CN103367515A - Supersaturated cell doped with efficient heterojunction and manufacturing method thereof - Google Patents

Supersaturated cell doped with efficient heterojunction and manufacturing method thereof Download PDF

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CN103367515A
CN103367515A CN2013102507730A CN201310250773A CN103367515A CN 103367515 A CN103367515 A CN 103367515A CN 2013102507730 A CN2013102507730 A CN 2013102507730A CN 201310250773 A CN201310250773 A CN 201310250773A CN 103367515 A CN103367515 A CN 103367515A
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silicon
selenium
amorphous silicon
supersaturation
solar cell
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赵会娟
张东升
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GD SOLAR Co Ltd
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GD SOLAR Co Ltd
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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
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a supersaturated cell doped with an efficient heterojunction and a manufacturing method thereof. The cell comprises crystalline silicon, positive electrodes, as well as an amorphous silicon membrane, a conductive thin film and metal electrodes which are arranged on the reverse side of the crystalline silicon from top to bottom in sequence, wherein a silicon-selenium doping layer which is formed by doping supersaturated selenium element is arranged on the upper surface of the crystalline silicon; the positive electrodes are arranged on the silicon-selenium doping layer. The manufacturing method comprises the steps of doping the selenium element in a crystalline silicon substrate in a supersaturated way to form the silicon-selenium doping layer on the upper surface of the crystalline silicon; preparing the positive electrodes on the silicon-selenium doping layer; preparing the amorphous silicon membrane on the reverse side of the crystalline silicon; preparing the conductive thin film and the metal electrodes on the amorphous silicon membrane in sequence. The supersaturated cell doped with the efficient heterojunction and the manufacturing method thereof have the advantages that the supersaturated selenium element is doped in the upper surface of the crystalline silicon of the cell to form the silicon-selenium doping layer, not only is the nonradiative recombination of deep energy level impurities effectively inhibited, is the harm to the carrier lifetime reduced, and is the S-Q theory limit broken through, but also the BSF (Back Surface Field) structure is formed on the reverse side, the long wave absorption is increased, the short-circuit current is improved, and thus the photoelectric conversion efficiency of the cell is improved.

