CN102208492B - Manufacturing method of solar battery - Google Patents
Manufacturing method of solar battery Download PDFInfo
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- CN102208492B CN102208492B CN2011101333215A CN201110133321A CN102208492B CN 102208492 B CN102208492 B CN 102208492B CN 2011101333215 A CN2011101333215 A CN 2011101333215A CN 201110133321 A CN201110133321 A CN 201110133321A CN 102208492 B CN102208492 B CN 102208492B
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- silicon chip
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a manufacturing method of a solar battery. The method comprises the following steps: forming multiple evenly distributed through holes on the front surface of a solar battery silicon wafer by using a plasma etching method; then diffusing and forming emitters in the emitter region of the back surface of the solar battery and though holes; and finally, respectively forming metal electrodes in the emitter electrode region and the base electrode region on the back surface. In the method, a manufacturing procedure is adopted, which is as follows: a plasma etching method is adopted to replace a laser drill for etching the through holes, thereby meeting the requirement of large-scale production, reducing the loss of a battery wafer and improving the precision control of the size of the hole; and then other processes are combined, so that an emitter penetrating through the solar battery is formed. Compared with the full back pole solar battery, in the emitter through structure, a P type silicon wafer with low carrier lifetime and cheap price can be used, thus the emitter through structure is an extremely potential battery structure with low cost and high conversion rate.
Description
Technical field
The invention relates to a kind of manufacture method of solar cell, belong to solar cell and make the field.
Background technology
Solar cell is the semiconductor assembly, and it can transfer sunlight to electric energy, so the efficient of solar cell will be closely bound up with the extinction situation on solar energy surface.
In the manufacture craft of crystal silicon solar energy battery, often there are a lot of metal grid lines in the sensitive surface of the solar cell that obtains in the conventional making flow process, and purpose is to be used for collected current and the pad of making assembly.On the one hand; The existence of metal grid lines has stopped the absorption of sunlight; Reduced the conversion efficiency of battery, on the other hand in the assembly production process, because the pad of both positive and negative polarity is the both sides at the battery sheet; Worry breaking of battery sheet in the welding process, more the use of big with thinner battery sheet is restricted.
A kind of manufacture method of full back electrode solar cell is disclosed among the US 7820475B2; In this patent documentation disclosed solar cell on the one hand since all metal grid lines all at the non-sensitive surface of battery sheet; Can fully absorb sunlight, improve the conversion efficiency of battery greatly, on the other hand; Because the welding of both positive and negative polarity is all on same plane; Make convenient that the welding of assembly becomes, also be beneficial to bigger and the more use of thin battery sheet, can further reduce cost of material and improve the assembly power output.
But the PN junction of this battery is formed entirely in the non-sensitive surface of battery; The diffusion length of the minority carrier that forms at the sensitive surface of battery sheet must can be greater than the thickness of battery sheet; Minority carrier can arrive the space charge region and form photogenerated current; Therefore very high to the requirement of original silicon chip, generally require to use minority carrier life time greater than 1 millisecond N type silicon chip, the cost of raw material is very high.
A kind of solar cell with the aperture that runs through is disclosed among the CN 101710596A; The aperture that runs through through laser; With metal lead wire the grid line of solar battery front side is connected to the back side formation circuit of solar cell, thereby has reduced stopping of frontal sunlight.But the front of this solar cell still needs a large amount of grid lines, and these grid lines also can the stop portions sunlight, on the conversion efficiency still not as full back electrode solar cell.Similarly; A kind of solar cell and preparation method thereof is also disclosed among the CN 101853899A; It can get the through hole that is used to conduct electricity on the cell silicon chip very much through laser after diffusion; But still need print front electrode at last, thereby also can the stop portions sunlight at solar battery front side, on the conversion efficiency also not as full back electrode solar cell.
