction obtains monocrystalline at last.
Vacuum tightness in the growth furnace in the described step 1) is 1 * 10
-2～1 * 10
-9Handkerchief.
The rare gas element in the described step 1) or the purity of nitrogen are 99.9～100%, and gaseous tension is 0.05～30 MPa in the burner hearth.
The present invention regulates radio frequency power and is suitably distributing aspect melt heating and the lifting melt two: promptly guaranteeing under the state of monocrystalline normal growth; make a part of contacting metal inner surface of crucible of melt; at contact interface formation one protective layer as thin as a wafer, form the good conductive contact of the AC and DC electric current of avoiding gas ionization discharge.Like this, the problem of chemical reaction and problem such as geseous discharge may take place on the contact surface of melt and crucible in growth all obtained solution between the melt contact contingent melt of crucible and crucible under the high temperature has also guaranteed the purity of melt and the safety of crucible in growth.
Specifically carry out according to the following steps:
(1) use crystal pulling method, growth apparatus is the metal mechanical lifting gear, growth material can be conductor or
Semi-conductor.
(2) use the heating of 45-300 kilohertz radio frequency, Heating temperature is the fusing point to 2500 ℃ of growth material.
(3) hold and the flux growth material with magnetic levitation metal water cold crucible.
(4) be to grow under the protective atmosphere environment at vacuum, rare gas element or nitrogen.When taking vacuum environment,
Vacuum tightness in the growth furnace is 1 * 10
-2-1 * 10
-9Handkerchief; Taking rare gas element or nitrogen for protecting
When protecting the atmosphere growth, shielding gas purity should be greater than 99.9%, and shielding gas pressure is in the burner hearth
0.05-30 MPa.
(5) make the metal cold crucible keep below 100 ℃ temperature.
(6) by selected growth material, selecting the charging capacity in the crucible is 10-100g.The radio frequency heating power
Be controlled in the 4-45 kilowatt of scope.Regulate radio frequency power melt heating and lifting melt two sides
Face suitably distributes: promptly under the state that guarantees the monocrystalline normal growth, make the part contact of melt
The metallic crucible internal surface at contact interface formation one protective layer as thin as a wafer, forms and avoids gas
Good conductive contact from the AC and DC electric current that discharges.Like this, melt under the high temperature in growth
The problem of chemical reaction and molten in growth between contact contingent melt of crucible and crucible
Problems such as geseous discharge may take place on the contact surface of body and crucible all obtained solution.Also guarantee
The purity of melt and the safety of crucible
(7) two output terminals that can produce the power supply of direct current or alternating-current are received respectively seed rod and
On the crucible support system,, make electric current with surely by the direct current or the alternating current of 0.1-50 ampere
Perseverance or pulse mode are flowing to melt both direction homomergic flow from melt-flow to crystal or from crystal
Cross solid-liquid interface, utilize the method for aforementioned control charging capacity and radio frequency heating power can form institute
The melt of stating suitably contacts the situation of inner surface of crucible.Like this, the crucible support system, melt,
Growth interface, the crystal in the growth, seed crystal and seed rod system just form a good direct current or
The alternating current path.If above-mentioned electric current adopts the form of pulse, the recurrent interval is at 0.1-1000
In second scope, pulse width is in 0.01-100 scope second.
(8) when single crystal growing, begin to break away from residual melt to the crystal of growth from seed crystal contact melt liquid level
Seed crystal in during the liquid level prolongs growth, necking down, shouldering growth, and isodiametric growth and fusing etc. are respectively
In growth phase and the operation, adopt described electric current to cause the seed of growing by solid-liquid interface
The variation of crystalline substance or crystalline lateral dimensions control longitudinal growth speed variation or to the growth circle
The face mark.
(9) adopt described electric current by solid-liquid interface, realize conscious admixture material or unconscious assorted
The cyclomorphosis of matter doping and modulation control.When the growing crystal starting material be two kinds or two kinds with
During last element, can realize control and modulation that the various compositions of the crystalline of growing into are changed, to growth
Issuable various defectives in the process are (as compound, dislocation, the fault, little of different structure
Angle crystal boundary, twin etc.) the control of crystalline lateral and longitudinal direction and periodically and
Acyclic arrangement.
The present invention can control the crystal growth size effectively, composition and labeling and growing interface in the control crystal, even can in a planned way introduce growth defect; Be high-purity, the high quality single crystal of preparation, the effective ways of preparation superstructure, superstructure body monocrystalline and research single crystal growing interfacial state.The present invention reacts soon, controls accurately; Can additionally when regulating growth velocity and growth temperature control growing size take present method accurately to control; Can realize meticulousr, growth interface mark and modulation doping that the edge is more complete.The present invention is applicable to the material that all can use magnetic levitation cold crucible radio frequency heating Czochralski grown monocrystalline.