Description

A kind of supersaturation efficient hetero-junction solar cell and preparation method thereof that mixes
Technical field
The present invention relates to a kind of manufacture method of solar cell, relate in particular to a kind of supersaturation efficient hetero-junction solar cell and preparation method thereof that mixes.
Background technology
The fossil energy environmental pollution is serious, but also is faced with resource danger less and less, and solar energy is expected to become one of following main energy sources as new green power.Solar cell is one of effective ways that utilize solar energy, and developing direction is the raising transformation efficiency, reduces production costs.At present, utilize amorphous silicon membrane as Window layer, monocrystalline silicon piece is as substrate, the heterojunction solar battery that forms had both utilized the thin film deposition processes of low temperature, brought into play again the advantage of crystalline silicon high mobility, preparation technology is simple, has to realize high efficiency, development prospect cheaply.
In existing heterojunction solar battery, because being arranged in the deep energy level of silicon band gap is the most effective charge carrier complex centre, photo-generated carrier had very large complex effect, reduce the life-span of charge carrier, and then have a strong impact on battery efficiency, so, in preparation, can do one's utmost to eliminate and avoid deep-level impurity.But when the doping content of deep-level impurity is enough high, high concentration deep level center wave function is mutually overlapping, when charge carrier can be done the communization motion between deep energy level, can form impurity band in the forbidden band.The formation of this Intermediate Gray can the establishment deep-level impurity non-radiative compound, reduce it to the harm of carrier lifetime.
Summary of the invention
Goal of the invention: goal of the invention of the present invention provides a kind of supersaturation efficient hetero-junction solar cell and preparation method thereof that mixes, battery crystal silicon upper surface mixes supersaturation selenium element and forms silicon-selenium doped layer, not only can the establishment deep-level impurity non-radiative compound, reduce it to the harm of carrier lifetime, break through the S-Q theoretical limit, and the back side forms the BSF structure, increase long wave absorption raising short circuit current, thereby the photoelectric conversion efficiency of raising battery.
Technical scheme: a kind of supersaturation of the present invention efficient hetero-junction solar cell that mixes, comprise crystal silicon, positive electrode, be positioned at successively amorphous silicon membrane, conductive film and the metal electrode at the crystal silicon back side from top to bottom, described crystal silicon upper surface is to mix the silicon that supersaturation selenium element forms-selenium doped layer, and described positive electrode is positioned on silicon-selenium doped layer.
Described amorphous silicon membrane comprises intrinsic amorphous silicon film and P+ type amorphous silicon membrane from top to bottom.
Described intrinsic amorphous silicon film and described P+ type amorphous silicon membrane all are hydrogenated nano-crystalline silicon thin films.
Described conductive film is nesa coating.
The mix manufacture method of efficient hetero-junction solar cell of a kind of supersaturation of the present invention may further comprise the steps:
Step 1, will remove the oversaturated selenium element that mixes in the crystal silicon substrate of surface damage layer and preparation matte, form upper surface silicon-selenium doped layer;
Step 2, prepare positive electrode at described silicon-selenium doped layer;
Step 3, prepare amorphous silicon membrane at the crystal silicon back side;
Step 4, on described amorphous silicon membrane, prepare successively conductive film and metal electrode.
In the described step 1, it is 6 * 10 that the method that adopts energetic ion to inject is infiltrated dosage at the crystal silicon substrate 15/ cm 2The selenium element is so that the silicon that crystal silicon upper surface formation supersaturation selenium mixes-selenium doped layer.
Step at silicon-selenium doped layer preparation positive electrode in the described step 2 comprises:
