CN117374154A - Method for improving TOPCO battery passivation effect and TOPCO battery - Google Patents

Method for improving TOPCO battery passivation effect and TOPCO battery Download PDF

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CN117374154A
CN117374154A CN202311309218.0A CN202311309218A CN117374154A CN 117374154 A CN117374154 A CN 117374154A CN 202311309218 A CN202311309218 A CN 202311309218A CN 117374154 A CN117374154 A CN 117374154A
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layer
amorphous silicon
doped amorphous
hydrogen
doped
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刘志强
杨星
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Suzhou Shengcheng Solar Equipment Co Ltd
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Suzhou Shengcheng Solar Equipment Co Ltd
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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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/548—Controlling the composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • H—ELECTRICITY
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    • 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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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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Abstract

The invention belongs to the technical field of solar cells, and relates to a method for improving a TOPCO battery passivation effect and a TOPCO battery. The method comprises the following steps: s1, preparing a silicon wafer substrate; s2, preparing an oxide layer on the surface of the silicon wafer substrate; s3, preparing n layers of doped amorphous silicon layers on the surface of the oxide layer by a PVD method, wherein n is more than or equal to 2, introducing argon, phosphane and hydrogen source gas into a vacuum environment by the PVD method, wherein the hydrogen content of the hydrogen source gas is sequentially decreased when each doped amorphous silicon layer is sputtered from inside to outside, and the sputtering power is sequentially decreased; s4, carrying out high-temperature annealing treatment on the doped amorphous silicon layer to convert the multi-layer doped amorphous silicon layer into a doped polycrystalline silicon layer. A TOPCon cell with a doped polysilicon layer prepared using the method. By adopting the method, the hydrogen content of the doped polycrystalline silicon outer layer is low, the problem that hydrogen overflows on the surface is difficult to generate during annealing is solved, the film layer is prevented from being damaged, the hydrogen content of the bottom layer is high, and the dangling bonds on the surface of the substrate and defects in the body can be well passivated.

