CN102751337B - N-type crystal silicon solar batteries and preparation method thereof - Google Patents

N-type crystal silicon solar batteries and preparation method thereof Download PDF

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Publication number
CN102751337B
CN102751337B CN201210270422.1A CN201210270422A CN102751337B CN 102751337 B CN102751337 B CN 102751337B CN 201210270422 A CN201210270422 A CN 201210270422A CN 102751337 B CN102751337 B CN 102751337B
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oxide film
silicon
passivation
silicon oxide
pellumina
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CN201210270422.1A
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CN102751337A (en
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杨德成
郎芳
李高非
胡志岩
熊景峰
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英利集团有限公司
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/068Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/547Monocrystalline silicon PV cells

Abstract

The invention provides a kind of N-type crystal silicon solar batteries and preparation method thereof.This N-type crystal silicon solar batteries comprises: N-type matrix; Boron emitter, is arranged on the front surface of N-type matrix; First passivation layer, be arranged on the surface of boron emitter away from N-type matrix, the first passivation layer comprises the silicon oxide film, pellumina and the silicon nitride film that from inside to outside arrange.N-type crystal silicon solar batteries of the present invention, the pellumina of boron emitter surface forms one deck fixed negative charge in interface, the minority carrier being diffused into surface is reflected back, decreases the speed of photo-generated carrier in surface recombination, good field effect passivation is provided; In addition, the protium that silicon nitride film is rich in sintering process is diffused into SiO 2/ Si interface, the passivation dangling bonds of interface, provide good chemical passivation effect.Therefore, use silicon nitride/alumina/silica trilamellar membrane Passivation of Boron emitter to provide field effect passivation and chemical passivation simultaneously.

Description

N-type crystal silicon solar batteries and preparation method thereof

Technical field

The present invention relates to area of solar cell, in particular to a kind of N-type crystal silicon solar batteries and preparation method thereof.

Background technology

Monocrystaline silicon solar cell by large-scale application to every field, its good stability and ripe technological process are the bases of its large-scale application.The technological process of production of monocrystaline silicon solar cell as shown in Figure 1, is first cleaned silicon chip, reaches the structuring process to silicon chip surface by chemical cleaning; Secondly the silicon chip after cleaning is carried out DIFFUSION TREATMENT, silicon chip forms p-n junction through boron diffusion technology; Afterwards periphery etching process is carried out, to remove the conductive layer that silicon chip edge in diffusion technology is formed to the silicon chip forming p-n junction; Then through chemical cleaning technology, to remove in diffusion process at the glassy layer that silicon chip surface is formed; Then through PECVD(plasma enhanced chemical vapor deposition method) process deposits antireflective coating-silicon nitride film; Last making through silk-screen printing technique, sintering process etc. successively again obtains satisfactory monocrystaline silicon solar cell.

In manufacture of solar cells process, usually deposit one deck silicon nitride film at silicon chip surface, antireflective effect can be played on the one hand, improve the utilance to luminous energy.On the other hand, silicon nitride is also the good passivating film of one deck, this is because silicon nitride film layer is rich in protium, these hydrogen can be diffused into SiOx/Si interface in sintering process, react with the dangling bonds of interface, effectively can reduce silicon chip surface interface state defects density by this chemical passivation effect, thus decrease the speed of photo-generated carrier in silicon chip surface compound; In addition, the silicon nitride of silicon chip surface deposition contains fixed positive charge, the electric field that these positive charges produce can reflect back being diffused into the positive charge (hole) come on surface, by this field effect passivation, decreases the compound of photo-generated carrier at silicon chip surface.If as passivating film be used for passivation N-type silicon chip surface, because positive charge is minority carrier, so at this moment silicon nitride film can play good passivation effect; But for P-type silicon sheet surface, negative electrical charge is minority carrier, if silicon nitride to be used for P type surface, then can to form one deck inversion layer at silicon chip surface place, exacerbate the speed of photo-generated carrier in silicon chip surface compound on the contrary.

For traditional P type solar cell, its emitter is the N-type silicon chip surface that phosphorus diffuses to form, and effectively can play passivation with silicon nitride.But for N-type solar cell, its emitter is the P-type silicon surface that boron diffuses to form, and silicon nitride loses its passivation.So a kind of effective passivation N-type solar cell boron emitter surface technology of development, become the key of restriction N-type solar cell development.

Current passivation N-type solar cell mainly uses nitrogenize silicon/oxidative silicon duplicature to carry out Passivation of Boron emitter, although good chemical passivation performance can be provided for silicon chip surface, but because silicon nitride is with fixed positive charge, inversion layer can be formed on P-type silicon sheet surface, accelerate the probability of photo-generated carrier compound on the contrary, thus reduce its chemical passivation performance to a certain extent.As can be seen here, above-mentioned two schemes is adopted all to be difficult to realize the effective passivation to N-type solar cell boron emitter surface.

