CN104159847B - Silicon casting mold, silicon casting method, silicon materials and the manufacture method of solaode - Google Patents
Silicon casting mold, silicon casting method, silicon materials and the manufacture method of solaode Download PDFInfo
- Publication number
- CN104159847B CN104159847B CN201280070752.4A CN201280070752A CN104159847B CN 104159847 B CN104159847 B CN 104159847B CN 201280070752 A CN201280070752 A CN 201280070752A CN 104159847 B CN104159847 B CN 104159847B
- Authority
- CN
- China
- Prior art keywords
- silicon
- mold
- casting mold
- additive
- solaode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 156
- 239000010703 silicon Substances 0.000 title claims abstract description 156
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 238000005266 casting Methods 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002210 silicon-based material Substances 0.000 title claims description 17
- 239000000463 material Substances 0.000 claims abstract description 87
- 239000000654 additive Substances 0.000 claims abstract description 69
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000007711 solidification Methods 0.000 claims description 17
- 230000008023 solidification Effects 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 description 75
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 41
- 230000007547 defect Effects 0.000 description 27
- 229920005591 polysilicon Polymers 0.000 description 22
- 239000002245 particle Substances 0.000 description 20
- 238000002425 crystallisation Methods 0.000 description 18
- 230000008025 crystallization Effects 0.000 description 18
- 239000012535 impurity Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004484 Briquette Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- -1 argon Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01B33/02—Silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
- H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/546—Polycrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electromagnetism (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Silicon Compounds (AREA)
Abstract
The silicon casting mold of the present invention is the silicon casting mold making silicon melt solidify, and at least base plate upper surface at the described inwall stating silicon casting mold is provided with the releasing material of the additive comprising mean diameter 0.1～3.0mm.
Description
Technical field
The present invention relates to a kind of silicon casting mold, use the system of its silicon casting method, silicon materials and solaode
Make method.
Background technology
As the succedaneum of the oil etc. that earth environment causes various problem, the utilization of natural energy resources receives publicity.Its
In, solaode is due to without bigger equipment, and does not produce noise etc. during operating, is especially amassed on the ground such as Japanese or European
Polar region introduces.
The part using the solaode of the compound semiconductors such as cadmium telluride has been also carried out practical, but with regard to material originally
The safety of body or actual achievement up to now, or, for cost-efficient aspect, use the solaode of crystalline silicon substrate
Account for larger proportion, wherein use the solaode (polysilicon solar cell) of polycrystalline silicon substrate to account for larger proportion.
As the substrate generally widely used polysilicon handle wafer of institute of polysilicon solar cell for will be made by mold
Molten silicon unidirectional solidification and obtain bigger polycrystalline silicon ingot the crystal ingot manufactured by the method being referred to as casting method cutting in bulk,
Carry out wafer by section to form.
By the polysilicon handle wafer manufactured by casting method according to the position of the short transverse in crystal ingot or block, be generally of as
The distribution of the output characteristics of the solaode shown in Fig. 3.
The characteristic distribution Producing reason of Fig. 3 is usually carried out explanation.
First, in the region I at the initial stage of unidirectional solidification, cause characteristic to drop due to the impact of impurity spread from mold
Low.At an upper portion thereof in the region II of side, by the takeing in or crystal defect in crystallization of the impurity in the raw material caused by segregation
Producing less, therefore, in block, characteristic is the best.And then in the region III of upper side, except in crystallization the impurity level that taken in by
Cumulative add beyond, the generation of crystal defect increases, and compares I characteristic with region I and reduces.And then in the region IV of upper side, remove
Beyond the impurity level taken in crystallizing in the same manner as the III of region or the generation of crystal defect increase further, crystal ingot is until
After rear solidification, from the counter diffusion of the hight-concentration parts generation impurity of impurity produced by uppermost surface part, impurity level enters
One step increases, and therefore, significantly reduces further with region III phase ratio characteristic.
In described above, it is contemplated that the impurity in raw material or the impact of the impurity from the dissolution of mold institute, but i.e. assuming not
In the case of there are these impacts, in III and IV of region, due to along with the knot becoming minority carrier trap towards top
Brilliant defect is gradually increased, and therefore there is the tendency that the characteristic of solaode reduces.
Think the stress caused by crystal defect Producing reason Temperature Distribution in crystal ingot, may refrain from its viewpoint and
Speech, proposes there are following 2 methods.
1st, such as, in Japanese Patent Laid-Open 2005-152985 publication (patent documentation 1), proposition has at unidirectional solidification
Time (casting), use the heat flux method as the mold holder being arranged at mold bottom more than periphery of central part.
2nd, such as, in International Publication the 2005/092791st (patent documentation 2), proposition has by making be heated (heat exchange)
Area becomes variable structure, in the method that the midway of ingot growth carries out hot-fluid control.
It addition, as the countermeasure that improve polycrystalline silicon ingot quality different from said method, propose to have to turn to big particle diameter
The method of purpose.
Such as, No. 4203603 publications of Japanese Patent No. (patent documentation 3) and Japanese Patent Laid-Open 2005-132671 public affairs
Report (patent documentation 4) in, propose have by cast base is quenched and bottom crystal ingot (at early solidification) produce branch
Shape crystallizes as the nuclei of crystallization, and the method making coarsening.
It addition, in No. 4054873 publications of Japanese Patent No. (patent documentation 5), propose to have to make the melting step at silicon raw material
Middle remained crystalline wafer (melting remnants) is grown up and makes crystal grain grow fat greatly, thus the method obtaining pseudosingle crystal.
