CN102797036A - Polycrystalline silicon ingot, manufacturing method thereof and solar cell - Google Patents
Polycrystalline silicon ingot, manufacturing method thereof and solar cell Download PDFInfo
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 188
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 9
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- 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
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Abstract
The invention discloses a manufacturing method of a polycrystalline silicon ingot. The manufacturing method comprises the steps of paving seed crystals on the bottom of a container in a polycrystalline silicon ingot growth furnace to form a seed crystal layer; loading solid silicon raw materials on the seed crystal layer; heating the container to melt the silicon raw materials and part of seed crystal layer to form a liquid layer, and at least keeping part of the seed crystal layer contacted with the bottom of the container to be in the solid state; controlling a thermal field in the polycrystalline silicon ingot growth furnace, and crystallizing the liquid layer to form a crystallization layer so as to move a solid-liquid interface to the direction far away from the bottom of the container; moving the solid-liquid interface to the direction far away from the bottom of the container by a corresponding distance, then conducting the meltback crystallization process, at least implementing the meltback crystallization process once to obtain the polycrystalline silicon ingot. The polycrystalline silicon ingot produced by adopting the method disclosed by the invention is low in impurity content, the produced solar cell is low in cost and attenuation coefficient, and the photoelectric conversion efficiency is high.
Description
Technical field
The present invention relates to the manufacturing technology and the photoelectric field of silicon single crystal, polysilicon, relate in particular to a kind of polycrystal silicon ingot and method of manufacture thereof, solar cell.
Background technology
Solar cell can be an electric energy with transform light energy, and the height of photoelectric transformation efficiency and the speed of cell decay are the important parameters of weighing solar cell quality quality.At present, according to the difference of material, solar cell mainly is divided into two kinds of monocrystaline silicon solar cell and polysilicon solar cells.
Wherein, Silicon single crystal ingot is with after the silicon raw materials melt that contains doping agent; Silicon metal is pulled out melt region and crystallization forms, and the method for produce single crystal silicon ingot has melt vertical pulling method (Czochralski is called for short the CZ method) and floating zone melting (abbreviation FZ method) usually; The CZ method is that silicon single crystal ingot is slowly pulled out from fused silicon liquid, and the FZ method is through melt region supply solid material and on the opposite side of said melt region, solidifies again.
Because intercrystalline orientation is a fixed, so the photoelectric transformation efficiency of monocrystaline silicon solar cell is higher, still; From production cost; The silicon single crystal single output that adopts these two kinds of methods to produce is few, and production cost is higher, and especially the size of the silicon single crystal rod of FZ method production is less; In view of the performance of the silicon single crystal rod produced; Comprise radially-arranged impurity and defective in the silicon single crystal rod, induce the ring and the space of stacking fault (OSF), perhaps " whirlpool " defective of vacancy cluster like oxygen; With the CZ method is example; Because the use of quartz crucible inevitably will comprise more oxygen impurities in silicon single crystal ingot inside, oxygen impurities combines the back to produce with adulterated boron boron oxygen (B-O) complex body is again the principal element that causes the solar cell decay; Therefore, use the reduction coefficient of the solar cell that this silicon single crystal rod makes higher.
Polycrystal silicon ingot normally adopts the method for casting to process, and casting polycrystalline silicon is that the fused raw silicon is placed quartz crucible, and the process of cooling through the control molten silicon, makes to obtain after the molten silicon crystallization.With respect to silicon single crystal ingot, there is more defective in the polycrystal silicon ingot, crystal grain is little; Crystal boundary and dislocation between the conventional polysilicon grain are more, thereby have caused the compound fast of electric charge carrier, cause minority carrier life time low; And; Because the orientation of intergranule is at random, causes being difficult to wafer surface is carried out texture preferably, makes conventional polysilicon solar cell lower than the photoelectric transformation efficiency of monocrystaline silicon solar cell; But the oxygen level in the polycrystal silicon ingot can be controlled at level preferably, thereby makes that the reduction coefficient of polysilicon solar cell is lower.
Summary of the invention
For solving the problems of the technologies described above; The invention provides a kind of polycrystal silicon ingot and method of manufacture thereof, solar cell; With respect to monocrystaline silicon solar cell of the prior art, at the bottom of the cost of the solar cell that the polycrystal silicon ingot that adopts the embodiment of the invention to provide is produced, reduction coefficient is lower, simultaneously; With respect to polysilicon solar cell of the prior art, the photoelectric transformation efficiency of the solar cell that the polycrystal silicon ingot that adopts the embodiment of the invention to provide is produced is higher.
