CN102668109A - Method for manufacturing a polycrystalline silicon block material, method for manufacturing a polycrystalline silicon wafer, and polycrystalline silicon block material - Google Patents

Method for manufacturing a polycrystalline silicon block material, method for manufacturing a polycrystalline silicon wafer, and polycrystalline silicon block material Download PDF

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Publication number
CN102668109A
CN102668109A CN2010800511331A CN201080051133A CN102668109A CN 102668109 A CN102668109 A CN 102668109A CN 2010800511331 A CN2010800511331 A CN 2010800511331A CN 201080051133 A CN201080051133 A CN 201080051133A CN 102668109 A CN102668109 A CN 102668109A
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polysilicon
bulk
polycrystalline silicon
manufacturing approach
manufacturing
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续桥浩司
池田洋
金井昌宏
胁田三郎
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Mitsubishi Materials Corp
Mitsubishi Materials Electronic Chemicals Co Ltd
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Mitsubishi Materials Corp
Mitsubishi Materials Electronic Chemicals Co Ltd
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    • 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 System
    • H01L31/182—Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment
    • 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
    • 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

Abstract

Disclosed are a method for manufacturing a polycrystalline silicon block material, a method for manufacturing a polycrystalline silicon wafer, and a polycrystalline silicon block material, wherein heat treatment can be performed appropriately, allowing the production of high-quality polycrystalline silicon wafers with longer lifetimes. The disclosed method for manufacturing a polycrystalline silicon block material, which is used as a raw material for solar cell substrates, is characterized by the provision of: a casting step (S1) in which a silicon melt is solidified, forming a polycrystalline silicon ingot; a cutting step (S2) in which the obtained polycrystalline silicon ingot is cut into blocks shaped like polygonal prisms, the heights of which are between 100 and 500 mm and the polygonal bases of which have diagonal lengths between 150 and 400 mm; and a heat-treatment step (S3) in which the blocks are heat-treated at a temperature between 500 DEG C and 600 DEG C with a hold time of 15 to 60 minutes and then cooled at a rate between 10 DEG C/min and 60 DEG C/min.

Description

The manufacturing approach of polysilicon bulk, the manufacturing approach of polysilicon chip and polysilicon bulk
Technical field
The manufacturing approach of the polysilicon bulk that the present invention relates to use, the manufacturing approach and the polysilicon bulk of polysilicon chip as the raw material of used for solar batteries substrate.
The application advocates in the special priority of being willing to 2009-296874 number of the Japan of japanese publication, its content to be herein incorporated on December 28th, 2009.
Background technology
As the used for solar batteries substrate, the silicon chip that uses monocrystalline silicon or polysilicon to constitute.For example, in patent documentation 1, disclose the polycrystal silicon ingot that obtains through unidirectional solidification has been cut off the technology that the polysilicon chip that obtains is used as the used for solar batteries substrate.
In this solar cell, the characteristic of used for solar batteries substrate (polysilicon chip) is performance such as left and right sides conversion efficiency to a great extent.
As the index of the quality of estimating polysilicon chip, use the so-called life-span.This life-span refers to the time till the carrier that excites disappears, and the life-span of the known polysilicon chip conversion efficiency of longer then solar cell improves more.
Impurity level in this life-span and the polysilicon chip has relation, if impurity level increases the trend that then shows the lost of life.Therefore, through making the high-purity polycrystalline ingot, the life-span that can improve polysilicon chip.
Yet, be that purpose is being developed to make the high-purity polycrystalline ingot all the time, very difficulty of further high-purityization.In addition, the polycrystal silicon ingot of making extreme high purity needs huge cost, in industry, can't be widely used as the used for solar batteries substrate.
Therefore, for example in patent documentation 2, disclose, made impurity condense upon the surface etc. of silicon chip, thereby improve method of life through polysilicon chip is implemented heat treatment.
In addition, the oxygen donor that contains in the polysilicon also is the main cause that shortens the above-mentioned life-span.Wherein, in non-patent literature 1, disclose near 650 ℃ oxygen donor and disappeared, through fast through near 450 ℃, thereby can prevent the generation again of oxygen donor.That is,,, also can suppress the influence of oxygen donor through polysilicon chip is implemented heat treatment like 2 records of patent documentation.
