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CN112186062B - Solar cell and manufacturing method thereof - Google Patents

Solar cell and manufacturing method thereof Download PDF

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Publication number
CN112186062B
CN112186062B CN202010955234.7A CN202010955234A CN112186062B CN 112186062 B CN112186062 B CN 112186062B CN 202010955234 A CN202010955234 A CN 202010955234A CN 112186062 B CN112186062 B CN 112186062B
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transparent conductive
conductive film
atoms
doped
solar cell
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CN112186062A (en
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徐琛
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Longi Green Energy Technology Co Ltd
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Longi Green Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/17—Photovoltaic cells having only PIN junction potential barriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • 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
    • C23C14/3457—Sputtering using other particles than noble gas ions
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    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/24—Deposition of silicon only
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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers
    • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
    • H—ELECTRICITY
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    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/244—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers
    • H10F77/251—Electrodes made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers comprising zinc oxide [ZnO]
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a solar cell and a manufacturing method thereof, relates to the technical field of photovoltaics, and aims to reduce the contact resistance between a transparent conducting layer and a negative electrode end of the solar cell and improve the conductivity. The solar cell comprises a cell piece with a positive electrode end and a negative electrode end, and a transparent conducting layer formed at the negative electrode end of the cell piece; the transparent conductive layer comprises a first transparent conductive film and a second transparent conductive film; the first transparent conductive film and the second transparent conductive film are laminated along the direction far away from the negative electrode end of the battery piece; the first transparent conductive film contains ZnO doped with H atoms. The manufacturing method provided by the invention is used for manufacturing the solar cell.

Description

Solar cell and manufacturing method thereof
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a solar cell and a manufacturing method thereof.
Background
Clean energy is one of effective ways to solve the problems of energy shortage and environmental pollution, and photovoltaic power generation is an important component of clean energy and is receiving much attention. In recent years, solar cell technology has rapidly developed.
Most of the existing solar cells adopt doped indium oxide from the flat panel display (FDP) industry as a transparent conductive layer (TCO) material. The doped indium oxide is typically In 2 O 3 And SnO 2 Mixture of (1), in 2 O 3 And SnO 2 Is generally 90:10. Because the work function of the doped indium oxide is higher, when the doped indium oxide is contacted with the cathode end of the cell, the contact resistance is larger, the conductivity is poorer, and the conversion efficiency of the solar cell is influenced.
Disclosure of Invention
The invention aims to provide a solar cell, which aims to reduce the contact resistance between a transparent conductive layer and a negative electrode end of the solar cell and improve the conductivity.
In a first aspect, the present invention provides a solar cell. The solar cell comprises a cell piece with a positive electrode end and a negative electrode end, and a transparent conducting layer formed at the negative electrode end of the cell piece; the transparent conductive layer comprises a first transparent conductive film and a second transparent conductive film; the first transparent conductive film and the second transparent conductive film are laminated along the direction far away from the negative electrode end of the battery piece; the first transparent conductive film contains ZnO doped with H atoms.
When the technical scheme is adopted, the transparent conducting layer at the negative electrode end of the battery piece comprises the first transparent conducting film and the second transparent conducting film, and the first transparent conducting film and the second transparent conducting film are stacked along the direction far away from the negative electrode end of the battery piece. At this time, the first transparent conductive film is in contact with the negative electrode end of the cell piece, and the first transparent conductive film contains ZnO doped with H atoms. On one hand, the ZnO-doped work function is 4.35 eV-4.45 eV, and is low in work function, so that the contact potential difference between the first transparent conductive film and the negative electrode end of the cell can be reduced, and the contact resistance between the first transparent conductive film and the negative electrode end of the cell is low. On the other hand, the ZnO is doped with H atoms, so that the crystal boundary defects of the ZnO film can be passivated, and lattice scattering is reduced, so that the carrier mobility in ZnO is improved, and the conductivity of the first transparent conductive film is improved. Further, H atoms serve as shallow donors, and when doping is performed in a small amount, the carrier concentration in ZnO can be increased, and the conductivity of the first transparent conductive film can be improved. Therefore, the solar cell provided by the invention can reduce the contact resistance between the transparent conductive layer and the cathode end of the cell piece, and improve the open-circuit voltage of the solar cell; and the conductivity of the transparent conductive layer can be improved, so that the filling factor and the conversion efficiency of the solar cell are improved.
In some possible implementations, the doping concentration of H atoms in the H atom-doped ZnO is 10 19 cm -3 ～10 20 cm -3 . At this time, the doping concentration of H atoms is low, and an increase in ionized impurity scattering centers introduced by doping can be reduced, thereby improving carrier mobility and conductivity in the first transparent conductive film. And the doping concentration of the H atoms is low, so that the over-high concentration of carriers in ZnO can be avoided, the absorption of the carriers to photons is reduced, and the light transmittance of the first transparent conductive film is improved.
In some possible implementations, the H atom-doped ZnO is n-type H atom-doped ZnO. At this time, the conductivity of ZnO can be finely adjusted by adjusting the concentration of n-type impurity atoms.
In some possible implementations, in the H atom-doped ZnO, znO may be a material doped with n-type impurity atoms, where the n-type impurity atoms are group iiia atoms, and the group iiia atoms include one or more of B, al, ga, and In.
In some possible implementations, the doping concentration of the n-type impurity atoms in the H atom-doped ZnO is 10 19 cm -3 ～10 20 cm -3 . At this time, the doping concentration of the n-type impurity atoms is low, so that the carrier concentration can be properly increased, the increase of ionized impurity scattering centers introduced by doping can be reduced, and the carrier mobility and the conductivity in ZnO can be improved. And the doping concentration is low, so that the over-high concentration of the current carriers can be avoided, the absorption of the current carriers to photons is reduced, and the light transmittance of the first transparent conductive film is improved.
In some possible implementations, the second transparent conductive film includes a transparent conductive oxide doped with H atoms. At this time, the doping of H atoms may passivate lattice defects and grain boundary defects in the second transparent conductive film, thereby improving carrier mobility and conductivity of the second transparent conductive film.
