CN114628543A - Heterojunction solar cell and manufacturing method thereof - Google Patents
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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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 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 heterojunction type
- H01L31/074—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 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 heterojunction type comprising a heterojunction with an element of Group IV of the Periodic System, e.g. ITO/Si, GaAs/Si or CdTe/Si 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
- H01L31/02—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 System
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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
Abstract
The invention provides a heterojunction solar cell and a manufacturing method thereof, wherein the heterojunction solar cell is provided with a first doping layer and a second doping layer which are respectively arranged on a light receiving surface and a backlight surface of a silicon substrate, at least one of the first doping layer and the second doping layer comprises at least two layers of doping films which are arranged in a laminated manner, and in two adjacent doping films, the doping concentration of the doping film far away from the silicon substrate is greater than that of the doping film close to the silicon substrate; in the invention, the doped film close to the silicon substrate in the first doped layer or/and the second doped layer has lower doping concentration, so that doped atoms can be reduced to the maximum extent to enter the corresponding intrinsic amorphous layer, and the defect density of the corresponding intrinsic amorphous layer can be reduced; the doped film far away from the silicon substrate in the first doped layer or/and the second doped layer has higher doping concentration, so that field passivation is facilitated, and contact resistance between the first doped layer or/and the second doped layer and the corresponding outer layer can be reduced.
Description
Technical Field
The invention relates to the field of photovoltaic manufacturing, in particular to a heterojunction solar cell and a manufacturing method thereof.
Background
The heterojunction solar cell is a relatively high-efficiency crystalline silicon solar cell at present, combines the characteristics of a crystalline silicon cell and a silicon-based thin film cell, and has the advantages of short manufacturing process, low process temperature, high conversion efficiency, more generated energy and the like. Fig. 1 is a schematic structural diagram of a heterojunction solar cell in the prior art, which sequentially includes, from top to bottom, a first collector electrode 51 ', a first transparent conductive film layer 41 ', a first doped layer 31 ', a first intrinsic amorphous layer 21 ', a silicon substrate 10 ', a second intrinsic amorphous layer 22 ', a second doped layer 32 ', a second transparent conductive film layer 42 ', and a second collector electrode 52 '.
In the prior art, the following problems exist: when the doping concentration in the first doping layer 31 ' and the second doping layer 32 ' is too high, the doping atoms enter the first intrinsic amorphous layer 21 ' and the second intrinsic amorphous layer 22 ', and the defect density of the first intrinsic amorphous layer 21 ' and the second intrinsic amorphous layer 22 ' is increased, thereby affecting the passivation effect on the silicon substrate 10 '; when the doping concentration of the first doped layer 31 'and the second doped layer 32' is too low, the resistivity of the first doped layer 31 'and the second doped layer 32' is high, which is not favorable for current transmission.
In view of the above, there is a need to provide an improved solution to the above problems.
Disclosure of Invention
The present invention is designed to solve at least one of the technical problems of the prior art, and to achieve the above object, the present invention provides a heterojunction solar cell, which is specifically designed as follows.
A heterojunction solar cell, comprising: the silicon substrate comprises a first intrinsic amorphous layer and a first doping layer which are sequentially stacked on a light receiving surface of the silicon substrate, a second intrinsic amorphous layer and a second doping layer, wherein the second intrinsic amorphous layer and the second doping layer are sequentially stacked on a backlight surface of the silicon substrate, and the doping type of the second doping layer is opposite to that of the first doping layer; at least one of the first doping layer and the second doping layer comprises at least two layers of doping films which are arranged in a stacked mode, and in two adjacent doping films, the doping concentration of the doping film far away from the silicon substrate is larger than that of the doping film close to the silicon substrate.
Further, the doped film is a doped amorphous silicon film, a doped amorphous silicon oxide film, a doped microcrystalline silicon film or a doped microcrystalline silicon oxide film.
Further, the average doping concentration of the first doping layer is less than the average doping concentration of the second doping layer.
Further, the number of layers of the doped films in the second doped layer is not more than that of the doped films in the first doped layer.
Further, the thickness of the first doped layer is less than or equal to the thickness of the second doped layer.
Further, the doping film forming the first doping layer is a phosphorus doping film, the phosphorus doping film comprises a first phosphorus doping film, a second phosphorus doping film and a third phosphorus doping film which are sequentially stacked and arranged outside the first intrinsic amorphous layer, and the phosphorus doping concentrations in the first phosphorus doping film, the second phosphorus doping film and the third phosphorus doping film are respectively 50-150ppm, 100-300ppm and 200-400 ppm.
Further, the thicknesses of the first phosphorus-doped film, the second phosphorus-doped film and the third phosphorus-doped film are respectively 2-4nm, 2-4nm and 1-3 nm.
Further, the doping film forming the second doping layer is a boron doping film, the boron doping film comprises a first boron doping film, a second boron doping film and a third boron doping film which are sequentially stacked and arranged outside the second intrinsic amorphous layer, and the boron doping concentrations in the first boron doping film, the second boron doping film and the third boron doping film are respectively 300-200-500 ppm, 400-600 ppm.
Further, the thicknesses of the first boron-doped film, the second boron-doped film and the third boron-doped film are respectively 2-5nm, 2-5nm and 1-3 nm.
Further, the first intrinsic amorphous layer and the second intrinsic amorphous layer respectively include at least two stacked intrinsic films, and each intrinsic film is formed by one of an intrinsic amorphous silicon film, an intrinsic amorphous silicon oxide film, and an intrinsic amorphous silicon carbide film.
