CN1311356A - Method and equipment for producing single crystal of oxides - Google Patents
Method and equipment for producing single crystal of oxides Download PDFInfo
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- CN1311356A CN1311356A CN 01104783 CN01104783A CN1311356A CN 1311356 A CN1311356 A CN 1311356A CN 01104783 CN01104783 CN 01104783 CN 01104783 A CN01104783 A CN 01104783A CN 1311356 A CN1311356 A CN 1311356A
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Abstract
To manufacture a single crystal of high purity at a 1ow cost by preventing elution of impurity oxide from a crucible, while preventing a oxygen shortage defect of the crystal. An annulus gap between a pulling up shaft 21 of the growing vessel 17 and a tubular opening part 24 on a lid body 19 of the vessel 17 is set between a range of 1-3 mm. The annulus gap-communicates with the atmosphere and a furnace. By controlling a flow rate of inert gas supply, oxygen concentration in the furnace is kept in the range 0.1-1.2%. Thereby contamination of the crystal caused by the oxidized impurity can be prevented.
Description
The present invention relates to extract a kind of fused raw material in crucible oxide monocrystal manufacturing installation and the manufacture method of making monocrystalline.
Lithium tantalate (LiTaO
3) monocrystalline and Lithium niobium trioxide (LiNbO
3) material of the oxide monocrystal of monocrystalline etc. optical element, piezoelectric element and the surface elastic wave filter etc. normally used as the modulated laser line.The oxide monocrystal Heat stability is good of lithium tantalate and Lithium niobium trioxide etc., the fusing point height, reactivity is fast again.Therefore, adopt the precious metal crucible of platinum (Pt), platinum rhodium (PtRh), iridium (Ir) etc. usually, with the quartz crucible of substituted single crystal silicon manufacturing usefulness.
Oxide monocrystal ties up to and uses this precious metal crucible, at nitrogen (N
2) and argon rare gas element ring atmosphere such as (Ar) in make with vertical pulling method.As everyone knows, on one side thus vertical pulling method is in the fused raw material in a kind of axle immersion crucible that front end is speckled with seed crystal, rotates this and slowly promote the technology that makes the single crystal growing shaping.
Yet the rhodium that crucible is used and the fusing point of iridium are very high, are easy to oxidation in high temperature, and the oxide compound of rhodium or the oxide compound of iridium are melted in the liquation as the lithium tantalate of crystal raw material and Lithium niobium trioxide, might become the impurity in the crystallization.
For preventing the oxidation of precious metal crucible, must improve with respect to being the resistance to air loss of breeding groove (cultivation container) internal space of crystal pulling furnace from the space that crucible promotes growth, to prevent sneaking into of extraneous air by the crystal pulling axle.For improving the resistance to air loss of breeding groove, it is that the crystallization cultivation portion that will comprise crucible is placed in the container of stainless steel (SUS) system that a kind of method is arranged, guide on the outside breakthrough part at the crystal pulling axle and to be provided with around the heat-resisting bellows of crystal pulling axle or the cylinder of stainless steel, to guarantee resistance to air loss.Used method that Here it is when common silicon single crystal makes.In the occasion of silicon single crystal, the crystal pulling axle is sneaked in lifting process in the process of cooling of oxygen behind crystallization of fused raw material and is formed supersaturation, becomes the reason of lattice imperfection.This phenomenon is very bad, so, must guarantee high-air-tightness.
On the other hand, in the occasion of oxide monocrystal, melting material itself must have oxygen to a certain degree.Otherwise, be in extreme hypoxia in case be placed with the atmosphere of the breeding groove inside of crucible, then can in oxide crystallization, produce the anoxybiotic problem, therefore, must make on breeding groove interior oxidation concentration remains on to a certain degree.For this reason, allow the occasion that impurity is to a certain degree sneaked in oxide crystallization, it is so unimportant that resistance to air loss just seems, therefore, also having a kind of method is to adopt quartz system cylindrical shell at upper opening as breeding groove.In this occasion, around the crystal pulling axle anything is not set, it fully is exposed in the atmosphere.Since also do not need with heat-resisting bellows seal the crystal pulling axle around, so can fully reduce the cost of whole crystal pulling furnace (oxide monocrystal manufacturing installation).Current, adopt in the container of stainless steel (SUS) system, to flow into to contain the 1% oxygen (O that has an appointment
2) nitrogen (N
2) or the method for argon gas (Ar) become main flow.
Yet, though the manufacturing oxide monocrystal needs oxygen to a certain degree,, can accelerate the oxidation of precious metal crucible in case problem is the oxygen that breeding groove inside enters volume, fusion goes out impurity (metal oxide containing precious metals) in melting material.
Again, when using the stainless steel container made, not only can increase substantially cost, and can not adjust resistance to air loss,, also can produce the too high situation of resistance to air loss the particularly manufacturing of oxide monocrystal of manufacturing object thing.
For this reason, must the oxygen concn in the breeding groove be guaranteed within the optimum range that can prevent the crucible oxidation preventing the oxide crystallization anoxybiotic while.
