CN104010968B - Polycrystal silicon ingot, its manufacture method and uses thereof - Google Patents

Polycrystal silicon ingot, its manufacture method and uses thereof Download PDF

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Publication number
CN104010968B
CN104010968B CN201280063468.4A CN201280063468A CN104010968B CN 104010968 B CN104010968 B CN 104010968B CN 201280063468 A CN201280063468 A CN 201280063468A CN 104010968 B CN104010968 B CN 104010968B
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crucible
manufacture method
polysilicon
silicon ingot
polycrystal silicon
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CN104010968A (en
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大石隆一
上野和也
梶本公彦
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Sharp Corp
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/006—Controlling or regulating
    • 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
    • C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
    • 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
    • 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
    • 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
    • Y02E10/547—Monocrystalline 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

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  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A kind of polycrystal silicon ingot manufacture method, this polycrystal silicon ingot manufacture method be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, detected temperatures near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm, in during described detected temperatures is reduced to (Tm-60) DEG C from (Tm-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.

Description

Polycrystal silicon ingot, its manufacture method and uses thereof
Technical field
The present invention relates to polycrystal silicon ingot, the manufacture method of this polycrystal silicon ingot and the purposes of this polycrystal silicon ingot.
Background technology
As the substitute of oil global environment being caused to various problem etc., the utilization of natural energy just receives publicity.Wherein, solar cell owing to not needing larger equipment, and can not produce noise etc. in the running, has therefore been incorporated into Japan, Europe etc. energetically especially.
Also some is actually applied the solar cell of the compound semiconductors such as use cadmium telluride, but from the viewpoint of the security of material self, real achievement up to now and cost performance, the solar cell of crystalline silicon substrates is used to occupy larger share of market, wherein, the solar cell (polysilicon solar cell) of polycrystalline silicon substrate is used to occupy larger share of market.
Usually the polysilicon chip of the substrate of polysilicon solar cell is widely used as, that the ingot casting of the method manufacture by being referred to as casting is cut into block, and becoming thin slice by section, above-mentioned casting in crucible, makes molten silicon unidirectional solidification and obtain larger polycrystal silicon ingot.
The polysilicon chip manufactured by casting has the distribution of the output characteristic of solar cell as shown in Figure 5 usually according to the difference of the short transverse position in ingot casting or block.
The reason producing the characteristic distribution of Fig. 5 is described as follows usually.
First in the region I at unidirectional solidification initial stage, be subject to the impact of the impurity spread from crucible, cause characteristic to reduce.In the region II of side at an upper portion thereof, because the impurity in the raw material that less generation causes because of segregation is to being mixed into and lattice defect in crystal, therefore in block, characteristic is best.More leaning in the region III of upper side, the impurity level be not only mixed in crystal increases gradually, and the generation of lattice defect also increases, so reduce compared to region II characteristic.In the region IV of upper side, the same with region III, the generation being mixed into impurity level in crystal and lattice defect increases further, and after ingot solidification is extremely last, from the back diffusion of hight-concentration parts generation impurity of impurity appearing at uppermost surface part, impurity level is increased further, and therefore compared to region III, characteristic obviously reduces further.
In the above description, although the impurity considered in raw material and the impact of the impurity of liquate from crucible, even but when supposing do not have these to affect, in III and IV of region, along with the transition gradually to top, the lattice defect becoming minority carrier trap (minority キ ャ リ ア ト ラ ッ プ) also can increase gradually, and therefore the characteristic of solar cell exists the trend reduced.
The reason of generation lattice defect is considered to the stress caused by temperature distribution in ingot casting, is suppressed, propose two following methods from the view point of to it.
First, in such as Japanese Unexamined Patent Publication 2005-152985 publication (patent documentation 1), propose a kind of method being arranged at the mold retainer of crucible bottom when mold retainer using the heat flux of central part larger than surrounding is used as unidirectional solidification (casting).
The second, in such as International Publication the 2005/092791st (patent documentation 2), propose a kind of method utilizing the structure of (heat exchange) variable area that can make to be heated to carry out hot-fluid control in ingot casting process of growth.
In addition, as the countermeasure of the quality of the raising polycrystal silicon ingot different from aforesaid method, propose by the method added for the purpose of Large stone.
