CN110062745A - The manufacturing method of alpha-silicon nitride powders, polycrystalline silicon ingot casting release agent and polycrystalline silicon ingot casting - Google Patents
The manufacturing method of alpha-silicon nitride powders, polycrystalline silicon ingot casting release agent and polycrystalline silicon ingot casting Download PDFInfo
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- CN110062745A CN110062745A CN201780076707.2A CN201780076707A CN110062745A CN 110062745 A CN110062745 A CN 110062745A CN 201780076707 A CN201780076707 A CN 201780076707A CN 110062745 A CN110062745 A CN 110062745A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
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Abstract
The purpose of the present invention is to provide a kind of alpha-silicon nitride powders, its release agent that can be suitably used as polycrystalline silicon ingot casting, even if the release property of polycrystalline silicon ingot casting is also good when the melting temperature of silicon of the release agent when increasing unidirectional solidification or when increasing the melting time of silicon.There is provided a kind of alpha-silicon nitride powders, which is characterized in that specific surface area 0.4m2/ g or more and 5m2/ g or less, wherein, the ratio of β type silicon nitride is 70 mass % or more, D50 is 2 μm or more and 20 μm or less, D90 is 8 μm or more and 60 μm hereinafter, the content ratio of Fe is 100ppm hereinafter, the content ratio of Al is 100ppm or less, the content ratio of metal impurities in addition to Fe and Al adds up to 100ppm hereinafter, the crystallite diameter of β type silicon nitride is set as DCWhen, DCFor 300nm or more.
Description
Technical field
The present invention relates to the silicon nitrides that can be formed in the mould with the adaptation of mold and the good release layer of release property
Powder, more particularly, to the alpha-silicon nitride powders for being suitable for release agent as polycrystalline silicon ingot casting.
Background technique
Polycrystalline silicon substrate used in solar battery is usually by using vertical Bu Liziman furnace to make molten silicon unidirectional solidification
And the polycrystalline silicon ingot casting manufactured obtains.Polycrystalline silicon substrate requires high performance and cost effective, in order to cope with the requirement, inhibits
Impurity being mixed into polycrystalline silicon ingot casting and to improve the yield rate of polycrystalline silicon ingot casting be critically important when the unidirectional solidification of molten silicon.
In the unidirectional solidification using the molten silicon of vertical Bridgman method, using the mold of quartz system etc., in order to improve polysilicon casting
The yield rate of ingot, mold require the release property of polycrystalline silicon ingot casting good, are coated with usually using inner wall (face contacted with molten silicon)
There is the mold of the release agent comprising alpha-silicon nitride powders.
Vertical Bu Liziman furnace its structurally, heat escape downwards from mold bottom surface, therefore, mold in above-below direction can
Big temperature gradient is generated, the temperature on mold top relatively heightens.In recent years, towards the polycrystalline silicon ingot casting of solar cell substrate
Increasingly tend to enlargement, temperature is increased when the silicon (fusing point: 1414 DEG C) of cast base sufficiently melts, sometimes because of cloth
The construction of Li Ziman furnace and so that the temperature on mold top is become 1500 DEG C or more such high temperature.In this case, it produces sometimes
Raw following problem: on the high mold top of temperature, the release property of polycrystalline silicon ingot casting is deteriorated or release layer is attached from mold peeling
In polycrystalline silicon ingot casting etc..Therefore, the release layer requirement of polycrystalline silicon ingot casting: though in high temperature, such as 1500 DEG C or more progress singly
To solidification, the adaptation of the release property of polycrystalline silicon ingot casting, release layer and mold is also good.
Based on such background, it is expected that developing a kind of alpha-silicon nitride powders, it is capable of forming following release layer, the demoulding
When even if layer improves unidirectional solidification to improve the yield rate of the polycrystalline silicon ingot casting for the substrate that can apply to solar battery
It is the release property of polycrystalline silicon ingot casting, also good with the adaptation of mold when the melting temperature of silicon.In addition, in order to obtain the more of strip
Crystal silicon ingot casting and when using the big mold of size in the up-down direction, especially mold top can be exposed to for a long time under high temperature,
Therefore, it is desirable to a kind of alpha-silicon nitride powders be developed, when which is capable of forming the melting of silicon when unidirectional solidification
Between it is long, the release property of polycrystalline silicon ingot casting, with the adaptation of mold also good release layer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-261832 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-71864 bulletin
Summary of the invention
Problems to be solved by the invention
Although describing in patent document 1: the alpha-silicon nitride powders that the concentration of Fe and D50 are set in specific range can
Firm release layer is formed, it is useful for manufacturing the polysilicon of high conversion efficiency of solar battery, still, nitridation is not recorded
Crystal structure, the crystallite diameter of Si powder, polysilicon when also not recording the melting temperature for increasing silicon or increasing the melting time of silicon
The adaptation of the release property of ingot casting, release layer and mold.
In addition, being shown in patent document 2: the ratio and specific metal impurities of size distribution and β phase being set in specific
The alpha-silicon nitride powders of range can reduce the impurity mixed volume in polycrystalline silicon ingot casting, be able to suppress the peeling of release agent, still,
Which show only the alpha-silicon nitride powders with lesser D50 and D90, the alpha-silicon nitride powders of the ratio of the β phase with 50 mass %
Be best able to inhibit release agent peeling, not record alpha-silicon nitride powders crystallite diameter, also do not record increase silicon melting temperature,
Or when increasing the melting time of silicon the release property of polycrystalline silicon ingot casting, release layer and mold adaptation.
Therefore, the object of the present invention is to provide a kind of alpha-silicon nitride powders, can suitably be used as polycrystalline silicon ingot casting
Release agent, even if when the melting temperature of silicon of the release agent when increasing unidirectional solidification or when increasing the melting time of silicon,
The release property of polycrystalline silicon ingot casting is also good.
The solution to the problem
The inventors of the present invention have made intensive studies to solve foregoing problems, discovery: using following alpha-silicon nitride powders
When release layer to form polycrystalline silicon ingot casting casting mold, even if the melting temperature of silicon when increasing unidirectional solidification, polysilicon
The release property and release layer of ingot casting are also good to the adaptation of mold, so as to complete the present invention, the alpha-silicon nitride powders tool
Have a specific specific surface area, the ratio and specific size distribution of specific β type silicon nitride, specific metal impurities and its other than
The content ratios of metal impurities be less than specific ratio, crystallite diameter is greater than specific value.That is, the present invention relates to things below
?.
(1) a kind of alpha-silicon nitride powders, which is characterized in that the specific surface area by BET method measurement is 0.4m2/ g or more and
5m2/ g is hereinafter, the ratio of β type silicon nitride is 70 mass % or more, by the volume reference measured by laser diffraction scattering method
When 50% partial size is set as D50,90% partial size is set as D90, D50 is 2 μm or more and 20 μm hereinafter, D90 is 8 μm or more and 60 μm
Hereinafter, the content ratio of Fe is 100ppm hereinafter, the content ratio of Al is 100ppm hereinafter, metal impurities in addition to Fe and Al
Content ratio add up to 100ppm hereinafter, Williamson-Hall formula will be used by the powder x-ray diffraction of β type silicon nitride
The crystallite diameter for the β type silicon nitride that pattern calculates is set as DCWhen, DCFor 300nm or more.
(2) alpha-silicon nitride powders described in above-mentioned (1), which is characterized in that nitrogenized using Williamson-Hall formula by β type
The crystal strain for the β type silicon nitride that the powder X-ray diffraction pattern of silicon calculates is 0.8 × 10-4Below.
(3) alpha-silicon nitride powders described in above-mentioned (1) or (2), which is characterized in that the ratio table that will be calculated by aforementioned specific surface area
Area equivalent diameter is set as DBETWhen, DBET/DCIt (nm/nm) is 5 or less.
(4) alpha-silicon nitride powders described in any one of above-mentioned (1)~(3), which is characterized in that D50 is 3 μm or more.
(5) alpha-silicon nitride powders described in any one of above-mentioned (1)~(4), which is characterized in that D90 is 50 μm or less.
(6) alpha-silicon nitride powders described in any one of above-mentioned (1)~(5), which is characterized in that D90 is 13 μm or more.
(7) alpha-silicon nitride powders described in any one of above-mentioned (1)~(6), which is characterized in that the ratio of β type silicon nitride is big
In 80 mass %.