Patent documentation 1: japanese kokai publication hei 10-245216 communique
Patent documentation 2: TOHKEMY 2005-166994 communique
Patent Document 1: ア cloth van nn su Suites Oh Toray ku Suites ro ni ku su I-4 van Hikaru bag crystal growth technology Editor: Geoncheon Keigo, Development Walker: Yamamoto grid, issuance of: Corporation BAIFUKAN, P.9
Yet,, when polysilicon chip is heat-treated,, therefore when heat treatment, need carry out atmosphere control with good precision owing to be prone to cause surface oxidation like 2 records of patent documentation.In addition, because to cutting to such an extent that thin polysilicon chip is operated, heat treatment operation is very miscellaneous.
At this, in order to implement heat treatment effectively, when directly polycrystal silicon ingot being heat-treated, if then cause polycrystal silicon ingot to crack through carrying out quenching near 450 ℃ fast.Thus, can not prevent the generation again of oxygen donor, and can not improve the life-span.
Summary of the invention
The present invention In view of the foregoing proposes; Its purpose is, the manufacturing approach of the polysilicon bulk that can heat-treat, can make the high-quality polysilicon chip that the life-span is improved rightly, the manufacturing approach and the polysilicon bulk of polysilicon chip are provided.
In order to solve above-mentioned problem, the manufacturing approach of the polysilicon bulk that the present invention relates to is that possess: casting process solidifies melted silicon and makes polycrystal silicon ingot as the manufacturing approach of the polysilicon bulk of the raw material use of used for solar batteries substrate; Cutting off operation, cut off resulting polycrystal silicon ingot, is that the above 400mm of 150mm is following, it highly is the compact body below the above 500mm of 100mm thereby cut out the diagonal angle line length that is polygonal column, this polygonal face; And heat treatment step, this compact body is carried out temperature more than 500 ℃ below 600 ℃, retention time heat treatment below 60 minutes, below the above 60 ℃/min of 10 ℃/min of cooling rate more than 15 minutes.
Manufacturing approach according to the polysilicon bulk of this technical scheme; Through cutting off polycrystal silicon ingot; The diagonal angle line length that cuts out this polygonal face is that the above 400mm of 150mm is following, it highly is the compact body below the above 500mm of 100mm; And this compact body heat-treated, therefore operation can be heat-treated operation simply than being easier to and the influence of surface oxidation is also lacked.
In addition, the diagonal angle line length of implementing the polygonal face of heat treated compact body is below the 400mm, it is highly for below the 500mm, even therefore in order in heat treatment, near 450 ℃, to carry out quenching fast, the compact body can not crack yet.Thus, in heat treated cooling procedure, oxygen donor can be do not produced again, high-quality polysilicon block can be made.
In addition and since with the temperature conditions of heat treatment step be set at more than 500 ℃, the retention time is set at more than 15 minutes, oxygen donor is disappeared and improve the life-span.
On the other hand, since with the temperature conditions of heat treatment step be set at below 600 ℃, the retention time is set at below 60 minutes, therefore can suppress the impurity element diffusion in the compact body.
Further, since with the cooling rate in the heat treatment step be set at 10 ℃/therefore more than the min, produce oxygen donor in the time of can being suppressed at cooling again.
On the other hand, since with the cooling rate in the heat treatment step be set at 60 ℃/therefore below the min, when cooling, can not worry that the compact body breaks.
Wherein, in the manufacturing approach of polysilicon bulk of the present invention, make said polycrystal silicon ingot through the unidirectional solidification method in the preferred said casting process.
Because silicon is the metal that expands when solidifying, need with in the inside of ingot not the mode of residual motlten metal cast.Therefore, through carrying out unidirectional solidification, can residual motlten metal in the inside of ingot, can prevent on the polycrystal silicon ingot of making, to crack.In addition, in the unidirectional solidification method,, therefore can obtain the high-purity polycrystalline ingot with comparalive ease because the impurity element in the melted silicon is discharged to liquid phase (motlten metal) from solid phase (ingot casting).
The manufacturing approach of the polysilicon chip that the present invention relates to is the manufacturing approach of the polysilicon chip that uses as the used for solar batteries substrate, possesses: cutting action, the polysilicon bulk of manufacturing approach manufacturing that will be through above-mentioned polysilicon bulk is cut into specific thickness.
