CN103247720B - A kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell - Google Patents
A kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell Download PDFInfo
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- CN103247720B CN103247720B CN201310171277.6A CN201310171277A CN103247720B CN 103247720 B CN103247720 B CN 103247720B CN 201310171277 A CN201310171277 A CN 201310171277A CN 103247720 B CN103247720 B CN 103247720B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 83
- 239000010703 silicon Substances 0.000 title claims abstract description 83
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 71
- 238000005468 ion implantation Methods 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 239000010408 film Substances 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 210000002268 Wool Anatomy 0.000 claims abstract description 8
- 235000008216 herbs Nutrition 0.000 claims abstract description 8
- 238000007650 screen-printing Methods 0.000 claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 7
- 238000001994 activation Methods 0.000 claims abstract description 6
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 8
- SBEQWOXEGHQIMW-UHFFFAOYSA-N [Si].[Si] Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 210000004027 cells Anatomy 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 210000002381 Plasma Anatomy 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating Effects 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N Disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003667 anti-reflective Effects 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- DMJZZSLVPSMWCS-UHFFFAOYSA-N diborane Chemical compound B1[H]B[H]1 DMJZZSLVPSMWCS-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
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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
- 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 kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, comprise the steps: (1) cleaning, corrosion making herbs into wool; (2) front and back of silicon chip is carried out Si ion implantation respectively, tow sides form one deck amorphous silicon membrane respectively; (3) amorphous silicon membrane of front side of silicon wafer is carried out twice B ion implantation; (4) amorphous silicon membrane of silicon chip back side is carried out B ion implantation; (5) amorphous silicon membrane of silicon chip back side is carried out P ion implantation; (6) hot activation process; (7) transparent conductive film layer is set at the tow sides of silicon chip; (8) silk screen printing, sinter and prepare metal electrode at silicon chip surface.Present invention obtains high-quality silicon/crystalline silicon heterogenous joint solar cell, define the crystal silicon of the integration of high-quality amorphous thin Film layers and few defect, non crystal heterogeneous agglomeration superposition interface, improve passivation effect and significantly reduce leakage current.
Description
Technical field
The present invention relates to a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, belong to technical field of solar.
Background technology
Along with the extensive use of solar module, photovoltaic generation more and more occupies important proportion in new forms of energy, obtains develop rapidly.In current business-like solar cell product, the market share of crystalline silicon (monocrystalline and polycrystalline) solar cell is maximum, keeps the occupation rate of market of more than 85% always.Therefore, one of the crystal silicon solar energy battery of high performance-price ratio or the R&D direction of various countries researcher is researched and developed.
At present, Japanese Sanyo company produces a kind of silicon/crystalline silicon heterogenous joint solar cell.So-called heterojunction, refer to that the PN junction of battery front side is made up of amorphous silicon and n type single crystal silicon substrate, amorphous silicon layer comprises P-type non-crystalline silicon thin layer and intrinsic amorphous silicon thin layer; Then back surface field is formed by intrinsic amorphous silicon thin layer and N-type amorphous thin Film layers at cell backside.Amorphous silicon is as direct gap semiconductor material, comparatively large to the absorption coefficient of incident light, the amorphous thin Film layers of very little thickness and the incident light of Absorbable rod considerable part; Meanwhile, the energy gap of amorphous silicon is 1.7eV, and much larger than the energy gap 1.1eV of crystalline silicon, therefore, the open circuit voltage of the solar cell of heterojunction structure can be significantly higher than conventional crystalline silicon solar cell, thus brings excellent performance.The technological process that Sanyo company produces heterojunction solar battery is roughly as follows: carry out corrosion making herbs into wool after first carrying out wet chemical process cleaning to the surface of n type single crystal silicon silicon chip, forms micron order pyramid suede structure at its front and back; Then use PECVD method to deposit one deck intrinsic amorphous silicon film and one deck P-type non-crystalline silicon film formation heterojunction emitter at front side of silicon wafer, deposit one deck intrinsic amorphous silicon film and one deck heavily doped N-type amorphous silicon membrane formation back of the body electric field at silicon chip back side; Then at silicon chip tow sides deposit transparent conductive film; Finally use silk screen printing and sinter and prepare metal electrode at silicon chip surface, obtain complete silicon/crystalline silicon heterogenous joint solar cell.
But in above processing step, the wet-chemical cleaning of the silicon chip surface of the first step is very crucial.This is because next use the thickness of the Multi-layer amorphous silicon thin film of PECVD deposition all very little, for nanoscale, so require very high to the clean-up performance of silicon chip surface, any impurity or dust granule all can become the fault of construction of heterojunction, have a strong impact on the interface state density of battery, affect the open circuit voltage of battery.Therefore, current industrial general employing multiple tracks chemical solution and the treatment fluid mode of repeatedly cleaning.But this method not only causes cost to raise, and operation is tediously long, and effect cannot be guaranteed, and also creates the environmental problems such as liquid waste processing.In addition, adopt in the process of PECVD sedimentation structure heterojunction, easily cause point discharge, affect amorphous silicon membrane quality, greatly reduce yields.
