CN113921656A - Heterojunction solar cell and preparation method thereof - Google Patents
Heterojunction solar cell and preparation method thereof Download PDFInfo
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- CN113921656A CN113921656A CN202111168807.2A CN202111168807A CN113921656A CN 113921656 A CN113921656 A CN 113921656A CN 202111168807 A CN202111168807 A CN 202111168807A CN 113921656 A CN113921656 A CN 113921656A
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 92
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- 239000000758 substrate Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 59
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
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- 238000002834 transmittance Methods 0.000 claims description 18
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- 239000000377 silicon dioxide Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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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
-
- 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
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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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
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
- H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
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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
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
- H01L31/1888—Manufacture of transparent electrodes, e.g. TCO, ITO methods for etching transparent electrodes
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a heterojunction solar cell and a preparation method thereof, wherein the heterojunction solar cell comprises: the first transparent conductive film is positioned on one side of the semiconductor substrate layer, and the material of the first transparent conductive film comprises doped zinc oxide; the first grid lines are positioned on the surface of one side, away from the semiconductor substrate layer, of part of the first transparent conductive film, and a plurality of the first grid lines are arranged at intervals; and the protective film is positioned on the surface of one side of part of the first transparent conductive film, which is far away from the semiconductor substrate layer, is arranged adjacent to the first grid line and at least shields part of the side wall of the first grid line. The first transparent conductive film of the heterojunction solar cell is made of doped zinc oxide, so that the use of rare and toxic materials containing indium is reduced, the optical performance is ensured, the cost of the heterojunction solar cell is reduced, and the environmental protection is facilitated; and the protection film can prevent that first transparent conductive film from receiving the steam influence, improves first transparent conductive film's stability.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a heterojunction solar cell and a preparation method thereof.
Background
Solar cells are devices that convert solar energy directly into electrical energy based on the photovoltaic effect. At present, crystalline silicon solar cells are the mainstream of the photovoltaic industry and occupy more than 80% of the market. The HeteroJunction (HJT) cell is an important solar cell, the HeteroJunction structure is centered on an N-type crystalline silicon substrate, a P-type amorphous silicon layer and an N-type amorphous silicon layer are arranged on two sides of the N-type crystalline silicon substrate, the HeteroJunction structure has excellent photoelectric characteristics that respective PN junctions of two semiconductors cannot reach, and the use of the HeteroJunction structure for preparing the cell is a solar cell technology with market competitiveness.
The solar cell generally further comprises a transparent conductive film for collecting carriers, and the transparent conductive film is required to have high light transmittance, low resistivity, low contact resistance, good stability and suitable performance for large-scale mass production, but in the prior art, the transparent conductive films on two sides of the substrate of the heterojunction solar cell are made of expensive indium-containing materials, so that the production cost is high, and a toxic environment may be generated. If the material of the transparent conductive film is changed, a series of problems such as deterioration of the stability of the transparent conductive film may occur. In order to achieve the synergistic effect and cost reduction, the structure of the transparent conductive film provided in the prior art needs to be improved.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the transparent conductive film of the heterojunction solar cell is poor in stability and high in cost, and therefore the heterojunction solar cell and the preparation method thereof are provided.
In one aspect, the present invention provides a heterojunction solar cell comprising: a semiconductor substrate layer; the first transparent conductive film is positioned on one side of the semiconductor substrate layer, and the material of the first transparent conductive film comprises doped zinc oxide; the first grid lines are positioned on the surface of one side, away from the semiconductor substrate layer, of part of the first transparent conductive film, and a plurality of the first grid lines are arranged at intervals; and the protective film is positioned on the surface of one side of part of the first transparent conductive film, which is far away from the semiconductor substrate layer, is arranged adjacent to the first grid line and at least shields part of the side wall of the first grid line.
Optionally, the doped zinc oxide comprises aluminum-doped zinc oxide or gallium-doped zinc oxide.
Optionally, the mass doping concentration of the first transparent conductive film is 1% to 3%; .
Optionally, the thickness of the first transparent conductive film is 50nm to 300 nm.
Optionally, the resistivity of the first transparent conductive film is 1 × 10-4Ω·cm～10×10-4Ω·cm。
Optionally, the carrier mobility of the first transparent conductive film is 20cm2/Vs～50cm2/Vs。
Optionally, the transmittance of the first transparent conductive film is greater than or equal to 88%.