Description

Method for improving TOPCO battery passivation effect and TOPCO battery
Technical Field
The invention relates to the technical field of solar cells, in particular to a method for improving the passivation effect of a TOPCO cell and the TOPCO cell prepared by using the method.
Background
TOPCon batteries have the characteristics of high efficiency, low attenuation, compatibility with the existing production line and the like, become the main stream of N-type batteries at present, three methods of LPCVD (low pressure chemical vapor deposition), PECVD (plasma enhanced chemical vapor deposition) and PVD (physical vapor deposition) are generally adopted for preparing an amorphous silicon layer for passivation contact on the back of the TOPCon batteries, and PVD is gradually accepted due to high film coating speed, good film uniformity, no use of gases such as silane and the like. Wherein LPCVD is carried out using SiH 4 Preparation of amorphous silicon by thermal decomposition, PECVD is the decomposition of SiH using plasma 4 Preparation of amorphous silicon due to SiH 4 A large amount of H atoms are generated in the decomposition process, the amorphous silicon prepared by the two methods has high H content, and the H atoms can effectively passivate dangling bonds on the surface of the silicon wafer and defects in the body, so that the recombination of carriers is reduced, and the passivation effect is improved. PVD uses sputtering to prepare amorphous silicon, and usually uses Ar ions to directly bombard a silicon target, the bombarded Si atoms or atomic groups are aggregated to form a film, amorphous silicon is formed, and then high-temperature annealing is performed to convert the amorphous silicon into polycrystalline silicon. In principle, it can be seen that the amorphous silicon produced by PVD is free of H, resulting in poor passivation. For example, chinese patent CN114335236a discloses a method for preparing a passivation structure of a solar cell by passivating a contact cell and a method for preparing the same, wherein a passivation layer is directly deposited after annealing has been performed, and the problem of passivation with H is not involved.
If amorphous silicon is to be passivated in the PVD process, a hydrogen source gas is required to be added to the amorphous silicon, and during the film plating process, the hydrogen source gas can ionize hanging bonds on the surface of the H ion passivated silicon wafer and defects in the body. However, because the amorphous silicon layer prepared by PVD is loose, and the high-temperature annealing temperature of the film layer prepared by PVD is very high (above 800 ℃), H atoms may be converted into hydrogen or water vapor overflows from the surface during the high-temperature annealing process, at this time, the surface layer structure of the polysilicon layer may be damaged, so that many microscopic holes are formed, the film layer is damaged, passivation fails, and the conversion efficiency of the battery is deteriorated, as shown in fig. 1.
There is therefore a need to improve the fabrication of back-doped polysilicon layers for TOPCon cells to address the above issues.
Disclosure of Invention
The invention mainly aims to provide a method for improving the passivation effect of a TOPCON battery, which can treat a doped polysilicon layer in a mode of decreasing hydrogen content and sputtering power, ensure the passivation effect of the surface of a silicon wafer and simultaneously avoid the surface of the film from being damaged.
The invention realizes the aim through the following technical scheme: a method for improving TOPCON battery passivation effect comprises the following steps:
s1, preparing a silicon wafer substrate;
s2, preparing an oxide layer on the surface of the silicon wafer substrate, wherein the thickness of the oxide layer is 0.5-3nm;
s3, preparing n layers of doped amorphous silicon layers on the surface of the oxide layer by a PVD method, wherein n is more than or equal to 2, argon, phosphane and hydrogen source gas are introduced into a vacuum environment by the PVD method, the flow of the phosphane is 1-2% of the flow of the argon, the flow of the hydrogen source gas is 0-100% of the flow of the argon, the hydrogen content of the hydrogen source is sequentially decreased when each layer of doped amorphous silicon layer is sputtered from inside to outside, and the sputtering power is sequentially decreased from 30kW to 10 kW;
s4, carrying out high-temperature annealing treatment on the doped amorphous silicon layer, quickly heating to 800-900 ℃, maintaining for 5-10min, and then cooling at the speed of 2-10 ℃/min to convert the multi-layer doped amorphous silicon layer into a doped polycrystalline silicon layer.
Specifically, the bottommost doped amorphous silicon layer is filled with water vapor during sputtering, and the hydrogen content of the water vapor is 5-30% of the hydrogen content of phosphane and hydrogen source gas filled during sputtering the bottommost doped amorphous silicon layer.
Specifically, the hydrogen source is hydrogen or ammonia.
Specifically, the thickness of each doped amorphous silicon layer is 5-60mm.
Specifically, the oxide layer is prepared by an LPCVD method or a PECVD method.
Another main objective of the present invention is to provide a TOPCon battery with good passivation effect, and the passivation film layer is not damaged by H escaping during high temperature annealing.
A TOPCO cell is provided, in which a doped polysilicon layer is fabricated.
The technical scheme of the invention has the beneficial effects that:
by adopting the method, the hydrogen content of the outermost layer is lower, and the sputtering power is low, so that the problem that hydrogen overflows on the surface is not easy to occur during annealing, the film layer is prevented from being damaged, and the bottom layer has higher hydrogen content, so that the dangling bonds on the surface of the substrate and defects in the body can be well passivated.
Drawings
FIG. 1 is a microscopic photograph of a prior art film layer broken due to hydrogen overflow;
FIG. 2 is a diagram of a film structure for preparing doped amorphous silicon according to the technical scheme;
fig. 3 is a microscopic image of the surface of doped polysilicon prepared by the present technique.
The figures represent the numbers:
1-a substrate, 11-an oxide layer;
2 a-a first doped amorphous silicon layer, 2 b-a second doped polysilicon layer, 2 c-a third doped polysilicon layer, 2 d-a fourth doped amorphous silicon layer.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples:
as shown in fig. 2, a method for improving passivation effect of a TOPCon battery according to the present invention includes the following steps:
s1, preparing a silicon wafer substrate 1.
S2, preparing an oxide layer 11 on the silicon wafer substrate 1, wherein the thickness of the oxide layer 11 is 0.5-3nm. Can be prepared by LPCVD method or PECVD method.
S3, preparing four doped amorphous silicon layers on the surface of the oxide layer 11 by a PVD method, wherein the first doped amorphous silicon layer 2a, the second doped polysilicon layer 2b, the third doped polysilicon layer 2c and the fourth doped amorphous silicon layer 2d are respectively arranged from inside to outside, argon, phosphane and hydrogen source gas are introduced into a high vacuum environment by the PVD method, the flow rate of the phosphane is 1-2% of the flow rate of the argon, the flow rate of the hydrogen source gas is 0-100% of the flow rate of the argon, the hydrogen content of the hydrogen source is gradually decreased when each doped amorphous silicon layer is sputtered from inside to outside, and the sputtering power is gradually decreased from 30kW to 10 kW. The specific coating process conditions are shown in table 1.
Table 1:
PH here 3 The doping element P may be provided to decompose P atoms and H atoms upon annealing and to participate in crystallization reactions upon annealing, but is limited by the amount of P atoms, where fewer H atoms can be provided. The H atoms are mainly provided by hydrogen. Hydrogen is only one of the hydrogen source gases, however, and the process can also provide H atoms via ammonia. The lower the sputtering power, the less susceptible hydrogen is to deposition.
In practical application, the number of the doped amorphous silicon layers is n, and n is more than or equal to 2. The number of doped amorphous silicon layers is not limited to four, since the purpose of the inner layer having a large hydrogen content and the outer layer having a small hydrogen content only needs to be achieved. The thickness of each doped amorphous silicon layer is 5-60mm. The amount of phosphane used is preferably sufficient to provide a sufficient amount of P atoms and may vary from 1 to 2%. The maximum flow rate of the hydrogen source gas does not exceed argon, and the minimum flow rate can be 0, so that the outermost layer can be ensured not to overflow hydrogen.
As can be seen from the above table, the bottommost doped amorphous silicon layer (i.e., the first doped amorphous silicon layer 2 a) was added with moisture having a hydrogen flow rate of 20% during sputtering, and the hydrogen content of the moisture was 5-30% of the hydrogen content of the phosphine and hydrogen sputtered from the first doped amorphous silicon layer 2 a. The moisture is partially decomposed into H ions and O ions at relatively high sputter powers, wherein the H ions produced here can likewise have a passivating effect. Since the first doped amorphous silicon layer 2a is on the oxide layer 11, here the O ions can diffuse into the oxide layer 11 and repair defects in the oxide layer 11 at the time of annealing.
S4, carrying out high-temperature annealing treatment on the doped amorphous silicon layer, quickly heating to 800-900 ℃, maintaining for 5-10min, and then cooling at the speed of 2-10 ℃/min to convert the multi-layer doped amorphous silicon layer into a doped polycrystalline silicon layer.
By the preparation method, the hydrogen content of the doped polysilicon layer can be reduced in an inside-out gradient. Because the surface layer has low hydrogen content, the surface is hardly damaged due to the overflow of hydrogen during annealing. As shown in fig. 3, the surface of the film layer is not provided with holes when seen from a microscopic test picture, so that the preparation method ensures the integrity of the film layer on the outer surface of the doped polysilicon layer and increases the passivation effect of the doped polysilicon layer.
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.