(a), using plasma enhancing chemical vapour deposition (CVD) (PECVD) method deposits the silicon dioxide of 1 μ m as mask at silicon-selenium doped layer;
(b), adopt the mode of resistance heat evaporation being photo-etched into picture surface evaporation titanium/palladium/silver electrode, then adopt acetone to go out electrode pattern, adopt again buffered hydrofluoric acid solution that the silicon dioxide etching in the figure is clean.
The step for preparing amorphous silicon membrane in the described step 3 at the crystal silicon back side comprises:
(a), take hydrogen, silane as reacting gas, under 250 ℃ temperature, the method that using plasma strengthens chemical vapour deposition (CVD) (PECVD) at crystal silicon backside deposition 5-10nm hydrogenated nano-crystalline silicon thin films as the intrinsic amorphous silicon film;
(b), take hydrogen, silane, diborane as reacting gas, under 250 ℃ temperature, with the method for plasma enhanced chemical vapor deposition (PECVD) at the hydrogenated nano-crystalline silicon thin films of intrinsic amorphous silicon film deposition 10nm as P+ type amorphous silicon membrane.
In the described step 5, adopt magnetron sputtering (PVD) technology successively depositing electrically conductive film and metal electrode on amorphous silicon membrane.
Beneficial effect: the present invention compares with existing heterojunction solar battery technology, its distinguishing feature is that battery crystal silicon upper surface mixes supersaturation selenium element formation silicon-selenium doped layer, not only can the establishment deep-level impurity non-radiative compound, reduce it to the harm of carrier lifetime, break through the S-Q theoretical limit, and the back side forms the BSF structure, increase long wave absorption raising short circuit current, thereby the photoelectric conversion efficiency of raising battery.
Description of drawings
Fig. 1 is the mix structural representation of efficient hetero-junction solar cell of the supersaturation in the embodiments of the invention;
Fig. 2 is positive electrode structure schematic diagram among Fig. 1.
Embodiment
The present invention will be further described below in conjunction with embodiment.
As shown in Figures 1 and 2, a kind of supersaturation that the embodiment of the invention provides efficient hetero-junction solar cell that mixes, comprise crystal silicon 3, positive electrode 1, be positioned at successively intrinsic amorphous silicon film 4, P+ type amorphous silicon membrane 5, nesa coating (TCO) 6 and the metal electrode 7 at crystal silicon 3 back sides from top to bottom, crystal silicon 3 upper surfaces are to mix the silicon that supersaturation selenium element forms-selenium doped layer 2, and positive electrode 1 is positioned on silicon-selenium doped layer 2.
Because crystal silicon 3 upper surfaces of battery are to mix the silicon that supersaturation selenium element forms-selenium doped layer 2, not only can the establishment deep-level impurity non-radiative compound, reduce it to the harm of carrier lifetime, break through the S-Q theoretical limit, and the back side forms the BSF structure, increase long wave and absorb the raising short circuit current, thereby improve the photoelectric conversion efficiency of battery.
The mix manufacture method embodiment one of efficient hetero-junction solar cell of the described a kind of supersaturation of the embodiment of the invention may further comprise the steps:
The sodium hydroxide solution of step 1, employing 25wt% stirs the mechanical damage that the crystal silicon surfaces were removed in corrosion in about 5 minutes under 80 ℃ temperature;
Step 2, adopt the sodium metasilicate mixed liquor of 1.5wt% NaOH, 5wt% isopropyl alcohol and 4wt% under 85 ℃ temperature, to stir to corrode and formed at random pyramid light trapping structure in 20 minutes on the crystal silicon surface;
Step 3, adoption rate are the sulfuric acid, hydrogen peroxide of 1:1:2 and complex compound and the alkaline matter that water mixed liquid is removed remained on surface, and with deionized water rinsing about 3 minutes;
Step 4, crystal silicon is packed in the Implantation chamber rapidly and vacuumize, the Implantation parameter is room temperature, burnishing surface, and the energy of 400KeV, dosage are 6 * 10 15/ cm 2The selenium element because selenium element doping concentration is considerably beyond the impurity solid solubility of selenium in silicon, so that the crystal silicon upper surface forms the silicon that supersaturation selenium mixes-selenium doped layer;
