CN110396723A - A kind of high-purity semi-insulating silicon carbide monocrystalline and its high efficiency preparation method and application - Google Patents
A kind of high-purity semi-insulating silicon carbide monocrystalline and its high efficiency preparation method and application Download PDFInfo
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- 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
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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
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Abstract
This application discloses a kind of high-purity semi-insulating silicon carbide monocrystalline and its high efficiency preparation method and applications, belong to field of semiconductor materials.The preparation method includes: assembling and long brilliant, silicon carbide polycrystalline block raw material setting cellular structure, and partial gas phase raw material of the cellular structure in one end of seed crystal setting gaseous phase outlet, raw material area is by cellular structure from gaseous phase outlet gas phase transmission to seed crystal.The application prepares the long brilliant high-efficient of single-crystal silicon carbide with the silicon carbide polycrystalline block with cellular structure, and the quality of single-crystal silicon carbide obtained is high, with high purity；Two pieces of single-crystal silicon carbide ingots can be grown simultaneously using same seed crystal, and the quality of two pieces of single crystal rods is similar, long brilliant at low cost, long brilliant high-efficient, and long crystalline substance path is short, gas phase transmission path is easy to control；By the long brilliant pressure change and pressure value of control single-crystal silicon carbide, avoids the compactness due to silicon carbide polycrystalline block and lead to the forming core disorder for preparing high-purity semi-insulating silicon carbide monocrystalline, improve the crystal growth quality of single-crystal silicon carbide.
Description
Technical field
This application involves a kind of high-purity semi-insulating silicon carbide monocrystalline and its high efficiency preparation method and applications, belong to semiconductor material
Material field.
Background technique
Demand with the fast development of the industries such as 5G communication, new-energy automobile to power electronic device is continuously increased, with
Silicon carbide (SiC) semiconductor is the third generation semiconductor material of representative, because having broad stopband, high heat conductance, high critical breakdown field
The excellent physical properties such as strong and high saturated electrons drift speed and be concerned.Since SiC single crystal preparation difficulty is very big, SiC
Single crystalline substrate is with high costs, therefore the SiC single crystal substrate for how efficiently preparing low cost becomes the above-mentioned new industry of solution to function
The key problem of rate device requirement.
Currently, it is physical vapor transport (PVT) method that SiC single crystal, which prepares most mature technology of preparing, i.e., in lower pressure
It is lower to be heated to certain temperature by synthesize SiC powder and so that it is distilled and be transmitted at seed crystal crystallization formation newly along temperature gradient
SiC single crystal.The key of PVT method preparation SiC single crystal is reasonably to design and control thermal field condition so that synthesis powder distils
To orderly being transmitted at seed crystal of gaseous component recrystallize.Therefore, the quality (including purity) and gas phase group of powder are synthesized
The technological core for dividing the control of transmission path to become PVT method.However, due to introduced in powder synthesis process impurity pollution, powder
The control difficulty of material granularity, crystal form etc. is larger, so that the powder synthesis of PVT method preamble process also has very big technical difficulty；And
Under high temperature at 2300 DEG C or so and the low pressure close to vacuum, the transmission control difficulty of gaseous component is equally very big.In addition, PVT
The long crystal type of method be powder is placed in growth chamber lower part, seed crystal is placed in the growth chamber top on powder, therefore single
Crystal growth be only able to achieve the preparation of single crystal, crystal preparation efficiency is lower, this is also that SiC single crystal cost is high
One of the major reasons.
Summary of the invention
To solve the above-mentioned problems, this application provides a kind of high-purity semi-insulating silicon carbide monocrystalline and its high efficiency preparation methods
And application.The preparation method of the high-purity semi-insulating silicon carbide monocrystalline prepares high-purity half with the silicon carbide polycrystalline block with cellular structure
Long brilliant high-efficient, the quality height of single-crystal silicon carbide ingot obtained, purity is high of insulating SiC silicon single crystal；It can using the same seed crystal
At low cost, long brilliant high-efficient to grow two pieces of single-crystal silicon carbides simultaneously, long crystalline substance path is short, gas phase transmission path is easy to control；It is logical
The long brilliant pressure change and pressure value for crossing control single-crystal silicon carbide, avoid the compactness due to silicon carbide polycrystalline block and cause
The forming core disorder for preparing high-purity semi-insulating silicon carbide monocrystalline, improves crystal growth quality.
