CN111206204A - Film coating equipment and film coating method - Google Patents

Film coating equipment and film coating method Download PDF

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Publication number
CN111206204A
CN111206204A CN201811303296.9A CN201811303296A CN111206204A CN 111206204 A CN111206204 A CN 111206204A CN 201811303296 A CN201811303296 A CN 201811303296A CN 111206204 A CN111206204 A CN 111206204A
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China
Prior art keywords
evaporation source
deposition chamber
metal
evaporation
sources
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CN201811303296.9A
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Inventor
辛科
杨立红
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Shanghai zuqiang Energy Co.,Ltd.
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Beijing Apollo Ding Rong Solar Technology Co Ltd
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Priority to CN201811303296.9A priority Critical patent/CN111206204A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623Sulfides, selenides or tellurides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02Pretreatment of the material to be coated
    • C23C14/024Deposition of sublayers, e.g. to promote adhesion of the coating
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694Halides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58After-treatment

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention provides a coating device and a coating method, wherein the coating device comprises a first deposition chamber and a second deposition chamber which are connected, the first deposition chamber and the second deposition chamber respectively comprise at least one row of non-metal evaporation sources, each row of non-metal evaporation sources corresponds to at least two rows of metal evaporation sources, and in the metal evaporation sources corresponding to each row of non-metal evaporation sources, the at least two rows of metal evaporation sources are symmetrically arranged relative to the row of non-metal evaporation sources; wherein the total number of the metal evaporation sources in each row in the second deposition chamber is 10. The method can generate the CIGS thin film with uniform thickness and good performance, and effectively improves the power generation efficiency of the solar cell.

Description

Film coating equipment and film coating method
Technical Field
The invention relates to the technical field of coating of solar cell substrates, in particular to coating equipment and a coating method.
Background
The thin-film solar cell converts light energy into electric energy, the conversion from the light energy to the electric energy can be completed as long as light exists, great convenience is provided for users, and particularly outdoor sporters do not need to consider the problem that the electric equipment needs to be charged by finding places even if the outdoor sporters stay outdoors for a long time.
In the prior art, a CIGS thin film is formed on a substrate by mainly adopting a magnetron sputtering method to form a solar cell, and the method mainly utilizes positive ions generated by gas discharge to move at a high speed under the action of an electric field so as to bombard a target serving as a cathode, so that atoms or molecules in the target serving as the cathode escape and are deposited on the surface of the substrate, and a thin film capable of converting solar energy into electric energy is formed on the substrate. The film formed by the magnetron sputtering method has better adhesiveness with the substrate, and the density of the formed film is higher.
However, the magnetron sputtering method adopts glow discharge under the control of an annular magnetic field, the film forming rate is poor, and magnetron sputtering equipment needs a high-voltage device, so that the equipment is complex and expensive, and is not favorable for large-scale production of solar cells. In addition, the CIGS thin film formed by magnetron sputtering has non-uniform thickness and poor quality, thereby resulting in poor performance of the solar cell and low power generation efficiency.
Disclosure of Invention
The embodiment of the invention provides a coating device and a coating method, which aim to solve the technical problems of low power generation efficiency of a solar cell caused by uneven thickness and poor performance of a CIGS thin film formed by a magnetron sputtering method in the prior art.
In a first aspect, the present invention provides a coating apparatus comprising a first deposition chamber and a second deposition chamber connected, wherein:
the first deposition chamber and the second deposition chamber respectively comprise at least one row of non-metal evaporation sources, each row of non-metal evaporation sources corresponds to at least two rows of metal evaporation sources, and in the metal evaporation sources corresponding to each row of non-metal evaporation sources, the at least two rows of metal evaporation sources are symmetrically arranged relative to the row of non-metal evaporation sources; wherein the total number of metal evaporation sources in each row in the second deposition chamber is 10.
Optionally, the metal evaporation source of the first deposition chamber is disposed at the bottom of the first deposition chamber, and the metal evaporation source In the first deposition chamber includes a Ga evaporation source and an In evaporation source; the non-metal evaporation source in the first deposition chamber comprises a Se evaporation source;
and/or
The metal evaporation source of the second deposition chamber is arranged at the bottom of the second deposition chamber, and comprises a Cu evaporation source, an In evaporation source and a Ga evaporation source; the non-metal evaporation source in the second deposition chamber comprises a Se evaporation source.
Metal evaporation sources are symmetrically arranged on the two sides of the first deposition chamber and the second deposition chamber and below the substrate, so that the coating film is more uniform, and the electrical property and the crystallization property are better.
Optionally, in the above coating apparatus, the bottom of the first deposition chamber includes two sides that are oppositely disposed, at least one row of metal evaporation sources is disposed on each side, and the total number of the metal evaporation sources in each row is M, where M is an integer greater than or equal to 2 and less than or equal to 7; the total number of the non-metal evaporation sources in each row of the first deposition chamber is N, wherein N is an integer which is greater than or equal to 3 and less than or equal to 9;
and/or
The bottom of the second deposition chamber comprises two opposite sides, and each side is provided with at least one row of metal evaporation sources; the total number of each row of non-metal evaporation sources of the second deposition chamber is Y, wherein Y is an integer which is greater than or equal to 7 and less than or equal to 15.
Optionally, the arrangement sequence of each row of metal evaporation sources of the first deposition chamber along the length direction of the first deposition chamber sequentially is:
an In evaporation source, a Ga evaporation source and an In evaporation source; or
A Ga evaporation source, an In evaporation source, and a Ga evaporation source; or
An In evaporation source, a Ga evaporation source, an In evaporation source and a Ga evaporation source; or
A Ga evaporation source, an In evaporation source, and an In evaporation source; or
Ga evaporation source, In evaporation source, Ga evaporation source, In evaporation source; or
An In evaporation source, a Ga evaporation source, and an In evaporation source; or
Ga evaporation source, In evaporation source, Ga evaporation source; or
An In evaporation source, a Ga evaporation source, and a Ga evaporation source;
and/or
The arrangement sequence of each row of metal evaporation sources of the second deposition chamber along the length direction of the second deposition chamber is as follows:
a Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
An In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
Ga evaporation source, In evaporation source, Cu evaporation source, Ga evaporation source, In evaporation source, Cu evaporation source, In evaporation source.
For random sequencing of the metal evaporation sources, the metal evaporation sources are distributed according to the distribution mode of the metal evaporation sources in the first deposition chamber and the second deposition chamber, so that the stability of the CIGS thin film can be improved, and the power generation efficiency and the yield of the thin-film solar cell are improved; the application further provides a thin film solar cell with stable performance and high efficiency.
Optionally, in the coating apparatus, a gap is formed between each two adjacent metal evaporation sources in each row of the first deposition chamber; when the metal evaporation sources on each side of the first deposition chamber are in multiple rows, the metal evaporation sources in the multiple rows are aligned or staggered;
a gap is reserved between each two adjacent rows of non-metal evaporation sources of the first deposition chamber; when the non-metal evaporation sources of the first deposition chamber are in multiple rows, the multiple rows of non-metal evaporation sources are aligned or staggered;
and/or
A gap is reserved between each two adjacent metal evaporation sources in each row of the second deposition chamber; when the metal evaporation sources on each side of the second deposition chamber are in multiple rows, the multiple rows of metal evaporation sources are aligned or staggered;
a gap is reserved between each two adjacent rows of non-metal evaporation sources of the second deposition chamber; when the non-metal evaporation sources of the second deposition chamber are in multiple rows, the multiple rows of non-metal evaporation sources are aligned or staggered. The arrangement of the metal evaporation source and the nonmetal evaporation source in the first deposition chamber and the second deposition chamber can make the coating more uniform, and the electrical property and the crystallization property are better.
Optionally, in the above coating apparatus, an inclined included angle α is formed between the metal evaporation source of the first deposition chamber and the metal evaporation source of the second deposition chamber and a reference line, the reference line is a straight line perpendicular to the bottom of the deposition chamber, and each inclined included angle α is 18-48 degrees.