In some possible implementations, in the H atom-doped transparent conductive oxide, the concentration of H atoms decreases in a direction away from the first transparent conductive film. At this time, the light transmittance and the conductivity of the second transparent conductive film can be adjusted by controlling the concentration of H atoms.
In some possible implementations, a surface of the second transparent conductive film facing away from the first transparent conductive film contains H atoms at a concentration of 0. The surface of the second transparent conductive film, which is far away from the first transparent conductive film, is contacted with the metal grid line, and H atoms are easy to react with the metal grid line, so that the conductivity of the metal grid line is influenced. When the concentration of H atoms contained on the surface of the second transparent conductive film in contact with the metal grid line is 0, the adverse effect of H free radicals on the conductivity of the metal grid line can be avoided, and the metal grid line is ensured to have better conductivity.
In some possible implementations, the transparent conductive oxide includes one or more of tin-doped indium oxide, tungsten-doped indium oxide, zinc-doped indium oxide, titanium-doped indium oxide, and fluorine-doped tin oxide. At this time, the first transparent conductive film has a relatively small contact resistance with the negative electrode end of the battery piece, and the second transparent conductive film does not need to consider the problem of contact with the negative electrode end of the battery piece.
In some possible implementations, the battery piece is a silicon heterojunction battery piece, a perovskite battery piece, a copper indium gallium selenide battery piece or a gallium arsenide battery piece.
In some possible implementations, the thickness of the first transparent conductive film is 3nm to 40nm.
In some possible implementations, the thickness of the second transparent conductive film is 70nm to 150nm. In view of the fact that the first transparent conductive film has a small work function and a small contact resistance, the second transparent conductive film has a good electrical property, and the first transparent conductive film with a small thickness and the second transparent conductive film with a large thickness can enable the transparent conductive layer to have a small contact resistance and a good conductivity.
In a second aspect, the invention further provides a manufacturing method of the solar cell. The manufacturing method of the solar cell comprises the following steps:
a battery piece is provided. The cell sheet has a positive terminal and a negative terminal.
Forming a transparent conductive layer at the negative electrode end of the cell; the transparent conductive layer comprises a first transparent conductive film and a second transparent conductive film. The first transparent conductive film and the second transparent conductive film are laminated in a direction away from the negative electrode end of the cell piece. The first transparent conductive film contains ZnO doped with H atoms.
The beneficial effects of the method for manufacturing a solar cell provided by the second aspect may refer to the beneficial effects of the solar cell described in the first aspect or any one of the possible implementation manners of the first aspect, and are not described herein again.
In some possible implementations, forming the transparent conductive layer at the negative end of the battery piece includes: forming a first transparent conductive film at the negative electrode end of the cell piece in the presence of a hydrogen doping source atmosphere, wherein the first transparent conductive film contains ZnO doped with H atoms; a second transparent conductive film is formed on the first transparent conductive film.
In some possible implementations, the hydrogen doping source is hydrogen gas or water vapor. When the hydrogen doping source is water vapor, oxygen atoms in the water vapor can be used for filling oxygen vacancies of sputtered zinc oxide particles, so that lattice defects in the first transparent conductive film are reduced, and the quality of the film is improved.
In some possible implementations, the process of forming the first transparent conductive film is a radio frequency sputtering process. The parameters of the radio frequency sputtering process are as follows: the preset temperature is 50-250 ℃, the vacuum degree is 0.01-0.05 Pa, and the power density is 0.2W/cm 2 ～1.5W/cm 2 The flow ratio of oxygen to argon is 1: (10-50), wherein the flow ratio of the hydrogen doping source to the argon gas is 1: (50-500), the target material is zinc oxide or zinc oxide doped with III-A group atom oxide.
When the radio frequency sputtering process is adopted to manufacture the first transparent conductive film, the problem of nodulation in the direct current sputtering process when water vapor participates can be well avoided. In addition, in the vacuum environment, when the first transparent conductive film is deposited, the deposition pressure is low, and the collision probability of sputtering particles before being deposited on the surface of the base material can be reduced, so that the kinetic energy lost due to collision is reduced, the particles deposited on the surface of the base material have enough kinetic energy to migrate, and the first transparent conductive film with strong adhesive force and good quality can be formed. And under the process parameters, the kinetic energy of the sputtering particles is not too high, so that the damage to the cathode end of the cell caused by the overhigh kinetic energy of the sputtering particles can be avoided.
In some possible implementations, the process of forming the second transparent conductive film is a dc sputtering process. The parameters of the direct current sputtering process are as follows: the deposition temperature is 80-250 ℃; the vacuum degree is 0.2Pa to 1.5Pa; the power density of the power supply is 0.5W/cm 2 ～8W/cm 2 (ii) a The flow ratio of the oxygen to the argon is 1 (8-50), and the initial flow ratio of the hydrogen doping source to the argon is 1: (50-500), and the target is transparent conductive oxide. At the moment, the specific direct current sputtering process parameters can moderate the carrier concentration in the second transparent conductive film, improve the light transmission of the second transparent conductive film and improve the current of the solar cell.
In some possible implementations, forming the second transparent conductive film on the first transparent conductive film includes: controlling the inflow of the argon and the oxygen to be constant under the condition that the outflow of the argon, the oxygen and the hydrogen doping source is constant, and reducing the inflow of the hydrogen doping source to 0 to form a second transparent conductive film on the first transparent conductive film; the second transparent conductive film contains a transparent conductive oxide doped with H atoms, and the concentration of the H atoms decreases progressively along the direction far away from the first transparent conductive film.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not limit the invention. In the drawings:
fig. 1 is a schematic structural diagram of a solar cell according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an n-type silicon heterojunction cell provided in an embodiment of the invention;
fig. 3 to 7 are schematic diagrams of states of various stages of a solar cell manufacturing process according to an embodiment of the present invention.