According to the one aspect of the application, a kind of preparation method of high-purity semi-insulating silicon carbide monocrystalline, the system are provided
Preparation Method includes the following steps:
1) it assembles: raw material area and seed crystal is set in crucible, and it is opposite with the seed crystal that at least one is placed by the raw material area
Silicon carbide polycrystalline block；
2) long brilliant: the crucible being completed to be placed in long crystal furnace, control long crystal furnace crystal growing condition makes the silicon carbide
Polycrystalline block distillation is phase feed, and the phase feed carries out long crystalline substance from raw material area gas phase transmission to seed crystal, is made high-purity half absolutely
Edge single-crystal silicon carbide；
Wherein, cellular structure is arranged in the silicon carbide polycrystalline block, and gas phase is arranged close to one end of seed crystal in the cellular structure
It exports, the partial gas phase raw material in raw material area is by cellular structure from gaseous phase outlet gas phase transmission to seed crystal.
Optionally, the cellular structure is the through-hole being axially arranged along the silicon carbide polycrystalline block.
Preferably, the cellular structure and the central area of the seed crystal are correspondingly arranged.
Optionally, multiple silicon carbide polycrystalline blocks are arranged in the raw material area, and the multiple silicon carbide polycrystalline block is along the crucible
Axial arranging, and radial passage is formed between adjacent silicon carbide polycrystalline block, the radial passage and the cellular structure connect
It is logical.Transmission of the phase feed from the radial passage between silicon carbide polycrystalline bulk to cellular structure is conducive to improve rate of sublimation, mention
Gao Changjing efficiency.
Optionally, the transmission that phase feed can be thus achieved is not contacted between adjacent SiC policrystalline silicon block, it is preferable that described
The width of radial passage is 5-10mm, and the width of the radial passage, which is capable of providing space, makes silicon carbide block sufficiently distil, and is risen
The gaseous component that China generates can radially temperature gradient collect to growth chamber center, and finally transmit along axial-temperature gradient
To seed crystal, to realize the effect of " rectification ".
Preferably, the silicon carbide polycrystalline block is set as the circular ring structure being adapted with the crucible internal diameter, the duct knot
Structure is cylindrical space.
It is highly preferred that the ratio of the outer diameter of the internal diameter of the cellular structure and the silicon carbide polycrystalline block is 0.25-0.5.
Most preferably, the ratio of the outer diameter of the internal diameter of the cellular structure and the silicon carbide polycrystalline block is 1/3.The cellular structure with
The setting of the ratio of the outer diameter of silicon carbide polycrystalline block, the consistency that phase feed can be kept to transmit.
Optionally, the silicon carbide polycrystalline block with a thickness of 5-30mm.Optionally, the thickness of the silicon carbide polycrystalline block
Range lower limit is selected from 10mm, 15mm, 20mm or 25mm, and the upper limit is selected from 10mm, 15mm, 20mm or 25mm.Preferably, the carbonization
Policrystalline silicon block with a thickness of 15-20mm.Silicon carbide polycrystalline block diameter should be depending on using crucible internal diameter when crystal growth.
Optionally, the raw material area includes the first raw material area and the second raw material area, and the first raw material area and the second raw material are distinguished
The two sides of seed crystal are not set.First raw material area and the second raw material area are located at the high-temperature region of thermal field, and seed crystal is located at thermal field
Low-temperature space heats silicon carbide polycrystalline bulk at high temperature and is allowed to distil and gaseous component is made to be quickly transferred to seed crystal from upper and lower two
Place's crystallization forms two pieces of single-crystal silicon carbides up and down, to efficiently prepare high-purity alpha-SiC monocrystalline.
Phase feed is transmitted to seed from the cellular structure and radial passage being placed in crucible between upper silicon carbide polycrystalline block upwards
Brilliant place simultaneously crystallizes, and cellular structure and radial passage of the phase feed under being placed in crucible between silicon carbide polycrystalline block are transmitted to downwards
It at seed crystal and crystallizes, to realize the synchronous growth of SiC single crystal up and down.
