CN102605418A - Solar cell substrate, manufacturing method of solar cell and crucible used for same - Google Patents
Solar cell substrate, manufacturing method of solar cell and crucible used for same Download PDFInfo
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- CN102605418A CN102605418A CN201210012899XA CN201210012899A CN102605418A CN 102605418 A CN102605418 A CN 102605418A CN 201210012899X A CN201210012899X A CN 201210012899XA CN 201210012899 A CN201210012899 A CN 201210012899A CN 102605418 A CN102605418 A CN 102605418A
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Abstract
The invention relates to a method used for preparing a silicon substrate with a majority of crystal orientation being (100) and a crucible with multiple pockets at the bottom of with the crucible. A silicon seed crystals with (100) crystal orientation is placed in each pocket of the crucible, a silicon material is filled in the crucible for casting, the crucible is placed in a casting unit, and the pockets are positioned below a heating and fusion zone; and heating and melting begin from the top of the crucible. Once the silicon material is melted to the bottom, the silicon fluid flows in the pockets and contacts with the child crystal; and then, the crucible is slowly lowered, a lower molten part begins to solidify and grows along the (100) direction of the seed crystals.
Description
Technical field
The present invention relates to make the method about the low-cost base mateiral of device, like solar-energy photo-voltaic cell, LED etc. more specifically, the present invention relates to make the method for low-cost silicon wafer.
Background technology
According to present technology, three main phase are arranged based on the manufacture of solar cells of polysilicon.At first, produce a large amount of silicon chips, common factory, the silicon chip of production 1,000,000 in every month for 25 megawatt yield-power as substrate.Secondly, these silicon chips are processed into solar cell through forming p-n junction and operplate printing.The 3rd, then these silicon chips " encapsulation " are become a module, so that be installed in user's the equipment.
The obnoxious flavour that contains Si-H-CL through thermolysis is made the silicon material of solar cell, this obnoxious flavour that contains Si-H-CL as, dichlorosilane and trichlorosilane, and then the polysilicon of production ultra-high purity are commonly referred to as nine nine, i.e. 99.9999999% purity.These gases are highly inflammable and deleterious, because gasification silicon works the mischief to environment and health, have only minority factory to have the ability to operate in the world, thereby cause the growth " bottleneck " of semi-conductor and solar cell industry.Recently the silicon gasification factory that proposes faces the resistance on local community environment and the safety-problems.These factories also need a large amount of capital investment and very long operation period.Therefore, always exist the silicon chip demand and the supply between imbalance.
The silicon of purifying (so-called polysilicon, the gasification and the decomposition of silane-based compound obtain polysilicon) provides to be fit to the application of semi-conductor and solar cell with particle or blocky form usually.Melting polycrystalline silicon then, and use young crystalline substance to pull out silicon single crystal rod or polycrystal ribbon silicon.Interchangeable, polysilicon is cast cylindrical.This silicon single crystal rod of pulling out is cut, and moulding also is polished into the circular silicon chip of 5-6 inch, can cut into square silicon chip later on.Then, the wet chemical etching in the alkali electroless etching is applied to leather producing process, like Pottasium Hydroxide.POCl
3Diffuse to form the pn knot.Using P ECVD silicon oxynitride forms the anti-reflection coating passivation then.Silk screen printing silver slurry on n type surfaces coated, and on p type surfaces coated aluminium paste.Then, metal paste forms electrical contact through pasting sintering.At last, test and classify according to solar cell characteristic separately, for example, their IV curve.
Above-mentioned technology is well-known, and in industry carries out for many years.Yet the most of cost in the semi-conductor (that is, being worth) is polished silicon slice is changed into the unicircuit of a running.But in the process that solar cell is made, the cost that is used to produce the polished silicon slice of solar battery sheet is higher than the manufacturing cost that polished silicon slice is changed into the solar cell of a running.That is to say, in business model, silicon wafer is converted into the process of solar cell, is not the manufacturing step of a high value-added in solar cell slab integral chain.Therefore, completely contradict with the improvement of solar cell manufacturing technology, the measure of the manufacturing cost of any improvement or minimizing beginning silicon chip will make the price of finished product solar panel sharply reduce.