Further, one of the first intrinsic amorphous layer and/or the second intrinsic amorphous layer, which is farthest from the silicon substrate, is an intrinsic amorphous silicon oxide film.
Further, the number of intrinsic film layers of the second intrinsic amorphous layer seed is not greater than the number of intrinsic film layers in the first intrinsic amorphous layer.
Further, in two adjacent intrinsic films, the hydrogen content of the intrinsic film close to the silicon substrate is larger than that of the intrinsic film far away from the silicon substrate.
Furthermore, the first intrinsic amorphous layer and the second intrinsic amorphous layer respectively comprise three layers of intrinsic films which are stacked, and the hydrogen content ranges of the three intrinsic films in the first intrinsic amorphous layer and the second intrinsic amorphous layer are respectively 20% -40%, 10% -25% and 8% -20% in sequence from the inner intrinsic film to the outer intrinsic film.
Furthermore, in the direction from the inner intrinsic film to the outer intrinsic film, the thicknesses of the three intrinsic films in the first intrinsic amorphous layer are 1-3nm, 2-4nm and 1-3nm in sequence, and the thicknesses of the three intrinsic films in the second intrinsic amorphous layer are 1-5nm, 3-10nm and 0-5nm in sequence.
The invention also provides a manufacturing method of the heterojunction solar cell, which comprises the following steps:
providing a silicon substrate;
sequentially forming a first intrinsic amorphous layer and a first doping layer on the light receiving surface of the silicon substrate;
sequentially forming a second intrinsic amorphous layer and a second doping layer on the backlight surface of the silicon substrate, wherein the doping type of the second doping layer is opposite to that of the first doping layer;
at least one of the first doped layer forming step and the second doped layer forming step comprises the sequential formation of at least two layers of doped films, and in two adjacent doped films which are sequentially formed, the doped concentration of the doped film far away from the silicon substrate is greater than that of the doped film close to the silicon substrate.
Further, the first doped layer forming step includes sequentially forming three phosphorus doped films on the surface of the first intrinsic amorphous layer, and forming three phosphorus doped films at a PH of the silicon doped films in a direction away from the silicon substrate3/SiH4The flow rate ratio ranges are 50-150ppm, 100-300ppm and 200-400ppm in sequence.
Further, the second doped layer forming step includes sequentially forming three boron doped films on the surface of the second intrinsic amorphous layer, and forming B of the three boron doped films in a direction away from the silicon substrate2H6/SiH4The flow rate ratio ranges are 50-150ppm, 100-250ppm and 200-300ppm in sequence.
Further, at least one of the first intrinsic amorphous layer forming step and the second intrinsic amorphous layer forming step includes sequentially forming at least two intrinsic films, and of two adjacent intrinsic films sequentially formed, the intrinsic film close to the silicon substrate has a hydrogen content greater than that of the intrinsic film far from the silicon substrate.
Further, the first intrinsic amorphous layer forming step and the second intrinsic amorphous layer forming step each include sequentially forming three intrinsic films, and forming H when three intrinsic films of the first intrinsic amorphous layer and the second intrinsic amorphous layer are formed in a direction from the inner intrinsic film to the outer intrinsic film2/SiH4The flow ratio ranges are 0, 3-10 and 10-20 in sequence.
Further, the forming of the first intrinsic amorphous layer and the forming of the second intrinsic amorphous layer further include: after forming an intrinsic film, introducing pure H to the surface of the intrinsic film2Or H2Dilute SiH4Carrying out plasma treatment; among them, H2 diluted SiH4 is H2/SiH4The dilution ratio is greater than 100.
The invention has the beneficial effects that: based on the specific structure of the heterojunction solar cell, the doped film close to the silicon substrate in the first doped layer or/and the second doped layer has lower doping concentration, so that doped atoms can be reduced to the maximum extent to enter the corresponding intrinsic amorphous layer, and the defect density of the corresponding intrinsic amorphous layer can be reduced; the doped film far away from the silicon substrate in the first doped layer or/and the second doped layer has higher doping concentration, so that field passivation is facilitated, and contact resistance between the first doped layer or/and the second doped layer and the corresponding outer layer can be reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a prior art heterojunction solar cell;
fig. 2 is a schematic diagram of a first embodiment of a heterojunction solar cell according to the present invention;
fig. 3 is a schematic diagram of a second embodiment of the heterojunction solar cell of the invention.
In the drawing, 10 is a silicon substrate, 21 is a first intrinsic amorphous layer, 31 is a first doped layer, 311 is a first phosphorus doped film, 312 is a second phosphorus doped film, 313 is a third phosphorus doped film, 41 is a first transparent conductive film layer, 51 is a first collector, 22 is a second intrinsic amorphous layer, 32 is a second doped layer, 321 is a first boron doped film, 322 is a second boron doped film, 323 is a third boron doped film, 42 is a second transparent conductive film layer, and 52 is a second collector.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Referring to fig. 2, the heterojunction solar cell according to the present invention includes: the silicon substrate 10 includes a first intrinsic amorphous layer 21 and a first doped layer 31 sequentially stacked on a light receiving surface of the silicon substrate 10, and a second intrinsic amorphous layer 22 and a second doped layer 32 sequentially stacked on a back surface of the silicon substrate 10. The doping types of the first doping layer 31 and the second doping layer 32 are opposite, one of the doping types is n-type doping, namely phosphorus doping is adopted; the other is p-type doping, i.e. boron doping is used.
More specifically, referring to fig. 2, in the present embodiment, the heterojunction solar cell includes: the first transparent conductive film layer 41 and the first collector electrode 51 are sequentially stacked outside the first doped layer 31, and the second transparent conductive film layer 42 and the second collector electrode 52 are sequentially stacked outside the second doped layer 32.