For addressing the above problem, the embodiment of the invention provides following technical scheme:
A kind of method of manufacture of polycrystal silicon ingot comprises:
Container bottom in the polycrystal silicon ingot reactors is laid seed crystal, forms inculating crystal layer;
Solid-state silicon raw material is loaded into the top of said inculating crystal layer;
Said container is heated, melt said silicon raw material and the said inculating crystal layer of part, to form liquid level, the part inculating crystal layer that keeps at least contacting with said container bottom is solid-state;
Control the thermal field in the said polycrystal silicon ingot reactors, said liquid level is carried out crystallization form crystallizing layer, so that solid-liquid interface moves to the direction away from said container bottom;
Said solid-liquid interface gets into the melt back crystallisation process after the direction away from said container bottom moves respective, behind the once said melt back crystallisation process of execution, obtain polycrystal silicon ingot at least;
Wherein, Said melt back crystallisation process comprises, controls the thermal field in the said polycrystal silicon ingot reactors, and said crystallizing layer is carried out melt back; Said solid-liquid interface is moved to the direction near said container bottom; Afterwards, control the thermal field in the said polycrystal silicon ingot reactors, liquid level is carried out crystallization; So that said solid-liquid interface moves the distance that the distance that said solid-liquid interface moves to the direction near said container bottom moves to the direction away from said container bottom less than said solid-liquid interface to the direction away from said container bottom.
Preferably, said polycrystal silicon ingot contains the large-sized monocrystalline silicon region of successive, and the crystalline orientation of said monocrystalline silicon region is identical with the crystalline orientation of the said seed crystal that is positioned at its below.
Preferably, said seed crystal is that crystalline orientation is the silicon single crystal of (100), (110) or (111).
Preferably, the process that solid-state silicon raw material is loaded into the top of said inculating crystal layer is specially:
Short grained silicon raw material is loaded into the top of said inculating crystal layer, to fill the slit between said seed intergranular slit and said inculating crystal layer and said container side wall;
The silicon raw material of big volume is loaded into the top of said small-particle silicon raw material.
Preferably, the thickness of said inculating crystal layer is 10mm-100mm.
Preferably, when beginning crystallization for the first time, the thickness of solid-state inculating crystal layer is 1mm-50mm.
Preferably, the area of said inculating crystal layer occupies the 50%-99% of said container bottom area.
Preferably, said container is quartz crucible, silicon carbide crucible or silicon nitride crucible.
The embodiment of the invention also discloses a kind of polycrystal silicon ingot that adopts aforesaid method to make, said polycrystal silicon ingot comprises the consistent continuous large-sized monocrystalline silicon region of crystalline orientation.
The embodiment of the invention also discloses a kind of solar cell, adopt above-described polycrystal silicon ingot, comprising:
Wafer has the consistent continuous large-sized monocrystalline silicon region of crystalline orientation on the said wafer;
P-N knot in the said wafer;
Conductive contact on the said wafer.
Compared with prior art, technique scheme has the following advantages:
The technical scheme that the embodiment of the invention provided; Adopt the method for casting to produce polycrystal silicon ingot, form inculating crystal layer through lay the big area seed crystal in advance at container bottom, by the growth of seed crystal guiding monocrystalline silicon region; And through repeatedly melt back crystallization; Make to comprise continuous large-sized monocrystalline silicon region in the polycrystal silicon ingot of producing, the polycrystal silicon ingot that promptly casts out is to be orientated consistent monocrystalline silicon region by most of with seed crystal, and the polysilicon region of few part composition.Because the inculating crystal layer of bottom has completely cut off the oxygen of container bottom in the castingprocesses, thereby has reduced the oxygen impurities content in the polycrystal silicon ingot, and, large-sized monocrystalline silicon region contained in the polycrystal silicon ingot.Therefore, the solar cell that the polycrystal silicon ingot that adopts the embodiment of the invention to provide is produced, monocrystaline silicon solar cell reduction coefficient more of the prior art is lower, and polysilicon solar cell photoelectric transformation efficiency more of the prior art is higher.