Therefore, develop a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, to prepare high-quality silicon/crystalline silicon heterogenous joint solar cell, there is positive realistic meaning.
Summary of the invention
The object of the invention is to provide a kind of silicon/crystalline silicon heterogenous joint solar cell.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, comprises the steps:
(1) n type single crystal silicon silicon chip is carried out surface chemistry cleaning, corrosion making herbs into wool;
(2) front and back of above-mentioned silicon chip is carried out Si ion implantation respectively, tow sides form one deck amorphous silicon membrane respectively;
(3) amorphous silicon membrane of above-mentioned front side of silicon wafer is carried out twice B ion implantation;
(4) amorphous silicon membrane of above-mentioned silicon chip back side is carried out B ion implantation;
(5) amorphous silicon membrane of above-mentioned silicon chip back side is carried out P ion implantation;
(6) amorphous silicon membrane of above-mentioned doping is carried out hot activation process;
(7) transparent conductive film layer is set at the tow sides of above-mentioned silicon chip;
(8) silk screen printing, sinter and prepare metal electrode at silicon chip surface, silicon/crystalline silicon heterogenous joint solar cell can be obtained.
Above, the Si ion implantation in described step (2) uses disilane or other silane based gas to make ion source.
B ion implantation in described step (3) and step (4) can use diborane, and boron trifluoride or other boron-containing gas make ion source.
Hot activation process in described step (6) can adopt anneal or rapid thermal anneal methods.The object of hot activation treatment process eliminates lattice damage, and make foreign atom occupy lattice position and be activated.
In described step (7), transparent conductive film layer can adopt the method preparation of reactive plasma deposition or magnetron sputtering, and transparent conductive film can use ITO, and one or more in IZO, IWO material deposit separately or codeposition.Preferred method is reactive plasma sedimentation, because the surface damage of the method to substrate is minimum.Described transparent conductive film layer plays antireflective effect simultaneously.
In described step (1), the pyramid suede structure that corrosion making herbs into wool is formed, its pyramid size controls usually at 5 to 20 microns.Usually the matte process means such as alkaline corrosion can be used to carry out smooth rounding process when forming described pyramid suede structure, to reach the object removing burr and pinnacle.
In step (3), twice B ion implantation is carried out to the amorphous silicon membrane of above-mentioned front side of silicon wafer, thus form P-type non-crystalline silicon thin layer on intrinsic amorphous silicon thin layer, so far define in the front of above-mentioned silicon chip
p/i/Nthe heterojunction of structure.In step (4), B ion implantation is carried out to the amorphous silicon membrane of above-mentioned silicon chip back side, thus make the bottom of N-type amorphous silicon membrane or Zone Full be transformed into intrinsic amorphous silicon thin layer; In step (5), P ion implantation is carried out to the amorphous silicon membrane of above-mentioned silicon chip back side, thus form N+ type amorphous silicon layer on the top layer of amorphous silicon membrane, so far define at the back side of above-mentioned silicon chip
n/i/N+the heterojunction of structure.
In described step (3), (4) and (5), can by controlling the energy injecting ion, concentration and duration reach the degree of depth accurately controlling ion implantation, the distribution of doping content and Doped ions.
In technique scheme, the thickness of the amorphous silicon membrane in described step (2) is 2 ~ 30nm.
In technique scheme, in described step (3), the degree of depth of B ion implantation is 1 ~ 30nm for the first time, and the degree of depth of second time B ion implantation is 1 ~ 15nm.
In technique scheme, in described step (4), the degree of depth of B ion implantation is 1 ~ 30nm.
In technique scheme, in described step (5), the degree of depth of P ion implantation is 1 ~ 15nm.
Corresponding another kind of technical scheme, a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, comprises the steps:
(1) p type single crystal silicon silicon chip is carried out surface chemistry cleaning, corrosion making herbs into wool;
(2) front and back of above-mentioned silicon chip is carried out Si ion implantation respectively, tow sides form one deck amorphous silicon membrane respectively;
(3) amorphous silicon membrane of above-mentioned front side of silicon wafer is carried out twice P ion implantation;
(4) amorphous silicon membrane of above-mentioned silicon chip back side is carried out P ion implantation;
(5) amorphous silicon membrane of above-mentioned silicon chip back side is carried out B ion implantation;
(6) amorphous silicon membrane of above-mentioned doping is carried out hot activation process;
(7) transparent conductive film layer is set at the tow sides of above-mentioned silicon chip;
(8) silk screen printing, sinter and prepare metal electrode at silicon chip surface, silicon/crystalline silicon heterogenous joint solar cell can be obtained.
