CN111793785A - Production method of TCO film and magnetron sputtering coating machine - Google Patents

Production method of TCO film and magnetron sputtering coating machine Download PDF

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Publication number
CN111793785A
CN111793785A CN202010714648.0A CN202010714648A CN111793785A CN 111793785 A CN111793785 A CN 111793785A CN 202010714648 A CN202010714648 A CN 202010714648A CN 111793785 A CN111793785 A CN 111793785A
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plasma treatment
plasma
substrate
tco film
mixed gas
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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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    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering

Abstract

The application provides a production method of a TCO film and a magnetron sputtering coating machine, and relates to the technical field of TCO film production. The production method of the TCO film comprises the following steps: performing plasma treatment on the first surface of the substrate by using a magnetron sputtering coating machine in a vacuum environment; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment; and plating the TCO film on the first surface treated by the plasma in a vacuum environment by using the magnetron sputtering coating machine. According to the embodiment of the invention, on the basis of not reducing the light transmittance of the TCO film, the conductivity of the plated TCO film is improved to a great extent.

Description

Production method of TCO film and magnetron sputtering coating machine
Technical Field
The invention relates to the technical field of film production, in particular to a production method of a TCO film and a magnetron sputtering coating machine.
Background
In a solar cell, a TCO (Transparent Conductive Oxide) thin film is generally disposed on a doped layer to reduce the series resistance of the cell and enhance the lateral transport capability of carriers. Thus, TCO films generally require higher conductivity.
At present, the doped layer is generally prepared by PECVD (Plasma Enhanced Chemical vapor deposition) or HWCVD (Hot-wire Chemical vapor deposition) in a vacuum environment, and then the silicon substrate provided with the doped layer is removed from the vacuum environment, exposed in an ultra-clean room environment for a certain period of time, and transferred to a magnetron sputtering coater for preparing the TCO film. However, the TCO film prepared by the existing TCO film production method has lower conductivity.
Disclosure of Invention
The invention provides a production method of a TCO film and a magnetron sputtering coating machine, and aims to solve the problem that the prepared TCO film is low in conductivity in the existing production method of the TCO film.
According to a first aspect of the present invention, there is provided a method for producing a TCO film, comprising the steps of:
performing plasma treatment on the first surface of the substrate by using a magnetron sputtering coating machine in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment;
and plating the TCO film on the first surface treated by the plasma in a vacuum environment by using the magnetron sputtering coating machine.
Optionally, the flow rate of the inert gas is 50-500sccm, the flow rate of the oxidizing gas is less than or equal to 20sccm, and the flow rate of the reducing gas is less than or equal to 10 sccm.
Optionally, the inert gas is argon, the oxidizing gas is oxygen, and the reducing gas is hydrogen.
Optionally, in the plasma treatment process, the pressure range of the magnetron sputtering coating machine is 0.1-1 Pa.
Optionally, the power density of the plasma treatment is 0.1-1W/cm2。
Optionally, the driving power supply for plasma processing is: a DC stabilized power supply or a radio frequency power supply.
Optionally, the radio frequency power supply is an intermediate frequency radio frequency power supply.
In the embodiment of the invention, a magnetron sputtering coating machine is adopted to carry out plasma treatment on the first surface of the substrate in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment; and plating the TCO film on the first surface treated by the plasma in a vacuum environment by using the magnetron sputtering coating machine. The plasma treatment and the TCO film plating are both carried out in the same magnetron sputtering coating machine in a vacuum environment without breaking vacuum, the doping layer is not exposed in a production environment, the first surface of the doping layer is basically not subjected to mechanical damage, and the reduction of the conductivity of the TCO film plated due to the mechanical damage caused by the exposure of the doping layer in the production environment is avoided. And the first surface of the substrate is subjected to plasma treatment, and the ionized inert gas is used for slightly etching the first surface, so that the doped layer is not damaged, and the pollution of the first surface in the substrate production process can be removed. Meanwhile, in the plasma treatment process, the first surface can be slightly oxidized by oxidizing gas, the proportion of amorphous silicon oxygen on the first surface is increased, the induced nucleation effect of the doping layer on the TCO film is weakened, and the nucleation density of the TCO film on the first surface is reduced; in the plasma treatment process, reducing atoms can be filled in the first surface through reducing gas, so that the nucleation energy of the TCO film on the first surface can be changed, the growth of crystal nuclei is inhibited, and the grain size is increased; the reduction of the nucleation density of the TCO film on the first surface and the increase of the grain diameter of the TCO film on the first surface are both beneficial to improving the carrier mobility of the TCO film, and the improvement of the carrier mobility not only can improve the conductivity of the TCO film, but also can not reduce the light transmission of the TCO film, so that the embodiment of the invention can improve the conductivity of the plated TCO film to a great extent on the basis of not reducing the light transmission of the TCO film. And the first surface after plasma treatment is basically free from pollution, so that the improvement of the conductivity of the TCO film plated on the first surface after plasma treatment is facilitated. Plasma treatment and film coating are carried out in a vacuum environment, so that the risks of exposing the surface of the doped layer to a production environment and bearing mechanical damage are reduced, and the complexity and the transformation cost of the magnetron sputtering film coating machine are reduced.