Optionally, the plating device further includes:
the device comprises a first deposition chamber, a second deposition chamber and a pretreatment chamber and/or a post-treatment chamber, wherein the pretreatment chamber is connected between the first deposition chamber and the second deposition chamber, and an alkali metal compound evaporation source is arranged in the pretreatment chamber; the post-processing chamber is connected behind the second deposition chamber, and an alkali metal compound evaporation source is arranged in the post-processing chamber.
In a second aspect, the present invention provides a coating method applied to any one of the above coating apparatuses, the method including:
controlling a temperature of a first deposition chamber, In which (In, Ga) is formed on a surface of a substrate by a deposition process, to a first predetermined temperature threshold2Se3A film;
controlling the temperature of a second deposition chamber In which the (In, Ga) is deposited by a deposition process to a second predetermined temperature threshold2Se3The surface of the film is deposited to form a CIGS film.
Optionally, In the above-mentioned coating method, the temperature of the second deposition chamber is controlled to reach a second preset temperature threshold, and the (In, Ga) is deposited In the second deposition chamber by a deposition process2Se3The surface deposition of thin films forms CIGS thin films, including:
controlling the temperature of the second deposition chamber to a second predetermined temperature threshold by a deposition process on said (In, Ga)2Se3Depositing Cu on the surface of the film to form Cu (In, Ga) lean In copper3Se5A film;
in the Cu (In, Ga) lean In copper3Se5Depositing Cu on the surface of the film to form Cu (In, Ga) Se rich In copper2Thin film and liquid phase Cu2Se;
In the Cu (In, Ga) Se rich In copper2Thin film and liquid phase Cu2And depositing In, Ga and Se on the surface of Se to form a CIGS thin film.
Optionally, in the above coating method, the temperature of the first deposition chamber is controlled to reach a first preset temperature threshold, and deposition is performed in the first deposition chamberThe process forms (In, Ga) on the surface of the substrate2Se3After the thin film is formed, controlling the temperature of the second deposition chamber to reach a second preset temperature threshold, and depositing the (In, Ga) In the second deposition chamber through a deposition process2Se3The surface deposition of the film, before forming the CIGS film, also includes:
in the above (In, Ga)2Se3Depositing alkali metal on the surface of the film; and/or
Controlling the temperature of the second deposition chamber In which the (In, Ga) is deposited by the deposition process to reach a second predetermined temperature threshold2Se3After the CIGS thin film is formed by depositing on the surface of the thin film, the method further comprises the following steps:
and performing deposition treatment of alkali metal on the surface of the CIGS thin film.
The embodiment of the invention adopts at least one technical scheme which can achieve the following beneficial effects:
compared with the prior art of forming a CIGS film by adopting a magnetron sputtering method, the invention provides the film coating equipment comprising two deposition chambers which are both provided with a metal evaporation source and a nonmetal evaporation source, the metal evaporation source in each deposition chamber is changed into a gas state from a solid state by heating to a certain temperature, the gas metal evaporation source rises to the top of the deposition chamber to be coated on a substrate, and finally, the film battery capable of converting solar energy into electric energy is formed. The method adopts a co-evaporation deposition method to form the CIGS thin film with uniform thickness, thereby not only reducing the manufacturing cost of equipment, but also improving the film forming speed, simultaneously improving the uniformity of CIGS film coating, improving the performance of the CIGS thin film and improving the power generation efficiency of the thin film solar cell.
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 not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram illustrating arrangement of metal evaporation sources and non-metal evaporation sources in a first deposition chamber according to an embodiment of the present invention;
FIG. 2a is a schematic diagram of the arrangement of a metal evaporation source and a non-metal evaporation source in a first deposition chamber according to another embodiment of the present invention;
FIG. 2b is a schematic diagram illustrating the arrangement of a metal evaporation source and a non-metal evaporation source in the first deposition chamber according to yet another embodiment of the present invention;
FIG. 2c is a schematic diagram illustrating the arrangement of metal evaporation sources and non-metal evaporation sources in the first deposition chamber according to yet another embodiment of the present invention;
FIG. 2d is a schematic diagram illustrating the arrangement of a metal evaporation source and a non-metal evaporation source in the first deposition chamber according to yet another embodiment of the present invention;
FIG. 2e is a schematic diagram illustrating the arrangement of a metal evaporation source and a non-metal evaporation source in the first deposition chamber according to yet another embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating the arrangement of metal evaporation sources and non-metal evaporation sources in a second deposition chamber according to an embodiment of the present invention;
FIG. 4a is a schematic diagram illustrating the arrangement of a metal evaporation source and a non-metal evaporation source in a second deposition chamber according to another embodiment of the present invention;
FIG. 4b is a schematic diagram illustrating the arrangement of metal evaporation sources and non-metal evaporation sources in the second deposition chamber according to yet another embodiment of the present invention;
FIG. 4c is a schematic diagram illustrating the arrangement of metal evaporation sources and non-metal evaporation sources in the second deposition chamber according to yet another embodiment of the present invention;
FIG. 4d is a schematic diagram illustrating the arrangement of the metal evaporation source and the non-metal evaporation source in the second deposition chamber according to yet another embodiment of the present invention;
FIG. 4e is a schematic diagram illustrating the arrangement of the metal evaporation source and the non-metal evaporation source in the second deposition chamber according to yet another embodiment of the present invention;
FIG. 5 is a schematic block diagram of a CIGS coating apparatus according to an embodiment of the present invention;
FIG. 6a is a schematic diagram illustrating the alignment of metal evaporation sources in the first deposition chamber according to an embodiment of the present invention;
FIG. 6b is a schematic diagram illustrating the arrangement of the metal evaporation sources in the first deposition chamber in a staggered manner according to an embodiment of the present invention;
FIG. 7a is a schematic diagram illustrating the alignment of metal evaporation sources in the second deposition chamber according to an embodiment of the present invention;
FIG. 7b is a schematic diagram illustrating the staggered arrangement of the metal evaporation sources in the second deposition chamber according to an embodiment of the present invention;
FIG. 8 is a side view of a metal evaporation source disposed at an oblique angle with respect to a bottom plate of a deposition chamber in an embodiment of the present invention;
FIG. 9 is a schematic block diagram of a CIGS coating apparatus according to another embodiment of the present invention;
FIG. 10 is a schematic diagram illustrating the arrangement of evaporation sources in the pretreatment chamber according to an embodiment of the present invention;
FIG. 11 is a schematic diagram illustrating the arrangement of evaporation sources in the post-processing chamber according to an embodiment of the present invention;
fig. 12 is a graph showing a temperature change of a substrate in a CIGS coating apparatus according to an embodiment of the present invention;
FIG. 13 is a flow chart of a CIGS coating method in an embodiment of the present invention;
fig. 14 is a flow chart of another CIGS coating method according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort, belong to the protection scope of the present invention.
The technical solutions provided by the embodiments of the present invention are described in detail below with reference to the accompanying drawings.
The embodiment of the invention discloses a coating device, which comprises a first deposition chamber 11 and a second deposition chamber 13 which are connected, wherein:
referring to fig. 1, the first deposition chamber 11 includes at least one row of non-metal evaporation sources 112, each row of non-metal evaporation sources 112 corresponds to at least two rows of metal evaporation sources 111, and in the metal evaporation sources 111 corresponding to each row of non-metal evaporation sources 112, the at least two rows of metal evaporation sources 111 are symmetrically arranged with respect to the row of non-metal evaporation sources 112. The at least one row includes one row, two rows, three rows, four rows and other odd or even rows greater than or equal to 1, the first at least two rows includes two rows, three rows, four rows, five rows, six rows and other odd or even rows greater than 2, and the second at least two rows refers specifically to two rows, four rows, six rows and other even rows greater than 2.
Alternatively, in one embodiment of the present invention, referring to fig. 2a, the first deposition chamber 11 includes a row of non-metal evaporation sources 112, the row of non-metal evaporation sources 112 corresponds to two rows of metal evaporation sources 111, and the two rows of metal evaporation sources 111 are symmetrically arranged with respect to the row of non-metal evaporation sources 112.