For the problem of the silicon raw material that overcomes solar cell, proposed recently to use cheap metallurgical silicon material to produce the method for solar cell.For example, USP 7956283,7951640 and 7960644.Though the conclusion of a lot of academic articles thinks that metallurgical silicon material can not be used to make solar cell; But; Sunpreme has developed and has verified the metallurgical grade silicon solar panel, and on efficient, can be equal to mutually with the solar cell that monocrystalline and polysilicon silicon chip are processed.
Causing polysilicon chip is the crystal orientation than one of inefficient problem of silicon single crystal wafer.That is to say that monocrystalline silicon wafer crystal can be regarded a single crystal orientation as, for example < 100 >, and polysilicon has multiple crystal orientation, for example, < 100 >, < 211 >, < 110 >.In order to increase the photoelectric current that solar cell produces, must be in silicon chip surface making herbs into wool so that capture more sunlight.The method in making herbs into wool < 100>crystal orientation is well-known, can produce the ideal Pyramid.Yet the polycrystalline surface that making herbs into wool has a different crystalline lattice direction will be stranded much more difficult, especially uses wet chemistry method, i.e. chemical milling.Specifically, be difficult to the suitable etching reagent of collocation, all lattice direction of silicon chip surface are etched into the ideal matte.
Summary of the invention
Below disclose the understanding for some aspect of the present invention and function is provided.Content of the present invention is not an extensive overview ot of the present invention, so its purpose is not concrete definite key of the present invention or important element or delimit scope of the present invention.Its sole purpose is to show notions more of the present invention with simple form, so that the present invention to be described below in more detail.
Various embodiment of the present invention provides the method for the silicon substrate that is used to make majority < 100>crystal orientation.According to the embodiment of the present invention, use the crucible that a plurality of pockets are arranged in crucible bottom.< 100>the young crystalline substance in crystal orientation is placed in each pocket of crucible, and in crucible, fills the appropriate Si material, then the high temperature ingot casting.In case the fusing of silicon material, the pocket of this kind production method can prevent to put young brilliant floating.Crucible is placed in the casting unit, is positioned at when the ingot casting below heating and the melting area to guarantee this pocket.Heat fused begins at the crucible top, is positioned at the pocket top.In case the silicon material is melted to the bottom, the silicon liquid-flow contacts with young crystalline substance in pocket.Slowly reduce crucible then, lower melt portions begins to solidify, and grows up along young brilliant < 100>direction.
Description of drawings
Others of the present invention and characteristic are seen embodiment and with reference to attached drawings.Embodiment and accompanying drawing provide the non-restrictive example of the various embodiments of the present invention, and it is defined by additional claim.
Incorporate into and and the annexed drawings that constitutes the present invention part embodied embodiment of the present invention, and explain and explain principle of the present invention with specification sheets.Accompanying drawing is for the mode with chart exemplified embodiment of the present invention to be described.Accompanying drawing is not described each characteristic of embodiment, does not describe the relative dimension of said element yet, and NTS is drawn.
Fig. 1 is according to the synoptic diagram of crucible before fusing of feeding shown in the embodiment of the present invention.
The 2nd, according to the vertical view of the crucible shown in the embodiment of the present invention.
Fig. 3 is according to the synoptic diagram of crucible between melting period of feeding shown in the embodiment of the present invention.
Fig. 4 is according to the synoptic diagram of crucible at solidificating period of feeding shown in the embodiment of the present invention.
Fig. 5 A and 5B are to use the solar cell of the silicon chip manufacturing of producing according to above-mentioned example.
Embodiment
Embodiment of the present invention can be produced the solar cell that reduces cost, and reduces in traditional solar cell manufacturing processed the harm for healthy and environment simultaneously.Academic opposite with tradition, the present invention has disclosed the metallurgical silicon material (MGSi) of use 3N-5N purity to make the method for substrate and solar cell.The thin film silicon solar cell efficiency of conversion that the various embodiments that the present invention discloses have combined crystal silicon solar energy battery and the technological battery of based thin film is greater than 16% benefit.In order to improve efficiency of conversion, handling through the matte of silicon chip surface before making solar cell increases short-circuit current, JC.Casting through on the young crystalline substance in a plurality of < 100>crystal orientation, carrying out metallurgical grade silicon can increase the percentage in < 100>crystal orientation and then help leather producing process.
