CN102272359B - 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
CN102272359B
CN102272359B CN201080004316.8A CN201080004316A CN102272359B CN 102272359 B CN102272359 B CN 102272359B CN 201080004316 A CN201080004316 A CN 201080004316A CN 102272359 B CN102272359 B CN 102272359B
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base
monocrystalline
manufacturing apparatus
ampoule
crystal manufacturing
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CN102272359A (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 single-crystal manufacturing apparatus of quartz ampoule and manufacture method of monocrystalline with maintenance material container.
Background technology
All the time, used the single-crystal manufacturing apparatus of the vertical boat method (vertical boat method) such as vertical bridgman method (VB method), vertical gradient freeze technique (VGF method) and the manufacture method of monocrystalline to be in the public eye.In this single-crystal manufacturing apparatus, for manufacturing monocrystalline, at crucible bottom configuration seed crystal, and will put under the state of this crucible inside as the polycrystalline of raw material, making these raw materials (raw material more top than seed crystal) become fusing point to form above the thermograde of vertical direction.And, by by crucible downwards (side that temperature is relatively low) extract out or be cooling gradually under the state that keeps thermograde, by the raw material of melting, manufacture monocrystalline (for example, with reference to Unexamined Patent 04-187585 communique (patent documentation 1) and JP 2005-298301 communique (patent documentation 2)) take seed crystal as starting point.
And, in above-mentioned patent documentation 1, for improving the quality of the monocrystalline obtaining, in the time that the raw material by melting (liquid phase) forms monocrystalline (solid phase), for making solid-liquid interface side-prominent to liquid phase one, propose to make the scheme that is configured to laminar construction of the base (supporter) of support crucible.Particularly, proposed to make the structural scheme of the lamellar parts that formed by the high material of thermal conductivity and the mutual lamination of lamellar parts being formed by the low material of thermal conductivity.And, be for example high purity carbon as the example of the high material of thermal conductivity, and be for example quartz as the example of the low material of thermal conductivity.
And, in patent documentation 2, the breakage when preventing the carrying of crucible in above-mentioned single-crystal manufacturing apparatus, and it is bad to prevent that monocrystalline from occurring while manufacture, discloses following formation.That is, crucible keeps by keeper, forms the handle part that can keep by hand or fixture on this keeper.And in single-crystal manufacturing apparatus, this keeper is equipped on the base (Stage) that can carry out lifting action.Keeper close contact, in the periphery of crucible, keeps this crucible.Comprise boron nitride (BN) as the material of crucible, and comprise 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: Unexamined Patent 04-187585 communique
Patent documentation 2: JP 2005-298301 communique
Summary of the invention
In above-mentioned existing single-crystal manufacturing apparatus, there is following problem.That is, because base is above-mentioned laminar construction, therefore complex structure, the manufacturing cost of device uprises.And, combine the thermal conductivity material different with thermal expansivity, therefore base can produce distortion, breakage, and the part contacting with base produces discontinuous temperature distribution, occurs the problem that crystalline quality reduces.
And, for the raw material maintaining part being formed 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 thermal treatment when monocrystalline is manufactured forms.Therefore, for example use thermal expansivity significantly when different material at keeper and base, the temperature variation in the thermal treatment while manufacture because of monocrystalline, the poor situation that makes base or keeper breakage of dimensional change that existence forms by thermal expansion.And the breakage of this constitution equipment also produces detrimentally affect to the monocrystalline quality obtaining.
The present invention occurs for solving above-mentioned problem, the object of the present invention is to provide a kind of manufacture method of single-crystal manufacturing apparatus and monocrystalline of the monocrystalline that can obtain better quality by better simply structure.
And other objects of the present invention are, the breakage of the single-crystal manufacturing apparatus that a kind of thermal treatment while preventing from manufacturing because of monocrystalline causes are provided and obtain the single-crystal manufacturing apparatus of monocrystalline and the manufacture method of monocrystalline of better quality.
In single-crystal manufacturing apparatus of the present invention, after the heating raw materials fusing that raw material is kept keeping in 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.Base supports raw material and keeps container.Well heater keeps container for heating raw.The thermal conductivity of material that forms 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 forms base, wavelength is that 1600nm light above, below 2400nm is below 10% for the transmittance of this material of thick 4mm.And for the material that forms base, preferably making above-mentioned transmittance is below 5%.
So, the material that forms base adopts the better simply formation that light above with respect to wavelength 1600nm, below 2400nm is opaque material, thereby within raw material keeps container, making raw material is molten state, while it being solidified from a direction (particularly from base one side), 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 raw material of melting can be directed to the direction (below) towards base lower surface.Result can make the boundary portion (solid-liquid interface) of part (solid phase) that the raw material (liquid phase) of melting and raw material solidify and become 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, starts width from base one side and become gradually large; Stretched portion, be connected with this wide diameter portion, wide variety rate is less than this wide diameter portion (for example width is constant in fact), in the situation that this wide diameter portion contacts with base, 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 obtaining, can suppress the bad generation of crystallization.
In addition, why make the thermal conductivity of the material that forms base value under be limited to 0.5W/ (mK), because the thermal conductivity of this material during lower than 0.5W/ (mK), raw material keeps the cooling efficiency of the raw material in container to reduce, and is difficult to make solid-liquid interface to become as mentioned above smooth shape 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 in the time that the thermal conductivity of material of formation base exceedes the value of thermal conductivity of this monocrystalline, be still difficult to make solid-liquid interface to become as mentioned above smooth shape or to the side-prominent shape of liquid phase one.And for the material that forms base, the light wavelength that why makes regulation transmittance is more than 1600nm, below 2400nm, be because the light wavelength producing by the well heater as thermal source in the time of single crystal growing is equivalent to above-mentioned wavelength region.And why making this transmittance is below 10%, be because if transmittance is below 10%, the light of relatively above-mentioned wavelength, it is opaque that the material of base can be considered in fact, the effect of the present invention that can conscientiously obtain.And the preferable range that why makes above-mentioned transmittance is below 5%, be because if transmittance is below 5%, the light of relatively above-mentioned wavelength, the material of subject matter can be considered as opaque more effectively, can obtain more effectively effect of the present invention.
Manufacture method based on monocrystalline of the present invention is the manufacture method that has used the monocrystalline of above-mentioned single-crystal manufacturing apparatus, implements following operation., implement to keep container to insert the operation of the raw material of seed crystal and monocrystalline to raw material.Thereby and implement by the operation of heater heats raw material maintenance container fused raw material material.Further, thus the raw material of implementing to make melting is solidified the operation of manufacturing monocrystalline gradually by seed crystal one side.
So, the material piece (heating process (S30)) of temporary transient fusing polycrystalline, while carrying out afterwards the processing (crystalline growth operation (S40)) for solidifying, can make to be directed to the direction (below) towards base lower surface from the raw material of melting to the hot-fluid of base transmission.Consequently, can make the boundary portion (solid-liquid interface) of part (solid phase) that the raw material (liquid phase) of melting and raw material solidify and become 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 large 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 in fact constant width), in the situation that this wide diameter portion contacts with base, in the time that 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 obtaining, can suppress to produce crystal defect.
Be the monocrystalline being formed by siliceous gallium arsenide based on monocrystalline of the present invention, comprise: monocrystalline wide diameter portion, becomes large gradually from seed crystal one side width; And stretched portion, being connected with monocrystalline wide diameter portion, wide variety rate is less than monocrystalline wide diameter portion.On the border of monocrystalline wide diameter portion and stretched portion, mean concns in the face vertical with the growth axis direction of monocrystalline, silicon is 1 × 10 17cm -3above, 7 × 10 17cm -3below, the mean value of dislocation desity is 0cm -22000cm above, -2below.
Therefore, in the border of monocrystalline wide diameter portion and stretched portion (shoulder), dislocation desity is controlled in above-mentioned scope, can effectively suppresses the generation of the linearity aging (lineage) in stretched portion.