Alternatively, in one embodiment of the present invention, referring to fig. 2b, the first deposition chamber 11 includes one row of non-metal evaporation sources 112, the row of non-metal evaporation sources 112 corresponds to three rows of metal evaporation sources 111, and two rows of metal evaporation sources 111 (i.e., the upper first row of metal evaporation sources 111 and the lower last row of metal evaporation sources 111 in fig. 2 b) are symmetrically disposed with respect to the row of non-metal evaporation sources 112, and the remaining one row of metal evaporation sources 111 (i.e., the upper second row of metal evaporation sources 111 in fig. 2 b) can be closely disposed in parallel to one row of symmetrically disposed metal evaporation sources 111 (close to and in parallel to the upper first row of metal evaporation sources 111 in fig. 2 b).
Alternatively, in one embodiment of the present invention, referring to fig. 2c, the first deposition chamber 11 includes two rows of non-metal evaporation sources 112, each row of non-metal evaporation sources 112 corresponds to two rows of metal evaporation sources 111, and the two rows of metal evaporation sources 111 are symmetrically arranged with respect to the corresponding row of non-metal evaporation sources 112.
Alternatively, in one embodiment of the present invention, referring to fig. 2d, the first deposition chamber 11 includes two rows of non-metal evaporation sources 112, each row of non-metal evaporation sources 112 corresponds to four rows of metal evaporation sources 111, and the four rows of metal evaporation sources 111 are symmetrically arranged with respect to the corresponding row of non-metal evaporation sources 112.
Alternatively, in one embodiment of the present invention, as shown in fig. 2e, the first deposition chamber 11 includes two rows of non-metal evaporation sources 112, the two rows of non-metal evaporation sources 112 can be seen as a whole, all non-metal evaporation sources 112 of the whole (the middle two rows of non-metal evaporation sources 112 in fig. 2e are whole) correspond to four rows of metal evaporation sources 111 (the upper two rows of metal evaporation sources 111 and the lower two rows of metal evaporation sources 111 in fig. 2 e), and the four rows of metal evaporation sources 111 are symmetrically arranged with respect to all non-metal evaporation sources 112 of the whole.
Referring to fig. 3, the second deposition chamber 13 includes at least one row of non-metal evaporation sources 132, each row of non-metal evaporation sources 132 corresponds to at least two rows of metal evaporation sources 131, and in the metal evaporation sources 131 corresponding to each row of non-metal evaporation sources 132, the at least two rows of metal evaporation sources 131 are symmetrically arranged with respect to the row of non-metal evaporation sources 132.
Alternatively, in one embodiment of the present invention, referring to fig. 4a, the second deposition chamber 13 includes a row of non-metal evaporation sources 132, the row of non-metal evaporation sources 132 corresponds to two rows of metal evaporation sources 131, and the two rows of metal evaporation sources 131 are symmetrically arranged with respect to the row of non-metal evaporation sources 132.
Alternatively, in one embodiment of the present invention, referring to fig. 4b, the second deposition chamber 13 includes a row of non-metal evaporation sources 132, the row of non-metal evaporation sources 132 corresponds to three rows of metal evaporation sources 131, two rows of metal evaporation sources 131 (i.e., the upper first row of metal evaporation sources 131 and the lower last row of metal evaporation sources 131 in fig. 4 b) are symmetrically disposed with respect to the row of non-metal evaporation sources 132, and the remaining row of metal evaporation sources 131 (i.e., the upper second row of metal evaporation sources 131 in fig. 4 b) can be closely disposed in parallel to the symmetrically disposed one row of metal evaporation sources 131 (i.e., close to and parallel to the upper first row of metal evaporation sources 131 in fig. 4 b).
Alternatively, in one embodiment of the present invention, referring to fig. 4c, the second deposition chamber 13 includes two rows of non-metal evaporation sources 132, each row of non-metal evaporation sources 132 corresponds to two rows of metal evaporation sources 131, and the two rows of metal evaporation sources 131 are symmetrically arranged with respect to the corresponding row of non-metal evaporation sources 132.
Alternatively, in one embodiment of the present invention, referring to fig. 4d, the second deposition chamber 13 includes two rows of non-metal evaporation sources 132, each row of non-metal evaporation sources 132 corresponds to four rows of metal evaporation sources 131, and the four rows of metal evaporation sources 131 are symmetrically arranged with respect to the corresponding row of non-metal evaporation sources 132.
Alternatively, in one embodiment of the present invention, referring to fig. 4e, the second deposition chamber 13 includes two rows of non-metal evaporation sources 132, the two rows of non-metal evaporation sources 132 can be seen as a whole, all non-metal evaporation sources 132 of the whole (the middle two rows of non-metal evaporation sources 132 in fig. 4e are whole) correspond to four rows of metal evaporation sources 131 (the upper two rows of metal evaporation sources 131 and the lower two rows of metal evaporation sources 131 in fig. 4 e), and the four rows of metal evaporation sources 131 are symmetrically arranged with respect to all non-metal evaporation sources 132 of the whole.
In the above embodiments, the first deposition chamber 11 and the second deposition chamber 13 may be selectively used in combination according to actual production requirements, and the number of rows and arrangement of the metal evaporation sources and the non-metal evaporation sources of each deposition chamber are not limited to the above case, so as to form a CIGS thin film that meets the requirement of a CIGS thin film with a coating thickness of about 2 μm) and has a uniform thickness.
In one embodiment of the present invention, referring to fig. 5, the bottom of the first deposition chamber 11 includes two sides disposed opposite to each other, all the non-metal evaporation sources 112 are disposed in the middle of the bottom (or bottom plate) of the first deposition chamber 11 along the length direction of the first deposition chamber 11, all the metal evaporation sources 111 are disposed on two sides of the bottom of the first deposition chamber 11 symmetrically with respect to all the non-metal evaporation sources 112 as a whole, and each row of the metal evaporation sources 111 is arranged along the length direction of the first deposition chamber 11.
The bottom of the second deposition chamber 13 includes two opposite sides, all the non-metal evaporation sources 132 are disposed in the middle of the bottom (or bottom plate) of the second deposition chamber 13 along the length direction of the second deposition chamber 13, all the metal evaporation sources 131 of the second deposition chamber 13 are integrally and symmetrically disposed on two sides of the bottom of the second deposition chamber 3 relative to all the non-metal evaporation sources 132, and each row of metal evaporation sources 131 is arranged along the length direction of the second deposition chamber 13; the total number of metal evaporation sources 131 per line in the second deposition chamber 13 is 10.
In the embodiment of the present invention, the metal evaporation sources are disposed on both sides of the bottom of the first deposition chamber 11 and/or the second deposition chamber 13, and the non-metal evaporation sources are disposed between the metal evaporation sources on both sides of the bottom of the first deposition chamber 11 and/or the second deposition chamber 13, so that the non-metal evaporation sources formed from solid non-metal powder in a gaseous state have better diffusibility than the metal in a gaseous state during the evaporation process due to the lower density of the non-metal material, and therefore, the metal evaporation sources are disposed on both sides of the first deposition chamber 11 and/or the second deposition chamber 13, and the non-metal evaporation sources are disposed between the metal evaporation sources on both sides of the bottom of the first deposition chamber 11 and/or the second deposition chamber 13, so that the formation of a solar power generation thin film with uniform thickness on the substrate of the CIGS thin film to be plated can be effectively ensured, thereby improving the quality, thereby effectively improving the high performance and the high power generation efficiency of the solar cell.
In one embodiment of the present invention, the metal evaporation sources 111 symmetrically disposed at both sides of the bottom of the first deposition chamber 11 include a Ga evaporation source and an In evaporation source; the non-metal evaporation source 112 of the first deposition chamber 11 includes a Se evaporation source, and/or the metal evaporation sources 131 symmetrically disposed at both sides of the bottom of the second deposition chamber 13 include a Cu evaporation source, an In evaporation source, and a Ga evaporation source; the non-metal evaporation source of the second deposition chamber 13 includes a Se evaporation source, and the pair of electrodes formed with uniform thickness (In, Ga) by the second deposition chamber 132Se3The substrate of the film is further subjected to a deposition process to form the CIGS film with uniform thickness and good performance.