(8) alpha-silicon nitride powders described in any one of above-mentioned (1)~(7), which is characterized in that the content ratio of Fe is
20ppm is hereinafter, the content ratio of Al is 20ppm hereinafter, the content ratio of the metal impurities in addition to Fe and Al adds up to 20ppm
Below.
(9) alpha-silicon nitride powders described in any one of above-mentioned (1)~(8), which is characterized in that laser diffraction and scattering will be passed through
When 10% partial size of the volume reference of method measurement is set as D10, D10 is 0.5 μm or more and 8 μm or less.
(10) a kind of polycrystalline silicon ingot casting release agent, it includes the silicon nitride powders described in any one of above-mentioned (1)~(9)
End.
(11) a kind of manufacturing method of silicon ingot casting, which is characterized in that it is to solidify the molten silicon being contained in mold
The manufacturing method of polycrystalline silicon ingot casting, as aforementioned mold, using be coated on the contact surface of aforementioned melt silicon above-mentioned (1)~
Any one of (9) mold of the alpha-silicon nitride powders described in.
The effect of invention
Using alpha-silicon nitride powders of the invention, it is capable of providing the silicon nitride powder for being suitable for use as the release agent of polycrystalline silicon ingot casting
End, the melting temperature of silicon of the release agent when increasing unidirectional solidification or increase the melting time of silicon, can be improved
The release property and release layer of polycrystalline silicon ingot casting and the adaptation of mold.
Detailed description of the invention
Fig. 1 is the dress of combustion synthesis reaction used in the manufacture of the alpha-silicon nitride powders of embodiment 1~13 and comparative example 1~10
The schematic diagram set.
Specific embodiment
The embodiment of alpha-silicon nitride powders of the invention is described in detail.
(alpha-silicon nitride powders)
Alpha-silicon nitride powders of the invention are characterized in that, to be 0.4m by the specific surface area that BET method measures2/ g or more
And 5m2The ratio of/g alpha-silicon nitride powders below, β type silicon nitride is 70 mass % or more, will be surveyed by laser diffraction scattering method
When 50% partial size of fixed volume reference is set as D50,90% partial size is set as D90, D50 is 2 μm or more and 20 μm hereinafter, D90
For 8 μm or more and 60 μm hereinafter, the content ratio of Fe be 100ppm hereinafter, the content ratio of Al be 100ppm hereinafter, except Fe and
The content ratio of metal impurities other than Al adds up to 100ppm hereinafter, Williamson-Hall formula will be used by β type silicon nitride
The crystallite diameter of β type silicon nitride that calculates of powder X-ray diffraction pattern be set as DCWhen, DCFor 300nm or more.
Alpha-silicon nitride powders of the invention are 0.4m by the specific surface area that BET method measures2/ g or more and 5m2/ g or less.Compare table
Area is capable of forming and the good release layer of the adaptation of mold in the range.The ratio that alpha-silicon nitride powders are measured by BET method
Surface area may be 4.0m2/ g or less, 3.0m2/ g or less, 2.0m2/ g or less.
The ratio of the β type silicon nitride of alpha-silicon nitride powders of the invention is 70 mass % or more.The ratio of β type silicon nitride is should
When range, the release property, the good release layer of adaptation with mold that are capable of forming polycrystalline silicon ingot casting.From this viewpoint, β
The ratio of type silicon nitride is further preferably greater than 80 mass %.The ratio of β type silicon nitride can also be greater than 85 mass %, be greater than 90
Quality %, it is greater than 95 mass %, or 100 mass %.
Ingredient other than silicon nitride is preferably smaller than 3 mass % and then less than 1 mass %, particularly less than 0.1 mass %.
There are when ingredient other than silicon nitride, there is following worry: even if it is such when increasing unidirectional solidification to obtain the present invention
Silicon melting temperature or increase silicon melting time in the case where also good polycrystalline silicon ingot casting release property.
Alpha-silicon nitride powders of the invention are set as by 50% partial size of the volume reference measured by laser diffraction scattering method
When D50, D50 is 2 μm or more and 20 μm or less.When D50 is the range, the mutual adaptation of silicon nitride particle, silicon nitride particle
It is easy to become good with the adaptation of mold, and therefore the release layer of densification easy to form is capable of forming polycrystalline silicon ingot casting
Release property, the good release layer of adaptation with mold.D50 is preferably 3 μm or more.D50 may be 5 μm or more, 10 μm
Above, 15 μm or more.In addition, D90 is 8 μm or more and 60 μm or less when 90% partial size is set as D90.D90 is the range
When, the surface of release layer is easy smoothened, is capable of forming the good release layer of release property of polycrystalline silicon ingot casting.D90 is further
Preferably 50 μm or less, particularly preferably 40 μm or less.D90 may be 13 μm or more, 14 μm or more, 15 μm or more, 17 μm
Above, 20 μm or more, 30 μm or more.
Alpha-silicon nitride powders of the invention are set as by 10% partial size of the volume reference measured by laser diffraction scattering method
When D10, D10 is preferably 0.5 μm or more and 8 μm or less.D10 may be 0.6 μm or more, 0.7 μm or more, 1.0 μm or more,
2.0 μm or more, 4.0 μm or more, 6.0 μm or more.When D10 is the range, release layer is easier to densify, and is capable of forming polysilicon
The release property of ingot casting, the more good release layer of adaptation with mold.
The content ratio of the Fe of alpha-silicon nitride powders of the invention is 100ppm or less.When the content ratio of Fe is the range,
It is able to suppress in polycrystalline silicon ingot casting and is mixed into Fe, therefore, can be applied to the finished product of the polycrystalline silicon ingot casting of solar battery purposes
Rate is got higher.The content ratio of Fe is preferably 20ppm hereinafter, particularly preferably 10ppm or less, 5ppm or less.In addition, of the invention
The content ratio of the Al of alpha-silicon nitride powders is 100ppm or less.When the content ratio of Al is the range, it is able to suppress in polysilicon
Al is mixed into ingot casting, therefore, the yield rate that can be applied to the polycrystalline silicon ingot casting of solar battery purposes is got higher.Al containing than
Example is preferably 20ppm hereinafter, particularly preferably 10ppm or less, 5ppm or less.In addition, metal impurities in addition to Fe and Al
Content ratio adds up to 100ppm or less.When the content ratio of metal impurities in addition to Fe and Al is the range, it is able to suppress
It is mixed into the metal impurities in addition to Fe and Al in polycrystalline silicon ingot casting, therefore, can be applied to the polycrystalline of solar battery purposes
The yield rate of silicon ingot casting is got higher.The content ratio of metal impurities in addition to Fe and Al is preferably 20ppm hereinafter, particularly preferably
10ppm or less, 5ppm or less.
The β type silicon nitride that Williamson-Hall formula will be used to be calculated by the powder X-ray diffraction pattern of β type silicon nitride
Crystallite diameter be set as DCWhen, the D of alpha-silicon nitride powders of the inventionCFor 300nm or more.DCWhen for the range, even if increasing silicon
Melting temperature increases the melting time, and the adaptation of the release property and mold that are also capable of forming polycrystalline silicon ingot casting is good de-
Mold layer.It could be speculated that by making DCFor 300nm or more, thus even if when long with molten silicon at a high temperature of such as 1500 DEG C or more
Between contact, alpha-silicon nitride powders of the invention are also able to maintain that the structural stability of crystal.From this viewpoint, DCPreferably
600nm or more, more preferably 1000nm or more, 1500nm or more.
It is preferable to use Williamson-Hall formulas by the powder x-ray diffraction of β type silicon nitride for alpha-silicon nitride powders of the invention
The crystal strain for the β type silicon nitride that pattern calculates is 0.8 × 10-4Below.When the crystal strain of β type silicon nitride is the range, i.e.,
Make the melting temperature for increasing silicon, release property, the good release layer of adaptation with mold that can also form polycrystalline silicon ingot casting.It can
Speculate, by making aforementioned crystalline strain be 0.8 × 10-4Even if hereinafter, to be contacted for a long time under at higher temperature with molten silicon, originally
The alpha-silicon nitride powders of invention are also able to maintain that the structural stability of crystal.From this viewpoint, aforementioned crystalline strain is further excellent
It is selected as 0.6 × 10-4Hereinafter, particularly preferably 0.5 × 10-4Below, 0.4 × 10-4Below, 0.3 × 10-4Below.