And then, in No. 4569957 publications of Japanese Patent No. (patent documentation 6), propose to have and configured by unified grain arrangement
In the crystal seed of the SiC etc. at the bottom of mold, silicon is made to carry out epitaxial growth (ヘ テ ロ エ ピ), thus the method obtaining pseudosingle crystal.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-152985 publication
Patent documentation 2: International Publication the 2005/092791st
Patent documentation 3: No. 4203603 publication of Japanese Unexamined Patent Publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-132671 publication
Patent documentation 5: No. 4054873 publications of Japanese Patent No.
Patent documentation 6: No. 4569957 publications of Japanese Patent No.
Summary of the invention
The problem that invention is to be solved
In the method for patent documentation 1, especially in the case of being positioned at mold side such as heater, there is problems in that and make
The shape of solid liquid interface is deteriorated further, it is impossible to obtains and reduces crystal defect density or prevent effects such as rupturing.
In the method for patent documentation 2, although the controlling of cooling from die walls can be improved, but there is problems in that
Apparatus structure is extremely complex, and the moving part of high temperature is more, and the cost of device increases or fault increases.
In the method for patent documentation 3～5, the characteristic caused by crystal boundary can be suppressed to reduce by the coarsening of crystal grain,
Particularly in the case of crystal ingot size is less, there is the stress due to Temperature Distribution less, the knot imported on the top of crystal ingot
The advantage that brilliant defect is suppressed the most to a certain extent.But, while crystal ingot becomes large-sized, the crystal defect of upper side increases
Add, therefore, although it can be seen that the characteristic of bottom improves, but still remain in the characteristic in the solaode that top makes and reduce
Problem.
In the method for patent documentation 6, the crystal seed of adjacent SiC etc. the silicon grown up crystallizes on the border contacted with each other
Part forms defect, for crystal ingot, even if being able to observe that monocrystalline on a macro scale, the most also comprises more defect.Or
Person, about top, while crystal ingot becomes large-sized, the crystal defect density on top uprises, and still remains in top making
The problem that characteristic in solaode reduces.
The problem to be solved in the present invention is to provide a kind of crystal defect density suppressing crystal ingot top, and can be prepared as
The silicon casting mold of the solaode that this efficiency is higher, silicon casting method, the manufacture method of silicon materials and solaode
Manufacture method.
The technical method of solution problem
The artificially solution the problems referred to above such as present inventor are repeated to be studied with keen determination, found that by silicon being melted in mold
Melting liquid when carrying out unidirectional solidification from bottom-up portion and manufacture silicon ingot, at least base plate upper surface part at mold arranges and comprises
The releasing material of the additive of particle diameter 0.1～3.0mm, it is possible to resolve the problems referred to above, thus complete the present invention.
So, according to the present invention, it is provided that a kind of silicon casting mold, it is the silicon casting casting making silicon melt solidify
Mould, and be provided with at least base plate upper surface of the inwall of above-mentioned silicon casting mold and comprise mean diameter 0.1～3.0mm
The releasing material of additive.
It addition, according to the present invention, it is provided that a kind of silicon casting method, comprising: make silicon in above-mentioned silicon casting mold
Fused solution solidifies；The manufacture method of a kind of silicon materials, it uses the silicon cast according to described silicon casting method thus obtains silicon
Material；And the manufacture method of a kind of solaode, described silicon materials are used as substrate and obtain solaode by it.
The effect of invention
According to the present invention, it is possible to provide a kind of crystal defect density suppressing crystal ingot top, and may be produced that this efficiency is relatively
The silicon casting mold of high solaode, silicon casting method, the manufacture method of silicon materials and the manufacturer of solaode
Method.
The effect that the silicon casting mold of the present invention is the most above-mentioned: releasing material is only arranged at the end
In the case of plate portion upper surface；The feelings of the material as main constituent with graphite or quartz (silicon dioxide) are comprised at silicon casting mold
Under condition；In the case of additive is with at least one in silicon nitride, carborundum, silicon oxide and graphite as main constituent；And
Releasing material on its surface with surface density 0.2～8.5/cm2In the case of comprising additive.
In this manual, so-called " top of crystal ingot " mean to make the silicon melt in silicon casting mold from bottom-up
The top of the silicon ingot that portion carries out unidirectional solidification and manufactures, i.e. coagulation step terminates the silicon ingot of side.On the other hand, will be with same
The bottom of the silicon ingot manufactured by the mode of sample, i.e. coagulation step start the silicon ingot of side and are referred to as " bottom of crystal ingot ".
It addition, so-called " silicon materials " mean " silicon ingot ", silicon ingot it is processed into " silico briquette " of corner post shape and silico briquette is entered
" Silicon Wafer " of row slice processing.
And then, so-called " silicon solar cell " means constitute " the silicon solar cell unit " of minimal modules and carry out it
" the solaode module " of multiple electrical connections.
Accompanying drawing explanation
Fig. 1 is particle diameter and the solar battery cell of additive contained in the releasing material representing silicon casting mold
The figure (test example 1) of relation of average output.
Fig. 2 is surface density and the solaode list of additive contained in the releasing material representing silicon casting mold
The figure (test example 2) of the relation of the average output of unit.
Fig. 3 is the position representing the short transverse by the common polycrystalline silicon ingot manufactured by the unidirectional solidification of silicon melt
Put the concept map of the relation of average output with made solar battery cell.