Optionally, the first transparent conductive film is a back transparent conductive film.
Optionally, the material of the protective film includes silicon dioxide.
Optionally, the thickness of the protective film is 2nm to 30 nm.
Optionally, the transmittance of the protective film is greater than or equal to 90%.
Optionally, the method further includes: and the second transparent conductive film is positioned on the side, away from the first transparent conductive film, of the semiconductor substrate layer, and the material of the second transparent conductive film comprises indium oxide.
Optionally, the indium oxide includes tin-doped indium oxide, tungsten-doped indium oxide, or molybdenum-doped indium oxide.
Optionally, the mass doping concentration of the indium oxide is 3% to 10%.
Optionally, the thickness of the second transparent conductive film is 50nm to 120 nm.
Optionally, the resistivity of the second transparent conductive film is 1 × 10-4Ω·cm～10×10-4Ω·cm。
Optionally, the mobility of the second transparent conductive film is 20cm2/Vs～100cm2/Vs。
Optionally, the transmittance of the second transparent conductive film is greater than or equal to 95%.
Optionally, the second transparent conductive film is a front transparent conductive film.
Optionally, the method further includes: a first semiconductor doping layer located between the first transparent conductive film and the semiconductor substrate layer; a first intrinsic semiconductor layer located between the first semiconductor doped layer and the semiconductor substrate layer; a second semiconductor doping layer located between the second transparent conductive film and the semiconductor substrate layer; a second intrinsic semiconductor layer located between the second semiconductor doped layer and the semiconductor substrate layer.
On the other hand, the invention also provides a preparation method of the heterojunction solar cell, which comprises the following steps: providing a semiconductor substrate layer; further comprising the steps of: forming a first transparent conductive film on one side of the semiconductor substrate layer, wherein the first transparent conductive film is made of doped zinc oxide; forming a protective film on the surface of one side, away from the semiconductor substrate layer, of a part of the first transparent conductive film, wherein the protective film exposes a part of the first transparent conductive film; and forming first grid lines on the surface of the part of the first transparent conductive film exposed by the protective film, wherein a plurality of first grid lines are arranged at intervals, and the protective film is arranged adjacent to the first grid lines and at least shields part of side walls of the first grid lines.
Optionally, forming the first transparent conductive film by using a physical vapor deposition process; the technological parameters for forming the first transparent conductive film comprise: the target material is an aluminum-zinc alloy target material or a gallium-zinc alloy target material, and the mass of aluminum in the aluminum-zinc alloy target materialThe doping concentration is 1 to 3 percent, the mass doping concentration of gallium in the gallium-zinc alloy target material is 1 to 3 percent, and the power density is 3kW/m2～15kW/m2The pressure of the chamber is 0.2 Pa-0.6 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.005: 1-0.02: 1.
optionally, the growth rate of the first transparent conductive film in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20 nm/s.
Optionally, the step of forming the protective film includes: forming a protective material layer on the surface of one side, away from the semiconductor substrate layer, of a part of the first transparent conductive film; and removing part of the protective material layer until part of the first transparent conductive film is exposed, so that the protective material layer forms the protective film.
Optionally, forming the protective material layer by using a physical vapor deposition process; the technological parameters for forming the protective material layer comprise: the target material comprises a silicon dioxide target material with the power density of 0.5kW/m2～5kW/m2The pressure of the chamber is 0.2 Pa-0.6 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.01: 1-0.2: 1.
optionally, the growth rate of the protective material layer in the direction perpendicular to the surface of the semiconductor substrate layer is 0.5nm/s to 10 nm/s.
Optionally, the process of etching a part of the protective material layer includes a screen printing etching process or a laser etching process.
Optionally, the etching ink adopted by the screen printing etching process includes sodium hydroxide or hydrofluoric acid.
Optionally, the method further includes: and forming a second transparent conductive film on the side of the semiconductor substrate layer, which is far away from the first transparent conductive film, wherein the material of the second transparent conductive film comprises indium oxide.