Such as, in Japanese Patent No. 4203603 publication (patent documentation 3) and Japanese Unexamined Patent Publication 2005-132671 publication (patent documentation 4), propose a kind of by chilling crucible bottom bottom ingot (at early solidification) produce dendritic crystal as the nuclei of crystallization, thus make the method that crystal grain becomes large.
In addition, in Japanese Patent No. 4054873 publication (patent documentation 5), proposes and a kind ofly to make in the melting operation of silicon raw material residual crystalline wafer (melting residuum) growth and make crystal grain become large, thus it is brilliant to obtain accurate monocrystalline (Yi Si Unit Knot) method.
Further, in Japanese Patent No. 4569957 publication (patent documentation 6), propose one and make silicon from seed crystal Heteroepitaxies such as SiC, thus obtain the method for accurate monocrystalline, wherein the seed crystal such as SiC is configured at the bottom of crucible in the mode that crystalline orientation is consistent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-152985 publication
Patent documentation 2: International Publication the 2005/092791st
Patent documentation 3: Japanese Patent No. 4203603 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-132671 publication
Patent documentation 5: Japanese Patent No. 4054873 publication
Patent documentation 6: Japanese Patent No. 4569957 publication
Summary of the invention
Invent technical problem to be solved
In the method for patent documentation 1, particularly when well heater is in crucible side, the result that the shape of solid-liquid interface is deteriorated further will be there is, there is this technical problem of effect that can not obtain and reduce defect concentrations in crystals, prevent from breaking etc.
In the method for patent documentation 2, although can improve the controllability from crucible wall heat extraction, apparatus structure is complicated especially, and the moving part of high temperature is more, there is the technical problem of the cost increase of device, fault increase.
In the method for patent documentation 3 ~ 5, there is following advantage: become by making crystal grain and the characteristic caused by crystal boundary can be suppressed greatly to reduce, particularly when cast ingot dimension is less, stress caused by temperature distribution is less, and the lattice defect imported in the top side of ingot casting is also suppressed to a certain extent.But owing to becoming large along with ingot contraction rule cun, the lattice defect of top side also increases, although therefore can see that the characteristic of bottom side improves, but still the technical problem that the characteristic leaving the solar cell made in top side reduces.
In the method for patent documentation 6, the silicon wafer grown from seed crystals such as adjacent SiC forms defect in the junction section encountered one another, even if ingot casting is macroscopically looking like monocrystalline, electrical resistance also comprises a lot of defect.In addition, about top side, along with cast ingot dimension becomes large, the defect concentrations in crystals of top side also uprises, the technical problem that the characteristic still leaving the solar cell made in top side reduces.
On the other hand, because the size of polycrystal silicon ingot is larger, more can suppress the price of every a slice polysilicon chip, therefore there is the large trend of change in the size of ingot casting.
Therefore, in order to realize high performance and the low price of final polycrystalline solar module, need a kind of can be easy and reduce defect concentrations in crystals at low cost, prevent the method for breaking in the manufacturing processed of larger-size polycrystal silicon ingot.
Technical problem of the present invention be to provide a kind of can the easy and purposes of the polycrystal silicon ingot reducing defect concentrations in crystals at low cost, prevent the manufacture method of the larger-size polycrystal silicon ingot broken, obtained by the manufacture method of this polycrystal silicon ingot and this polycrystal silicon ingot.
The technique means of technical solution problem
The present inventor conducts in-depth research repeated multiple timesly, found that, when the bottom making the molten silicon in crucible from crucible manufactures polycrystal silicon ingot to top unidirectional solidification, by the temperature starting to carry out the crucible bottom of solidifying (crystal growth) is controlled to the condition impelling the nuclei of crystallization to produce, above-mentioned technical problem can be eliminated, complete the present invention.
So, according to the present invention, a kind of polycrystal silicon ingot manufacture method is provided, this polycrystal silicon ingot manufacture method be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, detected temperatures near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm, in during described detected temperatures is reduced to (Tm-60) DEG C from (Tm-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
In addition, according to the present invention, a kind of polycrystal silicon ingot manufacture method is provided, this polycrystal silicon ingot manufacture method be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, the detected temperatures of the 20mm position, below near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm ', in during described detected temperatures is reduced to (Tm '-60) DEG C from (Tm '-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
In addition, according to the present invention, a kind of polycrystal silicon ingot by the manufacture of above-mentioned polycrystal silicon ingot manufacture method is provided, processes this polycrystal silicon ingot and the polysilicon block obtained, processes this polysilicon block and the polysilicon chip obtained and the polysilicon solar cell using this polysilicon chip to manufacture.
