Thin film, thin film solar cell and preparation method thereof
阅读说明：本技术 薄膜、薄膜太阳能电池及其制备方法 (Thin film, thin film solar cell and preparation method thereof ) 是由 徐强 白安琪 郭会永 于 2018-07-13 设计创作，主要内容包括：本发明实施例是关于一种薄膜、薄膜太阳能电池及其制备方法,涉及薄膜技术领域,主要解决的技术问题是覆盖膜层阻水性能较差。主要采用的技术方案为：薄膜的制备方法包括：采用涂覆工艺在树脂膜层的表面上形成第一覆盖层,使第一覆盖层将树脂膜层的表面的表孔封盖；采用沉积工艺在所述第一覆盖层上形成无机材料的第二覆盖层。相对于现有技术,本发明的实施例中,由于树脂膜层本身的表孔被第一覆盖层封盖,使得无机材料的第二覆盖层形成的无机薄膜层具备较好的阻水性能,薄膜、薄膜太阳能电池的阻水性能较高。(The embodiment of the invention relates to a film, a film solar cell and a preparation method thereof, relating to the technical field of films and mainly solving the technical problem that a covering film layer has poor water resistance. The main technical scheme adopted is as follows: the preparation method of the film comprises the following steps: forming a first covering layer on the surface of the resin film layer by adopting a coating process, and enabling the first covering layer to cover the surface hole of the surface of the resin film layer; a second capping layer of inorganic material is formed on the first capping layer using a deposition process. Compared with the prior art, in the embodiment of the invention, the surface hole of the resin film layer is covered by the first covering layer, so that the inorganic film layer formed by the second covering layer made of the inorganic material has better water resistance, and the water resistance of the film and the film solar cell is higher.)
1. A method of making a film, comprising:
forming a first covering layer on the surface of the resin film layer by adopting a coating process, and enabling the first covering layer to cover the surface hole of the surface of the resin film layer;
a second capping layer of inorganic material is formed on the first capping layer using a deposition process.
2. The production method according to claim 1,
and covering the surface of the resin film layer with organic silicon coating liquid, and drying the organic silicon coating liquid covering the surface of the resin film layer to form a first covering layer.
3. The production method according to claim 2,
the organic silicon coating liquid is prepared by the following method:
refluxing a mixture of tetraethoxysilane TEOS, water, hydrogen chloride and ethanol at 50-80 ℃ to obtain a silicon solution;
and dissolving the silicon solution in an ethanol solution added with an emulsifier to prepare the organic silicon coating solution.
4. The production method according to claim 2,
the drying temperature is 60-120 ℃, and the drying time is 1-5 hours.
5. The production method according to any one of claims 1 to 4,
the coating process is a spin-on-glass (SOG) process;
the deposition process is an atomic layer deposition, ALD, process.
6. The production method according to any one of claims 1 to 4,
the resin film layer is made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polytetramethylene terephthalate (PBT), Polyimide (PI) or nylon;
the inorganic material of the second covering layer is Al 2O 3Or TiN or TiO 2。
7. A film, comprising:
a resin film layer;
a first cover layer covering the surface hole of the resin film layer;
a second capping layer of an inorganic material disposed on the first capping layer.
8. The film of claim 7,
the film is prepared by the method of any one of claims 1 to 6;
the thickness of the first covering layer is 10-1000 nm;
the thickness of the second covering layer is 10-100 nm.
9. A thin film solar cell surface film layer, comprising:
the material of the fluorine-containing membrane is ethylene-tetrafluoroethylene copolymer ETFE, polyvinyl fluoride PVF or polyvinylidene fluoride PVDF;
a film comprising the film according to any one of claims 7 to 8, said film being bonded to said fluorine-containing film.
10. A thin film solar cell, comprising:
the thin film solar cell surface film layer of claim 9;
a substrate layer;
and the cell core layer is positioned between the surface film layer of the thin-film solar cell and the substrate layer, and the fluorine-containing film is exposed.
Technical Field
The embodiment of the invention relates to the technical field of films, in particular to a film, a film solar cell and a preparation method thereof.