In the above embodiment of the present invention, the metal evaporation sources on both sides of the bottom of the first deposition chamber 11 and/or the second deposition chamber 13 are symmetrically arranged, which is beneficial to the maintenance of the deposition chambers in the later period; on the other hand, the gaseous forms of the same substance have the same diffusivity, and the thicknesses of the thin films formed at the corresponding positions of the substrate are the same, so that the uniformity of the thickness of the CIGS thin film formed on the substrate can be effectively guaranteed, the performance of the CIGS thin film is improved, and the power generation efficiency of the thin film solar cell is improved.
In one embodiment of the present invention, at least one row of metal evaporation sources 111 is disposed at each side of the bottom of the first deposition chamber 11, and the total number of the metal evaporation sources 111 in each row is M, where M is an integer greater than or equal to 2 and less than or equal to 7; at least one row of metal evaporation sources 131 is disposed at each side of the bottom of the second deposition chamber 13, and the total number of the metal evaporation sources 131 in each row is 10.
Specifically, the number of rows of the metal evaporation sources 111 on each side of the first deposition chamber 11 and the metal evaporation sources 131 on each side of the second deposition chamber 13 is 1-5, and when the metal evaporation sources on each side are in multiple rows in the first deposition chamber 11, the multiple rows of metal evaporation sources may be aligned or staggered. If the substrate has a large size, it is found through many experiments that only one row of metal evaporation sources is respectively arranged on two sides of the first deposition chamber 11 and/or the second deposition chamber 13, so that the requirement of the coating size (meeting the requirement of the coating thickness of the CIGS thin film of about 2 μm) for forming a CIGS thin film with uniform thickness cannot be met, and more than one row of metal evaporation sources can be arranged on two sides of the first deposition chamber 11 and/or the second deposition chamber 13, for example, two or three rows of metal evaporation sources can be respectively arranged on two sides of the first deposition chamber 11 and/or the second deposition chamber 13. The deposition rate of the CIGS thin film can be improved by arranging a plurality of rows of metal evaporation sources.
In the first deposition chamber 11 and the second deposition chamber 13, each row of metal evaporation sources may be arranged as follows: (1) two adjacent metal evaporation sources in each row are arranged on the outer wall of the deposition chamber in a staggered manner; (2) two adjacent metal evaporation sources in each row are arranged on the outer wall of the deposition chamber with gaps and equal intervals; (3) two metal evaporation sources in each row are arranged on the outer wall of the deposition chamber with gaps and unequal intervals. The gaps arranged between the metal evaporation sources are used for avoiding or reducing the mutual interference between the adjacent metal evaporation sources and improving the uniformity and quality of the coating of the metal evaporation sources.
When the metal evaporation sources 111 on each side of the first deposition chamber 11 are arranged in multiple rows, the metal evaporation sources 111 in the multiple rows may be aligned or staggered; when the metal evaporation sources 131 on each side of the second deposition chamber 13 are arranged in a plurality of rows, the metal evaporation sources 131 may be aligned or staggered.
Alternatively, the two rows of metal evaporation sources 131 positioned at both sides of the second deposition chamber 13 may be aligned at one side, and the metal evaporation sources 131 at the other side are staggered. For example, 7 metal evaporation sources 111 are respectively disposed at the bottom side of the first deposition chamber 11 (the 7 metal evaporation sources are an In evaporation source, a Ga evaporation source, and a Ga evaporation source), and the 7 metal evaporation sources 111 are disposed In two rows, so that the arrangement between the two rows of metal evaporation sources 111 at the side can be aligned (as shown In fig. 6 a), or staggered (as shown In fig. 6 b), that is, the position of the first metal evaporation source 111 at the second row is located between the position of the first metal evaporation source 111 at the first row and the position of the second metal evaporation source 111 along the length direction of the first deposition chamber 11. For another example, the metal evaporation source 131 at one side of the second deposition chamber 13 is sequentially arranged as an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; the ten metal evaporation sources 131 are arranged in two rows, and when the two rows are aligned, the arrangement of the two rows can be shown in fig. 7a, and when the two rows of metal evaporation sources 131 are staggered, the arrangement of the two rows of metal evaporation sources 131 can be shown in fig. 7 b.
The arrangement mode (alignment or staggering) and the row spacing (vertical distance of two adjacent rows of metal evaporation sources) of the multiple rows of metal evaporation sources can be determined according to factors such as the length size of the deposition chamber, the gap between the metal evaporation sources, the evaporation rate of the metal evaporation sources, the size of the substrate and the like, so that the CIGS thin film with the thickness of about 2 mu m and uniform thickness can be formed on the substrate together with the non-metal evaporation sources arranged below, the quality and the performance of the CIGS thin film are improved, and the power generation efficiency of the thin-film solar cell is improved; meanwhile, the deposition efficiency of the CIGS thin film is improved, and the production efficiency of the thin film solar cell is improved.
At least one row of non-metal evaporation sources 112 is arranged between the metal evaporation sources 111 on the two sides in the first deposition chamber 11, and the total number of the non-metal evaporation sources 112 in each row in the first deposition chamber 11 is N, wherein N is an integer greater than or equal to 3 and less than or equal to 9; at least one row of non-metal evaporation sources 132 is arranged between the metal evaporation sources 131 on two sides in the second deposition chamber 13, and the total number of the non-metal evaporation sources 132 in each row in the second deposition chamber 13 is Y, wherein Y is an integer greater than or equal to 7 and less than or equal to 15. In the first deposition chamber 11 and the second deposition chamber 13, 1-5 rows of non-metal evaporation sources are arranged; or/and the inclination angles of the nonmetal evaporation sources and the straight line vertical to the bottom of the corresponding deposition chamber are 0-60 degrees, and the inclination angles of each nonmetal evaporation source and the straight line vertical to the bottom of the corresponding deposition chamber can be set to be the same or different. Or/and a gap is formed between every two adjacent nonmetal evaporation sources in each row and the two nonmetal evaporation sources are arranged at equal intervals or non-equal intervals. The gaps arranged between the nonmetal evaporation sources are used for improving the coating uniformity of the nonmetal evaporation sources.
When the non-metal evaporation sources 112 of the first deposition chamber 11 are in multiple rows, the multiple rows of non-metal evaporation sources can be aligned or staggered; when the non-metal evaporation sources 132 of the second deposition chamber 13 are provided in a plurality of rows, the plurality of rows of non-metal evaporation sources 132 may be aligned or staggered. The arrangement mode (alignment or staggering) and the row spacing (vertical distance of two adjacent rows of metal evaporation sources) of the multiple rows of non-metal evaporation sources can be determined according to factors such as the length size of the deposition chamber, the gap between the non-metal evaporation sources, the evaporation rate of the non-metal evaporation sources, the size of the substrate and the like, so that a CIGS thin film with the thickness of about 2 mu m and uniform thickness can be formed on the substrate together with the arranged metal evaporation sources, the quality and the performance of the CIGS thin film are improved, and the power generation efficiency of the thin-film solar cell is improved; meanwhile, the deposition efficiency of the CIGS thin film is improved, and the production efficiency of the thin film solar cell is greatly improved.