Reference numerals are as follows:
10-cell piece, 101-positive terminal, 102-negative terminal, 11-n type crystalline silicon piece, 12-first intrinsic amorphous silicon layer, 13-second intrinsic amorphous silicon layer, 14-n type doped amorphous silicon layer, 15-p type doped amorphous silicon layer, 20-transparent conducting layer, 21-first transparent conducting film, 22-second transparent conducting film and 30-electrode.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
It should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. The meaning of "a number" is one or more unless specifically limited otherwise.
In the description of the present invention, the terms "upper", "lower", "front", "rear", "left", "right", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "and/or" describes the association relationship of the associated object, indicating that there may be three relationships, for example, a and/or B, which may indicate: a exists alone, A and B exist simultaneously, and B exists alone, wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, at least one (one) of a, b, or c, may represent: a, b, c, a and b combination, a and c combination, b and c combination, or a, b and c combination, wherein a, b and c can be single or multiple.
Additionally, the words "exemplary" or "such as" are used herein to mean serving as an example, instance, or illustration. Any embodiment or design described herein as "exemplary" or "e.g.," is not necessarily to be construed as preferred or advantageous over other embodiments or designs. Rather, use of the word "exemplary" or "such as" is intended to present relevant concepts in a concrete fashion.
Clean energy is one of effective ways to solve the problems of energy shortage and environmental pollution, and photovoltaic power generation is always concerned as an important component of clean energy. In recent years, solar cell technology has been rapidly developed.
A solar cell generally includes a cell sheet having a photoelectric conversion function, and an electrode. The electrodes are formed on the front and back surfaces of the cell and are used for collecting the current generated by the cell and leading out the current. In practical applications, in order to improve the collection and transmission efficiency of photogenerated carriers generated by a cell, transparent conductive layers are often arranged on the front surface and the back surface of the cell.
When the transparent conducting layer is contacted with the negative electrode end of the battery piece, metal-semiconductor contact is formed at the joint. In general, if ohmic contact between the two is to be realized, firstly, TCO with low work function is adopted, so that the barrier of the metal-semiconductor junction is lower, and a carrier easily crosses the barrier through a thermionic emission effect and enters the TCO to realize the ohmic contact; and secondly, the doping concentration of the surface of the semiconductor is improved, the surface depletion region at the metal-semiconductor combination part is narrowed, and carriers can tunnel through a potential barrier into metal to obtain ohmic contact.
Most of the existing solar cells adopt doped indium oxide from the flat panel display (FDP) industry asA transparent conductive layer (TCO) material. The doped indium oxide is typically In 2 O 3 And SnO 2 Mixture of (1), in 2 O 3 And SnO 2 Is generally 90. Because the work function of the doped indium oxide is relatively high (the work function is generally 4.9 eV), when the doped indium oxide is contacted with the negative electrode end of the cell piece, a metal-semiconductor contact with a Schottky barrier is formed at the joint, the contact resistance is large, the conductivity is poor, and therefore the conversion efficiency of the solar cell is influenced.
In the prior art, in order to realize ohmic contact between the transparent conductive layer and the negative end of the cell, the doping concentration of the semiconductor surface (the negative end of the cell) is generally increased, so that the surface depletion region at the metal-semiconductor junction is narrowed, and carriers can tunnel into metal to obtain ohmic contact. However, when the negative electrode end surface of the cell piece is used as a solar cell window layer, the absorption of the film layer to the hot light is easily increased due to the higher doping concentration, and the conversion efficiency of the solar cell is reduced.
In order to solve the above technical problems, embodiments of the present invention provide a solar cell. The solar cell may be a silicon heterojunction solar cell, a perovskite solar cell, a copper indium gallium selenide solar cell or a gallium arsenide solar cell, but is not limited thereto.
As shown in fig. 1, a solar cell provided by an embodiment of the present invention includes a cell sheet 10 having a positive terminal 101 and a negative terminal 102, and a transparent conductive layer 20 formed at the negative terminal 102 of the cell sheet 10.
As shown in fig. 1, the battery piece 10 may be a silicon heterojunction battery piece, a perovskite battery piece, a copper indium gallium selenide battery piece or a gallium arsenide battery piece, but is not limited thereto. It should be understood that the type of the cell sheet 10 corresponds to the type of the solar cell. For example, when the cell piece 10 is a silicon heterojunction cell piece, the solar cell including the cell piece 10 is a silicon heterojunction solar cell.
As shown in fig. 1, the cell sheet 10 has a main structure for realizing a photoelectric conversion function. As shown in fig. 2, taking an n-type silicon heterojunction cell as an example, the n-type silicon heterojunction cell may include an n-type crystalline silicon wafer 11 having a textured surface, a first intrinsic amorphous silicon layer 12, a second intrinsic amorphous silicon layer 13, an n-type doped amorphous silicon (or microcrystalline silicon) layer, and a p-type doped amorphous silicon (or microcrystalline silicon) layer. The n-type crystalline silicon wafer 11 has a front surface and a back surface opposite to each other, the front surface is a light incident surface, the back surface is a backlight surface, the first intrinsic amorphous silicon layer 12 is formed on the front surface, and the second intrinsic amorphous silicon layer 13 is formed on the back surface. An n-type doped amorphous silicon layer 14 is formed on the first intrinsic amorphous silicon layer 12 and a p-type doped amorphous silicon layer 15 is formed on the second intrinsic amorphous silicon layer 13. The n-type doped amorphous silicon layer 14 is the negative terminal 102 of the n-type silicon heterojunction cell piece, and the p-type doped amorphous silicon layer 15 is the positive terminal 101 of the n-type silicon heterojunction cell piece.
As shown in fig. 1, the negative electrode terminal 102 of the battery piece 10 is formed with a transparent conductive layer 20. Of course, the positive electrode terminal 101 of the cell sheet 10 may be formed with the transparent conductive layer 20. The transparent conductive layer 20 serves to collect current and serves as an antireflection film. It should be understood that the electrodes 30 may also be formed on the transparent conductive layer 20 of the negative terminal 102 and the positive terminal 101 of the cell sheet 10. The electrode 30 may be a metal grid line formed by screen printing, and the material of the electrode 30 may be a metal with good conductivity, such as silver, copper, and the like.