And; Melt back crystalline mode forms polycrystal silicon ingot owing to adopt repeatedly in the present embodiment, has slowed down the crystalline setting rate to a certain extent, makes impurity (like silit, silicon nitride etc.) have time enough to carry out fractional condensation; Even be dissolved in the solution once more after impurities in raw materials can be separated out; Thereby avoided impurity to be deposited in the crystalline region that has solidified, and then reduced hard point and impurity enriched layer in the cast main body, the defect concentration in the polycrystal silicon ingot of producing is reduced greatly; Also improve minority carrier life time to a certain extent, thereby improved the photoelectric transformation efficiency of solar cell.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings
Fig. 1 is the schematic flow sheet of the method for manufacture of the embodiment of the invention one disclosed polycrystal silicon ingot;
Fig. 2 a-Fig. 2 d is the melt back process of growth synoptic diagram of the embodiment of the invention one disclosed polycrystal silicon ingot;
Fig. 3 is the schematic flow sheet of the method for manufacture of the embodiment of the invention two disclosed polycrystal silicon ingots;
Fig. 4 is the embodiment of the invention two disclosed seed crystal paving mode vertical views;
Fig. 5 is the sectional view of the embodiment of the invention two disclosed loading silicon raw material mode;
Fig. 6 is the sectional view of the polycrystal silicon ingot of production in the embodiment of the invention two.
Embodiment
Said as the background technology part, the silicon single crystal ingot production capacity that the mode of employing prior art is produced is little, and production cost is high, and because oxygen impurities is more, the reduction coefficient of the solar cell of feasible employing silicon single crystal ingot making of the prior art is higher; And the polycrystal silicon ingot of producing in the employing prior art; Though production capacity is big; But because polysilicon self grain orientation at random, can not adopt chemical process that texture is preferably carried out on its surface, thereby can better not reduce polysilicon surface to the reflection of light rate; Raising causes the polysilicon solar cell photoelectric transformation efficiency low to the characteristics such as specific absorption of light.
The defective of silicon single crystal is owing to the mode of production itself forms, and polysilicon grain orientation defective is at random produced same product by itself structures shape if still adopt in the same way, and these defectives are exactly inevitable.
In addition, polycrystal silicon ingot waits the defective of self structure except that grain orientation at random, also has other defective that causes because of technological reason; Like defectives such as impurity hard point and dislocation that causes and pits, the contriver discovers that the reason that these situation occur is; In the directional freeze process of crystal growth, because segregation coefficient is less, impurity such as the carbon in the silicon raw material, nitrogen can be in the enrichment of solid-liquid interface place; When the speed of growth when very fast, impurity has little time fractional condensation, will form silit, silicon nitride etc.; From solution, separate out, remain in the solid-state polysilicon after the crystallization, become the impurity enriched layer or the hard point of pinning in crystal.
If impurity is concentrated in cast main body and is stratiform and separates out, the part silico briquette that then comprises impurity layer will be excised, under some situation even can cause whole silico briquette to scrap; If impurity is separated out with the form of hard point, then can become the initiating accident sequence of defectives such as dislocation and pit, cause defect concentrations in crystals to increase; Downgrade, and, because the hardness of silit, silicon nitride all is higher than silicon crystal; In section and evolution process, its higher hardness can influence the quality of cutting greatly, forms stria, groove on the cutting surface; Even broken string, whole silico briquette is scrapped, can not be processed as the finished product.
Based on above reason; The contriver considers that the output of the polycrystal silicon ingot that castmethod is produced is bigger, and the oxygen level of the polycrystal silicon ingot of producing is lower, has exactly solved the defective of the mode of production of silicon single crystal ingot; And; Monocrystaline silicon solar cell does not exactly have many defectives of polysilicon solar cell because material, if the two advantage is combined; Adopt to produce the mode of polycrystal silicon ingot and remove to produce the polycrystal silicon ingot that contains large-sized monocrystalline silicon region, should be able to solve the shortcoming of monocrystaline silicon solar cell and polysilicon solar cell in the prior art to a certain extent.
And, adopt the method for casting to carry out can taking to slow down the mode of crystalline setting rate in the production process, reduce hard point and impurity enriched layer in the cast main body, thereby improve the quality of finished product.