In view of the above problems, the objective of the invention is to, provide a kind of and guarantee to make the required oxygen concn of good oxide monocrystal, and can be and prevent the crucible oxidation and oxide monocrystal manufacturing installation that oxygen concn is suppressed, easy and cheap and easy manufacture method thereof as far as possible.
As mentioned above, the objective of the invention is to, set the oxygen concn of best breeding groove inside.In oxide monocrystal of the present invention was made, so-called best oxygen concn was meant the scope more than 0.1%, below 1.2%, and this scope both can make not anoxic of oxide monocrystal, can make the precious metal nondiscoloration (oxidation) that constitutes crucible again.
For realizing this oxygen concn, oxide monocrystal manufacturing installation of the present invention comprises: place the also crucible of molten oxide crystal raw material, in crucible, extract crystalline crystal pulling axle the fused raw material, be placed with crucible and be provided with the breeding groove of inserting the peristome that leads to the crystal pulling axle, rare gas element is imported the ingress pipe of the inner usefulness of crystal pulling furnace and the flow director of regulating inert gas flow.It is characterized in that,
Breeding groove has the cylindrical shell of placing the refractory body around crucible and the crucible thereof and the lid that covers the cylindrical shell upper end, and the peristome that is used for inserting logical crystal pulling axle usefulness forms the gap of the wide 1mm～3mm that contacts with atmosphere in a tubular form around the crystal pulling axle.
Flow director is according to the size of tubular opening portion, and the flow of control rare gas element is in 0.1%～1.2% scope with the oxygen concn of guaranteeing crystal pulling furnace inside.
When using the manufacturing installation of this oxide monocrystal,, therefore, make the high purity monocrystalline easily owing to the oxygen concn in the crystal pulling furnace breeding groove can be set in the optimum range of oxide monocrystal manufacturing.
Tubular opening portion is 30mm～70mm along the axial length of crystal pulling, and it is related to the gap width that forms around the crystal pulling axle, requires to select its length according to the inner best oxygen concn of breeding groove.By tubular opening minister degree is set in this scope, can prevents that the crystal pulling axle from contacting with peristome, and can prevent that atmosphere from flowing into breeding groove inside from opening too much.
Tubular opening portion and lid are integrally formed, and lid cylindrical shell horizontal direction relatively slides.Specifically being the chimb that is provided with in the upper end of cylindrical shell around cylindrical shell, is level and smooth tabular surface above the chimb.At this lid is housed above the chimb, lid relies on deadweight to make breeding groove form roughly airtight state.
Perhaps, tubular opening portion and lid split are provided with, but the relative lid horizontal direction of tubular opening portion is slided.In this occasion, above the lid and the bottom surface of tubular opening portion all is level and smooth tabular surfaces of quartzy system, is easy to slide.Adopt this structure, even the crystal pulling axle contacts with the inwall of shape tube opening, because of piped opening itself can laterally slide, so but the absorbing contact impact reduces the influence to the monocrystalline in making.
Oxide monocrystal manufacture method of the present invention at first is with the oxide monocrystal raw materials melt in the crucible of the breeding groove inside that is configured in crystal pulling furnace.At this moment, for the oxygen concn that makes breeding groove inside reaches more than 0.1%, below 1.2%, rare gas element is imported in the breeding groove.Then, while rotate oxide monocrystal raw material after the crystal pulling axle extracts fusion, thus, cultivate oxide monocrystal at the front end of crystal pulling axle.
Should have the atmospheric gap of leading to that width 1mm is above, 3mm is following around the crystal pulling axle, be emitted in atmosphere by the slotting general peristome of the crystal pulling axle of setting according to above size by the rare gas element that will is gone in the breeding groove.
Rare gas element also can adopt and contain that melting concn is more than 0.1%, the nitrogen of 1.2% following oxygen.Use this mixed gas, just can be easily the oxygen concn of crystal pulling furnace inside be set in the scope more than 0.1%, below 1.2%.
Again, the importing of rare gas element is preferably according to the width of crystal pulling periaxial space, is controlled at flow and is in 2 liters/minute～10 liters/minute the scope.
In this manufacture method, owing to control the flow of rare gas element according to the axial gap length of crystal pulling, therefore, can be more correctly and promptly the oxygen concn of breeding groove inside is set in the optimum range.
Other effect of the present invention and feature give clearly by reference drawing and following detailed description.
The simple declaration of accompanying drawing
Fig. 1 is the oxide monocrystal manufacturing installation sectional view of the present invention's the 1st example.
Fig. 2 is the amplification view of configuration relation between device lid shown in Figure 1 and the crystal pulling axle.
Fig. 3 is the oxide monocrystal manufacturing installation sectional view of the present invention's the 2nd example.
Fig. 4 is the amplification view of configuration relation between device lid shown in Figure 3 and the crystal pulling axle.
Below, with reference to the good example of drawing explanation the present invention.