Fig. 1 is according to the casting crucible shown in the illustrative embodiments 100.In this embodiment, crucible is general rectangle.A plurality of pockets 105 are arranged at the bottom of crucible.Pocket is distributed on two dimensions of crucible bottom, and is as shown in Figure 2.< 100>silicon in crystal orientation young brilliant 110 is placed in the pocket 105, then, and with silicon material 135 crucible of packing into.Shown in mark among Fig. 1, when silicon material 135 melts to guarantee that young brilliant 110 do not float and withdraw from from pocket.Mark in Fig. 1 is an entering angle on the pocket exterior wall 115, and therefore the diameter of this pocket bottom is greater than pocket top diameter.That is to say that the wall 115 of each pocket 105 is the angles that get into again with acute angle, the bottom of this pocket is greater than its opening of opening to crucible bottom.At first silicon is young brilliant in an angle insertion, is placed on pocket bottom then.This can prevent young crystalline substance emersion from pocket.
According to the embodiment that discloses, the silicon material is the metalluragical silicon of many crystallizations cheaply, and purity is from about 39 to 59, and promptly silicon purity 99.9% to 99.999%.Metallurgical grade silicon is to let the two kinds of ores that can both find all over the world with electric arc furnace simply, quartzy (SiO
2) produce reduction reaction with coke (C).These two kinds of forms that nature is purified sand and coal.Graphite can be by other products substitutions that contains high-purity C that from oil or organic plant, produces.The metallurgical silicon material fusing, a certain amount of boron that mixes is to reach 5E17 atom * cm
-3P type doping content.In addition, phosphorus can be used as doping agent, to produce n type silicon chip.
Crucible is loaded into casting heavy stone used as an anchor stove, and is like electricity frequency or resistance furnace, the silicon material is fused into the silicon 140 of fusing, as shown in Figure 3.In this embodiment, stove comprises thermal baffle 125, and it intercepts part crucible and well heater 130.In position shown in Figure 3, crucible is the position in its superiors, like this pocket area of 125 shielding crucibles of thermal baffle.The silicon 140 of fusing flow in the pocket 105 and with young brilliant 110 and contacts.In case silicon melts fully, crucible slowly reduces, shown in arrow among Fig. 3.
Fig. 4 has explained the mid-way that reduces crucible.In position shown in Figure 4, thermal baffle prevents that heat is delivered to the bottom of crucible, thereby makes the silicon of fusing be frozen into polycrystal silicon 145.Because the bottom of the silicon 140 that in process of setting, melts and young brilliant the contact, so after solidifying, it is to a great extent along < 100>young brilliant 110 crystalline orientations.Therefore, polycrystal silicon 145 contains the generation of a high proportion of < 100>crystal orientation.
Crucible continue to reduce, and is frozen into single polycrystalline ingot casting up to the silicon 140 of all fusings.Knock crucible open the release silicon ingot then.The silicon ingot outermost partly is cut off, for example, and one inch.Then silicon ingot is cut into a plurality of little ingots, is sliced into silicon chip again.According to the embodiment of the present invention, the silicon chip that obtains is low-cost many crystalline metalluragical silicon, about 39 to 59 of purity, promptly 99.9% to 99.999%.
Use the silicon chip of above-mentioned Foundry Production can be reprocessed into solar battery sheet.Silicon chip at first must clean, and uses 100: 1 hydrofluoric acid to remove oxide on surface usually, uses NH
4OH/H
2O
2To remove organic contamination, then with hydrochloric acid with the elimination metal pollutant.Immerse in the potassium hydroxide solution and come making herbs into wool face.Because silicon chip contains a high proportion of < 100>crystal orientation, the effect of Pottasium Hydroxide etching generation matte along < 100>crystal orientation is remarkable.The matte that potassium hydroxide etch generated be one along < 100>crystal orientation " pyramid " structure.
Fig. 5 A is to use the solar battery sheet of the silicon chip manufacturing of producing according to above-mentioned example.P type silicon chip substrate 500 has been cleaned and making herbs into wool.In the plasma reinforced chemical vapour deposition equipment of standard, be utilized in the SiH that does not have impurity gas to add then
4And H
2Middle extremely thin (the 10-1000 of plasma growth one deck that produces
) layer 505, be usually less than 100
Thickness, unadulterated intrinsic amorphous silicon (a-Si:H) thin film layer.Next step, 510 layers of the a-Si:H through dopant deposition N type, it can continue to use identical equipment deposition, but except SiH
4And H
2Use PH outward,
3Plasma body generate N layer 510.The oxidic, transparent, conductive layers 520 of then growing up in the above is like Zn0
2, ITO, perhaps InSnO layer.Oxidic, transparent, conductive layers (TCO) forms top electrode, and sunshine passes the absorption layer that oxidic, transparent, conductive layers gets into crystalline silicon.For charge collection efficiency, a series of electrodes 515, it comprises the silver slurry usually, can be by wire mark on including transparent conducting oxide layer 520.Silicon chip bottom is the back side of the battery structure that arrives of low resistance contact, and it is to scribble 525 layers of aluminium, or through physical vapor deposition (PVD) technology or contain the deposition of aluminium wire netting, sintering forms low contact resistance then.Alternatively, thin P-type amorphous layer 530 was deposited on silicon chip behind before al deposition.