In technique scheme, the thickness of the amorphous silicon membrane in described step (2) is 2 ~ 30nm.
In technique scheme, in described step (3), the degree of depth of P ion implantation is 1 ~ 30nm for the first time, and the degree of depth of second time P ion implantation is 1 ~ 15nm.
In technique scheme, in described step (4), the degree of depth of P ion implantation is 1 ~ 30nm.
In technique scheme, in described step (5), the degree of depth of B ion implantation is 1 ~ 15nm.
Due to the employing of technique scheme, compared with prior art, tool of the present invention has the following advantages:
1. this invention exploits a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell newly, ion implantation is used to carry out alternative traditional PECVD sedimentation to prepare the heterojunction structure in silicon/crystalline silicon heterogenous junction battery, define the crystal silicon of the integration of high-quality amorphous thin Film layers and few defect, non crystal heterogeneous agglomeration superposition interface, improve passivation effect and significantly reduce leakage current, obtaining high-quality silicon/crystalline silicon heterogenous joint solar cell.
2. method of the present invention reduces the requirement to silicon chip surface chemically cleaning significantly, therefore adopts conventional cleaning and texturing technique can obtain the hetero-junction solar cell of stay in grade, has good versatility.
3. the present invention accurately can control the degree of depth of ion implantation, doping content, the distribution of Doped ions and the thickness of each thin layer by controlling to inject the energy of ion, concentration and time, ensure the precision of heterojunction structure in battery, thus obtain high-quality battery emitter, improve the open circuit voltage of battery, effectively improve the transformation efficiency of battery.
4. preparation method of the present invention is simple, and cost is low, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one
A preparation method for silicon/crystalline silicon heterogenous joint solar cell, comprises the steps:
The first step, carries out chemical surface cleaning by n type single crystal silicon silicon chip;
Second step, carries out corrosion making herbs into wool to above-mentioned silicon chip, forms micron order pyramid suede structure at its front and back;
Usually the matte process means such as alkaline corrosion can be used to carry out smooth rounding process when forming described pyramid suede structure, to reach the object removing burr and pinnacle;
3rd step, adopts ion implantation, injects Si ion, thus respectively form the thick amorphous silicon membrane of 2 ~ 30nm in silicon chip upper and lower surface at the front and back of above-mentioned silicon chip;
4th step, adopts ion implantation, carries out first time B ion implantation to the bottom of the amorphous silicon membrane of front side of silicon wafer, thus forms the intrinsic amorphous silicon thin layer of 1 ~ 15nm; Carry out second time B ion implantation again, thus form the P-type non-crystalline silicon thin layer of 1 ~ 15nm on the top layer of amorphous silicon membrane; So far define in the front of above-mentioned silicon chip
p/i/Nthe heterojunction of structure;
5th step, adopts ion implantation, carries out B ion implantation to the amorphous silicon membrane of silicon chip back side, thus forms the intrinsic amorphous silicon thin layer of 1 ~ 15nm at the bottom of amorphous silicon membrane;
6th step, carries out P ion implantation to this amorphous thin Film layers, thus forms the N+ type amorphous silicon layer of 1 ~ 15nm thickness on the top layer of amorphous silicon membrane; So far define at the back side of above-mentioned silicon chip
n/i/N+the heterojunction of structure;
7th step, adopt anneal or rapid thermal anneal methods, carry out activating process to the above-mentioned amorphous silicon membrane carrying out overdoping ion implantation, activating process can eliminate lattice damage, and makes foreign atom occupy lattice position and be activated;
8th step, utilizes reactive plasma to deposit or the method for magnetron sputtering prepares the thick transparent conductive film layer of 50 ~ 200nm on the surface of above-mentioned silicon chip;
Described transparent conductive film can use ITO, and one or more in the materials such as IZO, IWO carry out codeposition;
9th step, adopts silk screen printing and sintering or electric plating method form front and back metal electrode, can obtain described silicon/crystalline silicon heterogenous joint solar cell;
When adopting method for printing screen, the pictorial pattern of metal gates and depth-width ratio can be optimized to improve the performance of battery;
When adopting electro-plating method, the means such as mask lithography technique can be adopted to help to form metal electrode; The material of metal gates can be Ag, Cu, Al or other metal.