It more than is the application's core concept; To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention carried out clear, intactly description, obviously; Described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
A lot of details have been set forth in the following description so that make much of the present invention; But the present invention can also adopt other to be different from alternate manner described here and implement; Those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed specific embodiment.
Secondly, the present invention combines synoptic diagram to be described in detail, when the embodiment of the invention is detailed; For ease of explanation; The sectional view of expression device architecture can be disobeyed general ratio and done local the amplification, and said synoptic diagram is example, and it should not limit the scope of the present invention's protection at this.The three-dimensional space size that in actual fabrication, should comprise in addition, length, width and the degree of depth.
Embodiment one
On the basis based on above-mentioned research, the embodiment of the invention provides a kind of method of manufacture of polycrystal silicon ingot, and the schema of this method is as shown in Figure 1, may further comprise the steps:
Step S101: the container bottom in the polycrystal silicon ingot reactors is laid seed crystal, forms inculating crystal layer;
Wherein, said seed crystal is a crystalline orientation fixed silicon single crystal, and said inculating crystal layer comprises the monocrystalline silicon layer of at least a crystalline orientation, and is preferred, and the seed crystal in the present embodiment is the silicon single crystal of (100), (110) or (111) orientation.
Concrete, inculating crystal layer comprises the monocrystalline silicon layer of at least a crystalline orientation in the present embodiment, in other words; Said inculating crystal layer can all select to have same crystalline orientation silicon single crystal, like the silicon single crystal that whole employings have (100) orientation, also can partly select to have the silicon single crystal of first crystalline orientation; Another part selects to have the silicon single crystal of second crystalline orientation; Said first crystalline orientation is different with said second crystalline orientation, as: a part selects to have the silicon single crystal of (100) orientation, and another part selects to have the silicon single crystal of (110) orientation; Concrete which kind of seed crystal of selecting is decided according to the requirement to polycrystal silicon ingot.
Specifically do not limit the paving mode of said inculating crystal layer in the present embodiment; But in order to guarantee the quality of the silicon single crystal in the polycrystal silicon ingot; Preferably, said seed crystal is layed in the region intermediate of said container, in addition; In order better to control the making processes and the quality of said polycrystal silicon ingot, said inculating crystal layer should keep substantially parallel or approximate parallel with said container bottom.
Same, specifically do not limit the thickness of said inculating crystal layer in the present embodiment yet, decide with concrete production process and working condition; Preferably; The thickness of said inculating crystal layer is 2mm-400mm, and is preferred, and the thickness of said inculating crystal layer is 10mm-100mm; Preferred, the thickness of said inculating crystal layer is 10mm-60mm.
In addition, container shapes in the polycrystal silicon ingot reactors in the present embodiment and material are by deciding in the polycrystal silicon ingot reactors that adopts in the production process, generally speaking; Owing to be to adopt the mode of casting to produce polycrystal silicon ingot in the present embodiment; Said container is a crucible, and more general is quartz crucible, certainly; What said container can also be selected other castingprocesses that can be used for polycrystal silicon ingot can disposable crucible or reusable crucible, like silicon carbide crucible or silicon nitride crucible etc.
" casting " described in present embodiment process specifically is meant at the mould that is used for keeping molten silicon or container through molten silicon being cooled off the formation silicon ingot.Step S102: the top that solid-state silicon raw material is loaded into said inculating crystal layer;
Do not limit the mode of loading said solid-state silicon raw material in the present embodiment, specifically load the mode of silicon raw material and decide according to the size of silicon raw material, can be expecting reasonably be loaded in the container as long as guarantee, and can guarantee that the safety of melt process crucible etc. gets final product.
Step S103: said container is heated, melt said silicon raw material and the said inculating crystal layer of part, to form liquid level, the part inculating crystal layer that keeps at least contacting with said container bottom is solid-state;
Adopt different polycrystal silicon ingot reactors; The method that said container is heated also just is not quite similar; As adopt heat-exchanging method reactors, adopt the reactors of Bridgman method or adopt reactors of the two technology of combining; Its heating means are had nothing in common with each other, as long as can be with solid-state silicon raw material and the fusing of part inculating crystal layer, the fusing demand that satisfies this step gets final product.