And, be by after the heating raw materials fusing keeping in material container based on single-crystal manufacturing apparatus of the present invention, it is solidified from a direction, thereby produce the single-crystal manufacturing apparatus of monocrystalline, have: material container; Keep the quartz ampoule of material container in inside; Support the base of quartz ampoule; For the well heater of heating raw container.In base, form the thermal expansivity of the material at the position that at least contact with quartz ampoule, be formation quartz ampoule quartzy thermal expansivity ± 50% value containing with interior scope.
So, while passing through heater heats material container in order to manufacture monocrystalline, and by making because thereby the raw material that heating becomes liquid phase solidifies when obtaining monocrystalline and reducing the temperature of this material container, can fully reduce the poor of thermal expansion amount between quartz ampoule and base.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, the thermal expansivity that why makes the material that is formed in the position contacting with quartz ampoule in base is quartzy thermal expansivity ± 50% with interior (0.5 times of the thermal expansivity of quartz above, 1.5 times following), be based on following reason.That is, in the time that the thermal expansivity of this material departs from above-mentioned scope, for forming monocrystalline while heat-treating, the addendum modification producing for thermal expansion, it is larger poor between quartz ampoule and the corresponding position of base, to produce.Consequently, larger stress puts on the contact part of quartz ampoule and base, and quartz ampoule (or base) has greater probability to produce damage.In addition, the quartzy thermal expansivity that forms quartz ampoule 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 ", is about 5 × 10 -7(K -1), its ± 50% be equivalent to approximately 2.5 × 10 -7(K -1) above, approximately 7.5 × 10 -7(K -1) following scope.
Manufacture method based on monocrystalline of the present invention is the manufacture method that has used the monocrystalline of above-mentioned single-crystal manufacturing apparatus, has following operation., first implement to insert to material container the operation of the raw material of seed crystal and monocrystalline.And, by heater heats material container, thus the operation of enforcement fused raw material material.Further, solidify gradually from seed crystal one side by the raw material that makes melting, thereby the operation of monocrystalline is manufactured in enforcement.
So, temporary transient melt raw material, while carrying out the thermal treatment for solidifying afterwards, the thermal expansivity between quartz ampoule and base does not have larger 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 declines, and can stablize the monocrystalline that obtains high-quality.
According to the present invention, can obtain by the single-crystal manufacturing apparatus of better simply structure the monocrystalline of better quality.
And according to the present invention, can prevent the breakage that causes because of the thermal treatment in single-crystal manufacturing apparatus, obtain the monocrystalline of better quality.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that represents the embodiment 1 of single-crystal manufacturing apparatus of the present invention.
Fig. 2 is the schema that has represented to use the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Fig. 1.
Fig. 3 is the schematic diagram for the use state of the single-crystal manufacturing apparatus shown in explanatory view 1.
Fig. 4 is the enlarged diagram of the 1st variation of the single-crystal manufacturing apparatus shown in presentation graphs 1.
Fig. 5 is the enlarged diagram of the 2nd variation of the single-crystal manufacturing apparatus shown in presentation graphs 1.
Fig. 6 is the enlarged diagram of the 3rd variation of the single-crystal manufacturing apparatus shown in presentation graphs 1.
Fig. 7 is the schematic diagram that represents the embodiment 2 of single-crystal manufacturing apparatus of the present invention.
Fig. 8 is the enlarged diagram of the 1st variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.
Fig. 9 is the enlarged diagram of the 2nd variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.
Figure 10 is the enlarged diagram of the 3rd variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.
Figure 11 is the schematic diagram that represents the monocrystalline that uses single-crystal manufacturing apparatus manufacture of the present invention.
Figure 12 is the schematic diagram that represents the embodiment 4 of single-crystal manufacturing apparatus of the present invention.
Figure 13 is the schema that has represented to use the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Figure 12.
Figure 14 is the schematic diagram of the use state for the single-crystal manufacturing apparatus shown in Figure 12 is described.
Figure 15 is the enlarged diagram that represents the 1st variation of the single-crystal manufacturing apparatus shown in Figure 12.
Figure 16 is the enlarged diagram that represents the 2nd variation of the single-crystal manufacturing apparatus shown in Figure 12.
Figure 17 is the part enlarged diagram that represents the 3rd variation of the single-crystal manufacturing apparatus shown in Figure 12.
Figure 18 is the schematic diagram that represents the embodiment 5 of 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-fixing 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
Referring to accompanying drawing explanation embodiments of the present invention.And, to the additional same reference marker of part identical or suitable in the following drawings, do not repeat its explanation yet.
(embodiment 1)
Fig. 1 is the schematic diagram that represents the embodiment 1 of 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; Be mounted in the ampoule 3 on base 2; Remain on the crucible 4 of the inside of ampoule 3; Be used for the well heater 5 of the raw material that heats the inside that is filled in crucible 4.Base 2 is that planeform is for example circular cylinder, upper face have mortar shape rake 12, be positioned at the recess 11 of the inner circumferential side (substantial middle of upper face) of this rake 12.The planeform of recess 11 is for example circular, the width of this recess 11 substantially constant on depth direction.Rake 12 starts from the upper end of recess 11 along with near the outer circumferential side of base 2, becomes large tilt to form (diapire of base 2 relatively) apart from the distance of the diapire of base 2.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, as the object lesson of " monocrystalline that should form and thermal conductivity thereof " for example: in the time that the material of the monocrystalline that should form is gallium arsenide (GaAs), its thermal conductivity is about 50W/ (mK), and in the time that the material of the monocrystalline that should form is indium phosphide (InP), its thermal conductivity is about 70W/ (mK).In addition, the value of these thermal conductivitys is the values under room temperature.And the material that forms base 2 is preferred: wavelength is that 1600nm light above, below 2400nm is below 10% with respect to the transmittance of this material of thick 4mm.And this transmittance is further preferably below 5%.Wherein, transmittance refers to, the above-mentioned light intensity that incides this material and the ratio ((light intensity seeing through)/(light intensity of incident) × 100) of light intensity of this material that sees through thick 4mm.
And, material as base 2 is preferred: be have as form ampoule 3 quartzy thermal expansivity ± material of 50% thermal expansivity with interior scope, use the material for example, under the thermal treatment temp that is used to form monocrystalline with sufficient intensity (fusing point is higher than this thermal treatment temp).For example, preferably use opaque quartz as the material of base 2.
The ampoule 3 carrying on this base 2 is ampoules (quartz ampoule) of quartz 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 minor diameter part 21, has the sidewall tilting along the rake 12 of base 2; And stretched portion 23, being connected on wide diameter portion 22, planeform is for example circle identical with base 2, width substantially constant.In addition, it is large 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, for stretched portion 23, 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 sidewall of stretched portion 23 slightly tilts).And in stretched portion 23, the velocity of variation of the width in this stretched portion 23 is less than the velocity of variation of the width in wide diameter portion 22.In addition,, at this, width refers to the width in the direction of the bearing of trend perpendicular to ampoule 3 (horizontal direction).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 keeping 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 the crucible 4 of the inside of the minor diameter part 21 that is contained in ampoule 3.The planeform of minor diameter part 31 is for example circular.Start the wide diameter portion 22 along ampoule 3 from the upper end of this minor diameter part 31, form the wide diameter portion 32 of crucible 4.And, be connected and form stretched portion 33 with the upper end of this wide diameter portion 32.The inner peripheral surface configuration of the basic stretched portion 23 along ampoule 3 of stretched portion 33 of this crucible 4.And the periphery ground that surrounds base 2, ampoule 3 and crucible 4 configures well heater 5.
Then explanation has been used the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Fig. 1.Fig. 2 is the schema that has represented to use the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Fig. 1.As shown in Figure 2, in monocrystalline manufacture method of the present invention, first implement seed crystal preparatory process (S10).Particularly, insert the monocrystalline small pieces as seed crystal in the inside of the minor diameter part 31 of the crucible 4 shown in Fig. 1.