Optionally, forming the second transparent conductive film by using a physical vapor deposition process; the process parameters for forming the second transparent conductive film comprise: the target material adopts a tin-doped indium oxide target material, a tungsten-doped indium oxide target material or a molybdenum-doped indium oxide target material, and is doped with ionsThe concentration is 3 to 10 percent, and the power density is 3kW/m2～15kW/m2The pressure of the chamber is 0.3 Pa-1 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.005: 1-0.05: 1.
optionally, the film growth rate of the second transparent conductive film in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20 nm/s.
The technical scheme of the invention has the following beneficial effects:
1. according to the heterojunction solar cell provided by the invention, the material of the first transparent conductive film of the heterojunction solar cell comprises doped zinc oxide, and the use of rare and toxic material containing indium is reduced, so that the optical performance can be ensured, the cost of the heterojunction solar cell is reduced, and the environmental protection is facilitated; and the protection film can prevent that first transparent conductive film from receiving the steam influence, improves first transparent conductive film's stability.
2. Furthermore, the material of the protective film comprises silicon dioxide, and the silicon dioxide has good compactness and can prevent water vapor from invading the first transparent conductive film, and has certain light transmittance to meet the incidence of first sunlight.
3. According to the preparation method of the heterojunction solar cell, the material of the first transparent conductive film of the heterojunction solar cell comprises the doped zinc oxide, the use of rare and toxic materials containing indium is reduced, the cost of the heterojunction solar cell is reduced, and the environmental protection is facilitated; and the protection film can prevent that first transparent conductive film from receiving the steam influence, improves first transparent conductive film's stability.
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 description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a heterojunction solar cell according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for manufacturing a heterojunction solar cell according to an embodiment of the present invention.
Reference numerals:
1-a semiconductor substrate layer; 2-a first transparent conductive film; 3-a first gate line; 4-protective film; 5-a first semiconductor doped layer; 6-a first intrinsic semiconductor layer; 7-a second semiconductor doped layer; 8-a second intrinsic semiconductor layer; 9-a second gate line; 10-a second transparent conductive film.
Detailed Description
In the indium tin oxide transparent conductive film provided by the prior art, because indium in the indium tin oxide is a rare metal, the preparation cost of the transparent conductive film is high, and the indium has toxicity and is not beneficial to environmental protection.
The search for alternatives to indium tin oxide must meet the requirements of light conversion efficiency on the one hand and other requirements of electrical properties and structural stability on the other hand. At present, the photovoltaic industry has started many attempts to research and transform new materials, but none of them has obtained a better choice that can simultaneously achieve optical performance, structural stability and economy.
On the basis, the invention provides the heterojunction solar cell and the preparation method thereof, so that the stability of the back transparent conductive film is improved on the basis of ensuring the optical performance, and the cost is lower.
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; the two elements may be directly connected or indirectly connected through an intermediate medium, or may be communicated with each other inside the two elements, or may be wirelessly connected or wired connected. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The present embodiment provides a heterojunction solar cell, please refer to fig. 1, which includes:
a semiconductor substrate layer 1;
the first transparent conductive film 2 is positioned on one side of the semiconductor substrate layer 1, and the material of the first transparent conductive film 2 comprises doped zinc oxide;
the first grid lines 3 are positioned on the surface of one side, away from the semiconductor substrate layer 1, of a part of the first transparent conductive film 2, and a plurality of the first grid lines 3 are arranged at intervals;
and the protective film 4 is positioned on the surface of one side, away from the semiconductor substrate layer 1, of a part of the first transparent conductive film 2, and the protective film 4 is arranged adjacent to the first grid line 3 and at least shields a part of the side wall of the first grid line 3.
The semiconductor substrate layer 1 includes a silicon substrate, for example, an N-type crystalline silicon substrate.
The first grid lines 3 comprise silver grid lines.
In one embodiment, a plurality of the first gate lines 3 are arranged in parallel at intervals.
In one embodiment, the first transparent conductive film 2 is a backside transparent conductive film.
The doped zinc oxide comprises aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO).
The first transparent conductive film 2 has a mass doping concentration of 1% to 3%, for example, 1%, 1.5%, or 2%.