Silicon carbide polycrystalline block used in this application is compared to sic powder: 1) purity is higher；2) size, shape and crystal form
Consistency is good；3) silicon carbide polycrystalline block is fixed easily above seed crystal, and under the conditions of reasonable thermal field, gas phase transmission is the same as under seed crystal
The silicon carbide polycrystalline block in portion is consistent, grows two pieces of quality stabilizations, consistent carbon simultaneously using a seed crystal to be easier to realize
SiClx monocrystalline.
Optionally, the long crystalline substance of the step 2) includes: the first crystal growing stage: will be lazy by being filled in the long crystal furnace that vacuumizes
Property gas to 200-400mbar, be warming up to not less than 2100 DEG C, long crystalline substance 10-30h；Second crystal growing stage: with 1-10mbar/h's
Rate keeps to long crystalline substance terminating after being depressurized to 10-50mabr.
Optionally, the ratio of the volume in the long crystal furnace and the flow for being filled with inert gas is 200L:50-
100SLM。
Preferably, the ratio of the volume in the long crystal furnace and the flow for being filled with inert gas is 200L:60-
90SLM。
Usual SiC powder material bulk density is about 1.0g/cm3, and polycrystalline Si C block density is about 2.8~3.0g/cm3,
It is much higher than powder bulk density, and it is very fast that higher volume density will lead to crystal growth rate.The preparation method initial stage of the application
Rising to relatively high growth pressure is the rate of sublimation in order to control dense multicrystalline block, is caused to avoid too fast rate of sublimation
The gaseous component reacted at seed crystal is excessive and causes forming core disorder；Growth pressure is reduced later, is to step up polycrystalline block
The growth rate of body is stablized with keeping the gas phase reaction component at seed crystal sufficient.
A kind of preparation method as silicon carbide polycrystalline block includes: that the carborundum powder by impurity content not higher than 10ppm is set
It in graphite crucible, is sublimed up at the top of graphite crucible with the condition of 2100-2300 DEG C of temperature and pressure 5-10mbar, distillation is made
The first silicon carbide polycrystalline block obtained carries out mechanical treatment, and first silicon carbide polycrystalline block is made to have hollow cellular structure, obtains described
Silicon carbide polycrystalline block.
The preparation of silicon carbide polycrystalline block carries out polycrystalline bulk preparation using the SiC synthesis powder with certain purity, leads to
The progress high temperature, low-pressure heating in high purity graphite crucible is crossed, makes sic powder rapid sublimation and is tied at the top of graphite crucible
Crystalline substance is at polycrystalline bulk.Silicon carbide polycrystalline block growth rate is very fast, and without controlling defect in silicon carbide polycrystalline block growth course
The problems such as, therefore the preparation of silicon carbide polycrystalline block can be rapidly completed in short-term.Cellular structure is as subsequent silicon carbide polycrystalline block liter
Gaseous component transmission channel when magnificent.
According to the one aspect of the application, a kind of preparation method of any of the above-described high-purity semi-insulating silicon carbide monocrystalline is provided
Used in crucible assembly include:
Crucible, the crucible include the crucible cover of Crucible body and lid conjunction in the Crucible body；
Seed holder, the seed holder are fixed in the crucible, and the seed holder is for fixing the seed crystal；With
The raw material area in the crucible is arranged in polycrystalline block bracket, the polycrystalline block bracket, and the polycrystalline block bracket is used for
Support the silicon carbide polycrystalline block.
Optionally, the middle part of the crucible is arranged in the seed holder, and the polycrystalline block bracket is separately positioned on described
Above and below seed holder.
Preferably, the polycrystalline block bracket includes multiple single layer polycrystalline block brackets of split settings.
Preferably, at least one of the seed holder, polycrystalline block bracket, Crucible body and crucible cover are graphite material
Matter.
As an implementation, silicon carbide polycrystalline block obtained is sequentially placed on polycrystalline block bracket, by silicon carbide
Polycrystalline block and polycrystalline block bracket are successively stacked in inside crucible, and center is used to place the seed crystal of crystal growth.