Then as shown in Figure 2, implement raw material preparation process (S20).Particularly, dropping into using specified amount in the inside of crucible 4 should be as the material piece of the polycrystalline of crystal raw material.As the component of the material piece of above-mentioned monocrystalline small pieces and polycrystalline, can use crystalline material arbitrarily, for example the gallium arsenide that contains silicon (GaAs) can be used as this component.
Then as shown in Figure 2, implement heating process (S30).Particularly, switch on by the well heater 5 to shown in Fig. 1, the material piece of the polycrystalline of the inside of heating crucible 4 is also molten state.In addition,, now in order to make the not melting of monocrystalline small pieces of minor diameter part 31 inside that are configured in crucible 4, adjust the heating condition of well heater 5.
Then as shown in Figure 2, implement crystalline growth operation (S40).Particularly, use not shown lifting device etc., for well heater 5, make base 2, ampoule 3 and crucible 4 mobile to Fig. 1 downside (direction shown in the arrow 7 of Fig. 3), thereby the temperature of the polycrystal raw material of melting is declined gradually near being configured in the monocrystalline small pieces (seed crystal) of minor diameter part 31 inside of crucible 4.Consequently, the raw material of heating melting is from starting to solidify gradually (crystallization) near seed crystal.The part of solidifying like this becomes monocrystalline.And, by making gradually base 2, ampoule 3 and crucible 4 start from the inner circumferential side of well heater 5 to extract out to downside, make the raw material of melting near the downside of crucible 4 (be seed crystal) crystallization gradually.Can make like this single crystal growing.In addition, also can firm banking 2, ampoule 3 and crucible 4, well heater 5 is moved upward, or under the state of position of having fixed crucible 4, well heater 5, when making temperature distribution that it becomes regulation, reduce the temperature of well heater 5.And, if the raw material of melting solidifies completely, 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.
Now, for example use opaque quartz as the material of base 2, thereby in above-mentioned crystalline growth operation (S40), can suppress from crucible 4 and ampoule 3 because the thermoemittings such as infrared rays make heat be sent to the situation of outer circumferential side via base 2.Therefore, the hot-fluid that is sent to base 2 can be directed to the direction (below) towards the lower surface of base 2 from the raw material of melting, further preferably be directed to the direction towards the recess 11 of base 2.Its result as shown in Figure 3, in the wide diameter portion of crucible 4, can make to solidify as melting material 16 and raw material the solid-liquid interface 17 of the boundary portion of the monocrystalline 15 (solid phase) of growth, for smooth or to the side-prominent shape of melting material 16 1.Result, in the monocrystalline 15 obtaining, can suppress the generation of crystal defect.And Fig. 3 is the schematic diagram for the use state of the single-crystal manufacturing apparatus shown in explanatory view 1.
Fig. 4 is the enlarged diagram of the 1st variation of the single-crystal manufacturing apparatus shown in Fig. 1.With reference to the 1st variation of the single-crystal manufacturing apparatus 1 shown in Fig. 4 explanatory view 1.
With reference to Fig. 4, the 1st variation of single-crystal manufacturing apparatus of the present invention has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 1 substantially, but be with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 1, be formed with the concaveconvex shape portion 13 as anti-immovable bed on the surface of the rake 12 of base 2.So, can be suppressed to form ampoule 3 and base 2 fixing problem in rake 12 occurs when 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, in the preferred Ra of this surfaceness, be more than 1.5, below 7.0, in further preferred Ra, be more than 2.5, below 4.5.Rake concavo-convex in the time that Ra is too small, contact area increases, and the fixing of ampoule 3 and base 2 easily occurs.And in the time that Ra is excessive, the number of the protuberance contacting with ampoule 3 reduces, become large to the contact pressure of each protuberance, easily occur fixing.That is, in the preferred Ra of this surfaceness, be 0.5～9.5, more preferably 1.5～7.0, further preferably 2.5～4.5.
Fig. 5 is the enlarged diagram of the 2nd variation of the single-crystal manufacturing apparatus shown in presentation graphs 1.With reference to the 2nd variation of the single-crystal manufacturing apparatus 1 shown in Fig. 5 explanatory view 1.
With reference to Fig. 5, the 2nd variation of single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 1 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 1, forms anti-fixing processing layer 19 on the rake 12 of base 2.This anti-fixing processing layer 19 is the layers that are made up of the material relatively low with the quartzy reactivity while contacting between quartz (and compare) of material as forming ampoule 3, for example, can use SiC film, aluminum oxide film etc.And the thickness of this anti-fixing processing layer 19 is below the above 1mm of 10 μ m, preferably below the above 500 μ m of 50 μ m, further preferably below the above 300 μ m of 100 μ m.By adopting this formation, can obtain the effect identical with the single-crystal manufacturing apparatus shown in Fig. 4.
Fig. 6 is the enlarged diagram of the 3rd variation of the single-crystal manufacturing apparatus shown in presentation graphs 1.With reference to the 3rd variation of the single-crystal manufacturing apparatus 1 shown in Fig. 6 explanatory view 1.
With reference to Fig. 6, single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 1 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 1, between the surface 14 of the rake 12 of base 2 and ampoule 3, disposes releasing agent 20.By this formation, the same with the single-crystal manufacturing apparatus shown in Fig. 4, can prevent fixing between base 2 and ampoule 3.And, as releasing agent 20, for example, can use SiC powder, alumina powder etc.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, preferably below the above 15 μ m of 0.3 μ m, further preferably below the above 10 μ m of 0.5 μ m.
(embodiment 2)
Fig. 7 is the schematic diagram that represents the embodiment 2 of 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 the identical structure of single-crystal manufacturing apparatus 1 shown in Fig. 1 substantially, but and the difference of the single-crystal manufacturing apparatus 1 of Fig. 1 be, on base 2, directly carry crucible 4 (there is no the ampoule 3 shown in Fig. 1).Particularly, in the single-crystal manufacturing apparatus 1 shown in Fig. 7, there is the minor diameter part 31 of crucible 4 in recess 11 internal configuration of base 2.And, configure contiguously the wide diameter portion 32 of crucible 4 with the rake 12 of base 2.By this formation, also can obtain and the identical effect of single-crystal manufacturing apparatus 1 shown in Fig. 1.
Fig. 8 is the enlarged diagram of the 1st variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.With reference to the 1st variation of the single-crystal manufacturing apparatus 1 shown in Fig. 8 explanatory view 7.
With reference to Fig. 8, the 1st variation of single-crystal manufacturing apparatus of the present invention has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 7 substantially, but the same with the single-crystal manufacturing apparatus 1 shown in Fig. 4, be with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 7, form the concaveconvex shape portion 13 as anti-immovable bed on the surface of the rake 12 of base 2.So, can suppress to produce crucible 4 and base 2 fixing problem in rake 12 when monocrystalline forming.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, in the preferred Ra of this surfaceness, be more than 1.5, below 7.0, in further preferred Ra, be more than 2.5, below 4.5.Rake concavo-convex in the time that Ra is too small, contact area increases, and the fixing of crucible 4 and base 2 easily occurs.And in the time that Ra is excessive, the number of the protuberance contacting with crucible 4 reduces, become large towards the contact pressure of each protuberance, easily occur fixing.That is, the preferred Ra of this surfaceness is 0.5～9.5, more preferably 1.5～7.0, further preferably 2.5～4.5.
Fig. 9 is the enlarged diagram of the 2nd variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.With reference to the 2nd variation of the single-crystal manufacturing apparatus 1 shown in Fig. 9 explanatory view 7.