In a specific implementation, the light receiving surface of the silicon substrate 10 is a surface of the heterojunction solar cell directly receiving sunlight, and the back surface is a surface of the heterojunction solar cell not directly receiving sunlight, that is, a surface opposite to the light receiving surface.
In the present invention, at least one of the first doped layer 31 and the second doped layer 32 includes at least two stacked doped films, and of the two adjacent doped films, the doped film far from the silicon substrate 10 has a doping concentration greater than that of the doped film near the silicon substrate 10.
Based on the specific structure of the heterojunction solar cell according to the present invention, the doped film of the first doped layer 31 or/and the second doped layer 32 near the silicon substrate 10 has a lower doping concentration, so that the doped atoms can be reduced to the greatest extent to enter the corresponding intrinsic amorphous layer (i.e., the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22), and the defect density of the corresponding intrinsic amorphous layer can be reduced. The doped film of the first doped layer 31 or/and the second doped layer 32 far from the silicon substrate 10 has a higher doping concentration, which is beneficial to field passivation, and can also reduce the contact resistance between the first doped layer 31 or/and the second doped layer 32 and the corresponding outer layer (in this embodiment, including the first transparent conductive film layer 41 and the second transparent conductive film layer 42).
In the specific implementation process of the invention, the doped film is a doped amorphous silicon film, a doped amorphous silicon oxide film, a doped microcrystalline silicon film or a doped microcrystalline silicon oxide film. In general, for convenience of fabrication, the doped films constituting the first doped layer 31 are made of the same material, for example, doped amorphous silicon films; the multiple doped films constituting the second doped layer 32 are also made of the same material, and are all, for example, doped amorphous silicon oxide films; the doped films constituting the first doped layer 31 and the second doped layer 32 may be the same or different.
Preferably, in some embodiments of the present invention, the average doping concentration of the first doped layer 31 is less than the average doping concentration of the second doped layer 32. For the heterojunction solar cell, the light receiving surface is the main surface of the photo-generated current, and the first doping layer 31 has relatively low average concentration and can have higher mobility, so that the transmission of the current on the light receiving surface of the heterojunction solar cell is facilitated; on the back side of the heterojunction solar cell, the average doping concentration of the second doping layer 32 is relatively high, so that the resistance of the heterojunction solar cell can be reduced.
In further preferred embodiments of the present invention, the number of layers of doped films in the second doped layer 32 is not greater than the number of layers of doped films in the first doped layer 31. For a heterojunction solar cell, the light receiving surface of the heterojunction solar cell is used as the main surface of photo-generated current, the performance requirement on the first doping layer 31 is higher, and the comprehensive performance of the first doping layer 31 can be better optimized by arranging doping films with more layers.
Further, the thickness of the first doped layer 31 is less than or equal to the thickness of the second doped layer 32, wherein preferably, the thickness of the first doped layer 31 is less than the thickness of the second doped layer 32. Typically, the thickness of the first doped layer 31 is 5-11nm and the thickness of the second doped layer 32 is 5-13 nm.
For the heterojunction solar cell, the influence of the light absorption effect of the light receiving surface on the photoelectric conversion efficiency of the cell is far larger than the influence of the light absorption effect of the backlight surface on the photoelectric conversion efficiency of the cell, the loss of sunlight on the light receiving surface when the sunlight passes through the first doping layer 31 can be effectively reduced due to the relatively small thickness of the first doping layer 31, the short-circuit current of the heterojunction solar cell can be improved, and the heterojunction solar cell has better photoelectric conversion efficiency; the backlight surface does not need to consider the problem of light absorption too much, and the relatively thick second doped layer 32 can have better conductivity, thereby reducing the contact resistance between the second doped layer and the second transparent conductive film 42.
The silicon substrate 10 related in the present invention may specifically be a p-type single crystal silicon substrate, or may be an n-type single crystal silicon substrate; however, in a preferred embodiment of the present invention, the single crystal silicon substrate 10 is an n-type single crystal silicon substrate. When the monocrystalline silicon substrate 10 is an n-type monocrystalline silicon substrate, the first doping layer 31 is doped n-type, that is, doped with phosphorus; the second doped layer 32 is p-type doped, i.e. doped with boron.
In more specific embodiments, as shown in fig. 2, the doping film forming the first doping layer 31 is a phosphorus doping film. Specifically, the phosphorus doped film includes a first phosphorus doped film 311, a second phosphorus doped film 312 and a third phosphorus doped film 313 stacked in sequence outside the first intrinsic amorphous layer 21, wherein the phosphorus doping concentrations in the first phosphorus doped film 311, the second phosphorus doped film 312 and the third phosphorus doped film 312 are 50-150ppm, 100-300ppm and 200-400ppm, respectively.
Preferably, the thicknesses of the first phosphorus-doped film 311, the second phosphorus-doped film 312, and the third phosphorus-doped film 313 are 2-4nm, and 1-3nm, respectively.
Further, in the embodiment shown in fig. 2, the doped film constituting the second doped layer 32 is a boron doped film, and the boron doped film includes a first boron doped film 321, a second boron doped film 322, and a third boron doped film 323 sequentially stacked outside the second intrinsic amorphous layer 22. Wherein the boron doping concentrations in the first boron doping film 321, the second boron doping film 322 and the third boron doping film 323 are respectively 100-300ppm, 200-500ppm and 400-600 ppm. Since the boron doping concentrations in the first boron-doped film 321, the second boron-doped film 322, and the third boron-doped film 323 are sequentially greater than the phosphorus doping concentrations in the first phosphorus-doped film 311, the second phosphorus-doped film 312, and the third phosphorus-doped film 312, the average doping concentration of the first doped layer 31 can be smaller than the average doping concentration of the second doped layer 32.