Summary of the invention

The present invention aims to provide a kind of N-type crystal silicon solar batteries and preparation method thereof, is difficult to effectively obtain the problem of passivation to solve N-type solar cell boron emitter in prior art.

To achieve these goals, according to an aspect of the present invention, provide a kind of N-type crystal silicon solar batteries, N-type crystal silicon solar batteries comprises: N-type matrix; Boron emitter, is arranged on the front surface of N-type matrix; First passivation layer, be arranged on the surface of boron emitter away from N-type matrix, the first passivation layer comprises the silicon oxide film, pellumina and the silicon nitride film that from inside to outside arrange.

Further, the thickness of above-mentioned first passivating film is not more than 100nm.

Further, the thickness of above-mentioned silicon oxide film is within 10nm, and the thickness of pellumina is within 10nm, and the thickness of silicon nitride film is between 65 ~ 85nm.

Further, above-mentioned N-type crystal silicon solar batteries also comprises: back surface field, is arranged on the surface of N-type matrix away from boron emitter side; Second passivation layer, be arranged on the surface of back surface field away from N-type matrix side, the second passivation layer comprises the silicon oxide film and silicon nitride film that from inside to outside arrange.

According to another aspect of the invention, additionally provide a kind of manufacture method of N-type crystal silicon solar batteries, this manufacture method comprises: S1, form boron emitter at the front surface of N-type matrix; S2, on the surface of boron emitter away from N-type matrix, form the silicon oxide film and pellumina that arrange from inside to outside; And S3, on the surface of pellumina away from silicon oxide film, form silicon nitride film.

Further, on the surface of the back surface field of N-type matrix away from N-type matrix, silicon oxide film is formed being formed while silicon oxide film in above-mentioned steps S2.

Further, formed in the process of described aluminium oxide in above-mentioned steps S2, the back side any two being formed with the N-type matrix of silicon oxide film mutually by forming pellumina after placing on the surface of silicon oxide film away from boron emitter.

Further, above-mentioned manufacture method forms silicon nitride film upon step s 2 or on the surface of the silicon oxide film be also included in after S3 on the surface of back surface field away from N-type matrix.

Further, the preparation method of above-mentioned silicon oxide film is thermal oxidation method, PECVD band electrodeposition process or magnetron sputtering method; The preparation method of pellumina is atomic layer deposition method, sputtering method, PECVD band electrodeposition process or sol-gal process; The preparation method of silicon nitride film is PECVD band electrodeposition process.

N-type crystal silicon solar batteries of the present invention, the pellumina of boron emitter surface forms one deck fixed negative charge in interface, the electric field produced at silicon chip surface can reflect back being diffused into the minority carrier (electronics) come on surface, greatly reduce the quantity of minority carrier near silicon chip surface, thus decrease the speed of photo-generated carrier in surface recombination, good field effect passivation can be provided for silicon chip surface.In addition, the silicon oxide film of boron emitter surface can reduce SiO effectively 2/ Si interface state defects density, therefore plays good passivation effect to silicon chip surface, and the protium that silicon nitride film is rich in sintering process is diffused into SiO 2/ Si interface, the passivation dangling bonds of interface, for silicon chip surface provides good chemical passivation effect.Therefore, use silicon nitride/alumina/silica trilamellar membrane to carry out Passivation of Boron emitter can provide field effect passivation and chemical passivation simultaneously, thus obtain better passivation effect.Meanwhile, inventor finds there is great relation due to the inactivating performance of pellumina and the silicon oxide film of silicon chip surface, has important benefit at the silicon oxide film of silicon chip surface to pellumina thereon.

Accompanying drawing explanation

The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:

Fig. 1 shows the fabrication processing of N-type crystal silicon solar batteries in prior art;

Fig. 2 shows the structural representation according to N-type crystal silicon solar batteries of the present invention; And

The open circuit voltage test result that Fig. 3 shows embodiment 1,2 and comparative example 1,2 compares schematic diagram.

Embodiment

It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.

In a kind of typical execution mode of the present invention, provide a kind of N-type crystal silicon solar batteries, N-type crystal silicon solar batteries comprises: N-type matrix 1, boron emitter 2 and the first passivation layer 3, and boron emitter 2 is arranged on the front surface of N-type matrix 1; First passivation layer 3 is arranged on the surface of boron emitter 2 away from N-type matrix 1, and the first passivation layer 3 comprises the silicon oxide film, pellumina and the silicon nitride film that from inside to outside arrange.