Alpha-silicon nitride powders of the invention are preferably, and the specific surface area equivalent diameter calculated by aforementioned specific surface area is set as
DBETWhen, DBET/DCIt (nm/nm) is 5 or less.DBET/DCIt (nm/nm) may be 4 or less, 3 or less.DBET/DC(nm/nm) being should
When range, even if further increasing the melting temperature of silicon, it is also capable of forming the release property of polycrystalline silicon ingot casting and the adaptation of mold
Good release layer.Its reason is still uncertain, but can speculate are as follows: constitutes in a crystal grain of the silicon nitride of alpha-silicon nitride powders
The interfacial area hour of crystallite can further increase the knot of the crystal of silicon nitride when contacting for a long time with molten silicon at high temperature
Structure stability.
(polycrystalline silicon ingot casting release agent)
Polycrystalline silicon ingot casting of the invention release agent includes alpha-silicon nitride powders of the invention.Polycrystalline silicon ingot casting of the invention is used
In release agent, alpha-silicon nitride powders of the invention are principal component, also may include the ingredient other than silicon nitride, but can also be with
Only it is made of alpha-silicon nitride powders of the invention.
(manufacturing method of polycrystalline silicon ingot casting)
The manufacturing method of polycrystalline silicon ingot casting of the invention is illustrated below.The manufacturer of polycrystalline silicon ingot casting of the invention
Method is characterized in that, is the manufacture for making the polycrystalline silicon ingot casting of the molten silicon being contained in mold solidification (especially unidirectional solidification)
Method, as aforementioned mold, using with mold that alpha-silicon nitride powders of the invention are coated on the contact surface of aforementioned melt silicon.
(manufacturing methods of alpha-silicon nitride powders)
An example of the manufacturing method of alpha-silicon nitride powders of the invention is illustrated below.For silicon nitride powder of the invention
End, for example, synthesizing nitridation by the combustion synthesis method using the associated self-heating of the combustion reaction with silicon and propagation phenomenon
In silicon, silicon nitride combustion synthesis process, using specific manufacturing condition, specifically, with specific in raw material Si powder
Ratio mixed nitride Si powder as diluent, the metal for reducing raw material Si powder and the alpha-silicon nitride powders as diluent is miscellaneous
The content ratio of matter reduces the packed density of the mixture of Si powder and alpha-silicon nitride powders, carries out combustion reaction, makes anti-crushing strong
Small combustion product is spent, the small burning of the crushing strength that method that is small using size reduction energy and being not easy to be mixed into metal impurities will obtain
Product crushes, and thereby, it is possible to manufacture alpha-silicon nitride powders with the following characteristics, the feature are as follows: the content ratio of metal impurities
Less, the content ratio of β type silicon nitride is big, has the specific specific surface area of the present invention and particle diameter distribution, crystallite diameter greatly and crystallizes
It should become smaller.An example of the manufacturing method is specifically described below.
The preparation section > of < mixed raw material powder
Firstly, Si powder is mixed with the alpha-silicon nitride powders as diluent, mixed raw material powder is prepared.Conbustion synthesis is anti-
It should be 1800 DEG C or more of high temperature, therefore, melting/welding of silicon occur in the part that combustion reaction occurs sometimes.For inhibition
The purpose of the situation, it is preferred that in the range of not interfering the self propagation of combustion reaction, silicon nitride is added in raw material powder
Powder is as diluent.The adding rate of diluent be usually 10~50 mass % (silicon: the mass ratio of silicon nitride be 90:10~50:
It 50), and then is 15~40 mass %.In addition, the ratio of the β type silicon nitride of the combustion product obtained in adjustment combustion synthesis reaction
On the basis of example, NH can also be added4Cl, NaCl etc..These additives have reduced by sensible heat, latent heat and the endothermic reaction
The effect of reaction temperature.Here, the content ratio, the content ratio of Al of Fe in the mixed raw material powder obtained, except Fe and Al with
The content ratio of outer metal impurities is preferably set to 100ppm or less and then 50ppm or less, 10ppm or less respectively.Therefore, silicon
Powder, diluent alpha-silicon nitride powders it is preferable to use the powder of the few high-purity of the content ratio of metal impurities.In addition, raw material
The position that inner surface and blending agent of mixing vessel used in the mixing of powder etc. are contacted with raw material powder is preferably Al
And the raw material of the few nonmetallic system of content ratio of Fe etc..The mixed method of raw material powder is not particularly limited, for example, by using
In the case where ball milling mixing, the inner surface of mixing vessel is preferably made of resin, and the outer surface of blending agent is preferably silicon nitride system.
In addition, the heap density of mixed raw material powder is preferably smaller than 0.5g/cm3.In order to make the heap density of mixed raw material powder be less than 0.5g/
cm3, it is preferable to use heap density is 0.45g/cm3Si powder below is as raw material powder.The heap density of mixed raw material powder is less than
0.5g/cm3When, it is easy to make the crushing strength of block-like combustion product obtained in aftermentioned < combustion synthesis reaction process >
4MPa or less.
< combustion synthesis reaction process >
Then, the mixed raw material powder made burns in nitrogen containing atmosphere, makes the block-like combustion formed by silicon nitride
Burn product.For example, mixed raw material powder is contained in the containers such as graphite together with igniting agent, in combustion synthesis reaction device
It is interior to light igniting agent, cause the nitridation reaction of the silicon in mixed raw material powder by the nitridation combustion heat of igniting agent, keeps this anti-
It answers autobiography to cast to whole silicon to completion of combustion synthetic reaction, obtains the block-like combustion product formed by silicon nitride.
Here, the combustion product obtained preferably its crushing strength is 4MPa or less.The crushing strength of combustion product is 4MPa
When following, in crushing/classification process > of aftermentioned < combustion product, even if without metal impurities be mixed into become it is more or
The crystallinity of alpha-silicon nitride powders reduces the big crushing of such size reduction energy, can also be readily derived the specific specific surface of the present invention
Long-pending or size distribution (D50, D90 or D10) alpha-silicon nitride powders.
The crushing of < combustion product/classification process >
Then, coarse crushing is carried out to obtained block-like combustion product.The crushing means of coarse crushing are not particularly limited, and make
For crushing medium, it is preferable to use the raw material of the nonmetallic system of the few hard of the content ratio of Al and Fe etc., further preferably make
With the crushing medium of silicon nitride.Since combustion product is bulk, it is efficient for crush using kibbler roll, as roller
Formula crusher is preferably provided with the roller made of ceramics such as silicon nitride.
Alpha-silicon nitride powders obtained from the coarse crushing as above are sieved, especially coarse particle etc. is removed, by
This, can obtain alpha-silicon nitride powders of the invention.The sieve used that is sieved is preferably few nonmetallic of the content ratio of Al and Fe etc.
System, is preferably made of resin.
Furthermore, it is possible to carry out Crushing of Ultrafine to obtained alpha-silicon nitride powders according to desired specific surface area, D50 or D90.It is micro-
The crushing means of crushing are not particularly limited, and are crushed preferably by vibromill.The inner surface of the cylinder of vibromill and mixing
The position that medium etc. is contacted with raw material powder is preferably the raw material of the few nonmetallic system of the content ratio of Al and Fe etc..Cylinder it is interior
Surface is preferably made of resin, and blending agent is preferably silicon nitride system.It is suitable for condition (amplitude, vibration number, the crushing for adjusting vibromill
Time), alpha-silicon nitride powders desired specific surface area or size distribution (D50, D90 or D10), of the invention can be obtained.
As described above, alpha-silicon nitride powders of the invention are manufactured preferably by the manufacturing method of following alpha-silicon nitride powders:
Si powder is mixed with the alpha-silicon nitride powders as diluent, obtained mixed raw material powder is filled into container, benefit is passed through
Aforementioned Si powder is set to burn with the combustion synthesis method of the self-heating and propagation phenomenon associated with combustion reaction, and the burning to obtaining
Product is crushed, and in the manufacturing method, the content ratio of Fe of aforementioned mixed raw material powder, the content ratio of Al and removes Fe
Content ratio with the metal impurities other than Al is respectively 100ppm hereinafter, heap density is less than 0.5g/cm3, before further preferred
The crushing strength for stating combustion product is 4MPa hereinafter, using the powder of silicon nitride particularly preferably in the crushing of previous combustion product
Broken medium.