According to the another aspect of the application, a kind of high-purity semi-insulating silicon carbide monocrystalline is provided, by any of the above-described institute
The method for the high-purity semi-insulating silicon carbide monocrystalline stated is prepared or, crucible assembly described in its use is prepared.
According to another aspect of the application, a kind of application of high-purity semi-insulating silicon carbide monocrystalline, the application are provided
Application selected from high-purity semi-insulating silicon carbide monocrystalline in preparation single crystalline substrate, chip or electronic product.
Optionally, the electronic product is selected from mobile phone or computer.
In the application, the raw material area is located at the high-temperature region of thermal field, and seed crystal is located at the low-temperature space of thermal field, and phase feed utilizes
Axial-temperature gradient carries out long crystalline substance from raw material area gas phase transmission to seed crystal.
In the application, SLM is mark condition (0 DEG C, 1atm) L/min.
The beneficial effect of the application includes but is not limited to:
1, according to the preparation method of the high-purity semi-insulating silicon carbide monocrystalline of the application, with the silicon carbide with cellular structure
Polycrystalline block prepares the long brilliant high-efficient of high-purity semi-insulating silicon carbide monocrystalline；On the one hand, two pieces of the growth simultaneously on a piece of seed crystal
Single-crystal silicon carbide preparation cost can be greatly reduced in single-crystal silicon carbide；On the other hand, with the single-crystal silicon carbide of a piece of seed crystal preparation
It can guarantee to the greatest extent the proximity of monocrystalline quality, to improve the quality conformance of single-crystal silicon carbide and substrate.
2, according to the preparation method of the high-purity semi-insulating silicon carbide monocrystalline of the application, be conducive to the distillation point of silicon carbide polycrystalline block
Gaseous component needed for solving crystal growth；Also, the gaseous component that the setting of cellular structure decomposites silicon carbide polycrystalline block
It can be transmitted along unified path, to ensure that gas phase spreads defeated stability and consistency, and then after ensure that
The crystalline quality of continuous monocrystalline.
3, it according to the preparation method of the high-purity semi-insulating silicon carbide monocrystalline of the application, can be given birth to simultaneously using the same seed crystal
Long two pieces of single-crystal silicon carbide ingots, at low cost, long crystalline substance is high-efficient, long brilliant path is short and gas phase transmission path is easy to control.
4, according to the preparation method of the high-purity semi-insulating silicon carbide monocrystalline of the application, pass through the long brilliant of control single-crystal silicon carbide
Pressure change and pressure value, avoid the compactness due to silicon carbide polycrystalline block and cause to prepare high-purity semi-insulating silicon carbide list
Brilliant forming core disorder, improves crystal growth quality.
5, according to the high-purity semi-insulating silicon carbide monocrystalline of the application, purity is high, defect is few, quality is high and uniformity is good.
6, according to the high-purity semi-insulating silicon carbide single crystalline substrate of the application, purity is high, defect is few, quality is high and uniformity
It is good.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 be the invention relates to high-purity semi-insulating silicon carbide monocrystalline long crystalline substance in the signal of crucible assembly section
Figure.
Fig. 2 be the invention relates to support polycrystalline block polycrystalline block support schematic diagram.
Specific embodiment
For the clearer general idea for illustrating the application, carry out in an illustrative manner with reference to the accompanying drawings of the specification detailed
It describes in detail bright.
It can be more clearly understood that the above objects, features, and advantages of the application, with reference to the accompanying drawing and specific implementation
The application is further described in detail in mode.It should be noted that in the absence of conflict, embodiments herein
And the feature in embodiment can be combined with each other.
Many details are explained in the following description in order to fully understand the application, still, the application may be used also
To be implemented using other than the one described here other modes, therefore, the protection scope of the application is not by described below
Specific embodiment limitation.
In addition, in the description of the present application, it is to be understood that term " center ", "upper", "lower", "front", "rear",
The orientation of the instructions such as "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside", " axial direction ", " radial direction ", " circumferential direction "
Or positional relationship is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description the application and simplifies description, and
It is not that the device of indication or suggestion meaning or element must have a particular orientation, be constructed and operated in a specific orientation, therefore
It should not be understood as the limitation to the application.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include one or more this feature.In the description of the present application, the meaning of " plurality " is two or more, remove
It is non-separately to have clearly specific restriction.
