CN102272359A - Apparatus for manufacturing single crystal, method for manufacturing single crystal, and single crystal - Google Patents

Apparatus for manufacturing single crystal, method for manufacturing single crystal, and single crystal Download PDF

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Publication number
CN102272359A
CN102272359A CN2010800043168A CN201080004316A CN102272359A CN 102272359 A CN102272359 A CN 102272359A CN 2010800043168 A CN2010800043168 A CN 2010800043168A CN 201080004316 A CN201080004316 A CN 201080004316A CN 102272359 A CN102272359 A CN 102272359A
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monocrystalline
mentioned
base
manufacturing apparatus
crystal manufacturing
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CN102272359B (en
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藤井俊辅
川濑智博
羽木良明
桥尾克司
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/42—Gallium arsenide
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method

Abstract

Provided is an apparatus for manufacturing a single crystal, by which a single crystal having excellent qualities can be obtained with a relatively simple configuration. A method for manufacturing a single crystal, and a single crystal are also provided. In an apparatus (1) for manufacturing a single crystal, a raw material contained in a crucible (4) is melted with heat, and then a single crystal is manufactured by solidifying the material from one direction. The apparatus (1) is provided with an ampule (3), the crucible (4), a base (2) and a heater (5). The base (2) supports the ampule (3). The heater (5) is provided for the purpose of heating the ampule (3) and the crucible (4). The heat conductivity of the material configuring the base (2) is 0.5W/(mK) or more but not more than the value of the heat conductivity of the single crystal to be formed. As for the material configuring the base (2), the transmissivity of light at a wavelength of 1600 to 2400 nm is 10% or less when the material has a thickness of 4 mm.

Description

The manufacture method of single-crystal manufacturing apparatus, monocrystalline and monocrystalline
Technical field
The present invention relates to the manufacture method of a kind of single-crystal manufacturing apparatus and monocrystalline, particularly a kind of have the single-crystal manufacturing apparatus of the quartz ampoule that keeps material container and a manufacture method of monocrystalline.
Background technology
All the time, used vertical bridgman method (VB method), the single-crystal manufacturing apparatus of vertical gradient freeze technique vertical boat methods (vertical boat method) such as (VGF methods) and the manufacture method of monocrystalline to be in the public eye.In this single-crystal manufacturing apparatus, for making monocrystalline, at crucible bottom configuration seed crystal, and will put under the state of this crucible inside, and make these raw materials (leaning on last raw material) become the thermograde that fusing point forms vertical direction abovely than seed crystal as the polycrystalline of raw material.And, by crucible downward (side that temperature is low relatively) is extracted out or cooling gradually under the state that keeps thermograde, by the fused raw material, be that starting point is made monocrystalline (for example open flat 04-187585 communique (patent documentation 1) with reference to the spy and the spy opens 2005-298301 communique (patent documentation 2)) with the seed crystal.
And, in above-mentioned patent documentation 1, for improving the quality of the monocrystalline that obtains, when forming monocrystalline (solid phase) by fused raw material (liquid phase), for making solid-liquid interface side-prominent, proposed to make the scheme that is configured to laminar construction of the base (supporter) of support crucible to liquid phase one.Particularly, the lamellar parts that constitute by the high material of thermal conductivity, and the mutual laminated structural scheme of lamellar parts that constitutes by the low material of thermal conductivity have been proposed to make.And, for example be high purity carbon as the high examples of material of thermal conductivity, and for example be quartzy as the low examples of material of thermal conductivity.
And, in patent documentation 2, in order to prevent the breakage in crucible when carrying in the above-mentioned single-crystal manufacturing apparatus, and prevent to take place when monocrystalline from making bad, following formation is disclosed.That is, crucible keeps by keeper, and forming on this keeper can be by the handle part of hand or anchor clamps maintenance.And in single-crystal manufacturing apparatus, this keeper is equipped on the base (Stage) that can carry out lifting action.Keeper closely is contacted with the periphery of crucible, keeps this crucible.Material as crucible comprises boron nitride (BN), and comprises quartz, silicon carbide, silicon nitride, carbon, molybdenum etc. as the material of keeper.In addition, in patent documentation 2, not open for the material of base.
Patent documentation 1: the spy opens flat 04-187585 communique
Patent documentation 2: the spy opens the 2005-298301 communique
Summary of the invention
In above-mentioned existing single-crystal manufacturing apparatus, there is following problem.That is, because of base is above-mentioned laminar construction, so complex structure, the manufacturing cost of device uprises.And, made up thermal conductivity and materials having different thermal expansion coefficient, so base can produce distortion, breakage, the part that contacts with base produces discontinuous temperature distribution, the problem that crystalline quality reduces occurs.
And, for the raw material maintaining part that constitutes by crucible (or crucible and keeper (ampoule)), support the base of this raw material maintaining part, in above-mentioned existing single-crystal manufacturing apparatus, do not consider the thermal expansion that the thermal treatment when monocrystalline is made forms.Therefore, for example when keeper and base used the significantly different material of thermal expansivity, there was the situation that makes base or keeper breakage by the dimensional change difference of thermal expansion formation in the temperature variation in the thermal treatment when making because of monocrystalline.And the breakage of this constitution equipment also produces detrimentally affect to the monocrystalline quality that obtains.
The present invention occurs for solving above-mentioned problem, the object of the present invention is to provide a kind of single-crystal manufacturing apparatus of the monocrystalline that can obtain better quality by better simply structure and the manufacture method of monocrystalline.
And other purposes of the present invention are, the breakage of the single-crystal manufacturing apparatus that a kind of thermal treatment when preventing to make because of monocrystalline causes is provided and obtains the single-crystal manufacturing apparatus of monocrystalline of better quality and the manufacture method of monocrystalline.
In single-crystal manufacturing apparatus of the present invention, after the raw material heat fused that raw material is kept keeping in the container, for example as vertical bridgman method (VB method), vertical gradient freeze technique (VGF method), it is solidified from a direction, thereby produce monocrystalline, have: raw material keeps container, base, well heater.The base support raw material keeps container.Well heater is used for heating raw and keeps container.The thermal conductivity that constitutes the material of base is that 0.5W/ (mK) is above, below the value of the thermal conductivity of the monocrystalline that should form.For the material that constitutes base, wavelength is that 1600nm is above, the light below the 2400nm is below 10% for the transmittance of this material of thick 4mm.And for the material that constitutes base, preferably making above-mentioned transmittance is below 5%.
So, the material employing that constitutes base is the better simply formation of opaque material with respect to the light more than the wavelength 1600nm, below the 2400nm, thereby in raw material keeps container, making raw material is molten state, from a direction (particularly from base one side) when it is solidified, can suppress that infrared rays etc. causes, from raw material keep container by base outward Monday side thermoemitting.Consequently, the hot-fluid that is sent to base from the fused raw material can be directed to direction (below) towards base lower surface.The result can make fused raw material (liquid phase) and raw material solidify and become the boundary portion (solid-liquid interface) of part (solid phase) of monocrystalline for smooth shape or to the side-prominent shape of liquid phase one.For example, raw material keeps container to comprise: wide diameter portion begins width from base one side and becomes big gradually; Stretched portion is connected with this wide diameter portion, and the wide variety rate is less than this wide diameter portion (for example width is constant in fact), under this wide diameter portion and situation that base contacts, when solid-liquid interface was positioned at wide diameter portion, as mentioned above, can make this solid-liquid interface was smooth shape or to the side-prominent shape of liquid phase one.Consequently, in the monocrystalline that obtains, can suppress the bad generation of crystallization.
In addition, why make the following 0.5W/ of being limited to (mK) of value of the thermal conductivity of the material that constitutes base, be because the thermal conductivity of this material is when being lower than 0.5W/ (mK), raw material keeps the cooling efficiency of the raw material in the container to reduce, and is difficult to make solid-liquid interface to become smooth shape as mentioned above or to the side-prominent shape of liquid phase one.And, why make this thermal conductivity value on be limited to the value of the thermal conductivity of the monocrystalline that should form, be because when the thermal conductivity of the material that constitutes base during, still be difficult to make solid-liquid interface to become smooth shape as mentioned above or to the side-prominent shape of liquid phase one above the value of the thermal conductivity of this monocrystalline.And for the material that constitutes base, the light wavelength that why makes the regulation transmittance is more than the 1600nm, below the 2400nm, is because the light wavelength that produces by the well heater as thermal source when single crystal growing is equivalent to above-mentioned wavelength region.And why making this transmittance is below 10%, is because if transmittance is below 10%, the light of above-mentioned relatively wavelength then, and it is opaque that the material of base can be considered in fact, the effect of the present invention that can obtain conscientiously.And the preferable range that why makes above-mentioned transmittance is below 5%, is because if transmittance is below 5%, the light of above-mentioned relatively wavelength then, and the material of subject matter can be considered as opaque more effectively, can obtain effect of the present invention more effectively.
Be to use the manufacture method of the monocrystalline of above-mentioned single-crystal manufacturing apparatus based on the manufacture method of monocrystalline of the present invention, implemented following operation.That is, implement to keep container to insert the operation of the raw material of seed crystal and monocrystalline to raw material.And thereby enforcement keeps the operation of container fused raw material material by the heater heats raw material.Further, thus implement to make the fused raw material to solidify the operation of making monocrystalline gradually by seed crystal one side.
So, temporary transient fusing polycrystalline material piece (heating process (S30)), during the processing (crystalline growth operation (S40)) that is used to afterwards to solidify, can make from the fused raw material and be directed to direction (below) towards base lower surface to the hot-fluid of base transmission.Consequently, can make fused raw material (liquid phase), and raw material solidify and become the boundary portion (solid-liquid interface) of part (solid phase) of monocrystalline for smooth or to the side-prominent shape of liquid phase one.For example, raw material keeps container to comprise: wide diameter portion becomes big gradually from base one side width; And stretched portion, be connected with this wide diameter portion, the velocity of variation of width is less than this wide diameter portion (for example constant width) in fact, under this wide diameter portion and situation that base contacts, when solid-liquid interface is positioned at wide diameter portion, as mentioned above, can make this solid-liquid interface is smooth shape or to the side-prominent shape of liquid phase one.Consequently, in the monocrystalline that obtains, can suppress to produce crystal defect.
