CN103746007A - Passivation layer of P-type crystalline silicon solar cell and passivation technology for passivation layer - Google Patents
Passivation layer of P-type crystalline silicon solar cell and passivation technology for passivation layer Download PDFInfo
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- 238000005516 engineering process Methods 0.000 title abstract description 13
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- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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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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- 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
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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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Abstract
The invention discloses a passivation layer of a P-type crystalline silicon solar cell and a passivation technology for the passivation layer. The passivation layer consists of erbium oxide. The passivation technology for the passivation layer comprises the following steps: firstly depositing an erbium oxide passivation layer at the P-type side of the shady face of a P-type crystalline silicon substrate after an antireflection film process is finished on P-type crystalline silicon during manufacturing of the crystalline silicon solar cell, then, performing annealing treatment; forming an SiO2 buffer layer between the passivation layer and the P-type side of the shady face of the P-type crystalline silicon substrate to finish the preparation of the passivation layer. According to the passivation layer of the P-type crystalline silicon solar cell and the passivation technology for the passivation layer disclosed by the invention, the erbium oxide is used as the passivation layer of the crystalline silicon solar cell, and therefore the lattice matching degree can be improved, the defect mode density of a crystalline silicon surface is reduced, and a passivation effect is improved.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to and a kind ofly using erbium oxide as crystalline silicon solar cell inactivating layer and passivation technology thereof.
Background technology
The silicon chip adopting as solar cell substrate, its blemish will have a strong impact on the conversion efficiency of battery.For reducing the defect of silicon chip surface, reduce recombination-rate surface, conventionally adopt surface passivation layer technology to improve crystal silicon battery conversion efficiency.Surface passivation layer technology is mainly to utilize hydrogen ion or dielectric film to carry out defect to fill up minimizing surface defect density, avoids charge carrier compound in this generation.
Surface passivation tunic conventional in solar cell inactivating technique has silicon dioxide, silicon nitride, amorphous silicon and aluminium oxide etc.Silicon dioxide and amorphous silicon passivation layer technique are because limited its application to the hypersensitivity of high-temperature heat treatment.During silicon nitride passivation P type silicon face, due to a large amount of fixed positive charge effects, in interface, form inversion layer, thereby produce parasitic shunt effect, reduced short circuit current.Existing crystal silicon aluminium oxide passivation technology has had certain effect, but subject matter is the difference that aluminium oxide and crystal silicon still exist certain lattice parameter, causes at interface, there is certain density defect state density, thereby affects the conversion efficiency of battery.
Summary of the invention
The object of the present invention is to provide a kind of passivation layer of new P type crystal silicon solar energy battery, this passivation layer, for replacing traditional crystalline silicon passivation material, can provide fixing surface negative charge and improve Lattice Matching degree, thereby improves passivation effect.The present invention also provides the passivation technology of this passivation layer simultaneously.
For realizing the technical scheme that above-mentioned purpose of the present invention adopts, be: a kind of passivation layer of P type crystal silicon solar energy battery, is characterized in that this passivation layer is to consist of erbium oxide.
Passivation layer of the present invention can be applicable in the passivation layer of p type single crystal silicon, polysilicon solar cell.
The passivation technology of the passivation layer of above-mentioned a kind of P type crystal silicon solar energy battery, it is characterized in that in the making of P type crystal silicon solar energy battery, when P type crystalline silicon completes after depositing antireflection film operation, first adopt Atomic layer deposition method (ALD) at the P type one side deposition erbium oxide passivation layer of P type crystalline silicon substrate shady face, then carry out annealing in process, between passivation layer and P type one side of P type crystalline silicon substrate shady face, form SiO
2resilient coating, completes the preparation of passivation layer.
The erbium oxide passivation layer of P type one side at the described P type that is deposited on crystal silicon solar energy battery substrate (shady face) back side, its optimum thickness is 0.5 ~ 10nm.
In the ALD preparation method of described erbium oxide passivation layer, presoma is the organo-metallic compound of erbium, the supplier of oxygen is any in deionized water, ozone or oxygen, the reaction temperature of chamber is 150 ~ 500 ℃, pressure is 50 ~ 100Pa, evaporating temperature is 50 ~ 200 ℃, and the purge gas of chamber is inert gas Ar or N
2, deposition cycle is 5-100 cycle.
The organo-metallic compound of described erbium can be (CpMe)
3er, Er (thd)
3deng can be used to arbitrarily the organo-metallic compound as the presoma of erbium.