Need to prove that do not limit the contact condition of solid-liquid interface and container bottom in this step, solid-liquid interface can have little angle with container bottom; Perhaps solid-liquid interface has a spot of rough zone, also can be parallel with container bottom, but for the quality of the polysilicon that guarantees to produce; Be preferably in the present embodiment; Container is being carried out in the heat-processed, keeping solid-liquid interface substantially parallel with said container bottom or approximate parallel as far as possible, can make unfused seed crystal can occupy the entire container bottom; And unfused part inculating crystal layer can stop that the oxygen impurities from container (crucible) bottom gets in the molten silicon; To reduce the content of oxygen impurities in the cast main body, as reducing oxygen impurities combines formation with adulterated boron boron oxygen complex body, to reduce the reduction coefficient of solar cell.
Step S104: control the thermal field in the said polycrystal silicon ingot reactors; Said liquid level is carried out the crystallization first time form crystallizing layer; So that said solid-liquid interface moves to the direction away from said container bottom, when beginning crystallization for the first time in the present embodiment, the thickness of solid-state inculating crystal layer is 1mm-50mm; Be preferably 5mm-30mm, more preferably 20mm;
In this step, molten silicon is carried out in the crystallisation by cooling process; Because the deflegmation of impurity; Silicon impurities in raw materials (like silit, silicon nitride etc.) will be enriched in the solid-liquid interface place, and the foreign matter content in the solid-state polysilicon after the crystallization is seldom, if but crystallization velocity is too fast; Impurity such as silit, silicon nitride can have little time fractional condensation and remain in the solid-state polysilicon, becomes the impurity enriched layer or the hard point of pinning in crystal.
In the present embodiment for fear of form impurity enriched layer and hard point because of the speed of growth is too fast; Can come the speed of crystallization control as far as possible through the crystallization control variation of temperature; So that crystallization velocity is unlikely to too fast or slow excessively, specifically how controls and to decide according to the situation of production process.
Step S105: said solid-liquid interface gets into the melt back crystallisation process after the direction away from said container bottom moves respective, behind the once said melt back crystallisation process of execution, obtains polycrystal silicon ingot at least.
Wherein, Said melt back crystallisation process comprises, controls the thermal field in the said polycrystal silicon ingot reactors, and said crystallizing layer is carried out melt back; Said solid-liquid interface is moved to the direction near said container bottom; Afterwards, control the thermal field in the said polycrystal silicon ingot reactors, liquid level is carried out crystallization; So that said solid-liquid interface moves the distance that the distance that said solid-liquid interface moves to the direction near said container bottom moves to the direction away from said container bottom less than said solid-liquid interface to the direction away from said container bottom.
In addition, after crystal growth is accomplished, need crystal is cooled to certain temperature, from ingot furnace, remove polycrystal silicon ingot, afterwards polycrystal silicon ingot is further processed.
As above described in the step; The crystallization velocity of molten silicon can influence the quality of the finished product, can reduce hard point and impurity enriched layer in the product through the mode of slowing down the speed of growth, but because at the beginning crystallization initial stage; The crystalline speed of growth is difficult with control; For avoiding above-mentioned defective, therefore, increased the melt back crystallisation process among the step S105 in the present embodiment.
Through the melt back crystallisation process,, the crystal after the crystallization is carried out refuse (being melt back) promptly at certain growth phase; Can make and separate out the impurity that is deposited in the solid crystals and be dissolved in again in the solution again, in follow-up crystallisation process once more, impurity continues fractional condensation; So back and forth; Be equivalent to prolong to a certain extent the fractional condensation time of impurity, avoided impurity to separate out and be deposited in the crystal, improved the crystalline quality.
Need to prove; Present embodiment does not limit and carries out melt back when which kind of degree crystallisation process proceed to; Specifically do not limit melt back yet and after which kind of degree, carry out crystallization once more; Promptly do not limit said solid-liquid interface and move respective to direction what are, and said solid-liquid interface moves respective to the direction near said container bottom what are, as long as guarantee the height of each crystalline height greater than melt back away from said container bottom; Be the distance that distance that said solid-liquid interface moves to the direction near said container bottom moves to the direction away from said container bottom less than said solid-liquid interface, be in growth conditions to guarantee crystal.
In addition, do not limit the time that each melt back begins in the present embodiment, the number of times of what and the melt back that does not also limit each melt back, promptly the crystal growing process in the present embodiment can have multiplely, and the process of facing crystal growth in the present embodiment down describes.