In the present invention, " solar cell " represents " solar battery cell " of formation minimum unit and multiple " solar battery cell " electrical connection is obtained " solar module ".
Invention effect
According to the present invention, can provide a kind of can the easy and purposes of the polycrystal silicon ingot reducing defect concentrations in crystals at low cost, prevent the manufacture method of the larger-size polycrystal silicon ingot broken, obtained by the manufacture method of this polycrystal silicon ingot and this polycrystal silicon ingot.
That is, according to the present invention, the polycrystal silicon ingot of high-quality, polysilicon block and polysilicon chip can be manufactured with lower price, can, the high polysilicon solar cell that export high to market supply cost performance.
The manufacture method of polycrystal silicon ingot of the present invention when said temperature velocity of variation is 2 ~ 7 DEG C/h, temperature time of reducing with the rate of temperature change of above-mentioned 1 ~ 10 DEG C/h is when existing more than 20%, especially can play above-mentioned effect.
Accompanying drawing explanation
Fig. 1 is the figure (test example 2) of temperature variation when representing manufacture polycrystal silicon ingot near crucible lower surface central authorities.
The figure (test example 1) of the relation between rate of temperature change when Fig. 2 is output rating and the manufacture polycrystal silicon ingot representing solar cell.
The figure (test example 2) of the relation between the occupation rate of rate of temperature change when Fig. 3 is output rating and the manufacture polycrystal silicon ingot representing solar cell.
Fig. 4 is the general profile chart of the example representing the device used in the manufacture method of poly semiconductor ingot of the present invention.
Fig. 5 is the concept map of the relation between the position of the short transverse representing common polycrystalline silicon ingot and the output rating of solar cell made.
Embodiment
The feature of the manufacture method of polycrystal silicon ingot of the present invention is, be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, detected temperatures near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm, in during described detected temperatures is reduced to (Tm-60) DEG C from (Tm-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
Make raw material solid silicon in crucible when melting, above-mentioned detected temperatures " Tm " can be defined as before silicon is near completion melting, and silicon melt temperature is that the fusing point of silicon gets certain value and the detected temperatures of detected temperatures near crucible lower surface central authorities also roughly one timing.In this condition, silicon melt temperature becomes the fusing point of silicon, and Tm is the detected temperatures near crucible lower surface central authorities now.Because crucible platform is cooled all the time, therefore think that Tm is lower than the fusing point of silicon several degrees Celsius.The actual measurement absolute value of Tm because of the calibration steps of thermopair, degradation, individual difference, arrange to device time deviation etc. and in display, have some deviations, the error of actual measurement absolute value is larger.But, by taking Tm as the detected temperatures near benchmark correction crucible lower surface central authorities, the principal element of above-mentioned deviation can be got rid of, the reproducibility of crystal growth condition can be guaranteed.For above-mentioned reason, the actual measurement absolute value of the Tm in the present embodiment sometimes also can be higher than the fusing point of silicon, in the scope of 1407 DEG C ~ 1418 DEG C.
When injecting the manufacturing equipment for polysilicon ingot etc. of mode of silicon melt in crucible, such as, can measure the temperature of fused solution by utilizing radiation thermometer and the relation obtained between the detected temperatures near itself and crucible lower surface central authorities is determined above-mentioned " Tm ".
In addition, the feature of the manufacture method of polycrystal silicon ingot of the present invention is, be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, the detected temperatures of the 20mm position, below near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm ', in during described detected temperatures is reduced to (Tm '-60) DEG C from (Tm '-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
Above-mentioned detected temperatures " Tm ' " be only that measuring point for the temperature is different, can determine in the same manner with described " Tm ".At this, as measuring point for the temperature, have selected the 20mm position, below near crucible lower surface, as long as but and exist between crucible thermal conductance lead to and can and crucible in silicon temperature between obtain the region of relation, just can become measuring point for the temperature.
The present inventor has carried out the evaluation of lattice defect, analysis and research to a lot of polycrystal silicon ingot, found that, as the method for the defect concentrations in crystals of the top side of reduction ingot casting, except being considered to from continuously effective in the past and except the conventional method by suppressing to reduce stress to temperature distribution, also there is diverse method.