Further, in the embodiment of the present invention, two rows may be respectively disposed on two sides of the first deposition chamber 11, and the metal evaporation sources 111 on the two sides are symmetrically disposed, the number of the metal evaporation sources disposed on each side is M, M is an integer greater than or equal to 2 and less than or equal to 7, and then in the first deposition chamber 11, the arrangement sequence of the metal evaporation sources on each side along the length direction of the first deposition chamber 11 may be as follows in sequence:
(1) m is 2, and the arrangement mode is as follows: an In evaporation source and a Ga evaporation source; or, a Ga evaporation source, an In evaporation source;
(2) m is 3, and the arrangement mode is as follows: a Ga evaporation source, an In evaporation source, and a Ga evaporation source; or an In evaporation source, a Ga evaporation source and an In evaporation source;
(3) m is 4, and the arrangement mode is as follows: an In evaporation source, a Ga evaporation source, an In evaporation source and a Ga evaporation source; or a Ga evaporation source, an In evaporation source; or, a Ga evaporation source, an In evaporation source;
(4) m is 5, and the arrangement mode is as follows: ga evaporation source, In evaporation source, Ga evaporation source, In evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source and an In evaporation source; or, a Ga evaporation source, an In evaporation source, a Ga evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source, and a Ga evaporation source;
(5) m is 6, and the arrangement mode is as follows: an In evaporation source, a Ga evaporation source, and an In evaporation source; or, Ga evaporation source, In evaporation source, Ga evaporation source; or, Ga evaporation source, In evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source, and a Ga evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source; or an In evaporation source, a Ga evaporation source, and a Ga evaporation source;
(6) m is 7, and the arrangement mode is as follows: an In evaporation source, a Ga evaporation source, and a Ga evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source, a Ga evaporation source; or, Ga evaporation source, In evaporation source, Ga evaporation source, In evaporation source; or, a Ga evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source, a Ga evaporation source; or, Ga evaporation source, In evaporation source, Ga evaporation source, In evaporation source, Ga evaporation source; or an In evaporation source, a Ga evaporation source, an In evaporation source, and a Ga evaporation source; alternatively, an In evaporation source, a Ga evaporation source, an In evaporation source, and a Ga evaporation source.
In the embodiment of the present invention, one or more rows of metal evaporation sources 131 may be disposed in the second deposition chamber 13, wherein the total number of the metal evaporation sources 131 in each row is 10, and the arrangement order along the length direction of the second deposition chamber 13 is as follows:
(1) a Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
(2) A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
(3) A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
(4) A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
(5) A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
(6) A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
(7) A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
(8) A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
(9) An In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
(10) Ga evaporation source, In evaporation source, Cu evaporation source, Ga evaporation source, In evaporation source, Cu evaporation source, In evaporation source.
The design of the number of rows, the number of each row and the arrangement mode (gap, equal spacing or non-equal distance, alignment or staggering, etc.) of the metal evaporation sources and the non-metal evaporation sources in the first deposition chamber 11 and the second deposition chamber 13 can meet the requirement that the coating thickness of the CIGS thin film is about 2 mu m. Through the arrangement of the metal evaporation source and the nonmetal evaporation source in the first deposition chamber 11 and the second deposition chamber 13, the coating film can be more uniform, and the electrical property and the crystallization property are better. In addition, for the random sequencing of the metal evaporation sources, the metal evaporation sources are arranged according to the arrangement mode of the metal evaporation sources in the first deposition chamber 11 and the second deposition chamber 13, so that the stability of the CIGS thin film can be improved, and the power generation efficiency and the yield of the thin film solar cell are improved; the application further provides a thin film solar cell with stable performance and high efficiency.
In the embodiment of the present invention, referring to fig. 8, inclined angles α are formed between metal evaporation sources (including Cu evaporation source, In evaporation source, Ga evaporation source) disposed on both sides 20 of the second deposition chamber 13 and a reference line 14 (a straight line 14 perpendicular to the bottom 21 of the corresponding deposition chamber), and the inclined angles α are 18 to 48 degrees, such as 20 degrees, 25 degrees, 30 degrees, 35 degrees, 40 degrees or 45 degrees, where the arrangement direction of the metal evaporation sources is replaced by a direction of a connecting line 04 between the center of the bottom surface of the metal evaporation source and the center of the upper surface, and the evaporation and deposition speeds are different due to physical properties such as density of Cu, In and Ga materials, the inclination angle α formed by each metal evaporation source 111 and the reference line 14 In the first deposition chamber 11 may be the same or different, and the inclination angle α formed by each metal evaporation source 131 and the reference line 131 In the second deposition chamber 13 may be the same or different.
Example 1, the inclined included angles α of all the metal evaporation sources 111 In the first deposition chamber 11 are the same and 18 degrees, two sides of the first deposition chamber 11 are respectively provided with 5 metal evaporation sources 11 arranged In a row, and the metal evaporation sources 111 on each side are arranged In the following manner, for example, Ga evaporation sources, In evaporation sources, Ga evaporation sources;
the inclined angles α of all the metal evaporation sources 131 In the second deposition chamber 13 are the same and are 18 degrees, a row of 10 metal evaporation sources 131 arranged In a row is respectively arranged on both sides of the second deposition chamber 13, and the metal evaporation sources 131 on each side are arranged In the following manner, for example, a Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, and an In evaporation source.
In embodiment 2, the inclined included angles α of all the metal evaporation sources 111 in the first deposition chamber 11 are the same and are all 30 degrees, and the number and arrangement mode of the metal evaporation sources 111 in the first deposition chamber 11 are the same as those in embodiment 1;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same and are all 30 degrees, and the number and arrangement of the metal evaporation sources 131 in the second deposition chamber 13 are the same as those in embodiment 1.
In embodiment 3, the inclined included angles α of all the metal evaporation sources 111 in the first deposition chamber 11 are the same and 40 degrees, and the number and arrangement of the metal evaporation sources 111 in the first deposition chamber 11 are the same as those in embodiment 1;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same, and are all 40 degrees, and the number and arrangement of the metal evaporation sources 131 in the second deposition chamber 13 are the same as those in embodiment 1.
Embodiment 4, the inclined included angles α of all the metal evaporation sources 111 in the first deposition chamber 11 are the same, and are all 48 degrees, and the number and arrangement mode of the metal evaporation sources 111 in the first deposition chamber 11 are the same as those in embodiment 1;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same, and are all 48 degrees, and the number and arrangement of the metal evaporation sources 131 in the second deposition chamber 13 are the same as those in embodiment 1.
Comparative example 1 the inclined angles α of all the metal evaporation sources 111 In the first deposition chamber 11 are the same and 30 degrees, 8 metal evaporation sources 11 arranged In a row are respectively arranged on both sides of the first deposition chamber 11, and the metal evaporation source 111 on each side is arranged In the following manner, for example, an In evaporation source, a Ga evaporation source, an In evaporation source, and a Ga evaporation source;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same and are all 30 degrees, a row of 10 metal evaporation sources 131 arranged in a row is respectively arranged on both sides of the second deposition chamber 13, and the arrangement mode of the metal evaporation sources 131 on each side is the same as that of embodiment 1.
Comparative example 2 the inclined included angles α of all the metal evaporation sources 111 in the first deposition chamber 11 are the same and 10 degrees, and the number and arrangement of the metal evaporation sources 111 in the first deposition chamber 11 are the same as those in example 1;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same and 10 degrees, and the number and arrangement of the metal evaporation sources 131 in the second deposition chamber 13 are the same as those in embodiment 1.
Comparative example 3 the inclined angles α of all the metal evaporation sources 111 in the first deposition chamber 11 are the same and 60 degrees, 5 metal evaporation sources 11 arranged in a row are respectively arranged on both sides of the first deposition chamber 11, and the metal evaporation sources 111 on each side are arranged in the same manner as in example 1;
the inclined angles α of all the metal evaporation sources 131 in the second deposition chamber 13 are the same and are 60 degrees, two sides of the second deposition chamber 13 are respectively provided with 10 metal evaporation sources 131 arranged in a row, and the metal evaporation sources 131 on each side are arranged in the following manner as in embodiment 1.