According to a second aspect of the present invention, there is provided a magnetron sputter coating machine comprising: a plasma processing structure and a coating structure;
the plasma processing structure is used for carrying out plasma processing on the first surface of the substrate in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment;
the coating structure is used for coating a TCO film on the first surface after plasma treatment in a vacuum environment.
Optionally, the plasma processing structure includes a processing chamber, a plasma generator, a carrier plate, and a transmission member;
the processing chamber is used for providing a vacuum environment;
the plasma generator is used for carrying out plasma treatment on the first surface of the substrate in a vacuum environment;
the carrier plate is used for carrying the substrate, and a first surface of the substrate faces the plasma generator;
the transmission component is used for conveying a carrier plate carrying a substrate from one end of the processing cavity far away from the film coating structure to one end of the processing cavity close to the film coating structure.
Optionally, the number of the plasma generators is greater than or equal to 1, and when the number of the plasma generators is greater than 1, the plasma generators are respectively located on two sides of the substrate, the substrate includes a silicon wafer, the light-facing surface and the light-back surface of the silicon wafer are both sequentially provided with a passivation layer and a doping layer, and the plasma generators respectively located on two sides of the substrate simultaneously perform plasma treatment on the corresponding first surfaces.
The magnetron sputtering coating machine has the same or similar beneficial effects as the TCO film production method, and the repeated description is omitted here for avoiding the repetition.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments of the present invention will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without inventive exercise.
FIG. 1 shows a flow chart of the steps of a method for producing a TCO film in accordance with an embodiment of the present invention;
FIG. 2 shows a schematic structural diagram of a substrate in an embodiment of the invention;
FIG. 3 is a schematic structural diagram of a magnetron sputtering coating machine according to an embodiment of the invention;
FIG. 4 is a schematic diagram of a TCO film disposed on a substrate according to an embodiment of the invention;
FIG. 5 shows a schematic structural view of a TCO film disposed on a substrate according to another embodiment of the invention;
fig. 6 shows a schematic structural diagram of a solar cell according to an embodiment of the present invention.
Description of the figure numbering:
the manufacturing method comprises the following steps of 1-a silicon wafer, 2-a passivation layer, 3-a doping layer, 4-a TCO film, 5-an electrode, C1-a plasma processing structure of a magnetron sputtering film plating machine, C2-a film plating structure of the magnetron sputtering film plating machine, P1-a plasma generator, P2-a TCO target sputtering unit, P3-a plasma region, P4-a carrier plate and a substrate, P5-a transmission part and P6-a processing cavity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The inventors of the embodiments of the present invention found that the lower conductivity of the TCO film prepared by the conventional TCO film production method is mainly due to: on one hand, the first surface of the doping layer is exposed in an ultra-clean room environment for a period of time and then transferred to a magnetron sputtering film plating machine for preparing the TCO film, the first surface of the doping layer is inevitably oxidized by the ultra-clean room environment, abraded and polluted by a transmission device, settled particles suspended in air and the like, so that the first surface of the doping layer is damaged, contact resistance and surface potential barrier are increased, and the conductivity of the TCO film arranged subsequently is reduced. On the other hand, the prepared TCO film is a polycrystalline material consisting of a large number of crystal grains, and a grain boundary structure among the crystal grains can generate a scattering effect on carrier transport, so that the improvement of the carrier mobility is not facilitated. Specifically, the primary-plated TCO film often has a microstructure mainly made of an amorphous material and embedded with a large number of crystal nuclei. In the subsequent annealing process, the amorphous material is gradually transformed into a crystalline structure by taking crystal nuclei as centers, the crystal nuclei grow gradually until meeting with other crystal nuclei to form a crystal boundary, and the TCO film is transformed into a polycrystalline structure after annealing. The size of the crystal grains is related to the number density of the crystal nuclei, however, the denser the crystal nuclei, the smaller the crystal grains, and the lower the carrier mobility of the annealed TCO layer.
In the embodiment of the present invention, referring to fig. 1, fig. 1 shows a flowchart of steps of a method for producing a TCO film according to the embodiment of the present invention. The method comprises the following steps:
step S1, performing plasma treatment on the first surface of the substrate in a vacuum environment by adopting a magnetron sputtering coating machine; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: and sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment.
The substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked, and the number of the passivation layer and the doping layer in the substrate is not particularly limited. For example, the passivation layer and the doped layer may be provided only on the light-facing surface or the back-light surface of the silicon wafer. For another example, a passivation layer and a doped layer may be disposed on both the light-facing surface and the back-light surface of the silicon wafer. The substrate can be used for preparing a silicon heterojunction solar cell. In the embodiment of the present invention, this is not particularly limited.
The material of the passivation layer and the doped layer is not particularly limited. For example, the passivation layer may be an intrinsic passivation layer, the intrinsic passivation layer may be an amorphous silicon thin film, and the doped layer may be a phosphorus-doped or boron-doped amorphous silicon, microcrystalline silicon, or an oxygen-doped thin film.
Because the conductivity of the passivation layer and the doped layer is low, the collection of photon-generated carriers is not facilitated, and therefore, a TCO film needs to be arranged on the first surface of the doped layer, which is far away from the passivation layer, so that the series resistance of the battery is reduced, and the lateral transmission capability of the carriers is enhanced. Therefore, the TCO film needs to have both high electrical conductivity and light transmittance. Factors affecting the conductivity of TCO films are mainly: the carrier concentration and the carrier mobility are generally higher, the higher the carrier concentration is, the higher the conductivity of the TCO film is, and the higher the carrier mobility is, the higher the conductivity of the TCO film is. However, the inventors of the embodiments of the present invention found that: the carrier concentration and the transmittance are inversely related, for example, in the case of a constant carrier mobility, an increase in the carrier concentration causes deterioration of the transmittance. Alternatively, the conductivity of the TCO film can be increased by preparing a TCO stack instead of a single TCO film to improve transmittance and conductivity, but this results in a longer process route. Therefore, the conductivity of the TCO film is improved mainly by improving the carrier mobility.
The substrate can be obtained by the following process: cleaning and texturing a silicon wafer, and then forming a passivation layer and a doping layer on the surface of the silicon wafer in sequence by adopting a deposition mode such as PECVD or HWCVD. Referring to fig. 2, fig. 2 is a schematic structural diagram of a substrate according to an embodiment of the present invention. In fig. 2, 1 is a silicon wafer, 2 is a passivation layer, and 3 is a doped layer.
The first surface of the substrate is a surface of the doped layer far away from the passivation layer. The first surface of the substrate is the surface to be plated with the TCO film. As shown in fig. 2, the first surface of the substrate is the upper surface of the doped layer 3.
The mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas. That is, the mixed gas is a mixed gas of an inert gas and an oxidizing gas, or a mixed gas is a mixed gas of an inert gas and a reducing gas. The oxidizing gas is a gas having an oxidizing action, and the reducing gas is a gas having a reducing action. The inert gas, the oxidizing gas, and the reducing gas are not particularly limited.
Optionally, the inert gas is argon, the oxidizing gas is oxygen, and the reducing gas is hydrogen, so that the mixed gas formed by the gases is simple in obtaining mode and low in cost.
And carrying out plasma treatment on the first surface of the substrate by adopting a magnetron sputtering coating machine in a vacuum environment. The plasma treatment comprises the following steps: and performing plasma treatment by using one of the two mixed gases, or performing plasma treatment by sequentially using one of the two mixed gases and the other mixed gas. Namely, the first surface of the substrate is subjected to plasma treatment by using a magnetron sputtering coater in a vacuum atmosphere using only a mixed gas of an inert gas and an oxidizing gas. Or, a magnetron sputtering coating machine is adopted, and the plasma treatment is carried out on the first surface of the substrate only by adopting mixed gas formed by inert gas and reducing gas under the vacuum environment. Or, in a vacuum environment, the first surface of the substrate is subjected to plasma treatment by using a mixed gas of an inert gas and a reducing gas, and then the first surface of the substrate is subjected to plasma treatment by using a mixed gas of an inert gas and an oxidizing gas. Or, the first surface of the substrate is plasma-treated with a mixed gas of an inert gas and an oxidizing gas, and then plasma-treated with a mixed gas of an inert gas and a reducing gas. In the embodiment of the present invention, the selected mixed gas is not particularly limited to be subjected to plasma processing. In the process of plasma treatment by using two mixed gases, the sequence of the two mixed gases is not specifically limited, and the duration of one plasma treatment is not specifically limited.