Described annealing in process forms SiO
2the technique of resilient coating; to deposit the P type crystalline silicon battery plate of erbium oxide passivation layer; put into the annealing furnace that is connected with protective gas; annealing temperature is 300 ~ 600 ℃; take annealing temperature as 400 ~ 500 ℃ as best; annealing time 0.5 ~ 4 hour forms SiO between passivation layer and P type one side of P type crystalline silicon substrate shady face
2resilient coating.
Protective gas in described annealing treating process can adopt Ar, N
2, N
2o, H
2, O
2in at least one.
Described SiO
2buffer layer thickness is 0.5 ~ 2nm.
In technique scheme of the present invention, when P type crystalline silicon completes after substrate cleaning, making herbs into wool, diffusion phosphorus, etching edge, depositing antireflection film operation, use Atomic layer deposition method (ALD) at the P type one side deposition erbium oxide passivation layer of crystal silicon chip substrate shady face, and carry out annealing in process formation SiO
2resilient coating, the preparation that then adopts the methods such as printing, sputter, plating or ink-jet to carry on the back electric field and gate line electrode.
Erbium oxide is wide bandgap semiconductor materials, has identical crystalline structure with crystalline silicon, is cubic system, and lattice constant match degree is very high, as crystal silicon battery passivation layer, can improve Lattice Matching degree, thereby reduce the defect state density on crystal silicon surface, improve passivation effect.
Erbium oxide, as the passivation layer of crystal silicon cell, has two kinds of passivation mechanisms: chemical passivation mechanism and field effect passivation mechanisms.The H ion that chemical passivation derives from the predecessor while preparing erbium oxide is diffused into silicon face, is combined and carries out passivation with the dangling bonds of silicon; Field effect passivation derives from erbium oxide rete has fixed negative charge, and the electrostatic field of formation attracts hole to improve its collection rate, thereby electron drift probability is so far declined greatly, has reduced the recombination rate of electron-hole.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation with the P type crystal silicon solar energy battery of erbium oxide passivation layer.
Accompanying drawing 2 is the P type crystal silicon solar energy battery preparation flow figure with erbium oxide passivation layer.
Embodiment
Below in conjunction with accompanying drawing and the concrete example of implementing, the present invention is done to further detailed description, yet described embodiment should not explain in the mode of restriction.
Of the present inventionly using in the passivation technology of erbium oxide as the crystal silicon solar energy battery of passivation layer, in the making of P type crystalline silicon, when P type crystalline silicon completes after depositing antireflection film operation, first adopt Atomic layer deposition method (ALD) at the P type one side deposition erbium oxide passivation layer of P type crystalline silicon substrate shady face, in the ALD of erbium oxide passivation layer deposition process, presoma is the organo-metallic compound of erbium, the supplier of oxygen is deionized water, any in ozone or oxygen, the reaction temperature of chamber is 150 ~ 500 ℃, pressure is 50 ~ 100Pa, evaporating temperature is 50 ~ 200 ℃, the purge gas of chamber is inert gas Ar or N
2, deposition cycle is 5-100 cycle.Then carry out annealing in process, form SiO
2resilient coating, completes the preparation of passivation layer.Annealing in process forms SiO
2the technique of resilient coating is: the cell piece that deposits erbium oxide passivation layer is put into the annealing furnace that is connected with protective gas; controlling annealing temperature is 300～600 ℃; annealing time is 0.5～4 hour, forms the SiO of 0.5～2nm between passivation layer and P type one side of P type crystalline silicon substrate shady face
2resilient coating.
Embodiment 1:
The preparation flow figure of the P type crystal silicon solar energy battery with erbium oxide passivation layer providing from Fig. 2, can find out, passivation layer of the present invention is applied in crystal silicon solar energy battery, and its flow process of preparing P type crystal silicon solar energy battery is as follows:
A, use NaOH or KOH aqueous slkali carry out cleaning and texturing to P type single crystalline silicon substrate, to remove mechanical damage layer, greasy dirt and metal impurities, form up-and-down pyramid matte simultaneously on surface, to increase surface area and then increase light absorption; Then p type single crystal silicon substrate is put into diffuser chamber, pass into phosphorus source, make P elements diffuse into P type crystal silicon surface, form N layer, form PN junction; Then use the mixing material of HNO3 and HF to carry out periphery etching, remove the N layer of marginal deposit to make cell piece and external insulation; Then with HF, wash, with HF, wash the materials such as silicon dioxide that form in diffusion process off; Use PECVD method in its surface deposition layer of sin antireflection layer (to increase the absorption of cell piece to light), form P type crystal-silicon battery slice.Be more than the common process in solar cell preparation process, at this, do not repeat.