Manufacturing approach according to the polysilicon chip of this technical scheme; To carry out heat treated polysilicon bulk and be cut into specific thickness; Therefore need not under the state of wafer, to heat-treat, can be easily and with low cost make the life-span grow, the high-quality polysilicon chip of no surface oxidation.
The polysilicon bulk that the polysilicon bulk that the present invention relates to uses for the raw material as the used for solar batteries substrate; Be the polygonal column; The diagonal angle line length of this polygonal face is below the above 400mm of 150mm, it is highly for below the above 500mm of 100mm; Impurity level is that its life-span is more than the 1 μ sec in the scope below the above 1ppm of 0.01ppm.
The polysilicon bulk of this technical scheme is owing to be the polygonal column, and the diagonal angle line length of this polygonal face is below the above 400mm of 150mm, and therefore the cross section shape about equally of formation and polysilicon chip through this polysilicon bulk of cutting, can make polysilicon chip.
In addition, because the diagonal angle line length of polygonal face is that 150mm is above, it is highly for more than the 100mm, can processing ease and heat-treat simply.In addition, because the influence of surface oxidation is few, therefore need not excessively to carry out atmosphere control.
Further, because the diagonal angle line length of polygonal face is below the 400mm, it is highly for below the 500mm, therefore in heat treatment, even in order near 450 ℃, to carry out quenching fast, the polysilicon bulk can not crack yet.
So can heat-treat rightly, so the inner oxygen donor of polysilicon bulk disappears and the impurity cohesion, the life-span is improved.
Thus, even impurity level is in the scope below the above 1ppm of 0.01ppm, also can the life-span be extended to more than the 1 μ sec.That is, need not to make the polycrystal silicon ingot of extreme high purity, can make sufficiently long high-quality polysilicon chip of life-span.
And when measuring the life-span, its surface roughness is brought big influence.Thus, the surface roughness of working sample is set at 10 mean roughness Rzjis (JIS B 0601:2001) and counts 1 μ m.
Wherein, in polysilicon bulk of the present invention, preferably through the moulding of unidirectional solidification method, by constituting towards a plurality of column crystals that solidify the direction extension.
In the unidirectional solidification method, the impurity element in the melted silicon is discharged to the liquid phase (motlten metal) from solid phase (ingot casting), so the purity of polysilicon bulk raises.Thus, can prolong the life-span of this polysilicon bulk.
So, according to the present invention, the manufacturing approach of the polysilicon bulk that can heat-treat, can make the high-quality polysilicon chip that the life-span is improved rightly, the manufacturing approach and the polysilicon bulk of polysilicon chip can be provided.
Description of drawings
Fig. 1 is the brief description figure of the polysilicon bulk of embodiment of the present invention.
Fig. 2 is the brief description figure that becomes the raw-material polycrystal silicon ingot of polysilicon bulk shown in Figure 1.
Fig. 3 is for making the brief description figure of the employed manufacturing equipment for polysilicon ingot of polycrystal silicon ingot shown in Figure 2.
Fig. 4 is the flow chart of the manufacturing approach of manufacturing approach and the polysilicon chip of the polysilicon bulk of expression embodiment of the present invention.
Embodiment
Followingly the manufacturing approach of the polysilicon bulk of embodiment of the present invention, the manufacturing approach and the polysilicon bulk of polysilicon chip are described with reference to accompanying drawing.
The polysilicon bulk 1 of this execution mode is the raw material as the polysilicon chip of used for solar batteries substrate.
As shown in Figure 1, this polysilicon bulk 1 is the polygonal column, in this execution mode, is tetragonal column.And the height H 1 of this polysilicon bulk 1 is set in the scope of 100mm≤H1≤500mm, in this execution mode, is set to H1=300mm.
In addition, the diagonal angle line length D1 of tetragonal face is set in the scope of 150mm≤D1≤400mm.And in this execution mode, tetragonal face is one side and is the square of 156mm, and its diagonal angle line length D1 is about 221mm.
In addition, the impurity level of this polysilicon bulk 1 is that its life-span is more than the 1 μ sec in the scope below the above 1ppm of 0.01ppm.
At this, the life-span refers to, to the surface irradiation light of working sample, and the time till the carrier that produces through optical excitation (photoelectron hole to) disappears.We know that the surface state of working sample can be brought bigger influence when measuring the life-span.Therefore, the life-span in the polysilicon bulk 1 of this execution mode is the surface roughness of working sample to be counted 1 μ m with 10 mean roughness Rzjis (JIS B 0601:2001) measure the value that obtains.