In the plasma processing process, the first surface can be slightly oxidized by oxidizing gas, the proportion of amorphous silicon oxygen on the first surface is increased, the induced nucleation effect of the doping layer on the TCO film is weakened, and the nucleation density of the subsequent TCO film on the first surface is reduced; in the plasma treatment process, reducing atoms can be filled in the first surface through reducing gas, so that the nucleation energy of a subsequent TCO film on the first surface can be changed, the growth of crystal nuclei is inhibited, and the grain size is increased; the reduction of the nucleation density of the subsequent TCO film on the first surface and the increase of the grain diameter of the subsequent TCO film on the first surface are both beneficial to improving the carrier mobility of the TCO film, and the improvement of the carrier mobility not only can improve the conductivity of the TCO film, but also can not reduce the light transmission of the TCO film, so that the embodiment of the invention can improve the conductivity of the plated TCO film to a great extent on the basis of not reducing the light transmission of the TCO film.
And the first surface of the substrate is subjected to plasma treatment, and the ionized inert gas is used for slightly etching the first surface, so that the doped layer is not damaged, and the pollution of the first surface in the substrate production process can be removed.
And step S2, plating a TCO film on the first surface after the plasma treatment in a vacuum environment by using the magnetron sputtering film plating machine.
And plating the TCO film on the first surface after the plasma treatment in a vacuum environment by adopting a magnetron sputtering coating machine. The plasma treatment and the TCO film plating are both carried out in the same magnetron sputtering coating machine in a vacuum environment without breaking vacuum, the doping layer is not exposed in a production environment, the first surface of the doping layer is basically not subjected to mechanical damage, and the reduction of the conductivity of the TCO film plated due to the mechanical damage caused by the exposure of the doping layer in the production environment is avoided. And the first surface after plasma treatment is basically free from pollution, so that the improvement of the conductivity of the TCO film plated on the first surface after plasma treatment is facilitated.
It should be noted that, in the prior art, in the case of manufacturing a substrate, a magnetron sputtering coating machine is directly used to plate a TCO film on a first surface of a doped layer in the substrate, the first surface being far away from a passivation layer. In the embodiment of the invention, under the condition of manufacturing the substrate, a magnetron sputtering coating machine is adopted firstly, the first surface of the substrate is subjected to plasma processing in a vacuum environment, the magnetron sputtering coating machine is continuously adopted subsequently, and the TCO film is coated on the first surface after the plasma processing in the vacuum environment. The plasma treatment and the TCO film plating are both carried out in the same magnetron sputtering coating machine in a vacuum environment without breaking vacuum, the doping layer is not exposed in a production environment, the first surface of the doping layer is basically not subjected to mechanical damage, and the reduction of the conductivity of the TCO film plated due to the mechanical damage caused by the exposure of the doping layer in the production environment is avoided. The ionized inert gas slightly etches the first surface, so that the doped layer cannot be damaged, the pollution of the first surface in the substrate production process can be removed, the first surface after plasma treatment is basically free of pollution, and the improvement of the conductivity of the TCO film plated on the first surface after plasma treatment is facilitated. The first surface can be slightly oxidized by oxidizing gas, the proportion of amorphous silicon oxygen on the first surface is increased, the induced nucleation effect of the doping layer on the TCO film is weakened, and the nucleation density of the TCO film on the first surface is reduced; in the plasma treatment process, reducing atoms can be filled in the first surface through reducing gas, so that the nucleation energy of the TCO film on the first surface can be changed, the growth of crystal nuclei is inhibited, and the grain size is increased; the reduction of the nucleation density of the TCO film on the first surface and the increase of the grain diameter of the TCO film on the first surface are both beneficial to improving the carrier mobility of the TCO film, and the improvement of the carrier mobility not only can improve the conductivity of the TCO film, but also can not reduce the light transmission of the TCO film, so that the embodiment of the invention can improve the conductivity of the plated TCO film to a great extent on the basis of not reducing the light transmission of the TCO film.
For example, referring to fig. 3, fig. 3 is a schematic structural diagram of a magnetron sputtering coating machine according to an embodiment of the present invention. In fig. 3, the part C2 on the right side of the dotted line is the original part of the magnetron sputtering coater in the prior art, and the part C2 is the coating structure of the magnetron sputtering coater. The part C1 on the left side of the dotted line is the added part of the magnetron sputtering coating machine. Part C1 is the plasma processing structure of a magnetron sputter coater. The plasma processing structure C1 of the magnetron sputtering film plating machine carries out plasma processing on the first surface of the substrate in a vacuum environment, and the film plating structure C2 of the magnetron sputtering film plating machine plates a TCO film on the first surface after the plasma processing in the vacuum environment. For example, in the coating structure C2 of the magnetron sputtering coater, a TCO film is coated on the first surface of the plasma-treated substrate by using a TCO target in a vacuum environment. The magnetron sputtering coating machine can achieve the same or similar beneficial effects as the TCO film production method, and the repeated description is omitted here to avoid repetition. Moreover, the magnetron sputtering coating machine is small in improvement and simple to realize on the basis of the existing magnetron sputtering coating machine.