Preferably, the thicknesses of the first boron-doped film 321, the second boron-doped film 322, and the third boron-doped film 323 are 2-5nm, and 1-3nm, respectively.
As a preferred embodiment of the present invention, the first intrinsic amorphous layer 31 and the second intrinsic amorphous layer 32 each include at least two intrinsic films stacked one on another, wherein each intrinsic film is formed of one of an intrinsic amorphous silicon film, an intrinsic amorphous silicon oxide film, and an intrinsic amorphous silicon carbide film. Referring to fig. 3, in this embodiment, the first intrinsic amorphous layer 31 and the second intrinsic amorphous layer 32 each include three intrinsic films stacked, and specifically, the first intrinsic amorphous layer 21 includes a first intrinsic film 211, a second intrinsic film 212, and a third intrinsic film 213 stacked in this order on the light receiving surface of the silicon substrate 10; the second intrinsic amorphous layer 22 includes a fourth intrinsic film 221, a fifth intrinsic film 222, and a sixth intrinsic film 223 sequentially stacked on the back surface of the silicon substrate 10.
Since the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 each include at least two intrinsic films stacked on each other, the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 having better overall performance can be formed by controlling the characteristics of each film in the specific implementation process.
As a preferable aspect of the present invention, in the detailed implementation, one of the first intrinsic amorphous layer 21 and/or the second intrinsic amorphous layer 22, which is farthest from the silicon substrate 10, is provided as an intrinsic amorphous silicon oxide film. Referring to fig. 3, in this embodiment, the third intrinsic film 213 is an intrinsic film of the first intrinsic amorphous layer 21 farthest from the single crystal silicon substrate 10, and the third intrinsic film 213 in this embodiment is preferably an intrinsic amorphous silicon oxide film. It is to be understood that in other embodiments of the present invention, the layer of the intrinsic film of the second intrinsic amorphous layer 22 farthest from the single crystal silicon substrate 10 may also be provided as an intrinsic amorphous silicon oxide film, i.e., the sixth intrinsic film 223 farthest from the silicon substrate 10 in the embodiment shown in fig. 3 may also be provided as an intrinsic amorphous silicon oxide film.
The passivation effect of the intrinsic amorphous silicon oxide film is inferior to that of the intrinsic amorphous silicon film and the intrinsic amorphous silicon carbide film, but the intrinsic amorphous silicon oxide film has better light transmittance compared with the intrinsic amorphous silicon film and the intrinsic amorphous silicon carbide film, in the heterojunction solar cell, the intrinsic film, which is the layer farthest from the silicon substrate 10, of the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 has a limited passivation effect on the silicon substrate 10 due to the distance, and the intrinsic amorphous silicon oxide film with the optimal light transmittance is set to be the intrinsic amorphous silicon oxide film, so that the light transmittance can be correspondingly increased through the intrinsic layer, and the photoelectric conversion efficiency of the heterojunction solar cell can be optimized to a certain extent.
In addition, in still other preferred embodiments of the present invention, the number of intrinsic films in the second intrinsic amorphous layer 22 is not greater than the number of intrinsic films in the first intrinsic amorphous layer 21. For a heterojunction solar cell, the light receiving surface of the heterojunction solar cell is used as the main surface for generating the photo current, the performance requirement on the first intrinsic amorphous layer 21 is higher, and the comprehensive performance of the first intrinsic amorphous layer 21 can be better optimized by arranging more intrinsic films.
Further, the thickness of the first intrinsic amorphous layer 21 is less than or equal to the thickness of the second intrinsic amorphous layer 22, wherein preferably, the thickness of the first intrinsic amorphous layer 21 is less than the thickness of the second intrinsic amorphous layer 22. Typically, the thickness of the first intrinsic amorphous layer 21 is 4 to 10nm, and the thickness of the second intrinsic amorphous layer 22 is 4 to 20 nm. For the specific reason, reference may be made to the description of the thickness configuration of the first doping layer 31 and the second doping layer 32, which is not described herein again.
As a further preference of the present invention, of the two adjacent intrinsic films, the intrinsic film close to the silicon substrate 10 has a hydrogen content larger than that of the intrinsic film far from the silicon substrate 10. Specifically, as shown in fig. 3, in this embodiment, the hydrogen contents of the first intrinsic film 211, the second intrinsic film 212, and the third intrinsic film 213 in the first intrinsic amorphous layer 21 are sequentially reduced, and the hydrogen contents of the fourth intrinsic film 221, the fifth intrinsic film 222, and the sixth intrinsic film 223 in the second intrinsic amorphous layer 22 are also sequentially reduced.
It can be easily understood that the intrinsic films of the first and second intrinsic amorphous layers 21 and 22 closer to the silicon substrate 10 have more significant passivation effect, and the first and fourth intrinsic films 211 and 221 are directly attached to the silicon substrate 10, which have the highest hydrogen content to enable the first and second intrinsic amorphous layers 21 and 22 to have the optimal passivation effect on the silicon substrate 10. Specifically, the hydrogen content of the first intrinsic film 211 and the fourth intrinsic film 221 is higher, and dangling bonds at the surface position of the silicon substrate 10 can be passivated better.