The thickness of the first transparent conductive film 2 is 50nm to 300nm, for example, 50nm, 100nm, 150nm, 200nm, 250nm, or 300 nm. The thickness of the first transparent conductive film 2 is thick, and the resistance of the first transparent conductive film 2 can be reduced, so that the number of the first gate lines 3 can be reduced, the use of silver materials can be reduced by reducing the first gate lines 3, and the cost can be reduced to a certain extent.
The first transparent conductive film 2 has a resistivity of 1 × 10-4Ω·cm～10×10-4Ω · cm, e.g. 1X 10-4Ω·cm、3×10-4Ω·cm、5×10-4Ω·cm、7×10-4Ω·cm、9×10-4Omega cm or 10X 10-4Ω·cm。
The first transparent conductive film 2 has a carrier mobility of 20cm2/Vs～50cm2Vs, e.g. 20cm2/Vs、30cm2/Vs、40cm2Vs or 50cm2/Vs。
The first transparent conductive film has a transmittance of 88% or more, for example, 88%, 90%, 92%, 95%, or 98%. The transmittance of the first transparent conductive film is larger than or equal to 88%, so that when sunlight irradiates the heterojunction solar cell, sufficient sunlight enters the semiconductor substrate layer 1 to generate enough photon-generated carriers, and the loss of the sunlight entering the heterojunction solar cell from the backlight surface can be reduced.
The material of the protective film 4 comprises silicon dioxide, the silicon dioxide has good compactness and can prevent water vapor from invading the first transparent conductive film 2, and certain light transmittance can meet the incidence of the reflected back sunlight.
The thickness of the protective film 4 is 5nm to 30nm, for example, 5nm, 10nm, 15nm, 20nm, 25nm, or 30 nm. In this embodiment, the thickness of the protective film 4 is smaller than that of the first gate line 3, that is, the protective film 4 is disposed adjacent to the first gate line 3 and at least shields a part of the sidewall surface of the first gate line 3. The thickness of the protective film 4 and the thickness of the first gate line 3 both refer to the dimension in the direction perpendicular to the surface of the semiconductor substrate layer 1. The thickness of protection film 4 is less than first grid line 3, does benefit to protection film 4 and has high transmissivity, and secondly, the thickness more than or equal to 5nm of protection film 4 makes protection film 4 can effectual prevention steam invasion first transparent conductive film 2 like this.
The protective film 4 has a transmittance of 90% or more, for example, 90%, 92%, or 95%.
That is, in the present embodiment, the back surface adopts a ZnO-based transparent conductive film composite structure, such as (AZO, GZO)/SiO2The structure is adopted, so that the film material with high transmittance, low resistance, good stability and low raw material cost is provided.
The heterojunction solar cell further comprises: and a second transparent conductive film 10 located on a side of the semiconductor substrate layer 1 away from the first transparent conductive film 2, wherein the material of the second transparent conductive film 10 includes an indium oxide.
The indium oxide includes tin-doped indium oxide, tungsten-doped indium oxide, or molybdenum-doped indium oxide.
In one embodiment, the second transparent conductive film 10 is a front transparent conductive film.
In one embodiment, the indium-based oxide has a mass doping concentration of 3% to 10%, such as 3%, 5%, 7%, or 10%.
In one embodiment, the thickness of the second transparent conductive film 10 is 50nm to 120nm, for example, 50nm, 70nm, 90nm, 110nm, or 120 nm.
In one embodiment, the second transparent conductive film 10 has a resistivity of 1 × 10-4Ω·cm～10×10-4Ω · cm, e.g. 1X 10-4Ω·cm、3×10-4Ω·cm、5×10-4Ω·cm、7×10-4Ω·cm、9×10-4Omega cm or 10X 10-4Ω·cm。
In one embodiment, the second transparent conductive film 10 has a mobility of 20cm2/Vs～100cm2Vs, e.g. 20cm2/Vs、30cm2/Vs、40cm2/Vs、60cm2/Vs、80cm2Vs or 100cm2/Vs。
In one embodiment, the second transparent conductive film 10 has a transmittance greater than or equal to 95%, such as 95%, 96%, 97%, 98%, or 99%.