Background
Compared with the conventional crystalline silicon solar cell, the thin-film solar cell has the advantages of light weight, thin thickness, foldability and the like, is easy to realize large-scale commercial production, and is a solar cell with high photovoltaic power generation efficiency.
Thin film solar cells typically include a substrate layer, a cell core layer, and a cover film layer. The thin film solar cell is usually in a harsh environment, and under various conditions of wind, rain and sun, the covering film layer needs to have high light transmission efficiency and good water resistance, oxygen insulation and the like, wherein the requirement on the water resistance of the covering film layer of the common thin film solar cell needs to reach 10 -4g/m 2The day is less.
The covering film layer is made of a plurality of layers of resin, and the surface layer of the covering film layer is a fluorine-containing transparent polymer and mainly has the functions of reinforcement, weather resistance, ultraviolet resistance, moisture resistance, low dielectric constant, high breakdown voltage and the like. The bottom layer of the covering film layer is made of resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) after surface treatment, the resin mainly has the functions of water resistance and oxygen isolation, and the surface layer and the bottom layer are adhered by an adhesive.
The bottom layer treatment process of the covering film layer is to deposit a thin layer of inorganic material on the surface of PET or PEN by adopting an Atomic Layer Deposition (ALD) method to prepare a thin covering film layer meeting the market demand, and after the test, the water resistance of the thin covering film layer is less than 10 -4g/m 2The performance requirement of ultrathin high water resistance can not be met every day.
Disclosure of Invention
In view of this, embodiments of the present invention provide a film, a thin film solar cell and a method for manufacturing the same, and mainly solve the technical problem that a covering film layer has poor water blocking performance.
In order to achieve the above purpose, the embodiments of the present invention mainly provide the following technical solutions:
in one aspect, an embodiment of the present invention provides a method for preparing a thin film, including:
forming a first covering layer on the surface of the resin film layer by adopting a coating process, and enabling the first covering layer to cover the surface hole of the surface of the resin film layer;
a second capping layer of inorganic material is formed on the first capping layer using a deposition process.
The purpose of the embodiments of the present invention and the technical problems solved thereby can be further realized by the following technical measures.
Optionally, in the preparation method, an organic silicon coating liquid is used to cover the surface of the resin film layer, and the organic silicon coating liquid covering the surface of the resin film layer is dried to form the first covering layer.
Alternatively, the preparation method comprises the following steps:
refluxing a mixture of tetraethoxysilane TEOS, water, hydrogen chloride and ethanol at 50-80 ℃ to obtain a silicon solution;
and dissolving the silicon solution in an ethanol solution added with an emulsifier to prepare the organic silicon coating solution.
Optionally, in the preparation method, the drying temperature is 60-120 ℃, and the drying time is 1-5 hours.
Optionally, in the preparation method, the coating process is a Spin-on-Glass (SOG) process;
the Deposition process is an Atomic Layer Deposition (ALD) process.
Optionally, in the preparation method, the resin film layer is made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polytetramethylene terephthalate (PBT), Polyimide (PI), or nylon;
the inorganic material of the second covering layer is Al 2O 3Or TiN or TiO 2。
In another aspect, embodiments of the present invention provide a film, including:
a resin film layer;
a first cover layer covering the surface hole of the resin film layer;
a second capping layer of an inorganic material disposed on the first capping layer.
The purpose of the embodiments of the present invention and the technical problems solved thereby can be further realized by the following technical measures.
Optionally, the film described above, wherein the thickness of the first capping layer is in the range of 10-1000 nm;
the thickness of the second covering layer is 10-100 nm.
In another aspect, an embodiment of the present invention provides a thin film solar cell surface film layer, including:
a fluorine-containing film which is a fluorine-containing polymer;
the film is attached to the fluorine-containing film.
In another aspect, an embodiment of the present invention provides a thin film solar cell, including:
the surface film layer of the thin film solar cell;
a substrate layer;
and the cell core layer is positioned between the surface film layer of the thin-film solar cell and the substrate layer, and the fluorine-containing film is exposed.