(the 1st example)
Fig. 1 is an oxide monocrystal manufacturing installation of the present invention (crystal pulling furnace) 10, and Fig. 2 is a manufacturing installation partial enlarged drawing shown in Figure 1.Device 10 comprises: place and the precious metal system crucible 11 of the fused raw material 27 of molten oxide monocrystalline, the fused raw material 27 in crucible 11 extract monocrystalline 28 crystal pulling axle 21, be placed with crucible 11 and the breeding groove (cultivation container) 17 of inserting the tubular opening 24 that leads to crystal pulling axle 21 and the ingress pipe 26 that rare gas element is imported breeding groove 17 inner usefulness arranged.In addition, preferably be equipped with the flow director (MFC) 29 of regulating inert gas flow.
As shown in Figure 2, the tubular opening 24 of breeding groove 17 is sized to the gap that has the institute's Fixed width degree that contacts with atmosphere around crystal pulling axle 21.In the 1st example, when using the crystal pulling axle of diameter 10mm, the internal diameter of tubular opening portion 24 is set at 13mm, so that crystal pulling axle both sides produce the 1.5mm gap.Tubular opening portion 24 is 50mm along the axial length measured of crystal pulling axle.
The crucible 11 of precious metal system is made of iridium (Ir).Configuration surrounds the lagging material 12 of refractory body crucible around crucible 11.On the top of crucible 11, the annular reflex plate 13 that configuration is made of precious metal and on the top of reflector 13, the post-heater 14 of the precious metal system of layout circle tubular or frustum-like shape etc.In the outside of lagging material 12, high frequency (RF) load coil 15 is set.
Crucible 11 is supported in above the lagging material seat 30 of trough of belt.Heat insulation foam materials in filling in the gap of crucible 11 and lagging material 12.
The tubular opening portion 24 slotting crystal pulling axles 21 that leading at lid 19.Crystal pulling axle 21 has the operating portion 21a that is connected with not shown hoisting appliance and the crystal pulling rod 21b that is made of aluminum oxide etc. that is connected with operating portion 21a bottom one.Front end at crystal pulling rod 21b is installed with seed crystal 23.
The bottom of the breeding groove 17 of oxide monocrystal manufacturing installation 10 is provided with and imports the ingress pipe (or pipeline) 26 that rare gas element is used in breeding groove.Flow director 29 is set on ingress pipe 26.Flow director 29 is according to the tubular opening portion 24 of lid 19 and the gap length between the crystal pulling axle 24, and control enters the inert gas flow in the breeding groove, so that the oxygen concn in the stove maintains in 0.1%～1.2% scope.Rare gas element can adopt nitrogen (N
2) or argon (Ar), helium (He) gas etc.The 1st example has used nitrogen.Enter the groove of gas through on lagging material seat 30, forming of breeding groove through gas introduction tube 26, by being filled in the foam materials in crucible 11 and lagging material 12 gaps, flow to breeding groove top again.
In addition,, extract gas in the stove out, detect meter monitoring oxygen concn by the oxygen of breeding groove outside by not shown take-off pipe in about 1/3 position above breeding groove 17.Being equipped with as the mass flow controller (MFC) of flow director 29 o'clock, by this measured value is fed back to the flow that MFC controls rare gas element, guarantee oxygen concn in the stove be in decide in the scope.
The part of breeding groove 17 except tubular opening portion 24 shown in Figure 1 preferably has sufficient resistance to air loss.If can only discharge rare gas element from the gap of crystal pulling axle 21 tubular opening portion 24 on every side, then the linear velocity of the discharge gas of gap portion can be accelerated, and extraneous air is difficult for invading, and, can prevent that the oxygen concn of breeding groove 17 inside from surpassing institute's definite value that is.If the other parts of breeding groove 17 have the gap of aperture or seam, then can spill rare gas element from this, the impetus from the discharge gas in gap between tubular opening portion 24 and the crystal pulling axle 21 is died down.The result makes extraneous air sneak into easily, exists the oxygen concn that makes in the stove and rises to the above possibility of institute's definite value.
If require the part beyond the gap between tubular opening portion 24 and the crystal pulling axle 21 all to seal fully, then can increase cost, therefore, reach that the gastight degree is just passable basically.Even this is because resistance to air loss is a little bit poorer slightly, by increasing inert gas flow to breeding groove 17 internal feeds, the internal pressure that is set at breeding groove 17 is higher than extraneous air presses, and also the oxygen concn of breeding groove inside can be maintained institute and decide in the scope, so in fact not have problems.
The axial length of the crystal pulling of tubular opening portion 24 must have the dimensions by tool.If in the breeding groove 17 is the room temperature degree, then the convection current of rare gas element is very little, so even shorten the length of tubular opening portion 24, sneaking into of extraneous air is also less.Yet, when extracting action, form the condition of high temperature more than 1000 ℃ in the breeding groove 17, can produce fierce gaseous exchange and turbulent flow.Certainly, near the air-flow that also produces fierceness of tubular opening portion 24, if shorten along the crystal pulling direction of principal axis length measured of tubular opening portion 24, then extraneous air directly enters in the breeding groove 17, can make oxygen concn rising in the stove.