Specifically, the present inventor with by adding the antipodal design of technology that large grain size suppresses the characteristic caused by crystal boundary to reduce this patent documentation 3 ~ 6 to record, find compared with the polycrystal silicon ingot larger with crystal particle diameter, the polycrystal silicon ingot comparatively proof stress that crystal particle diameter is less, is difficult to produce lattice defect.
According to the opinion of the present inventor, (1) in polycrystal silicon ingot, even tightly adjacent part, the grain that crystal particle diameter is larger and the less grain of crystal particle diameter import inner defect concentrations in crystals and also differ widely, (2) between the crystal particle diameter of ingot casting and the defect concentrations in crystals of its top side, there is relation, (3) although there is exception, crystal particle diameter is less, and the defect concentrations in crystals of the top side of ingot casting is lower.Be difficult to the adjacent part thought in ingot casting, there is larger difference in the thermal stresses suffered when ingot casting grows, therefore, think that the less part of crystal particle diameter makes stress suffered in crystal grain be relaxed by the slippage etc. of grain boundary portion, result inhibits lattice defect to import in crystal grain.
Therefore, when manufacturing polycrystal silicon ingot when the molten silicon unidirectional solidification made in crucible, produce the nuclei of crystallization and reduction crystal particle diameter by impelling in crucible bottom, the characteristic that can relax the top side of polycrystal silicon ingot reduces.
In order to reduce the lattice defect of the top side of polycrystal silicon ingot, think up to now always and need to make the smooth grade of solid-liquid interface, reduce the thermal stresses putting on ingot casting, in contrast, in the present invention, control by means of only the crystal particle diameter reducing crystal particle diameter, just can reduce the lattice defect of the top side of polycrystal silicon ingot.
The manufacturing equipment for polysilicon ingot that can be used in the manufacture method of polycrystal silicon ingot of the present invention, not by particular restriction, can use known manufacturing installation to implement.
If row are given one example, then such as can utilize the enforcement such as manufacturing installation as under type: utilize the cooling body as refrigeration cycle being located at the base side of crucible to cool crucible bottom surface, and utilize lift drive mechanism make crucible from heating arrangements away from, thus the molten silicon in crucible is solidified gradually from the molten silicon near the bottom of crucible.Now, by known method, specifically thermopair, radiation thermometer control heater temperature, the melting monitoring silicon and the rate of temperature change etc. solidifying, cool.
The manufacture method > of < polycrystal silicon ingot
Be described based on the manufacture method of accompanying drawing to polycrystal silicon ingot of the present invention below, but the present invention is not limited to this embodiment.
Even if the manufacture method of poly semiconductor ingot of the present invention uses the known device shown in Fig. 4 can implement too.
Fig. 4 is the general profile chart of the example representing the device used in the manufacture method of poly semiconductor ingot of the present invention.
This device normally uses to manufacture polycrystal silicon ingot, has the chamber (encloses container) 7 forming resistance heading furnace.
Have crucible 1 in the internal configuration of chamber 7, this crucible 1 is graphite-made, quartz (SiO 2) system etc., the environment of chamber 7 inside can remain air-tight state.
In the chamber 7 holding crucible 1, be configured with the crucible platform 3 of the graphite-made of supporting crucible 1.Crucible platform 3 can utilize lift drive mechanism 12 to be elevated, and the refrigeration agent (water coolant) in cooling tank 11 is in the internal recycling of this crucible platform 3.
Be configured with outer crucible 2 on the top of crucible platform 3, this outer crucible 2 is graphite-made etc., is configured with crucible 1 wherein.Also the cover of outer crucible 2 and configuration encirclement crucible 1 can be replaced, this cover graphite-made etc.
This resistance heating body 10 of graphite heater is configured with in the mode of surrounding outer crucible 2, and, be configured with lagging material 8 in the mode covering these components from top.
Resistance heating body 10 can heat from the surrounding of crucible 1, and the raw silicon 4 in crucible 1 is melted.
As long as the lift action of the cooling that the heating can undertaken by resistance heating body 10, above-mentioned cooling tank 11 are carried out below crucible 1 and lift drive mechanism 12 pairs of crucibles 1 performs temperature of the present invention and controls, form, the configuration of the heating arrangements such as heating element are not subject to particular restriction.