Referring to fig. 4, fig. 4 is a schematic structural diagram illustrating a TCO film disposed on a substrate according to an embodiment of the present invention. In fig. 4, 1 is a silicon wafer, 2 is a passivation layer, 3 is a doped layer, and 4 is a TCO film.
Optionally, the plasma processing structure comprises a processing chamber, a plasma generator, a carrier plate and a transmission component. The processing chamber is used for providing a vacuum environment, and the plasma generator is used for carrying out plasma processing on the first surface of the substrate in the vacuum environment. The carrier plate is used for carrying a substrate, and a first surface of the substrate faces the plasma generator. The transmission component is used for conveying the carrier plate carrying the substrate from one end of the processing chamber far away from the film coating structure to one end of the processing chamber close to the film coating structure. The plasma generator is used for carrying out plasma treatment on the first surface of the substrate in a vacuum environment in the process of conveying from one end of the treatment cavity far away from the coating structure to one end of the treatment cavity close to the coating structure. For the plasma treatment, reference may be made to the above description, and details thereof will not be repeated here to avoid redundancy.
As shown in FIG. 3, the plasma processing configuration C1 of the magnetron sputter coater includes: a processing chamber P6, a plasma generator P1, a carrier plate, and a transport component P5. The carrier plate carries a substrate, the carrier plate and the substrate are P4 in fig. 3, a first surface of the doped layer in the substrate, which is far away from the passivation layer, faces the plasma generator P1, and further, a plasma region P3 of the plasma generator P1 is opposite to the first surface of the doped layer in the substrate, which is far away from the passivation layer. The transport unit P5 transports the carrier plate carrying the substrate from the end of the process chamber P6 remote from the coating structure C2 to the end C2 of the process chamber P6 near the coating structure. During the process that the carrier plate carrying the substrate is conveyed by the conveying part P5 from one end of the processing chamber P6 far away from the coating structure C2 to one end C2 of the processing chamber P6 near the coating structure, the plasma generator P1 carries out plasma processing on the first surface of the substrate in a vacuum environment. The plasma treatment comprises the following steps: carrying out plasma treatment by using one mixed gas of a mixed gas formed by an inert gas and an oxidizing gas and a mixed gas formed by an inert gas and a reducing gas; or, the plasma treatment is: plasma treatment is performed using one mixed gas and the other mixed gas of the two mixed gases in this order. In fig. 3, in the coating structure C2, P2 is a TCO target sputtering unit, and P5 is a transfer unit.
Optionally, in the plasma processing process, the flow rate of the inert gas is 50-500sccm (standard-steady-state center analyzer minute), the flow rate of the oxidizing gas is less than or equal to 20sccm, and the flow rate of the reducing gas is less than or equal to 10 sccm.
For example, during the plasma treatment, the inert gas Ar has a flow rate of 50 to 500sccm and the oxidizing gas O2Is less than or equal to 20sccm, reducing gas H2Is less than or equal to 10 sccm.
Optionally, in the plasma processing process, the pressure range of the magnetron sputtering coating machine is 0.1-1Pa, and in the pressure range, the plasma processing is favorably performed on the first surface of the substrate.
Optionally, the power density of the plasma treatment is 0.1-1W/cm2I.e. the power per unit area on the first surface is in the range of 0.1-1W/cm during plasma treatment of the first surface of the substrate2At this power density, the plasma treatment does not substantially affect the doped layer, but can provide a slight etching and cleaning action on the surface of the doped layer.
As shown in FIG. 3, the plasma generator P1 in the plasma processing structure C1 of the magnetron sputtering coater has a power density per unit area of 0.1-1W/cm on the first surface of the substrate during the first surface plasma processing of the substrate2。
Optionally, the driving power supply for plasma processing is: the direct current stabilized power supply or the radio frequency power supply is common in driving power supply and low in cost, and the power supply does not substantially influence the doped layer, but can slightly etch and clean the surface of the doped layer.
As shown in FIG. 3, the driving power of the plasma generator P1 in the plasma processing structure C1 of the magnetron sputtering coating machine is a DC stabilized power supply or a radio frequency power supply.
Optionally, the driving power supply for plasma processing is: the medium-frequency radio-frequency power supply in the radio-frequency power supply has smaller influence on the doped layer and can generate slight etching and cleaning effects on the surface of the doped layer.