Consequent solar battery structure comprises following new characteristic at least.The cost of the PN junction that the amorphous silicon membrane of a N layer is formed on light absorbing zone p type polycrystalline metallurgical grade silicon chip is than no matter be to use traditional silicon chip PN junction of sun power or semiconductor grade polysilicon to lack approximately about ten times.The young brilliant casting of the use that cost advantage is arranged is used in silicon chip production.Silicon chip surface making herbs into wool is with the absorption of increase light, thus the raising electric current.Thickness is that the light absorbing zone of the metallurgical p type polysilicon of 250-500 μ m is cast by having boron doped metallurgical silicon material, rather than uses more expensive solar-grade polysilicon.Between metallurgical substrate of p type and n type thin film silicon (a-Si:H), insert of the chain rupture influence of available middle intrinsic (mixing) film (ia-Si:H), thereby improve the photovoltaic efficiency of conversion with passivation metalluragical silicon surface impurity.Potassium hydroxide treatment < 100>crystal orientation lattice generates matte.This matte reduces reflection of light, thereby electric current is increased.
Fig. 5 B is an another embodiment of the invention.The embodiment of Fig. 5 B is similar to the embodiment of Fig. 5 A, except dopant profile is opposite.That is to say that the substrate 500 that absorbs light source is the metalluragical silicon manufacturings by the n type.Sedimentary amorphous layer 510 is opposite polarity, i.e. the knot of p type.
Can find out that the embodiment of Fig. 1-5B provides the film joint solar cell of the metallurgical grade silicon substrate that has at high proportion < 100>crystal orientation.Because the attribute of metalluragical silicon and matte, this has the advantage of better photoabsorption.Therefore, efficiency of conversion improves.On the other hand, the use of metallurgical silicon chip provides than traditional sun power or the lower cost of semiconductor grade silicon chip.In addition, through using metallurgical grade silicon silicon chip as herein described, reduced harm to healthy and environment.
Example of the present invention all is intended to explanation and nonrestrictive relation in every respect.It will be understood by a person skilled in the art that, hardware, the multiple different combinations of software and firmware all will be applicable to the present invention.In addition, to those skilled in the art, the technology technical ability of other standards that other realize disclosing from the present invention of the present invention and practice is obvious.It should be noted that only property as an example of explanation and example, the spirit and scope of the present invention represent through appended claim.
Claims (19)
1. be used to make the method for the substrate of solar cell, comprise:
Obtain crucible, said crucible has a plurality of pockets in its bottom;
It is young brilliant in said pocket to load silicon, and the young crystalline substance of said silicon has < 100>crystal orientation;
Load silicon and expect said crucible;
Melt said silicon material to generate silicon melt, said silicon melt flows in the pocket;
Said silicon melt is solidified, and said curing originates in crucible bottom, to obtain the solid silicon ingot.
2. method according to claim 1 is characterized in that, it further comprises the pocket that prevents that young crystalline substance from floating.
3. method according to claim 2 is characterized in that, it further is included in fusing and the solidification process said pocket is carried out thermoshield.
4. method according to claim 2 is characterized in that, it further is included in fusing and the solidification process said pocket is cooled off.
5. method according to claim 1 is characterized in that, wherein said loading silicon material comprises the silicon material that loads metallurgical grade silicon purity about 99.9% to 99.999%.
6. method according to claim 1 is characterized in that, it further comprises said silicon heavy stone used as an anchor is cut into silica brick, is cut into silicon chip again.
7. method according to claim 6 is characterized in that, it further comprises the making herbs into wool of use KOH solution.