In order to detect the temperature of crucible 1 bottom surface, thermopair 5 under crucible is configured with near crucible 1 lower surface central authorities, near the central authorities of outer crucible lower surface, be configured with thermopair 6 under outer crucible, input the output of these thermopairs to control device 9, the heated condition of controlling resistance heating member 10.Except above-mentioned thermopair, the thermopair of detected temperatures, radiation thermometer can also be configured for.
Its inside can be remained air-tight state by chamber 7, to avoid the outside inflow such as oxygen, nitrogen, usually, after the silicon raw materials such as polysilicon are dropped into and before silicon raw materials melt, making in chamber 7 is vacuum, imports the rare gas elementes such as argon gas afterwards, makes to keep inert environments in chamber 7.
Utilize the device of this structure, manufacture polycrystal silicon ingot basically by following operation: in crucible 1, fill silicon raw material 4; By degassed (formation vacuum) and importing rare gas element to carrying out gas displacement in chamber 7; Silicon raw material 4 melting is made by heating; Melting confirms and keeps; To be controlled by temperature and the action of lift drive mechanism 12 makes to solidify beginning; Confirm that solidification completes and anneals; Take out ingot casting.
In manufacture method of the present invention, be set to following condition: detected temperatures when silicon temperature becomes the fusing point of silicon near crucible lower surface central authorities is Tm, in during detected temperatures is reduced to (Tm-60) DEG C from (Tm-20) DEG C, there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h.
In addition, in manufacture method of the present invention, be set to following condition: silicon temperature become the fusing point of silicon time crucible lower surface central authorities near the detected temperatures of 20mm position, below be Tm ', in during detected temperatures is reduced to (Tm '-60) DEG C from (Tm '-20) DEG C, there is the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h.
The present inventor confirms following content.
When making silicon raw material melt in crucible, before melting is near completion, the temperature of the 20mm position, below near the temperature near crucible lower surface central authorities and crucible lower surface central authorities roughly shows as certain value.If using this certain value as reference temperature (be respectively Tm, Tm '), then as previously mentioned, even if individual difference (deviation) also can be got rid of when such as having changed thermopair, temperature condition can be made to stablize.When completing melting, rise along with liquid temperature, under crucible, temperature also temporarily rises, but usually will enter unidirectional solidification process after this, therefore temperature slowly declines.
Measuring point for the temperature may not be the 20mm position, below near crucible lower surface central authorities, near crucible lower surface central authorities, the position being convenient to arrange thermopair can be selected, as long as in crucible bottom surface produce core temperature range in crucible lower surface central authorities near the related position of temperature.But, the temperature of the measuring point for the temperature of selection like this preferably with crucible lower surface central authorities near temperature remain roughly certain difference and change, such as, if in crucible platform, then desirably crucible platform as far as possible top quadrate part, the central part that is difficult to the impact being subject to heater wattage output change in face.
Such as, in the device of Fig. 4, detected temperatures near the detected temperatures being arranged at the thermopair near outer crucible 2 lower surface central authorities and crucible 1 lower surface central authorities has certain temperature head all the time, detected temperatures near outer crucible 2 lower surface central authorities when silicon is become necessarily (fusing point of silicon) by silicon temperature before melting is set to Tm ", equivalence during detected temperatures during making the detected temperatures near outer crucible lower surface central authorities be reduced to (Tm "-60) DEG C from (Tm "-20) DEG C and near crucible lower surface central authorities is reduced to (Tm-60) DEG C from (Tm-20) DEG C, temperature control can be carried out.
Specifically, described in embodiment, the detected temperatures being arranged at the thermopair of (20mm position, below) near outer crucible 2 lower surface central authorities and the detected temperatures near crucible 1 lower surface central authorities have the temperature head of-10 DEG C all the time, can carry out the temperature control in manufacture method of the present invention during being reduced to (Tm '-60) DEG C from (Tm '-20) DEG C.
According to the opinion of the present inventor, within the scope of said temperature, from the molten silicon of crucible bottom, produce the nuclei of crystallization, its crystal particle diameter is considered to the generation probability of the nuclei of crystallization depending on crucible bottom and the speed of growth of the nuclei of crystallization.