In the above-mentioned prior art; Through on silicon chip, adopting laser drill; Can partly overcome the problem that front electrode stops that sunlight is too much, thereby the diffusion length of minority carrier is not had very high requirement, that is to say and to lower the quality of raw material silicon chip; Can save material cost significantly, and can the comparatively cheap P type silicon chip of use cost.In the above-mentioned prior art, employing be the method for laser drill, on the solar battery sheet of typical 156mm*156mm, if via densities is at 300/cm
2, then need on a battery sheet, bore above 72000 through holes, present laser drill method approximately reaches 1 second and bores 100 holes; About 50 microns of the diameter in hole, then every processing a slice silicon chip needs 12 minutes, and this is that current battery sheet large-scale production institute is insupportable; And laser drill also causes the silicon chip surface damage easily; Must increase extra affected layer and remove step, uncontrollable to the precision control of the size in hole, limited the quantity and the risk of short-circuits that has increased backplate of through hole.
Summary of the invention
Therefore, the technical problem that the present invention will solve provides a kind of manufacture method of solar cell, to reduce or to avoid problem noted earlier.
Specifically; The present invention proposes a kind of manufacture method of solar cell; It adopts the plasma etching method on silicon chip of solar cell, to carve a large amount of through holes, and speed is fast, efficient is high, and need not to be provided with any electrode at solar battery front side; Have and the intimate identical advantage of full back electrode solar cell, and the quality requirement of silicon chip is lower than full back electrode solar cell.
The present invention proposes a kind of manufacture method of solar cell; Said solar cell comprises silicon chip, and said silicon chip has front and back, and said front is the sensitive surface of said silicon chip when normally using; The said back side is the relative one side in said front, and said manufacture method comprises the steps:
A, the silicon chip that is used to make said solar cell is carried out affected layer remove, and form oxide-film in said silicon chip back;
B, employing plasma etching method are at the equally distributed a plurality of through holes of the positive formation of said silicon chip, and the density of said through hole is 100～500/cm
2, the aperture is the 20-100 micron, the etching gas in the said plasma etching method is SF
6, CHF
3, one of Ar or its combination, the pressure of etching gas is the 5-100 millitorr, the flow of etching gas be 50-200 flow standard liter/minute, the source electrode power is 100-1500W, bias electrode power is 1-10W;
C, form matte in the positive and said through hole at said silicon chip;
Said oxide-film is removed in D, the place that need form emitter electrode at the said silicon chip back side; Expose the emitter electrode zone; And remove the said oxide-film between said emitter electrode zone and the said through hole, and keep said oxide-film in the place of needs making base electrode;
E, in said emitter region and said through hole, diffuse to form emitter;
The oxide-film that F, the said silicon chip of the removal back side keep exposes the base electrode zone under it; Form metal electrode in said emitter electrode zone and base electrode regional location respectively then.
Preferably, further comprise in the said step e: remove the phosphorosilicate glass that is formed at said silicon chip surface after said silicon chip is spread.
Preferably; It is characterized in that; Further comprise in the said step F: removing after the oxide-film of said silicon chip back side reservation, is the antireflection nitride film of 500-1500
at the positive formation of said silicon chip thickness.
Preferably, further comprise in the said step F: after forming said metal electrode said silicon chip is carried out the edge insulation etching.
Preferably, among the said step D, use one step of laser ablation method to accomplish and remove said oxide-film.
Preferably, among the said step D, the step of removing said oxide-film comprises: after needs being removed the position use ink-jet method coating photoresist of said oxide-film, utilize the method for plasma etching or wet etching to accomplish.
Preferably, in the said step e, adopt POCL
3Diffuse to form said emitter, the square resistance of the said emitter that the diffusion back forms is 30-200 Ω/every square.
Preferably, in the said steps A, adopt plasma-reinforced chemical gaseous phase deposition method to form said oxide-film.
Preferably, in the said step F, adopt silk screen printing and sintering to form said metal electrode.
The present invention has adopted the method for plasma etching to replace laser drill to carry out via etch; Can satisfy requirement of large-scale production; Reduce loss simultaneously, improve the precision control of the size in hole, combine other technology to form the making flow process that emitter connects solar cell at last again the battery sheet; Compare with full backplane solar cell; The emitter communicating structure allows to use lower, the cheap P type silicon chip of minority carrier life time specification, is the battery structure of very potential low cost and high conversion.