In this application unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected, can also be communication；It can be directly connected, can also indirectly connected through an intermediary, it can be with
It is the interaction relationship of the connection or two elements inside two elements.For the ordinary skill in the art, may be used
To understand the concrete meaning of above-mentioned term in this application as the case may be.
In this application unless specifically defined or limited otherwise, fisrt feature in the second feature " on " or " down " can be with
It is that the first and second features directly contact or the first and second features pass through intermediary mediate contact.In retouching for this specification
In stating, the description of reference term " one embodiment ", " some embodiments ", " example ", " specific example " or " some examples " etc.
Mean that particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one of the application
In embodiment or example.In the present specification, schematic expression of the above terms are not required to be directed to identical implementation
Example or example.Moreover, particular features, structures, materials, or characteristics described can be in any one or more embodiment or examples
In can be combined in any suitable manner.
Unless otherwise instructed, the raw material in embodiments herein, catalyst and gas are bought by commercial sources.
Analysis method is as follows in embodiments herein:
1, total using Thermo Fisher company Element GD-PLUS type double focusing glow discharge mass spectroscopy instrument row
Impurity content analysis, Al element, Fe element, Ni element, B element, P element, S element, Cl constituent content analysis.
With reference to Fig. 1,2, this application discloses crucibles used in a kind of method for preparing high quality high-purity silicon carbide monocrystalline
Component schematic cross-section.Crucible assembly includes crucible, seed holder and polycrystalline block bracket 300.Crucible includes 110 He of Crucible body
Lid closes the crucible cover 120 in Crucible body 110, at least one seed holder, the raw material area in Crucible body 110 are arranged in crucible
Polycrystalline block bracket 300 is set.
Seed holder is fixed on the mode in crucible without limiting, and needs to be fixed in crucible not according to seed crystal 400
With position, different fixed forms is set.For example, when seed crystal 400 is fixed on the middle part of crucible, seed holder be set as relative to
The inwardly protruded boss of 110 inner sidewall of Crucible body or seed crystal 400 are adhered to 110 inner sidewall of Crucible body；When seed crystal 400 is solid
When being scheduled on the top of crucible, seed crystal 400 adheres to or is fastened on crucible cover medial surface；When seed crystal 400 is fixed on the bottom of crucible,
Seed crystal 400 can be directly placed at 110 bottom of Crucible body.
As long as support silicon carbide polycrystalline block 500 may be implemented in polycrystalline block bracket 300, not to the structure of polycrystalline block bracket
It is defined.As an implementation, polycrystalline block bracket 300 includes annular brace column and is fixed on the inwardly protruding of support column
At least one supporting table；Preferably, support column extends along the inner sidewall of Crucible body 110, and supporting table is along Crucible body 110
It radially extends.Implement as preferred, polycrystalline block bracket 300 includes annular brace column and a supporting table, when the multiple carbon of use
When SiClx polycrystalline block 500 is as raw material, after silicon carbide polycrystalline block 500 is placed in polycrystalline block bracket 300, by silicon carbide polycrystalline block
500 and polycrystalline block bracket 300 be successively stacked in inside crucible, 110 center of Crucible body is used to place the seed crystal of crystal growth
400, the fixed form that silicon carbide polycrystalline block 500 is separately fixed above and below seed crystal 400 may be implemented, and in seed crystal
Brilliant single-crystal silicon carbide 610 and single-crystal silicon carbide 620 are grown above and below in the of 400 respectively.
Further, seed holder, polycrystalline block bracket, Crucible body and crucible cover are graphite material, preferably high-purity stone
Ink.