With reference to Fig. 9, the 2nd variation of single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 7 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 1, is formed with anti-fixing processing layer 19 on the rake 12 of base 2.This anti-fixing processing layer 19 be by with the reactivity of material that forms crucible 4 material relatively low than the material that forms base 2 form layer, for example in the time that crucible 4 is quartz, can use SiC film, aluminum oxide film etc.And the thickness of this anti-fixing processing layer 19 is below the above 1mm of 10 μ m, preferably below the above 500 μ m of 50 μ m, further preferably below the above 300 μ m of 100 μ m.By adopting this formation, can obtain the effect identical with the single-crystal manufacturing apparatus shown in Fig. 8.
Figure 10 is the enlarged diagram of the 3rd variation of the single-crystal manufacturing apparatus shown in presentation graphs 7.With reference to the 3rd variation of the single-crystal manufacturing apparatus shown in Figure 10 explanatory view 7.
With reference to Figure 10, single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Fig. 7 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Fig. 7, between the surface 14 of the rake 12 of base 2 and crucible 4, disposes releasing agent 20.By this formation, the same with the single-crystal manufacturing apparatus shown in Fig. 8, can prevent fixing between base 2 and crucible 4.And, as releasing agent 20, for example, can use SiC powder, alumina powder etc.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, preferably below the above 15 μ m of 0.3 μ m, further preferably below the above 10 μ m of 0.5 μ m.
(embodiment 3)
Figure 11 is the schematic diagram that represents the monocrystalline that uses single-crystal manufacturing apparatus manufacture of the present invention.Illustrate based on monocrystalline 40 of the present invention with reference to Figure 11.
With reference to Figure 11, the monocrystalline 40 being made up of silication gallium is the monocrystalline that use the single-crystal manufacturing apparatus shown in Fig. 1 to manufacture, and substantially has the identical profile of interior shape with the crucible 4 of the single-crystal manufacturing apparatus 1 of Fig. 1.That is, be positioned at the lower end of the monocrystalline 40 of Figure 11 as the seed crystal of the basic point of crystalline growth, comprise: monocrystalline wide diameter portion, from this lower end, it is large 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 monocrystalline wide diameter portion.The boundary portion of monocrystalline wide diameter portion and stretched portion is called to shoulder 41.And, using the central part of the length direction of stretched portion (crystalline growth direction) as main part central authorities 42, using the upper end of stretched portion as afterbody 43.On the border of monocrystalline wide diameter portion and stretched portion (shoulder 41), mean concns in the face vertical with the growth axis direction of monocrystalline 40, silicon is 1 × 10 17cm -3above, 7 × 10 17cm -3below, the mean value of dislocation desity is 0cm -22000cm above, -2below.
Wherein, while using single-crystal manufacturing apparatus 1 of the present invention to form monocrystalline 40, in the time that 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.In the monocrystalline 40 that result can suppress to obtain, produce crystal defect., contriver finds, by being " smooth or outstanding shape " by the solid-liquid interface shape control of 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 shoulder 41.Thereby find, can significantly reduce the frequency of the problems such as linearity in crystallization main part (becoming the part of the products such as wafer) is aging.In addition, the linear aging dislocation that refers to high density focuses on local problem, exists the part of this problem can not make product.
Wherein, first the inventor finds: be in the monocrystalline 40 below a certain amount of at silicon concentration, having the linear aging problem that easily occurs, is certain density when following but make the dislocation of shoulder 41, has suppressed the aging generation of linearity as the stretched portion (crystallization main part) of the part of product.Further, in the larger crystallization of the ratio (ratio of the length of stretched portion and diameter) of " diameter of length/stretched portion of stretched portion ", be particularly in more than 1.5 crystallizations at the ratio of " diameter of length/stretched portion of stretched portion ", 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 causes of dislocation, be certain density (2000cm in dislocation desity -2) when following, find that this hole obviously reduces.
Particularly, the silicon concentration in shoulder 41 is 1 × 10 17cm -3～7 × 10 17cm -3time (this silicon concentration decides corresponding to the product design of monocrystalline), dislocation desity is 2000cm -2below, preferred 1500cm -2below, further preferred 1000cm -2when following, can suppress the aging generation of linearity of stretched portion, obtain higher productivity.And, the ratio of " diameter of length/stretched portion of stretched portion " is that 1.5 × (diameters (mm) of 77 ÷ stretched portions) obtain good effect when above, when this is than being that 2.0 × (diameters (mm) of 77 ÷ stretched portions) are when above, can further obtain good effect, when this is than being 2.5 × (diameters (mm) of 77 ÷ stretched portions) when above, obtain best effect.
In addition,, while adding silicon to gallium arsenide (GaAs) is middle, the crystal defect that is called as dislocation (translocation position) reduces.The concentration of the silicon in GaAs is higher, misplaces fewer, and 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 manufacture.Silicon concentration in shoulder 41 is low to moderate 1 × 10 17cm -3～7 × 10 17cm -3time, in existing stretched portion, exist and easily produce linear aging problem.First the inventor finds, is below certain value by making the dislocation desity of shoulder 41, can suppress the aging generation of linearity in stretched portion.
Adding in the monocrystalline 40 of silicon, from shoulder 41 towards afterbody 43, silicon concentration rises.Therefore, more approach afterbody 43, be more difficult to produce new dislocation., dislocation desity reduces to afterbody 43 from shoulder 41.Therefore, contriver finds, by controlling the dislocation desity of shoulder 41, can reduce by leaps and bounds the aging incidence of linearity in stretched portion.In addition, when the silicon concentration in shoulder 41 (mean concns of silicon) exceedes 7 × 10 17cm -3time, original be just difficult for forming linear aging, so what can obviously obtain effect of the present invention is that silicon concentration in shoulder 41 is 7 × 10 17cm -3when following.And, can think, not adding in the monocrystalline of silicon, in stretched portion, also easily misplace, therefore only control the dislocation desity of shoulder 41, be difficult to the generation that suppresses linear aging.Therefore, making the silicon concentration in shoulder 41 is above-mentioned 1 × 10 17cm -3above 7 × 10 17cm -3when following, successful of the present invention, this silicon concentration is 1 × 10 17cm -3above 5.5 × 10 17cm -3when following, effect of the present invention can be further obvious, and this silicon concentration is 1 × 10 17cm -3above 4.0 × 10 17cm -3when following, effect of the present invention becomes more obvious.
And inventor's discovery, silicon concentration, along with the mode of natural coagulation, above increases towards afterbody 43 from shoulder 41 at crystallization length direction (bearing of trend of monocrystalline 40).Therefore, the ratio of monocrystalline length and diameter (" ratio of straight body length/stretched portion diameter " hour, silicon concentration increases in the longitudinal direction rapidly, has therefore suppressed the generation of dislocation.On the contrary, in the time of the length of monocrystalline and diameter larger, silicon concentration increases in the longitudinal direction gradually.Therefore in stretched portion, till the dislocation that shoulder 41 produces is assembled, easily form linear aging.Therefore, in the monocrystalline 40 of the ratio of this monocrystalline length and diameter large (ratio of the length of stretched portion and diameter is more than 1.5), the particular significant effect of " suppressing linear aging formation " of the present invention.
(embodiment 4)
Figure 12 is the schematic diagram that represents the embodiment 4 of 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; Be mounted in the ampoule 3 on base 52; Remain on the crucible 4 of the inside of ampoule 3; Be used for the well heater 5 of the raw material that heats the inside that is filled in crucible 4.Base 52 is that planeform is for example circular cylinder, upper face have mortar shape rake 12, be positioned at the recess 11 of the inner circumferential side (substantial middle of upper face) of this rake 12.The planeform of recess 11 is for example circular, the width of this recess 11 substantially constant on depth direction.The formation of rake 12 is, along with the upper end from recess 11 is towards the outer circumferential side of base 52, becomes large tilt (diapire of base 52 relatively) apart from the distance of the diapire of base 52.The material of base 52 for example can use quartz.And, as the material of base 52, be have form ampoule 3 quartzy thermal expansivity ± material of 50% thermal expansivity with interior scope, for example, if there is the abundant intensity material of (fusing point is greater than this thermal treatment temp) under the thermal treatment temp that is used to form monocrystalline, can use material arbitrarily.For example, can use mixture or the porous silica etc. of quartz, quartz and aluminum oxide as the material of base 52.