The heterojunction solar cell further comprises: a first semiconductor doping layer 5 located between the first transparent conductive film 2 and the semiconductor substrate layer 1; a first intrinsic semiconductor layer 6 located between said first doped semiconductor layer 5 and said semiconductor substrate layer 1; a second semiconductor doping layer 7 located between the second transparent conductive film 10 and the semiconductor substrate layer 1; a second intrinsic semiconductor layer 8 located between the second semiconductor doping layer 7 and the semiconductor substrate layer 1; and the second grid line 9 is positioned on the surface of one side, away from the semiconductor substrate layer 1, of the second transparent conductive film 10.
According to the heterojunction solar cell provided by the embodiment, the material of the first transparent conductive film 2 of the heterojunction solar cell comprises doped zinc oxide, and the use of rare and toxic material containing indium is reduced, so that the optical performance can be ensured, the cost of the heterojunction solar cell is reduced, and the environmental protection is facilitated; and the protective film 4 can prevent the first transparent conductive film 2 from being affected by moisture, and improve the stability of the first transparent conductive film 2.
Example 2
The present embodiment provides a method for manufacturing a heterojunction solar cell, please refer to fig. 2, which includes the following steps:
s1, providing a semiconductor substrate layer 1;
s2, forming a first transparent conductive film 2 on one side of the semiconductor substrate layer 1, wherein the material of the first transparent conductive film 2 comprises doped zinc oxide;
s3, forming a protective film 4 on the surface of one side, away from the semiconductor substrate layer 1, of a part of the first transparent conductive film 2, wherein the protective film 4 exposes a part of the first transparent conductive film 2;
and S4, forming first grid lines on the surface of the part of the first transparent conductive film 2 exposed by the protective film 4, wherein a plurality of the first grid lines are arranged at intervals, and the protective film is arranged adjacent to the first grid lines and at least shields partial side walls of the first grid lines.
In this embodiment, the method further includes: forming a first intrinsic semiconductor layer 6 on one side surface of the semiconductor substrate layer 1; forming a second intrinsic semiconductor layer 8 on the other side surface of the semiconductor substrate layer 1; forming a first semiconductor doping layer 5 on the surface of one side, away from the semiconductor substrate layer 1, of the first intrinsic semiconductor layer 6; a second semiconductor doping layer 7 is formed on the surface of the second intrinsic semiconductor layer 8 on the side facing away from the semiconductor substrate layer 1. After the first semiconductor doping layer 5 is formed, the first transparent conductive film 2 is formed.
In this embodiment, the first transparent conductive film 2 is formed by a physical vapor deposition process.
The process parameters for forming the first transparent conductive film 2 include: the target material is an aluminum-zinc alloy target material or a gallium-zinc alloy target material, the mass doping concentration of aluminum in the aluminum-zinc alloy target material is 1% -3%, for example, 1%, 2% or 3%, if the doping concentration is too low, the resistance of the film layer is increased, and if the doping concentration is too high, the light transmittance of the film layer is reduced. The mass doping concentration of gallium in the gallium-zinc alloy target material is 1% -3%, for example, 1%, 2% or 3%; the power density is 3kW/m2～15kW/m2For example, 3kW/m2、5kW/m2、7kW/m2、9kW/m2、11kW/m2、13kW/m2Or 15kW/m2If the power density is too low, the deposition process cannot reach the glow starting condition, and if the power density is too high, the temperature rise of the deposition chamber is higher, the target material is easy to crack, and meanwhile, the requirement on cooling is higher; the chamber pressure is 0.2Pa to 0.6Pa, e.g., 0.2Pa, 0.4Pa, 0.5Pa, or 0.6 Pa; if the pressure is too low, the glow instability will result, and if the pressure is too highHigh results in increased sheet resistance. The chamber has oxygen and argon in a flow ratio of 0.005: 1-0.02: 1, if the flow rate of oxygen is too low, the flow rate is not easy to control, and if the flow rate of oxygen is too high, the resistance is increased. For example, 0.005: 1. 0.01: 1. 0.015: 1. 0.017 by weight: 1. 0.019: 1 or 0.02: 1, the temperature of the chamber is 25-250 ℃.
The growth rate of the first transparent conductive film 2 in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20nm/s, for example, 3nm/s, 5nm/s, 7nm/s, 9nm/s, 11nm/s, 13nm/s, 15nm/s, 17nm/s, 19nm/s or 20nm/s, and if the growth rate is too low or too high, it is not favorable for forming a uniform and dense film structure.