There is the N-type crystal silicon solar batteries of said structure, the pellumina on boron emitter 2 surface forms one deck fixed negative charge in interface, the electric field produced at silicon chip surface can reflect back being diffused into the minority carrier (electronics) come on surface, greatly reduce the quantity of minority carrier near silicon chip surface, thus decrease the speed of photo-generated carrier in surface recombination, good field effect passivation can be provided for silicon chip surface.In addition, the silicon oxide film on boron emitter 2 surface can reduce SiO effectively 2/ Si interface state defects density, therefore plays good passivation effect to silicon chip surface, and the protium that silicon nitride film is rich in sintering process is diffused into SiO 2/ Si interface, the passivation dangling bonds of interface, for boron emitter 2 surface provides good chemical passivation effect.Therefore, use silicon nitride/alumina/silica trilamellar membrane to carry out Passivation of Boron emitter can provide field effect passivation and chemical passivation simultaneously, thus obtain better passivation effect.Meanwhile, inventor finds there is great relation due to the inactivating performance of pellumina and the silicon oxide film of silicon chip surface, has important benefit at the silicon oxide film of silicon chip surface to pellumina thereon.

In order to avoid the performance being positioned at the first passivating film 3 pairs of boron emitters 2 on boron emitter 2 causes adverse effect, preferably the thickness of the first passivating film 3 is not more than 100nm.

In a kind of preferred embodiment of the present invention, the thickness of silicon oxide film is within 10nm, and the thickness of pellumina is within 10nm, and the thickness of silicon nitride film is between 65 ~ 85nm.When silicon oxide film, pellumina and silicon nitride film thickness between the foregoing time, to silicon chip surface, there is obvious passivation effect.

The N-type crystal silicon solar batteries with said structure also comprises back surface field 4 and the second passivation layer 5, and back surface field 4 is arranged on the surface of N-type matrix 1 away from emitter 2 side; Second passivation layer 5 is arranged on the surface of back surface field 4 away from N-type matrix 1 side, and the second passivation layer 5 comprises the silicon oxide film and silicon nitride film that from inside to outside arrange.Arrange back surface field 4 and the second passivation layer 5 to be conducive to reducing minority carrier recombination rate overleaf at the back side of N-type crystal silicon solar batteries, increase short circuit current and open circuit voltage.And preferably the second passivation layer 5 and the first passivation layer 3 have the silicon oxide film of same thickness, the second passivation layer 5 and the first passivation layer 3 have the silicon nitride film of different-thickness.

In another typical execution mode of the present invention, additionally provide a kind of manufacture method of N-type crystal silicon solar batteries, manufacture method comprises: S1, form boron emitter at the front surface of N-type matrix; S2, on the surface of boron emitter away from N-type matrix, form the silicon oxide film and pellumina that arrange from inside to outside; And S3, on the surface of pellumina away from silicon oxide film, form silicon nitride film.

Si on the P-type silicon surface of the boron emitter formed after being positioned at boron diffusion forms silicon oxide film through peroxidation, pellumina is formed in the outside of silicon oxide film, then forms silicon nitride film in the outside of pellumina thus obtains silicon nitride/alumina/silica three layers of passivation film structure.Silicon oxide film and pellumina can be formed in two steps and also can a step be formed, and namely make it form silica at the silicon of the simultaneous oxidation boron emitter preparing pellumina, thus obtain silicon oxide film.

In order to form the good silicon oxide film of quality and pellumina, preferably both utilize two-step method to be formed, and above-mentioned steps S2 also comprises: S21, on the surface of boron emitter away from N-type matrix, form silicon oxide film; S22, on the surface of silicon oxide film away from boron emitter, form pellumina.Prepare separately silicon oxide film and can form high-quality silicon oxide film on boron emitter, thus ensure that the pellumina grown on silicon oxide film has good uniformity and more fixed charge amount.

In a kind of preferred embodiment of the present invention, in above-mentioned steps S2, while forming silicon oxide film, on the surface of the back surface field of N-type matrix away from N-type matrix, form silicon oxide film.Silicon oxide film on the back surface of N-type matrix of the present invention can be prepared separately and also can prepare with the silicon oxide film on boron emitter simultaneously.

In order to simplify the preparation method of pellumina, preferred steps S22 also comprises in the process of middle formation aluminium oxide, and the back side of any two being prepared the N-type matrix of silica film, mutually by after placing, the surface of silicon oxide film away from boron emitter forms pellumina.Due to pellumina be only formed in be positioned on boron emitter on the outer surface of silicon oxide film, therefore when preparing pellumina by any two back-to-back placements of N-type matrix, only form pellumina in the front of N-type matrix, thus simplify the preparation method of pellumina.

The outside of the silicon oxide film preferably on the back surface of N-type matrix of the present invention also has one deck silicon nitride film, and then manufacture method forms silicon nitride film upon step s 2 or on the surface of the silicon oxide film be also included in after S3 on the surface of back surface field away from N-type matrix.