Optionally, the number of the plasma generators in the magnetron sputtering film plating machine is greater than or equal to 1, and under the condition that the number of the plasma generators is greater than 1, the plurality of plasma generators are respectively located on two sides of the substrate, the substrate includes a silicon wafer, the light facing surface and the light back surface of the silicon wafer are both sequentially provided with a passivation layer and a doping layer, and the plasma generators respectively located on two sides of the substrate respectively and simultaneously perform plasma treatment on the corresponding first surfaces. That is to say, the passivation layer and the doping layer are sequentially arranged on the two sides of the light facing surface and the two sides of the backlight surface of the silicon wafer, and the first surfaces, far away from the passivation layer, of the doping layers on the two sides are required to be subjected to TCO film production, so that the plasma generators respectively located on the two sides of the substrate respectively perform plasma treatment on the corresponding first surfaces at the same time, and further the treatment efficiency is high.
For example, referring to fig. 5, fig. 5 shows a schematic structural diagram of a TCO film disposed on a substrate according to another embodiment of the present invention. In fig. 5, 1 is a silicon wafer, 2 is a passivation layer, 3 is a doped layer, and 4 is a TCO film. For the substrate shown in fig. 5, a passivation layer 2 and a doping layer 3 are sequentially arranged on both sides of the light-facing surface and the backlight surface of the silicon wafer 1, and the TCO film 4 needs to be produced on the first surfaces of the doping layers 3 on both sides far away from the passivation layer 2. Then, the number of plasma generators in the magnetron sputtering coater may be 2, and 2 plasma generators are respectively located at both sides of the substrate, that is, 1 plasma generator located at the upper side of the substrate and 1 plasma generator located at the lower side of the substrate. And the 1 plasma generator positioned on the upper side of the substrate performs plasma treatment on the first surface of the upper doped layer 3 far away from the passivation layer 2, and the 1 plasma generator positioned on the lower side of the substrate performs plasma treatment on the first surface of the lower doped layer 3 far away from the passivation layer 2. 2 plasma generators can be simultaneously carried out, and the plasma treatment efficiency is high.
It should be noted that, in the structure in which the TCO film is provided on the substrate, the electrode is provided on the side of the TCO film away from the doped layer, so that the solar cell can be obtained. For example, referring to fig. 6, fig. 6 is a schematic structural diagram of a solar cell according to an embodiment of the present invention. On the basis of fig. 5, in fig. 6, an electrode 5 is disposed on the side of the TCO film 4 on the upper side of the silicon wafer 1 away from the doped layer 3, and an electrode 5 is disposed on the side of the TCO film 4 on the lower side of the silicon wafer 1 away from the doped layer 3, thereby obtaining the solar cell. Of the 2 doped layers 3 located on both sides of the silicon wafer 1, 1 doped layer 3 may be a thin film material such as phosphorus-doped amorphous silicon, microcrystalline silicon, or microcrystalline silicon, and the other 1 doped layer 3 may be a thin film material such as boron-doped amorphous silicon, microcrystalline silicon, or microcrystalline silicon, and the solar cell may be a Silicon Heterojunction (SHJ) solar cell.
An embodiment of the present invention further provides a magnetron sputtering coating machine, and as shown in fig. 3, the magnetron sputtering coating machine includes: plasma treated structure C1 and coated structure C2.
The plasma processing structure C1 is used for performing plasma processing on the first surface of the substrate in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas comprises: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: plasma treatment is performed using one mixed gas and the other mixed gas of the two mixed gases in this order.
The coating structure C2 is used for coating a TCO film on the plasma-treated first surface in a vacuum environment.
Alternatively, referring to fig. 3, the plasma processing structure C1 includes a processing chamber P6, a plasma generator P1, a carrier plate, and a transfer unit P5. The processing chamber P6 is used to provide a vacuum environment; the plasma generator P1 is used for performing plasma processing on the first surface of the substrate in a vacuum environment. The carrier plate is used for carrying the substrate, the first surface of the substrate faces the plasma generator, and further, the plasma area P3 of the plasma generator faces the first surface of the substrate. The transport unit P5 is used to transport a carrier board carrying substrates from one end of the process chamber P6, which is remote from the coating structure C2, to one end of the process chamber P6, which is close to the coating structure C2.
Optionally, the number of the plasma generators in the magnetron sputtering film plating machine is greater than or equal to 1, and when the number of the plasma generators is greater than 1, the plurality of plasma generators are respectively located on two sides of the substrate, the substrate includes a silicon wafer, the light facing surface and the light back surface of the silicon wafer are both sequentially provided with a passivation layer and a doping layer, and the plasma generators respectively located on two sides of the substrate simultaneously perform plasma treatment on the corresponding first surfaces.
For the magnetron sputtering coater, reference may be made to the related content of the above-mentioned TCO film production method, and the same or similar beneficial effects can be achieved, so that the details are not repeated herein for the sake of avoiding repetition.