The conductivity and crystallization properties of the above examples 1-4 and comparative examples 1-3 were tested and are detailed in the following table:
Figure BDA0001852919900000181
the square resistance is a test index of the conductivity, the crystallization property is a test index of the crystal size, the lower the square resistance is, the better the conductivity is, and the larger the crystal size is, the better the crystallization property is. Thus, from the above table:
(1) the sheet resistance of 0.18. omega./Sq of example 2 is lower than that of 0.30. omega./Sq of comparative example 1, and the crystal size of 47nm of example 2 is larger than that of 32nm of comparative example 1, so that the conductive property and the crystalline property of example 2 are better than those of comparative example 1, indicating that: the conductivity and crystallization performance of the CIGS thin film with 5 pairs of linearly arranged metal evaporation sources 111 in the first deposition chamber 11 and 10 pairs of linearly arranged metal evaporation sources 131 in the second deposition chamber 13 are superior to those of the CIGS thin film with 8 pairs of linearly arranged metal evaporation sources 111 in the first deposition chamber 11 and 10 pairs of linearly arranged metal evaporation sources 131 in the second deposition chamber 13;
(2) the sheet resistance of 0.42 omega/Sq of the comparative example 2 is higher than the sheet resistances of 0.15 omega/Sq, 0.18 omega/Sq, 0.21 omega/Sq and 0.13 omega/Sq of the examples 1 to 4, the crystal size of 23nm of the comparative example 2 is lower than the crystal sizes of 49nm, 47nm, 39nm and 46nm of the examples 1 to 4, so the conductivity and the crystallization performance of the examples 1 to 4 are better than those of the comparative example 2, and the conductivity and the crystallization performance of α degrees are 18-48 degrees and are better than those of 10 degrees;
(3) the sheet resistance 0.31 Ω/Sq of comparative example 3 is higher than the sheet resistances 0.15 Ω/Sq, 0.18 Ω/Sq, 0.21 Ω/Sq, and 0.13 Ω/Sq of examples 1 to 4, and the crystal size 33nm of comparative example 3 is lower than the crystal sizes 49nm, 47nm, 39nm, and 46nm of examples 1 to 4, so the conductivity and crystallinity of examples 1 to 4 are superior to those of comparative example 3, which shows that 5 pairs of metal evaporation sources 111 arranged linearly in the first deposition chamber 11 and 10 pairs of metal evaporation sources 131 arranged linearly in the second deposition chamber 13, α is 18 to 48 degrees, and the conductivity and crystallinity are superior to those of 5 pairs of metal evaporation sources 111 arranged linearly in the first deposition chamber 11 and 10 pairs of metal evaporation sources 131 arranged linearly in the second deposition chamber 13, and α is 60 degrees.
(4) The film thicknesses of examples 1 to 4 were 1.96 μm, 1.97 μm, 2.05 μm and 2.06 μm, respectively, and the film uniformity was the best when the film thickness was 1.8 to 2.3 μm according to the film uniformity index, so that the film uniformity of examples 1 to 4 was significantly better than that of comparative examples 1 to 3.
In summary, in the present application, 5 pairs of metal evaporation sources 111 are linearly arranged in each row in the first deposition chamber 11, and 10 pairs of metal evaporation sources 131 are linearly arranged in each row in the second deposition chamber 13, and α is the best in electrical conductivity, crystallization performance, and coating uniformity at 18-48 degrees.
It is noted that, In the embodiments of the present invention, the metal evaporation source is only an example of a Cu evaporation source, an In evaporation source and a Ga evaporation source, and the nonmetal evaporation source is an example of a Se evaporation source, which is not a limitation of a material for forming a solar cell thin film.
In an embodiment of the present invention, referring to fig. 9, the CIGS coating apparatus further includes a pre-treatment chamber 12 and/or a post-treatment chamber 14, a first feeding chamber 10, and a second feeding chamber 100, wherein the substrate first passes through the first feeding chamber 10 and the second feeding chamber 100 before entering the first deposition chamber 11, so as to perform a transferring and vacuum-pumping process on the substrate.
As shown in fig. 9, in the embodiment of the present invention, a first heating chamber 15 is connected in series between the second feeding chamber 100 and the first deposition chamber 11, and the first heating chamber 15 is used for heating the substrate, so that the temperature of the substrate meets the requirements of the first deposition chamber 11 and the coating film; the pretreatment chamber 12 is connected behind the first deposition chamber 11, a second heating chamber 16 is arranged between the first deposition chamber 11 and the pretreatment chamber 12, and the second heating chamber 16 is used for heating the substrate so that the temperature of the substrate is satisfied with that the substrate deposits a layer of alkali metal on the surface of the substrate in the pretreatment chamber 12 for pretreatment; a third heating chamber 17 is arranged between the pre-processing chamber 12 and the second deposition chamber 13 and is used for heating the substrate so that the temperature of the substrate meets the requirement of depositing Cu, In, Ga and Se In the second deposition chamber 13; a fourth heating chamber 18 is provided between the second deposition chamber 13 and the post-processing chamber 14 for heating the substrate to a temperature that meets the requirements of the post-processing for depositing the alkali metal in the post-processing chamber 14.
In the embodiment of the present invention, referring to the structure shown In fig. 10, at least a pair (even number of 2 or more) of NaF evaporation sources are provided In the pre-treatment chamber 12 of the coating apparatus, and the NaF evaporation sources can be symmetrically provided at opposite sides of the pre-treatment chamber 12 for the deposition of (In, Ga) In the first deposition chamber 112Se3The film is subjected to an alkali metal deposition treatment to deposit an alkali metal on (In, Ga)2Se3A layer of alkali metal is deposited on the surface of the film. The method specifically comprises the following steps:
filling NaF into the evaporation source, and changing NaF powder into NaF vapor when the evaporation source is heated to a certain temperature, so that a trace amount of NaF is deposited on (In, Ga)2Se3The surface of the film, in turn, improves the conductivity and crystallinity of the CIGS film to be formed.
In the embodiment of the present invention, referring to the structure shown in fig. 11, at least one pair (even number greater than or equal to 2) of alkali metal compound evaporation sources are disposed in the post-treatment chamber 14 of the coating apparatus, and preferably, KF evaporation sources are symmetrically disposed at two opposite sides of the post-treatment chamber 14 for performing the post-treatment process on the surface of the CIGS thin film. The method specifically comprises the following steps:
KF is filled in the evaporation source, and after the evaporation source is heated to the required temperature, KF powder is changed into KF steam, so that trace KF is deposited on the surface of the CIGS thin film, the defect state density of the CIGS thin film is further improved, and the surface of the CIGS thin film is smooth as much as possible.
A first cooling chamber 19, a second cooling chamber 110 and a discharging chamber 120 are arranged behind the post-processing chamber 14, the substrate passes through the post-processing chamber 14, the first cooling chamber 19, the second cooling chamber 10 and the discharging chamber 120 in sequence, and a coated substrate with the temperature not higher than 100 ℃ is formed after passing through the first cooling chamber 19 and the second cooling chamber 10, so that potential safety hazards caused by overhigh temperature are effectively avoided, and the safety is improved; and the product of the discharge chamber 120 is a substrate plated with a NaF film layer, a CIGS film layer, and a KF film layer.
Referring to the temperature profile shown in FIG. 12, the temperature of the first heating chamber 15 is 150 ℃ and 250 ℃ to heat the substrate; the temperature of the first deposition chamber 11 is 200-400 ℃, which can effectively meet the requirement of (In, Ga) thickness on the surface evaporation plating of the substrate2Se3A film; on the surface of which is deposited (In, Ga)2Se3The substrate of the thin film is continuously heated by the second heating chamber 16, the temperature of the second heating chamber 16 is 300-370 ℃, and the temperature of the pretreatment chamber 12 is 300-400 ℃, which can effectively meet the requirement of depositing (In, Ga)2Se3Depositing a trace amount of NaF film on the surface of a substrate of the film, thereby improving the crystallinity and the conductivity of the CIGS film to be formed; is deposited with (In, Ga)2Se3The substrates of the film and the NaF film are continuously heated by the third heating chamber 17 with the temperature of 400-560 ℃ so as to enter the second deposition chamber 13 with the temperature of 500-560 ℃, the temperature can meet the requirement that vaporized Cu, In and Ga can be deposited on the surface of the substrate to form a CIGS film, and the thickness can meet the preset requirement; the substrate with the CIGS thin film formed on the surface is heated by a fourth heating chamber 18 (although the substrate is a heating chamber, in practice, a cooling chamber relative to the second deposition chamber 13) with the temperature of 530-400 ℃, and then enters a post-processing chamber 14 with the temperature of 400-300 ℃ and a post-processing chamber 14 is such that vaporized KF can be evaporated onto the surface of the CIGS thin film to improve the defect state density of the CIGS thin film and make the CIGS thin film as smooth as possible.