This polysilicon bulk 1 obtains through cutting off polycrystal silicon ingot shown in Figure 2 10.
As shown in Figure 2, this polycrystal silicon ingot 10 is tetragonal column, and its height H 2 is set in the scope of 100mm≤H2≤500mm, in this execution mode, is set to H2=300mm.
In addition, the diagonal angle line length D2 of tetragonal face is set in the scope of 150mm≤D2≤1600mm.And in this execution mode, tetragonal face is one side and is the square of 680mm, and its diagonal angle line length D2 is about 962mm.
As shown in Figure 2, can make 16 polysilicon bulks 1 by this polycrystal silicon ingot 10.
Then, the manufacturing equipment for polysilicon ingot 20 that uses when making this polycrystal silicon ingot 10 with reference to Fig. 3 describes.
This manufacturing equipment for polysilicon ingot 20 possesses: store melted silicon L crucible 21, carry the coldplate 22 put this crucible 21, from the bottom heater 23 of this coldplate 22 of supported underneath be provided in the top heater 24 of the top of crucible 21.In addition, around crucible 21, be provided with adiabatic material 25.
Wherein, crucible 21 is that horizontal cross sectional geometry is the silicon dioxide system crucible of square (quadrangle) or ring shape (circle).In this execution mode, horizontal cross sectional geometry is square (quadrangle).
In addition, coldplate 22 is a hollow structure, through supply pipe 26 to internal feed Ar gas.
Then, with reference to flow chart shown in Figure 4 the manufacturing approach of the polysilicon bulk of this execution mode and the manufacturing approach of polysilicon chip are described.
(casting process S1)
At first, use above-mentioned manufacturing equipment for polysilicon ingot 20, casting polycrystalline silicon ingot 10.
During through above-mentioned manufacturing equipment for polysilicon ingot 20 manufacturing polycrystalline silicon ingots 10, at first, the silicon raw material of in crucible 21, packing into.To top heater 24 with bottom heater 23 energisings heat and fuse this silicon raw material.Thus, in crucible 21, store melted silicon L.
Then, stop energising to bottom heater 23, through supply pipe 26 to the internal feed Ar of coldplate 22 gas.Thus, the bottom of cooling crucible 21.Further, through the energising of slow minimizing to top heater 24, melted silicon L begins to be cooled from the bottom of crucible 21, and forms unidirectional solidification from the lower direction top.Thus, can make the polycrystal silicon ingot 10 of the column crystal formation of extending to the top from the bottom.
The polycrystal silicon ingot 10 of quadrangular prism shape so, shown in Figure 2 is through the moulding of unidirectional solidification method.
And the impurity level in this polycrystal silicon ingot 10 is adjusted in the scope below the above 1ppm of 0.01ppm.
(cutting off operation S2)
The polycrystal silicon ingot 10 that will obtain through casting process S1 as illustrated in fig. 2 with the mode of one side quartering of tetragonal face with cut-outs such as band sawing machines, make 16 compact bodies 11.This compact body 11 is the quadrangular prism shape, and the diagonal angle line length of tetragonal face is below the above 400mm of 150mm, it is highly for below the above 500mm of 100mm, and in this execution mode, the diagonal of tetragonal face is about to 221mm, highly be 300mm.
(heat treatment step S3)
Then, compact body 11 is heat-treated.Use the heat-treatment furnace of Ar gas atmosphere, heat-treat in 60 ℃ of 10 ℃ of heat treatment temperature more than 500 ℃ below 600 ℃, retention time more than 15 minutes below 60 minutes, cooling rates/more than the min/(heat treatment temperature is to room temperature) below the min.And in this execution mode, temperature is 600 ℃, and the retention time is 60 minutes, and cooling rate is 30 ℃/min.
Through this heat treatment, impurity cohesion when the oxygen donor in the compact body 11 disappears, even impurity level is in the scope below the above 1ppm of 0.01ppm, also can make the life-span is the above polysilicon bulk 1 shown in Figure 1 of 1 μ sec
(cutting action S4)
Then, the polysilicon bulk 1 that obtains as stated is cut into the thickness of regulation.Thus, can make polysilicon chip.