As a preferable aspect of the present invention, when the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 respectively include three intrinsic films stacked, the hydrogen content of the three intrinsic films in the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 respectively ranges from 20% to 40%, from 10% to 25%, and from 8% to 20% in the direction from the inner intrinsic film to the outer intrinsic film. That is, the hydrogen content of the first and fourth intrinsic films 201 and 204 ranges from 20% to 40%, the hydrogen content of the second and fifth intrinsic films 212 and 222 ranges from 10% to 25%, and the hydrogen content of the third and sixth intrinsic films 213 and 223 ranges from 8% to 20%.
Further preferably, in the embodiment shown in fig. 3, the hydrogen content of the first and fourth intrinsic films 211 and 221 ranges from 24% to 30%, the hydrogen content of the second and fifth intrinsic films 212 and 222 ranges from 12% to 18%, and the hydrogen content of the third and sixth intrinsic films 213 and 223 ranges from 10% to 15%.
As a further preferred embodiment of the present invention shown in FIG. 3, the intrinsic films in the first intrinsic amorphous layer have thicknesses of 1-3nm, 2-4nm, and 1-3nm in this order, and the intrinsic films in the second intrinsic amorphous layer have thicknesses of 1-5nm, 3-10nm, and 0-5nm in this order, from the inner intrinsic film to the outer intrinsic film. Specifically, the thicknesses of the first intrinsic film 211, the second intrinsic film 212, and the third intrinsic film 213 in the first intrinsic amorphous layer 21 are sequentially 1 to 3nm, 2 to 4nm, and 1 to 3nm, and the thicknesses of the fourth intrinsic film 221, the fifth intrinsic film 222, and the sixth intrinsic film 223 in the second intrinsic amorphous layer 22 are sequentially 1 to 5nm, 3 to 10nm, and 0 to 5 nm.
The invention further provides a manufacturing method of the heterojunction solar cell. The method specifically comprises the following steps:
providing a silicon substrate 10;
forming a first intrinsic amorphous layer 21 and a first doping layer 31 on a light receiving surface of a silicon substrate 10 in this order;
a second intrinsic amorphous layer 22 and a second doped layer 32 are sequentially formed on the back surface of the silicon substrate, and the doping type of the second doped layer 32 is opposite to that of the first doped layer 31.
In the above steps, at least one of the first doping layer 31 forming step and the second doping layer 32 forming step includes sequentially forming at least two doping films, and of two adjacent doping films sequentially formed, a doping concentration of a doping film far from the silicon substrate 10 is greater than a doping concentration of a doping film near the silicon substrate.
One specific implementation of the step of providing the silicon substrate 10 is as follows: selecting an n-type monocrystalline silicon wafer, removing a damage layer by using a KOH aqueous solution with the volume ratio of 15%, forming a pyramid suede structure on the surface of the n-type monocrystalline silicon wafer by using KOH and an anisotropic wool making additive solution, treating the n-type monocrystalline silicon wafer with the pyramid suede structure on the surface by using an ozone aqueous solution with the concentration of 10-50ppm, removing an oxide layer on the surface of the n-type monocrystalline silicon wafer by using a 2% HF solution, and finally washing and drying to obtain the silicon substrate 10. Typically, the pyramid height in the pyramid structure is 0.5-3um, and the matte reflectivity is about 10%.
The first intrinsic amorphous layer 21, the first doping layer 31, the second intrinsic amorphous layer 22 and the second doping layer 32 in the present invention are formed by a PECVD process.
In the case of the heterojunction solar cell having the structure shown in fig. 2, the first doping layer 31 is formed by sequentially forming three phosphorus-doped films on the surface of the first intrinsic amorphous layer 21, and forming the three phosphorus-doped films at PH in a direction away from the silicon substrate3/SiH4The flow rate ratio ranges are 50-150ppm, 100-300ppm and 200-400ppm in sequence. The second doping layer 32 forming step includes sequentially forming three boron doped films on the surface of the second intrinsic amorphous layer 22, B when forming the three boron doped films in a direction away from the silicon substrate2H6/SiH4The flow rate ratio ranges are 50-150ppm, 100-250ppm and 200-300ppm in sequence.
More specifically, one specific formation step of the first doping layer 31 is: heating the PECVD coating cavity to 180 ℃, and controlling the pressurePrepared at 30-200 pa; introducing PH to the surface of the first intrinsic amorphous layer 213、 SiH4And H2Control of pH3/SiH4The flow rate proportion value is 50-150ppm, and a first phosphorus doped film 311 is formed by deposition; then adjust the pH3/SiH4The flow rate ratio is 100-300ppm, and a second phosphorus-doped film 312 is deposited; finally adjusting the pH3/SiH4The flow rate ratio is 200-400ppm, and a third phosphorus doped film 313 is deposited. All the doped films in the first doped layer 31 formed by this step are doped amorphous silicon films, and SiH is maintained during the formation of the first doped layer 314The flow is not changed, and H is adjusted2Flow rate to maintain constant chamber pressure.
In still other embodiments of the present invention, when all the doped films of the first doped layer 31 are doped amorphous silicon oxide films, a specific forming step of the first doped layer 31 is: heating the PECVD coating cavity to 180 ℃, and controlling the pressure to be 30-200 pa; introducing PH to the surface of the first intrinsic amorphous layer 213、SiH4、CO2And H2Control of pH3/SiH4Flow rate ratio of 50-150ppm, CO2/SiH4The flow ratio value is 0.5-2, and a first phosphorus doped film 311 is formed by deposition; then adjusting the pH3/SiH4The flow rate ratio is 100-300ppm, CO2/SiH4The flow ratio value of 0.5-2, and depositing to form a second phosphorus-doped film 312; finally adjusting the pH3/SiH4The flow rate ratio is 200-400ppm, CO2/SiH4The flow ratio value of (3) is 0.5-2, and the third phosphorus-doped film 313 is deposited. During the formation of the first doped layer 31 by this step, SiH is maintained4The flow is not changed, and H is adjusted2Flow rate to maintain constant chamber pressure.