It as an implementation, the use of the method that crucible assembly prepares high-purity semi-insulating silicon carbide monocrystalline include following steps
It is rapid:
1) it assembles: raw material area being set in crucible and at least one silicon carbide opposite with seed crystal is placed in seed crystal, raw material area
Polycrystalline block, raw material area are located at high-temperature region, and seed crystal is located at low-temperature space, and cellular structure is arranged in silicon carbide polycrystalline block, and cellular structure is close
Gaseous phase outlet is arranged in one end of seed crystal, and the partial gas phase raw material A in raw material area passes through cellular structure from gaseous phase outlet gas phase transmission
To seed crystal；
2) long brilliant: the crucible being completed to be placed in long crystal furnace, control long crystal furnace crystal growing condition makes the policrystalline silicon that is carbonized
Block distillation is phase feed, and phase feed carries out long crystalline substance from raw material area gas phase transmission to seed crystal, high-purity semi-insulating silicon carbide is made
Monocrystalline；
The region that silicon carbide polycrystalline block is placed in graphite crucible main body is raw material area.
With reference to Fig. 1, cellular structure can be through-hole or groove structure, and groove structure is the structure being recessed relative to seed crystal；
Preferably, cellular structure is the through-hole being axially arranged along silicon carbide polycrystalline block；It is highly preferred that the center of cellular structure and seed crystal
Domain is correspondingly arranged.Cellular structure is conducive to improve the surface area of the distillation of polycrystalline block, improves rate of sublimation, improves long brilliant rate.
Long crystalline substance raw material can be one or more silicon carbide polycrystalline blocks.When raw material is multiple silicon carbide polycrystalline blocks, multiple carbon
The structure of SiClx polycrystalline block can be identical or different；Preferably, the structure of multiple silicon carbide polycrystalline blocks is identical, and multiple silicon carbide are more
Along the axial arranging of crucible, the cellular structure of silicon carbide polycrystalline block is correspondingly arranged crystal block, and between adjacent silicon carbide polycrystalline block
Radial passage is formed, radial passage is connected to cellular structure.The arrangement mode of multiple silicon carbide polycrystalline blocks, not only further increases
Long brilliant efficiency, and be conducive to further increase the purity of single-crystal silicon carbide obtained.
Further, silicon carbide polycrystalline block is set as the circular ring structure being adapted with crucible internal diameter, and cellular structure is to form circle
Cylindrical space.Preferably, the ratio of the outer diameter of the internal diameter of cellular structure and silicon carbide polycrystalline block is 0.25-0.5.Cellular structure with
The setting of the ratio of the outer diameter of silicon carbide polycrystalline block, the consistency that phase feed can be kept to transmit.
Silicon carbide polycrystalline block with a thickness of 5-30mm；Preferably, silicon carbide polycrystalline block with a thickness of
15-20mm.The thickness of the silicon carbide polycrystalline block is conducive to the abundant distillation of silicon carbide, at the same guarantee block quantity with
Sufficient gas phase reaction component is provided.Silicon carbide polycrystalline block diameter should be depending on using crucible internal diameter when crystal growth.
In order to further increase long brilliant efficiency and reduce cost.Raw material area includes the first raw material area and the second raw material area, the
One raw material area and the second raw material area are separately positioned on the two sides of seed crystal.First raw material area and the second raw material area are located at thermal field
High-temperature region, seed crystal are located at the low-temperature space of thermal field, heat at high temperature silicon carbide polycrystalline bulk be allowed to distil and make gaseous component from
It is quickly transferred at upper and lower two at seed crystal and crystallizes to form two pieces of single-crystal silicon carbides up and down, to efficiently prepare high-purity alpha-SiC list
It is brilliant.
As an implementation, the long crystal method of high-purity semi-insulating silicon carbide monocrystalline includes the following steps:
The preparation of silicon carbide polycrystalline block: the carborundum powder by impurity content not higher than 10ppm is placed in graphite crucible, with temperature
The condition of 2000-2300 DEG C of degree and pressure 5-50mbar sublime up at the top of graphite crucible, be just carbonized policrystalline silicon obtained to distillation
Block carries out mechanical treatment, and first silicon carbide polycrystalline block is made to have hollow cellular structure, obtains the silicon carbide polycrystalline block；
First crystal growing stage: being placed in crucible post package for seed crystal and silicon carbide polycrystalline block, and the crucible of encapsulation is placed in life
Long burner hearth and seal vacuumize, after vacuum at room temperature with gas flow be 50-100SLM be passed through into 200L burner hearth it is lazy
Property gas (preferably argon gas and helium) rapid pressure 200mbar-400mbar；After boosting, temperature is slowly increased to 2100 DEG C
Silicon carbide polycrystalline block is sublimed up at seed crystal to crystallize, keep 10-30h forming core to terminate under high pressure；
Second crystal growing stage: 10-50mabr is depressurized to gradually with the rate of 1-10mbar/h, steps up polycrystalline bulk
Growth rate is stablized with keeping the gas phase reaction component at seed crystal sufficient.