According to the manufacturing approach of the polysilicon bulk of this execution mode of this technical scheme, the manufacturing approach and the polysilicon bulk 1 of polysilicon chip; Cut off polycrystal silicon ingot 10; Thereby the diagonal angle line length that cuts out polygonal face (tetragonal face) is (being about 221mm in this execution mode) below the above 400mm of 150mm, it highly is the compact body 11 of (being 300mm in this execution mode) below the above 500mm of 100mm; This compact body 11 is heat-treated; Thus operation than be easier to, the influence of surface oxidation also lacks, and can heat-treat operation simply.
In addition; For implementing heat treated compact body 11; The diagonal angle line length of polygonal face (tetragonal face) is below the 400mm, it is highly for below the 500mm, even therefore in order in heat treatment, near 450 ℃, to carry out quenching fast, compact body 11 can not crack yet.
In addition and since with the temperature conditions of heat treatment step S3 be set at more than 500 ℃, the retention time is set at more than 15 minutes, oxygen donor in the compact body 11 is disappeared and improve the life-span.
On the other hand, since with the temperature conditions of heat treatment step S3 be set at below 600 ℃, the retention time is set at below 60 minutes, therefore can suppress the impurity element diffusion, can realize the raising in life-span.
Further, since with the cooling rate among the heat treatment step S3 be set at 10 ℃/therefore more than the min, produce oxygen donor in the time of can being suppressed at cooling again.
On the other hand, since with the cooling rate among the heat treatment step S3 be set at 60 ℃/therefore below the min, when cooling, can not worry that compact body 11 breaks.
In addition; In the polysilicon bulk 1 of this execution mode; Because the cross section shape about equally of the polysilicon chip that the diagonal angle line length that is polygonal column and this polygonal face is the above 400mm of 150mm is following, form and made; Therefore through this polysilicon bulk 1 of cutting, can make polysilicon chip.
In addition, owing to can heat-treat rightly, so impurity cohesion when disappearing of polysilicon bulk 1 inner oxygen donor, the life-span is improved.Thus, even in the scope below impurity level is the above 1ppm of 0.01ppm, also can the life-span be extended to more than the 1 μ sec.
Further, in this execution mode, polysilicon bulk 1 cuts off through the polycrystal silicon ingot 10 that will utilize the moulding of unidirectional solidification method and makes.Wherein because silicon is the metal that expands when solidifying, need with in the inside of polycrystal silicon ingot 10 not the mode of residual motlten metal cast.Therefore, through carrying out unidirectional solidification, can residual motlten metal in the inside of polycrystal silicon ingot 10, can prevent on polycrystal silicon ingot 10, to crack.In addition, in the unidirectional solidification method,, therefore can obtain high-purity polycrystalline ingot 10 with comparalive ease because the impurity element in the melted silicon is discharged to liquid phase (motlten metal) from solid phase (ingot casting).
More than the manufacturing approach of the polysilicon bulk of execution mode of the present invention, the manufacturing approach and the polysilicon bulk of polysilicon chip are illustrated, but be not limited thereto, can carry out suitable design alteration.
For example, be illustrated, but be not limited thereto, also can make polycrystal silicon ingot through the manufacturing equipment for polysilicon ingot of other structure to making polycrystal silicon ingot through manufacturing equipment for polysilicon ingot shown in Figure 3.
In addition, size, the shape of polycrystal silicon ingot are not limited by this execution mode, as long as can obtain size, the shape of polysilicon bulk of the present invention.
Further, be that the situation of quadrangular prism shape is illustrated to the polysilicon bulk, but be not limited thereto, as long as be the polygonal column.
Embodiment
The affirmation result of experiment of carrying out in order to confirm effect of the present invention shown in the embodiment.Use the manufacturing equipment for polysilicon ingot of explaining in this execution mode, make the different a plurality of polycrystal silicon ingots of impurity level.In addition, cut off these polycrystal silicon ingots, obtain the different a plurality of compact bodies of size with band sawing machine.
Under various heat-treat conditions, a plurality of compact bodies that so obtain are implemented heat treatment, make the polysilicon bulk.
The compact body that obtains as stated and the life-span of polysilicon bulk are measured, confirmed before the heat treatment and afterwards life-span.