The one, when the molten silicon crystalline growth is to certain altitude in step S104, carry out methback process one time, make solid-state crystalline silicon carry out secondary fusion; The fusing height less than the growth height, when melt back behind certain altitude, carry out the secondary crystal process; Make the interior temperature maintenance of reactors at lower level always, accomplish until the polycrystal silicon ingot growth, as shown in Figure 2; This process is crystallization-melt back-crystallization, accomplishes until growth, wherein; Fig. 2 a is the view before the said silicon crystal crystallization, and Fig. 2 b is the view of said silicon crystal after crystallization on the basis of Fig. 2 a, and Fig. 2 c is the view of said silicon crystal behind melt back on the basis of Fig. 2 b; Fig. 2 d is the view of said silicon crystal after crystallization on the basis of Fig. 2 c, has illustrated among Fig. 2: silicon liquid 91, solid-liquid interface 92, silicon crystal 93 and crucible bottom 94.The height of silicon crystal described in h1, h2, h3, h4 difference presentation graphs 2a～Fig. 2 d among the figure, then the relation between the height of silicon crystal is h4＞h2＞h3＞h1 described in Fig. 2 a～Fig. 2 d; The 2nd, at first through the circulation of melt back crystallisation process several times, make the stepped growth certain altitude of crystal after, reduce temperature in the stove always; Make crystal continue crystallization; Be that solid-liquid interface is advanced along the direction away from container bottom always, until the process of growth of accomplishing polycrystal silicon ingot, after this process is multiple process; Crystallization is always accomplished until growth; The 3rd, carry out melt back-crystallisation process in the whole crystalline process of growth always, this process is accomplished until the silicon ingot growth for repeat crystallization-melt back-crystallisation process always.Specifically select above-mentioned which kind of crystal growing process for use, do not do concrete qualification in the present embodiment, the foundation of selection should be under the prerequisite of the quality that guarantees polycrystal silicon ingot as far as possible, saves the time of crystal growth and required energy waste.
Specifically select above-mentioned which kind of crystal growing process for use, do not do concrete qualification in the present embodiment, the foundation of selection should be under the prerequisite of the quality that guarantees polycrystal silicon ingot as far as possible, saves the time of crystal growth and required energy waste.
The technical scheme that the embodiment of the invention provided; Adopt the method for casting to produce polycrystal silicon ingot; Form inculating crystal layer through lay the big area seed crystal in advance at container bottom; Growth by seed crystal guiding monocrystalline silicon region makes to comprise continuous large-sized monocrystalline silicon region in the polycrystal silicon ingot of producing, and the crystalline orientation of said monocrystalline silicon region is identical with the crystalline orientation of the said seed crystal that is positioned at its below.
Because the oxygen that the inculating crystal layer of bottom has completely cut off container bottom in the castingprocesses spreads in the silicon raw material; Thereby reduced the content of the oxygen in the polycrystal silicon ingot, and, owing to contain large-sized monocrystalline silicon region in the polycrystal silicon ingot; The crystalline chip area is big; Corresponding crystal boundary density just greatly reduces, therefore, and the solar cell that the polycrystal silicon ingot that adopts the embodiment of the invention to provide is produced; Monocrystaline silicon solar cell reduction coefficient more of the prior art is lower, and polysilicon solar cell photoelectric transformation efficiency more of the prior art is higher.
And melt back crystalline mode forms polycrystal silicon ingot owing to adopt repeatedly in the present embodiment, has been equivalent to slow down to a certain extent the fractional condensation speed of crystalline setting rate and impurity on the whole; Make impurity (like silit, silicon nitride etc.) that time enough arranged and can carry out fractional condensation fully; Even if the impurity of separating out in advance in follow-up methback process, also can be dissolved in the silicon liquid once more; Thereby avoided impurity to be deposited in the crystalline region that has solidified; And then reduced the foreign matter content in the cast main body, improve minority carrier life time, thereby improved the electricity conversion of solar cell.