For preventing that atmosphere from sneaking in the stove, the crystal pulling direction of principal axis length measured lengthening by with tubular opening portion 24 just can make the extraneous air of sneaking into be trapped in the tubulose gap, relies on the impetus from the interior discharge gas of breeding groove 17 that it is discharged to the outside.In the 1st example, the length setting of tubular opening portion 24 shown in Figure 2 is 50mm.
In the 1st example, the gap between tubular opening portion 24 and the crystal pulling axle 21 is set at 1.5mm, be 50mm with the length setting of tubular opening portion 24, at this moment, the flow of rare gas element in stove is preferably more than 2 liters/minute.This flux values is not fixed, but sets the size of tubular opening portion 24 earlier, adjusts flow thereafter in the abstraction process of reality, is in 0.1%～1.2% scope so that get the oxygen concn of furnace interior.
Again, as previously mentioned, the lid 19 that constitutes breeding groove 17 rely on deadweight be supported in slidably chimb 18a that cylindrical shell 18 upper ends form above, form airtight conditions roughly.Lid 19 and cylindrical shell 18 all are that quartz is made, and all have level and smooth interface.Lid 19 relative cylindrical shells 18 slidably in case crystal pulling axle 21 contacts with the inwall of tubular opening portion 24, also can absorb this impact.That is, the internal diameter of tubular opening portion 24 is set at and can makes rare gas element discharge not the form that is coupling and touches with crystal pulling from breeding groove inside to the outside.But consider to making crystalline growth when crystal pulling axle 21 promotes,,, can contact with the inwall of tubular opening portion 24 so lifting rod 21b is synchronous with rotation while promote because of crystal pulling rod 21b rotates.In this occasion,, absorbed by tubular opening portion by the caused impact of contact, to prevent applying enormous impact to the growth crystallization of crystal pulling rod 21b and front end thereof by making lid 19 relative cylindrical shells 18 slidably.Thus, can prevent from growing crystal to produce phenomenon such as fracture.
In manufacturing installation illustrated in figures 1 and 2, the size of tubular opening portion 24 (internal diameter and pipe range) be set in the fixed scope, by the flow of control rare gas element in breeding groove, can guarantee the oxygen concn of breeding groove inside, needn't use the SUS container made of high price.Its result can prevent from the oxygen lack of oxide monocrystal from can prevent the oxidation of precious metal crucible again.Compare with the occasion of using the SUS container made, oxide monocrystal manufacturing installation of the present invention not only can reduce cost significantly, and can produce and sneak into crucible composition high purity monocrystalline seldom.
Again, consider long-time use SUS container made after, because of high-temperature oxide is subjected to oxidation, also can cause in crystallization the root that imports iron contamination.To this, the 1st example has adopted the breeding groove 17 that is made of quartz system cylindrical shell 18 and quartzy system lid 19, just can not produce the problem that iron contamination is sneaked into, and helps the manufacturing of high purity monocrystalline.In addition, the material of cylindrical shell 18 and lid 19 is not limited to quartz, also can adopt other material with thermotolerance and resistance to sudden heating.
Below, the oxide monocrystal manufacture method that manufacturing installation illustrated in figures 1 and 2 is used is described.Oxide monocrystal is to make lithium tantalate (LiTaO
3) describe for example.
(a) at first, raw material is added in the crucible 11,, set the internal diameter at tubular opening portion 24 places of lid 19 according to producing the requirement that width is about the 1.5mm annular gap between crystal pulling axle 21 and the tubular opening portion 24.For example, when setting this gap, be ready to have the multiple lid 19 of the tubular opening portion of different inner diameters in advance, select to produce the lid in the gap of suitable width according to material therefor and crystal pulling shaft diameter, according to different occasions, in 20～60 times of scopes of the gap width of setting, select the length of tubular opening portion again.
(b) after the gap of setting between tubular opening portion 24 and the crystal pulling axle 21, carry out induction heating one by one with 15 pairs of crucibles 11 of RF load coil.Become liquation 27 by the heating and melting raw material.At this moment, in breeding groove 17, supply with nitrogen, nitrogen flow is controlled at the oxygen concn that can guarantee breeding groove inside is in 0.1%～1.2% scope by ingress pipe 26.For example, flow control can feed back to the method for mass flow controller (MFC) 29 for carrying out by detecting the output of counting, will detect meter from the outside excessively oxygen of the gas stream of extraction in the breeding groove 17.The supply of rare gas element and flow control are being proceeded thereafter.In addition, also can be without nitrogen, contain 0.1%～1.0% nitrogen that mixes oxygen and use instead.
(c) then, adjust, the surface temperature of liquation 27 is adjusted to the temperature of suitable crystalline growth to the RF of RF load coil 15 electric power.In the occasion of lithium tantalate, the surface temperature of liquation 27 is heated to about 1650 ℃ or a little higher than this temperature.At this moment, the breeding groove internal temperature is about 1100 ℃～1300 ℃ at the upper space of breeding groove 17.After crystal pulling axle 21 is descended, make to be contained in front end seed crystal 23 and to contact with the surface of liquation 27.Under this state, adjust the RF electric power that to RF load coil 15 drops on one side, rotate crystal pulling axle 21 at leisure on one side, crystal pulling axle 21 is promoted.Along with the rotation of crystal pulling axle 21 is risen, that can cultivate into oxide compound in the bottom of seed crystal 23 breeds monocrystalline 28.Cultivate operation through this monocrystalline, continue in stove, to supply with the nitrogen that mixes oxygen, the gap between crystal pulling axle 21 and tubular opening portion 24 nitrogen of supplying with is discharged, be in 0.1%～1.2% scope with the oxygen concn of guaranteeing breeding groove inside.