Description of drawings
Describe the present invention below in conjunction with drawings and Examples:
Fig. 1 is a schematic diagram of the present invention, wherein:
1 power supply, 2 seed rods, 3 seed crystals, 4 crystal 5 solid-liquid interfaces
6 melts, 7 magnetic levitation metal water cold crucibles, 8 metallic support
Fig. 2 utilizes the present invention Tb that grows
2Fe
16The interface of Si monocrystalline indicates,
Fig. 3 utilizes present method growth Tb
2Fe
11The defective layered structure of Ti,
Fig. 4 utilizes present method growth Ni
52Mn
24Ga
24The strain of monocrystalline-magneticstrength curve, 1.2T after the match magnetic-field-induced strain can reach 1.0%,
Fig. 5 utilizes present method growth Ni
52Mn
24Ga
24The magnetic field of monocrystalline strengthens shape memory effect,
Fig. 6 is the asymmetric shape memory effect of NiMnGa alloy 10% strained.
Embodiment
Embodiment is as described below: as shown in Figure 1,1 for can produce the interchange of 0.1-50 ampere or the power supply of galvanic current, electric current is introduced seed rod 2 by lead, by seed crystal 3, crystal 4, the solid-liquid interface 5 by crystal and melt enters melt 6 again, contact part through melt 6 and metal cold crucible 7 enters the metal cold crucible, and the metallic support part by the metal cold crucible 8 is returned power supply through lead at last.Above-mentioned electric current also can be introduced in opposite direction.In the circuit that electric current flows through, the direct current resistance in the circuit is beaten up nurse at 0.001 ohm-20.Above-mentioned electric current produces Pa Er card refrigeration and thermal effect in solid-liquid interface 5.
Embodiment 1:
Adopting growth parameter(s) is the radio frequency heating of 245 kilohertzs, the argon gas atmosphere protection, and in magnetic levitation cold crucible, heating power is 20 kilowatts.With 55 gram purity is that 99.9% Ni is a raw material, and the Ni monocrystalline is a seeded growth Ni monocrystalline.Adopt 20 amperes galvanic current, connect and introduce electric current in the mode of Fig. 1, realize the single crystal growing size control, obtain diameter and be 20 millimeters high quality single crystal, its shape controlling dimension sees Table 1.
Embodiment 2:
With purity is 99.9% Tb, and Fe, Si are raw material growth Tb
2Fe
16The Si monocrystalline adopts the growth parameter(s) among the embodiment 1, adopts 25 amperes electric current, is protective atmosphere with nitrogen, connect and introduce electric current in the mode of Fig. 1, with the recurrent interval be 10 seconds, pulse width is 1 second, the interface flags parameters that obtains in monocrystalline as shown in Figure 2.
Embodiment 3:
With purity is 99.9% Tb, and Fe, Ti are that raw material is by Tb
1.2Fe
11The prescription growth TbFe of Ti
11The Ti monocrystalline adopts the growth parameter(s) of embodiment 1, with the recurrent interval be 1 second, pulse width is 10 seconds, connects in the mode of Fig. 1 and introduces 10 amperes direct current, the defective layered structure parameter of acquisition as shown in Figure 3.
Embodiment 4:
With purity is 99.9% Ni and Mn, and purity is that 99.99% Ga is a raw material, presses Ni
51Mn
24.5Ga
24.5Prescription, the growth Ni
52Mn
24Ga
24Monocrystalline, adopt the growth parameter(s) of embodiment 1, in the stove is vacuum, connect and introduce electric current by Fig. 1 mode, press the mode control growing size of embodiment 1, and adopt 1 second recurrent interval, pulse width 0.1 second, the homogeneity of additional 1 ampere galvanic current control growing component, the magnetic-field-induced strain of the monocrystalline of acquisition on [001] direction seen Fig. 4.
Embodiment 5:
With embodiment 4, preparation method's difference is that additional 10 amperes galvanic current forms the defective layered structure, and the magnetic of the monocrystalline of acquisition on [001] direction strengthens shape memory effect and sees Fig. 5.
Embodiment 6:
With embodiment 4, preparation method's difference is that the extra-pulse width is 20 seconds, and the defective layered structure that forms in monocrystalline produces asymmetric bidirectional shape memory effect, and maximum strain is 10%, as shown in Figure 6.