In a specific embodiment, the process parameters for forming the first transparent conductive film 2 are: the chamber temperature is 100 ℃, the flow rate of argon is 1000sccm, the flow rate of oxygen is 10sccm, the chamber pressure is 0.4Pa, and the power density is 5kW/m2. The first transparent conductive film 2 was formed to have a thickness of 70 nm.
The step of forming the protective film 4 includes: forming a protective material layer on the surface of a part of the first transparent conductive film 2, which is away from the semiconductor substrate layer 1, wherein the thickness of the protective material layer is 2 nm-30 nm, such as 5nm, 10nm, 15nm, 20nm, 25nm or 30 nm; and removing part of the protective material layer until part of the first transparent conductive film 2 is exposed, so that the protective material layer forms the protective film, and the thickness of the protective film is 2 nm-30 nm.
In this embodiment, the protective material layer is formed by a physical vapor deposition process.
The technological parameters for forming the protective material layer comprise: the target material comprises a silicon dioxide target material with the power density of 0.5kW/m2～5kW/m2For example, 0.5kW/m2、1kW/m2、2kW/m2、3kW/m2、4kW/m2Or 5kW/m2If the power density is too low, the deposition process cannot reach the glow starting condition, and if the power density is too high, the temperature rise of the deposition chamber is higher, the target material is easy to crack, and meanwhile, the requirement on cooling is higher; pressure of the chamberThe intensity is 0.2Pa to 0.6Pa, for example, 0.2Pa, 0.4Pa, 0.5Pa or 0.6Pa, if the pressure is too low, the glow is unstable, and if the pressure is too high, the sheet resistance is increased; the flow ratio of oxygen to argon in the chamber was 0.01: 1-0.2: 1, for example, 0.01: 1. 0.03: 1. 0.05: 1. 0.1: 1. 0.15: 1 or 0.2: 1, if the flow of oxygen is too low, the flow is not easy to control, and if the flow of oxygen is too high, the resistance is increased; the temperature of the chamber is 25-100 ℃.
The growth rate of the protective material layer is 0.5nm/s to 10nm/s, for example, 0.5nm/s, 1nm/s, 3nm/s, 5nm/s, 7nm/s, 9nm/s, or 10 nm/s.
In a specific embodiment, the process parameters for forming the protective material layer are as follows: the chamber temperature is 100 ℃, the flow rate of argon is 800sccm, the flow rate of oxygen is 80sccm, the chamber pressure is 0.3Pa, and the power density is 1kW/m2. The thickness of the formed protective material layer was 20 nm.
The process for removing part of the protective material layer comprises a screen printing corrosion process or a laser etching process. Specifically, the etching ink adopted by the screen printing corrosion process comprises sodium hydroxide or hydrofluoric acid; after the protective material layer is formed, a layer of etching ink is printed at the position where the first grid line 3 needs to be arranged, and the etching ink corrodes the protective material layer to enable the protective material layer to form a protective film 4. Or, the position of the protective material layer where the first gate line 3 needs to be arranged is etched through a laser etching process so that the protective material layer forms the protective film 4.
The preparation method of the heterojunction solar cell further comprises the following steps: a second transparent conductive film 10 is formed on a side of the semiconductor substrate layer 1 away from the first transparent conductive film 2, and a material of the second transparent conductive film 10 includes an indium oxide.
In this embodiment, the second transparent conductive film 10 is formed by a physical vapor deposition process.
The process parameters for forming the second transparent conductive film 10 include: the target material is tin-doped indium oxide target material, tungsten-doped indium oxide target material or molybdenum-doped indium oxide target material, and the concentration of doped ions in the target material is 3-10%, for example, 3%, 5%,7%, 9% or 10%, if the doping concentration is too low, the resistance of the film layer is increased, and if the doping concentration is too high, the light transmittance of the film layer is reduced; the power density is 3kW/m2～15kW/m2For example, 3kW/m2、5kW/m2、7kW/m2、9kW/m2、11kW/m2、13kW/m2Or 15kW/m2If the power density is too low, the deposition process cannot reach the glow starting condition, and if the power density is too high, the temperature rise of the deposition chamber is higher, the target material is easy to crack, and meanwhile, the requirement on cooling is higher; the chamber pressure is 0.3Pa to 1Pa, for example, 0.3Pa, 0.5Pa, 0.7Pa, 0.9Pa or 1Pa, if the pressure is too low, the glow instability is caused, and if the pressure is too high, the sheet resistance is increased; the chamber has oxygen and argon in a flow ratio of 0.005: 1-0.05: 1, for example, 0.005: 1. 0.01: 1. 0.02: 1. 0.03: 1. 0.04: 1 or 0.05: 1, if the flow of oxygen is too low, the flow is not easy to control, and if the flow of oxygen is too high, the resistance is increased; the temperature of the chamber is 25-250 ℃.