And, there is the time cooled with above-mentioned rate of temperature change, therefore the speed of growth of the horizontal direction of the nuclei of crystallization of crucible bottom can be suppressed, the generation density of the result nuclei of crystallization uprises, can crystal particle diameter be controlled less, the lattice defect of the top side of polycrystal silicon ingot can be lowered and relax the reduction of its characteristic.
If the rate of temperature change of cooling is more than 0 DEG C/h and less than 1 DEG C/h, then comparatively good in the meaning that crystal particle diameter is controlled less, but crystal growth is spended time too, in addition, consequently promotion metallic impurity are to the diffusion (liquate) in molten silicon or coagulated silicon from crucible, therefore likely advantage offseted.In addition, if the rate of temperature change of cooling is more than 10 DEG C/h, then can not suppresses the speed of growth of the horizontal direction of the nuclei of crystallization produced in crucible bottom, consequently, the generation density of the nuclei of crystallization can not be improved.Therefore, the rate of temperature change of cooling is preferably 1 ~ 10 DEG C/h of this interval.Preferred rate of temperature change is 2 ~ 7 DEG C/h.
In manufacture method of the present invention, in during said temperature reduces, the ratio of the time that temperature reduces with the rate of temperature change of 1 ~ 10 DEG C/h is preferably higher, and such as preferably more than 20%, more preferably more than 40%.By making this ratio higher, the generation density of the nuclei of crystallization of crucible bottom uprises, and the ratio in the controlled obtained less region of crystal particle diameter increases.
< polycrystal silicon ingot >
Polycrystal silicon ingot of the present invention is manufactured by polycrystal silicon ingot manufacture method of the present invention.
< polysilicon block >
Polysilicon block of the present invention obtains by processing polycrystal silicon ingot of the present invention.
Polysilicon block such as can by use the known device such as band saw in polycrystal silicon ingot of the present invention, the surface portion of the hidden danger that there is the diffusion of contaminants such as crucible material carries out cut-outs and processes and obtain.
In addition, also attrition process can be carried out to the surface of polysilicon block as required.
< polysilicon chip >
Polysilicon chip of the present invention obtains by processing polysilicon block of the present invention.
Thickness desired by polysilicon block slice processing one-tenth of the present invention such as can obtain by using the known devices such as multi-line cutting machine by polysilicon chip.At present, thickness normally about 170 ~ 200 μm, but due to trend be cost reduction, therefore there is lightening trend.
In addition, also can process the surface grinding of polysilicon chip as required.
< polysilicon solar cell >
Polysilicon solar cell of the present invention uses crystal silicon chip of the present invention manufacture.
Polysilicon solar cell unit such as can use crystal silicon chip of the present invention by known solar battery cell technical process manufacture.That is, when being mixed with the silicon chip of impurity of p-type, use known material, by known method, the impurity mixing N-shaped, to form n-layer thus to form pn knot, forms surface electrode and backplate and obtains polysilicon solar cell unit.
Equally, when the silicon chip of the impurity for being mixed with N-shaped, the impurity mixing p-type, to form p-type layer thus to form pn knot, forms surface electrode and backplate and obtains polysilicon solar cell unit.Or, except utilizing the polysilicon solar cell unit of these silicon pn knot each other, also there is the MIS type solar cell obtained across thinner insulation layer evaporation metal etc., the silicon film such as making the conductivity type amorphousness contrary from multi-wafer etc. and utilizing constructs different p-types, polysilicon solar cell unit etc. that N-shaped is silicon heterogenous.In addition, by multiple polysilicon solar cell unit electrical connection, polycrystalline solar module is obtained.
As mentioned above, in this manual, as comprising " solar battery cell " concept with " solar module ", be only called " solar cell ".Therefore, such as, as long as describe the part of " polysilicon solar cell ", then it comprises the meaning of " polysilicon solar cell unit " and " polycrystalline solar module " exactly.
Embodiment
Below, specifically describe the present invention by test example, but the present invention is not limited by these test examples.