Based on monocrystalline of the present invention is the monocrystalline that is made of siliceous gallium arsenide, comprising: the monocrystalline wide diameter portion becomes big gradually from seed crystal one side width; And stretched portion, being connected with the monocrystalline wide diameter portion, the wide variety rate is less than the monocrystalline wide diameter portion.Border in monocrystalline wide diameter portion and stretched portion, with mean concns in vertical of the growth axis direction of monocrystalline, silicon be 1 * 10 17Cm -3More than, 7 * 10 17Cm -3Below, the mean value of dislocation desity is 0cm -2More than, 2000cm -2Below.
Therefore, in the border of monocrystalline wide diameter portion and stretched portion (shoulder), dislocation desity is controlled in the above-mentioned scope, can effectively suppresses the generation of the linearity aging (lineage) in the stretched portion.
And, be the raw material heat fused that will keep in the material container based on single-crystal manufacturing apparatus of the present invention after, it is solidified from a direction, thereby produces the single-crystal manufacturing apparatus of monocrystalline, have: material container; The quartz ampoule that keeps material container in inside; Support the base of quartz ampoule; The well heater that is used for the heating raw container.In base, constitute the material coefficient of thermal expansion coefficient at position contact with quartz ampoule at least, be the formation quartz ampoule quartz thermal expansivity ± 50% value that contains with interior scope.
So, when passing through the heater heats material container in order to make monocrystalline, thereby and, can fully reduce the poor of thermal expansion amount between quartz ampoule and the base by the raw material that becomes liquid phase because of heating being solidified obtain monocrystalline when reducing the temperature of this material container.Consequently, can suppress to produce the problem that makes quartz ampoule or base breakage because of differing from of this thermal expansion amount.
In addition, why make the material coefficient of thermal expansion coefficient that is formed in the position that contacts with quartz ampoule in the base be quartzy thermal expansivity ± 50% with interior (quartzy more than 0.5 times of thermal expansivity, below 1.5 times), be based on following reason.That is, when this material coefficient of thermal expansion coefficient broke away from above-mentioned scope, when heat-treating for forming monocrystalline, for the addendum modification that thermal expansion produces, it was bigger poor to produce between the corresponding position of quartz ampoule and base.Consequently, bigger stress puts on the contact part of quartz ampoule and base, and quartz ampoule (or base) has big probability to produce damage.In addition, the thermal expansivity of quartz that constitutes quartz ampoule is about 5 * 10 for example as described in " SHIN-ETSU HANTOTAI's quartz (strain) Ji Intraoperative ガ イ De chemico-physical properties PC-TG-CFC-004,2005,10,01 edition " -7(K -1), its ± 50% be equivalent to about 2.5 * 10 -7(K -1) above, about 7.5 * 10 -7(K -1) following scope.
Be to use the manufacture method of the monocrystalline of above-mentioned single-crystal manufacturing apparatus based on the manufacture method of monocrystalline of the present invention, had following operation.That is, at first implement to insert the operation of the raw material of seed crystal and monocrystalline to material container.And, by the heater heats material container, thus the operation of enforcement fused raw material material.Further, solidify gradually from seed crystal one side, thereby the operation of monocrystalline is made in enforcement by making the fused raw material.
So, temporary transient melt raw material, during the thermal treatment that is used to afterwards to solidify, the thermal expansivity between quartz ampoule and the base does not have bigger poor, therefore can suppress quartz ampoule, base produces damaged problem.Consequently, the monocrystalline quality that can suppress to cause because of quartz ampoule, base breakage descends, and can stablize to obtain high-quality monocrystalline.
According to the present invention, can obtain the monocrystalline of better quality by the single-crystal manufacturing apparatus of better simply structure.
And according to the present invention, can prevent the breakage that causes because of the thermal treatment in the single-crystal manufacturing apparatus, obtain the monocrystalline of better quality.
Description of drawings
Fig. 1 is the synoptic diagram of the embodiment 1 of expression single-crystal manufacturing apparatus of the present invention.
Fig. 2 is the schema that the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 1 has been used in expression.
Fig. 3 is the synoptic diagram that is used to illustrate the user mode of single-crystal manufacturing apparatus shown in Figure 1.
Fig. 4 is the enlarged diagram of the 1st variation of expression single-crystal manufacturing apparatus shown in Figure 1.
Fig. 5 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 1.
Fig. 6 is the enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 1.
Fig. 7 is the synoptic diagram of the embodiment 2 of expression single-crystal manufacturing apparatus of the present invention.
Fig. 8 is the enlarged diagram of the 1st variation of expression single-crystal manufacturing apparatus shown in Figure 7.
Fig. 9 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 7.
Figure 10 is the enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 7.
Figure 11 is the synoptic diagram that the monocrystalline of single-crystal manufacturing apparatus manufacturing of the present invention is used in expression.
Figure 12 is the synoptic diagram of the embodiment 4 of expression single-crystal manufacturing apparatus of the present invention.
Figure 13 is the schema that the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 12 has been used in expression.
Figure 14 is the synoptic diagram that is used to illustrate the user mode of single-crystal manufacturing apparatus shown in Figure 12.
Figure 15 is the enlarged diagram of the 1st variation of expression single-crystal manufacturing apparatus shown in Figure 12.
Figure 16 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 12.
Figure 17 is the part enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 12.
Figure 18 is the synoptic diagram of the embodiment 5 of expression single-crystal manufacturing apparatus of the present invention.
Reference numeral
1 single-crystal manufacturing apparatus
2,52 bases
3 ampoules
4 crucibles
5 well heaters
7 arrows
11 recesses
12 rakes
13 concaveconvex shape portions
14 surfaces
15 monocrystalline
16 melting materials
17 solid-liquid interfaces
19 anti-fixedly processing layers
20 releasing agents
21,31 minor diameter parts
22,32 wide diameter portions
23,33 stretched portions
25 matrixes
26 quartz members
40 monocrystalline
41 shoulders
42 main part central authorities
43 afterbodys
Embodiment
Following with reference to the description of drawings embodiments of the present invention.And,, do not repeat its explanation to the additional same reference marker of part identical or suitable in the following drawings yet.
(embodiment 1)
Fig. 1 is the synoptic diagram of the embodiment 1 of expression single-crystal manufacturing apparatus of the present invention.With reference to Fig. 1 single-crystal manufacturing apparatus of the present invention is described.
With reference to Fig. 1, single-crystal manufacturing apparatus 1 has: base 2; The ampoule 3 of lift-launch on base 2; Remain on the crucible 4 of the inside of ampoule 3; Be used to heat the well heater 5 of the raw material of the inside that is filled in crucible 4.Base 2 is that planeform for example is circular cylinder, upper face have the mortar shape rake 12, be positioned at the recess 11 of all sides (substantial middle of upper face) of this rake 12.The planeform of recess 11 for example is circular, the width of this recess 11 substantially constant on depth direction.Rake 12 begins from the upper end of recess 11 along with the outer circumferential side near base 2, becomes big apart from the distance of the diapire of base 2 and tilts to constitute (diapire of base 2 relatively).Material as base 2 for example can use quartz.And, as the material of base 2, preferably its thermal conductivity be that 0.5W/ (mK) is above, below the value of the thermal conductivity of the monocrystalline that should form.Wherein, object lesson as " monocrystalline that should form and thermal conductivity thereof " for example is: its thermal conductivity is about 50W/ (mK) when the material of the monocrystalline that should form is gallium arsenide (GaAs), and its thermal conductivity is about 70W/ (mK) when the material of the monocrystalline that should form is indium phosphide (InP).In addition, the value of these thermal conductivitys is the values under the room temperature.And the material that constitutes base 2 is preferred: wavelength is that 1600nm is above, the light below the 2400nm is below 10% with respect to the transmittance of this material of thick 4mm.And this transmittance is further preferred below 5%.Wherein, transmittance is meant, incides the above-mentioned light intensity of this material and the ratio ((light intensity that sees through)/(incident light intensity) * 100) of the light intensity of this material that sees through thick 4mm.
And, material as base 2 is preferred: be have as the thermal expansivity of the quartz that constitutes ampoule 3 ± 50% material with the thermal expansivity of interior scope, use be used to form have sufficient intensity under the thermal treatment temp of the monocrystalline material of (for example fusing point is than this thermal treatment temp height).For example, the material as base 2 preferably uses opaque quartz.
The ampoule 3 that carries on this base 2 is ampoules (quartz ampoule) of quartzy system, and its shape is roughly cylindric.The bottom surface of ampoule 3 is the shapes that can carry the upper face of above-mentioned base 2.Particularly, ampoule 3 has: minor diameter part 21, be housed in the inside of the recess 11 of base 2, and planeform is roughly circle; Wide diameter portion 22 is connected on the minor diameter part 21, has rake 12 angled side walls along base 2; And stretched portion 23, being connected on the wide diameter portion 22, planeform is identical with base 2 for example circular, the width substantially constant.In addition, it is big that the width of stretched portion 23 can become gradually along with leaving wide diameter portion 22, also can be at the velocity of variation that changes width midway of stretched portion 23.That is,, as mentioned above, not only comprise the substantially invariable situation of width, also exist width to a certain degree to change the situation of (outer peripheral sidewall of the relative base 2 of the sidewall of stretched portion 23 slightly tilts) for stretched portion 23.And in the stretched portion 23, the velocity of variation of the width in this stretched portion 23 gets final product less than the velocity of variation of the width in the wide diameter portion 22.In addition, at this, width is meant at the width perpendicular to the direction (horizontal direction) of the bearing of trend of ampoule 3.Minor diameter part 21 wide substantially constant on the optional position of depth direction.Minor diameter part 21 is the shapes along the inwall of the recess 11 of base 2.(sidewall of stretched portion 23 relatively) angle of inclination of sidewall in the wide diameter portion 22 of ampoule 3 is basic identical with (outer peripheral sidewall of relative base 2) angle of inclination of the rake 12 of base 2.