Embodiment
Being exemplified below concrete example, the present invention will be described in more detail.Alpha-silicon nitride powders of the invention, as raw material powder
Si powder that end uses, raw material mixed powder end and combustion product physical property measurement and alpha-silicon nitride powders of the invention are used for
The evaluation of the release property of polycrystalline silicon ingot casting when the release agent of mold is carried out using the following method.
(the measuring method and specific surface area equivalent diameter D of the specific surface area of alpha-silicon nitride powdersBETCalculation method)
The specific surface area of alpha-silicon nitride powders of the invention uses Mountech corporation Macsorb, inhales using based on nitrogen
Attached 1 method of BET is measured and finds out.
In addition, specific surface area equivalent diameter DBETAssume that the whole particles for constituting powder are the ball of same diameter, under utilization
State what formula (1) was found out.
DBET=6/ (ρS×S)···(1)
Here, ρS(pass through α-Si for the real density of silicon nitride3N4Real density 3186kg/m3、β-Si3N4Real density
3192kg/m3, α phase and β phase ratio calculate true average densities, as real density.), S be specific surface area (m2/g)。
(measuring method of the ratio of the β type silicon nitride of alpha-silicon nitride powders)
The ratio of the β type alpha-silicon nitride powders of alpha-silicon nitride powders of the invention calculates as follows.For silicon nitride powder of the invention
End utilizes the range with 0.02 ° of step-length at 15~80 ° of the angle of diffraction (2 θ) using the target and graphite monochromator formed by the pipe of copper
The timing step scan method for carrying out step-scan to X-ray detector carries out X-ray diffraction measure.Alpha-silicon nitride powders include to denitrogenate
In the case where ingredient other than SiClx, the peak of these ingredients is compared with the corresponding peak of the standard sample of these ingredients, by
This can find out the ratio of these ingredients.It is true by obtained powder X-ray diffraction pattern in following all examples and comparative example
Recognize alpha-silicon nitride powders of the invention to be only made of alpha-form si nitride and β type silicon nitride.In turn, the β of alpha-silicon nitride powders of the invention
The ratio of type silicon nitride utilizes G.P.Gazzara and D.P.Messier, " Determination of Phase Content
In of Si3N4by X-ray Diffraction Analysis ", Am.Ceram.Soc.Bull., 56 [9] 777-80 (1977)
The method of the Gazzara&Messier of record calculates.
(measuring method of D10, D50 and D90 of alpha-silicon nitride powders)
The size distribution of the Si powder used in alpha-silicon nitride powders of the invention, the present invention as raw material is surveyed as follows
It is fixed.Aforementioned powder is put into 0.2 mass % aqueous solution of calgon, using in the stainless steel for being equipped with diameter 26mm
The ultrasonic homogenizer of heart cone carries out 6 minutes decentralized processings with the output power of 300W, prepares weak solution, as measurement sample.Make
With laser diffraction/scattering formula particle size distribution analyzer (Nikkiso Company Limited MICROTRAC MT3000) to measurement sample
Size distribution be measured, obtain volume reference size distribution curve and its data.By obtained size distribution curve and
Its data calculates the Si powder used in D50, D90 and D10 and the present invention of alpha-silicon nitride powders of the invention as raw material
D50.
(alpha-silicon nitride powders, Fe, Al of Si powder and raw material mixed powder end and the metal impurities in addition to Fe and Al contain
Proportional measuring method)
The Fe of the Si powder and raw material mixed powder end that are used in alpha-silicon nitride powders of the invention, the present invention as raw material and
Al, metal impurities in addition to Fe and Al content ratio be measured as follows.It is mixed into accommodating by hydrofluoric acid and nitric acid
Liquid container in put into above-mentioned powder and cover tightly, which is heated, divides silicon nitride or silicon completely
Solution carries out constant volume to obtained decomposed solution using ultrapure water, as detection liquid.Use SII NanoTechnology Inc. system
ICP-AES (SPS5100 type), by the wavelength detected and its luminous intensity to Fe, Al in detection liquid and in addition to Fe and Al
Metal impurities quantified, calculate the content ratio of Fe, Al and the metal impurities in addition to Fe and Al.
(the crystallite diameter D of β type silicon nitrideCAnd the measuring method of crystal strain)
The crystallite diameter D of the β type silicon nitride of alpha-silicon nitride powders of the inventionCAnd crystal strain is measured as follows.For
Alpha-silicon nitride powders of the invention are utilized using the target and graphite monochromator formed by the pipe of copper with 0.02 ° of step-length in the angle of diffraction (2
θ) the timing step scan method that 15~80 ° of range carries out step-scan to X-ray detector carries out X-ray diffraction measure.By
The X-ray diffraction pattern of obtained alpha-silicon nitride powders of the invention calculates (101), (110), (200), (201) of β type silicon nitride
And the respective integral breadth in (210) face, aforementioned integral width is substituted into the Williamson-Hall formula of following formula (2).Will under
" the 2sin θ/λ " for stating formula (2) maps as x-axis, " β cos θ/λ " as y-axis, using least square method, finds out by this
The intercept and slope for the straight line that Williamson-Hall formula obtains.Then, the crystallite for calculating β type silicon nitride by aforementioned intercept is straight
Diameter Dc, also, by the crystal strain of aforementioned slope calculating β type silicon nitride.
β cos θ/λ=η × (2sin θ/λ)+(1/Dc) (2)
(β: integral breadth (rad), θ: Bragg angle (rad), η: crystal strain, λ: wavelength (nm), the Dc of x-ray source: micro-
Brilliant diameter (nm))
(measuring method of the heap density of mixed raw material powder)
The heap density of mixed raw material powder obtained in the present invention, which utilizes, is based on the JIS R1628 " heap of fine ceramics powder
The method of density measurement method " is found out.
(measuring method of the crushing strength of combustion product)
The crushing strength of combustion product obtained in the present invention is measured as follows.Spontaneous combustion product cuts 5 side lengths
The cube of 10mm, as measurement sample.Using hand crushing strength measurement device (Aikoh Engineering Co.,
Ltd system, MODEL-1334 type) the aforementioned crushing strength for measuring sample of measurement.Load is applied to the measurement sample for being placed in pedestal,
Compression test is carried out, crushing strength is calculated by the maximum load measured.The crushing strength of combustion product obtained in the present invention is adopted
The average value of the crushing strength of sample is measured with 5.
(evaluation method of the release property of polycrystalline silicon ingot casting)
In the present invention, uses and be coated with the mold that alpha-silicon nitride powders of the invention make as release agent, progress polysilicon
The unidirectional solidification of ingot casting is tested, and polycrystalline silicon ingot casting is demoulded from mold, evaluates alpha-silicon nitride powders of the invention as follows.By polysilicon
Ingot casting can demould from mold and be denoted as zero the case where not confirming the attachment of release layer on polycrystalline silicon ingot casting, and polysilicon is cast
Ingot can demould from mold but be denoted as △ the case where confirming the attachment of release layer on polycrystalline silicon ingot casting, by polycrystalline silicon ingot casting
Cannot be demoulded from mold or allow to demoulding, polycrystalline silicon ingot casting also cracks or the case where notch be denoted as ×.
(measuring methods of metal impurities contained in polycrystalline silicon ingot casting)
Following operation measures Fe, Al contained in the polycrystalline silicon ingot casting obtained in unidirectional solidification experiment and removes Fe and Al
Metal impurities in addition.It is divided into two with the polycrystalline silicon ingot casting that the section mode parallel relative to solidification direction will obtain,
On the central axis of the section, using up the position of 1cm utilizes flight time secondary ion matter as locating from bottom
Spectrometry (ULVAC-PHI, Inc. system (TRIFT V nano TOF type)) carries out surface analysis.By Fe, Al and in addition to Fe and Al
Metal impurities second order ms standardization secondary ion intensity be 1 × 10-4Above situation, which is denoted as, to be detected, will be less than 1
×10-4The case where be denoted as and be not detected.Here, standardization secondary ion intensity refer to by each mass spectrographic secondary ion intensity divided by
Value obtained from all mass spectrographic secondary ion intensity detected.