The ampoule 3 that is equipped on this base 52 is ampoules (quartz ampoule) of quartz 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 minor diameter part 21, has the sidewall tilting along the rake 12 of base 52; And stretched portion 23, being connected on wide diameter portion 22, planeform is for example circle identical with base 52, the velocity of variation of width (diameter) is less 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 is held 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 the crucible 4 of the inside of the minor diameter part 21 that is contained in ampoule 3.The planeform of minor diameter part 31 is for example circular.Start the wide diameter portion 22 along ampoule 3 from the upper end of this minor diameter part 31, form the wide diameter portion 32 of crucible 4.And, be connected and form stretched portion 33 with the upper end of this wide diameter portion 32.The inner peripheral surface configuration of the basic stretched portion 23 along ampoule 3 of stretched portion 33 of this crucible 4.And the periphery ground that surrounds base 52, ampoule 3 and crucible 4 configures well heater 5.
Then explanation has been used the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Figure 12.Figure 13 is the schema that has represented to use the monocrystalline manufacture method of the single-crystal manufacturing apparatus shown in Figure 12.As shown in figure 13, in monocrystalline manufacture method of the present invention, first implement monocrystalline preparatory process (S10).Particularly, insert the monocrystalline small pieces as seed crystal in the inside of the minor diameter part 31 of the crucible 4 shown in Figure 12.
Then as shown in figure 13, implement raw material preparation process (S20).Particularly, dropping into using specified amount in the inside of crucible 4 should be as the material piece of the polycrystalline of crystal raw material.As the component of the material piece of above-mentioned monocrystalline small pieces and polycrystalline, can use crystalline material arbitrarily, for example the gallium arsenide that contains silicon (GaAs) can be used as this component.And, be the high material of dissociation pressure as gallium arsenide time, quartz ampoule can be sealed in a vacuum.
Then as shown in figure 13, implement heating process (S30).Particularly, switch on by the well heater 5 to shown in Figure 12, the material piece of the polycrystalline of the inside of heating crucible 4 is also molten state.In addition,, now in order to make the not melting of monocrystalline small pieces of minor diameter part 31 inside that are configured in crucible 4, adjust the heating condition of well heater 5.
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 to side shifting under Figure 12, thereby the temperature of the polycrystal raw material of melting is declined gradually near of monocrystalline small pieces (seed crystal) of minor diameter part 31 inside that are configured in crucible 4.Consequently, the raw material of heating melting is from starting to solidify gradually (crystallization) near seed crystal.The part of therefore, solidifying becomes monocrystalline.And, extract out to downside by gradually base 52, ampoule 3 and crucible 4 being started from the inner circumferential side of well heater 5, make the raw material of melting near the downside of crucible 4 (be seed crystal) crystallization gradually.Can make like this single crystal growing.If the raw material of melting solidifies completely, 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.
Now, for example use vitreous silica as the material of base 52, thereby the difference of the thermal expansivity between ampoule 3 and the base 52 that can make to be made up of quartz is reduced in fact insignificant degree.Therefore,, while making the temperature variation of base 52 and ampoule 3 in order to make above-mentioned single crystal growing, 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.Therefore, can prevent from causing because of the temperature variation of base 52 and ampoule 3 problem of ampoule 3 breakages.
And, passing through to use the transparent components such as transparent 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,, in the time that the solid-liquid interface 17 of the monocrystalline 15 of growing and melting material 16 arrives the stretched portion 33 of crucible 4, can make solid-liquid interface 17 become the shape side-prominent to melting material 16 1.Result is in the monocrystalline 15 forming, and near the crystallization bad (linear aging) in bottom that can suppress stretched portion 33 produces.In addition, Figure 14 is the schematic diagram of the use state for the single-crystal manufacturing apparatus shown in Figure 12 is described.
Wherein, transparent component refers to that for the transmitance of the photometric units length (1cm) of wavelength 2000nm be more than 90% material.In addition, transmittance refers to the ratio ((light intensity seeing through)/(light intensity of incident) × 100) that incides the above-mentioned light intensity of this transparent component and seen through the light intensity of transparent component.The silica glass such as GE124 that therefore, for example can use Momentive Performance Materials company to manufacture as transparent component.
Figure 15 is the enlarged diagram that represents the 1st variation of the single-crystal manufacturing apparatus shown in Figure 12.The 1st variation of the single-crystal manufacturing apparatus 1 shown in Figure 12 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 and the same structure of single-crystal manufacturing apparatus 1 shown in Figure 12 substantially, but be with the difference of the single-crystal manufacturing apparatus 1 shown in Figure 12, form the concaveconvex shape portion 13 as anti-immovable bed on the surface of the rake 12 of base 52.So, can be suppressed to form ampoule 3 and base 52 fixing problem in rake 12 occurs when 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, further preferably Ra is more than 2.5, below 4.5.Rake concavo-convex in the time that Ra is too small, contact area increases, and the fixing of ampoule 3 and base 52 easily occurs.And in the time that Ra is excessive, the number of the protuberance contacting with ampoule 3 reduces, become large towards the contact pressure of each protuberance, easily occur fixing.That is, the preferred Ra of this surfaceness is 0.5～9.5, more preferably 1.5～7.0, further preferably 2.5～4.5.
Figure 16 is the enlarged diagram that represents the 2nd variation of the single-crystal manufacturing apparatus shown in Figure 12.The 2nd variation of the single-crystal manufacturing apparatus 1 shown in Figure 12 is described with reference to Figure 16.
With reference to Figure 16, the 2nd variation of single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Figure 12 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Figure 12, forms anti-fixing processing layer 19 on the rake 12 of base 52.This anti-fixing processing layer 19 is the layers that are made up of the material relatively low with the quartzy reactivity while contacting between quartz (and compare) of material as forming ampoule 3, for example, can use SiC film, aluminum oxide film etc.And the thickness of this anti-fixing processing layer 19 is below the above 1mm of 10 μ m, preferably below the above 500 μ m of 50 μ m, further preferably below the above 300 μ m of 100 μ m.By adopting this formation, can obtain the effect identical with the single-crystal manufacturing apparatus shown in Figure 15.
Figure 17 is the enlarged diagram that represents the 3rd variation of the single-crystal manufacturing apparatus shown in Figure 12.With reference to the 3rd variation of the single-crystal manufacturing apparatus shown in Figure 17 explanatory view 1.
With reference to Figure 17, single-crystal manufacturing apparatus has and the same structure of single-crystal manufacturing apparatus 1 shown in Figure 12 substantially, but is with the difference of the single-crystal manufacturing apparatus 1 shown in Figure 12, between the surface 14 of the rake 12 of base 52 and ampoule 3, disposes releasing agent 20.By this formation, the same with the single-crystal manufacturing apparatus shown in Figure 15, can prevent fixing between base 52 and ampoule 3.And, as releasing agent 20, for example, can use SiC powder, alumina powder etc.And the particle diameter of releasing agent 20 is below the above 20 μ m of 0.1 μ m, preferably below the above 15 μ m of 0.3 μ m, further preferably below the above 10 μ m of 0.5 μ m.
(embodiment 5)
Figure 18 is the schematic diagram that represents the embodiment 5 of 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 the identical structure of single-crystal manufacturing apparatus 1 shown in Figure 12 substantially, but and the difference of the single-crystal manufacturing apparatus 1 of Figure 12 be the structure of base 52.Particularly, in the single-crystal manufacturing apparatus 1 shown in Figure 18, the quartz member 26 that base 52 is configured on this matrix 25 by matrix 25, lamination forms.Quartz member 26 comprises the rake 12 directly contacting with the wide diameter portion of ampoule 3.And matrix 25 can use the differing materials beyond quartz.On the other hand, quartz member 26 is made up of transparent quartz.The shape of the base 52 that the matrix 25 shown in Figure 18 and quartz member 26 form substantially with the single-crystal manufacturing apparatus 1 shown in Figure 12 in base 52 identical.