(the 2nd example)
Fig. 3 and Fig. 4 represent the oxide monocrystal manufacturing installation of the present invention's the 2nd example.Be that with the 1st example difference in the 2nd example, lid 19 divides the 2nd member 19b with tubular opening portion 24 of body structure to be constituted by the 1st member 19a on the chimb 18a that is bearing in cylindrical shell 18 with the 1st member.Tubular opening portion 24 and the 2nd member 19b are integrally formed, and relative the 1st member 19a of the 2nd member 19b of lid 19 slidably.
In the abstraction process of oxide monocrystal, even crystal pulling axle 21 contacts with tubular opening portion 24, because of the 2nd member 19 of lid laterally slides, so can relax the impact of contact.The 2nd split type member 19b is small-sized, in light weight, also is easy to slide, and ballistic assimilation effect is big.
Even owing to when setting required width gap around the crystal pulling axle 21, also can from ready multiple the 2nd split type member 19b, select member, therefore, be easy to select and set tubular opening portion again with best internal diameter.
Other structure is identical with the 1st example, at identical structure place mark prosign.
The following describes specific embodiment.
(embodiment 1)
Crucible 11 adopts the iridium goods of diameter 180mm, height 150mm.In this crucible 11, put into Li
2CO
3, Ta
2O
5The raw materials for sintering 7-10kg that burns till after the powder weighing so that ratio of components Li/Ta=0.943 (wasting that ratio) carries out the RF induction heating with 15 pairs of crucibles of RF load coil 11, makes the raw materials for sintering fusion, obtains solution 27.Thereafter, add raw material in crucible 11, make gross weight reach 15kg, make its fusion with load coil 15 again, making gross weight in crucible 11 is the solution 27 of 15kg.
So long as at breeding groove between heating period, promptly should in breeding groove 17, supply with nitrogen by ingress pipe 26 with 4 liters/minute flow constantly from extracting the bottom of pipeline 17.In addition, the crystal pulling rod 21b of crystal pulling axle 21 adopts the aluminum products of diameter 10mm.In the integrally formed tubular opening of the central part of quartzy lid 19 portion 24, the internal diameter of tubular opening portion 24 is 13mm, and length is 50mm.
Behind the liquation 27 that makes gross weight 15kg, adjust RF output from RF load coil 15, make the surface temperature of liquation 27 be stabilized in suitable temp (about 1650 ℃).Under this state, crystal pulling axle 21 descends, and seed crystal 23 contact with the surface of liquation 27, on one side the RF that adjusts from RF load coil 15 export, crystal pulling axle 21 is rotated on one side makes its lifting.Make the LiTaO of straight trunk diameter 107mm, weight 6.5kg in the bottom of seed crystal 23
3 Breed monocrystalline 28 growth.
The method of the 2nd later crystalline growth is to put into crucible 11 with the previous raw material of breeding monocrystalline 28 identical weight, as the liquation of gross weight 15kg, to carry out same lifting with the crystal pulling axle and get final product.
(embodiment 2)
Below, use the crystal pulling axle of diameter 10mm, the length of tubular opening portion 24 is fixed as 50mm, and stabilize at the nitrogen flow that mixes oxygen under 4 liters/minute the state, the internal diameter of change tubular opening portion 24 in 11mm～18mm scope (that is, the gap between peristome 24 and the crystal pulling axle 21 is in 0.5mm～3mm scope).Extract the gas in the breeding groove 17 out, detect instrumentation with the outer oxygen of stove and decide oxygen concn.Its result sees table 1 for details.Because oxygen concn has subtle change in each operation of extracting, therefore, the measured value when being in a shoulder shape part with this oxygen concn does one relatively again.
Table 1
| The internal diameter of opening 24 [mm] | Breeding groove oxygen concn [%] | Crystal form | Other |
| ????11 | ????0.08 | The latter half of crystallization distortion of straight trunk | The Ir member does not have variable color, and |
| ????12 | ????0.26 | The afterbody crystallization is twisted slightly | The Ir member does not have variable color, and |
| ????13 | ????0.53 | Straight | The Ir member does not have variable color |
| ????14 | ????1.18 | Straight | The Ir member does not have variable color |
| ????16 | ????2.87 | Straight | The Ir member does not have variable color |
| ????18 | ????5.42 | Straight | Ir member blackening (oxidation) |
From the result of table 1, as can be seen, when the length of body 24 is 50mm,,, just can make to reach sufficient low oxygen concentration in the breeding groove 17 as long as around aluminum extraction unit 21b, guarantee 1mm～1.5mm with interior gap even inert gas flow is stable.On the other hand, in case the gap between crystal pulling axle 21 and the tubular opening portion 24 less than 0.5mm, then the oxygen concns in the breeding groove 17 are lower than 0.1%, breed the crystallization on latter half of of the straight trunk of monocrystalline 28 and obviously twist, and are difficult to whole extractions.And, too narrow because of the gap, be difficult to avoid crystal pulling rod 21b to contact with the inwall of tubular opening portion 24.Impact because of this contact can make crystal pulling rod 21b all be subjected to mechanicalness at every turn, impact also being passed to the growth crystallization.This mechanicalness impact can impel crystallization that the inconsistent phenomenon of fracture one of the main reasons takes place, and therefore must avoid.When using the tubular opening portion 24 of internal diameter 11mm, growing crystal can produce fracture in cooling.