The film growth rate of the second transparent conductive film 10 in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20nm/s, for example, 3nm/s, 5nm/s, 7nm/s, 9nm/s, 11nm/s, 13nm/s, 15nm/s, 17nm/s, 19nm/s, or 20 nm/s.
In a specific embodiment, the process parameters for forming the second transparent conductive film 10 are: the chamber temperature is 100 ℃, the flow rate of argon is 1500sccm, the flow rate of oxygen is 30sccm, the chamber pressure is 0.7Pa, and the power density is 5kW/m2. The thickness of the second transparent conductive film 10 was 90 nm.
And finally, using a four-probe tester, a spectrophotometer and a Hall tester to respectively test the sheet resistance, the transmittance, the carrier concentration and the mobility of the first transparent conductive film 2.
Through the tests of the inventor of the application, the battery obtained by adopting the preparation method of the heterojunction solar cell has the square resistance of 5-200 omega-sq of the first transparent conductive film 2 and the resistivity of 1 multiplied by 10-4Ω·cm～10×10-4Omega cm, loadMobility of the flow is 20cm2/Vs～80cm2Vs, transmittance of sunlight having a wavelength of 300nm to 1100nm of not less than 88%. That is, the first transparent conductive film 2 according to the present embodiment has performance equivalent to that of the conventional transparent conductive film.
According to the preparation method of the heterojunction solar cell provided by the embodiment, the material of the first transparent conductive film 2 of the heterojunction solar cell comprises doped zinc oxide, and the use of rare and toxic materials containing indium is reduced, so that the optical performance can be ensured, the cost of the heterojunction solar cell is reduced, and the environmental protection is facilitated; and the protective film 4 can prevent the first transparent conductive film 2 from being affected by moisture, and improve the stability of the first transparent conductive film 2.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A heterojunction solar cell, comprising:
a semiconductor substrate layer;
the first transparent conductive film is positioned on one side of the semiconductor substrate layer, and the material of the first transparent conductive film comprises doped zinc oxide;
the first grid lines are positioned on the surface of one side, away from the semiconductor substrate layer, of part of the first transparent conductive film, and a plurality of the first grid lines are arranged at intervals;
and the protective film is positioned on the surface of one side of part of the first transparent conductive film, which is far away from the semiconductor substrate layer, is arranged adjacent to the first grid line and at least shields part of the side wall of the first grid line.
2. The heterojunction solar cell of claim 1, wherein the doped zinc oxide comprises aluminum-doped zinc oxide or gallium-doped zinc oxide;
preferably, the mass doping concentration of the first transparent conductive film is 1-3%;
preferably, the thickness of the first transparent conductive film is 50nm to 300 nm;
preferably, the first transparent conductive film has a resistivity of 1 × 10-4Ω·cm～10×10-4Ω·cm；
Preferably, the first transparent conductive film has a carrier mobility of 20cm2/Vs～50cm2/Vs；
Preferably, the transmittance of the first transparent conductive film is greater than or equal to 88%;
preferably, the first transparent conductive film is a back transparent conductive film.
3. The heterojunction solar cell of claim 1, wherein the material of the protective film comprises silicon dioxide;
preferably, the thickness of the protective film is 2nm to 30 nm;
preferably, the protective film has a transmittance of 90% or more.