Fig. 4 system represents the profile signal of an example of the applicable casting device of silicon casting method of the present invention.
Detailed description of the invention
The silicon casting mold of the present invention is the silicon casting mold making silicon melt solidify, and casts in above-mentioned silicon casting
At least base plate upper surface of the inwall of mould is provided with the releasing material of the additive comprising mean diameter 0.1～3.0mm.
Present inventor et al. for the multiple silicon ingots having carried out unidirectional solidification in mold carried out the evaluation of crystal defect,
Analyze and research, found that the method for the crystal defect density as the top reducing crystal ingot, except being considered have so far
Effect and conventional mat are reduced by the suppression of Temperature Distribution and there is additive method beyond stress.
Specifically, present inventor et al. is with described the suppressing by the coarsening of crystal grain with patent documentation 3～6
The antipodal idea of technology that the characteristic caused by crystal boundary reduces, finds polycrystalline silicon ingot and crystallization that crystallization particle diameter is less
The polycrystalline silicon ingot phase specific stress that particle diameter is bigger is stronger, it is difficult to produce crystal defect.
According to the opinion of present inventor et al., (1) even if proximate portion in polycrystalline silicon ingot, the crystallization bigger grain of particle diameter with
The crystal defect density being directed into inside in less grain also has larger difference；(2) knot crystallizing particle diameter and its top of crystal ingot
Have interrelated between brilliant defect concentration；(3) although there being exception, but crystallization particle diameter is the least, and the crystal defect on the top of crystal ingot is close
Spend the lowest.Owing to being difficult to think in part adjacent in crystal ingot, thermal stress suffered during ingot growth has bigger difference, therefore recognizes
Be stress suffered in relaxing crystal grain by the slip of grain boundary portion etc. for the crystallization less part of particle diameter, result suppression to
Crystal defect is imported in crystal grain.
Therefore, the silicon melt in making mold carry out unidirectional solidification and during cast silicon crystal ingot, by promoting cast base
The generation of the nuclei of crystallization and make crystallization particle diameter diminish, it is possible to decrease the crystal defect on the top of silicon ingot.
In order to reduce the crystal defect on the top of silicon ingot, be presently considered planarization of being necessary to carry out solid liquid interface etc.,
Put on the reduction of the thermal stress of crystal ingot, on the other hand, in the present invention, only by reducing the control of the crystallization particle diameter of crystallization particle diameter
The crystal defect on the top of polycrystalline silicon ingot can be reduced.The mold of the application of the invention, can control crystal grain footpath for less.
(silicon casting mold)
The silicon casting mold of the present invention, at least base plate upper surface of the inwall of silicon casting mold, is provided with and comprises
The releasing material of the additive of mean diameter 0.1～3.0mm.
If the silicon casting mold of the present invention is in the scope of the effect that can obtain the present invention, then its material there is no limit especially
Fixed, the mold of existing used material can be used.
In view of the impact of impurity being mixed into silicon melt and silicon ingot from mold, cost, thermostability etc., the present invention's
Silicon casting mold preferably comprises the material as main constituent with graphite or quartz (silicon dioxide).
If the shape of mold and size are in the scope of the effect that can obtain the present invention, then it is not particularly limited, for example, it is possible to
For in rectangle, cylindrical shape any one, as long as being that there is the size shape of the silicon ingot that can keep silicon melt and solidification.Tool
For body, the mold used in test example can be enumerated.
In silicon casting mold, generally, take out silicon ingot from mold after casting for silicon and be provided with releasing material, but
In the present invention, releasing material comprises the additive with specific mean diameter.
Research according to present inventor et al., it is known that when silicon melt solidifies, there are specific in releasing material
The position of additive become core (nuclei of crystallization) and produce the probability of position higher than other parts.To the silicon melt in mold from it
Base plate carries out unidirectional solidification towards top, and major part obtains silicon ingot.Therefore, by least producing the casting started to initial core
The releasing material of the base plate upper surface portion of mould imports specific additive, the probability that core produces can be improved, make crystallization
Particle diameter diminishes, it addition, as its result, can suppress the crystal defect on the top of silicon ingot.
In order to effectively obtain the effect above, the releasing material of the silicon casting mold of the present invention is preferably provided only on
The base plate upper surface of the inwall of silicon casting mold.I.e., preferably in the side of inwall of mold, it is provided with without additive
Releasing material.
Be also equipped with the releasing material comprising specific additive in the side of the inwall of mold in the case of, even if sometimes
The probability produced at side core also increases and grows up from the direction of side separation on the crystallization edge of side core generation, crystal grain boundary
Tilt relative to the above-below direction of crystal ingot.The periphery of the silicon ingot of this kind of crystalline state not as used for solar batteries preferably
Cylindric crystallization.
If additive can obtain the scope of the effect of the present invention, then its material is not particularly limited, but in view of by adding
Add the impact of the impurity that thing is mixed into silicon melt and silicon ingot, cost, thermostability etc., be preferably with selected from silicon nitride, carbonization
In silicon, silicon oxide and graphite, at least one is main constituent.
The mean diameter of additive is 0.1～3.0mm.
If the scope that the mean diameter of additive is above-mentioned, then can expect the silicon sun using the silicon ingot of the present invention to make
The output of energy battery is improved, and described silicon ingot utilizes the silicon casting mold of the present invention to manufacture.This means silicon wafer
Crystalline state in ingot is good, and meaning can provide a kind of solaode that cannot be only used for can be preferably also used for other purposes
Silicon ingot.More preferably in the range of 0.3～2.8mm, and then preferably in the range of 0.8～2.2mm.