According to the CIGS coating equipment provided by the embodiment of the invention, a CIGS thin film is not formed on the substrate by adopting a magnetron sputtering method to form the solar cell, but a deposition method is adopted, and the heater arranged in each evaporation source is heated to deposit substances in the evaporation source onto the surface of the substrate to form the CIGS thin film.
The CIGS coating equipment provided by the embodiment of the invention is provided with four process chambers (a first deposition chamber 11, a second deposition chamber 13, a pre-treatment chamber 12 and a post-treatment chamber 14), and compared with three process chambers (a pre-treatment chamber (doped with any alkali metal such as Na, K and the like), a CIGS coating process chamber and a post-treatment chamber (doped with any alkali metal such as K, Na and the like), the CIGS coating equipment does not simply add one deposition process chamber (namely the first deposition chamber 11 of the embodiment of the invention), but optimizes the arrangement of metal evaporation sources and non-metal evaporation sources in two chambers on the basis of two deposition process chambers (the first deposition chamber 11 and the second deposition chamber 13), thereby shortening the beat of single equipment, improving the productivity of single equipment and reducing the production cost.
In addition, In the present invention, the method for preparing a CIGS thin film is adaptively improved based on the proposed novel coating apparatus by first forming (In, Ga) on the surface of the substrate2Se3Compared with the existing method for preparing the CIGS thin film in one step (method), the CIGS film coating method improves the deposition efficiency of the CIGS thin film, and simultaneously, the more compact the growth of the CIGS thin film is, the larger the crystallinity and the grain size are, the better the quality of the thin film is, the performance of the CIGS thin film is improved, and the conversion of the solar cell is improvedEfficiency.
Referring to fig. 13, an embodiment of the present invention further discloses a CIGS coating method, where the CIGS coating apparatus including the first deposition chamber 11, the pretreatment chamber 12, the second deposition chamber 13, and the post-treatment chamber 14 disclosed in the above embodiment is used, and the CIGS coating method includes:
step S1, controlling the temperature of the first deposition chamber to be a first preset temperature threshold, and forming (In, Ga) on the surface of the substrate by the deposition process In the first deposition chamber2Se3A film;
wherein a Ga evaporation source, an In evaporation source, and a Se evaporation source are provided In the first deposition chamber 11;
in an embodiment of the present invention, the first predetermined temperature threshold is 200-400 deg.C, which is a temperature that allows vaporized Ga, In and Se to be deposited on the surface of the substrate.
Step S3, controlling the temperature of the second deposition chamber 13 to be a second predetermined temperature threshold, wherein (In, Ga) is formed In the second deposition chamber 13 by the deposition process2Se3Depositing a substrate of the film to form CuInxGa(1-x)Se2A film; wherein a Ga evaporation source, an In evaporation source, a Se evaporation source, and a Cu evaporation source are disposed In the second deposition chamber 13.
In the embodiment of the present invention, the second predetermined temperature threshold is 500-560 ℃, which is effective for the deposition of vaporized Ga, In, Se and Cu onto (In, Ga)2Se3And forming a CIGS thin film on the surface of the film.
In this embodiment of the present invention, step S3 specifically includes:
1) controlling the temperature of the second deposition chamber 13 to a second predetermined temperature threshold, and forming (In, Ga) by the deposition process2Se3Substrate deposition of Cu to form Cu (In, Ga) depleted In Cu3Se5A film;
2) cu (In, Ga) poor In copper3Se5Continuing to deposit Cu on the substrate of the thin film to form Cu (In, Ga) Se rich In copper2Thin film and liquid phase Cu2Se;
3) Cu (In, Ga) Se formed with copper2Film and liquid phase Cu2In, Ga and Se are continuously deposited on the Se substrate to form CuInxGa(1-x)Se2(wherein, 0<x<1) A film.
In the embodiment of the present invention, as shown in fig. 14, the method further includes:
step S2, Forming a surface (In, Ga)2Se3The substrate of (2) is subjected to alkali metal pretreatment, specifically:
the temperature of the pre-treatment chamber 12 is controlled to be 300-400 ℃, at which vaporized NaF is deposited to (In, Ga)2Se3The surface of the film to improve the conductivity and crystallinity of the CIGS film to be formed.
In the embodiment of the present invention, the method further includes:
step S4 for forming CuInxGa(1-x)Se2The method comprises the following steps of carrying out post-treatment process on a substrate of the film to improve the defect state density of the surface of the CIGS film, and specifically comprises the following steps:
the temperature of the post-treatment chamber 14 is controlled to be 530-400 ℃, which is suitable for the vaporized alkali metal to be deposited on the surface of the CIGS thin film to form an alkali metal thin film with a predetermined thickness, such as KF, thereby improving the defect state density of the surface of the CIGS thin film and smoothing the surface of the CIGS thin film as much as possible.
In an embodiment of the present invention, the method further comprises:
the substrate is controlled to pass through a heating chamber and is heated before entering the first deposition chamber 11, the pre-treatment chamber 12, the second deposition chamber 13 and the post-treatment chamber 14 respectively. The method specifically comprises the following steps:
after the substrate passes through the first deposition chamber 11 and before the substrate enters the pre-treatment chamber 12, the substrate needs to be heated by the second heating chamber 16 with the temperature of 300-370 ℃; after the substrate passes through the pre-treatment chamber 12 and before the substrate enters the second deposition chamber 13, the substrate needs to be heated by the third heating chamber 17 with the temperature of 400-500 ℃; the substrate after the second deposition chamber 13 and before the substrate enters the post-processing chamber 14 needs to be heated through the fourth heating chamber 18 with the temperature of 530 ℃ and 400 ℃. Before the substrate enters the first deposition chamber 11 (i.e., the GIS deposition chamber), the substrate is first heated by the first heating chamber 15 at a temperature of 150-.
Controlling the temperature of the first deposition chamber 11 to be a first temperature threshold, specifically:
controlling the temperature of the first deposition chamber 11 to be 200-400 ℃;
controlling the temperature of the second deposition chamber 13 to be a second temperature, specifically:
the temperature of the second deposition chamber 13 is controlled to be 500-560 ℃.
In an embodiment of the present invention, the method further comprises:
before the substrate enters the first deposition chamber 11, the method comprises the following steps:
controlling the substrate to pass through the first feeding chamber 11 and the second feeding chamber 100 in sequence;
after the substrate passes through the post-processing chamber 14, comprising:
the substrate is controlled to pass through the first cooling chamber 19, the second cooling chamber 110, and the outfeed chamber 120 in sequence.
In the CIGS coating method disclosed by the embodiment of the invention, a substrate is controlled to sequentially pass through a first deposition chamber 11, a pretreatment chamber 12, a second deposition chamber 13 and a post-treatment chamber 14, deposition is carried out on the surface of the substrate in the first deposition chamber 11 and the second deposition chamber 13 to form a CIGS film, and alkali metal deposition treatment on the substrate is completed in the pretreatment chamber 12 to deposit a layer of alkali metal film, such as a NaF film, on the surface of the substrate, so that the crystallinity and the conductivity of the CIGS film are improved; in the post-treatment chamber 14, the substrate coated with the CIGS thin film is subjected to a subsequent treatment to deposit an alkali metal thin film, such as KF thin film, on the surface of the CIGS thin film, thereby improving the defect state density of the CIGS thin film and making the surface of the CIGS thin film as smooth as possible.
In the embodiment of the invention, a CIGS thin film is not formed on the surface of the substrate by adopting a magnetron sputtering method, but is formed on the surface of the substrate by adopting a deposition process.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A coating apparatus, comprising a first deposition chamber and a second deposition chamber connected, wherein:
the first deposition chamber and the second deposition chamber respectively comprise at least one row of non-metal evaporation sources, each row of non-metal evaporation sources corresponds to at least two rows of metal evaporation sources, and in the metal evaporation sources corresponding to each row of non-metal evaporation sources, the at least two rows of metal evaporation sources are symmetrically arranged relative to the row of non-metal evaporation sources;
wherein the total number of the metal evaporation sources in each row in the second deposition chamber is 10.