As shown in fig. 1, since the material of the transparent conductive layer 20, which is commonly used and is doped with indium oxide or the like, has a high work function, and can form a good ohmic contact when it is in contact with the positive electrode terminal 101 of the cell piece 10, the material of the transparent conductive layer 20 formed on the positive electrode terminal 101 of the cell piece 10 may be selected to have a good conductivity without considering a large contact resistance. For example, the material of the transparent conductive layer 20 formed on the positive electrode terminal 101 of the battery piece 10 may be one or more of tin-doped indium oxide, tungsten-doped indium oxide, zinc-doped indium oxide, titanium-doped indium oxide, and fluorine-doped tin oxide, but is not limited thereto. The transparent conductive layer 20 formed at the negative terminal 102 of the battery piece 10 is described in detail below.
As shown in fig. 1, the transparent conductive layer 20 formed at the negative terminal 102 of the battery piece 10 includes a first transparent conductive film 21 and a second transparent conductive film 22. The first transparent conductive film 21 and the second transparent conductive film 22 are laminated in a direction away from the negative electrode end 102 of the battery piece 10. The thickness of the first transparent conductive film 21 may be 3nm to 10nm. For example, the thickness of the first transparent conductive film 21 may be 3nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 15nm, 20nm, 30nm, 35nm, and 40nm. The thickness of the second transparent conductive film 22 may be 70nm to 150nm. For example, the thickness of the second transparent conductive film 22 may be 70nm, 80nm, 95nm, 100nm, 110nm, 125nm, 130nm, 140nm, 145nm, or 150nm.
As shown in fig. 1, the first transparent conductive film 21 contains ZnO doped with H atoms. At this time, the first transparent conductive film 21 is in contact with the negative electrode terminal 102 of the cell piece 10, and the first transparent conductive film 21 contains ZnO doped with H atoms. On the one hand, the work function of the doped ZnO is 4.35eV to 4.45eV, and the work function is low, so that the contact potential difference between the first transparent conductive film 21 and the negative electrode end 102 of the cell piece 10 can be reduced, and the contact resistance between the first transparent conductive film 21 and the negative electrode end 102 of the cell piece 10 is low. On the other hand, when the ZnO is doped with H atoms, the grain boundary defects of the ZnO film can be passivated, and lattice scattering is reduced, so that the carrier mobility in the ZnO is improved, and the conductivity of the first transparent conductive film 21 is improved. Further, H atoms serve as shallow donors, and when doping is performed in a small amount, the carrier concentration in ZnO can be increased, and the conductivity of the first transparent conductive film 21 can be improved. As can be seen, the first transparent conductive film 21 provided in the embodiment of the present invention can not only reduce the contact resistance between the first transparent conductive film 21 and the negative electrode 102 of the battery piece 10, but also improve the conductivity of the first transparent conductive film 21. It is to be understood that the first transparent conductive film 21 may also contain other materials having a lower work function.
The doping concentration of H atoms in the ZnO doped with H atoms is 10 19 cm -3 ～10 20 cm -3 . At this time, the H atom doping concentration is low, and an increase in ionized impurity scattering centers introduced by doping can be reduced, thereby improving carrier mobility and conductivity in the first transparent conductive film 21. And the doping concentration of the H atoms is low, so that the over-high concentration of carriers in ZnO can be avoided, the absorption and blocking of the carriers to photons (near infrared bands) are reduced, and the light transmittance of the first transparent conductive film is improved.
Compared with the heavily doped ZnO transparent conductive film, the H-atom doped ZnO can improve the conductivity of the first transparent conductive film 21 by reducing lattice defects and improving the carrier mobility, without excessively high doping concentration. At this time, not only the introduction of more ionized impurity scattering centers can be avoided, but also the absorption and blocking of photons due to too high carrier concentration in the first transparent conductive film 21 can be avoided, and the light transmittance can be improved.
In order to further adjust the conductivity of the first transparent conductive film 21, of ZnO doped with H atoms, znO may be a material having n-type doped atoms. That is, znO is also doped with n-type impurity atoms. The n-type impurity atom may be a group iiia atom. Specifically, the n-type impurity atoms contained In the H atom-doped ZnO include one or more of B, al, ga, and In, but are not limited thereto. For example, when the n-type impurity atom contained in the H atom-doped ZnO is Al, the first transparent conductive film 21 is H atom-doped aluminum-doped ZnO. In practical applications, the conductivity of ZnO can be adjusted by adjusting the concentration of n-type impurity atoms.
The doping concentration of the n-type impurity atoms in the H atom-doped ZnO may be 10 19 cm -3 ～10 20 cm -3 . At this time, the doping concentration of the n-type impurity atoms is low, so that the carrier concentration can be properly increased, the increase of ionized impurity scattering centers introduced by doping can be reduced, and the carrier mobility and the conductivity in ZnO can be improved. And the doping concentration is low, so that the carrier concentration can be prevented from being too high, the absorption and blocking of the carriers to photons are reduced, and the light transmittance of the first transparent conductive film is improved.
The second transparent conductive film 22 may contain a transparent conductive oxide doped with H atoms. The transparent conductive oxide comprises one or more of tin-doped indium oxide, tungsten-doped indium oxide, zinc-doped indium oxide, titanium-doped indium oxide, and fluorine-doped tin oxide. In view of the fact that the first transparent conductive film 21 has a relatively low contact resistance with the negative end 102 of the battery piece 10, the second transparent conductive film 22 does not need to consider the problem of contact with the negative end 102 of the battery piece 10, and therefore, when selecting the material of the second transparent conductive film 22, one or more materials with better conductivity can be selected without considering the work function of the material.
Similar to the first transparent conductive film 21, when the second transparent conductive film 22 is doped with H atoms, the doped H atoms may passivate lattice defects and grain boundary defects in the second transparent conductive film 22, thereby improving carrier mobility and conductivity of the second transparent conductive film 22. In practical applications, the conductivity and transparency of the second transparent conductive film 22 can be adjusted by adjusting the doping concentration of H atoms.