Specifically, the mean diameter (mm) of additive be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,
1.0、1.5、2.0、2.5、3.0。
Releasing material is preferably on its surface with surface density 0.2～8.5/cm2Comprise additive.
If surface density does not reaches 0.2/cm2, the effect of the crystallization size controlling of silicon reduces the most sometimes.On the other hand, if face
Density is more than 8.5/cm2, then the crystallization particle diameter of silicon becomes too small, although can be by the crystal defect density contact on crystal ingot top
Relatively low, but the crystal grain boundary sometimes becoming the center that is bonded again of electron hole pair becomes too much.This silicon ingot is with regard to solar-electricity
For the viewpoint of the conversion efficiency in pond not preferred, the scope of the surface density of above-mentioned additive most preferably value in the range of, more excellent
Selecting scope is 2.0～6.5/cm2, and further preferred range is 2.5～6.0/cm2。
Specifically, surface density (individual/cm2) it is 2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0.
The silicon casting mold of the present invention can be manufactured by known method, is not particularly limited, but the most permissible
Such a way manufactures.
That is, make the main material of releasing material and the dispersion of above-mentioned additive prepare in a solvent solids concentration 1～
The slurry of about 5%, coats the inner face of mold by the slurry obtained, and is dried smearing of being obtained, burns till, thus
Obtain releasing material.
Suitably set powder and the amount of additive powder of main material, make additive in the surface of releasing material
Surface density becomes above-mentioned scope.
As the main material of releasing material, the material of known release materials can be used, such as, average particle can be enumerated
Silicon nitride, silicon oxide and the powder of their mixture of footpath 0.1～60 μm.
Concrete mean diameter (μm) is 0.1,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,
6.0、6.5、7.0、7.5、8.0、8.5、9.0、9.5、10、15、20、25、30、35、40、45、50、55、60。
As solvent, if disappearing in burning till step and releasing material not produced harmful effect, then without limit especially
Fixed, such as, polyvinyl alcohol can be enumerated.
It is coated with, is dried and burns till step and can suitably be imposed a condition by known method and implement, in order to obtain certain films
Thick releasing material, it is possible to be repeated a number of times coating and drying steps.
Firing temperature and time thereof also rely on the conditions such as used material or the thickness of releasing material that formed,
It it is about 800～1100 DEG C and about 1～8 hour.
Concrete firing temperature (DEG C) is 800,825,850,875,900,925,950,975,1000,1025,1050,
1075,1100, concrete firing time (time) is 1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8.
The thickness of releasing material is about 150～600 μm.
In the case of the thickness of releasing material is thinner than the particle diameter of additive, obtain the effect of the present invention the most significantly
Really.On the contrary, in the case of the thickness of releasing material is thicker than the particle diameter of additive, additive imbeds the interior of releasing material
Portion, the surface configuration of releasing material is not added the shape reflection of thing, becomes protuberance close of the additive of core generating unit
Degree reduces, therefore, it is difficult to obtain the effect of the present invention significantly.
Concrete thickness (μm) is 150,175,200,225,250,275,300,325,350,375,400,425,450,
475、500、525、550、575、600。
Therefore, in order to ensure the thickness as releasing material, simultaneously, it is thus achieved that the effect of the present invention, it is possible to be only coated with bag
Form the releasing material of specific thickness containing the slurry of additive, but also can not comprise additive by coating and only comprise master
After wanting the slurry of material, slurry that coating comprises additive and form the releasing material that comprises multiple layer.
As it has been described above, in the silicon ingot of silicon solar cell, the side of mold produce the core side with regard to its battery behavior
For face not preferred, therefore, releasing material is preferably only arranged at the base plate upper surface of mold.In this case, only
Base plate upper surface at mold forms the releasing material comprising additive, forms taking off without additive in the side of mold
Mold materials layer.
(silicon casting method)
The silicon casting method of the present invention is characterised by: in the silicon casting mold of the present invention, makes silicon melt solidify.
According to the method, a kind of silicon ingot being applicable to the higher solaode of cost efficiency can be manufactured.
For the silicon melt in silicon casting mold, the silicon raw material of solid can be made in mold to melt, or also can make
Silicon melt flows in mold.
If it addition, the solidification of silicon melt can obtain in the range of the effect of the present invention, then its form there is no limit especially
Fixed, set felicity condition according to the device used.
The silicon casting method of the present invention such as can use known device as shown in Figure 4 to implement, but the present invention is not
It is defined in this embodiment.
Fig. 4 is the constructed profile of an example of the applicable casting device of silicon casting method representing the present invention.
This device usually uses for casting polycrystalline silicon ingot, has chamber (the airtight appearance constituting resistance-heated furnace
Device) 7.
In the inside of chamber 7, it is configured with graphite system, quartz (SiO2) mold 1 of system etc., can be by the atmosphere within chamber 7
Remain air-tight state.
In the chamber 7 being accommodated with mold 1, it is configured with the mold table 3 of the graphite of supporting mold 1.Mold table 3 is by rising
Fall drive mechanism 12 can lift, and makes the coolant (cooling water) in cooling bath 11 circulate therein.