Description of drawings
Following accompanying drawing only is intended to the present invention is done schematic illustration and explanation, not delimit the scope of the invention.Wherein,
Fig. 1 shows be silicon chip of solar cell according to a specific embodiment of the present invention after removing affected layer, form the cross sectional representation of oxide-film at the silicon chip back side;
What Fig. 2 showed is the situation after forming through hole on the silicon chip shown in Figure 1;
What Fig. 3 showed is the situation that on Fig. 2 basis, forms matte;
What Fig. 4 showed is the situation after removing partial oxide film on Fig. 3 basis;
What Fig. 5 showed is the situation that on Fig. 4 basis, diffuses to form emitter;
What Fig. 6 showed is the situation after removing whole oxide-films on Fig. 5 basis;
What Fig. 7 showed is the situation after the formation metal electrode on Fig. 6 basis.
Embodiment
To understand in order technical characterictic of the present invention, purpose and effect being had more clearly, to contrast description of drawings embodiment of the present invention at present.Wherein, identical parts adopt identical label.
Manufacture method according to a kind of solar cell of a specific embodiment of the present invention can be described in detail with reference to Fig. 1-7, and is as shown in the figure, in the manufacture method of solar cell of the present invention; Said solar cell comprises silicon chip 1; In the present embodiment, said silicon chip 1 is a P type silicon chip, and said silicon chip 1 has the front 10 and the back side 20; Said positive 10 sensitive surfaces when being said silicon chip 1 normal the use; The said back side 20 is said positive 10 relative one sides, and solar cell of the present invention can be made according to the following steps flow process, and the manufacture method of said solar cell comprises the steps:
Steps A: the silicon chip 1 that is used to make said solar cell is carried out affected layer remove; And 20 form oxide-films 30 at the back side of said silicon chip 1; As shown in Figure 1; Its demonstration be silicon chip of solar cell 1 after removing affected layer, form the cross sectional representation of oxide-films 30 at silicon chip 1 back side 20.Affected layer is removed and can be used the hydrofluoric acid nitrate mixture to carry out.Oxide-film 30 can use plasma-reinforced chemical gaseous phase deposition method to form, and the thickness of the oxide-film 30 that forms at last is 200-3000
Step B: adopt the plasma etching method at the equally distributed a plurality of through holes 40 of said silicon chip 1 positive formation, the density of said through hole 40 is 100～500/cm
2, the aperture is the 20-100 micron, and is as shown in Figure 2, just on the basis of silicon chip 1 shown in Figure 1, forms through hole 40 from the front.
The plasma etching method of this step can be specially: the definition front description; Use ink-jet method to carry out the coating of photoresist mask layer, the thickness 1um-10um of photoresist; Use SF
6, CHF
3, one of Ar or its combination be as etching gas, the pressure of etching gas is the 5-100 millitorr, the flow of etching gas be 50-200 flow standard liter/minute, the source electrode power is 100-1500W, bias electrode power is 1-10W; Remove front photoresist and etch by-products at last.Remove front photoresist and etch by-products and can use the dioxysulfate aqueous mixtures.
Step C: at the said silicon chip 1 positive matte 11 that forms, in said through hole 40, also formed matte 11 simultaneously, as shown in Figure 3, wherein, form matte 11 and can use the dioxysulfate aqueous mixtures.
Step D: said oxide-film 30 is removed in the place in that said silicon chip 1 back side 20 needs to form emitter electrode; Expose emitter electrode zone 50; And remove the said oxide-film 30 between said emitter electrode zone 50 and the said through hole 40, and keep said oxide-film 30 in the place of needs making base electrode; As shown in Figure 4, its demonstration be the situation after removing partial oxide film 30 on Fig. 3 basis.