In the transparent conductive oxide doped with H atoms, the concentration of H atoms may decrease in a direction away from the first transparent conductive film 21. In a specific implementation, in order to decrease the concentration of H atoms in the second transparent conductive film 22, the second transparent conductive film 22 may be manufactured in stages, and the concentration of H atoms doped in each stage is different, so that the concentration of H atoms is made to decrease in a gradient in a direction away from the first transparent conductive film 21.
As shown in fig. 1, a surface of the second transparent conductive film 22 away from the first transparent conductive film 21 contacts an electrode 30 (typically, a metal gate line), and H atoms doped in the second transparent conductive film 22 easily react with the metal gate line, thereby affecting the conductivity of the metal gate line. In order to avoid adverse effects of H radicals doped in the second transparent conductive film 22 on the conductivity of the metal gate line, and ensure that the metal gate line has better conductivity, the surface of the second transparent conductive film 22 away from the first transparent conductive film 21 contains H atoms with a concentration of 0. At this time, the concentration of H atoms doped in the second transparent conductive film 22 decreases in a direction away from the first transparent conductive film 21, and decreases to 0 at a surface of the second transparent conductive film 22 away from the first transparent conductive film 21.
As can be seen from the above, the contact resistance between the first transparent conductive film 21 and the negative electrode terminal 102 of the battery piece 10 is small, and the conductivity of the first transparent conductive film 21 and the second transparent conductive film 22 is good. It can be seen that the contact resistance between the transparent conductive layer 20 including the first transparent conductive film 21 and the second transparent conductive film 22 and the negative electrode terminal 102 of the cell piece 10 is small, and the open-circuit voltage of the solar cell can be increased. Meanwhile, the transparent conductive layer 20 of the negative terminal 102 of the cell piece 10 has better conductivity, so that the fill factor of the solar cell can be improved, and the conversion efficiency can be improved.
The embodiment of the invention also provides a manufacturing method of the solar cell. The manufacturing method of the solar cell comprises the following steps:
as shown in fig. 3, a battery piece 10 is provided. The cell sheet 10 has a positive terminal 101 and a negative terminal 102. Taking an n-type silicon heterojunction cell as an example, the manufacturing method of the cell 10 may include the following steps: an n-type crystalline silicon wafer 11 is provided. The n-type crystal silicon wafer 11 is sequentially subjected to polishing, texturing and cleaning to form the n-type crystal silicon wafer 11 with the textured surface. And depositing intrinsic amorphous silicon layers on two sides of the n-type crystal silicon wafer 11 by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) process to form a first intrinsic amorphous silicon layer 12 positioned on the front surface of the n-type crystal silicon wafer 11 and a second intrinsic amorphous silicon layer 13 positioned on the back surface of the n-type crystal silicon wafer 11. An n-type doped amorphous silicon (or microcrystalline silicon) layer is deposited on the first intrinsic amorphous silicon layer 12 by PECVD process to form a window layer. A P-type doped amorphous silicon (or microcrystalline silicon) layer is deposited on the second intrinsic amorphous silicon layer 13 by using a PECVD process to form a P-type emitter.
As shown in fig. 4, a first transparent conductive film 21 having a thickness of 3nm to 10nm is formed on the negative electrode end 102 of the cell piece 10 in the presence of a hydrogen doping source atmosphere, and the first transparent conductive film 21 contains ZnO doped with H atoms. The hydrogen doping source can be hydrogen or water vapor. When the hydrogen doping source is water vapor, oxygen atoms in the water vapor can also be used for filling oxygen vacancies in the sputtered zinc oxide material, so that lattice defects in the first transparent conductive film 21 are reduced, and the film quality is improved.
Specifically, the process of forming the first transparent conductive film 21 may be a radio frequency sputtering process. The parameters of the radio frequency sputtering process are as follows: the preset temperature is 50-250 ℃, the vacuum degree is 0.01-0.05 Pa, and the power density is 0.2W/cm 2 ～1.5W/cm 2 The flow ratio of oxygen to argon is 1: (10-50), wherein the flow ratio of the hydrogen doping source to the argon gas is 1: (50-500), the target material can be zinc oxide, and can also be zinc oxide doped with III-A atom oxide.
In practical applications, the battery piece 10 may be transported into a sputtering chamber of a Physical Vapor Deposition (PVD) apparatus, and operating parameters of the sputtering chamber are set according to the parameters of the rf sputtering process, and then the first transparent conductive film 21 is prepared in the sputtering chamber.
If a direct current sputtering process is adopted, the process atmosphere contains water vapor, the water vapor atmosphere is easy to induce the target material to decompose to generate zinc oxide with low conductivity, so that the sputtering rate of the low-conductivity area is reduced, the target material sputtering is shielded, and the problem of nodulation is caused. In the radio frequency sputtering process, the target does not need to be conductive, so that the influence of the target material in a low-conductivity area on the sputtering rate can be avoided. Therefore, the radio frequency sputtering process can well avoid the problem of nodulation in the direct current sputtering process when water vapor participates. In addition, in the vacuum environment, when the first transparent conductive film 21 is deposited, the deposition pressure is low, and the collision probability of the sputtered particles before being deposited on the surface of the substrate can be reduced, so that the kinetic energy lost due to collision is reduced, the particles deposited on the surface of the substrate have enough kinetic energy to migrate, and the first transparent conductive film 21 with strong adhesion and good quality can be formed. Moreover, under the above process parameters, the kinetic energy of the sputtered particles is not too high, so that the damage to the negative electrode end 102 of the cell 10 due to the too high kinetic energy of the sputtered particles can be avoided.
As shown in fig. 5, a second transparent conductive film 22 having a thickness of 70nm to 150nm is formed on the first transparent conductive film 21. In view of the fact that the first transparent conductive film 21 has a small work function and a small contact resistance, and the second transparent conductive film 22 has a good electrical property, the first transparent conductive film 21 having a small thickness and the second transparent conductive film 22 having a large thickness can make the transparent conductive layer 20 have a small contact resistance and a good conductivity.