Embodiment two
The schema of the castmethod of disclosed polycrystal silicon ingot is as shown in Figure 3 in the present embodiment, and different with a last embodiment is, will load the process of silicon raw material in the present embodiment and specialize, and this method may further comprise the steps:
Step S201: the container bottom in the polycrystal silicon ingot reactors, adopt the identical seed crystal splicing tiling of crystalline orientation to form said inculating crystal layer, said inculating crystal layer is substantially parallel with said container bottom;
The silicon single crystal tiling that is preferably employing (100) orientation in the present embodiment forms said inculating crystal layer; Preferably, the area of said inculating crystal layer occupies the per-cent of said container bottom area, and promptly to occupy the per-cent of said container bottom area be 50%-99% to the area of said inculating crystal layer; Preferred; The area of said inculating crystal layer occupies the 70%-99% of said container bottom area, and is preferred, and the area of said inculating crystal layer occupies the 90%-99% of said container bottom area; Preferred, the area of said inculating crystal layer occupies the 95%-99% of said container bottom area.
Step S202: short grained silicon raw material is loaded into the top of said inculating crystal layer, to fill the slit between said seed intergranular slit and said inculating crystal layer and said container side wall;
Owing to adopt the seed crystal paving of fritter to form inculating crystal layer, consider in the paving process and can between the position of splicing seams and inculating crystal layer and container side wall, the slit can occur, in castingprocesses in the present embodiment; These slits cause occurring in the cast main body defectives such as hole easily; Thereby influence quality product, adopt the blind of short grained silicon raw material, can avoid the cavity blemish in the cast main body on the one hand; Can also get rid of the foreign gas in the slit; Reducing swirl defect and various oxygen is induced defective etc., and can utilize the bigger specific surface area that has of small-particle silicon raw material, the advantage of more or less freely heat absorption fusing; Blind can better stop the impurity such as oxygen of container bottom.
Step S203: the silicon raw material of big volume is loaded into the top of said small-particle silicon raw material, is filled, promptly accomplish the loading process of silicon raw material until container (crucible).
Accomplish the laden synoptic diagram of silicon raw material such as Fig. 4 and shown in Figure 5 in the present embodiment; Fig. 4 is a vertical view, and the inculating crystal layer that silicon single crystal 21 pavings that are orientated by (100) among the figure form is surrounded by silicon raw material 22, and Fig. 5 is a sectional view; Inculating crystal layer 23 tops are short grained silicon raw material 24; The top is the silicon raw material 26 of big volume again, and inculating crystal layer 23 does not directly contact with the sidewall of crucible 25, and the slit between the sidewall of inculating crystal layer 23 and crucible 25 has small-particle silicon raw material 24 to fill.
Performing step S204-step S206 melts-crystallization-melt back crystallisation process said silicon raw material and part inculating crystal layer afterwards, and the step S103-step S105 among this process and the last embodiment is similar, repeats no more here.
The sectional view of the polycrystal silicon ingot that the method for employing present embodiment is produced is as shown in Figure 6, and the middle portion of this polycrystal silicon ingot is a monocrystalline silicon region 31, and monocrystalline silicon region 31 has consistent crystalline orientation with the seed crystal of its below; Around monocrystalline silicon region 31, because impurity is more in the sidewall of crucible 32, the reason of nucleation very easily; Therefore around monocrystalline silicon region 31, form crystalline orientation polysilicon region 33 at random, also have unfused inculating crystal layer 23, owing to have the slit between the seed crystal of paving in crucible bottom; What fill between the slit is short grained silicon raw material; Thereby there is crystal boundary 34 in 31 of the monocrystalline silicon regions of the polycrystal silicon ingot of producing, but because the chip area of monocrystalline silicon region 31 is big, therefore; Polycrystal silicon ingot more of the prior art, the density of the crystal boundary 34 of the polycrystal silicon ingot of making in the present embodiment greatly reduces.
Embodiment three
Present embodiment discloses the method polycrystal silicon ingot of producing and the solar wafer and the solar cell that adopt the polycrystal silicon ingot making of producing that adopts above each embodiment.
Wherein, Comprise the consistent continuous large-sized monocrystalline silicon region of crystalline orientation in the said polycrystal silicon ingot; After the impurity enriched layer excision with said polycrystal silicon ingot two ends; Other body region cutting is obtained solar wafer, utilize said wafer fabrication solar cell, said solar cell comprises:
Wafer has the consistent continuous large-sized monocrystalline silicon region of crystalline orientation on the said wafer;
P-N knot in the said wafer;
Conductive contact on the said wafer.