High-purity silicon carbide monocrystalline is prepared according to above-mentioned long crystal method, with reference to Fig. 1, the crucible assembly used includes: seed crystal position
Among crucible, the first raw material area is located at the top of seed crystal and the second raw material area and is located at below seed crystal, is arranged 5 in the first raw material area
A silicon carbide polycrystalline block, is arranged 5 silicon carbide polycrystalline blocks in the second raw material area, silicon carbide polycrystalline block structure it is identical and with crucible,
The setting of seed crystal coaxial line has radial passage between adjacent silicon carbide polycrystalline block.
Specific preparation parameter and above-mentioned long crystal method difference are as shown in table 1, and the internal diameter and silicon carbide of cellular structure are more
The ratio of the outer diameter of crystal block is r/R, and the inert gas being filled with is argon gas, and high-purity semi-insulating silicon carbide monocrystalline 1#-4#, comparison is made
High-purity semi-insulating silicon carbide monocrystalline D1#-D3#.Compare high-purity semi-insulating silicon carbide monocrystalline D3# and high-purity semi-insulating silicon carbide monocrystalline
1# the difference is that, silicon carbide polycrystalline block at the beginning of the first raw material area and the second raw material area are respectively set one, volume with
The volume of silicon carbide polycrystalline block in high-purity semi-insulating silicon carbide monocrystalline 1# is identical.
Table 1
Known to according to the result of table 1: preparing high-purity semi-insulating silicon carbide list with the silicon carbide polycrystalline block with cellular structure
Brilliant long crystalline substance is high-efficient, at low cost, long brilliant path is short, gas phase transmission path is easy to control.
Single-crystal silicon carbide preparation cost can be greatly reduced by growing two pieces of single-crystal silicon carbides simultaneously on a piece of seed crystal；Together
The single-crystal silicon carbide of a piece of seed crystal preparation can guarantee to the greatest extent the proximity of monocrystalline quality, to improve single-crystal silicon carbide
And the quality conformance of substrate.
The rate of sublimation of polycrystalline block is influenced by silicon and carbon component vapor partial pressure.Since polycrystalline block is fine and close polycrystalline
Body structure is expected between block there is no the vapor partial pressure of silicon and carbon component is poor, silicon carbide block if imporosity exists between block
Can not just distil gaseous component needed for decompositing crystal growth.In addition, the setting in duct enables the gaseous component decomposited
It is transmitted along unified path, to ensure that gas phase spreads defeated stability and consistency, and then ensure that subsequent list
Brilliant crystalline quality.This method is equally applicable to seed crystal and is placed in the scheme of polycrystalline block two sides.
By the long brilliant pressure change and pressure value of control single-crystal silicon carbide, the cause due to silicon carbide polycrystalline block is avoided
Close property and lead to the forming core disorder for preparing high-purity semi-insulating silicon carbide monocrystalline, improve crystal growth quality.
By obtained high-purity semi-insulating silicon carbide monocrystalline 1#-4# obtained, comparison high-purity semi-insulating silicon carbide monocrystalline D1#-
D3# is similarly cut respectively, is ground and polishing method, be made respectively high-purity semi-insulating silicon carbide single crystalline substrate 1#-4#,
High-purity semi-insulating silicon carbide single crystalline substrate D1#-D3# is compared, purity is high, defect is few, quality is high and uniformity is good.
The above, only embodiments herein, the protection scope of the application is not by these specific embodiments
Limitation, but determined by following claims.To those skilled in the art, the application can have various
Change and variation.All any modification, equivalent replacement, improvement and so within the technical idea and principle of the application, should all
Comprising within the scope of protection of this application.