Aspect the making of the crystal pulling rod 21b of oxidation aluminum, normally make it have a little bending.When extracting,, then be difficult to avoid contact because of rotation in case tubular opening portion 24 internal diameters are too little.
Internal diameter at the body shown in the table 1 24 is the 12nm occasion, promptly and crystal pulling axle 21 between the gap be the 1mm occasion, oxidation aluminum crystal pulling rod 21b and rotation are synchronously, can contact slightly with the inwall of body 24, but because of tubular opening portion slidably, impact so can absorb mechanicalness, can't see phenomenon of rupture.
In case the internal diameter of tubular opening portion 24 is excessive, the atm number that then enters in the breeding groove 17 increases, and the interior oxygen concn of stove is increased.In this occasion, the precious metal that constitutes crucible 11 turns black because of oxidation, and oxide compound fuses into and becomes impurity in the liquation.Therefore, as can be seen, the oxygen concn in the stove must be guaranteed in the scope that the precious metal that constitutes crucible 11 does not turn black.
From the experimental result of table 1, as the internal diameter of establishing tubular opening portion 24 is R, and the external diameter of crystal pulling rod 21b is Rj, then can be set at the relation of following size.
Rj+2mm≤R≤Rj+4mm????(1)
Internal diameter in tubular opening portion 24 is 14mm, promptly and the gap width between the crystal pulling rod 21b when being 2mm, can be described as variable color that can't see crucible 11, and the oxygen concn of breeding groove 17 inside rises to till 1.18%.Here it is because of the small temperature variation in the breeding groove is easy to cause a kind of state of crucible oxidation, needs to reduce oxygen concn.
(embodiment 3)
Even if the internal diameter in tubular opening portion 24 is the occasion of 16mm, also can increase the inert gas flow that imports in the breeding groove 17, the oxygen concn of breeding groove 17 inside is reduced to suitable scope.For this reason, the internal diameter of tubular opening portion 24 is fixed as 16mm, length is fixed as 50mm, the oxygen concn variation in the breeding groove 17 and the state of crystal form and crucible thereof are measured and observed to the flow of the rare gas element that change imports, and the result sees table 2 for details.
Table 2
| Inert gas flow [rise/minute] | Oxygen concn [%] in the breeding groove | Crystal form | Other |
| ????4 | ????2.87 | Straight | Ir member blackening (oxidation) |
| ????6 | ????1.52 | Straight | The blackening of Ir member |
| ????8 | ????0.83 | Straight | The Ir member does not have variable color |
| ????10 | ????0.41 | Crystallization bending slowly | The Ir member does not have variable color |
From its result as can be seen, even the gap between tubular opening portion 24 and the crystal pulling axle 21 is 3mm, also can be by suitable dominant discharge, to guarantee best oxygen concn.
But the internal diameter in tubular opening portion 24 is the 18mm occasion, and situation is just different.Certainly, increase nitrogen flow, just can reduce the oxygen concn in the breeding groove 17 more, can reach the best interior oxygen concn of stove.Yet, for reaching the required nitrogen flow of oxygen concn in the best stove more than 20 liters/minute.From experiment, occurred surpassing the new problem that 20 liters of/minute post crystallization bendings are cultivated when nitrogen flow.It is generally acknowledged that this is because the cause of the poor heat stability in the stove.
For this reason, in order to cultivate good crystallization, nitrogen flow must be suppressed at lesser extent, the diameter of tubular opening is the upper limit with 16mm as can be seen.
(embodiment 4)
In embodiment 4, the internal diameter of tubular opening portion 24 is fixed as 13mm, the flow of rare gas element is fixed as 4 liters/minute, the length of tubular opening portion 24 0mm～100mm scope in changed on one side test furnace in the optimizing of oxygen concn on one side.The result sees table 3 for details.In addition, because the oxygen degree of depth has subtle change in each stage, therefore make comparisons with the measured value of oxygen concn when forming shoulder shape part.