4. The heterojunction solar cell of any of claims 1-3, further comprising: the second transparent conductive film is positioned on one side, away from the first transparent conductive film, of the semiconductor substrate layer, and the material of the second transparent conductive film comprises indium oxide;
preferably, the indium oxide includes tin-doped indium oxide, tungsten-doped indium oxide, or molybdenum-doped indium oxide;
preferably, the mass doping concentration of the indium oxide is 3 to 10 percent;
preferably, the thickness of the second transparent conductive film is 50nm to 120 nm;
preferably, the second transparent conductive film has a resistivity of 1 × 10-4Ω·cm～10×10-4Ω·cm；
Preferably, the second transparent layerThe mobility of the conductive film was 20cm2/Vs～100cm2/Vs；
Preferably, the transmittance of the second transparent conductive film is greater than or equal to 95%;
preferably, the second transparent conductive film is a front transparent conductive film.
5. The heterojunction solar cell of claim 4, further comprising: a first semiconductor doping layer located between the first transparent conductive film and the semiconductor substrate layer; a first intrinsic semiconductor layer located between the first semiconductor doped layer and the semiconductor substrate layer; a second semiconductor doping layer located between the second transparent conductive film and the semiconductor substrate layer; a second intrinsic semiconductor layer located between the second semiconductor doped layer and the semiconductor substrate layer.
6. A method of fabricating a heterojunction solar cell, comprising the steps of: providing a semiconductor substrate layer; it is characterized by also comprising the following steps:
forming a first transparent conductive film on one side of the semiconductor substrate layer, wherein the material of the first transparent conductive film comprises doped zinc oxide;
forming a protective film on the surface of one side, away from the semiconductor substrate layer, of a part of the first transparent conductive film, wherein the protective film exposes a part of the first transparent conductive film;
and forming first grid lines on the surface of the part of the first transparent conductive film exposed by the protective film, wherein a plurality of first grid lines are arranged at intervals, and the protective film is arranged adjacent to the first grid lines and at least shields part of side walls of the first grid lines.
7. The method of claim 6, wherein the first transparent conductive film is formed using a physical vapor deposition process;
the technological parameters for forming the first transparent conductive film comprise: the target material is an aluminum-zinc alloy target material or a gallium-zinc alloy target materialThe mass doping concentration of aluminum in the aluminum-zinc alloy target material is 1-3%, the mass doping concentration of gallium in the gallium-zinc alloy target material is 1-3%, and the power density is 3kW/m2～15kW/m2The pressure of the chamber is 0.2 Pa-0.6 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.005: 1-0.02: 1;
preferably, the growth rate of the first transparent conductive film in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20 nm/s.
8. The method of fabricating a heterojunction solar cell of claim 6, wherein the step of forming the protective film comprises: forming a protective material layer on the surface of one side, away from the semiconductor substrate layer, of a part of the first transparent conductive film; removing part of the protective material layer until part of the first transparent conductive film is exposed, so that the protective material layer forms the protective film;
preferably, the protective material layer is formed by adopting a physical vapor deposition process;
the technological parameters for forming the protective material layer comprise: the target material comprises a silicon dioxide target material with the power density of 0.5kW/m2～5kW/m2The pressure of the chamber is 0.2 Pa-0.6 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.01: 1-0.2: 1;
preferably, the growth rate of the protective material layer in the direction vertical to the surface of the semiconductor substrate layer is 0.5 nm/s-10 nm/s.
9. The method of claim 8, wherein the etching of the protective material layer comprises screen printing or laser etching;
preferably, the etching ink adopted by the screen printing etching process comprises sodium hydroxide or hydrofluoric acid.
10. The method of fabricating a heterojunction solar cell of claim 6, further comprising: forming a second transparent conductive film on the side, away from the first transparent conductive film, of the semiconductor substrate layer, wherein the material of the second transparent conductive film comprises indium oxide;
preferably, the second transparent conductive film is formed by a physical vapor deposition process;
the process parameters for forming the second transparent conductive film comprise: the target material is a tin-doped indium oxide target material, a tungsten-doped indium oxide target material or a molybdenum-doped indium oxide target material, the concentration of doped ions in the target material is 3-10%, and the power density is 3kW/m2～15kW/m2The pressure of the chamber is 0.3 Pa-1 Pa, oxygen and argon are contained in the chamber, and the flow ratio of the oxygen to the argon is 0.005: 1-0.05: 1;
preferably, the growth rate of the second transparent conductive film in the direction perpendicular to the surface of the semiconductor substrate layer is 3nm/s to 20 nm/s.
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