The method preparing above-mentioned silicon oxide film, pellumina and silicon nitride film has multiple, and the preparation method of preferential oxidation silicon fiml of the present invention is thermal oxidation method, PECVD band electrodeposition process or magnetron sputtering method; The preparation method of pellumina is atomic layer deposition method, sputtering method, PECVD band electrodeposition process or sol-gal process; The preparation method of silicon nitride film is PECVD band electrodeposition process.When especially adopting atomic layer deposition method to prepare pellumina, accurately can control the growth quality of every one deck aluminium oxide, thus more be conducive to obtaining the ultrathin alumina film aluminium oxide with high homogeneity.

Below with reference to embodiment and comparative example, further illustrate beneficial effect of the present invention.

Embodiment 1

Preparation N-type crystal silicon solar batteries:

The front being diffused in silicon chip matrix through boron forms the silicon chip that boron emitter obtains having p-n junction, first adopt magnetron sputtering method respectively to prepare the silicon oxide film of a layer thickness at about 5nm at the silicon chip tow sides with p-n junction, wherein silicon oxide film is evenly distributed on positive and negative two surfaces of silicon chip; Deposit on the silicon oxide film being positioned at boron emitting surface by pyrogen sublayer sedimentation subsequently and form the ultrathin alumina film that a layer thickness is about 3nm, in deposition process, silicon chip adopts back-to-back placement, thus pellumina is only deposited on boron emitter; Finally use PECVD method deposition to form silicon nitride film, wherein silicon nitride film deposition is on positive and negative two surfaces of silicon chip, and the thickness of front side silicon nitride film is at about 80nm, and the thickness of back side silicon nitride is at about 70nm.

Test the open circuit voltage of above-mentioned N-type crystal silicon solar batteries, result as shown in Figure 3.

Embodiment 2

The front being diffused in silicon chip matrix through boron forms the silicon chip that boron emitter obtains having p-n junction, first adopt thermal oxidation method respectively to prepare the silicon oxide film of a layer thickness at about 3nm at the silicon chip tow sides with p-n junction, wherein silicon oxide film is evenly distributed on positive and negative two surfaces of silicon chip; Deposit on the silicon oxide film being positioned at boron emitting surface by PECVD method subsequently and form the pellumina aluminium oxide that a layer thickness is about 7nm; Finally use PECVD method deposition to form silicon nitride film, wherein silicon nitride film deposition is on positive and negative two surfaces of silicon chip, and the thickness of front side silicon nitride film is at about 80nm, and the thickness of back side silicon nitride is at about 70nm.

Test the open circuit voltage of above-mentioned N-type crystal silicon solar batteries, result as shown in Figure 3.

Comparative example 1

Test has the open circuit voltage that silicon nitride/aluminium oxide duplicature carrys out the N-type crystal silicon solar batteries of Passivation of Boron emitter surface, and result as shown in Figure 3.

Comparative example 2

Test has the open circuit voltage that nitrogenize silicon/oxidative silicon duplicature carrys out the N-type crystal silicon solar batteries of Passivation of Boron emitter surface, and result as shown in Figure 3.

As seen from Figure 3, the open circuit voltage of comparative example 1 and comparative example 2 is about the same, because open circuit voltage directly reflects the quality of battery surface passivation effect, therefore can judge that the passivation effect of these two kinds of structures of silicon nitride/aluminium oxide and nitrogenize silicon/oxidative silicon to battery boron emitter is almost the same; And the battery with silicon nitride/alumina/silica three layers of passivating film of embodiment 1 and embodiment 2, its open circuit voltage is higher than the battery only having duplicature passivation, so Fig. 3 also demonstrates silicon nitride/alumina/silica three layers of passivating film have good passivation effect.

The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (1)

1. a manufacture method for N-type crystal silicon solar batteries, is characterized in that, described manufacture method comprises:
S1, form boron emitter at the front surface of N-type matrix;
S2, on the surface of described boron emitter away from described N-type matrix, form the silicon oxide film and pellumina that arrange from inside to outside; And
S3, on the surface of described pellumina away from described silicon oxide film, form silicon nitride film,
Wherein, formed in the process of described aluminium oxide in described step S2, the back side any two being formed with the N-type matrix of silicon oxide film, mutually by after placing, the surface of described silicon oxide film away from described boron emitter forms pellumina,
On the surface of the back surface field of described N-type matrix away from described N-type matrix, silicon oxide film is formed being formed while described silicon oxide film in described step S2,
The preparation method of described silicon oxide film is thermal oxidation method or magnetron sputtering method;
The preparation method of described pellumina is atomic layer deposition method or PECVD band electrodeposition process;
The preparation method of described silicon nitride film is PECVD band electrodeposition process,
Described manufacture method is also included on silicon oxide film on the surface of the described back surface field surface away from described N-type matrix and forms silicon nitride film after described step S2 or after S3.
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