In this step, can use laser ablation method one step to accomplish and remove said oxide-film 30, perhaps also can use ink-jet method to apply photoresist to the position that needs removed said oxide-film 30 after, utilize the method for plasma etching or wet etching to accomplish.Wherein wet etching can use hydrofluoric acid, and plasma etching can use the gas of carbon containing fluorine (like C
5F
8) and the mixture of oxygen as etching gas.
Step e: in said emitter electrode zone 50 and said through hole 40, diffuse to form emitter 12, as shown in Figure 5, its demonstration be the situation that on Fig. 4 basis, diffuses to form emitter 12.In this step, can adopt POCL
3Diffuse to form said emitter 12, the square resistance of the said emitter 12 that the diffusion back forms is 30-200 Ω/every square.
In addition, can also further comprise the step of removing the phosphorosilicate glass that is formed at said silicon chip 1 surface after spreading to said silicon chip 1, the removal of phosphorosilicate glass can be used hydrofluoric acid or BOE (buffer oxide film etching agent).
Step F: remove the oxide-film 30 that said silicon chip 1 back side 20 keeps, expose the base electrode zone 60 under it, as shown in Figure 6; Form corresponding metal electrode 51,61 respectively in said emitter electrode zone 50 and base electrode zone 60 respectively then; As shown in Figure 7; Wherein, what Fig. 7 showed is on Fig. 6 basis, to form metal electrode 51, the situation after 61, clear for representing; Omitted the part Reference numeral among Fig. 6 among Fig. 7, but those skilled in the art can be according to Fig. 6 reference in addition.
In this step, can adopt silk screen printing and sintering to form said metal electrode 51,61.In addition, forming said metal electrode 51, after 61, can also further carry out the edge insulation etching said silicon chip 1.
And; In this step; Can further include and forming thickness in the front 10 of said silicon chip 1 is the step (not shown) of the antireflection nitride film of 500-1500
, and generation type can be the plasma-reinforced chemical vapor deposition method.
Should benly be; Among the present invention; Through the aperture 40 on the solar cell itself is diffused into for emitter; Make aperture 40 can be communicated with positive diffusion zone, and the present invention still diffuses out the zone 50 that can supply to be communicated with emitter electrode around the aperture 40 of rear surface of solar cell, made the present invention metal electrode 51 to be set emitter electrode zone 50 overleaf; Thereby make metal electrode 51 can be communicated with the front of solar cell through the emitter that aperture 40 diffuses out; Need not as in the prior art, metal grid lines to be set, to stopping of sunlight can be little a lot (, almost can ignore) to the loss that the solar radiation area causes because small aperture is very little in the front.On the other hand; Compare with full back electrode solar cell; The diffusion length of the minority carrier that forms at the sensitive surface of battery sheet need not the thickness greater than the battery sheet; Being that emitter communicating structure of the present invention allows to use lower, the cheap P type silicon chip of minority carrier life time specification, is the battery structure of very potential low cost and high conversion.
Though the step of diffusion after the laser drilling is disclosed among the CN 101710596A equally,, this small aperture of the prior art will be much larger than the present invention, and the density of aperture is also very little, can only use as the path of passing metal lead wire.That is to say; Even if this aperture of the prior art has also formed with the similar structure of emitter after diffusion and (has been merely hypothesis here; Do not have this kind description or enlightenment in this prior art, the applicant does not think that this prior art discloses this technical scheme), still; Because this prior art is not provided with the emitter electrode zone at the back side of solar cell; Emitter electrode zone is not communicated with aperture yet, so the aperture that forms in this prior art in actual use, can not be as described in the invention; A part that self becomes emitter circuit is communicated with the metal electrode of rear surface of solar cell positive; Therefore formed aperture only is a lead channels in this prior art, and it still need make grid line being communicated with positive emitter at solar battery front side, with the structure (density, aperture) and the effect (as the emitter of conduction usefulness) of aperture provided by the present invention be diverse.
In a word; Among the present invention; The minority carrier that sensitive surface forms is directly to import in the metal electrode at the back side through the emitter that forms in the aperture, and in the above-mentioned prior art, after the minority carrier that sensitive surface forms is at first collected through positive grid line; Be pooled to via the plain conductor that forms in the aperture in the grid line at the back side, thereby there is difference in essence in formed aperture with this aperture of the prior art among the present invention.