The crucible 4 that keeps in the inside of this ampoule 3 has substantially along the shape of the interior perimeter surface of ampoule 3.Particularly, the bottom center of crucible 4 is formed with the minor diameter part 31 of crucible 4 of the inside of the minor diameter part 21 that is contained in ampoule 3.The planeform of minor diameter part 31 for example is circular.Begin wide diameter portion 22 from the upper end of this minor diameter part 31, form the wide diameter portion 32 of crucible 4 along ampoule 3.And, form stretched portion 33 with the upper end of this wide diameter portion 32 with being connected.The stretched portion 33 of this crucible 4 is substantially along the inner peripheral surface configuration of the stretched portion 23 of ampoule 3.And the periphery ground that surrounds base 2, ampoule 3 and crucible 4 disposes well heater 5.
Then the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 1 has been used in explanation.Fig. 2 is the schema that the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 1 has been used in expression.As shown in Figure 2, in monocrystalline manufacture method of the present invention, at first implement seed crystal preparatory process (S10).Particularly, insert monocrystalline small pieces in the inside of the minor diameter part 31 of crucible shown in Figure 14 as seed crystal.
Then as shown in Figure 2, implement raw material preparation process (S20).Particularly, should be as the polycrystalline material piece of crystal raw material in the inside of crucible 4 with the specified amount input.As the component of above-mentioned monocrystalline small pieces and polycrystalline material piece, can use crystalline arbitrarily material, for example the gallium arsenide (GaAs) that contains silicon can be used as this component.
Then as shown in Figure 2, implement heating process (S30).Particularly, by switching on to well heater shown in Figure 15, the polycrystalline material piece of the inside of heating crucible 4 also is molten state.In addition, adjust the heating condition of well heater 5 in order to make the not fusion of monocrystalline small pieces of minor diameter part 31 inside that are configured in crucible 4 this moment.
Then as shown in Figure 2, implement crystalline growth operation (S40).Particularly, use not shown lifting device etc., for well heater 5, base 2, ampoule 3 and crucible 4 are moved to Fig. 1 downside (direction shown in the arrow 7 of Fig. 3), thereby the temperature that makes the fused polycrystal raw material descend gradually near the monocrystalline small pieces (seed crystal) of minor diameter part 31 inside that are configured in crucible 4.Consequently, heating and fused raw material solidify (crystallization) gradually near the beginning seed crystal.The part of solidifying like this becomes monocrystalline.And, begin to extract out from interior all sides of well heater 5 by making base 2, ampoule 3 and crucible 4 gradually to downside, make the fused raw material near the downside of crucible 4 (be seed crystal) crystallization gradually.Can make single crystal growing like this.In addition, but also firm banking 2, ampoule 3 and crucible 4 are moved upward well heater 5, or under the state of the position of having fixed crucible 4, well heater 5, when making its temperature distribution that becomes regulation, reduce the temperature of well heater 5.And,, then implement refrigerating work procedure (S50) if the fused raw material solidifies fully.In refrigerating work procedure (S50), reduce the temperature of well heater 5 etc., make the monocrystalline cool to room temperature of crucible 4 inside.
At this moment, for example use opaque quartz, thereby in above-mentioned crystalline growth operation (S40), can suppress from crucible 4 and ampoule 3 because thermoemittings such as infrared rays make heat be sent to the situation of outer circumferential side via base 2 as the material of base 2.Therefore, the hot-fluid that is sent to base 2 from the fused raw material can be directed to direction (below), further preferably be directed to direction towards the recess 11 of base 2 towards the lower surface of base 2.Its result in the wide diameter portion of crucible 4, can make the solid-liquid interface 17 of boundary portion of solidifying the monocrystalline 15 (solid phase) of growth as melting material 16 and raw material as shown in Figure 3, for smooth or to the side-prominent shape of melting material 16 1.The result can suppress the generation of crystal defect in the monocrystalline 15 that obtains.And Fig. 3 is the synoptic diagram that is used to illustrate the user mode of single-crystal manufacturing apparatus shown in Figure 1.
Fig. 4 is the enlarged diagram of the 1st variation of single-crystal manufacturing apparatus shown in Figure 1.The 1st variation of single-crystal manufacturing apparatus shown in Figure 11 is described with reference to Fig. 4.
With reference to Fig. 4, the 1st variation of single-crystal manufacturing apparatus of the present invention has the structure same with single-crystal manufacturing apparatus shown in Figure 11 substantially, but be with the difference of single-crystal manufacturing apparatus 1 shown in Figure 1, be formed with concaveconvex shape portion 13 on the surface of the rake 12 of base 2 as anti-immovable bed.So, can be suppressed at generation ampoule 3 and base 2 fixed problem in rake 12 when forming monocrystalline.In addition, the surfaceness in the concaveconvex shape portion 13 of rake 12 is more than 0.5, below 9.5 in Ra (with reference to JIS B0601-1994).And, be more than 1.5, below 7.0 among the preferred Ra of this surfaceness, be more than 2.5, below 4.5 among the further preferred Ra.Rake concavo-convex when Ra is too small, contact area increases, and the fixing of ampoule 3 and base 2 easily takes place.And when Ra was excessive, the number of the protuberance that contacts with ampoule 3 reduced, and is big to the contact pressure change of each protuberance, easily takes place fixing.That is, be 0.5～9.5 among the preferred Ra of this surfaceness, more preferably 1.5～7.0, further preferred 2.5～4.5.
Fig. 5 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 1.The 2nd variation of single-crystal manufacturing apparatus shown in Figure 11 is described with reference to Fig. 5.
With reference to Fig. 5, the 2nd variation of single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 11 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 1, forms anti-fixedly processing layer 19 on the rake 12 of base 2.Should anti-fixedly processing layer 19 be by with as the relatively low material formation of the reactivity of the quartz of the material that constitutes ampoule 3 when contact between the quartz (and compare) layer, for example can use SiC film, aluminum oxide film etc.And this anti-fixedly thickness of processing layer 19 is below the above 1mm of 10 μ m, below the above 500 μ m of preferred 50 μ m, further below the above 300 μ m of preferred 100 μ m.By adopting this formation, can obtain the effect identical with single-crystal manufacturing apparatus shown in Figure 4.
Fig. 6 is the enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 1.The 3rd variation of single-crystal manufacturing apparatus shown in Figure 11 is described with reference to Fig. 6.
With reference to Fig. 6, single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 11 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 1, disposes releasing agent 20 between the surface 14 of the rake 12 of base 2 and ampoule 3.By this formation, the same with single-crystal manufacturing apparatus shown in Figure 4, can prevent fixing between base 2 and the ampoule 3.And,, for example can use SiC powder, alumina powder etc. as releasing agent 20.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, below the above 15 μ m of preferred 0.3 μ m, further below the above 10 μ m of preferred 0.5 μ m.
(embodiment 2)
Fig. 7 is the synoptic diagram of the embodiment 2 of expression single-crystal manufacturing apparatus of the present invention.The embodiment 2 of single-crystal manufacturing apparatus of the present invention is described with reference to Fig. 7.
With reference to Fig. 7, single-crystal manufacturing apparatus 1 has and single-crystal manufacturing apparatus shown in Figure 11 identical construction substantially, but and the difference of the single-crystal manufacturing apparatus 1 of Fig. 1 be, on base 2, directly carry crucible 4 (promptly not having ampoule shown in Figure 1 3).Particularly, in single-crystal manufacturing apparatus shown in Figure 71, the minor diameter part 31 of crucible 4 is arranged in recess 11 internal configuration of base 2.And, dispose the wide diameter portion 32 of crucible 4 contiguously with the rake 12 of base 2.By this formation, also can obtain the effect identical with single-crystal manufacturing apparatus shown in Figure 11.
Fig. 8 is the enlarged diagram of the 1st variation of expression single-crystal manufacturing apparatus shown in Figure 7.The 1st variation of single-crystal manufacturing apparatus shown in Figure 71 is described with reference to Fig. 8.
With reference to Fig. 8, the 1st variation of single-crystal manufacturing apparatus of the present invention has the structure same with single-crystal manufacturing apparatus shown in Figure 71 substantially, but it is the same with single-crystal manufacturing apparatus 1 shown in Figure 4, be with the difference of single-crystal manufacturing apparatus 1 shown in Figure 7, form concaveconvex shape portion 13 on the surface of the rake 12 of base 2 as anti-immovable bed.So, when forming monocrystalline, can suppress to produce crucible 4 and base 2 fixed problem in rake 12.In addition, the surfaceness in the concaveconvex shape portion 13 of rake 12 is more than 0.5, below 9.5 in Ra (with reference to JIS BO601-1994).And, be more than 1.5, below 7.0 among the preferred Ra of this surfaceness, be more than 2.5, below 4.5 among the further preferred Ra.Rake concavo-convex when Ra is too small, contact area increases, and the fixing of crucible 4 and base 2 easily takes place.And when Ra was excessive, the number of the protuberance that contacts with crucible 4 reduced, and is big towards the contact pressure change of each protuberance, easily takes place fixing.That is, the preferred Ra of this surfaceness is 0.5～9.5, more preferably 1.5～7.0, further preferred 2.5～4.5.
Fig. 9 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 7.The 2nd variation of single-crystal manufacturing apparatus shown in Figure 71 is described with reference to Fig. 9.
With reference to Fig. 9, the 2nd variation of single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 71 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 1, is formed with anti-fixedly processing layer 19 on the rake 12 of base 2.Should anti-fixedly processing layer 19 be by with the reactivity of the material that constitutes crucible 4 material more relatively low than the material that constitutes base 2 constitute layer, for example when crucible 4 is quartz, can use SiC film, aluminum oxide film etc.And this anti-fixedly thickness of processing layer 19 is below the above 1mm of 10 μ m, below the above 500 μ m of preferred 50 μ m, further below the above 300 μ m of preferred 100 μ m.By adopting this formation, can obtain the effect identical with single-crystal manufacturing apparatus shown in Figure 8.
Figure 10 is the enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 7.The 3rd variation of single-crystal manufacturing apparatus shown in Figure 7 is described with reference to Figure 10.