The process of forming the second transparent conductive film 22 may be a dc sputtering process. The parameters of the direct current sputtering process are as follows: the deposition temperature is 80-250 ℃; the vacuum degree is 0.2Pa to 1.5Pa; the power density of the power supply is 0.5W/cm 2 ～8W/cm 2 (ii) a The flow ratio of the oxygen to the argon is 1 (8-50), the initial flow ratio of the hydrogen doping source to the argon is 1: (50-500), the target is transparent conductive oxide. At this time, specific DC sputteringThe process parameters can moderate the carrier concentration in the second transparent conductive film 22, improve the light transmission of the second transparent conductive film, and increase the current of the solar cell.
In order to decrease the concentration of H atoms in the second transparent conductive film 22 to 0 in the direction away from the first transparent conductive film 21, the inflow amount of the argon gas and the oxygen gas may be controlled to be constant and the inflow amount of the hydrogen dopant source may be decreased to 0 while the outflow amounts of the argon gas, the oxygen gas, and the hydrogen dopant source are constant. At this time, the second transparent conductive film 22 formed on the first transparent conductive film 21 contains a transparent conductive oxide doped with H atoms, and the concentration of H atoms decreases to 0 in a direction away from the first transparent conductive film 21.
In practical applications, the rf power source in the sputtering chamber may be changed to a direct current (dc) power source, and the second transparent conductive film 22 is formed in the sputtering chamber. And setting working parameters of each sputtering chamber according to the parameters of the direct current sputtering process, setting the temperature gradient rise of each sputtering chamber, and controlling the gradient decrease of the hydrogen doping source of each sputtering chamber through a flow pump. The cell sheet 10 having the first transparent conductive film 21 is sequentially processed in each sputtering process, thereby forming the second transparent conductive film 22 on the first transparent conductive film 21.
After the above steps, the transparent conductive layer 20 is formed on the negative electrode end 102 of the battery piece 10. The transparent conductive layer 20 includes a first transparent conductive film 21 and a second transparent conductive film 22. The first transparent conductive film 21 and the second transparent conductive film 22 are laminated in a direction away from the negative electrode end 102 of the battery piece 10. The first transparent conductive film 21 contains ZnO doped with H atoms.
As shown in fig. 6 and 7, the method for manufacturing a solar cell may further include: a transparent conductive layer 20 is formed on the positive electrode terminal 101 of the battery sheet 10, and an electrode 30 is formed on the transparent conductive layer 20.
In order to verify the performance of the solar cell provided in the embodiment of the present invention, an n-type silicon heterojunction solar cell is taken as an example, and the following description is made by comparing the example with a comparative example.
Example one
The method for manufacturing an n-type silicon heterojunction solar cell provided in this embodiment specifically includes the following steps:
in the first step, an n-type crystal silicon wafer is provided. And sequentially carrying out polishing, texturing and cleaning on the n-type crystal silicon wafer to form the n-type crystal silicon wafer with the textured surface.
And secondly, depositing a first intrinsic amorphous silicon layer on the front surface of the n-type crystal silicon wafer by adopting a PECVD (plasma enhanced chemical vapor deposition) process, and depositing a second intrinsic amorphous silicon layer on the back surface of the n-type crystal silicon wafer.
And thirdly, depositing an n-type doped amorphous silicon layer on the first intrinsic amorphous silicon layer by adopting a PECVD (plasma enhanced chemical vapor deposition) process.
And fourthly, depositing a p-type doped amorphous silicon layer on the second intrinsic amorphous silicon layer by adopting a PECVD process.
And fifthly, forming a first transparent conductive film (with the thickness of 3 nm) containing ZnO doped with H atoms on the n-type doped amorphous silicon layer of the cell by adopting a radio frequency sputtering process.
The parameters of the radio frequency sputtering process are as follows: the preset temperature is 50 ℃, the vacuum degree is 0.01Pa, and the power density is 0.2W/cm 2 The flow ratio of oxygen to argon is 1:10, the flow ratio of water vapor to argon gas is 1:50, the target material is zinc oxide.
And a sixth step of forming a second transparent conductive film (with a thickness of 70 nm) on the first transparent conductive film by a direct current sputtering process.
The parameters of the direct current sputtering process are as follows: the deposition temperature is 80 ℃; the vacuum degree is 0.2Pa; the power density of the power supply is 0.5W/cm 2 (ii) a The flow ratio of oxygen to argon is 1: and 50, reducing the flow of water vapor to 0, wherein the target material is indium oxide and tin oxide, and the mass ratio of the indium oxide to the tin oxide is 90.
And seventhly, forming a transparent conducting layer made of tin-doped indium oxide on the p-type doped amorphous silicon layer by adopting a magnetron sputtering process.
And eighthly, forming silver electrode grid lines on the transparent conductive layers on the front side and the back side of the battery piece by adopting a screen printing process.
Example two
The method for manufacturing an n-type silicon heterojunction solar cell provided in this embodiment specifically includes the following steps:
in the first step, an n-type crystal silicon wafer is provided. And sequentially carrying out polishing, texturing and cleaning on the n-type crystal silicon wafer to form the n-type crystal silicon wafer with the textured surface.
And secondly, depositing a first intrinsic amorphous silicon layer on the front side of the n-type crystal silicon wafer by adopting a PECVD (plasma enhanced chemical vapor deposition) process, and depositing a second intrinsic amorphous silicon layer on the back side of the n-type crystal silicon wafer.
And thirdly, depositing an n-type doped amorphous silicon layer on the first intrinsic amorphous silicon layer by adopting a PECVD (plasma enhanced chemical vapor deposition) process.
And fourthly, depositing a p-type doped amorphous silicon layer on the second intrinsic amorphous silicon layer by adopting a PECVD process.
And fifthly, forming a first transparent conductive film (with the thickness of 10 nm) containing ZnO doped with H atoms on the n-type doped amorphous silicon layer of the cell by adopting a radio frequency sputtering process.