8. be used to make the method for solar cell, comprise:
Obtain crucible, said crucible has a plurality of pockets in its bottom;
It is young brilliant in said pocket to load silicon, and the young crystalline substance of said silicon has < 100>crystal orientation;
Load silicon and expect said crucible;
Melt said silicon material to generate silicon melt, said silicon melt flows in the pocket;
Said silicon melt is solidified, and said curing originates in crucible bottom, to obtain the solid silicon ingot;
Said silicon heavy stone used as an anchor is cut into silica brick, be cut into silicon chip again;
With said silicon chip making herbs into wool;
Connect face in the manufacturing of said silicon chip front end surface.
9. method according to claim 8 is characterized in that, it further comprises the generation P type silicon substrate that mixes.
10. method according to claim 9 is characterized in that, it further is included in and makes n type layer on the silicon chip.
11. method according to claim 10 is characterized in that, it further is included in and makes the intrinsic thin layer between P type substrate and the n type layer.
12. method according to claim 11 is characterized in that, it further is included in the method that n type layer top is made the top contact surface and bottom substrate, made the bottom contact surface.
13. method according to claim 8 is characterized in that, it further comprises the generation N type silicon substrate that mixes.
14. method according to claim 13 is characterized in that, it further is included in and makes p type layer on the silicon chip.
15. method according to claim 14 is characterized in that, it further is included in and makes the intrinsic thin layer between N type substrate and the p type layer.
16. method according to claim 15 is characterized in that, it further is included in the method that p type layer top is made the top contact surface and bottom substrate, made the bottom contact surface.
17. be used to make the crucible of solidification of silicon, said crucible comprises:
Rectangular body, it has a bottom and four sides, and wherein said bottom comprises a plurality of pockets that can place the young crystalline substance of silicon.
18. crucible according to claim 17, wherein said pocket are the young brilliant pocket that floats that prevents with sloped sidewall.
19. crucible according to claim 17, the wherein said pocket that prevents that young crystalline substance from floating is included in a plurality of pocket openings and the pocket bottom of crucible bottom, and the diameter of each pocket bottom is greater than the diameter of corresponding pocket openings.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766904A (en) * | 2012-08-15 | 2012-11-07 | 常熟华融太阳能新型材料有限公司 | Silica ceramic crucible |
| CN103628132A (en) * | 2012-08-21 | 2014-03-12 | 国硕科技工业股份有限公司 | Polycrystalline silicon chip, polycrystalline silicon ingot and method for manufacturing polycrystalline silicon ingot |
| CN103762155A (en) * | 2013-12-23 | 2014-04-30 | 上海申和热磁电子有限公司 | Silicon wafer cleaning process |
| CN103849925A (en) * | 2012-11-30 | 2014-06-11 | 王金青 | An improved crucible used for ingot casting |
| CN105720134A (en) * | 2016-02-22 | 2016-06-29 | 成都振中电气有限公司 | Production technology of solar cell panel |
| CN108546990A (en) * | 2018-06-28 | 2018-09-18 | 晶科能源有限公司 | A kind of method and apparatus improving polysilicon grain boundary defect |
| CN112899777A (en) * | 2019-11-19 | 2021-06-04 | 苏州阿特斯阳光电力科技有限公司 | Seed wafer, preparation method thereof and preparation method of crystalline silicon ingot |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766904A (en) * | 2012-08-15 | 2012-11-07 | 常熟华融太阳能新型材料有限公司 | Silica ceramic crucible |
| CN103628132A (en) * | 2012-08-21 | 2014-03-12 | 国硕科技工业股份有限公司 | Polycrystalline silicon chip, polycrystalline silicon ingot and method for manufacturing polycrystalline silicon ingot |
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| CN103762155A (en) * | 2013-12-23 | 2014-04-30 | 上海申和热磁电子有限公司 | Silicon wafer cleaning process |
| CN105720134A (en) * | 2016-02-22 | 2016-06-29 | 成都振中电气有限公司 | Production technology of solar cell panel |
| CN108546990A (en) * | 2018-06-28 | 2018-09-18 | 晶科能源有限公司 | A kind of method and apparatus improving polysilicon grain boundary defect |
| CN112899777A (en) * | 2019-11-19 | 2021-06-04 | 苏州阿特斯阳光电力科技有限公司 | Seed wafer, preparation method thereof and preparation method of crystalline silicon ingot |
| CN112899777B (en) * | 2019-11-19 | 2022-05-13 | 苏州阿特斯阳光电力科技有限公司 | Seed wafer, preparation method thereof and preparation method of crystalline silicon ingot |
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Application publication date: 20120725 |