With reference to Figure 10, single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 71 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 7, disposes releasing agent 20 between the surface 14 of the rake 12 of base 2 and crucible 4.By this formation, the same with single-crystal manufacturing apparatus shown in Figure 8, can prevent fixing between base 2 and the crucible 4.And,, for example can use SiC powder, alumina powder etc. as releasing agent 20.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, below the above 15 μ m of preferred 0.3 μ m, further below the above 10 μ m of preferred 0.5 μ m.
(embodiment 3)
Figure 11 is the synoptic diagram that the monocrystalline of single-crystal manufacturing apparatus manufacturing of the present invention is used in expression.Illustrate based on monocrystalline 40 of the present invention with reference to Figure 11.
With reference to Figure 11, the monocrystalline that the monocrystalline 40 that is made of the silication gallium is to use single-crystal manufacturing apparatus shown in Figure 1 to make has the identical profile of interior shape with the crucible 4 of the single-crystal manufacturing apparatus 1 of Fig. 1 basically.That is, be positioned at the lower end of the monocrystalline 40 of Figure 11, comprise as the seed crystal of the basic point of crystalline growth: the monocrystalline wide diameter portion, from this lower end, it is big that its diameter becomes gradually; And stretched portion (main part), being connected with this monocrystalline wide diameter portion, the velocity of variation of width (diameter) is less than the monocrystalline wide diameter portion.The boundary portion of monocrystalline wide diameter portion and stretched portion is called shoulder 41.And, with the central part of the length direction (crystalline growth direction) of stretched portion as main part central authorities 42, with the upper end of stretched portion as afterbody 43.On the border of monocrystalline wide diameter portion and stretched portion (shoulder 41), with mean concns in vertical of the growth axis direction of monocrystalline 40, silicon be 1 * 10 17Cm -3More than, 7 * 10 17Cm -3Below, the mean value of dislocation desity is 0cm -2More than, 2000cm -2Below.
Wherein, when using single-crystal manufacturing apparatus 1 of the present invention to form monocrystalline 40, when solid-liquid interface is positioned at wide diameter portion, as mentioned above, can make this solid-liquid interface form smooth or outstanding shape to liquid phase one side.Produce crystal defect in the monocrystalline 40 that the result can suppress to obtain.That is, the contriver finds, is controlled to be " smooth or outstanding shape " by the solid-liquid interface shape with wide diameter portion, can significantly reduce the dislocation desity in the border (shoulder 41) of monocrystalline wide diameter portion and stretched portion.Consequently, under lower silicon concentration, also can reduce the dislocation desity in the shoulder 41.Thereby find, can significantly reduce the frequency of problems such as linearity in the crystallization main part (promptly becoming the part of products such as wafer) is aging.In addition, linear wearing out is meant that the dislocation of high density focuses on partial problem, exists the part of this problem can not make product.
Wherein, the inventor at first finds: in silicon concentration is monocrystalline 40 below a certain amount of, having the linear aged problem that easily takes place, is certain density when following but make the dislocation of shoulder 41, has suppressed the linear aged generation as the stretched portion (crystallization main part) of the part of product.Further, in the bigger crystallization of the ratio (ratio of the length of stretched portion and diameter) of " diameter of the length of stretched portion/stretched portion ", particularly in the ratio of " diameter of the length of stretched portion/stretched portion " is crystallization more than 1.5, find that the present invention has significant effect.Further, be low to moderate 1 * 10 at silicon concentration 17Cm -3～7 * 10 17Cm -3Crystallization in, in the grinding step of wafer, can produce the hole (small depression) that dislocation causes, be certain density (2000cm in dislocation desity -2) when following, find that this hole obviously reduces.
Particularly, the silicon concentration in the shoulder 41 is 1 * 10 17Cm -3～7 * 10 17Cm -3The time (this silicon concentration decides corresponding to the product design of monocrystalline), dislocation desity is 2000cm -2Below, preferred 1500cm -2Below, further preferred 1000cm -2When following, the linear aged that can suppress stretched portion takes place, and obtains higher productivity.And, the ratio of " diameter of the length of stretched portion/stretched portion " is the 1.5 * good effect of acquisition when (diameters (mm) of 77 ÷ stretched portions) are above, when this than be 2.0 * when (diameters (mm) of 77 ÷ stretched portions) are above, can further obtain good effect, when this than being 2.5 * when (diameters (mm) of 77 ÷ stretched portions) are above, obtaining best effect.
In addition, when adding silicon in gallium arsenide (GaAs), the crystal defect that is called as dislocation (translocation position) reduces.The concentration of the silicon among the GaAs is high more, and it is few more to misplace, the dislocation desity step-down.On the other hand, according to the device category difference that should form, desired silicon concentration, dislocation desity are also different, therefore consider the silicon concentration of the monocrystalline 40 that these condition designs will be made.Silicon concentration in shoulder 41 is low to moderate 1 * 10 17Cm -3～7 * 10 17Cm -3The time, exist in the existing stretched portion easily to produce linear aged problem.The inventor at first finds, is below the certain value by the dislocation desity that makes shoulder 41, and the linear aged that can suppress in the stretched portion takes place.
In adding the monocrystalline 40 of silicon, from shoulder 41 towards afterbody 43, silicon concentration rises.Therefore, more near afterbody 43, be difficult to produce new dislocation more.That is dislocation desity 43 minimizings, from shoulder 41 to afterbody.Therefore, the contriver finds that the dislocation desity by control shoulder 41 can reduce the linear aged incidence in the stretched portion by leaps and bounds.In addition, the silicon concentration in shoulder 41 (mean concns of silicon) surpasses 7 * 10 17Cm -3The time, original just be difficult for forming linear aging, so what can obviously obtain effect of the present invention is that silicon concentration in the shoulder 41 is 7 * 10 17Cm -3When following.And, can think, in the monocrystalline that does not add silicon, in stretched portion, also easily misplace, therefore only control the dislocation desity of shoulder 41, be difficult to suppress linear aged and take place.Therefore, making the silicon concentration in the shoulder 41 is above-mentioned 1 * 10 17Cm -3More than 7 * 10 17Cm -3When following, effect of the present invention is obvious, and this silicon concentration is 1 * 10 17Cm -3More than 5.5 * 10 17Cm -3Effect of the present invention can be further obvious when following, and this silicon concentration is 1 * 10 17Cm -3More than 4.0 * 10 17Cm -3When following, effect of the present invention becomes more obvious.
And the inventor finds that silicon concentration is gone up 43 increases from shoulder 41 towards afterbody along with the mode of natural coagulation at crystallization length direction (bearing of trend of monocrystalline 40).Therefore, the ratio of monocrystalline length and diameter (promptly " ratio of stretched minister degree/stretched portion diameter " hour, silicon concentration increases in the longitudinal direction rapidly, has therefore suppressed the generation of dislocation.On the contrary, when the length of monocrystalline and diameter bigger, silicon concentration increases in the longitudinal direction gradually.Therefore in stretched portion, arrive the dislocation that produces till the shoulder 41 and assemble, it is aging easily to form linearity.Therefore, in the monocrystalline 40 of the ratio of this monocrystalline length and diameter big (ratio of the length of stretched portion and diameter is more than 1.5), the particular significant effect of " suppressing linear aged forms " of the present invention.
(embodiment 4)
Figure 12 is the synoptic diagram of the embodiment 4 of expression single-crystal manufacturing apparatus of the present invention.With reference to Figure 12 single-crystal manufacturing apparatus of the present invention is described.
With reference to Figure 12, single-crystal manufacturing apparatus 1 has: base 52; The ampoule 3 of lift-launch on base 52; Remain on the crucible 4 of the inside of ampoule 3; Be used to heat the well heater 5 of the raw material of the inside that is filled in crucible 4.Base 52 is that planeform for example is circular cylinder, upper face have the mortar shape rake 12, be positioned at the recess 11 of all sides (substantial middle of upper face) of this rake 12.The planeform of recess 11 for example is circular, the width of this recess 11 substantially constant on depth direction.The formation of rake 12 is, along with from the upper end of recess 11 towards the outer circumferential side of base 52, become big apart from the distance of the diapire of base 52 and tilt (diapire of base 52 relatively).The material of base 52 for example can use quartz.And, material as base 52, be have the quartz that constitutes ampoule 3 thermal expansivity ± 50% material with the thermal expansivity of interior scope, if, then can use material arbitrarily being used to form the material that has abundant intensity (for example fusing point is greater than this thermal treatment temp) under the thermal treatment temp of monocrystalline.For example, can use the mixture of quartz, quartz and aluminum oxide or porous silica etc. as the material of base 52.
The ampoule 3 that is equipped on this base 52 is ampoules (quartz ampoule) of quartzy system, and its shape is roughly cylindric.The bottom surface of ampoule 3 is the shapes that can carry the upper face of above-mentioned base 52.Particularly, ampoule 3 has: minor diameter part 21, be housed in the inside of the recess 11 of base 52, and planeform is roughly circle; Wide diameter portion 22 is connected on the minor diameter part 21, has rake 12 angled side walls along base 52; And stretched portion 23, being connected on the wide diameter portion 22, planeform is identical with base 52 for example circular, the velocity of variation of width (diameter) is littler than wide diameter portion 22.The width of minor diameter part 21 is substantially constant on the optional position of depth direction.Minor diameter part 21 is the shapes along the inwall of the recess 11 of base 52.(sidewall of stretched portion 23 relatively) angle of inclination of sidewall in the wide diameter portion 22 of ampoule 3 is basic identical with (outer peripheral sidewall of relative base 52) angle of inclination of the rake 12 of base 52.
The crucible 4 that remains in the inside of this ampoule 3 has substantially along the shape of the interior perimeter surface of ampoule 3.Particularly, the bottom center of crucible 4 forms the minor diameter part 31 of crucible 4 of the inside of the minor diameter part 21 be contained in ampoule 3.The planeform of minor diameter part 31 for example is circular.Begin wide diameter portion 22 from the upper end of this minor diameter part 31, form the wide diameter portion 32 of crucible 4 along ampoule 3.And, form stretched portion 33 with the upper end of this wide diameter portion 32 with being connected.The stretched portion 33 of this crucible 4 is substantially along the inner peripheral surface configuration of the stretched portion 23 of ampoule 3.And the periphery ground that surrounds base 52, ampoule 3 and crucible 4 disposes well heater 5.