2. The plating device according to claim 1,
the metal evaporation source of the first deposition chamber is arranged at the bottom of the first deposition chamber and comprises a Ga evaporation source and an In evaporation source; the non-metal evaporation source of the first deposition chamber comprises a Se evaporation source;
and/or
The metal evaporation source of the second deposition chamber is arranged at the bottom of the second deposition chamber and comprises a Cu evaporation source, an In evaporation source and a Ga evaporation source; the non-metal evaporation source of the second deposition chamber comprises a Se evaporation source.
3. The plating device according to claim 2,
the bottom of the first deposition chamber comprises two opposite sides, at least one row of metal evaporation sources is arranged on each side, and the total number of the metal evaporation sources in each row is M, wherein M is an integer which is more than or equal to 2 and less than or equal to 7; the total number of each row of non-metal evaporation sources of the first deposition chamber is N, wherein N is an integer which is more than or equal to 3 and less than or equal to 9;
and/or
The bottom of the second deposition chamber comprises two opposite sides, and each side is provided with at least one row of metal evaporation sources; the total number of each row of non-metal evaporation sources of the second deposition chamber is Y, wherein Y is an integer which is greater than or equal to 7 and less than or equal to 15.
4. The plating device according to claim 3,
the arrangement sequence of each row of metal evaporation sources of the first deposition chamber along the length direction of the first deposition chamber is as follows:
an In evaporation source, a Ga evaporation source and an In evaporation source; or
A Ga evaporation source, an In evaporation source, and a Ga evaporation source; or
An In evaporation source, a Ga evaporation source, an In evaporation source and a Ga evaporation source; or
A Ga evaporation source, an In evaporation source, and an In evaporation source; or
Ga evaporation source, In evaporation source, Ga evaporation source, In evaporation source; or
An In evaporation source, a Ga evaporation source, and an In evaporation source; or
Ga evaporation source, In evaporation source, Ga evaporation source; or
An In evaporation source, a Ga evaporation source, and a Ga evaporation source;
and/or
The arrangement sequence of each row of metal evaporation sources of the second deposition chamber along the length direction of the second deposition chamber is as follows:
a Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
A Cu evaporation source, an In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
An In evaporation source, a Cu evaporation source, a Ga evaporation source, an In evaporation source, a Cu evaporation source, an In evaporation source; or
Ga evaporation source, In evaporation source, Cu evaporation source, Ga evaporation source, In evaporation source, Cu evaporation source, In evaporation source.
5. The plating device according to claim 3,
a gap is reserved between each two adjacent metal evaporation sources in each row of the first deposition chamber; when the metal evaporation sources on each side of the first deposition chamber are in multiple rows, the metal evaporation sources in the multiple rows are aligned or staggered;
a gap is reserved between each two adjacent rows of non-metal evaporation sources of the first deposition chamber; when the non-metal evaporation sources of the first deposition chamber are in multiple rows, the multiple rows of non-metal evaporation sources are aligned or staggered;
and/or
A gap is reserved between each two adjacent metal evaporation sources in each row of the second deposition chamber; when the metal evaporation sources on each side of the second deposition chamber are in multiple rows, the multiple rows of metal evaporation sources are aligned or staggered;
a gap is reserved between each two adjacent rows of non-metal evaporation sources of the second deposition chamber; when the non-metal evaporation sources of the second deposition chamber are in multiple rows, the multiple rows of non-metal evaporation sources are aligned or staggered.
6. The plating apparatus according to any one of claims 1 to 5, wherein the metal evaporation source of the first deposition chamber and the metal evaporation source of the second deposition chamber form an inclined angle α with a reference line, the reference line is a straight line perpendicular to the bottom of the deposition chamber, and the inclined angles α are 18 to 48 degrees.
7. The plating device according to any one of claims 1 to 5, further comprising:
the device comprises a first deposition chamber, a second deposition chamber and a pretreatment chamber and/or a post-treatment chamber, wherein the pretreatment chamber is connected between the first deposition chamber and the second deposition chamber, and an alkali metal compound evaporation source is arranged in the pretreatment chamber; the post-processing chamber is connected behind the second deposition chamber, and an alkali metal compound evaporation source is arranged in the post-processing chamber.
8. A plating method applied to the plating apparatus according to any one of claims 1 to 9, comprising:
controlling the temperature of a first deposition chamber, In which (In, Ga) is formed on the surface of the substrate by a deposition process, to a first predetermined temperature threshold2Se3A film;
controlling the temperature of a second deposition chamber In which the (In, Ga) is deposited by a deposition process to a second predetermined temperature threshold2Se3The surface of the film is deposited to form a CIGS film.
9. The method for coating according to claim 8 wherein the temperature of the second deposition chamber In which the (In, Ga) is deposited is controlled to a second predetermined temperature threshold2Se3The surface deposition of thin films forms CIGS thin films, including:
controlling the temperature of the second deposition chamber to a second predetermined temperature threshold by a deposition process on said (In, Ga)2Se3Depositing Cu on the surface of the film to form Cu (In, Ga) lean In copper3Se5A film;
in the Cu (In, Ga) lean In copper3Se5Depositing Cu on the surface of the film to form Cu (In, Ga) Se rich In copper2Thin film and liquid phase Cu2Se;
In the Cu (In, Ga) Se rich In copper2Thin film and liquid phase Cu2And depositing In, Ga and Se on the surface of Se to form a CIGS thin film.
10. The plating method according to claim 8 or 9, wherein the first control is performedThe temperature of the deposition chamber reaches a first predetermined temperature threshold, and (In, Ga) is formed on the surface of the substrate by a deposition process In the first deposition chamber2Se3After the thin film is formed, controlling the temperature of the second deposition chamber to reach a second preset temperature threshold, and depositing the (In, Ga) In the second deposition chamber through a deposition process2Se3Before the CIGS thin film is formed by depositing on the surface of the thin film, the method further comprises the following steps:
in the above (In, Ga)2Se3Depositing alkali metal on the surface of the film; and/or
Controlling the temperature of the second deposition chamber In which the (In, Ga) is deposited by the deposition process to reach a second predetermined temperature threshold2Se3The surface deposition of the film, after forming the CIGS film, also includes:
and performing deposition treatment of alkali metal on the surface of the CIGS thin film.
CN201811303296.9A 2018-11-02 2018-11-02 Film coating equipment and film coating method Pending CN111206204A (en)

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US20130224901A1 (en) * 2012-02-26 2013-08-29 Jiaxiong Wang Production Line to Fabricate CIGS Thin Film Solar Cells via Roll-to-Roll Processes
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CN105428457A (en) * 2015-12-08 2016-03-23 中国电子科技集团公司第十八研究所 Method of industrialized production of CIGS solar cell absorption layer by deposition and equipment thereof
CN106531826A (en) * 2016-11-16 2017-03-22 深圳市金光能太阳能有限公司 Preparation method of copper indium gallium selenium thin-film solar cell
CN207418851U (en) * 2017-09-22 2018-05-29 云谷(固安)科技有限公司 Evaporation source
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101599515A (en) * 2004-03-05 2009-12-09 索里布罗研究公司 CIGS technology is carried out the method and apparatus of in-line arrangement process control
CN102763230A (en) * 2010-02-22 2012-10-31 太阳能光电股份公司 Method and device for producing a semiconductor layer
CN102653852A (en) * 2011-03-03 2012-09-05 住友重机械工业株式会社 Film forming apparatus
US20130224901A1 (en) * 2012-02-26 2013-08-29 Jiaxiong Wang Production Line to Fabricate CIGS Thin Film Solar Cells via Roll-to-Roll Processes
CN103866236A (en) * 2012-12-18 2014-06-18 北京汉能创昱科技有限公司 Arrangement method of copper-indium-gallium-selenium thin-film battery co-evaporation linear sources
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CN106531826A (en) * 2016-11-16 2017-03-22 深圳市金光能太阳能有限公司 Preparation method of copper indium gallium selenium thin-film solar cell
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