By this formation, can obtain and the same effect of single-crystal manufacturing apparatus 1 shown in Figure 12.Further, base 52 is made up of matrix 25 and quartz member 26, therefore in order to adjust the characteristic such as thermal conduction characteristic, intensity of base 52, for example, can change arbitrarily the material of matrix 25.
And the single-crystal manufacturing apparatus of the invention described above is applicable to the manufacture of semiconductor monocrystal, is particularly useful for the manufacture of arsenide gallium monocrystal and indium phosphide single crystal.
Below enumerate characteristic of the present invention structure, it has part repetition with the description of above-mentioned embodiment.
Based on single-crystal manufacturing apparatus 1 of the present invention be, after raw material (material piece of the polycrystalline) heat fused that raw material is kept keeping in container (ampoule 3 of Fig. 1 and the crucible 4 of crucible 4 or Fig. 7), it is solidified from a direction, thereby the single-crystal manufacturing apparatus 1 that produces monocrystalline, has: 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 for heating the ampoule 3 of Fig. 1 and the crucible 4 of crucible 4 or Fig. 7.The thermal conductivity of material that forms base 2 is that 0.5W/ (mK) is above, below the value of the thermal conductivity of the monocrystalline that should form.Form in the material of base 2, wavelength is that 1600nm light above, below 2400nm is below 10% with respect to the transmittance of the above-mentioned materials of thick 4mm.And for the material that forms base 2, preferred above-mentioned transmittance is below 5%.And, below 1/2 of thermal conductivity of the monocrystalline that the thermal conductivity of the material of formation base 2 preferably should form, below 1/4 of the thermal conductivity of the monocrystalline that further preferably should form.
So, the material that forms base 2 adopts the better simply formation that relative wavelength 1600nm light above, below 2400nm is opaque material, thereby the material piece that makes polycrystalline in crucible 4 is molten state, when it is solidified from a direction (particularly from base 2 one sides), the hot-fluid that is sent to base 2 can be directed to the direction (below) towards base 2 lower surfaces from the raw material of melting.Result can make the melting material 16 (liquid phase) of Fig. 3 and raw material solidify and become the solid-liquid interface 17 of the boundary portion of the 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 obtaining, can suppress the bad generation of crystallization.
In above-mentioned single-crystal manufacturing apparatus 1, in base 2, can form on the surface of the part contacting with the ampoule 3 of Fig. 4～Fig. 6 or with the crucible 4 of Fig. 8～Figure 10 anti-immovable bed (concaveconvex shape portion 13, anti-fixing processing layer 19, releasing agent 20).Wherein, when the raw material of accommodating in crucible 4 heating by well heater 5 in order to manufacture monocrystalline, become the also heated state of crucible 4 shown in ampoule 3 or Fig. 8～Figure 10 of the maintenance crucible 4 shown in Fig. 4～Fig. 6.And, ampoule 3 or crucible 4 in heating are supported the region (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, by the deadweight of ampoule 3 and crucible 4 (with reference to Fig. 4～Fig. 6) or crucible 4 (with reference to Fig. 8～Figure 10), become the state that ampoule 3 or crucible 4 are pushed by base.Consequently, exist ampoule 3 or crucible 4 to be fixed on the situation of base 2.Therefore, in the time that ampoule 3 or crucible 4 are fixed on base 2, while heat-treating for forming monocrystalline (when carrying out heating process (S30) and the crystalline growth operation (S40) in Fig. 2 and further carrying out the processing (refrigerating work procedure (S50)) for cool to room temperature), poor because of the thermal expansion amount of ampoule 3 or crucible 4 and base 2, above-mentioned fixing part produces stress.This stress is the reason that causes ampoule 3, crucible 4 or base 2 breakages.
Therefore, as mentioned above, prevent that by forming anti-immovable bed (concaveconvex shape portion 13, anti-fixing processing layer 19, releasing agent 20) ampoule 3 or crucible 4 are fixed on base 2, ampoule 3 and crucible 4 and base 2 independent expansion/contraction respectively, therefore can suppress to be derived from the generation of above-mentioned fixing stress.Consequently, can reduce the possibility of ampoule 3, crucible 4 or base 2 breakages.
In above-mentioned single-crystal manufacturing apparatus 1, raw material keeps container as shown in Fig. 1, Fig. 3～Fig. 6, also can comprise: as the crucible 4 of material container that keeps raw material; Keep the ampoule 3 of the quartz ampoule of this crucible 4 as inside.The thermal expansivity that is formed in the material at the position at least contacting with ampoule 3 in base 2 can be form ampoule 3 quartzy thermal expansivity ± 50% value with interior scope.
So, in order to manufacture monocrystalline when well heater 5 heating crucible 4, thereby and by making because the raw material that heating becomes liquid phase solidifies when obtaining monocrystalline and reducing the temperature of this former crucible 4, can fully reduce the poor of thermal expansion amount between ampoule 4 and 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 being supported by base 2, and the material that is formed in the position at least contacting with ampoule 3 in base 2 can be also quartz.And the material that preferably forms base 2 is quartz.Now, base 2 is made up of the material identical with ampoule 3.Therefore, ampoule 3 is identical with the thermal expansivity of base 2, can conscientiously suppress the damaging problem causing because of the difference of above-mentioned thermal expansion amount.
In above-mentioned single-crystal manufacturing apparatus 1, as shown in Fig. 4 or Fig. 8, anti-immovable bed can be concaveconvex shape portion 13.This concaveconvex shape portion 13 for example can be by forming above-mentioned surface (rake 12) roughening in base 2.Now, in the above-mentioned surface of base 2, can reduce the area directly contacting with ampoule 3 or crucible 4.Its result can reduce ampoule 3 or crucible 4 and be fixed on the possibility of base 2.
And above-mentioned anti-immovable bed, as shown in Fig. 5 or Fig. 9, can be and form the quartzy reactive of quartz ampoule or form the reactivity of the material of crucible 4, the anti-fixing processing layer 19 forming than the low material of material of main part that forms base 2.Anti-fixing processing layer 19 can be single layer, can be also multiple laminar construction of pressing layer by layer.And, as anti-fixing processing layer 19, can use the modified layer that the base 2 modifying surface processing crystallization processing of susceptor surface (for example for) are obtained.Now, also can reduce ampoule 3 or crucible 4 and be fixed on the possibility of base 2.
Manufacture method based on monocrystalline of the present invention is the manufacture method that has used the monocrystalline of above-mentioned single-crystal manufacturing apparatus 1, implements following operation., 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 (material piece of polycrystalline) 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 the raw material of melting (material piece of polycrystalline) thus making gradually it solidify from seed crystal one side manufactures the operation (crystalline growth operation (S40)) of monocrystalline.
So, the material piece (heating process (S30)) of temporary transient fusing polycrystalline, while carrying out afterwards the processing (crystalline growth operation (S40)) for solidifying, can make to be directed to the direction (below) towards base 2 lower surfaces from the raw material of melting towards the hot-fluid of base 2.Consequently, as shown in Figure 3, can make melting material 16 (liquid phase) and raw material solidify and the boundary portion (solid-liquid interface 17) of monocrystalline 15 (solid phase) that becomes the part of monocrystalline for smooth or to the side-prominent shape of melting material 16 1.Therefore,, in the time that 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 obtaining, can suppress to produce crystal defect.