On the top of mold table 3, it is configured with the outer mold 2 of graphite etc., is configured with mold 1 wherein.Can also be configured as
The outer housing of the graphite etc. surrounding mold 1 replaces outer mold 2.
In the way of surrounding outer mold 2, configure such as the resistance heating body 10 of graphite heater, and then to cover from above this
A little modes configures heat-barrier material 8.
Silicon raw material 4 in resistance heating body 10 can carry out heating from the surrounding of mold 1 and make mold 1 melts.Herein, as
Heater, can enumerate resistance heating manner, but alternatively induction heating mode.
In order to detect the temperature of the bottom surface of mold 1, and near mold 1 lower surface central authorities, configure thermocouple under mold respectively
5, configure thermocouple 6 under outer mold near the central authorities of mold lower surface outside, these output is inputted to controlling device 9, control
System produces heated condition by resistance heating body 10.The thermoelectricity for detecting temperature is can also be configured occasionally in addition to above-mentioned thermocouple
Radiation thermometer, is also not particularly limited it addition, above-mentioned thermocouple arranges position.
It is air-tight state that chamber 7 keeps it internal, makes the oxygen of outside, nitrogen etc. cannot flow into, and generally, puts into polycrystalline
After the silicon raw materials such as silicon and before it is melted, in making chamber 7, become vacuum, import thereafter the noble gases such as argon, remain
Inert atmosphere.
By the device of this kind of structure, basically by steps casting polycrystalline silicon ingot: to the silicon raw material of mold 1
Gas displacement in the filling of 4, the chamber 7 carried out by degassing (evacuation) and the importing of noble gas, by heating
The silicon raw material 4 carried out melted, melted confirm to keep with it, controlled by temperature and the action of lift drive mechanism 12 and carry out
Solidification start, solidify end confirm and annealing and take out crystal ingot.It should be noted that list silicon raw material in casting herein
Carry out in mould heating, the example of the device of melted type, but be possible with in addition at the crucible different from silicon casting mold
In Deng, silicon raw material is added heat fusing, silicon melt is injected the device etc. of type in silicon casting mold.
(silicon materials)
The silicon materials of the present invention are that the silicon casting method by the present invention manufactures.
That is, the silicon materials of the present invention such as mean by making the silicon melt in the silicon casting mold of the present invention solidify
Manufacture " polycrystalline silicon ingot ", will should " polycrystalline silicon ingot " cut into corner post shape " polysilicon block " and should " polysilicon
Block " it is processed into " polysilicon handle wafer " cut into slices.These silicon materials are applicable to the material of the higher solaode of cost effectiveness
Material.
" polysilicon block " such as can be by using the known devices such as band saw, by above-mentioned " polycrystalline silicon ingot " processing angulation
Column, required size and obtain.
Adding man-hour, dangerous, the surface portion of polycrystalline silicon ingot that can spread the impurity that there is molding material etc. are entered
Row cutting, it is possible to the surface of attrition process polysilicon block as required.
Above-mentioned " polysilicon block " such as can be cut into slices by " polysilicon handle wafer " by using the known devices such as multi-line cutting machine
It is processed into required thickness and obtains.
Under present situation, usually about thickness 170～200 μm, but as tendency, have and carry out slimming to cut down cost
Tendency.It addition, also dependent on the surface needing attrition process polysilicon handle wafer.
(silicon solar cell)
The silicon solar cell of the present invention is the silicon materials (polysilicon handle wafer) of the present invention to be used as substrate manufacture.
Silicon solar cell exists various structure, the Silicon Wafer of the present invention can be used, by known solaode
Operation and manufacture.Such as, in the case of doped with the Silicon Wafer of n-type impurity, p-type impurity (such as phosphorus) is made to expand from surface
Dissipate (doping) and form n-layer, thus form pn junction, form surface electrode and backplate and obtain polycrystalline silicon solar electricity
Pool unit.Similarly, in the case of doped with the Silicon Wafer of p-type impurity, n-type impurity (such as boron) is made (to mix from diffusion into the surface
Miscellaneous) and form p-type layer, thus form pn junction, form surface electrode and backplate and obtain polysilicon solar cell list
Unit.Or, in addition to these utilize silicon pn junction person each other, also have the MIS of clamping relatively thin insulating barrier and evaporation metal etc.
(Metal Insulator Semiconductor, Metal-Insulator-Semi-Conductor) type solaode, such as, have manufacture and Silicon Wafer
The silicon thin film of the amorphism etc. of contrary conductivity type, utilizes the p-type of different structure, the heterogeneous joint of n-type silicon etc..It addition, by right
It carries out multiple electrical connection, and obtains polysilicon solar cell module.
As it has been described above, in this specification, as comprising the concept of " solar battery cell " and " solaode module ",
Referred to as " solaode ".If it is therefoie, for example, be recited as " polysilicon solar cell ", then it is for comprising " the polysilicon sun
Energy battery unit " and the implication of " polysilicon solar cell module ".
Embodiment
Specifically describe the present invention below according to test example, but limit the invention not by these test examples.
(test example 1) is about the research of the mean diameter of additive contained in releasing material
Use the additive only comprising the various materials with specific mean diameter in the coating of mold base plate upper surface
Releasing material and formed quartz system silicon casting mold 1, manufacture polycrystalline silicon ingot, by obtained crystal ingot processing many
Crystal silicon wafer, uses the wafer manufacturing silicon solar cell obtained, and evaluates output and the interpolation of the solaode obtained
The relation of the mean diameter of thing.