Table 3
| The length of opening 24 [mm] | Oxygen concn in the breeding groove | Crystal form | Other |
| ????0 | ????9.18 | Straight | Ir member blackening (oxidation) |
| ????20 | ????3.43 | Straight | Ir member blackening (oxidation) |
| ????30 | ????1.38 | Straight | The blackening slightly of Ir member |
| ????40 | ????0.97 | Straight | The Ir member does not have variable color |
| ????50 | ????0.53 | Straight | The Ir member does not have variable color |
| ????60 | ????0.45 | Straight | The Ir member does not have variable color |
| ????70 | ????0.38 | Straight | The Ir member does not have variable color |
| ????100 | ????0.17 | The crystallization distortion of afterbody | The Ir member does not have variable color |
From the result of table 3, as can be seen, be 13mm at the internal diameter of body 24, promptly and the gap between the crystal pulling axle be the 1.5mm occasion, if the length of body 24 surpasses 30mm, the effect that will occur low oxygen concentration in breeding groove 17 if surpass 50mm, then forms sufficient low oxygen concentration.The length of tubular opening portion 24 is long more, and the oxygen concn in the breeding groove 17 is just low more.Yet, in case tubular opening portion 24 is long, because of the crystal pulling rod 21b of oxidation aluminum contacts with the inwall of body 24 easily, so monocrystalline is extracted unfavorable.In embodiment 4, when the length of body 24 is 100mm, can confirm crystal pulling rod 21b and rotation synchronously, can slightly contact with the inwall of body 24, but the crystallization of extracting is provided with the appearance fracture.
From its result, the occasion with the length of tubular opening portion 24 is made as can be set at following size relationship.
30mm≤L≤70mm????(2)
(embodiment 5)
In embodiment 5, the internal diameter of tubular opening portion 24 is fixed as 13mm, length is fixed as 50mm, Yi Bian the flow of rare gas element is changed in 1 liter/minute～10 liters of/minute scopes, Yi Bian the optimizing of oxygen concn in the test furnace, the result sees table 4 for details.
Table 4
| Nitrogen flow [rise/minute] | Oxygen concn [%] in the breeding groove | Crystal form | Other |
| ????1 | ????4.72 | Straight | Ir member blackening (oxidation) |
| ????2 | ????1.23 | Straight | The Ir member does not have variable color |
| ????3 | ????0.75 | Straight | The Ir member does not have variable color |
| ????4 | ????0.53 | Straight | The Ir member does not have variable color |
| ????5 | ????0.26 | Straight | The Ir member does not have variable color |
| ????6 | ????0.14 | The crystallization bending of afterbody | The Ir member does not have variable color |
| ????8 | ????0.08 | Directly trunk is latter half of can not control diameter | The Ir member does not have variable color |
| ????10 | ????0.06 | Directly trunk is latter half of can not control diameter | The Ir member does not have variable color |
Though also can decide, from the result of table 4, as can be seen,, just can obtain sufficient low oxygen concentration as long as the flow of rare gas element is about 2 liters/minute by the shape (thickness and length) of tubular opening portion 24.
In addition, in each embodiment, used the crucible 11 of iridium system, but the crucible of also available platinum rhodium (PtPh) alloy system etc.In addition, the crystallization that is extracted is a lithium tantalate, but to as Lithium niobium trioxide (LiNbO
3) wait niobate, as (R
3Ga
5SiO
14) type compound etc. silicate, as (Lu
xYi
1-x) Al
5O
12Deng aluminate, LiB
4O
7Deng borate, have again even, for also being suitable for as sensu lato oxide monocrystals such as perovskite-type compounds.And, singly not oxide monocrystal, need in breeding groove, keep monocrystalline in the oxygen concn scope about 0.1%～1% to extract in the atmosphere to all and all have equal effect, can be fit to use.
The rare gas element of supplying with in breeding groove 17 has used nitrogen, but also rare gas element such as available argon also can be the mixed gas of 0.1%～1% oxygen scope of wherein mixing at this.
Above-mentioned example is the raw materials melt example with the RF induction heating mode, but also infrared rays (IR) lamp of available halogen lamp etc. heats and comes fused raw material.
Adopt the present invention, not only can prevent the anoxic of oxide monocrystal, and can reduce the oxide impurity of sneaking into from precious metal components such as crucibles, can be easily and make the high purity monocrystalline at low cost.
Claims (9)
1. an oxide monocrystal manufacturing installation is characterized in that, described device comprises:
Place the also crucible of molten oxide crystal raw material,
Extract crystalline crystal pulling axle the described raw material in being melted in described crucible,
Be placed with described crucible and have the breeding groove of inserting the peristome that leads to described crystal pulling axle,
Import the ingress pipe that rare gas element is used to described crystal pulling furnace inside, and
Regulate the flow director of described inert gas flow,
Described breeding groove has places described crucible and refractory body on every side cylindrical shell of using and the lid that covers described cylindrical shell upper end; The peristome of inserting logical described crystal pulling axle in a tubular form so that described lid forms the gap that contacts with atmosphere more than the width 1mm, below the 3mm around described crystal pulling axle.
2. oxide monocrystal manufacturing installation as claimed in claim 1 is characterized in that, described flow director is according to the described inert gas flow of the size control of described opening, with the oxygen concn of guaranteeing crystal pulling furnace inside be in more than 0.1%, in the 1.2% following scope.