Accordingly, one specific forming step of the second doping layer 32 is: heating the PECVD coating cavity to 180 ℃, and controlling the pressure to be 30-200 pa; b is introduced facing the surface of the second intrinsic amorphous layer 222H6、SiH4And H2Control of B2H6/SiH4The flow rate ratio is 50-150ppm, and a first boron doped film is formed by deposition321; then adjust B2H6/SiH4Depositing to form a second boron doped film 322 when the flow ratio value is 100-250 ppm; finally, adjust B2H6/SiH4The flow rate ratio is 200-300ppm, and a third boron doped film 323 is deposited. All the doped films of the second doped layer 32 formed by this step are doped amorphous silicon films, and SiH is maintained during the formation of the second doped layer 324The flow is not changed, and H is adjusted2Flow rate to maintain constant chamber pressure.
In still other embodiments of the present invention, when all doped films of the second doped layer 32 are doped amorphous silicon oxide films, a specific forming step of the second doped layer 32 is: heating the PECVD coating cavity to 180 ℃, and controlling the pressure to be 30-200 pa; b is introduced facing the surface of the second intrinsic amorphous layer 222H6、SiH4、 CO2And H2Control of B2H6/SiH4Flow rate ratio of 50-150ppm, CO2/SiH4The flow ratio value of 0.5-2, and depositing to form a first boron-doped film 321; then adjust B2H6/SiH4The flow rate ratio is 100-250ppm, CO2/SiH4The flow ratio value is 0.5-2, and a second boron-doped film 322 is formed by deposition; finally, adjust B2H6/SiH4The flow rate ratio value is 200-300ppm, CO2/SiH4The flow ratio value of 0.5-2, and a third boron-doped film 323 is deposited. During the formation of the second doped layer 32 by this step, SiH is maintained4The flow is not changed, and H is adjusted2Flow rate to maintain constant chamber pressure.
It is understood that in the specific implementation process, the thickness of each doped film can be controlled by controlling the forming time of each doped film.
For the heterojunction solar cell shown in fig. 3, at least one of the first intrinsic amorphous layer 21 forming step and the second intrinsic amorphous layer 22 forming step includes sequentially forming at least two intrinsic films, and of two adjacent intrinsic films sequentially formed, the intrinsic film near the silicon substrate 10 has a hydrogen content greater than that of the intrinsic film far from the silicon substrate 10.
In some embodiments of the present invention, as shown in conjunction with fig. 3, the first intrinsic amorphous layer 21 forming step and the second intrinsic amorphous layer 22 forming step each include sequentially forming three intrinsic films. In order to make the hydrogen content of the intrinsic film close to the silicon substrate 10 larger than that of the intrinsic film far from the silicon substrate 10, in the implementation of the present embodiment, H is generated when three intrinsic films of the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 are formed in a direction from the inner intrinsic film toward the outer intrinsic film2/SiH4The flow ratio ranges are 0, 3-10 and 10-20 in sequence.
As a specific embodiment, when all the eigenmodes constituting the first intrinsic amorphous layer 21 are an intrinsic amorphous silicon film, the first intrinsic amorphous layer 21 is specifically formed by a process including: heating the PECVD coating cavity to 180 ℃, and controlling the pressure to be 30-200 pa; pure SiH is firstly introduced to the light receiving surface of the silicon substrate 104A first intrinsic layer 211 is deposited, as will be appreciated pure SiH4I.e. corresponding to H2/SiH4The flow ratio is 0; then, the mixture is passed through a channel H2Dilute SiH4A second intrinsic layer film 212 is deposited on the first intrinsic layer film 211, at this time, H2/SiH4The flow ratio range of (A) is 3-10; continuously introducing into the channel H2Dilute SiH4A third intrinsic layer 213 is deposited over the second intrinsic layer 212, at which time H is adjusted2/SiH4The flow ratio of (a) to (b) is in the range of 10-20.
The first intrinsic amorphous layer 21 is filled with pure SiH4The method is formed by deposition, an intrinsic layer with high hydrogen content (namely, more bonding hydrogen) can be formed, and the growth of epitaxial silicon at the interface can be inhibited. However, a porous structure such as a micropore is easily formed in the first intrinsic amorphous layer 21 with high hydrogen content, the quality of the film body is poor, and H is introduced into the second intrinsic layer 212 and the third intrinsic layer 2132Dilute SiH4Although the bonding hydrogen content in the corresponding intrinsic layer is reduced, a dense structure can be formed, and the film thickness of the second intrinsic layer film 212 and the third intrinsic layer film 213 is dense, which can prevent the doped atoms in the first doped layer 31 from entering the first intrinsic amorphous layer 21, thereby preventing the first intrinsic amorphous layer from being reducedThe passivation effect of the intrinsic amorphous layer 21.
In the embodiment shown in fig. 3, when all the eigenmodes constituting the second intrinsic amorphous layer 22 are intrinsic amorphous silicon films, the specific forming step of the second intrinsic amorphous layer 22 can refer to the specific forming step of the first intrinsic amorphous layer 21, which is not described herein in detail.