(embodiment 1-1)
D50 is 4.0 μm, heap density is 0.40g/cm3, Fe content ratio be 3ppm, Al content ratio be 4ppm,
The content ratio of metal impurities in addition to Fe and Al is in the Si powder of 3ppm, with the adding rate of silicon nitride for 20 mass %
The mode of (silicon: the mass ratio of silicon nitride is 80:20) adds the alpha-silicon nitride powders (Ube Industries, Ltd as diluent
System, product name " the SN-E10 " (content ratio of Fe: the content ratio of 9ppm, Al: 2ppm, the metal impurities in addition to Fe and Al
Content ratio: 4ppm)), as raw material powder.Aforementioned raw material powder is contained in filled with silicon nitride ball, inner wall
In the cylinder for having carried out the nylon of liner with carbamate, using intermittent vibromill with vibration number 1200cpm, amplitude 8mm
Mixing 0.5 hour, obtains mixed raw material powder.
Combustion synthesis reaction device 1 used in the combustion synthesis reaction of silicon in the present embodiment is shown in Fig. 1.It will mixing
It is 200 × 400mm, depth 30mm, with a thickness of 10mm that mixed raw material powder 2 obtained from aforementioned raw material powder, which is contained in bottom surface,
Rectangular casket shape graphite container 3 in.At this point, the heap density of mixed raw material powder is 0.45g/cm3.By titanium powder and carbon dust
End is with titanium: the mass ratio that carbon is 4:1 mixes, and is formed, prepares igniting agent 4 used in combustion synthesis reaction, by igniting agent 4
It is positioned on mixed raw material powder 2.Then, the graphite container 3 for accommodating mixed raw material powder 2 and igniting agent 4 is contained in
In the resistance to pressure container 6 for having the carbon heater 5 of igniting agent heating, so that carbon heater 5 is located at the surface of igniting agent 4.
Using vacuum pump 7 to being de-gassed in resistance to pressure container 6 after, is imported by nitrogen gas tank 8 in Xiang Qianshu reaction vessel
Nitrogen makes atmosphere pressures 0.6MPa.Then, it is powered to carbon heater 5, igniting agent 4 is heated, aforementioned mixed raw material is made
Powder point, which is fought, starts combustion synthesis reaction.In combustion synthesis reaction, the nitrogen atmosphere pressure almost constant of resistance to pressure container 6 is
0.6MPa.The inside of resistance to pressure container 6 from sight glass 9, combustion synthesis reaction for about terminating after twenty minutes.React end
Afterwards, graphite container 3 is taken out from resistance to pressure container 6, recycles block-like combustion product.
The part around igniting agent is removed from obtained combustion product, and remainder has been subjected to amino using inner surface
Formic acid esters is coated with and the kibbler roll for having silicon nitride roller carries out coarse crushing, is carried out with 100 μm of mesh of nylon system sieve
Sieve recycles the powder under sieve, obtains the alpha-silicon nitride powders of embodiment 1-1.
By the physics value of Si powder used in raw material powder in embodiment 1-1 and diluent, the object of mixed raw material powder
Property value and the crushing strength of combustion product are shown in table 1, also, the physics value of alpha-silicon nitride powders is shown in table 2.
[table 1]
[table 2]
The alpha-silicon nitride powders of embodiment 1-1 are implemented as follows as the evaluation of the release agent of polycrystalline silicon ingot casting casting mold.
The alpha-silicon nitride powders of embodiment 1-1 are contained in the polyethylene container that can be covered tightly, water are added, thus with nitrogen
The mixing ratio of SiClx powder becomes the mode of 20 mass % to prepare.Nitridation is put into the container for accommodating alpha-silicon nitride powders and water
Silicon ball simultaneously covers tightly, and obtains Silicon Nitride using intermittent vibromill with amplitude 5mm, vibration number 1780cpm mixing 5 minutes.
It being preheating to 90 DEG C and the porosity is 16%, bottom surface by the Silicon Nitride spraying coating of obtained embodiment 1-1
It is then dried 15 hours at 90 DEG C for the square of 100mm, the inner surface of the quartz crucible of depth 100mm.At this time
Release layer with a thickness of about 0.2mm.In turn, it using air atmosphere furnace, is kept for 3 hours, is added at 1100 DEG C in air
Heat treatment, obtains the polycrystalline silicon ingot casting casting mold that release layer applies the alpha-silicon nitride powders of embodiment 1-1.
Purity 7N, the silicon particle 300g having a size of 2~5mm are filled into aforementioned mold, are contained in Bu Liziman furnace.?
The argon gas circulation of atmospheric pressure is lower will to be warming up to 1500 DEG C with 5 hours in furnace, melt silicon particle.It is kept for 24 hours at 1500 DEG C
Later, aforementioned mold was reduced with 50mm/ hours reduction speed, makes molten silicon unidirectional solidification, and then be cooled to room temperature.In addition,
The polycrystalline silicon ingot casting casting mold for making 1 embodiment 1-1 again using the mold, and will keep temperature to be changed to 1550 DEG C,
In addition to this, same method progress unidirectional solidification experiment is tested using with aforementioned unidirectional solidification.
Polycrystalline silicon ingot casting is demoulded from the aforementioned mold of taking-up, is utilized " evaluation method of polycrystalline silicon ingot casting casting mold "
The polycrystalline silicon ingot casting casting mold and polycrystalline silicon ingot casting of the method evaluation embodiment 1-1 of middle explanation.It the results are shown in table 3.
[table 3]
(embodiment 1-2)
The sieving after coarse crushing, in addition to this, same as embodiment 1-1 to operate, production are carried out using 120 μm of mesh of sieve
The alpha-silicon nitride powders of embodiment 1-2.Then, using the alpha-silicon nitride powders of embodiment 1-2, using with the same side embodiment 1-1
Legal system makees 2 polysilicon casting molds.Using these molds, using method same as embodiment 1-1 carry out 1500 DEG C and
Unidirectional solidification experiment under 1525 DEG C of two kinds of in-furnace temperatures, evaluates polycrystalline silicon ingot casting using method same as embodiment 1-1
Casting mold.
(embodiment 1-3)
The sieving after coarse crushing, in addition to this, same as embodiment 1-1 to operate, production are carried out using 80 μm of mesh of sieve
The alpha-silicon nitride powders of embodiment 1-3.Then, using the alpha-silicon nitride powders of embodiment 1-3, using with the same side embodiment 1-1
Legal system makees 2 polysilicon casting molds.Using these molds, method same as embodiment 1-1 progress and embodiment are utilized
Unidirectional solidification experiment under the same two kinds of in-furnace temperatures of 1-1, evaluates polycrystalline silicon ingot casting using method same as embodiment 1-1
Casting mold.
(embodiment 1-4)
The sieving after coarse crushing, in addition to this, same as embodiment 1-1 to operate, production are carried out using 125 μm of mesh of sieve
The alpha-silicon nitride powders of embodiment 1-4.Then, using the alpha-silicon nitride powders of embodiment 1-4, using with the same side embodiment 1-1
Legal system makees 3 polysilicon casting molds.Using these molds, using method same as embodiment 1-1 carry out 1500 DEG C,
Unidirectional solidification experiment under 1525 DEG C and 1550 DEG C of three kinds of in-furnace temperatures, is evaluated more using method same as embodiment 1-1
Crystal silicon ingot casting casting mold.
(embodiment 1-5)
Alpha-silicon nitride powders obtained from carrying out coarse crushing and being sieved are contained in filled with silicon nitride ball, inner wall benefit
In the cylinder for having carried out the nylon of liner with carbamate, using intermittent vibromill with vibration number 1780cpm, amplitude 5mm
20 minutes Crushing of Ultrafine are carried out, it is in addition to this, same as embodiment 1-1 to operate, make the alpha-silicon nitride powders of embodiment 1-5.It needs
Illustrate, when being crushed using intermittent vibromill, as grinding aid, addition is 1 matter relative to combustion product
Measure the ethyl alcohol of %.Then, using the alpha-silicon nitride powders of embodiment 1-5, using method same as embodiment 1-1 production more than 2
Crystal silicon casting mold.Using these molds, same as embodiment 1-1 two are carried out using method same as embodiment 1-1
Unidirectional solidification experiment under kind in-furnace temperature, utilizes method same as embodiment 1-1 to evaluate polycrystalline silicon ingot casting casting mold.