B, complete after above step, ALD method deposition erbium oxide passivation layer for P type one side (P type one side of PN junction) at P type crystal silicon chip substrate shady face, the thickness of erbium oxide passivation layer can be controlled in 0.5 ~ 10nm, the present embodiment thickness is chosen 3nm, the organo-metallic compound (CpMe) that in the ALD preparation method of erbium oxide, presoma is erbium
3er, the supplier of oxygen is any in deionized water, ozone or oxygen, the reaction temperature of chamber is 150 ~ 500 ℃, pressure is 50 ~ 100Pa, evaporating temperature is 50 ~ 200 ℃, the purge gas of chamber is conventional inert gas Ar, and deposition cycle is 30 cycles, makes the cell piece that contains erbium oxide passivation layer.
C, deposited erbium oxide passivation layer after, carry out annealing in process, between passivation layer and P type one side of P type crystalline silicon substrate shady face, generate SiO
2resilient coating.Cell piece is put into and is connected with N
2in the annealing furnace of inert gas, annealing temperature is set as 400 ℃, and annealing time 0.5 hour makes to form between passivation layer and P type one side of crystal silicon substrate shady face the SiO of 1nm left and right
2thin layer (SiO
2resilient coating).
D, on erbium oxide passivation layer silk screen printing aluminum back electric field and metal palisade back electrode, back metal gate line electrode for printing aluminium paste, the width of gate-shaped electrode is 0.5 ~ 2mm; Then at the positive silk screen printing front electrode of cell piece, metal grid lines electrode is printing Ag slurry, and the width of thin gate-shaped electrode is 0.05 ~ 0.1mm, and main grid shape electrode width is 0.5 ~ 2mm.Finally by crossing after oven dry, sintering circuit, the complete crystal silicon solar battery structure with erbium oxide passivation layer forms.
From the structural representation of the P type crystal silicon solar energy battery with erbium oxide passivation layer shown in Fig. 1, can find out, in P type crystalline silicon substrate 1, spread phosphorus, form N diffusion layer 2, on N diffusion layer 2, adopt PECVD method at its surface deposition layer of sin antireflection layer 3, P type one side of P type crystal silicon substrate 1 shady face has deposited erbium oxide passivation layer 4 by ALD method, erbium oxide passivation layer 4, through annealing in process, forms SiO
2resilient coating 5, SiO
2resilient coating 5 between passivation layer 4 and P type one side of P type crystal silicon substrate 1 shady face, then silk screen printing aluminum back electric field 6 and metal grid lines back electrode 7 again on passivation layer 4, electrode 8 before screen-printed metal grid line on antireflection layer 3.
Embodiment 2: with the preparation of the P type crystal silicon solar energy battery of erbium oxide passivation layer.Its preparation method similar embodiment 1, difference is: in passivation procedure, the THICKNESS CONTROL of erbium oxide passivation layer is at 10nm, and the supplier of oxygen is oxygen, and the purge gas of chamber is conventional inert gas N
2, deposition cycle is 100 cycles; In annealing operation, protective gas is H
2, annealing temperature is set as 500 ℃, annealing time 4 hours, the SiO of formation 2nm
2resilient coating.
Embodiment 3: with the preparation of the P type crystal silicon solar energy battery of erbium oxide passivation layer.Its preparation method similar embodiment 1, difference is: in passivation procedure, the THICKNESS CONTROL of erbium oxide passivation layer is at 0.5nm, and the supplier of oxygen is ozone, and the purge gas of chamber is conventional inert gas N
2, deposition cycle is 5 cycles; In annealing operation, protective gas is O
2, annealing temperature is set as 300 ℃, annealing time 0.5 hour, the SiO of formation 0.5nm
2resilient coating.
Embodiment 4: with the preparation of the P type crystal silicon solar energy battery of erbium oxide passivation layer.Its preparation method similar embodiment 1, difference is: in the ALD preparation method of erbium oxide, the supplier of oxygen is the mist of ozone and oxygen, the reaction temperature of chamber is 170 ~ 330 ℃, pressure is 66Pa, and evaporating temperature is 95 ℃, and the purge gas of chamber is conventional inert gas Ar, the THICKNESS CONTROL of erbium oxide passivation layer is at 12nm, and deposition cycle is 100 cycles.