Then the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 12 has been used in explanation.Figure 13 is the schema that the monocrystalline manufacture method of single-crystal manufacturing apparatus shown in Figure 12 has been used in expression.As shown in figure 13, in monocrystalline manufacture method of the present invention, at first implement monocrystalline preparatory process (S10).Particularly, insert monocrystalline small pieces in the inside of the minor diameter part 31 of crucible shown in Figure 12 4 as seed crystal.
Then as shown in figure 13, implement raw material preparation process (S20).Particularly, should be as the polycrystalline material piece of crystal raw material in the inside of crucible 4 with the specified amount input.As the component of above-mentioned monocrystalline small pieces and polycrystalline material piece, can use crystalline arbitrarily material, for example the gallium arsenide (GaAs) that contains silicon can be used as this component.And, when being the high material of dissociation pressure as gallium arsenide, quartz ampoule can be sealed in a vacuum.
Then as shown in figure 13, implement heating process (S30).Particularly, by switching on to well heater shown in Figure 12 5, the polycrystalline material piece of the inside of heating crucible 4 also is molten state.In addition, adjust the heating condition of well heater 5 in order to make the not fusion of monocrystalline small pieces of minor diameter part 31 inside that are configured in crucible 4 this moment.
Then as shown in figure 13, implement crystalline growth operation (S40).Particularly, use not shown lifting device etc., for well heater 5, make base 52, ampoule 3 and crucible 4 side shifting under Figure 12, thereby the temperature that makes the fused polycrystal raw material descends gradually near the of monocrystalline small pieces (seed crystal) of minor diameter part 31 inside that are configured in crucible 4.Consequently, heating and fused raw material solidify (crystallization) gradually near the beginning seed crystal.The part of therefore, solidifying becomes monocrystalline.And,, make the fused raw material near the downside of crucible 4 (be seed crystal) crystallization gradually by gradually base 52, ampoule 3 and crucible 4 being begun to extract out to downside from interior all sides of well heater 5.Can make single crystal growing like this.If the fused raw material solidifies fully, then implement refrigerating work procedure (S50).In refrigerating work procedure (S50), reduce the temperature of well heater 5 etc., make the monocrystalline cool to room temperature of crucible 4 inside.
At this moment, for example use vitreous silica, thereby can make the ampoule 3 that constitutes by quartz and the difference of the thermal expansivity between the base 52 be reduced in fact insignificant degree as the material of base 52.Therefore, when making the temperature variation of base 52 and ampoule 3, can reduce the value that differs from the thermal stresses that is applied to ampoule 3 because of the thermal expansivity of base 52 and ampoule 3 in order to make above-mentioned single crystal growing.Therefore, can prevent that temperature variation because of base 52 and ampoule 3 from causing the problem of ampoule 3 breakages.
And, passing through to use transparent transparent components such as quartz as the material of base 52, radiant heat is sent to the outer circumferential side of base 52 from crucible 4 via the rake 12 of base 52.Therefore as shown in figure 14, when the solid-liquid interface 17 of the monocrystalline 15 of growth and melting material 16 arrives the stretched portion 33 of crucibles 4, solid-liquid interface 17 is become to the side-prominent shape of melting material 16 1.The result is in the monocrystalline 15 that forms, and near the crystallization bad (linear aging) in bottom that can suppress stretched portion 33 produces.In addition, Figure 14 is the synoptic diagram that is used to illustrate the user mode of single-crystal manufacturing apparatus shown in Figure 12.
Wherein, transparent component is meant that the transmitance for the photometric units length (1cm) of wavelength 2000nm is the material more than 90%.In addition, transmittance is meant the above-mentioned light intensity that incides this transparent component and has seen through the ratio ((light intensity that sees through)/(incident light intensity) * 100) of the light intensity of transparent component.Therefore, the silica glasss such as GE124 that for example can use Momentive Performance Materials company to make as transparent component.
Figure 15 is the enlarged diagram of the 1st variation of expression single-crystal manufacturing apparatus shown in Figure 12.The 1st variation of single-crystal manufacturing apparatus shown in Figure 12 1 is described with reference to Figure 15.
With reference to Figure 15, the 1st variation of single-crystal manufacturing apparatus of the present invention has the structure same with single-crystal manufacturing apparatus shown in Figure 12 1 substantially, but be with the difference of single-crystal manufacturing apparatus 1 shown in Figure 12, form concaveconvex shape portion 13 on the surface of the rake 12 of base 52 as anti-immovable bed.So, can be suppressed at generation ampoule 3 and base 52 fixed problem in rake 12 when forming monocrystalline.In addition, the surfaceness in the concaveconvex shape portion 13 of rake 12 is more than 0.5, below 9.5 in Ra (with reference to JIS B0601-1994).And the preferred Ra of this surfaceness is more than 1.5, below 7.0, and further preferred Ra is more than 2.5, below 4.5.Rake concavo-convex when Ra is too small, contact area increases, and the fixing of ampoule 3 and base 52 easily takes place.And when Ra was excessive, the number of the protuberance that contacts with ampoule 3 reduced, and is big towards the contact pressure change of each protuberance, easily takes place fixing.That is, the preferred Ra of this surfaceness is 0.5～9.5, more preferably 1.5～7.0, further preferred 2.5～4.5.
Figure 16 is the enlarged diagram of the 2nd variation of expression single-crystal manufacturing apparatus shown in Figure 12.The 2nd variation of single-crystal manufacturing apparatus shown in Figure 12 1 is described with reference to Figure 16.
With reference to Figure 16, the 2nd variation of single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 12 1 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 12, forms anti-fixedly processing layer 19 on the rake 12 of base 52.Should anti-fixedly processing layer 19 be by with as the relatively low material formation of the reactivity of the quartz of the material that constitutes ampoule 3 when contact between the quartz (and compare) layer, for example can use SiC film, aluminum oxide film etc.And this anti-fixedly thickness of processing layer 19 is below the above 1mm of 10 μ m, below the above 500 μ m of preferred 50 μ m, further below the above 300 μ m of preferred 100 μ m.By adopting this formation, can obtain the effect identical with single-crystal manufacturing apparatus shown in Figure 15.
Figure 17 is the enlarged diagram of the 3rd variation of expression single-crystal manufacturing apparatus shown in Figure 12.The 3rd variation of single-crystal manufacturing apparatus shown in Figure 1 is described with reference to Figure 17.
With reference to Figure 17, single-crystal manufacturing apparatus has the structure same with single-crystal manufacturing apparatus shown in Figure 12 1 substantially, but is with the difference of single-crystal manufacturing apparatus 1 shown in Figure 12, disposes releasing agent 20 between the surface 14 of the rake 12 of base 52 and ampoule 3.By this formation, the same with single-crystal manufacturing apparatus shown in Figure 15, can prevent fixing between base 52 and the ampoule 3.And,, for example can use SiC powder, alumina powder etc. as releasing agent 20.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, below the above 15 μ m of preferred 0.3 μ m, further below the above 10 μ m of preferred 0.5 μ m.
(embodiment 5)
Figure 18 is the synoptic diagram of the embodiment 5 of expression single-crystal manufacturing apparatus of the present invention.The embodiment 5 of single-crystal manufacturing apparatus of the present invention is described with reference to Figure 18.
With reference to Figure 18, single-crystal manufacturing apparatus 1 has and single-crystal manufacturing apparatus shown in Figure 12 1 identical construction substantially, but and the difference of the single-crystal manufacturing apparatus 1 of Figure 12 be the structure of base 52.Particularly, in single-crystal manufacturing apparatus shown in Figure 180 1, base 52 is made of the quartz member 26 that matrix 25, lamination are configured on this matrix 25.Quartz member 26 comprises the rake 12 that directly contacts with the wide diameter portion of ampoule 3.And matrix 25 can use quartzy differing materials in addition.On the other hand, quartz member 26 is made of transparent quartz.The shape of the base 52 that matrix 25 shown in Figure 180 and quartz member 26 constitutes is identical with base 52 in the single-crystal manufacturing apparatus 1 shown in Figure 12 basically.
By this formation, can obtain the effect same with single-crystal manufacturing apparatus shown in Figure 12 1.Therefore further, base 52 is made of matrix 25 and quartz member 26, for characteristics such as the thermal conduction characteristic of adjusting base 52, intensity, for example can change the material of matrix 25 arbitrarily.
And the single-crystal manufacturing apparatus of the invention described above is applicable to the manufacturing of semiconductor monocrystal, is particularly useful for the manufacturing of arsenide gallium monocrystal and indium phosphide single crystal.
Below enumerate characteristic of the present invention structure, its record with above-mentioned embodiment has the part repetition.
Based on single-crystal manufacturing apparatus 1 of the present invention be, after raw material (polycrystalline material piece) heat fused that raw material is kept keeping in the container (ampoule 3 of Fig. 1 and the crucible 4 of crucible 4 or Fig. 7), it is solidified from a direction, thereby produce the single-crystal manufacturing apparatus 1 of monocrystalline, have: raw material keeps container (ampoule 3 of Fig. 1 and the crucible 4 of crucible 4 or Fig. 7); Base 2; Well heater 5.Base 2 supports the ampoule 3 of Fig. 1 or the crucible 4 of Fig. 7.Well heater is used to heat the ampoule 3 of Fig. 1 and the crucible 4 of crucible 4 or Fig. 7.The thermal conductivity that constitutes the material of base 2 is that 0.5W/ (mK) is above, below the value of the thermal conductivity of the monocrystalline that should form.Constitute in the material of base 2, wavelength is that 1600nm is above, the light below the 2400nm is below 10% with respect to the transmittance of the above-mentioned materials of thick 4mm.And for the material that constitutes base 2, preferred above-mentioned transmittance is below 5%.And, constitute below 1/2 of thermal conductivity of the monocrystalline that the thermal conductivity of the material of base 2 preferably should form, further the thermal conductivity of the monocrystalline that preferably should form below 1/4.