The invention is further illustrated by the following specific examples.
Comparative example
The production method of the solar cell includes steps SA1-SA 3:
and step SA1, cleaning and texturing the silicon wafer, and forming a passivation layer and a doping layer on two sides of the silicon wafer on two opposite surfaces of the silicon wafer by adopting PECVD or HWCVD to obtain a substrate. The light facing surface of the silicon chip in the substrate is sequentially provided with a passivation layer and a doping layer, and the backlight surface of the silicon chip is also sequentially provided with the passivation layer and the doping layer.
And step SA2, plating a TCO film on the first surface of the substrate in a vacuum environment by using a magnetron sputtering coating machine.
Step SA3, disposing an electrode on the TCO film on the side away from the doped layer, so as to obtain the solar cell shown in fig. 6.
In the comparative example, the first surface of the substrate was not plasma treated prior to plating the TCO film on the first surface of the substrate.
Example 1
The method for producing a solar cell includes steps SB1-SB 4:
and step SB1, cleaning and texturing the silicon wafer, and forming a passivation layer and a doping layer on two sides of the silicon wafer on two opposite surfaces of the silicon wafer by adopting PECVD or HWCVD to obtain the substrate. The light facing surface of the silicon chip in the substrate is sequentially provided with a passivation layer and a doping layer, and the backlight surface of the silicon chip is also sequentially provided with the passivation layer and the doping layer.
The step SB1 corresponds to the same step as the step SA1 described above.
Step SB2, using a magnetron sputtering film plating machine, and using Ar and O on the first surface of the substrate in a vacuum environment2The resulting mixed gas is subjected to plasma treatment.
In the step SB2, the flow rate of Ar is 200sccm and O2The flow rate of (3) was 6sccm, and the power density of the plasma treatment was 0.15W/cm2。
And step SB3, plating a TCO film on the first surface after the plasma treatment in a vacuum environment by using the magnetron sputtering film plating machine. The process of plating the TCO film is the same as the process of plating the TCO film in the step SA 2.
And step SB4, arranging an electrode on the side of the TCO film far away from the doped layer to obtain the solar cell shown in FIG. 6. The step SB4 corresponds to the same step as the step SA3 described above.
In example 1, before the first surface of the substrate is coated with the TCO film, Ar and O are applied to the first surface of the substrate under a vacuum environment2The resulting mixed gas is subjected to plasma treatment.
Example 2
The method for producing a solar cell comprises the steps SC1-SC 4:
and step SC1, cleaning and texturing the silicon wafer, and then forming a passivation layer and a doping layer on two sides of the silicon wafer on two opposite surfaces of the silicon wafer by adopting PECVD or HWCVD to obtain the substrate. The light facing surface of the silicon chip in the substrate is sequentially provided with a passivation layer and a doping layer, and the backlight surface of the silicon chip is also sequentially provided with the passivation layer and the doping layer.
Step SC2, adopting a magnetron sputtering film plating machine, and using Ar and H to the first surface of the substrate in a vacuum environment2The resulting mixed gas is subjected to plasma treatment.
In step SC2, the flow rate of Ar is 200sccm, H2The flow rate of (A) was 0.5sccm, and the power density of plasma treatment was 0.15W/cm2。
And step SC3, plating a TCO film on the first surface after plasma treatment in a vacuum environment by using the magnetron sputtering film plating machine. The process of plating the TCO film is the same as the process of plating the TCO film in the step SA 2.
And step SC4, arranging an electrode on the side of the TCO film far away from the doped layer, and obtaining the solar cell shown in FIG. 6. This step SC4 corresponds to the aforementioned SA 3.
In example 2, before the first surface of the substrate is coated with the TCO film, Ar and H are applied to the first surface of the substrate under a vacuum environment2The resulting mixed gas is subjected to plasma treatment.
And (3) performance testing:
in the same experimental environment, the short-circuit current density Isc of the solar cells prepared in comparative example, example 1 and example 2 was measured in units of: mA/cm2Open circuit voltage Voc in mV, fill factor FF, conversion efficiency Eff, and the test results are given in table 1 below. Wherein, table 1 is: the results of the test on the solar cells manufactured in the comparative example, example 1 and example 2 in the identical experimental environment are shown in the table.