Embodiment 5: with the preparation of the P type crystal silicon solar energy battery of erbium oxide passivation layer.Its preparation method similar embodiment 1, difference is: in the ALD preparation method of erbium oxide, presoma is metal beta diketone salt Er (thd)
3, the supplier of oxygen is ozone, and the reaction temperature of chamber is 250 ~ 375 ℃, and the THICKNESS CONTROL of erbium oxide passivation layer is at 2.5nm, and deposition cycle is 10 cycles.
Atomic layer deposition method of the present invention (ALD) is that in this area, those of ordinary skill is in common knowledge, no longer repeats.
Be more than to explanation of the present invention and non-limiting, other execution modes based on inventive concept, all within protection scope of the present invention.
Claims (9)
1. a passivation layer for P type crystal silicon solar energy battery, is characterized in that this passivation layer is to consist of erbium oxide.
2. according to the passivation layer of P type crystal silicon solar energy battery claimed in claim 1, it is characterized in that described passivation layer is for shady face P type one side of P type crystal silicon solar energy battery.
3. the technique of the passivation layer of the P type crystal silicon solar energy battery described in a passivation claim 1 or 2, it is characterized in that in the making of P type crystal silicon solar energy battery, when P type crystalline silicon completes after depositing antireflection film operation, first P type one side at P type crystalline silicon substrate shady face deposits erbium oxide passivation layer, then carry out annealing in process, between passivation layer and P type one side of P type crystalline silicon substrate shady face, form SiO
2resilient coating, completes the preparation of passivation layer.
4. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 3, it is characterized in that the erbium oxide passivation layer of P type one side of the described P type that is deposited on crystal silicon solar energy battery substrate shady face, its thickness is 0.5 ~ 10nm.
5. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 3, it is characterized in that described erbium oxide passivation layer preparation method is ALD method.
6. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 5, it is characterized in that in the ALD preparation method of described erbium oxide passivation layer, presoma is the organo-metallic compound of erbium, the supplier of oxygen is any one or several in deionized water, ozone or oxygen, the reaction temperature of chamber is 150 ~ 500 ℃, pressure is 50 ~ 100Pa, and evaporating temperature is 50 ~ 200 ℃, and the purge gas of chamber is inert gas Ar or N
2, deposition cycle is 5-100 cycle.
7. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 3, it is characterized in that described annealing in process forms SiO
2the technique of resilient coating; be to deposit the P type crystalline silicon battery plate of erbium oxide passivation layer, to put into the annealing furnace that is connected with protective gas, annealing temperature is 300 ~ 600 ℃; annealing time 0.5 ~ 4 hour forms SiO between passivation layer and P type one side of P type crystalline silicon substrate shady face
2resilient coating.
8. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 7, it is characterized in that the protective gas in described annealing treating process adopts Ar, N
2, N
2o, H
2, O
2in at least one.
9. according to the technique of the passivation layer of passivation P type crystal silicon solar energy battery claimed in claim 3, it is characterized in that described SiO
2buffer layer thickness is 0.5 ~ 2nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101997039A (en) * | 2010-09-29 | 2011-03-30 | 上海电力学院 | Antireflection material for solar cell and manufacturing method thereof |
| CN102157572A (en) * | 2011-03-09 | 2011-08-17 | 浙江大学 | Crystalline silicon solar battery |
| US20130153019A1 (en) * | 2011-12-20 | 2013-06-20 | Innovalight | Methods of forming a high efficiency solar cell with a localized back surface field |
| US20130186460A1 (en) * | 2012-01-20 | 2013-07-25 | National Taiwan University | Solar cell and method of manufacturing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101997039A (en) * | 2010-09-29 | 2011-03-30 | 上海电力学院 | Antireflection material for solar cell and manufacturing method thereof |
| CN102157572A (en) * | 2011-03-09 | 2011-08-17 | 浙江大学 | Crystalline silicon solar battery |
| US20130153019A1 (en) * | 2011-12-20 | 2013-06-20 | Innovalight | Methods of forming a high efficiency solar cell with a localized back surface field |
| US20130186460A1 (en) * | 2012-01-20 | 2013-07-25 | National Taiwan University | Solar cell and method of manufacturing the same |
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