The parameters of the radio frequency sputtering process are as follows: the preset temperature is 250 ℃, the vacuum degree is 0.05Pa, and the power density is 1.5W/cm 2 The flow ratio of oxygen to argon is 1:50, the flow ratio of hydrogen to argon is 1:500, the target material can be zinc oxide and aluminum oxide, and the mass ratio of the zinc oxide to the aluminum oxide is 98.
And a sixth step of forming a second transparent conductive film (with a thickness of 150 nm) on the first transparent conductive film by a direct-current sputtering process.
The parameters of the direct current sputtering process are as follows: the deposition temperature is 250 ℃; the vacuum degree is 1.5Pa; the power density of the power supply is 8W/cm 2 (ii) a The flow ratio of oxygen to argon was 1:500, the hydrogen flow is decreased to 0, the target is indium oxide and tin oxide, and the mass ratio of the indium oxide to the tin oxide is 90.
And seventhly, forming a transparent conducting layer made of tin-doped indium oxide on the p-type doped amorphous silicon layer by adopting a magnetron sputtering process.
And eighthly, forming silver electrode grid lines on the transparent conductive layers on the front side and the back side of the battery piece by adopting a screen printing process.
EXAMPLE III
The method for manufacturing an n-type silicon heterojunction solar cell provided in this embodiment specifically includes the following steps:
in the first step, an n-type crystal silicon wafer is provided. And sequentially carrying out polishing, texturing and cleaning treatment on the n-type crystal silicon wafer to form the n-type crystal silicon wafer with the textured surface.
And secondly, depositing a first intrinsic amorphous silicon layer on the front side of the n-type crystal silicon wafer by adopting a PECVD (plasma enhanced chemical vapor deposition) process, and depositing a second intrinsic amorphous silicon layer on the back side of the n-type crystal silicon wafer.
And thirdly, depositing an n-type doped amorphous silicon layer on the first intrinsic amorphous silicon layer by adopting a PECVD (plasma enhanced chemical vapor deposition) process.
And fourthly, depositing a p-type doped amorphous silicon layer on the second intrinsic amorphous silicon layer by adopting a PECVD process.
And fifthly, forming a first transparent conductive film (with the thickness of 5 nm) containing ZnO doped with H atoms on the n-type doped amorphous silicon layer of the cell piece by adopting a radio frequency sputtering process.
The parameters of the radio frequency sputtering process are as follows: the preset temperature is 100 ℃, the vacuum degree is 0.02Pa, and the power density is 0.8W/cm 2 The flow ratio of oxygen to argon is 1:20, the flow ratio of water vapor to argon gas is 1:200, the target material is zinc oxide.
And a sixth step of forming a second transparent conductive film (with a thickness of 100 nm) on the first transparent conductive film by a direct-current sputtering process.
The parameters of the direct current sputtering process are as follows: the deposition temperature is 100 ℃; the vacuum degree is 1Pa; the power density of the power supply is 3W/cm 2 (ii) a The flow ratio of oxygen to argon is 1:200, the flow of water vapor is reduced to 0, the target material is zinc oxide and indium oxide, and the mass ratio of the zinc oxide to the indium oxide is 90.
And seventhly, forming a transparent conducting layer made of tin-doped indium oxide on the p-type doped amorphous silicon layer by adopting a magnetron sputtering process.
And eighthly, forming silver electrode grid lines on the transparent conductive layers on the front side and the back side of the battery piece by adopting a screen printing process.
Example four
The method for manufacturing an n-type silicon heterojunction solar cell provided in this embodiment specifically includes the following steps:
in the first step, an n-type crystal silicon wafer is provided. And sequentially carrying out polishing, texturing and cleaning treatment on the n-type crystal silicon wafer to form the n-type crystal silicon wafer with the textured surface.
And secondly, depositing a first intrinsic amorphous silicon layer on the front surface of the n-type crystal silicon wafer by adopting a PECVD (plasma enhanced chemical vapor deposition) process, and depositing a second intrinsic amorphous silicon layer on the back surface of the n-type crystal silicon wafer.
And thirdly, depositing an n-type doped amorphous silicon layer on the first intrinsic amorphous silicon layer by adopting a PECVD (plasma enhanced chemical vapor deposition) process.
And fourthly, depositing a p-type doped amorphous silicon layer on the second intrinsic amorphous silicon layer by adopting a PECVD process.
And fifthly, forming a first transparent conductive film (with the thickness of 8 nm) containing ZnO doped with H atoms on the n-type doped amorphous silicon layer of the cell piece by adopting a radio frequency sputtering process.
The parameters of the radio frequency sputtering process are as follows: the preset temperature is 200 ℃, the vacuum degree is 0.04Pa, and the power density is 1.2W/cm 2 The flow ratio of oxygen to argon is 1:40, the flow ratio of hydrogen to argon is 1:400, the target material is zinc oxide and boron oxide, and the mass ratio of the zinc oxide to the boron oxide is 97.
And a sixth step of forming a second transparent conductive film (with a thickness of 120 nm) on the first transparent conductive film by a direct-current sputtering process.
The parameters of the direct current sputtering process are as follows: the deposition temperature is 200 ℃; the vacuum degree is 1.3Pa; the power density of the power supply is 6W/cm 2 (ii) a The flow ratio of oxygen to argon was 1:300, the hydrogen flow is decreased to 0, the target is indium oxide and tungsten oxide, and the mass ratio of the indium oxide to the tungsten oxide is 99.
And seventhly, forming a transparent conducting layer made of tin-doped indium oxide on the p-type doped amorphous silicon layer by adopting a magnetron sputtering process.
And eighthly, forming silver electrode grid lines on the transparent conductive layers on the front side and the back side of the battery piece by adopting a screen printing process.
Comparative example 1
The method for fabricating the n-type silicon heterojunction solar cell provided in this comparative example is substantially the same as the method described in the first example, except that: and omitting the fifth step and the sixth step, and forming a transparent conducting layer made of tin-doped indium oxide on the n-type doped amorphous silicon layer by adopting a magnetron sputtering process.