Embodiment 7:
With the material composition among the embodiment 4 at Ni
50+x+yMn
25-xGa
25-yIn the scope of (x=-4 ~+4, y=-4 ~+4), the various NiMnGa alloy monocrystallines of growth see Table 2.
Table 1 Ni-monocrystal growth data
| Ni monocrystalline weight (g) | Mean diameter (mm) | Diameter error |
| 5 | 3 | 5％ |
| 15 | 10 | 5％ |
| 25 | 15 | 5％ |
| 40 | 15-20 | 5％ |
| 100 | 20-25 | 5％ |
Table 2 NiMnGa alloy growth data
| The X value | The Y value | Monocrystalline weight (mm) |
| -4 | -4 | 5-30 |
| +1 | +1 | 5-30 |
| 0 | +1 | 5-50 |
| 0 | 2 | 4-60 |
| 0 | 0 | 4-60 |
| 1.5 | 1.5 | 4-100 |
| 4 | 4 | 3-20 |
Claims (4)
1. one kind is utilized paltie effect to realize the method that single crystal growing is controlled, it adopts crystal pulling method, growth apparatus is the metal mechanical lifting gear, two output terminals of a power supply are received respectively on seed rod and the crucible support system, electric current is introduced seed rod through lead, pass through seed crystal, crystal, the solid-liquid interface of crystal and melt, melt, the contact interface of melt and magnetic levitation metal water cold crucible, magnetic levitation metal water cold crucible, the metallic support part of magnetic levitation metal water cold crucible, after lead returns power supply, but this electric current is Flow Injection Chemiluminescence Method also, and its detailed process comprises the steps:
(1) be protective atmosphere with vacuum, rare gas element or nitrogen, growth material is dropped into magnetic levitation metal water cold crucible, frequency of utilization is that 45～300 kilohertzs and power are that growth material is treated in 4～45 kilowatts radio frequency heating, the Heating temperature scope is the fusing point to 2500 ℃ of growth material, and magnetic levitation metal water cold crucible keeps below 100 ℃ temperature, make the melt of described growth material contact, form solid-liquid interface at contact interface with magnetic levitation metal water cold crucible surface;
(2) when single crystal growing, the galvanic current that adopts 10～25 amperes is by solid-liquid interface, can cause the seed crystal of growing or the variation of crystalline lateral dimensions, thereby control the variation of longitudinal growth speed or to the growth interface mark, obtained monocrystalline at last.
2. by the described method of utilizing paltie effect to realize single crystal growing control of claim 1, also comprise the steps: when the growing crystal starting material be when being selected from two or three element of Fe, Tb, Si, Ti, Ni, Mn, Ga, adopt the alternating current of impulse form, recurrent interval was at 1～10 second, pulse width was at 1～20 second, or the galvanic current of 1～10 ampere of additional galvanic current, the defective that produces in can the control growing process and in the arrangement of crystalline lateral and longitudinal direction obtains monocrystalline at last.
3. by the described method of utilizing paltie effect to realize single crystal growing control of claim 1, it is characterized in that: the vacuum tightness in the growth furnace in the described step 1) is 1 * 10
-2～1 * 10
-9Handkerchief.
4. by the described method of utilizing paltie effect to realize single crystal growing control of claim 1, it is characterized in that: the rare gas element in the described step 1) or the purity of nitrogen are 99.9～100%, and gaseous tension is 0.05～30 MPa in the burner hearth.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132620 CN1131342C (en) | 2000-11-17 | 2000-11-17 | Method for implementing monocrystal growth control by using paltie effect |
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|---|---|---|---|
| CN 00132620 CN1131342C (en) | 2000-11-17 | 2000-11-17 | Method for implementing monocrystal growth control by using paltie effect |
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| CN1131342C true CN1131342C (en) | 2003-12-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100559175C (en) * | 2007-08-09 | 2009-11-11 | 同济大学 | Peltier low temperature differential heat analyzer |
| CN102677170B (en) * | 2012-05-29 | 2015-09-02 | 江苏中电振华晶体技术有限公司 | A kind of method and system controlling sapphire growth size |
| CN113447785B (en) * | 2020-03-24 | 2022-05-27 | 中国科学院化学研究所 | Method for testing Peltier effect of organic semiconductor material |
| CN112410870B (en) * | 2020-11-20 | 2022-02-01 | 中电化合物半导体有限公司 | Growth control method and system for growing silicon carbide crystal based on liquid phase epitaxial method |
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