Table 1: comparative example, example 1, and example 2, the test results of the solar cells in the identical experimental environment are compared in the table
Figure BDA0002597655890000171
As can be seen from table 1, the conversion efficiency (Eff) of the solar cells corresponding to examples 1 and 2 is significantly improved compared to the comparative example in which the first surface of the substrate is not plasma-treated before the TCO film is plated on the first surface of the substrate, wherein the improvement is 0.21% of the maximum solar cell corresponding to example 2. Ar and O for different mixed gases taken in plasma treatment, relative to comparative example2The plasma treatment, in response to the formation of a mixed gas, causes a slight decrease in the open circuit voltage (Voc) and the fill factor FF, but a slight increase in the short circuit current (Isc), and a slight increase in the overall conversion efficiency Eff; ar and H2The plasma treatment corresponding to the formed mixed gas not only increases the fill factor FF but also improves the open-circuit voltage Voc, so that the conversion efficiency Eff has larger gain.
Compared with the conventional or comparative TCO film production method, the TCO film production method disclosed by the embodiment of the invention has the advantages that the first surface of the substrate is subjected to plasma treatment, the crystal structure and the chemical state of the first surface, away from the passivation layer, of the doped layer in the substrate are adjusted, the number density of crystal nuclei in the TCO film is reduced, the size of crystal grains is increased, the higher carrier mobility is obtained, and the conversion efficiency of solar energy formed by the TCO film prepared by the method is obviously improved.
It should be noted that for simplicity of description, the method embodiments are described as a series of acts or combination of acts, but those skilled in the art will recognize that the present invention is not limited by the illustrated order of acts, as some steps may occur in other orders or concurrently depending on the embodiment of the invention. Furthermore, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred and that no particular act is required to implement the invention.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative rather than restrictive, and it will be apparent to those skilled in the art that many more modifications and variations can be made without departing from the spirit of the invention and the scope of the appended claims.

Claims (10)

1. A method for producing a TCO film, comprising the steps of:
performing plasma treatment on the first surface of the substrate by using a magnetron sputtering coating machine in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment;
and plating the TCO film on the first surface treated by the plasma in a vacuum environment by using the magnetron sputtering coating machine.
2. The method for producing a TCO film according to claim 1, wherein the inert gas has a flow rate of 50 to 500 seem, the oxidizing gas has a flow rate of 20 seem or less, and the reducing gas has a flow rate of 10 seem or less.
3. The method for producing a TCO film according to claim 1, wherein the inert gas is argon, the oxidizing gas is oxygen, and the reducing gas is hydrogen.
4. The method for producing a TCO film according to claim 1, wherein the pressure of the magnetron sputtering coater during the plasma treatment is in the range of 0.1 to 1 Pa.
5. The method for producing a TCO film according to claim 1 wherein the power density of the plasma treatment is 0.1-1W/cm2。
6. The method for producing a TCO film according to any one of claims 1 to 5, wherein the driving power source for the plasma treatment is: a DC stabilized power supply or a radio frequency power supply.
7. The method for producing a TCO film according to claim 6, wherein the radio frequency power source is an intermediate frequency radio frequency power source.
8. A magnetron sputtering coating machine is characterized by comprising: a plasma processing structure and a coating structure;
the plasma processing structure is used for carrying out plasma processing on the first surface of the substrate in a vacuum environment; the substrate includes: the silicon chip, the passivation layer and the doping layer are sequentially stacked; the first surface is the surface of the doped layer far away from the passivation layer; the plasma treatment comprises the following steps: carrying out plasma treatment by using mixed gas; the mixed gas is: one of mixed gas formed by inert gas and oxidizing gas and mixed gas formed by inert gas and reducing gas; or, the plasma treatment is: sequentially using one mixed gas and the other mixed gas of the two mixed gases to perform plasma treatment;
the coating structure is used for coating a TCO film on the first surface after plasma treatment in a vacuum environment.
9. The magnetron sputter coater of claim 8 wherein said plasma processing structure comprises a process chamber, a plasma generator, a carrier plate, a transport member;
the processing chamber is used for providing a vacuum environment;
the plasma generator is used for carrying out plasma treatment on the first surface of the substrate in a vacuum environment;
the carrier plate is used for carrying the substrate, and a first surface of the substrate faces the plasma generator;
the transmission component is used for conveying a carrier plate carrying a substrate from one end of the processing cavity far away from the film coating structure to one end of the processing cavity close to the film coating structure.
10. The magnetron sputter coating machine according to claim 9 wherein the number of said plasma generators is greater than or equal to 1, and in the case where the number of said plasma generators is greater than 1, a plurality of said plasma generators are respectively located on both sides of a substrate, said substrate comprises a silicon wafer, a passivation layer and a doping layer are sequentially disposed on both light-facing surfaces and a backlight surface of the silicon wafer, and the plasma generators respectively located on both sides of the substrate simultaneously plasma-treat the corresponding first surfaces respectively.
CN202010714648.0A 2020-07-22 2020-07-22 Production method of TCO film and magnetron sputtering coating machine Pending CN111793785A (en)

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