In the manufacture method of above-mentioned monocrystalline, the monocrystalline of manufacture can be made up of the gallium arsenide that contains silicon (Si) (GaAs).Monocrystalline can comprise: monocrystalline wide diameter portion, becomes large gradually from seed crystal one side width; And stretched portion, being connected with monocrystalline wide diameter portion, wide variety rate is less than above-mentioned monocrystalline wide diameter portion (for example width is constant in fact).Also can be that mean concns in face in the border of monocrystalline wide diameter portion and stretched portion (in the monocrystalline 15 shown in Fig. 3 the wide diameter portion of enlarged-diameter and be connected with this wide diameter portion and the border of the erection part that diameter is constant in fact), vertical with the growth axis direction of monocrystalline, silicon is 1 × 10 17cm -3above, 7 × 10 17cm -3below.And the mean value of the dislocation desity on this border can be also 0cm -22000cm above, -2below.Therefore,, while forming monocrystalline for above-mentioned siliceous GaAs, as being suitable for manufacture method of the present invention, the effect that suppresses bad generation is more remarkable.
And, from different perspectives, are the monocrystalline 40 that formed by the gallium arsenide that contains silicon based on monocrystalline 40 of the present invention, comprising: monocrystalline wide diameter portion (than the shoulder of Figure 11 41 part on the lower), starts width from seed crystal one side and become gradually large; And stretched portion (the substantially invariable main part of diameter in Figure 11), it is connected to monocrystalline wide diameter portion, and wide variety rate is less than monocrystalline wide diameter portion.In the border of monocrystalline wide diameter portion and erection part (shoulder 41), mean concns in the face vertical with the growth axis direction of monocrystalline 40, silicon is 1 × 10 17cm -3above, 7 × 10 17cm -3below, the mean value of dislocation desity is 0cm -22000cm above, -2below.
Therefore,, by dislocation desity being controlled to above-mentioned scope in shoulder 41, can effectively suppress to produce in main part linear aging.And in the time being the mean concns of above-mentioned silicon, the grinding step of the wafer cutting from this monocrystalline, exist and produce the hole (small depression) that dislocation causes, but as mentioned above, in the wafer cutting from the monocrystalline of having controlled the dislocation desity shoulder 41, can suppress the generation in this hole.
And in above-mentioned monocrystalline 40, the ratio (length/diameter of stretched portion) of the diameter of length/stretched portion of stretched portion is preferably more than 1.5.Therefore,, in the length of stretched portion and the larger monocrystalline of diameter, effect of the present invention is especially obvious.
And the diameter of the monocrystalline 40 of acquisition is larger, the depression of the solid-liquid interface in more difficult inhibition wide diameter portion, therefore shoulder 41 Dislocations density easily increase.And solid-liquid interface also easily caves in main part (stretched portion), and the larger temperature head of the inner easily generation of crystallization, so linear aging formation becomes obvious.Monocrystalline of the present invention and manufacture method thereof are 77mm successful when above at shoulder diameter, and diameter is 102mm when above, can obtain more positive effect, and 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, the raw material (material piece of polycrystalline) keeping in to material container (crucible 4) heats after melting, by making it solidify the single-crystal manufacturing apparatus 1 of manufacturing monocrystalline from a direction, have: as the crucible 4 of material container; Keep the quartz ampoule (ampoule 3) of crucible 4 in inside; Support the base 52 of ampoule 3; And for the well heater 5 of heating crucible 4.The thermal expansivity that is formed in the material at the position at least contacting with ampoule 3 in base 52 be included in form ampoule 3 quartzy thermal expansivity ± 50% value with interior scope.
So, for manufacturing monocrystalline while pass through well heater 5 heating crucible 4, thereby and when making to solidify acquisition monocrystalline and reduce the temperature of this crucible 4 because of the raw material that heating becomes liquid phase, can fully reduce the poor of thermal expansion amount between ampoule 3 and base 52.Consequently, can suppress to cause because of the difference of this thermal expansion amount the problem of ampoule 3 or base 52 breakages.
In above-mentioned single-crystal manufacturing apparatus 1, as shown in Figure 15～Figure 17, in base 52, can form on the surface of the part contacting with ampoule 3 anti-immovable bed (concaveconvex shape portion 13, anti-fixing processing layer 19, releasing agent 20).Wherein, while passing through well heater 5 heating crucible 4 for manufacturing monocrystalline, ampoule 3 also becomes heated state.And, ampoule 3 in heating is supported by base 52 in the region (part that the wide diameter portion 22 of ampoule 3 contacts with the rake 12 of base 52) of (contacting with base 52), because of by the deadweight of ampoule 3, become the state that ampoule 3 is pushed by base.Consequently, exist ampoule 3 to be fixed on the situation of base 52.When ampoule 3 is fixed on base 52 like this, while heat-treating in order to form monocrystalline (while carrying out heating process (S30) in Figure 13, crystalline growth operation (S40) and refrigerating work procedure (S50)), poor because of the thermal expansion amount of ampoule 3 and base 52, above-mentioned fixing part produces stress.This stress is the reason that causes ampoule 3 or base 52 breakages.
Therefore, as mentioned above, prevent fixing to base 52 of ampoule 3 by forming anti-immovable bed (concaveconvex shape portion 13, anti-fixing processing layer 19, releasing agent 20), ampoule 3 and base 52 independent expansion/contraction respectively, therefore can suppress the generation of the above-mentioned stress fixedly causing.Consequently, can reduce the possibility of ampoule 3 or base 52 breakages.
In above-mentioned single-crystal manufacturing apparatus 1, the material that forms base 52 can be also quartz.And in above-mentioned single-crystal manufacturing apparatus 1, the material that is formed in the position at least contacting with quartz ampoule in base can be also quartz.Now, base 52 is made up of the material identical with ampoule 3.Therefore, ampoule 3 is identical with the thermal expansivity of base 52, can conscientiously suppress the damaging problem causing because of the difference of above-mentioned thermal expansion amount.
In above-mentioned single-crystal manufacturing apparatus 1, as shown in figure 15, anti-immovable bed can be concaveconvex shape portion 13.This concaveconvex shape portion 13 for example can be by forming above-mentioned surface (rake 12) roughening in base 52.Now, in the above-mentioned surface of base 52, can reduce the area directly contacting with ampoule 3.Its result can reduce ampoule 3 and be fixed on the possibility of base 52.
And above-mentioned anti-immovable bed as shown in figure 16, can be the anti-fixing processing layer 19 that the material lower with the quartzy reactivity that forms quartz ampoule forms.Anti-fixing processing layer 19 can be single layer, can be also multiple laminar construction of pressing layer by layer.And, as anti-fixing processing layer 19, for example can use, to base 52 modifying surface processing (the crystallization processing to susceptor surface) and the modified layer that obtains.Now, also can reduce ampoule 3 and be fixed on the possibility of base 2.
In above-mentioned single-crystal manufacturing apparatus 1, base 52 can be made up of transparent component.Now, while formation by non-transparent parts with base 52, compare, promoted via transparent base 52 heat radiation that the radiation of (direction from crucible 4 towards base 52) causes downwards from crucible 4 and the ampoule 3 of heating.Therefore,, near the bottom of stretched portion 33, as shown in figure 14, can make to become the shape side-prominent to liquid phase one as the solid-liquid interface 17 at the interface of melting material 16 (liquid phase) and the monocrystalline 15 (solid phase) that solidifies.Therefore,, by making solid-liquid interface 17 side-prominent to liquid phase one, can suppress the defect of the monocrystalline 15 that solid-liquid interface 17 produces when side-prominent to solid phase one.
Manufacture method based on monocrystalline of the present invention is the manufacture method that has used the monocrystalline of above-mentioned single-crystal manufacturing apparatus 1, has following operation., first implement to insert to material container (crucible 4) operation (the seed crystal preparatory process (S10) of Figure 13 and raw material preparation process (S20)) of the raw material (material piece of polycrystalline) of seed crystal (monocrystalline 15) and monocrystalline.And, implement by well heater 5 heating raw containers (crucible 4), thus the operation of the material piece of melting polycrystalline (heating process (S30)).Further, thereby enforcement makes the raw material (material piece of polycrystalline) of melting solidifies gradually the operation (crystalline growth operation (S40)) of manufacturing monocrystalline from seed crystal one side.