(embodiment 1-6)
The fine time is set as 40 minutes, it is in addition to this, same as embodiment 1-5 to operate, production embodiment 1-6's
Alpha-silicon nitride powders.Then, using the alpha-silicon nitride powders of embodiment 1-6, using method same as embodiment 1-1 production more than 2
Crystal silicon casting mold.Using these molds, same as embodiment 1-1 two are carried out using method same as embodiment 1-1
Unidirectional solidification experiment under kind in-furnace temperature, utilizes method same as embodiment 1-1 to evaluate polycrystalline silicon ingot casting casting mold.
(embodiment 1-7)
The fine time is set as 50 minutes, it is in addition to this, same as embodiment 1-5 to operate, production embodiment 1-7's
Alpha-silicon nitride powders.Then, using the alpha-silicon nitride powders of embodiment 1-7, using method same as embodiment 1-1 production more than 2
Crystal silicon casting mold.Using these molds, same as embodiment 1-1 two are carried out using method same as embodiment 1-1
Unidirectional solidification experiment under kind in-furnace temperature, utilizes method same as embodiment 1-1 to evaluate polycrystalline silicon ingot casting casting mold.
(embodiment 1-8)
The sieving after coarse crushing, in addition to this, same as embodiment 1-7 to operate, production are carried out using 20 μm of mesh of sieve
The alpha-silicon nitride powders of embodiment 1-8.Then, using the alpha-silicon nitride powders of embodiment 1-8, using with the same side embodiment 1-1
Legal system makees 2 polysilicon casting molds.Using these molds, method same as embodiment 1-2 progress and embodiment are utilized
Unidirectional solidification experiment under the same two kinds of in-furnace temperatures of 1-2, evaluates polycrystalline silicon ingot casting using method same as embodiment 1-1
Casting mold.
(embodiment 1-9)
Use jet mill (the Nisshin Engineering Inc. for the liner for having silicon nitride in kiss portion
SJ-1500 type processed), with necessary air capacity 3.0m3The condition of/minute, raw material feed speed 250g/ minutes or so are to progress coarse powder
Alpha-silicon nitride powders obtained from broken are crushed, and the alpha-silicon nitride powders of embodiment 1-9 are made.Then, using the nitrogen of embodiment 1-9
SiClx powder makes 2 polysilicon casting molds using method same as embodiment 1-1.Using these molds, using with
The same method of embodiment 1-1 carries out the unidirectional solidification under two kinds of in-furnace temperatures same with embodiment 1-1 and tests, using with reality
Apply the same method evaluation polycrystalline silicon ingot casting casting mold of a 1-1.
(embodiment 1-10)
In raw material powder, as additive, ammonium chloride (He Guangchun medicine system, purity 99.9%) 6.9 matter are further added
% (so that the mass ratio of the mixed-powder and ammonium chloride of silicon and silicon nitride is 93.1:6.9) is measured, in addition to this, with embodiment 1-6
Same operation, makes the alpha-silicon nitride powders of embodiment 1-10.Then, using the alpha-silicon nitride powders of embodiment 1-10, using with reality
It applies the same method of a 1-1 and makes 2 polysilicon casting molds.Using these molds, using with the same side embodiment 1-1
Method carries out the unidirectional solidification experiment under two kinds of in-furnace temperatures same as embodiment 1-1, utilizes method same as embodiment 1-1
Evaluate polycrystalline silicon ingot casting casting mold.
(embodiment 1-11)
The adding proportion of additive ammonium chloride is set as 9.2 mass % (so that the mixed-powder and chlorination of silicon and silicon nitride
The mass ratio of ammonium is 90.8:9.2), it is in addition to this, same as embodiment 1-10 to operate, make the silicon nitride powder of embodiment 1-11
End.Then, using the alpha-silicon nitride powders of embodiment 1-11,3 polysilicons is made using method same as embodiment 1-1 and are cast
Use mold.Using these molds, temperature in three kinds of furnaces same as embodiment 1-4 is carried out using method same as embodiment 1-1
Unidirectional solidification experiment under degree, evaluates polycrystalline silicon ingot casting casting mold using method same as embodiment 1-1.
(embodiment 1-12)
The Si powder of raw material powder using D50 is 3.3 μm, heap density is 0.36g/cm3, Fe content ratio be 3ppm
Si powder, the content ratio of Al is set as 3ppm, the content ratio of metal impurities in addition to Fe and Al is set as 3ppm, and diluent makes
With the SKW corporation alpha-silicon nitride powders (content ratio of Fe: the content ratio of 310ppm, Al: 145ppm, in addition to Fe and Al
The content ratio of metal impurities: 42ppm), it is in addition to this, same as embodiment 1-1 to operate, make the silicon nitride of embodiment 1-12
Powder.Then, using the alpha-silicon nitride powders of embodiment 1-12,2 polysilicons is made using method same as embodiment 1-1 and are cast
It makes and uses mold.Using these molds, carried out in two kinds of furnaces same as embodiment 1-1 using method same as embodiment 1-1
At a temperature of unidirectional solidification experiment, utilize method same as embodiment 1-1 evaluate polycrystalline silicon ingot casting casting mold.
(embodiment 1-13)
The Si powder of raw material powder using D50 is 3.3 μm, heap density is 0.36g/cm3, Fe content ratio be 3ppm,
The Si powder that the content ratio of Al is 3ppm, the content ratio of metal impurities in addition to Fe and Al is 3ppm, diluent use
The VESTA Si corporation alpha-silicon nitride powders (content ratio of Fe；The content ratio of 224ppm, Al；500ppm, in addition to Fe and Al
Metal impurities content ratio；174ppm), in addition to this, same as embodiment 1-7 to operate, make the nitrogen of embodiment 1-13
SiClx powder.Then, using the alpha-silicon nitride powders of embodiment 1-13,2 polycrystalline are made using method same as embodiment 1-1
Silicon casting mold.Using these molds, two kinds same as embodiment 1-1 are carried out using method same as embodiment 1-1
Unidirectional solidification experiment under in-furnace temperature, evaluates polycrystalline silicon ingot casting casting mold using method same as embodiment 1-1.
(comparative example 1-1)
It is in addition to this, same as embodiment 1-1 to operate without the sieving after coarse crushing, the nitridation of comparison example 1-1
Si powder.Alpha-silicon nitride powders obtained in comparative example 1-1 are as shown in table 2, and specific surface area is small, are 0.25m2/ g, D10, D50, D90
It is larger, respectively 15.50 μm, 26.34 μm, 62.34 μm.Then, using the alpha-silicon nitride powders of comparative example 1-1, using with reality
It applies the same method of a 1-1 and makes 1 polysilicon casting mold.Using the mold, method same as embodiment 1-1 is utilized
The unidirectional solidification experiment under only 1500 DEG C of in-furnace temperature is carried out, is cast using method same as embodiment 1-1 evaluation polysilicon
Ingot casting mold.
(comparative example 1-2)
The fine time is set as 60 minutes, in addition to this, utilizes method comparison example same as embodiment 1-5
The alpha-silicon nitride powders of 1-2.Alpha-silicon nitride powders obtained in comparative example 1-2 are as shown in table 2, specific surface area 5.70m2/ g, D90 be
5.69 μm, be the small powder of partial size.Then, using the alpha-silicon nitride powders of comparative example 1-2, using with the same side embodiment 1-1
Legal system makees 1 polysilicon casting mold.Using the mold, carried out using the same method of comparative example 1-1 same with comparative example 1-1
Unidirectional solidification experiment under the in-furnace temperature of sample utilizes method same as embodiment 1-1 evaluation polycrystalline silicon ingot casting casting casting
Mould.
(comparative example 1-3)
In raw material powder, as additive, ammonium chloride (He Guangchun medicine system, purity 99.9%) 12.3 matter are further added
% (so that the mass ratio of the mixed-powder and ammonium chloride of silicon and silicon nitride is 87.7:12.3) is measured, in addition to this, with embodiment 1-
7 same operations, the alpha-silicon nitride powders of comparison example 1-3.Alpha-silicon nitride powders obtained in comparative example 1-3 are as shown in table 2, are β
The powder that the ratio of type silicon nitride is few and is 64%.Then, using the alpha-silicon nitride powders of comparative example 1-3, using with embodiment 1-1
Same method makes 1 polysilicon casting mold.Using the mold, using the same method of comparative example 1-1 carry out with than
Unidirectional solidification experiment under in-furnace temperature same compared with example 1-1, evaluates polycrystalline silicon ingot casting using method same as embodiment 1-1
Casting mold.