Also comprise in addition and be coated with the antireflective coating that is plated on the said wafer,, strengthen absorption light to reduce wafer to reflection of light.
The content of oxygen, carbon and other impurity is all lower in the polycrystal silicon ingot in the present embodiment; And defectives such as crystal boundary density reduce greatly; Owing in the production process point of the hard in the cast main body has been carried out good control, so the defect concentration in the cast main body reduces greatly also.
Because the wafer that obtains has the consistent monocrystalline silicon region of crystalline orientation of continuous large-area; Therefore can adopt chemical process preferential etch pyramid matte; Wafer surface is carried out texture preferably, increase absorption light, and; Lower crystal boundary density in the wafer can effectively have been avoided the low defective of photoelectric transformation efficiency because of the too high solar battery sheet that causes of crystal boundary density in the material.
In sum; With respect to monocrystaline silicon solar cell of the prior art; Solar cell in the present embodiment has lower reduction coefficient, and with respect to polysilicon solar cell of the prior art, the solar cell in the present embodiment has higher photoelectric transformation efficiency.
Various piece adopts the mode of going forward one by one to describe in this specification sheets, and what each part stressed all is and the difference of other parts that identical similar part is mutually referring to getting final product between the various piece.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to embodiment illustrated herein, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the method for manufacture of a polycrystal silicon ingot is characterized in that, comprising:
Container bottom in the polycrystal silicon ingot reactors is laid seed crystal, forms inculating crystal layer;
Solid-state silicon raw material is loaded into the top of said inculating crystal layer;
Said container is heated, melt said silicon raw material and the said inculating crystal layer of part, to form liquid level, the part inculating crystal layer that keeps at least contacting with said container bottom is solid-state;
Control the thermal field in the said polycrystal silicon ingot reactors, said liquid level is carried out crystallization form crystallizing layer, so that solid-liquid interface moves to the direction away from said container bottom;
Said solid-liquid interface gets into the melt back crystallisation process after the direction away from said container bottom moves respective, behind the once said melt back crystallisation process of execution, obtain polycrystal silicon ingot at least;
Wherein, Said melt back crystallisation process comprises, controls the thermal field in the said polycrystal silicon ingot reactors, and said crystallizing layer is carried out melt back; Said solid-liquid interface is moved to the direction near said container bottom; Afterwards, control the thermal field in the said polycrystal silicon ingot reactors, liquid level is carried out crystallization; So that said solid-liquid interface moves the distance that the distance that said solid-liquid interface moves to the direction near said container bottom moves to the direction away from said container bottom less than said solid-liquid interface to the direction away from said container bottom.
2. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, said polycrystal silicon ingot contains the large-sized monocrystalline silicon region of successive, and the crystalline orientation of said monocrystalline silicon region is identical with the crystalline orientation of the said seed crystal that is positioned at its below.
3. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, said seed crystal is that crystalline orientation is the silicon single crystal of (100), (110) or (111).
4. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, the process that solid-state silicon raw material is loaded into the top of said inculating crystal layer is specially:
Short grained silicon raw material is loaded into the top of said inculating crystal layer, to fill the slit between said seed intergranular slit and said inculating crystal layer and said container side wall;
The silicon raw material of big volume is loaded into the top of said small-particle silicon raw material.
5. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, the thickness of said inculating crystal layer is 10mm-100mm.
6. the method for manufacture of polycrystal silicon ingot according to claim 5 is characterized in that, when beginning crystallization for the first time, the thickness of solid-state inculating crystal layer is 1mm-50mm.
7. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, the area of said inculating crystal layer occupies the 50%-99% of said container bottom area.
8. the method for manufacture of polycrystal silicon ingot according to claim 1 is characterized in that, said container is quartz crucible, silicon carbide crucible or silicon nitride crucible.
9. a polycrystal silicon ingot that adopts the described method of claim 1-8 to produce is characterized in that, said polycrystal silicon ingot comprises the consistent continuous large-sized monocrystalline silicon region of crystalline orientation.
10. a solar cell adopts the described polycrystal silicon ingot of claim 10, it is characterized in that, comprising:
Wafer has the consistent continuous large-sized monocrystalline silicon region of crystalline orientation on the said wafer;
P-N knot in the said wafer;
Conductive contact on the said wafer.
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