So, the material piece (heating process (S30)) of temporary transient fusing polycrystalline, the processing that makes it afterwards to solidify (crystalline growth operation (S40) while carrying out the processing (refrigerating work procedure S50) of cool to room temperature, the ampoule 3 forming because of quartz and the thermal expansivity of base 52 do not have larger poor, therefore 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 declines can be suppressed, the monocrystalline of high-quality can be stably obtained.
In the manufacture method of above-mentioned monocrystalline, monocrystalline also can be by not forming containing the gallium arsenide of silicon (Si) as additive or the gallium arsenide (GaAs) of siliceous (Si).Monocrystalline comprises: monocrystalline wide diameter portion, starts width from seed crystal one side and become gradually large; And stretched portion, being connected with this monocrystalline wide diameter portion, wide variety rate is less than above-mentioned monocrystalline wide diameter portion.The concentration of the silicon (Si) on the border of monocrystalline wide diameter portion and stretched portion (wide diameter portion of enlarged-diameter in the monocrystalline 15 shown in Figure 14, be connected on this wide diameter portion and the border of the stretched portion of constant diameter) is 7 × 10 17cm -3below, preferably 5.5 × 10 17cm -3below, further preferably 4.0 × 10 17cm -3below.Therefore, while especially above-mentioned siliceous GaAs being formed to monocrystalline, as being suitable for manufacturer's rule of the present invention, to suppress the effect of defect generation especially obvious.In addition,, containing referring to and deliberately do not add silicon as the gallium arsenide of the silicon of additive, be included in the situation that contains silicon as inevitable impurity, 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 manufacturing under various conditions the monocrystalline of GaAs.
(experiment condition)
(a) crystalline growth of the gallium arsenide of 3 inch diameters
Use device of the present invention to carry out the growth of the gallium arsenide crystallization of 3 siliceous inch diameters.Use front end to there is crucible seed crystal resettlement section, thermolysis boron nitride (pBN) system.In this crucible, accommodate seed crystal, carried out preparing synthetic gallium arsenide (GaAs) raw material, boron oxide (B as sealing agent 20 3), as the silicon (Si) of doping agent, the ampoule of quartz system is carried out to vacuum-sealing.And, ampoule processed this quartz is loaded to the base in opaque quartz system.Make the test film of the thick 2mm of the identical material of opaque quartz using with base, the thermal conductivity of being undertaken under room temperature by laser pulse method is measured, result obtains the value (to the result under experiment condition described herein, 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 substantially see through the light of the wavelength region may of dominance under the growth temperature of gallium arsenide crystallization (1238 ℃ of fusing points).And for preventing that quartz ampoule from fixing, base rake is adjusted into Ra=3.5 by attrition process, further carries out the thermal treatment of 1200 ℃, 72 hours in atmosphere, makes the processing of surface crystallization.
And the well heater to encirclement quartz ampoule, crucible periphery configuring is switched on and heats, after making gallium arsenide raw material and boron nitride be molten state, use the lifting device arranging on base, reduce base, quartz ampoule, crucible, be retracted to low temperature one side of well heater, make fused raw material solidify to a direction from seed crystal to afterbody, make siliceous arsenide gallium monocrystal growth.After crystalline growth finishes, cool to room temperature, takes off quartz ampoule from base, and cut-out is opened, and takes out crystallization.Crystallization diameter is 77mm at shoulder.
To the monocrystalline obtaining, measure the silicon concentration of shoulder.Silicon concentration is obtained as follows: in crystallization shoulder, near the end of the central authorities of the wafer vertically cutting with length direction, wafer and middle, make totally 3 chips that 10mm is square, carry out sims analysis, obtain the mean value of 3.
And monocrystalline is measured to the dislocation desity of shoulder.Dislocation desity is obtained as follows: by after KOH for wafer (potassium hydroxide) etching being obtained by monocrystalline shoulder, use Nuo Mansiji microscope on radial direction, to measure the number of corrosion pit with 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 from shoulder, using Superficial Foreign Body inspection units (Surfscan6220 that KLA-Tencor company manufactures), measuring the number of the body at random of whole wafer face.
And, by the operation same with the monocrystalline of above-mentioned 3 inch diameters, also form the arsenide gallium monocrystal that shoulder diameter is 85mm, 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 is made to use the same method measure.Wherein, base rake carries out sandblasting after attrition process, is adjusted into Ra=7.0.And, for base rake, after surface crystallizationization is processed, be finally coated with the alumina powder that particle diameter is 10 μ m.And after crystalline growth finishes, cool to room temperature, takes off quartz ampoule from base, cut-out is opened, and takes out crystallization.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 is made to use the same method measure.Wherein, base rake carries out sandblasting after attrition process, is adjusted into Ra=9.5.And, for base rake, after surface crystallizationization is processed, be finally coated with the SiC powder of particle diameter 20 μ m.And after crystalline growth finishes, cool to room temperature, takes off quartz ampoule from base, cut-out is opened, and takes out crystallization.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 as 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, table 2 refers to, from the shoulder 41 of the monocrystalline 40 shown in Figure 11 till the length of afterbody 43.From table 1 and table 2, in experiment 2 of the present invention～experiment 8, experiment 12, experiment 13 monocrystalline that obtain, do not produce linearity aging, 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 as shown in table 2, table 3.
From table 2 and table 3, in the monocrystalline obtaining based on experiment 16 of the present invention～experiment 19, do not produce linearity aging, 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 showing Dislocations density with 0 experiment representing, refer to that the mean value of dislocation desity is less than 0.5cm -2time.
(c) the gallium arsenide crystallization of 6 inch diameters
Experimental result is as shown in table 3.
As known from Table 3, in the monocrystalline obtaining based on experiment 23 of the present invention～experiment 26, do not produce linearity aging, 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 manufacture of monocrystalline, confirm its weather resistance.The investigation result of material, the weather resistance of the base that test is used is as shown in table 4.
Table 4
Figure BPA00001403343300361
Table 4 represents the breakage generation number of thermal expansivity, quartz ampoule or the base of base.Base uses vitreous silica, or is greater than quartzy materials'use quartz and the mixture of aluminum oxide 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, be less than quartzy material as thermal expansivity, use porous silica.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, there is no base breakage.
In addition, on base rake, to form concavo-convex and Ra be more than 0.5 material below 9.5, formed anti-fixing processing layer material, configured in the material etc. of releasing agent, during monocrystalline more than 100 is manufactured, the problem that quartz ampoule, base breakage can not occur completely yet, the circulation ratio of monocrystalline quality is extremely good.
This time disclosed embodiment is only example from every side, is not restrictive.Scope of the present invention does not depend on above-mentioned explanation, and as shown in claim scope, comprise with the impartial implication of claim scope and scope in all changes.
The present invention is particularly useful for using vertical boat method (Longitudinal type ボ mono-ト method) manufacture the situation of monocrystalline.

Claims (4)

1. a single-crystal manufacturing apparatus (1), after the heating raw materials fusing that raw material is kept keeping in container (3,4), makes it solidify from a direction, thereby manufactures 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 for heating the well heater (5) that above-mentioned raw materials keeps container (3,4),
The thermal conductivity that forms the material of above-mentioned base (2) is 0.5W/(mK) below the value of the thermal conductivity of above, the monocrystalline that should form,
For the material that forms above-mentioned base (2), wavelength is that 1600nm light above, below 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 contacting 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) being supported by above-mentioned base (2),
The material that is formed in the position at least contacting with above-mentioned quartz ampoule (3) in above-mentioned base (2) is quartz.
4. a manufacture method for monocrystalline, has been used the single-crystal manufacturing apparatus described in any one in claims 1 to 3, 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 melting above-mentioned raw materials material;
The above-mentioned raw materials material of melting is solidified gradually from above-mentioned seed crystal side, thereby manufacture the operation (S40) of monocrystalline.
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