(comparative example 1-4)
Raw material powder using D50 is 6.0 μm, heap density is 0.60g/cm3, Fe content ratio be that 4ppm, Al containing
The Si powder that ratio is 4ppm, the content ratio of metal impurities in addition to Fe and Al is 4ppm, in addition to this, with embodiment 1-
7 same operations, the alpha-silicon nitride powders of comparison example 1-4.Alpha-silicon nitride powders obtained in comparative example 1-4 are as shown in table 2, are micro-
Brilliant diameter DcIt is smaller and be 290nm, crystal strain is larger and is 0.92 × 10-4Powder.Then, using the nitrogen of comparative example 1-4
SiClx powder makes 1 polysilicon casting mold using method same as embodiment 1-1.Using the mold, using comparing
The same method of example 1-1 carries out the unidirectional solidification under in-furnace temperature same with comparative example 1-1 and tests, using with embodiment 1-1
Same method evaluates polycrystalline silicon ingot casting casting mold.
(comparative example 1-5)
The fine time is set as 100 minutes, in addition to this, same as comparative example 1-4 to operate, comparison example 1-5
Alpha-silicon nitride powders.Alpha-silicon nitride powders obtained in comparative example 1-5 are as shown in table 2, are crystallite diameter DcIt is smaller and be 182nm,
Crystal strain is larger and is 1.25 × 10-4Powder.Then, using the alpha-silicon nitride powders of comparative example 1-5, using with embodiment 1-
1 same method makes 1 polysilicon casting mold.Using the mold, using the same method of comparative example 1-1 carry out with than
Unidirectional solidification experiment under in-furnace temperature same compared with example 1-1, evaluates polycrystalline silicon ingot casting using method same as embodiment 1-1
Casting mold.
(comparative example 1-6)
Raw material powder using D50 is 5.0 μm, heap density is 0.50g/cm3, Fe content ratio be that 205ppm, Al containing
It is proportional be 220ppm, the Si powder that the content ratio of metal impurities in addition to Fe and Al is 503ppm, in addition to this, with than
It is equally operated compared with example 1-4, the alpha-silicon nitride powders of comparison example 1-6.Such as 2 institute of table of alpha-silicon nitride powders obtained in comparative example 1-6
Show, be Fe content ratio be 109ppm, Al content ratio be 127ppm, metal impurities in addition to Fe and Al containing than
Example is the powder more than 271ppm and the content ratio of metal impurities.Then, using the alpha-silicon nitride powders of comparative example 1-6, using with
The same method of embodiment 1-1 makes 1 polysilicon casting mold.Using the mold, the same method of comparative example 1-1 is utilized
The unidirectional solidification experiment under in-furnace temperature same as comparative example 1-1 is carried out, is evaluated using method same as embodiment 1-1 more
Crystal silicon ingot casting casting mold.
(comparative example 1-7)
Raw material powder using D50 is 8.5 μm, heap density is 0.70g/cm3, Fe content ratio be that 2ppm, Al containing
The Si powder that ratio is 1ppm, the content ratio of metal impurities in addition to Fe and Al is 2ppm, raw material powder is contained in and is filled out
In the cylinder of nylon filled with oxidation aluminum ball, ethyl alcohol is used to carry out 24 hours ball milling mixings as solvent, is aoxidized using having
The kibbler roll of aluminum roller carries out the coarse crushing of combustion product, carries out coarse crushing using 150 μm of mesh of sieve of stainless steel
Sieving afterwards, in addition to this, same as embodiment 1-1 to operate, the alpha-silicon nitride powders of comparison example 1-7.In comparative example 1-7
The alpha-silicon nitride powders arrived are as shown in table 2, be Al content ratio be 846ppm and metal impurities content ratio is more, specific surface area
It is small and be 0.21m2/ g, D10, D50, D90 be larger and respectively 15.43 μm, 26.50 μm, 62.44 μm of powder.Then, make
With the alpha-silicon nitride powders of comparative example 1-7,1 polysilicon casting mold is made using method same as embodiment 1-1.It uses
The mold carries out the unidirectional solidification under in-furnace temperature same as comparative example 1-1 using the same method of comparative example 1-1 and tests,
Polycrystalline silicon ingot casting casting mold is evaluated using method same as embodiment 1-1.
(comparative example 1-8)
Raw material powder using D50 is 5.0 μm, heap density is 0.50g/cm3, Fe content ratio be that 205ppm, Al containing
It is proportional be 220ppm, the Si powder that the content ratio of metal impurities in addition to Fe and Al is 503ppm, by raw material powder benefit
It is mixed 1 hour with the planetary ball mill filled with oxidation aluminum ball, in addition to this, same as embodiment 1-6 to operate, comparison
The alpha-silicon nitride powders of example 1-8.Alpha-silicon nitride powders obtained in comparative example 1-8 are as shown in table 2, are that the content ratio of Fe is
The content ratio of 109ppm, Al is 420ppm, the content ratio of metal impurities in addition to Fe and Al is 312ppm and metal is miscellaneous
The content ratio of matter is more, crystallite diameter DcIt is smaller and be 290nm powder.Then, using the alpha-silicon nitride powders of comparative example 1-8,
1 polysilicon casting mold is made using method same as embodiment 1-1.It is same using comparative example 1-1 using the mold
Method carry out the unidirectional solidification under same with comparative example 1-1 in-furnace temperature and test, utilize method same as embodiment 1-1
Evaluate polycrystalline silicon ingot casting casting mold.
(comparative example 1-9)
By D50 be 2.5 μm, heap density is 0.26g/cm3, Fe content ratio be 2ppm, Al content ratio be 3ppm,
The content ratio of metal impurities in addition to Fe and Al is that the Si powder of 3ppm is filled in the mold of internal diameter 30mm, with
1500kg/cm2Pressure carry out uniaxial molding, obtain the uniaxial formed body of Si powder.Aforementioned formed body is filled in graphite system
It in container, is then accommodated in intermittent nitriding furnace, after being replaced as nitrogen atmosphere in furnace, is warming up to 1450 under nitrogen atmosphere
DEG C, it is kept for 3 hours.After being cooled to room temperature, nitridation product is taken out.Carbamate coating, tool have been carried out using inner surface
The kibbler roll of standby silicon nitride roller carries out coarse crushing to obtained nitridation product, is sieved using the nylon system that mesh is 100 μm
It is sieved, the powder under recycling sieve.Then, aforementioned powder is contained in and utilizes amino filled with silicon nitride ball, inner surface
Formic acid esters has carried out in the cylinder of oxidation aluminum of liner, using intermittent vibromill with vibration number 1780cpm, amplitude 5mm progress
30 minutes Crushing of Ultrafine, the as a result, alpha-silicon nitride powders of comparison example 1-9.As the direct nitridation method for being not belonging to conbustion synthesis
Alpha-silicon nitride powders obtained in comparative example 1-9 are as shown in table 2, are that specific surface area is larger and be 6.10m2The ratio of/g, β type silicon nitride
Example it is less and be 50%, D10, D50 are smaller and are 0.40 μm, 1.60 μm, crystallite diameter DcIt is smaller and be 55nm, crystal strain
It is larger and be 3.01 × 10-4、DBET/DcIt is larger and be 5.6 powder.Then, it using the alpha-silicon nitride powders of comparative example 1-9, utilizes
Method same as embodiment 1-1 makes 1 polysilicon casting mold.It is similarly square using comparative example 1-1 using the mold
Method carries out the unidirectional solidification experiment under in-furnace temperature same as comparative example 1-1, is evaluated using method same as embodiment 1-1
Polycrystalline silicon ingot casting casting mold.
(comparative example 1-10)
The fine time is set as 10 minutes, in addition to this, same as comparative example 1-9 to operate, comparison example 1-10
Alpha-silicon nitride powders.Such as table of alpha-silicon nitride powders obtained in comparative example 1-10 as the direct nitridation method for being not belonging to conbustion synthesis
Shown in 2, be β type silicon nitride ratio it is less and be 58%, D15, D90 are smaller and are 1.60 μm, 5.90 μm, crystallite diameter Dc
It is smaller and be 88nm, crystal strain is larger and is 1.90 × 10-4、DBET/DcIt is larger and be 6.7 powder.Then, using comparing
The alpha-silicon nitride powders of example 1-10 make 1 polysilicon casting mold using method same as embodiment 1-1.Use the casting
Mould carries out the unidirectional solidification under in-furnace temperature same as comparative example 1-1 using the same method of comparative example 1-1 and tests, utilizes
Method same as embodiment 1-1 evaluates polycrystalline silicon ingot casting casting mold.