Claims (6)

1. A method for improving the passivation effect of a TOPCon battery, comprising the steps of:
s1, preparing a silicon wafer substrate;
s2, preparing an oxide layer on the surface of the silicon wafer substrate, wherein the thickness of the oxide layer is 0.5-3nm;
s3, preparing n layers of doped amorphous silicon layers on the surface of the oxide layer by a PVD method, wherein n is more than or equal to 2, argon, phosphane and hydrogen source gas are introduced into a vacuum environment by the PVD method, the flow of the phosphane is 1-2% of the flow of the argon, the flow of the hydrogen source gas is 0-100% of the flow of the argon, the hydrogen content of the hydrogen source is sequentially decreased when each layer of doped amorphous silicon layer is sputtered from inside to outside, and the sputtering power is sequentially decreased from 30kW to 10 kW;
s4, carrying out high-temperature annealing treatment on the doped amorphous silicon layer, quickly heating to 800-900 ℃, maintaining for 5-10min, and then cooling at the speed of 2-10 ℃/min to convert the multi-layer doped amorphous silicon layer into a doped polycrystalline silicon layer.
2. The method for improving the passivation effect of a TOPCon battery according to claim 1, characterized in that: the bottom doped amorphous silicon layer is filled with water vapor during sputtering, and the hydrogen content of the water vapor is 5-30% of the hydrogen content of phosphane and hydrogen source gas filled during sputtering the bottom doped amorphous silicon layer.
3. The method for improving the passivation effect of a TOPCon battery according to claim 1, characterized in that: the hydrogen source gas is hydrogen or ammonia.
4. The method for improving the passivation effect of a TOPCon battery according to claim 1, characterized in that: the thickness of each doped amorphous silicon layer is 5-60mm.
5. The method for improving the passivation effect of a TOPCon battery according to claim 1, characterized in that: the oxide layer is prepared by LPCVD method or PECVD method.
6. A TOPCon battery characterized by: the method is used for manufacturing the doped polysilicon layer in the TOPCO battery.
CN202311309218.0A 2023-10-11 2023-10-11 Method for improving TOPCO battery passivation effect and TOPCO battery Pending CN117374154A (en)

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