Alpha-silicon nitride powders and 3% polyvinyl alcohol to particle diameter 1～60 μm of the main material as releasing material are water-soluble
Liquid carries out mixing makes weight ratio become 1:1, the powder of the additive shown in interpolation table 1 and make it disperse and obtain slurry A.
It should be noted that the amount suitably setting the powder of additive makes the surface density of additive become the most about
3.0/cm2。
Similarly, alpha-silicon nitride powders and 3% polyvinyl alcohol water solution are carried out mixing and makes weight ratio become 1:1, and make it
Disperse and obtain slurry B.
The side surface part of mold only coating sizing-agent B also makes it be dried at about 50 DEG C, is burnt by the film obtained at 900 DEG C
Becoming 2 hours, the side surface part at mold forms the releasing material of thickness about 250 μm.
Coating process is expressed as the releasing material on " top layer " by table 1 include lower floor without additive and comprise interpolation
The upper strata of thing, is formed in such a way.
The slurry B obtained only coated the base plate upper surface of mold and makes it be dried at about 50 DEG C, then will
The slurry A obtained only coats the base plate upper surface of mold and makes it be dried at about 50 DEG C, is existed by the film obtained
Burn till at 900 DEG C 2 hours, form the about 3.0/cm of surface density of additive2, the releasing material of thickness about 250 μm.
On the other hand, coating process is expressed as by table 1 releasing material of " mixing " only by the layer group comprising additive
Become, formed as follows.
The slurry A obtained only coated the base plate upper surface of mold and makes it be dried at about 50 DEG C, will be obtained
The film obtained burns till 2 hours at 900 DEG C, forms the about 3.0/cm of surface density of additive2, the Mould release material of thickness about 250 μm
The bed of material.
It should be noted that in order to obtain specific thickness, and the coating of slurry is suitably repeated with dry.
It addition, the above-mentioned film burnt till as mold side and base plate upper surface is carried out simultaneously.
It addition, in this test example, use the slurry A comprising the alpha-silicon nitride powders as main material with additive, but also
Can similarly use the slurry only comprising additive.
It addition, shown herein as using the silicon nitride example as the main material of release materials, but the present invention does not limit
Due to silicon nitride, even if being the multi-ply construction etc. of other material or silicon nitride and silicon oxide, as long as can obtain the present invention's
In the range of effect.
The mold table 3 of the graphite surrounded by heat-barrier material 8 in the casting device shown in Fig. 4 (880mm × 880mm ×
Thickness 200mm) on, arrange graphite outer mold 2 (inside dimension: 900mm × 900mm × highly 460mm, base plate wall thickness and
Side wall thickness 20mm), it is provided with mold 1 (inside dimension: 830mm × 830mm × 420mm, base plate wall thickness and the side of quartz system
Face the wall and meditate thick 22mm).It addition, the thermocouple 5 and 6 of temperature measuring is respectively arranged near mold 1 lower surface central authorities and outer casting
At near mould 2 lower surface central authorities 2.
Then, silicon raw material 4 obtained by the concentration of boron is adjusted in the way of the ratio resistance by crystal ingot being become about 1.4 Ω cm
After 420kg loads in mold 1, carry out application of vacuum in the chamber 7 of device, replace with argon.Thereafter, as device
Heating means, use to be positioned at the resistance heating body (graphite heater) 10 on mold side and control device 9 and melt silicon raw material 4
Solve, after confirming that all raw materials melt, use and control device 9 and possess the lift drive mechanism 12 of cooling bath 11, with the bar specified
Part (setting rate about 8mm/ hour) makes silicon unidirectional solidification.
Use band saw that the respective polycrystalline silicon ingot obtained is processed into polysilicon block (156mm × 156mm × 200mm)
25, and then use scroll saw to cut into slices, it is thus achieved that polysilicon handle wafer (156mm × 156mm × thickness 0.18mm) about 12000.
The polysilicon handle wafer obtained being put in common solar battery cell operation, every 1 crystal ingot is prepared about
12000 solar battery cells (profile 156mm × 156mm × thickness 0.18mm), measure its output (W).With each crystal ingot it is
Unit calculates the meansigma methods of output, standardized result is shown in Table 1.
For standardization, the average of solar battery cell using the crystal ingot of casting to be obtained exports, and calculates it
The meansigma methods of the output calculated in units of each crystal ingot when being set to 100, the crystal ingot of described casting is not by by containing of being formed
The mold of the releasing material of additive obtains.
As silicon for solar cell raw material be the most highly purified in the case of, in 1 crystal ingot, solaode is defeated
The major part of the reason going out reduction is the crystal defect on the top of crystal ingot and by the mold of the bottom of crystal ingot and is produced by release materials
Any one in raw impurity diffusion.Therefore, under the specified conditions in the crystal ingot of unidirectional solidification, due to setting time substantially
Fixing, therefore the impurity of the bottom of crystal ingot spreads without bigger difference, can be by the solaode list obtained by each crystal ingot
The average output of unit compares and evaluates the crystal defect on crystal ingot top.
It addition, in the case of the particle diameter of additive contained in releasing material is relatively big, polycrystalline silicon ingot is carried out block
Adding man-hour, bottom produces rupturing of being considered that stress caused.This presence or absence ruptured is also depicted in table 1.
And then, in Fig. 1, represent particle diameter and the solar-electricity of additive contained in the releasing material of silicon casting mold
The relation of the average output of pool unit.