By Si powder and diluent used in embodiment 1-2~1-13 and comparative example 1-1~1-10, raw material powder
Physics value, mixed raw material powder physics value and combustion product crushing strength it is shown in table 1, in addition, by alpha-silicon nitride powders
Physics value is shown in table 2.In addition, by the polycrystalline silicon ingot casting casting mold of embodiment 1-2~1-13 and comparative example 1-1~1-10 and
Polycrystalline silicon ingot casting evaluation result is shown in table 3.
(embodiment 2-1)
Using method described below, the polysilicon with the release layer of the alpha-silicon nitride powders comprising embodiment 1-1 is made
Ingot casting casting mold implements the evaluation of polycrystalline silicon ingot casting casting mold and silicon ingot casting.
The alpha-silicon nitride powders of embodiment 1-1 are contained in can be closed polyethylene container in, addition silica it is dense
Spend the silicon dioxide gel (chemical company, Japan system, product name " PL-3 ") and water of 20 mass %.At this point, according to by quality ratio
Silicon nitride: silicon dioxide gel: water is that the mode of 20:8:72 is mixed.Then, to accommodating alpha-silicon nitride powders, titanium dioxide
Silicon nitride ball and closed is put into the container of silica solution and water, using intermittent vibromill, utilizes amplitude 5mm, vibration number
The vibromill of 1780rpm mixes 5 minutes, obtains Silicon Nitride.
By the Silicon Nitride spraying coating of obtained embodiment 2-1 be preheating to 90 DEG C, the porosity 16%, bottom surface be
The inner wall of the quartz crucible of the square and depth 100mm of 100mm obtains having and includes dry 15 hours at 90 DEG C
The polycrystalline silicon ingot casting casting mold of the release layer of the alpha-silicon nitride powders of embodiment 2-1.Release layer at this time with a thickness of about
0.2mm。
It is same as embodiment 1-1 to operate using the polysilicon casting mold of obtained embodiment 2-1, unidirectionally coagulated
It is solid to test, utilize the polysilicon casting mold and polycrystalline silicon ingot casting of method same as embodiment 1-1 evaluation embodiment 2-1.
It the results are shown in table 4.
[table 4]
(embodiment 2-2~2-13, comparative example 2-1~2-10)
It is in addition to this, same as embodiment 2-1 to operate using alpha-silicon nitride powders shown in table 4, Silicon Nitride is made,
Manufacture polysilicon casting mold.Using the polysilicon casting mold of obtained each embodiment and each comparative example, with embodiment
1-1 is equally operated, and carries out unidirectional solidification experiment, utilizes method same as embodiment 1-1 evaluation polycrystalline silicon ingot casting casting casting
Mould and silicon ingot casting.It the results are shown in table 4.
As can be observed from the foregoing, alpha-silicon nitride powders of the invention by carrying out hot place at high temperature after being coated on mold
Reason, can substantially form adaptation and the good release layer of release property in the mould with its own, in addition, by with titanium dioxide
Silica solution is mixed and is coated in the mould, can form adaptation and release property in the mould the heat treatment without high temperature
Good release layer.
Industrial availability
Alpha-silicon nitride powders of the invention as can form and the adaptation of mold and the good demoulding of release property in the mould
Layer release agent be it is useful, especially as the polysilicon that can obtain high quality silicon substrate used for solar batteries with high finished product rate
The release agent of ingot casting is useful.In addition, alpha-silicon nitride powders of the invention can form fine and close release layer and crystallinity is high,
It therefore, is also useful as the raw material for showing high-intensitive silicon nitride sinter at high temperature.
Description of symbols
1 combustion synthesis reaction device
2 mixed raw material powder
3 graphite containers
4 igniting agents
5 carbon heaters
6 resistance to pressure containers
7 vacuum pumps
8 nitrogen gas tanks
9 sight glasses
Claims (11)
1. a kind of alpha-silicon nitride powders, which is characterized in that the specific surface area by BET method measurement is 0.4m2/ g or more and 5m2/ g with
Under,
The ratio of β type silicon nitride is 70 mass % or more,
When being set as D50 by 50% partial size of the volume reference measured by laser diffraction scattering method, 90% partial size be set as D90,
D50 be 2 μm or more and 20 μm hereinafter, D90 be 8 μm or more and 60 μm hereinafter,
The content ratio of Fe be 100ppm hereinafter,
The content ratio of Al be 100ppm hereinafter,
The content ratio of metal impurities in addition to Fe and Al add up to 100ppm hereinafter,
Williamson-Hall formula will be used by the micro- of the β type silicon nitride of the powder X-ray diffraction pattern calculating of β type silicon nitride
Brilliant diameter is set as DCWhen, DCFor 300nm or more.
2. alpha-silicon nitride powders according to claim 1, which is characterized in that nitrogenized using Williamson-Hall formula by β type
The crystal strain for the β type silicon nitride that the powder X-ray diffraction pattern of silicon calculates is 0.8 × 10-4Below.
3. alpha-silicon nitride powders according to claim 1 or 2, which is characterized in that the ratio table that will be calculated by the specific surface area
Area equivalent diameter is set as DBETWhen, DBET/DCIt (nm/nm) is 5 or less.
4. alpha-silicon nitride powders described in any one of claim 1 to 3, which is characterized in that D50 is 3 μm or more.
5. alpha-silicon nitride powders according to any one of claims 1 to 4, which is characterized in that D90 is 50 μm or less.
6. alpha-silicon nitride powders according to any one of claims 1 to 5, which is characterized in that D90 is 13 μm or more.
7. alpha-silicon nitride powders described according to claim 1~any one of 6, which is characterized in that the ratio of β type silicon nitride is greater than
80 mass %.
8. alpha-silicon nitride powders according to any one of claims 1 to 7, which is characterized in that the content ratio of Fe is 20ppm
Hereinafter,
The content ratio of Al be 20ppm hereinafter,
The content ratio of metal impurities in addition to Fe and Al adds up to 20ppm or less.
9. alpha-silicon nitride powders described according to claim 1~any one of 8, which is characterized in that laser diffraction and scattering will be passed through
When 10% partial size of the volume reference of method measurement is set as D10, D10 is 0.5 μm or more and 8 μm or less.
10. a kind of polycrystalline silicon ingot casting release agent, it includes alpha-silicon nitride powders according to any one of claims 1 to 9.
11. a kind of manufacturing method of silicon ingot casting, which is characterized in that it is the silicon ingot casting for solidifying the molten silicon being contained in mold
Manufacturing method, as the mold, using be coated on the contact surface of the molten silicon it is any in claim 1~9
The mold of alpha-silicon nitride powders described in.
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| JP2016240750 | 2016-12-12 | ||
| PCT/JP2017/044606 WO2018110560A1 (en) | 2016-12-12 | 2017-12-12 | Silicon nitride powder, release agent for polycrystalline silicon ingot, and method for producing polycrystalline silicon ingot |
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| CN115702130A (en) * | 2020-06-30 | 2023-02-14 | 株式会社德山 | Silicon nitride sintered substrate |
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| JP7353994B2 (en) * | 2020-01-17 | 2023-10-02 | 株式会社トクヤマ | Silicon nitride manufacturing method |
| WO2023210649A1 (en) * | 2022-04-27 | 2023-11-02 | 株式会社燃焼合成 | COLUMNAR PARTICLES OF β-SILICON NITRIDE, COMPOSITE PARTICLES, SINTERED SUBSTRATE FOR HEAT RADIATION, RESIN COMPOSITE, INORGANIC COMPOSITE, METHOD FOR PRODUCING COLUMNAR PARTICLES OF β-SILICON NITRIDE, AND METHOD FOR PRODUCING COMPOSITE PARTICLES |
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| JPWO2018110560A1 (en) | 2019-07-04 |
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| JP6693575B2 (en) | 2020-05-13 |
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