So, the material that constitutes base 2 adopts more than the relative wavelength 1600nm, the following light of 2400nm is the better simply formation of opaque material, thereby making the polycrystalline material piece in crucible 4 is molten state, make it when solidifying, the hot-fluid that is sent to base 2 from the fused raw material can be directed to direction (below) towards base 2 lower surfaces from a direction (particularly from base 2 one sides).The result can make the melting material 16 (liquid phase) of Fig. 3 and raw material solidify and become the solid-liquid interface 17 of boundary portion of monocrystalline 15 (solid phase) of Fig. 3 of the part of monocrystalline, for smooth shape or to the side-prominent shape of melting material 16 1.Therefore, when solid-liquid interface 17 be positioned at crucible 4 wide diameter portion 32 time, as mentioned above, can make this solid-liquid interface 17 for smooth shape or to the side-prominent shape of melting material 16 1.Consequently, in the monocrystalline 15 that obtains, can suppress the bad generation of crystallization.
In above-mentioned single-crystal manufacturing apparatus 1, in base 2, can form anti-immovable bed (concaveconvex shape portion 13, anti-fixedly processing layer 19, releasing agent 20) on surface with the ampoule 3 of Fig. 4～Fig. 6 or the part that contacts with the crucible 4 of Fig. 8～Figure 10.Wherein, to the raw material of accommodating in the crucible 4 during, become the ampoule 3 or Fig. 8～also heated state of crucible 4 shown in Figure 10 of the maintenance crucible 4 of Fig. 4～shown in Figure 6 in order to make monocrystalline by well heater 5 heating.And, ampoule 3 or crucible 4 in heating support the zone (part that the wide diameter portion 22 of the ampoule 3 of Fig. 4～Fig. 6 contacts with the rake 12 of base 2 of (contacting with base 2) by base 2, or the part that contacts of the rake 12 of wide diameter portion 32 in the crucible 4 of Fig. 8～Figure 10 and base 2) in, ((deadweight with reference to Fig. 8～Figure 10) becomes the state that ampoule 3 or crucible 4 are pushed by base with reference to Fig. 4～Fig. 6) or crucible 4 by ampoule 3 and crucible 4.Consequently, exist ampoule 3 or crucible 4 to be fixed in the situation of base 2.Therefore, when ampoule 3 or crucible 4 are fixed in base 2, (carry out heating process (S30) among Fig. 2 and crystalline growth operation (S40) and go forward side by side a step when being used for the processing (refrigerating work procedure (S50)) of cool to room temperature) when heat-treating for forming monocrystalline, poor because of the thermal expansion amount of ampoule 3 or crucible 4 and base 2, the part of said fixing produces stress.This stress is to cause ampoule 3, crucible 4 or base 2 damage reasons.
Therefore, as mentioned above, prevent that by forming anti-immovable bed (concaveconvex shape portion 13, anti-fixedly processing layer 19, releasing agent 20) ampoule 3 or crucible 4 are fixed in base 2, ampoule 3 and crucible 4 and base 2 independent expansion respectively then, so can suppress to be derived from the generation of the stress of said fixing.Consequently, can reduce the possibility of ampoule 3, crucible 4 or base 2 breakages.
In above-mentioned single-crystal manufacturing apparatus 1, raw material maintenance container such as Fig. 1, Fig. 3～shown in Figure 6, also can comprise: as the crucible 4 of the material container that keeps raw material; The ampoule 3 that keeps the quartz ampoule of this crucible 4 as inside.The material coefficient of thermal expansion coefficient that is formed in the position that contacts with ampoule 3 at least in the base 2 can be constitute ampoule 3 quartz thermal expansivity ± 50% value with interior scope.
So, in order to make monocrystalline when well heater 5 heating crucibles 4, thereby and by the raw material that becomes liquid phase because of heating being solidified obtain monocrystalline when reducing the temperature of this former crucible 4, can fully reduce the poor of thermal expansion amount between ampoule 4 and the base 2.Consequently, can suppress to produce the problem that makes ampoule 3 or base 2 breakages because of differing from of this thermal expansion amount.
In above-mentioned single-crystal manufacturing apparatus 1, raw material keeps container can comprise the ampoule 3 as quartz ampoule that is supported by base 2, and the material that is formed in the position that contacts with ampoule 3 at least in the base 2 also can be quartzy.And the material that preferably constitutes base 2 is quartzy.At this moment, base 2 is by constituting with ampoule 3 identical materials.Therefore, ampoule 3 is identical with the thermal expansivity of base 2, can suppress the damaging problem that the difference because of above-mentioned thermal expansion amount causes conscientiously.
In above-mentioned single-crystal manufacturing apparatus 1, as Fig. 4 or shown in Figure 8, anti-immovable bed can be a concaveconvex shape portion 13.This concaveconvex shape portion 13 for example can form by making above-mentioned surface (rake 12) roughening in the base 2.At this moment, in the above-mentioned surface of base 2, can reduce the area that directly contacts with ampoule 3 or crucible 4.Its result can reduce the possibility that ampoule 3 or crucible 4 are fixed in base 2.
And above-mentioned anti-immovable bed such as Fig. 5 or shown in Figure 9 can be with the reactive of the quartz that constitutes quartz ampoule or constitute the reactivity of the material of crucible 4, the anti-fixedly processing layer 19 that the material lower than the material of the main part that constitutes base 2 constitutes.Anti-fixedly processing layer 19 can be single layer, also can be the laminated laminar construction of a plurality of layers.And,, can use modification processing (for example handling for the crystallization of susceptor surface) is carried out and the modified layer of acquisition in base 2 surfaces as anti-fixedly processing layer 19.At this moment, also can reduce the possibility that ampoule 3 or crucible 4 are fixed in base 2.
Be to use the manufacture method of the monocrystalline of above-mentioned single-crystal manufacturing apparatus 1 based on the manufacture method of monocrystalline of the present invention, implemented following operation.That is, implement to keep container (crucible 4 of Fig. 1, Fig. 3～Figure 10) to insert the operation (the seed crystal preparatory process (S10) of Fig. 2 and raw material preparation process (S20)) of the raw material (polycrystalline material piece) of seed crystal and monocrystalline to raw material.And, implement to keep container (ampoule 3 of Fig. 1, Fig. 3～Figure 10 and crucible 4, or the crucible 4 of Fig. 7～Figure 10) by well heater 5 heating raws, thus the operation of fused raw material material (heating process (S30)).Further, implement fused raw material (polycrystalline material piece) thus make it solidify the operation (crystalline growth operation (S40)) of making monocrystalline gradually from seed crystal one side.
So, temporary transient fusing polycrystalline material piece (heating process (S30)), during the processing (crystalline growth operation (S40)) that is used to afterwards to solidify, can make from the fused raw material towards base 2 hot-fluid be directed to direction (below) towards base 2 lower surfaces.Consequently, as shown in Figure 3, can make melting material 16 (liquid phase), and raw material solidifies and the boundary portion (solid-liquid interface 17) of monocrystalline 15 (solid phase) of part that becomes monocrystalline for smooth or to the side-prominent shape of melting material 16 1.Therefore, when solid-liquid interface 17 is positioned at the wide diameter portion 32 of crucible 4, as mentioned above, can make this solid-liquid interface 17 for smooth shape or to the side-prominent shape of melting material 16 1.Consequently, in the monocrystalline 15 that obtains, can suppress to produce crystal defect.
In the manufacture method of above-mentioned monocrystalline, the monocrystalline of manufacturing can be made of the gallium arsenide that contains silicon (Si) (GaAs).Monocrystalline can comprise: the monocrystalline wide diameter portion becomes big gradually from seed crystal one side width; And stretched portion, being connected with the monocrystalline wide diameter portion, the wide variety rate is less than above-mentioned monocrystalline wide diameter portion (for example width is constant in fact).Also can be, in the border of monocrystalline wide diameter portion and stretched portion (in monocrystalline shown in Figure 3 15 wide diameter portion of enlarged-diameter, and be connected with this wide diameter portion and the diameter border of constant erection part in fact), and vertical of the growth axis direction of monocrystalline in, the mean concns of silicon is 1 * 10 17Cm -3More than, 7 * 10 17Cm -3Below.And the mean value of the dislocation desity on this border also can be 0cm -2More than, 2000cm -2Below.Therefore, when forming monocrystalline for above-mentioned siliceous GaAs, as being suitable for manufacture method of the present invention, the effect that then suppresses bad generation is more remarkable.
And, from different perspectives, are the monocrystalline 40 that constitute by the gallium arsenide that contains silicon based on monocrystalline 40 of the present invention, comprising: the monocrystalline wide diameter portion (than the shoulder 41 of Figure 11 by under part), begin width from seed crystal one side and become big gradually; And stretched portion (the substantially invariable main part of diameter among Figure 11), it is connected to the monocrystalline wide diameter portion, and the wide variety rate is less than the monocrystalline wide diameter portion.In the border of monocrystalline wide diameter portion and erection part (shoulder 41), with mean concns in vertical of the growth axis direction of monocrystalline 40, silicon be 1 * 10 17Cm -3More than, 7 * 10 17Cm -3Below, the mean value of dislocation desity is 0cm -2More than, 2000cm -2Below.
Therefore, by in shoulder 41, dislocation desity being controlled at above-mentioned scope, can effectively suppress to produce in the main part linear aging.And when being the mean concns of above-mentioned silicon, the grinding step of the wafer that cuts from this monocrystalline, exist to produce the hole (small depression) that dislocation causes, but as mentioned above, in the wafer of the monocrystalline of the dislocation desity from controlled shoulder 41 cutting, can suppress the generation in this hole.
And in above-mentioned monocrystalline 40, the ratio of the diameter of the length of stretched portion/stretched portion (length/diameter of stretched portion) is preferably more than 1.5.Therefore, in the bigger monocrystalline of the length of stretched portion and diameter, effect of the present invention is especially obvious.
And the diameter of the monocrystalline 40 of acquisition is big more, the depression of the solid-liquid interface in the difficult more inhibition wide diameter portion, so dislocation desity easily increases in the shoulder 41.And solid-liquid interface also easily caves in main part (stretched portion), and the bigger temperature head of the inner easily generation of crystallization, becomes obvious so linear aged forms.Monocrystalline of the present invention and manufacture method thereof shoulder diameter be 77mm when above effect obvious, diameter is 102mm when above, can obtain more positive effect, when diameter is 152mm when above, it is obvious that effect further becomes.