< test example 1> is about the research of the interdependence of rate of temperature change
On graphite-made crucible platform 3 (880mm × 880mm × thickness 200mm) in the manufacturing equipment for polysilicon ingot shown in Fig. 4, be provided with graphite-made outer crucible 2 (interior dimensions: 900mm × 900mm × height 460mm, base plate wall thickness and side wall thickness are 20mm), in this graphite-made outer crucible 2, be provided with quartz crucible 1 (interior dimensions: 830mm × 830mm × 420mm, base plate wall thickness and side wall thickness are 22mm) processed.In addition, the thermopair of temperature measuring to be arranged near crucible 1 lower surface central authorities and these two positions near outer crucible 2 lower surface central authorities.
Then, after the raw silicon 4 of 420kg is loaded crucible 1, vacuumize, and utilize argon gas to replace in device, this raw silicon 4 be have adjusted boron dope agent concentration and is become about 1.5 Ω cm to make the resistivity of ingot casting.Afterwards, the heating arrangements (graphite heater 10) that is configured at crucible side is used to be melted by silicon raw material as the heating installation of device, after the whole raw material of confirmation melts, make silicon with following condition generation unidirectional solidification, the annealing of two hours is carried out with 1200 DEG C, make it cooling with the speed of cooling of 100 DEG C/h, and take out polycrystal silicon ingot from device.
Solidifying in operation, by control heater temperature and dropping speed of the crucible, in during detected temperatures near crucible lower surface central authorities is reduced to Tm-60 DEG C from Tm-20 DEG C, the rate of temperature change forming thermopair is respectively roughly certain condition of 0.5 DEG C/h, 1 DEG C/h, 2 DEG C/h, 5 DEG C/h, 7 DEG C/h, 10 DEG C/h, 15 DEG C/h and 20 DEG C/h." rate of temperature change " represents the negative tendency in cooling.In this experiment, the measured value of Tm is in the scope of 1410 DEG C ~ 1418 DEG C.
Temperature condition beyond the rate of temperature change of thermopair is roughly the same condition, can only evaluate the impact that the core bottom ingot casting produces especially.
To when near crucible 1 lower surface central authorities, near outer crucible 2 lower surface central authorities, the relation of the detected temperatures of (the 20mm positions, below near crucible lower surface central authorities) confirms, confirm them remain the difference of roughly 10 DEG C and change, and the detected temperatures near crucible 1 lower surface central authorities from Tm-20 DEG C to Tm-60 DEG C this temperature range and the detected temperatures near outer crucible 2 lower surface central authorities from Tm '-20 DEG C to Tm '-60 DEG C be corresponding.
Use band saw obtained polycrystal silicon ingot to be processed into block (156mm × 156mm × 200mm), and use wire cutting machine section further, obtain about 12000 polysilicon chips (156mm × 156mm × thickness 0.18mm).
Obtained polysilicon chip is put in common solar battery cell technical process, each ingot casting corresponding has made 12000 solar cells (profile 156mm × 156mm × thickness 0.18mm), and determines its output rating (W).
Usually, the reason major part that the output rating of known is solar cell reduces is the lattice defect of the top side of ingot casting, is particularly the diffusion of contaminants of the bottom side of ingot casting when the manufacturing time of the time of crystal growth, namely ingot casting is extremely grown.
Therefore, by evaluating the output distribution of solar cell, the quality of known ingot casting.
The lower limit output rating of grade 1 be set to 100 and the output rating of each solar cell be categorized as from high outgoing side grade 1 ~ 3, calculating it for each ingot casting and there is ratio (%).
Grade 1: output rating more than 100
Grade 2: output rating more than 93 and less than 100
Grade 3: output rating is less than 93
The result of gained is as shown in table 1 and Fig. 2.
[table 1]
From table 1 and Fig. 2 result obviously, when rate of temperature change is 1 ~ 10 DEG C/h, especially less than 2 ~ 7 DEG C/h when, the production rate of high-grade product is high, and ingot casting quality is good.
On the other hand, known at rate of temperature change less than when when 1 DEG C/h and more than 10 DEG C/h, the production rate of inferior grade product is high, and ingot casting quality is bad.
In addition, learn when carrying out visual observation to the crystal particle diameter of obtained polycrystal silicon ingot, rate of temperature change is larger, and crystal particle diameter is larger.
< test example 2> is about the research of the occupation rate of rate of temperature change
Solidifying in operation, by control heater temperature and dropping speed of the crucible, the ratio (occupation rate) of rate of temperature change shared by the time of 1 ~ 10 DEG C/h defining thermopair is respectively the condition of 0%, 20%, 40%, 60%, 80% and 100%, then manufacture polycrystal silicon ingot in the same manner as test example 1 in addition, make solar cell, their output distribution has been evaluated.Except the scope that rate of temperature change is 1 ~ 10 DEG C/h, also to have carried out adjusting making average ramp rate be 25 DEG C/time.