In other embodiments of the present invention, when the eigenmode is an intrinsic amorphous silicon oxide film, the gas introduced is further increased with CO based on the gas composition for forming the intrinsic amorphous silicon film2(ii) a And preferably, SiH4/CO2The flow ratio of (A) is in the range of 0.5-2. Correspondingly, when the eigenmode is an intrinsic amorphous silicon carbide film, CH is added to the gas introduced by the intrinsic amorphous silicon carbide film on the basis of the gas composition for manufacturing the intrinsic amorphous silicon film4(ii) a And preferably, SiH4/CH4The flow ratio of (A) is in the range of 0.5-2.
Further, the steps of forming the first intrinsic amorphous layer 21 and the second intrinsic amorphous layer 22 further include: after forming an intrinsic film, introducing pure H to the surface of the intrinsic film2Or H2Dilute SiH4Carrying out plasma treatment; among them, H2 diluted SiH4 is H2/SiH4The dilution ratio is greater than 100.
Specifically, in some embodiments of the present invention, as shown in fig. 3, in the step of forming the first intrinsic amorphous layer 21, pure H may be added once after the first intrinsic film 211, the second intrinsic film 212, and the third intrinsic film 213 are formed2Or H2Dilute SiH4Plasma treatment is performed. Wherein preferably pure H is added once after each intrinsic film formation2Or H2Dilute SiH4Carrying out plasma treatment; less preferably, pure H is added only once after the third intrinsic film 213 is formed2Or H2Dilute SiH4Plasma treatment is performed.
Accordingly, in the formation step of the second intrinsic amorphous layer 22, after the formation of the fourth intrinsic film 221, after the formation of the fifth intrinsic film 222, and after the sixth intrinsic filmAfter the film 223 is formed, pure H may also be added once2Or H2Dilute SiH4Plasma treatment is performed. Wherein preferably pure H is added once after each intrinsic film formation2Or H2Dilute SiH4Carrying out plasma treatment; less preferably, pure H is added only once after the sixth intrinsic film 223 is formed2Or H2Dilute SiH4Plasma treatment is performed.
In this example, by increasing pure H2Or H2Dilute SiH4The hydrogen content of the corresponding intrinsic film is further increased by performing the plasma treatment, and the passivation effect of the first and second intrinsic amorphous layers 21 and 22 on the silicon substrate 10 is further increased.
It can be understood that the method for manufacturing a heterojunction solar cell according to the present invention further comprises:
a transparent conductive film manufacturing step: the first transparent conductive film layer 41 and the second transparent conductive film layer 42 are respectively formed on the surfaces of the first doped layer 31 and the second doped layer 32 by PVD deposition, RPD deposition or magnetron sputtering deposition.
A collector manufacturing step: respectively printing a layer of low-temperature conductive silver paste on the first transparent conductive film layer 41 and the second transparent conductive film layer 42 by a screen printing method, and then sintering at a low temperature of 150-300 ℃ to form good ohmic contact, thereby forming a first collector 51 and a second collector 52.
One specific implementation manner of the first transparent conductive film 41 and the second transparent conductive film 42 is as follows: heating a deposition chamber of the PVD equipment to 190 ℃; placing the silicon substrate 10 with the first doping layer 31 and the second doping layer 32 on a carrier plate and conveying the silicon substrate into a deposition chamber; ITO (In) is used on the surface of the first doped layer 312O3：SnO297: 3) coating a target to deposit and form a first transparent conductive film layer 41 with the thickness of 70-100 nm; ITO (In) is adopted on the surface of the second doping layer 322O3：SnO2When the ratio is 90: 10) the target is coated to deposit a second transparent conductive film layer 42 of 70-100 nm.
It can be understood that ITO(In2O3：SnO297: 3) the target refers to In ITO target material2O3With SnO2The mass proportion is 97: 3, ITO (In)2O3：SnO2When the ratio is 90: 10) the target refers to In ITO target material2O3With SnO2The mass proportion is 90: 10. oxide SnO doped in first transparent conductive film layer 412The content of the first transparent conductive film layer 41 is relatively low, so that the light transmission of the first transparent conductive film layer 41 is better, and the light receiving surface of the heterojunction solar cell is beneficial to the light receiving effect; oxide SnO doped in the second transparent conductive film layer 422The content of (b) is relatively high so that the second transparent conductive film layer 42 has better conductivity, and the contact resistance between the second transparent conductive film layer 42 and the second collector electrode can be optimized.
It should be understood that although the specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it will be appreciated by those skilled in the art that the specification as a whole may be appropriately combined to form other embodiments as will be apparent to those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (21)
1. A heterojunction solar cell, comprising: the silicon substrate comprises a first intrinsic amorphous layer and a first doping layer which are sequentially stacked on a light receiving surface of the silicon substrate, a second intrinsic amorphous layer and a second doping layer, wherein the second intrinsic amorphous layer and the second doping layer are sequentially stacked on a backlight surface of the silicon substrate, and the doping type of the second doping layer is opposite to that of the first doping layer; the silicon substrate is characterized in that at least one of the first doping layer and the second doping layer comprises at least two layers of doping films which are arranged in a stacked mode, and in the two adjacent doping films, the doping concentration of the doping film far away from the silicon substrate is larger than that of the doping film close to the silicon substrate.
2. The heterojunction solar cell of claim 1, wherein the doped film is a doped amorphous silicon film, a doped amorphous silicon oxide film, a doped microcrystalline silicon film, or a doped microcrystalline silicon oxide film.
3. The heterojunction solar cell of claim 1, wherein the average doping concentration of the first doped layer is less than the average doping concentration of the second doped layer.
4. The heterojunction solar cell of claim 1, wherein the number of doped layers in the second doped layer is not greater than the number of doped layers in the first doped layer.
5. The heterojunction solar cell of claim 1, wherein the thickness of the first doped layer is less than or equal to the thickness of the second doped layer.