Equally; In CN 101853899A; Laser beam drilling carries out after diffusion, thereby the through hole that laser forms can not be through diffuseing to form emitter, therefore as described in the invention; Formed aperture can only use as lead channels equally in this prior art, with the structure of aperture provided by the present invention and effect also be diverse.
Another innovative point of the present invention just is; Adopted the method for plasma etching to replace laser drill and carried out via etch, can satisfy requirement of large-scale production, reduced loss simultaneously the battery sheet; Improve the precision control of the size in hole; Combine other technology to form the making flow process that emitter connects solar cell at last again, compare with full backplane solar cell, the emitter communicating structure allows to use the minority carrier life time specification lower; Cheap P type silicon chip is the battery structure of very potential low cost and high conversion.
Though the technical scheme that forms circuit pattern through plasma etching is also arranged in the prior art, and these technologies all lack the optimization process of system, especially some crucial technical parameters all quite lack.And in the actual application; Each different processing technology step all is closely-related with concrete parameter, for example, and in the present invention; Though have some steps and usual manner similar a bit; But because processing technology is to have certain sequence, each step all can influence generating step thereafter, thereby has determined the parameter of subsequent step.
Therefore; Judging difference with the prior art of the present invention and creationary the time; It should be understood by those skilled in the art that be not two or more prior aries just can be beyond all doubt be combined into each step of the present invention, thereby can obtain same technique effect; On the contrary; Those skilled in the art more should understand; In order to obtain specific technique effect, the present invention has carried out meticulous optimization process to each step, thereby has obtained to possess creationary technological process in regular turn; And, the sequencing of technological process of the present invention with select to exist necessary relation in preceding parameter.
For example, in the prior art just never the someone expected that it was 100～500/cm that method through plasma etching forms density on solar cell
2, the aperture is the through hole of 20-100 micron, constitutes the emitter of perforation with this.In the present invention, etching speed is relevant with the percentage that etch areas accounts for the gross area, supposes via densities 300/cm
2, the diameter in hole is 50 microns, the ratio of carving the open region probably accounts for 0.5%; Use SF6 as main etching gas, etch rate can reach 3um/s, and then handling a slice silicon chip needs 1 minute; And can handle 100-200 sheet battery simultaneously, satisfy the requirement of battery sheet large-scale production fully, the plasma etching method is little to the damage of battery sheet in addition and the size accuracy in hole high; Can reduce the follow-up affected layer operation of going, also can reduce the requirement of follow-up metal electrode technology.
Describing according to the mode of a plurality of embodiment though it will be appreciated by those skilled in the art that the present invention, is not that each embodiment only comprises an independently technical scheme.Narration like this only is for the sake of clarity in the specification; Those skilled in the art should do specification as a wholely to understand, and regard technical scheme related among each embodiment as the mode that can be combined into different embodiment each other understand protection scope of the present invention.
The above is merely the schematic embodiment of the present invention, is not in order to limit scope of the present invention.Any those skilled in the art, revises and combines the equivalent variations of under the prerequisite that does not break away from design of the present invention and principle, being done, and all should belong to the scope that the present invention protects.
Claims (9)
1. the manufacture method of a solar cell is characterized in that, said solar cell comprises silicon chip; Said silicon chip has front and back; Said front is the sensitive surface of said silicon chip when normally using, and the said back side is the relative one side in said front, and said manufacture method comprises the steps:
A, the silicon chip that is used to make said solar cell is carried out affected layer remove, and form oxide-film in said silicon chip back;
B, employing plasma etching method are at the equally distributed a plurality of through holes of the positive formation of said silicon chip, and the density of said through hole is 100～500/cm
2, the aperture is the 20-100 micron, the etching gas in the said plasma etching method is SF
6, CHF
3, one of Ar or its combination, the pressure of etching gas is the 5-100 millitorr, the flow of etching gas be 50-200 flow standard liter/minute, the source electrode power is 100-1500W, bias electrode power is 1-10W;
C, form matte in the positive and said through hole at said silicon chip;
Said oxide-film is removed in D, the place that need form emitter electrode at the said silicon chip back side; Expose the emitter electrode zone; And remove the said oxide-film between said emitter electrode zone and the said through hole, and keep said oxide-film in the place of needs making base electrode;
E, in said emitter region and said through hole, diffuse to form emitter;
The oxide-film that F, the said silicon chip of the removal back side keep exposes the base electrode zone under it; Form metal electrode in said emitter electrode zone and base electrode regional location respectively then.