In this experiment, the measured value of Tm is in the scope of 1407 DEG C ~ 1415 DEG C.
In FIG, the relation between the elapsed time (hour) when occupation rate is 60% and the detected temperatures (DEG C) near crucible lower surface central authorities is shown.In figure, TG1, TG10 and TG25 represent that rate of temperature change is the line of 1 DEG C/h, 10 DEG C/h and 25 DEG C/h respectively.
That is, in test example 2, the same with test example 1, also can only evaluate the impact that the core bottom ingot casting produces especially.
The result of gained is as shown in table 2 and Fig. 3.
[table 2]
From table 2 and Fig. 3 result obviously, when the occupation rate of specific rate of temperature change is more than 20%, particularly more than 40%, the production rate of inferior grade product reduces, and can obtain the ingot casting that quality is good.
Description of reference numerals
1 crucible
2 outer crucibles
3 crucible platforms
4 raw silicons
Thermopair under 5 crucibles
Thermopair (under crucible 20mm thermopair) under 6 outer crucibles
7 chambers
8 lagging materials
9 control device
10 resistance heating bodies (graphite heater)
11 cooling tanks
12 lift drive mechanisms
TG1 rate of temperature change is the line of 1 DEG C/h
TG10 rate of temperature change is the line of 10 DEG C/h
TG25 rate of temperature change is the line of 25 DEG C/h

Claims (10)

1. the manufacture method of a polycrystal silicon ingot, it is characterized in that, be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, detected temperatures near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm, in during described detected temperatures is reduced to (Tm-60) DEG C from (Tm-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 2 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
2. the manufacture method of polycrystal silicon ingot according to claim 1, is characterized in that, the time that described temperature reduces with the rate of temperature change of 2 ~ 10 DEG C/h exists more than 20%.
3. a manufacture method for polysilicon block, is characterized in that, carries out cut-out processing and obtain polysilicon block to the surface portion of the polycrystal silicon ingot of the manufacture method manufacture by polycrystal silicon ingot according to claim 1.
4. a manufacture method for polysilicon chip, is characterized in that, carries out slice processing and obtain polysilicon chip to the polysilicon block of the manufacture method manufacture by polysilicon block according to claim 3.
5. a manufacture method for polysilicon solar cell, is characterized in that, the polysilicon chip of the manufacture method manufacture by polysilicon chip according to claim 4 forms electrode and obtains polysilicon solar cell.
6. the manufacture method of a polycrystal silicon ingot, it is characterized in that, be make the molten silicon in crucible from the bottom of described crucible unidirectional solidification and manufacture the method for polycrystal silicon ingot upward, the detected temperatures of the 20mm position, below near crucible lower surface central authorities when silicon temperature being become the fusing point of silicon is set to Tm ', in during described detected temperatures is reduced to (Tm '-60) DEG C from (Tm '-20) DEG C, under the condition that there is the time that temperature reduces with the rate of temperature change of 2 ~ 10 DEG C/h, make described molten silicon unidirectional solidification and obtain polycrystal silicon ingot.
7. the manufacture method of polycrystal silicon ingot according to claim 6, is characterized in that, the time that described temperature reduces with the rate of temperature change of 2 ~ 10 DEG C/h exists more than 20%.
8. a manufacture method for polysilicon block, is characterized in that, carries out cut-out processing and obtain polysilicon block to the surface portion of the polycrystal silicon ingot of the manufacture method manufacture by polycrystal silicon ingot according to claim 6.
9. a manufacture method for polysilicon chip, is characterized in that, carries out slice processing and obtain polysilicon chip to the polysilicon block of the manufacture method manufacture by polysilicon block according to claim 8.
10. a manufacture method for polysilicon solar cell, is characterized in that, the polysilicon chip of the manufacture method manufacture by polysilicon chip according to claim 9 forms electrode and obtains polysilicon solar cell.
CN201280063468.4A 2011-12-22 2012-08-06 Polycrystal silicon ingot, its manufacture method and uses thereof Expired - Fee Related CN104010968B (en)

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