Claims (11)
1. a kind of preparation method of high-purity semi-insulating silicon carbide monocrystalline, which is characterized in that the preparation method includes the following steps:
1) it assembles: raw material area being set in crucible and at least one carbon opposite with the seed crystal is placed in seed crystal, the raw material area
SiClx polycrystalline block；
2) long brilliant: the crucible being completed to be placed in long crystal furnace, control long crystal furnace crystal growing condition makes the carbonization policrystalline silicon
Block distillation is phase feed, and the phase feed carries out long crystalline substance from raw material area gas phase transmission to seed crystal, high-purity semi-insulating carbon is made
SiClx monocrystalline；
Wherein, cellular structure is arranged in the silicon carbide polycrystalline block, and gaseous phase outlet is arranged close to one end of seed crystal in the cellular structure,
Partial gas phase raw material in raw material area is by cellular structure from gaseous phase outlet gas phase transmission to seed crystal.
2. preparation method according to claim 1, which is characterized in that the cellular structure is along the silicon carbide polycrystalline block
The through-hole being axially arranged；
Preferably, the cellular structure and the central area of the seed crystal are correspondingly arranged.
3. preparation method according to claim 2, which is characterized in that multiple silicon carbide polycrystalline blocks are arranged in the raw material area,
The multiple silicon carbide polycrystalline block and is formed radial logical along the axial arranging of the crucible between adjacent silicon carbide polycrystalline block
Road, the radial passage are connected to the cellular structure；
Preferably, the silicon carbide polycrystalline block is set as the circular ring structure being adapted with the crucible internal diameter, and the cellular structure is
Cylindrical space；
It is highly preferred that the ratio of the outer diameter of the internal diameter of the cellular structure and the silicon carbide polycrystalline block is 0.25-0.5.
4. preparation method according to claim 1, which is characterized in that the silicon carbide polycrystalline block with a thickness of 5-30mm；
Preferably, the silicon carbide polycrystalline block with a thickness of 15-20mm.
5. preparation method according to claim 1, which is characterized in that the raw material area includes that the first raw material area and second are former
Expect that area, first raw material area and the second raw material area are separately positioned on the two sides of the seed crystal.
6. preparation method according to claim 1, which is characterized in that the long crystalline substance of the step 2) includes:
First crystal growing stage: inert gas is filled with to 200-400mbar by passing through in the long crystal furnace vacuumized, is warming up to and is not less than
2100 DEG C, long crystalline substance 10-30h；
Second crystal growing stage: it is depressurized to after 10-50mabr with the rate of 1-10mbar/h and keeps to long crystalline substance terminating.
7. preparation method according to claim 6, which is characterized in that the volume in the long crystal furnace is filled with inertia with described
The ratio of the flow of gas is 200L:50-100SLM；
Preferably, the ratio of the volume in the long crystal furnace and the flow for being filled with inert gas is 200L:60-90SLM.
8. crucible assembly used in a kind of preparation method of any of claims 1-7 characterized by comprising
Crucible, the crucible include the crucible cover of Crucible body and lid conjunction in the Crucible body；
Seed holder, the seed holder are fixed in the crucible, and the seed holder is for fixing the seed crystal；With
The raw material area in the crucible is arranged in polycrystalline block bracket, the polycrystalline block bracket, and the polycrystalline block bracket is used to support
The silicon carbide polycrystalline block.
9. crucible assembly according to claim 8, which is characterized in that the seed holder is arranged in the crucible
Portion, the polycrystalline block bracket are separately positioned on above and below the seed holder；
Preferably, the polycrystalline block bracket includes multiple single layer polycrystalline block brackets of split settings.
10. a kind of high-purity semi-insulating silicon carbide monocrystalline, which is characterized in that it is by method of any of claims 1-7
It is prepared or, it is prepared using crucible assembly described in claim 8 or 9.
11. a kind of application of high-purity semi-insulating silicon carbide monocrystalline described in any one of claim 10, which is characterized in that the application is selected from
Application of the high-purity semi-insulating silicon carbide monocrystalline in preparation single crystalline substrate, chip or electronic product.
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