Above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.The present invention may be used for the heterojunction solar battery based on p type single crystal silicon sheet equally, or the manufacture of the various solar cell such as the silicon heterogenous battery of pedion (pedia).Those of ordinary skill in the art should be appreciated that and can modify to technical scheme of the present invention or equivalent replacement, and does not depart from the scope of technical solution of the present invention, and it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. a preparation method for silicon/crystalline silicon heterogenous joint solar cell, is characterized in that, comprises the steps:
(1) n type single crystal silicon silicon chip is carried out surface chemistry cleaning, corrosion making herbs into wool;
(2) front and back of above-mentioned silicon chip is carried out Si ion implantation respectively, tow sides form one deck amorphous silicon membrane respectively;
(3) amorphous silicon membrane of above-mentioned front side of silicon wafer is carried out twice B ion implantation;
First time B ion implantation is carried out to the bottom of the amorphous silicon membrane of front side of silicon wafer, forms intrinsic amorphous silicon thin layer; Carry out second time B ion implantation again, form P-type non-crystalline silicon thin layer on the top layer of amorphous silicon membrane; So far define in the front of above-mentioned silicon chip
p/i/Nthe heterojunction of structure;
(4) amorphous silicon membrane of above-mentioned silicon chip back side is carried out B ion implantation; Intrinsic amorphous silicon thin layer is formed at the bottom of amorphous silicon membrane;
(5) amorphous silicon membrane of above-mentioned silicon chip back side is carried out P ion implantation; N+ type amorphous silicon layer is formed on the top layer of amorphous silicon membrane;
So far define at the back side of above-mentioned silicon chip
n/i/N+the heterojunction of structure;
(6) amorphous silicon membrane of above-mentioned doping is carried out hot activation process;
(7) transparent conductive film layer is set at the tow sides of above-mentioned silicon chip;
(8) silk screen printing, sinter and prepare metal electrode at silicon chip surface, silicon/crystalline silicon heterogenous joint solar cell can be obtained.
2. preparation method according to claim 1, is characterized in that: the thickness of the amorphous silicon membrane in described step (2) is 2 ~ 30nm.
3. preparation method according to claim 1, is characterized in that: in described step (3), the degree of depth of B ion implantation is 1 ~ 30nm for the first time, and the degree of depth of second time B ion implantation is 1 ~ 15nm.
4. preparation method according to claim 1, is characterized in that: in described step (4), the degree of depth of B ion implantation is 1 ~ 30nm.
5. preparation method according to claim 1, is characterized in that: in described step (5), the degree of depth of P ion implantation is 1 ~ 15nm.
6. a preparation method for silicon/crystalline silicon heterogenous joint solar cell, is characterized in that, comprises the steps:
(1) p type single crystal silicon silicon chip is carried out surface chemistry cleaning, corrosion making herbs into wool;
(2) front and back of above-mentioned silicon chip is carried out Si ion implantation respectively, tow sides form one deck amorphous silicon membrane respectively;
(3) amorphous silicon membrane of above-mentioned front side of silicon wafer is carried out twice P ion implantation;
First time P ion implantation is carried out to the bottom of the amorphous silicon membrane of front side of silicon wafer, forms intrinsic amorphous silicon thin layer; Carry out second time P ion implantation again, form N-type amorphous thin Film layers on the top layer of amorphous silicon membrane; So far define in the front of above-mentioned silicon chip
n/i/Pthe heterojunction of structure;
(4) amorphous silicon membrane of above-mentioned silicon chip back side is carried out P ion implantation; Intrinsic amorphous silicon thin layer is formed at the bottom of amorphous silicon membrane;
(5) amorphous silicon membrane of above-mentioned silicon chip back side is carried out B ion implantation; P+ type amorphous silicon layer is formed on the top layer of amorphous silicon membrane;
So far define at the back side of above-mentioned silicon chip
p/i/P+the heterojunction of structure;
(6) amorphous silicon membrane of above-mentioned doping is carried out hot activation process;
(7) transparent conductive film layer is set at the tow sides of above-mentioned silicon chip;
(8) silk screen printing, sinter and prepare metal electrode at silicon chip surface, silicon/crystalline silicon heterogenous joint solar cell can be obtained.
7. preparation method according to claim 6, is characterized in that: the thickness of the amorphous silicon membrane in described step (2) is 2 ~ 30nm.
8. preparation method according to claim 6, is characterized in that: in described step (3), the degree of depth of P ion implantation is 1 ~ 30nm for the first time, and the degree of depth of second time P ion implantation is 1 ~ 15nm.
9. preparation method according to claim 6, is characterized in that: in described step (4), the degree of depth of P ion implantation is 1 ~ 30nm.
10. preparation method according to claim 6, is characterized in that: in described step (5), the degree of depth of B ion implantation is 1 ~ 15nm.
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| CN102446990A (en) * | 2011-12-14 | 2012-05-09 | 杭州赛昂电力有限公司 | Film solar battery based on crystalline silicon and formation method thereof |
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