6. The heterojunction solar cell of any one of claims 1 to 5, wherein the doped film constituting the first doped layer is a phosphorus doped film, the phosphorus doped film comprises a first phosphorus doped film, a second phosphorus doped film and a third phosphorus doped film sequentially stacked and disposed outside the first intrinsic amorphous layer, and the phosphorus doping concentrations in the first phosphorus doped film, the second phosphorus doped film and the third phosphorus doped film are 50-150ppm, 100-300ppm and 200-400ppm, respectively.
7. The heterojunction solar cell of claim 6, wherein the thicknesses of the first, second and third phosphorus-doped films are 2-4nm, 1-3nm, respectively.
8. The heterojunction solar cell of any one of claims 1 to 5, wherein the doped film constituting the second doped layer is a boron doped film, the boron doped film comprises a first boron doped film, a second boron doped film and a third boron doped film sequentially stacked and disposed outside the second intrinsic amorphous layer, and boron doping concentrations in the first boron doped film, the second boron doped film and the third boron doped film are respectively 100-300ppm, 200-500ppm and 400-600 ppm.
9. The heterojunction solar cell of claim 8, wherein the thicknesses of the first, second and third boron-doped films are 2-5nm, 1-3nm, respectively.
10. The heterojunction solar cell according to any one of claims 1 to 5, wherein said first intrinsic amorphous layer and said second intrinsic amorphous layer respectively comprise at least two intrinsic films stacked one on top of the other, each of said intrinsic films being composed of one of intrinsic amorphous silicon film, intrinsic amorphous silicon oxide film and intrinsic amorphous silicon carbide film.
11. The heterojunction solar cell of claim 10, wherein one of the first and/or second intrinsic amorphous layers that is farthest from the silicon substrate is an intrinsic amorphous silicon oxide film.
12. The heterojunction solar cell of claim 10, wherein the number of intrinsic films in the second intrinsic amorphous layer is not greater than the number of intrinsic films in the first intrinsic amorphous layer.
13. The heterojunction solar cell of claim 10, wherein the hydrogen content of the intrinsic film closer to the silicon substrate is greater than the hydrogen content of the intrinsic film farther from the silicon substrate in two adjacent intrinsic films.
14. The heterojunction solar cell of claim 13, wherein the first intrinsic amorphous layer and the second intrinsic amorphous layer respectively comprise three layers of intrinsic films stacked one on top of the other, and the hydrogen content of the three layers of intrinsic films in the first intrinsic amorphous layer and the second intrinsic amorphous layer is in the range of 20% -40%, 10% -25% and 8% -20% in sequence from the inner intrinsic film to the outer intrinsic film.
15. The heterojunction solar cell of claim 14, wherein the intrinsic films of the three intrinsic films in the first intrinsic amorphous layer have thicknesses of 1-3nm, 2-4nm and 1-3nm in sequence, and the intrinsic films of the three intrinsic films in the second intrinsic amorphous layer have thicknesses of 1-5nm, 3-10nm and 0-5nm in sequence, in a direction from the inner intrinsic film to the outer intrinsic film.
16. A method for manufacturing a heterojunction solar cell comprises the following steps:
providing a silicon substrate;
sequentially forming a first intrinsic amorphous layer and a first doping layer on the light receiving surface of the silicon substrate;
sequentially forming a second intrinsic amorphous layer and a second doped layer on the backlight surface of the silicon substrate, wherein the doping type of the second doped layer is opposite to that of the first doped layer;
the method is characterized in that at least one of the first doped layer forming step and the second doped layer forming step comprises the step of sequentially forming at least two layers of doped films, and in two adjacent doped films which are sequentially formed, the doped concentration of the doped film far away from the silicon substrate is greater than that of the doped film close to the silicon substrate.
17. The method according to claim 16, wherein the first doped layer forming step comprises sequentially forming three phosphorus-doped films on the surface of the first intrinsic amorphous layer, and forming three phosphorus-doped films at PH in a direction away from the silicon substrate3/SiH4The flow rate ratio ranges are 50-150ppm, 100-300ppm and 200-400ppm in sequence.
18. Root of herbaceous plantThe method of claim 16, wherein the second doped layer forming step comprises sequentially forming three boron doped films on the surface of the second intrinsic amorphous layer, and forming B of the three boron doped films in a direction away from the silicon substrate2H6/SiH4The flow rate ratio ranges are 50-150ppm, 100-250ppm and 200-300ppm in sequence.
19. The method of any one of claims 16-18, wherein at least one of the first and second intrinsic amorphous layer forming steps comprises sequentially forming at least two intrinsic films, and wherein of two adjacent intrinsic films sequentially formed, the intrinsic film closer to the silicon substrate has a hydrogen content greater than the intrinsic film farther from the silicon substrate.
20. The method according to claim 19, wherein the first intrinsic amorphous layer forming step and the second intrinsic amorphous layer forming step each comprise sequentially forming three intrinsic films, and H is the H of the three intrinsic films of the first intrinsic amorphous layer and the second intrinsic amorphous layer from the inner intrinsic film toward the outer intrinsic film2/SiH4The flow ratio ranges are 0, 3-10 and 10-20 in sequence.
21. The method of fabricating a heterojunction solar cell according to claim 20, wherein in the step of forming the first intrinsic amorphous layer and the step of forming the second intrinsic amorphous layer, further comprising: after forming an intrinsic film, introducing pure H to the surface of the intrinsic film2Or H2Dilute SiH4Carrying out plasma treatment; among them, H2 diluted SiH4 is H2/SiH4The dilution ratio is greater than 100.
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