And the mensuration in life-span is led damped method (μ-PCD) measure through RF-MW Photonics.Determinator uses the WT-2000 of SEMILAB corporate system.In addition, the wavelength of microwave is 904nm.Further, the surface roughness of working sample is adjusted with the mode that 10 mean roughness Rzjis (JIS B 0601:2001) count 1 μ m.
The result is as shown in table 1.
Figure BDA00001628484800101
Be the comparative example 1 of 600mm, highly produced crackle in the block after being to have seen heat treatment in the comparative example 8 of 80 ℃/min for the comparative example 2 of 600mm and cooling rate at the diagonal angle line length.Supposition is that in the inside and the outside temperature difference that produces of block, the thermal deformation that causes owing to this temperature difference cracks because too fast with respect to the size cooling rate of block.
In addition, in comparative example 3 ~ 7, all do not see the significantly raising in life-span.
In the heat treated retention time is that supposition is because heat treatment is insufficient, can not fully carry out the disappearance of oxygen donor, the cohesion of impurity element, so is not improved the life-span in the comparative example 5 that comparative example 3 and heat treated retention time of 400 ℃ is 10min.
In the heat treated retention time is that supposition is because the inner impurity element of block spreads widely, so the life-span is not improved in the comparative example 6 that comparative example 4 and heat treated retention time of 700 ℃ is 80min.
In cooling rate is in the comparative example 7 of 5min, and supposition is to produce oxygen donor again owing in the cooling procedure, so the life-span is not improved.
Therewith relatively, in the present invention example 1 ~ 9, the life-span fully improves, and is that life-span more than the 0.01ppm, before the heat treatment is that the life-span after the heat treatment also is more than the 1 μ sec in the present invention's example 7,8 below the 1 μ sec at impurity level particularly.And, be in the present invention example 9 more than the 1ppm at impurity level, though the life-span improve, yet even owing to make the impurity cohesion also can be at the inner residual impurity of block through heat treatment, so the life-span be more than 1 μ sec.
Like this, confirm high-quality polysilicon bulk and the polysilicon chip that life-span length can be provided according to the present invention.
Utilizability on the industry
According to the present invention, can easily make the polysilicon bulk that life-span of being suitable as the used for solar batteries baseplate material is improved through the simple heat treatment operation.
Symbol description
1 polysilicon bulk
10 polycrystal silicon ingots

Claims (5)

1. the manufacturing approach of a polysilicon bulk, the manufacturing approach of the polysilicon bulk that uses for the raw material as the used for solar batteries substrate is characterized in that possessing:
Casting process solidifies melted silicon and makes polycrystal silicon ingot;
Cut off operation, cut off resulting polycrystal silicon ingot, be below the above 400mm of 150mm, highly be the following compact body of the above 500mm of 100mm thereby cut out the diagonal angle line length that is polygonal column, this polygonal face; With
Heat treatment step carries out temperature more than 500 ℃ below 600 ℃, retention time heat treatment below 60 minutes, below the above 60 ℃/min of 10 ℃/min of cooling rate more than 15 minutes to this compact body.
2. the manufacturing approach of polysilicon bulk according to claim 1 is characterized in that, makes said polycrystal silicon ingot through the unidirectional solidification method in the said casting process.
3. the manufacturing approach of a polysilicon chip, the manufacturing approach for the polysilicon chip that uses as the used for solar batteries substrate is characterized in that possessing:
Cutting action, the polysilicon bulk of manufacturing approach manufacturing that will be through claim 1 or the described polysilicon bulk of claim 2 is cut into specific thickness.
4. polysilicon bulk, the polysilicon bulk for the raw material as the used for solar batteries substrate use is characterized in that,
Be the polygonal column, the diagonal angle line length of this polygonal face is below the above 400mm of 150mm, and the height of polysilicon bulk is below the above 500mm of 100mm,
Impurity level is that the life-span of polysilicon bulk is more than the 1 μ sec in the scope below the above 1ppm of 0.01ppm.
5. polysilicon bulk according to claim 4 is characterized in that, through the moulding of unidirectional solidification method, by constituting towards a plurality of column crystals that solidify the direction extension.
CN2010800511331A 2009-12-28 2010-12-24 Method for manufacturing a polycrystalline silicon block material, method for manufacturing a polycrystalline silicon wafer, and polycrystalline silicon block material Pending CN102668109A (en)

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