Step 5, crystal silicon adopt temperature to be about 1000 ℃, and the time is 10 seconds fast infrared thermal annealing, and behind 10 second high annealings, adopt nitrogen stream to cool off fast, realize lattice reparation and impurity activation;
Step 6, using plasma strengthen chemical vapour deposition (CVD) (PECVD) method and deposit 1 μ m silicon dioxide as mask at silicon-selenium doped layer;
The mode of step 7, the evaporation of employing resistance heat is being photo-etched into picture surface evaporation titanium/palladium/silver electrode, then adopts acetone to go out electrode pattern, adopts buffered hydrofluoric acid solution that the silicon dioxide etching in the figure is clean again;
Step 8, take hydrogen, silane as reacting gas, under 250 ℃ temperature, the method that using plasma strengthens chemical vapour deposition (CVD) (PECVD) at crystal silicon backside deposition 5nm hydrogenated nano-crystalline silicon thin films as the intrinsic amorphous silicon film;
Step 9, take hydrogen, silane, diborane as reacting gas, under 250 ℃ temperature, with the method for plasma enhanced chemical vapor deposition (PECVD) at the hydrogenated nano-crystalline silicon thin films of intrinsic amorphous silicon film deposition 10nm as P type amorphous silicon membrane;
Step 10, adopt magnetron sputtering (PVD) technology successively deposition of transparent conductive film (TCO) and metal electrode on P+ type amorphous silicon membrane.
The mix manufacture method embodiment two of efficient hetero-junction solar cell of the described a kind of supersaturation of the embodiment of the invention may further comprise the steps:
The sodium hydroxide solution of step 1, employing 25wt% stirs the mechanical damage that the crystal silicon surfaces were removed in corrosion in about 5 minutes under 80 ℃ temperature;
Step 2, adopt the sodium metasilicate mixed liquor of 1.5wt% NaOH, 5wt% isopropyl alcohol and 4wt% under 85 ℃ temperature, to stir to corrode and formed at random pyramid light trapping structure in 25 minutes on the crystal silicon surface;
Step 3, adoption rate are the sulfuric acid, hydrogen peroxide of 1:1:2 and complex compound and the alkaline matter that water mixed liquid is removed remained on surface, and with deionized water rinsing about 3 minutes;
Step 4, crystal silicon is packed in the Implantation chamber rapidly and vacuumize, the Implantation parameter is room temperature, burnishing surface, and the energy of 400KeV, dosage are 6 * 10 15/ cm 2The selenium element because selenium element doping concentration is considerably beyond the impurity solid solubility of selenium in silicon, so that the crystal silicon upper surface forms the silicon that supersaturation selenium mixes-selenium doped layer;
Step 5, crystal silicon adopt temperature to be about 1000 ℃, and the time is 10 seconds fast infrared thermal annealing, and behind 10 second high annealings, adopt nitrogen stream to cool off fast, realize lattice reparation and impurity activation;
Step 6, using plasma strengthen chemical vapour deposition (CVD) (PECVD) method and deposit 1 μ m silicon dioxide as mask at silicon-selenium doped layer;
The mode of step 7, the evaporation of employing resistance heat is being photo-etched into picture surface evaporation titanium/palladium/silver electrode, then adopts acetone to go out electrode pattern, adopts buffered hydrofluoric acid solution that the silicon dioxide etching in the figure is clean again;
Step 8, take hydrogen, silane as reacting gas, under 250 ℃ temperature, the method that using plasma strengthens chemical vapour deposition (CVD) (PECVD) at crystal silicon backside deposition 10nm hydrogenated nano-crystalline silicon thin films as the intrinsic amorphous silicon film;
Step 9, take hydrogen, silane, diborane as reacting gas, under 250 ℃ temperature, with the method for plasma enhanced chemical vapor deposition (PECVD) at the hydrogenated nano-crystalline silicon thin films of intrinsic amorphous silicon film deposition 10nm as P+ type amorphous silicon membrane;
Step 10, adopt magnetron sputtering (PVD) technology successively deposition of transparent conductive film (TCO) and metal electrode on P+ type amorphous silicon membrane.