Comparative example No. two
The method for fabricating the n-type silicon heterojunction solar cell provided in this comparative example is substantially the same as the method described in the first example, except that: the fifth step is changed as follows: and forming a first transparent conductive film made of aluminum-doped zinc oxide on the n-type doped amorphous silicon layer by adopting a radio frequency sputtering process. The sixth step is changed into: and forming a second transparent conductive film made of tin-doped indium oxide on the first transparent conductive film by adopting a direct-current sputtering process.
The cell performance of the solar cell provided in the example of the present invention is compared with that of the solar cell manufactured in the comparative example, as shown in table 1.
TABLE 1 comparison of Performance of different solar cells
Figure GDA0003456747350000161
Figure GDA0003456747350000171
As can be seen from table 1, the fill factor of the solar cell provided by the embodiment of the present invention is increased by 1.2%, and the open circuit voltage is increased by 1mV.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (12)

1. A solar cell, comprising:
a battery piece having a positive end and a negative end;
and a transparent conductive layer formed at the negative electrode end of the cell sheet; wherein,
the transparent conductive layer comprises a first transparent conductive film and a second transparent conductive film; the first transparent conductive film and the second transparent conductive film are laminated along a direction far away from the negative electrode end of the battery piece; the first transparent conductive film contains ZnO doped with H atoms, and the doping concentration of the H atoms in the ZnO doped with the H atoms is 10 19 cm -3 ～10 20 cm -3 ；
The second transparent conductive film contains a transparent conductive oxide doped with H atoms, the concentration of the H atoms in the transparent conductive oxide doped with H atoms is gradually reduced along the direction far away from the first transparent conductive film, and the concentration of the H atoms contained on the surface of the second transparent conductive film far away from the first transparent conductive film is 0.
2. The solar cell according to claim 1, wherein the H-atom doped ZnO is n-type H-atom doped ZnO.
3. The solar cell according to claim 2, wherein, in the H atom-doped ZnO, znO is a material doped with n-type impurity atoms, the n-type impurity atoms are IIIA group atoms, and the IIIA group atoms include one or more of B, al, ga, in; and/or the presence of a gas in the atmosphere,
the doping concentration of the n-type impurity atoms is 10 19 cm -3 ～10 20 cm -3 。
4. The solar cell according to any of claims 1-3, wherein the transparent conductive oxide comprises one or more of tin-doped indium oxide, tungsten-doped indium oxide, zinc-doped indium oxide, titanium-doped indium oxide, fluorine-doped tin oxide.
5. The solar cell according to any one of claims 1 to 3,
the battery piece is a silicon heterojunction battery piece, a perovskite battery piece, a copper indium gallium selenide battery piece or a gallium arsenide battery piece.
6. The solar cell according to any one of claims 1 to 3, wherein the thickness of the first transparent conductive film is 3nm to 40nm, and/or the thickness of the second transparent conductive film is 70nm to 150nm.
7. A method for fabricating a solar cell, comprising:
providing a battery piece, wherein the battery piece is provided with a positive electrode end and a negative electrode end;
forming a transparent conducting layer at the negative end of the battery piece; wherein,
the transparent conductive layer comprises a first transparent conductive film and a second transparent conductive film; the first transparent conductive film and the second transparent conductive film are laminated along the direction far away from the negative electrode end of the battery piece; the first transparent conductive film contains ZnO doped with H atoms, and the doping concentration of the H atoms in the ZnO doped with the H atoms is 10 19 cm -3 ～10 20 cm -3 ；
The second transparent conductive film contains a transparent conductive oxide doped with H atoms, the concentration of the H atoms in the transparent conductive oxide doped with H atoms is gradually reduced along the direction far away from the first transparent conductive film, and the concentration of the H atoms contained on the surface of the second transparent conductive film far away from the first transparent conductive film is 0.
8. The method for manufacturing the solar cell according to claim 7, wherein the forming of the transparent conductive layer at the negative electrode end of the cell piece comprises:
forming the first transparent conductive film at the negative electrode end of the cell piece in the presence of a hydrogen doping source atmosphere, wherein the first transparent conductive film contains ZnO doped with H atoms;
the second transparent conductive film is formed on the first transparent conductive film.
9. The method of claim 8, wherein the hydrogen doping source is hydrogen or water vapor.
10. The method for manufacturing the solar cell according to claim 8, wherein the process for forming the first transparent conductive film is a radio frequency sputtering process, and the parameters of the radio frequency sputtering process are as follows: the preset temperature is 50-250 ℃, the vacuum degree is 0.01-0.05 Pa, and the power density is 0.2W/cm 2 ～1.5W/cm 2 The flow ratio of oxygen to argon is 1: (10-50), wherein the flow ratio of the hydrogen doping source to the argon gas is 1: (50-500), the target material is zinc oxide or zinc oxide doped with III-A group atom oxide.
11. The method for manufacturing the solar cell according to claim 8, wherein the process for forming the second transparent conductive film is a dc sputtering process, and the parameters of the dc sputtering process are as follows: the deposition temperature is 80-250 ℃; the vacuum degree is 0.2Pa to 1.5Pa; the power density of the power supply is 0.5W/cm 2 ～8W/cm 2 (ii) a The flow ratio of the oxygen to the argon is 1 (8-50), the initial flow ratio of the hydrogen doping source to the argon is 1: (50-500), and the target is transparent conductive oxide.
12. The method of claim 11, wherein forming the second transparent conductive film on the first transparent conductive film comprises:
controlling the inflow amount of the argon and the oxygen to be constant under the condition that the outflow amounts of the argon, the oxygen and the hydrogen doping source are constant, and reducing the inflow amount of the hydrogen doping source to 0, so as to form the second transparent conductive film on the first transparent conductive film; the second transparent conductive film contains a transparent conductive oxide doped with H atoms, and the concentration of the H atoms decreases progressively along a direction away from the first transparent conductive film.
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