Based on single-crystal manufacturing apparatus 1 of the present invention be, after the raw material (polycrystalline material piece) that keeps in to material container (crucible 4) heats fusion, by making it solidify the single-crystal manufacturing apparatus 1 of making monocrystalline, have: as the crucible 4 of material container from a direction; The quartz ampoule (ampoule 3) that keeps crucible 4 in inside; Support the base 52 of ampoule 3; And the well heater 5 that is used for heating crucible 4.The material coefficient of thermal expansion coefficient that is formed in the position that contacts with ampoule 3 at least in the base 52 be included in the quartz that constitutes ampoule 3 thermal expansivity ± 50% value with interior scope.
So, when pass through well heater 5 heating crucibles 4 for making monocrystalline, thereby and in order to make the raw material that becomes liquid phase because of heating solidify the acquisition monocrystalline to reduce the temperature of this crucible 4, can fully reduce thermal expansion amount poor between ampoule 3 and the base 52.Consequently, can suppress to cause the problem of ampoule 3 or base 52 breakages because of the difference of this thermal expansion amount.
In above-mentioned single-crystal manufacturing apparatus 1,, in base 52, can form anti-immovable bed (concaveconvex shape portion 13, anti-fixedly processing layer 19, releasing agent 20) on the surface of the part that contacts with ampoule 3 as Figure 15～shown in Figure 17.Wherein, when passing through well heater 5 heating crucibles 4 for making monocrystalline, ampoule 3 also becomes heated state.And, to support in the zone (part that the wide diameter portion 22 of ampoule 3 contacts with the rake 12 of base 52) of (contacting) by base 52 at the ampoule 3 of heating with base 52, the deadweight because of by ampoule 3 becomes the state that ampoule 3 is pushed by base.Consequently, exist ampoule 3 to be fixed in the situation of base 52.When ampoule 3 is fixed in base 52 like this, when heat-treating (when carrying out heating process (S30), crystalline growth operation (S40) among Figure 13 and refrigerating work procedure (S50)) in order to form monocrystalline, poor because of the thermal expansion amount of ampoule 3 and base 52, the part of said fixing produces stress.This stress is to cause ampoule 3 or base 52 damage reasons.
Therefore, as mentioned above, prevent the fixing of 3 pairs of bases 52 of ampoule by forming anti-immovable bed (concaveconvex shape portion 13, anti-fixedly processing layer 19, releasing agent 20), ampoule 3 and base 52 independent expansion respectively then, so can suppress the generation of the stress that said fixing causes.Consequently, can reduce the possibility of ampoule 3 or base 52 breakages.
In above-mentioned single-crystal manufacturing apparatus 1, the material that constitutes base 52 also can be quartzy.And in above-mentioned single-crystal manufacturing apparatus 1, the material that is formed in the position that contacts with quartz ampoule at least in the base also can be quartzy.At this moment, base 52 is by constituting with ampoule 3 identical materials.Therefore, ampoule 3 is identical with the thermal expansivity of base 52, can suppress the damaging problem that the difference because of above-mentioned thermal expansion amount causes conscientiously.
In above-mentioned single-crystal manufacturing apparatus 1, as shown in figure 15, anti-immovable bed can be a concaveconvex shape portion 13.This concaveconvex shape portion 13 for example can form by making above-mentioned surface (rake 12) roughening in the base 52.At this moment, in the above-mentioned surface of base 52, can reduce the area that directly contacts with ampoule 3.Its result can reduce the possibility that ampoule 3 is fixed in base 52.
And above-mentioned anti-immovable bed can be the anti-fixedly processing layer 19 that constitutes with the lower material of the reactivity of the quartz that constitutes quartz ampoule as shown in figure 16.Anti-fixedly processing layer 19 can be single layer, also can be the laminated laminar construction of a plurality of layers.And,, can use modification processing (for example the crystallization of susceptor surface being handled) is carried out and the modified layer of acquisition in base 52 surfaces as anti-fixedly processing layer 19.At this moment, also can reduce the possibility that ampoule 3 is fixed in base 2.
In above-mentioned single-crystal manufacturing apparatus 1, base 52 can be made of transparent component.At this moment, compare when constituting by non-transparent parts, promoted via the heat radiation that transparent base 52 radiation of (from the direction of crucible 4 towards base 52) downwards causes from the crucible 4 and the ampoule 3 of heating with base 52.Therefore, near the bottom of stretched portion 33, as shown in figure 14, solid-liquid interface 17 as the interface of melting material 16 (liquid phase) and the monocrystalline 15 (solid phase) that solidifies is become to the side-prominent shape of liquid phase one.Therefore, side-prominent by making solid-liquid interface 17 to liquid phase one, can suppress the defective of the monocrystalline 15 that solid-liquid interface 17 produces when solid phase one is side-prominent.
Be to use the manufacture method of the monocrystalline of above-mentioned single-crystal manufacturing apparatus 1 based on the manufacture method of monocrystalline of the present invention, had following operation.That is, at first implement to insert the operation (the seed crystal preparatory process (S10) of Figure 13 and raw material preparation process (S20)) of the raw material (polycrystalline material piece) of seed crystal (monocrystalline 15) and monocrystalline to material container (crucible 4).And, implement by well heater 5 heating raw containers (crucible 4), thus the operation of fusion polycrystalline material piece (heating process (S30)).Further, enforcement makes fused raw material (polycrystalline material piece) thereby the operation (crystalline growth operation (S40)) of solidifying the manufacturing monocrystalline from seed crystal one side gradually.
So, temporary transient fusing polycrystalline material piece (heating process (S30)), the processing that makes it afterwards to solidify (crystalline growth operation (S40) and when carrying out the processing (refrigerating work procedure S50) of cool to room temperature, the ampoule 3 that constitutes because of quartz and the thermal expansivity of base 52 not have bigger poor, so can suppress the problem of ampoule 3, base 52 breakages.Consequently, the problem that monocrystalline quality that the breakage of ampoule 3, base 52 causes descends can be suppressed, high-quality monocrystalline can be stably obtained.
In the manufacture method of above-mentioned monocrystalline, monocrystalline also can be made of the gallium arsenide (GaAs) of the gallium arsenide that does not contain the silicon (Si) as additive or siliceous (Si).Monocrystalline comprises: the monocrystalline wide diameter portion begins width from seed crystal one side and becomes big gradually; And stretched portion, being connected with this monocrystalline wide diameter portion, the wide variety rate is less than above-mentioned monocrystalline wide diameter portion.The border of monocrystalline wide diameter portion and stretched portion (wide diameter portion of enlarged-diameter in the monocrystalline 15 shown in Figure 14, with this wide diameter portion on be connected and the border of the stretched portion of constant diameter) the concentration of silicon (Si) be 7 * 10 17Cm -3Below, preferred 5.5 * 10 17Cm -3Below, further preferred 4.0 * 10 17Cm -3Below.Therefore, when especially above-mentioned siliceous GaAs being formed monocrystalline, the effect that then suppresses the defective generation as suitable manufacture method of the present invention is especially obvious.In addition, do not contain gallium arsenide as the silicon of additive and be meant and deliberately do not add silicon, be included under the situation that contains silicon as unavoidable impurities, initiatively do not add the gallium arsenide of silicon as additive.
(embodiment 1)
For confirming effect of the present invention, as described below, the experiment of making the monocrystalline of GaAs under various conditions.
(experiment condition)
(a) crystalline growth of the gallium arsenide of 3 inch diameters
Use device of the present invention to carry out the gallium arsenide crystalline growth of 3 siliceous inch diameters.Use front end to have the crucible seed crystal resettlement section, thermolysis boron nitride (pBN) system.In this crucible, accommodate seed crystal, carried out preparation synthetic gallium arsenide (GaAs) raw material, as the boron oxide (B of sealing agent 20 3), as the silicon (Si) of doping agent, the ampoule of quartz system is carried out vacuum-sealing.And, with this quartz system ampoule mounting in the base of opaque quartz system.The test film of the thick 2mm of making and the identical material of the employed opaque quartz of base, measure by the thermal conductivity that laser pulse method carries out under the room temperature, the result obtains the value (to the result under the experiment condition of this explanation, with reference to the experiment 4 of following table 1) of 1.4W/ (mK).And, make the test film of thick 4mm, use spectrophotometer to carry out the mensuration of transmittance, results verification transmittance in the wavelength region may of wavelength 1600～2400nm is below 10%, does not see through the light of the wavelength region may of dominance under the growth temperature of gallium arsenide crystallization (1238 ℃ of fusing points) substantially.And, to fix for preventing quartz ampoule, the base rake is adjusted into Ra=3.5 by attrition process, further carries out 1200 ℃, 72 hours thermal treatment in atmosphere, makes the processing of surface crystallizationization.
And the well heater that disposes to encirclement quartz ampoule, crucible periphery ground is switched on and is heated, after making gallium arsenide raw material and boron nitride be molten state, use the lifting device that is provided with on the base, reduce base, quartz ampoule, crucible, be retracted to low temperature one side of well heater, to afterbody fused raw material is solidified from seed crystal to a direction, make siliceous arsenide gallium monocrystal growth.After crystalline growth finished, cool to room temperature took off quartz ampoule from base, and cut-out is opened, and took out crystallization.The crystallization diameter is 77mm at shoulder.
To the monocrystalline that obtains, measure the silicon concentration of shoulder.Silicon concentration is following to be obtained: in the crystallization shoulder, near the end of the central authorities of the wafer that vertically cuts with length direction, wafer and middle, make totally 3 chips that 10mm is square, carry out sims analysis, obtain 3 mean value.
And monocrystalline is measured the dislocation desity of shoulder.Dislocation desity is following to be obtained: the wafer that will obtain by the monocrystalline shoulder with KOH (potassium hydroxide) etching after, use the Nuo Mansiji microscope on radial direction, to measure the number of corrosion pit with the 5mm spacing, obtain the mean value of dislocation desity.
And measure the number of the body at random of shoulder for monocrystalline.Particularly, take wafer and grind use Superficial Foreign Body inspection units (Surfscan6220 that KLA-Tencor company makes), the number of the body at random of mensuration entire wafer face from shoulder.