Claims (9)

1. a supersaturation efficient hetero-junction solar cell that mixes, comprise crystal silicon 3, positive electrode 1, be positioned at successively amorphous silicon membrane, conductive film 6 and the metal electrode 7 at the crystal silicon back side from top to bottom, it is characterized in that: described crystal silicon 3 upper surfaces are to mix the silicon that supersaturation selenium element forms-selenium doped layer 2, and described positive electrode 1 is positioned on silicon-selenium doped layer 2.
2. a kind of supersaturation according to claim 1 efficient hetero-junction solar cell that mixes, it is characterized in that: described amorphous silicon membrane comprises the non-silicon thin film 4 of intrinsic and P+ type amorphous silicon membrane 5 from top to bottom.
3. a kind of supersaturation according to claim 2 efficient hetero-junction solar cell that mixes, it is characterized in that: described intrinsic amorphous silicon film 4 and P+ type amorphous silicon membrane 5 all are hydrogenated nano-crystalline silicon thin films.
4. a kind of supersaturation according to claim 1 efficient hetero-junction solar cell that mixes, it is characterized in that: described conductive film 6 is nesa coating (TCO).
5. a kind of supersaturation according to claim 1 manufacture method of efficient hetero-junction solar cell of mixing is characterized in that may further comprise the steps:
Step 1, will remove the oversaturated selenium element that mixes in the crystal silicon substrate of surface damage layer and preparation matte, form upper surface silicon-selenium doped layer;
Step 2, prepare positive electrode at described silicon-selenium doped layer;
Step 3, prepare amorphous silicon membrane at the crystal silicon back side;
Step 4, on described amorphous silicon membrane, prepare successively conductive film and metal electrode.
6. a kind of supersaturation according to claim 5 manufacture method of efficient hetero-junction solar cell of mixing, it is characterized in that: in the described step 1, the method that adopts energetic ion to inject is 6 * 10 at the oversaturated infiltration dosage of crystal silicon substrate 15/ cm 2The selenium element is so that the silicon that crystal silicon upper surface formation supersaturation selenium mixes-selenium doped layer.
7. a kind of supersaturation according to claim 5 manufacture method of efficient hetero-junction solar cell of mixing, it is characterized in that: the step at silicon-selenium doped layer preparation positive electrode in the described step 2 comprises:
(a), using plasma enhancing chemical vapour deposition (CVD) (PECVD) method deposits the silicon dioxide of 1 μ m as mask at silicon-selenium doped layer;
(b), adopt the mode of resistance heat evaporation being photo-etched into picture surface evaporation titanium/palladium/silver electrode, then adopt acetone to go out electrode pattern, adopt again buffered hydrofluoric acid solution that the silicon dioxide etching in the figure is clean.
8. a kind of supersaturation according to claim 5 manufacture method of efficient hetero-junction solar cell of mixing, it is characterized in that: the step for preparing amorphous silicon membrane in the described step 3 at the crystal silicon back side comprises:
(a), take hydrogen, silane as reacting gas, under 250 ℃ temperature, the method that using plasma strengthens chemical vapour deposition (CVD) (PECVD) at crystal silicon backside deposition 5-10nm hydrogenated nano-crystalline silicon thin films as the intrinsic amorphous silicon film;
(b), take hydrogen, silane, diborane as reacting gas, under 250 ℃ temperature, with the method for plasma enhanced chemical vapor deposition (PECVD) at the hydrogenated nano-crystalline silicon thin films of intrinsic amorphous silicon film deposition 10nm as P+ type amorphous silicon membrane.
9. a kind of supersaturation according to claim 5 manufacture method of efficient hetero-junction solar cell of mixing is characterized in that: in the described step 5, adopt magnetron sputtering (PVD) technology successively depositing electrically conductive film and metal electrode on amorphous silicon membrane.
CN2013102507730A 2013-06-21 2013-06-21 Supersaturated cell doped with efficient heterojunction and manufacturing method thereof Pending CN103367515A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102064216A (en) * 2010-11-22 2011-05-18 晶澳（扬州）太阳能科技有限公司 Novel crystalline silicon solar cell and manufacturing method thereof
CN102169918A (en) * 2010-05-26 2011-08-31 中国科学院半导体研究所 Silicon photo-detector having gain under low bias voltage and preparation method of silicon photo-detector
CN102496638A (en) * 2011-11-28 2012-06-13 中国科学院半导体研究所 Deep-level impurity-doped crystalline silicon infrared detector and preparation method thereof
CN203325954U (en) * 2013-06-21 2013-12-04 国电光伏有限公司 Supersaturation doped high-efficiency heterojunction battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102169918A (en) * 2010-05-26 2011-08-31 中国科学院半导体研究所 Silicon photo-detector having gain under low bias voltage and preparation method of silicon photo-detector
CN102064216A (en) * 2010-11-22 2011-05-18 晶澳（扬州）太阳能科技有限公司 Novel crystalline silicon solar cell and manufacturing method thereof
CN102496638A (en) * 2011-11-28 2012-06-13 中国科学院半导体研究所 Deep-level impurity-doped crystalline silicon infrared detector and preparation method thereof
CN203325954U (en) * 2013-06-21 2013-12-04 国电光伏有限公司 Supersaturation doped high-efficiency heterojunction battery

Non-Patent Citations (1)

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Title
李辛毅: "硒元素过饱和掺杂在硅太阳电池制备中的应用", 《第12届中国光伏大会暨国际光伏展览会论文》, 31 December 2012 (2012-12-31), pages 1 - 5 *

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Application publication date: 20131023