2. the manufacture method of solar cell according to claim 1 is characterized in that, further comprises in the said step e: remove the phosphorosilicate glass that is formed at said silicon chip surface after said silicon chip is spread.
3. the manufacture method of solar cell according to claim 2; It is characterized in that; Further comprise in the said step F: removing after the oxide-film of said silicon chip back side reservation, is the antireflection nitride film of
at the positive formation of said silicon chip thickness.
4. the manufacture method of solar cell according to claim 3 is characterized in that, further comprises in the said step F: after forming said metal electrode said silicon chip is carried out the edge insulation etching.
5. according to the manufacture method of one of claim 1-4 described solar cell, it is characterized in that, among the said step D, use one step of laser ablation method to accomplish and remove said oxide-film.
6. according to the manufacture method of one of claim 1-4 described solar cell; It is characterized in that; Among the said step D; The step of removing said oxide-film comprises: after needs being removed the position use ink-jet method coating photoresist of said oxide-film, utilize the method for plasma etching or wet etching to accomplish.
7. according to the manufacture method of one of claim 1-4 described solar cell, it is characterized in that, in the said step e, adopt POCL
3Diffuse to form said emitter, the square resistance of the said emitter that the diffusion back forms is 30-200 Ω/every square.
8. according to the manufacture method of one of claim 1-4 described solar cell, it is characterized in that, in the said steps A, adopt plasma-reinforced chemical gaseous phase deposition method to form said oxide-film.
9. according to the manufacture method of one of claim 1-4 described solar cell, it is characterized in that, in the said step F, adopt silk screen printing and sintering to form said metal electrode.
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| CN2011101333215A CN102208492B (en) | 2011-05-20 | 2011-05-20 | Manufacturing method of solar battery |
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|---|---|---|---|
| CN2011101333215A CN102208492B (en) | 2011-05-20 | 2011-05-20 | Manufacturing method of solar battery |
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| CN102208492B true CN102208492B (en) | 2012-08-08 |
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| CN103390660A (en) * | 2012-05-09 | 2013-11-13 | 上海太阳能工程技术研究中心有限公司 | Crystalline silicon solar cell and manufacturing method thereof |
| NL2008970C2 (en) * | 2012-06-08 | 2013-12-10 | Tempress Ip B V | Method of manufacturing a solar cell and solar cell thus obtained. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360990A (en) * | 1993-03-29 | 1994-11-01 | Sunpower Corporation | P/N junction device having porous emitter |
| CN101710596A (en) * | 2009-11-23 | 2010-05-19 | 宁波太阳能电源有限公司 | Silicon solar battery |
| CN101853899A (en) * | 2010-03-31 | 2010-10-06 | 晶澳(扬州)太阳能光伏工程有限公司 | Method for preparing solar cell by using local area back field |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101443893B (en) * | 2005-12-21 | 2012-02-01 | 太阳能公司 | Back side contact solar cell structures and fabrication processes |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360990A (en) * | 1993-03-29 | 1994-11-01 | Sunpower Corporation | P/N junction device having porous emitter |
| CN101710596A (en) * | 2009-11-23 | 2010-05-19 | 宁波太阳能电源有限公司 | Silicon solar battery |
| CN101853899A (en) * | 2010-03-31 | 2010-10-06 | 晶澳(扬州)太阳能光伏工程有限公司 | Method for preparing solar cell by using local area back field |
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