[table 1]
From the result of table 1 and Fig. 1, the average output of solar battery cell and the material of additive be carborundum,
Silicon oxide, silicon nitride or graphite are unrelated, depend on the mean diameter of additive.That is, the mean diameter at additive be 0.1～
In the case of in the range of 3.0mm, and it is simply formed with compared with the situation of the releasing material of additive averagely exporting raising.
In the case of particularly the mean diameter of additive is in the range of 0.3～2.8mm, the increase rate of relative average output is
More than 0.5%, in the case of the mean diameter of additive is in the range of 0.8～2.2mm, become relative average output
Increase rate is the preferred result of more than 1.0%.Therefore, it is known that use the solar battery cell that above-mentioned average output improves
The output of made solaode module is improved.
It addition, in the mean diameter of additive in the case of the scope of 0.1～3.0mm, without the rupturing of bottom of silico briquette,
Better.
(test example 2) is about the research of the surface density of additive contained in releasing material
Use only to be coated with at mold base plate upper surface and there is the surface density of specific additive and comprise mean diameter
The releasing material of the additive of the various materials of 0.8mm and the silicon casting mold 1 of quartz system that formed, with test example 1
Same mode, manufactures polycrystalline silicon ingot, by the crystal ingot processing polysilicon handle wafer obtained, uses the wafer obtained to prepare silicon
Solaode, evaluates the relation of the output of the solaode obtained and the surface density of additive.
The result obtained is shown in table 2 and Fig. 2.In Fig. 2, represent contained in the releasing material of silicon casting mold
The relation of average output of surface density and solar battery cell of additive.
[table 2]
Knowable to the result of table 2 and Fig. 2, the average output of solar battery cell and the material of additive and release materials
The coating process of layer is unrelated, depends on the surface density of additive.That is, the surface density at additive is 0.2～8.5/cm2Model
In the case of in enclosing, and it is simply formed with compared with the situation of the releasing material of additive averagely exporting raising.Especially exist
The surface density of additive is 2.0～6.5/cm2In the range of situation time, the increase rate of relative average output is 0.5%
Above, the surface density at additive is 2.5～6.0/cm2In the range of situation time, become carrying of relative average output
High rate is the preferred result of more than 1.0%.Therefore, it is known that use the solar battery cell institute that above-mentioned average output improves
The output of the solaode module made is improved.
It should be noted that in test example 2, owing to using the relatively fine additive of mean diameter 0.8mm, therefore silicon
The bottom crack-free of block, more well.
Symbol description
1 mold
2 outer molds
3 mold table
4 silicon raw materials
Thermocouple under 5 molds
Thermocouple under 6 outer molds
7 chambers
8 heat-barrier materials
9 control device
10 resistance heating bodies (graphite heater)
11 cooling baths
12 lift drive mechanisms
Claims (9)
1. a silicon casting mold, it is the silicon casting mold making silicon melt solidify, and at above-mentioned silicon casting mold
At least base plate upper surface of inwall be provided with releasing material, described release materials comprises mean diameter 0.8～2.2mm
Additive.
2. silicon casting mold as claimed in claim 1, wherein, described releasing material is only arranged at table in above-mentioned base plate
Face.
3. silicon casting mold as claimed in claim 1, wherein, described silicon casting mold is by being main one-tenth with graphite or quartz
The material divided is constituted.
4. silicon casting mold as claimed in claim 1, wherein, described additive is with selected from silicon nitride, carborundum, silicon oxide
And at least one in graphite is main constituent.
5. silicon casting mold as claimed in claim 1, wherein, the surface of described releasing material is with 0.2～8.5/cm2
Surface density comprise described additive.
6. a silicon casting method, it is included in the silicon casting mold described in claim 1 and makes silicon melt solidify.
7. a silicon casting method, comprising: use the silicon casting mold being provided with releasing material on inwall, at described silicon
Under the state that the base plate upper surface of casting mold exists the powder that mean diameter is 0.8～2.2mm, the casting of described silicon is made to use
Silicon solution solidification in mold.
8. a manufacture method for silicon materials, it includes that use is cast according to the silicon casting method described in claim 6 or 7
Silicon and obtain silicon materials.