3. oxide monocrystal manufacturing installation as claimed in claim 1 is characterized in that, the axial length of described crystal pulling of described tubular opening portion 11 is 30mm～70mm.
4. oxide monocrystal manufacturing installation as claimed in claim 1 is characterized in that, described tubular opening portion and described lid are integrally formed, but the described relatively cylindrical shell horizontal direction of described lid is slided.
5. oxide monocrystal manufacturing installation as claimed in claim 1 is characterized in that, described tubular opening portion and described lid are split type, but the described relatively lid horizontal direction of described tubular opening portion is slided.
6. an oxide monocrystal manufacture method is characterized in that, described method comprises the steps:
The operation of the oxide monocrystal raw materials melt in the crucible of breeding groove inside will be configured in;
For the oxygen concn that makes described breeding groove inside is controlled at more than 0.1%, below 1.2%, and in described breeding groove, import the operation of rare gas element, and
Rotate the crystal pulling axle on one side, promote on one side, make the operation that generates oxide monocrystal in the end of crystal pulling axle.
7. oxide monocrystal manufacture method as claimed in claim 6, it is characterized in that, make producing of described crystal pulling axle can lead to the gap that atmospheric width 1mm is above, 3mm is following on every side, described rare gas element is inserted general peristome by the crystal pulling axle that is set at above-mentioned size and is emitted in atmosphere.
8. as claim 6 or 7 described oxide monocrystal manufacture method, it is characterized in that the importing operation of described rare gas element is that melting concn is with containing, the nitrogen of 1.2% following oxygen imports more than 0.1%.
9. oxide monocrystal manufacture method as claimed in claim 7 is characterized in that, the importing operation of described rare gas element is in flow is 2 liters/minute～10 liters/minute scope, imports according to the width in described gap.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000047517 | 2000-02-24 | ||
| JP47517/00 | 2000-02-24 | ||
| JP47517/2000 | 2000-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1311356A true CN1311356A (en) | 2001-09-05 |
| CN1272475C CN1272475C (en) | 2006-08-30 |
Family
ID=18569757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01104783 Expired - Fee Related CN1272475C (en) | 2000-02-24 | 2001-02-23 | Method and equipment for producing single crystal of oxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1272475C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408529A (en) * | 2013-09-25 | 2016-03-16 | Lg矽得荣株式会社 | Crucible and ingot growing device comprising same |
| CN106352816A (en) * | 2016-10-30 | 2017-01-25 | 云南蓝晶科技有限公司 | Sapphire crystal bar crystal axis detection and positioning device |
| JP2017081779A (en) * | 2015-10-28 | 2017-05-18 | 住友金属鉱山株式会社 | Method of raising lithium tantalate single crystal |
| JP2017114725A (en) * | 2015-12-24 | 2017-06-29 | 住友金属鉱山株式会社 | Method for raising lithium tantalate single crystal |
| CN107304481A (en) * | 2016-04-21 | 2017-10-31 | 国立大学法人信州大学 | The manufacture device of gallium oxide crystal and the manufacture method of gallium oxide crystal |
| US10343573B2 (en) | 2014-12-19 | 2019-07-09 | Brose Fahrzeugteile Gmbh & Co. Kg, Coburg | Vehicle seat assembly having a reset device |
| CN112609237A (en) * | 2019-10-04 | 2021-04-06 | 信越化学工业株式会社 | Single crystal cultivation device |
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2001
- 2001-02-23 CN CN 01104783 patent/CN1272475C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105408529A (en) * | 2013-09-25 | 2016-03-16 | Lg矽得荣株式会社 | Crucible and ingot growing device comprising same |
| US10343573B2 (en) | 2014-12-19 | 2019-07-09 | Brose Fahrzeugteile Gmbh & Co. Kg, Coburg | Vehicle seat assembly having a reset device |
| JP2017081779A (en) * | 2015-10-28 | 2017-05-18 | 住友金属鉱山株式会社 | Method of raising lithium tantalate single crystal |
| JP2017114725A (en) * | 2015-12-24 | 2017-06-29 | 住友金属鉱山株式会社 | Method for raising lithium tantalate single crystal |
| CN107304481A (en) * | 2016-04-21 | 2017-10-31 | 国立大学法人信州大学 | The manufacture device of gallium oxide crystal and the manufacture method of gallium oxide crystal |
| CN107304481B (en) * | 2016-04-21 | 2021-11-05 | 国立大学法人信州大学 | Gallium oxide crystal manufacturing device and gallium oxide crystal manufacturing method |
| CN106352816A (en) * | 2016-10-30 | 2017-01-25 | 云南蓝晶科技有限公司 | Sapphire crystal bar crystal axis detection and positioning device |
| CN106352816B (en) * | 2016-10-30 | 2019-01-25 | 云南蓝晶科技有限公司 | Sapphire ingot crystallographic axis detects positioning device |
| CN112609237A (en) * | 2019-10-04 | 2021-04-06 | 信越化学工业株式会社 | Single crystal cultivation device |
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|---|---|
| CN1272475C (en) | 2006-08-30 |
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