And, by the operation same, also form the arsenide gallium monocrystal that shoulder diameter is 85mm with the monocrystalline of above-mentioned 3 inch diameters, carry out same mensuration.
(b) crystalline growth of the gallium arsenide of 4 inch diameters
By with the essentially identical method of crystalline growth of the gallium arsenide of above-mentioned 3 inch diameters, form the arsenide gallium monocrystal of 4 inch diameters, and same project made to use the same method measure.Wherein, the base rake carries out sandblasting after attrition process, be adjusted into Ra=7.0.And,, after the surface crystallization processing, be coated with the alumina powder that particle diameter is 10 μ m at last for the base rake.And after crystalline growth finished, cool to room temperature took off quartz ampoule from base, and cut-out is opened, and took out crystallization.The crystallization diameter is 102mm at shoulder.
And, by with the identical operation of above-mentioned 4 inch diameter monocrystalline, also form the arsenide gallium monocrystal of shoulder diameter 110mm, carry out same mensuration.
(c) crystalline growth of the gallium arsenide of 6 inch diameters
By with the essentially identical method of crystalline growth of the gallium arsenide of above-mentioned 3 inch diameters, form the arsenide gallium monocrystal of 6 inch diameters, and same project made to use the same method measure.Wherein, the base rake carries out sandblasting after attrition process, be adjusted into Ra=9.5.And,, after the surface crystallization processing, be coated with the SiC powder of particle diameter 20 μ m at last for the base rake.And after crystalline growth finished, cool to room temperature took off quartz ampoule from base, and cut-out is opened, and took out crystallization.The crystallization diameter is 152mm at shoulder.
And, by with the identical operation of above-mentioned 6 inch diameter monocrystalline, also form the arsenide gallium monocrystal of shoulder diameter 160mm, carry out same mensuration.
(result)
(a) the gallium arsenide crystallization of 3 inch diameters
Experimental result is shown in table 1, table 2.
Figure BPA00001403343300321
Figure BPA00001403343300331
Table 1 and table 2 have represented that base " thermal conductivity " and " transmittance ", " silicon concentration of shoulder " and " dislocation desity ", main part " have or not linear aging ", the relation of " ratio of the length of crystallization main part and diameter ".In addition, the length of the crystallization main part in table 1, the table 2 is meant, the length till from the shoulder 41 of monocrystalline shown in Figure 11 40 to afterbody 43.From table 1 and table 2 as can be known, in experiment 2 of the present invention～experiment 8, experiment 12, experiment 13 monocrystalline that obtained, produce linear agingly, and the body number at random of shoulder is also few.And the monocrystalline of shoulder diameter 85mm also has the effect identical with the present invention.
(b) the gallium arsenide crystallization of 4 inch diameters
Experimental result is shown in table 2, table 3.
Figure BPA00001403343300351
From table 2 and table 3 as can be known, by based in the monocrystalline that experiment 16 of the present invention～experiment 19 obtains, produce linear agingly, and the body number at random of shoulder is also few.And the monocrystalline of shoulder diameter 110mm also can obtain the effect the same with the present invention.In addition, for the experiment of dislocation desity in table with 0 expression, the mean value that is meant dislocation desity is less than 0.5cm -2The time.
(c) the gallium arsenide crystallization of 6 inch diameters
Experimental result is as shown in table 3.
As known from Table 3, by based in the monocrystalline that experiment 23 of the present invention～experiment 26 obtains, produce linear wearing out, and the body number at random of shoulder is also few.And the monocrystalline of shoulder diameter 160mm also can obtain the effect the same with the present invention.
(embodiment 2)
For confirming effect of the present invention, prepare to have the base of different thermal expansivity, use this base to carry out the manufacturing of monocrystalline, confirm its weather resistance.The material of the base that test is used, the investigation result of weather resistance are as shown in table 4.
Table 4
Figure BPA00001403343300361
The breakage generation number of thermal expansivity, quartz ampoule or the base of table 4 expression base.Base uses vitreous silica, or uses the mixture of quartzy and aluminum oxide greater than the material of quartz as thermal expansivity.The adjustment of the thermal expansivity of the mixture of quartz and aluminum oxide is undertaken by the ratio that contains of adjusting aluminum oxide.And,, use porous silica as the material of thermal expansivity less than quartz.The adjustment of the thermal expansivity of porous silica is undertaken by adjusting void content.As known from Table 4, to thermal expansivity be quartzy thermal expansivity ± 50% with interior base 2～4, do not have the base breakage.
In addition, to form concavo-convex and Ra on the base rake be the material below 9.5 0.5 or more, formed in the material of preventing fixing processing layer, the material that has disposed releasing agent etc., in the monocrystalline more than 100 is made, the problem of quartz ampoule, base breakage can not take place fully yet, and the circulation ratio of monocrystalline quality is extremely good.
This time disclosed embodiment only is example from every side, is not restrictive.Scope of the present invention does not depend on above-mentioned explanation, and shown in the claim scope, comprise with impartial implication of claim scope and scope in all changes.
The present invention is particularly useful for using vertical boat method (Longitudinal type ボ one ト method) make the situation of monocrystalline.

Claims (12)

1. a single-crystal manufacturing apparatus (1) after the raw material heat fused that raw material is kept keeping in the container (3,4), makes it solidify from a direction, thereby makes monocrystalline, and this single-crystal manufacturing apparatus is characterised in that to have:
Raw material keeps container (3,4);
Support the base (2) that above-mentioned raw materials keeps container (3,4);
Be used to heat the well heater (5) that above-mentioned raw materials keeps container (3,4),
The thermal conductivity that constitutes the material of above-mentioned base (2) is that 0.5W/ (mK) is above, below the value of the thermal conductivity of the monocrystalline that should form,
For the material that constitutes above-mentioned base (2), wavelength is that 1600nm is above, the light below the 2400nm is below 10% with respect to the transmittance of the above-mentioned materials of thick 4mm.
2. single-crystal manufacturing apparatus according to claim 1, wherein,
In above-mentioned base (2), be formed with anti-immovable bed (13,19,20) on the surface of the part that contacts with above-mentioned raw materials maintenance container (3,4).
3. single-crystal manufacturing apparatus according to claim 1 (1), wherein,
Above-mentioned raw materials keeps container (3,4) to comprise the quartz ampoule (3) that is supported by above-mentioned base (2),
The material that is formed in the position that contacts with above-mentioned quartz ampoule (3) at least in the above-mentioned base (2) is quartzy.
4. the manufacture method of a monocrystalline has been used the described single-crystal manufacturing apparatus of claim 1, and the manufacture method of this monocrystalline is characterised in that to have following operation:
Keep container (3,4) to insert the operation (S10, S20) of the raw material of seed crystal and monocrystalline to above-mentioned raw materials
Keep container (3,4) by above-mentioned well heater (5) heating above-mentioned raw materials, thus the operation (S30) of fusion above-mentioned raw materials material;
Fused above-mentioned raw materials material is solidified gradually from above-mentioned seed crystal side, thereby make the operation (S40) of monocrystalline.
5. a monocrystalline is made of siliceous gallium arsenide, it is characterized in that,
Comprise: become big monocrystalline wide diameter portion gradually from seed crystal side width; And be connected with above-mentioned monocrystalline wide diameter portion, the wide variety rate is less than the stretched portion of above-mentioned monocrystalline wide diameter portion,
Border in above-mentioned monocrystalline wide diameter portion and above-mentioned stretched portion, with vertical of the growth axis direction of above-mentioned monocrystalline in, the mean concns of above-mentioned silicon is 1 * 10 17Cm -3More than, 7 * 10 17Cm -3Below, the mean value of dislocation desity is 0cm -2More than, 2000cm -2Below.
6. monocrystalline according to claim 5, the length of above-mentioned stretched portion and the ratio of diameter are more than 1.5.
7. a single-crystal manufacturing apparatus (1) after the raw material heat fused that keeps in the material container (4), makes it solidify from a direction, thereby makes monocrystalline, and this single-crystal manufacturing apparatus is characterised in that to have:
Material container (4);
The quartz ampoule (3) that keeps the above-mentioned raw materials container in inside;
Support the base (52) of above-mentioned quartz ampoule;
Be used to heat the well heater (5) of above-mentioned raw materials container (4),
The material coefficient of thermal expansion coefficient that is formed in the position that contacts with above-mentioned quartz ampoule (3) at least in the above-mentioned base (52) be comprised in the quartz that constitutes above-mentioned quartz ampoule (3) thermal expansivity ± 50% value with interior scope.
8. single-crystal manufacturing apparatus according to claim 7 (1), wherein,
In above-mentioned base (52), be formed with anti-immovable bed (13,19,20) on the surface of the part that contacts with above-mentioned quartz ampoule (3).
9. single-crystal manufacturing apparatus according to claim 7, above-mentioned base (52) is made of transparent component.
10. single-crystal manufacturing apparatus according to claim 7 (1), the material that is formed in the position that contacts with above-mentioned quartz ampoule (3) at least in the above-mentioned base (52) are quartzy.
11. the manufacture method of a monocrystalline is used the described single-crystal manufacturing apparatus of claim 7 (1), the manufacture method of this monocrystalline is characterised in that to have following operation:
Insert the operation (S10, S20) of the raw material of seed crystal and monocrystalline to above-mentioned material container (4);
By above-mentioned well heater (5) heating above-mentioned raw materials container (4), thus the operation (S30) of fusion above-mentioned raw materials material;
Fused above-mentioned raw materials material is solidified gradually from above-mentioned seed crystal side, thereby make the operation (S40) of monocrystalline.
12. the manufacture method of monocrystalline according to claim 11, wherein,
Above-mentioned monocrystalline constitutes by not containing as the gallium arsenide of the silicon of additive or siliceous gallium arsenide,
Above-mentioned monocrystalline comprises: become big monocrystalline wide diameter portion gradually from above-mentioned seed crystal side width; And be connected with above-mentioned monocrystalline wide diameter portion, the wide variety rate is less than the stretched portion of above-mentioned monocrystalline wide diameter portion,
Above-mentioned silicon is 7 * 10 in the concentration of the boundary of above-mentioned monocrystalline wide diameter portion and above-mentioned stretched portion 17Cm -3Below.
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