9. a manufacture method for solaode, it includes according to the silicon materials manufactured by the manufacture method of claim 8
Solaode is obtained as substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012042116A JP6014336B2 (en) | 2012-02-28 | 2012-02-28 | Silicon casting mold, silicon casting method, silicon material manufacturing method, and solar cell manufacturing method |
| JP2012-042116 | 2012-02-28 | ||
| PCT/JP2012/082227 WO2013128758A1 (en) | 2012-02-28 | 2012-12-12 | Mold for silicon casting, method for silicon casting, silicon material, and method for manufacturing solar cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104159847A CN104159847A (en) | 2014-11-19 |
| CN104159847B true CN104159847B (en) | 2016-10-19 |
Family
ID=49081977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280070752.4A Expired - Fee Related CN104159847B (en) | 2012-02-28 | 2012-12-12 | Silicon casting mold, silicon casting method, silicon materials and the manufacture method of solaode |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6014336B2 (en) |
| CN (1) | CN104159847B (en) |
| TW (1) | TWI458863B (en) |
| WO (1) | WO2013128758A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334603B1 (en) * | 1998-02-26 | 2002-01-01 | Mitsubishi Materials Corporation | Mold for producing silicon ingot and method for fabricating the same |
| WO2011122585A1 (en) * | 2010-03-31 | 2011-10-06 | 三菱マテリアル株式会社 | Multilayer crucible for casting silicon ingot and method for manufacturing the crucible |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06144824A (en) * | 1992-09-16 | 1994-05-24 | Kawasaki Steel Corp | Production of polycrystalline silicon |
| JP3250149B2 (en) * | 1998-02-27 | 2002-01-28 | 三菱マテリアル株式会社 | Silicon ingot casting mold and method of manufacturing the same |
| JP3206540B2 (en) * | 1998-02-26 | 2001-09-10 | 三菱マテリアル株式会社 | Laminated crucible for producing silicon ingot and method for producing the same |
| JP4484501B2 (en) * | 2003-11-27 | 2010-06-16 | 京セラ株式会社 | Silicon casting equipment |
| US7867334B2 (en) * | 2004-03-29 | 2011-01-11 | Kyocera Corporation | Silicon casting apparatus and method of producing silicon ingot |
| JP4741221B2 (en) * | 2004-11-25 | 2011-08-03 | 京セラ株式会社 | Polycrystalline silicon casting method, polycrystalline silicon ingot, polycrystalline silicon substrate and solar cell element using the same |
| JP4838591B2 (en) * | 2006-01-18 | 2011-12-14 | 新日鉄マテリアルズ株式会社 | Silicone coagulation mold and method for producing the same |
| EP2543751A3 (en) * | 2009-07-16 | 2013-06-26 | MEMC Singapore Pte. Ltd. | Coated crucibles and methods for preparing and use thereof |
-
2012
- 2012-02-28 JP JP2012042116A patent/JP6014336B2/en not_active Expired - Fee Related
- 2012-12-12 WO PCT/JP2012/082227 patent/WO2013128758A1/en active Application Filing
- 2012-12-12 CN CN201280070752.4A patent/CN104159847B/en not_active Expired - Fee Related
- 2012-12-19 TW TW101148492A patent/TWI458863B/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6334603B1 (en) * | 1998-02-26 | 2002-01-01 | Mitsubishi Materials Corporation | Mold for producing silicon ingot and method for fabricating the same |
| WO2011122585A1 (en) * | 2010-03-31 | 2011-10-06 | 三菱マテリアル株式会社 | Multilayer crucible for casting silicon ingot and method for manufacturing the crucible |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI458863B (en) | 2014-11-01 |
| WO2013128758A1 (en) | 2013-09-06 |
| TW201335443A (en) | 2013-09-01 |
| JP6014336B2 (en) | 2016-10-25 |
| CN104159847A (en) | 2014-11-19 |
| JP2013177274A (en) | 2013-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8871169B2 (en) | Methods and apparatuses for manufacturing cast silicon from seed crystals | |
| TWI445851B (en) | Methods and apparatuses for manufacturing geometric multicrystalline cast silicon and geometric multicrystalline cast silicon bodies for photovoltaics | |
| TWI534307B (en) | Method of manufacturing crystalline silicon ingot | |
| FR2908125A1 (en) | PROCESS FOR PURIFYING METALLURGICAL SILICON BY DIRECTED SOLIDIFICATION | |
| Ganesh et al. | Growth and characterization of multicrystalline silicon ingots by directional solidification for solar cell applications | |
| JP2005159312A (en) | Base material of polycrystalline silicon substrate for solar battery, and the polycrystalline silicon substrate for solar battery | |
| CN107109692A (en) | The manufacture method and solar cell of study on floating zone silicon used for solar batteries | |
| CN112144117B (en) | Hydrogen, phosphorus and nitrogen doped monocrystalline silicon, preparation method thereof and solar cell | |
| CN104010968B (en) | Polycrystal silicon ingot, its manufacture method and uses thereof | |
| CN104159847B (en) | Silicon casting mold, silicon casting method, silicon materials and the manufacture method of solaode | |
| JP6046780B2 (en) | Method for producing polycrystalline silicon ingot | |
| WO2016075092A1 (en) | Method for manufacturing an n-type monocrystalline silicon ingot | |
| CN111996594B (en) | Gallium, hydrogen and nitrogen doped monocrystalline silicon, preparation method thereof and solar cell | |
| CN104797745B (en) | Include the method for multiple monolithic Silicon Wafers vertically tied for manufacturing | |
| CN112151628A (en) | Solar cell and preparation method of gallium and hydrogen doped monocrystalline silicon | |
| CN105263859A (en) | Method for producing silicon ingot, and silicon ingot | |
| CN106794993B (en) | Method for producing polycrystalline silicon ingot, method for producing use of polycrystalline silicon ingot, and polycrystalline silicon ingot | |
| JP5140778B1 (en) | Method for producing polycrystalline silicon ingot | |
| JP4638012B2 (en) | Semiconductor substrate, solar cell using the same, and manufacturing method thereof | |
| WO2013125133A1 (en) | Heat treatment method of solid phase raw material and device thereof, and method of producing ingot, article and solar cell | |
| JP5220935B1 (en) | Silicon for solar cell, polycrystalline silicon material, polycrystalline silicon solar cell, and method for producing silicon for solar cell | |
| CN112071929A (en) | Solar cell and preparation method of phosphorus-hydrogen doped monocrystalline silicon | |
| JP2013220951A (en) | Polycrystalline silicon ingot, and method of manufacturing the same, and use thereof | |
| JP2004161565A (en) | Method of manufacturing granular silicon crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161019 |