By the technical scheme, the thin film solar cell and the preparation method thereof provided by the technical scheme of the invention at least have the following advantages:
in the technical scheme provided by the embodiment of the invention, in the preparation method of the film, the first covering layer is coated on the surface of the resin film layer, the surface hole on the surface of the resin film layer is covered by the first covering layer, and then the second covering layer made of the inorganic material is formed on the first covering layer by adopting the deposition process.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the embodiments of the present invention more clear and clear, and to implement the technical solutions according to the contents of the description, the following detailed description is made with reference to the preferred embodiments of the present invention and accompanying drawings.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing a thin film according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a resin film layer in a method for manufacturing a film according to an embodiment of the present invention;
fig. 3 is a schematic structural view after a first cover layer is formed on a surface of a resin film layer in a method for manufacturing a film according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a thin film manufacturing method according to an embodiment of the present invention after forming a second capping layer of an inorganic material on the first capping layer;
fig. 5 is a schematic structural diagram of a thin film solar cell according to an embodiment of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the purpose of the predetermined embodiments of the invention, the following detailed description will be given to the embodiments, structures, features and effects of the thin film and the thin film solar cell and the method for manufacturing the same according to the embodiments of the present invention with reference to the accompanying drawings and the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The inventor finds that the inorganic thin film layer can not completely cover the surface holes of the resin film layer due to the high shape-retaining property (high step coverage rate) of the atomic layer deposition process, so that the water resistance of the final surface modified resin film layer is not good, and the ultra-thin high water resistance performance requirement can not be met.
In the preparation method of the film provided by this embodiment, the first covering layer is formed by coating on the surface of the resin film layer, so that the surface hole of the surface of the resin film layer is covered by the first covering layer, and then the deposition process of the second covering layer of the inorganic material is performed.
Referring to fig. 1 to 4, a method for manufacturing a thin film according to an embodiment of the present invention includes:
forming a first covering
A
In the preparation method of the film, the first covering layer is coated on the surface of the resin film layer, the surface hole of the surface of the resin film layer is sealed by the first covering layer, and then the second covering layer made of the inorganic material is formed on the first covering layer by adopting the deposition process.
The coating process can adopt coating liquid to coat the surface of the resin film layer, and after the coating liquid coated on the surface of the resin film layer is naturally dried or baked, a first covering layer is formed on the surface of the resin film layer to seal and cover the surface hole. In some preferred embodiments, the coating liquid may be an organic silicon coating liquid, the surface of the resin film layer is covered with the organic silicon coating liquid, and the organic silicon coating liquid covering the surface of the resin film layer is dried to form the first covering layer. Because the organic silicon coating liquid has certain fluidity, the surface hole of the surface of the resin film layer can be well covered. Specifically, in order to prevent the resin film layer from keeping better physical properties during drying, the drying temperature can be 60-120 ℃, and the drying time is 1-5 hours, so that SiO is formed 2The first covering layer can keep the original characteristics of the resin film layer under the condition of finishing drying the organic silicon coating liquid. Wherein, the organic silicon coating liquid is prepared by the following method: refluxing a mixture of Tetraethoxysilane (TEOS), water, hydrogen chloride and ethanol at 50-80 ℃ to obtain a silicon solution; and dissolving the silicon solution in an ethanol solution added with an emulsifier to prepare the organic silicon coating solution. The emulsifier can be Poloxamer (Poloxamer) or the like. Specifically, the coating process is a spin-on-glass process, and the organic silicon coating liquid is prepared fromAs an organosilicon spin-on solution.
The deposition process can be an atomic layer deposition process, wherein the atomic layer deposition process is carried out at a deposition temperature of 50-150 ℃, a deposition pressure of 10-100 torr, a thickness of the second deposition layer of 10-100nm, and the deposited inorganic material is Al 2O 3Or TiN or TiO 2And the like.
According to the embodiment provided by the invention, on one hand, the integral water vapor barrier performance of the film is improved, on the other hand, the coating process is shorter in time consumption and lower in cost than the atomic layer deposition process, and the thickness of the film layer required to be deposited in the atomic layer deposition process can be reduced, so that the time and the cost for preparing the film can be reduced.
In the film provided by the embodiment, the first covering layer is firstly arranged on the surface of the resin film layer, so that the surface hole of the surface of the resin film layer is covered by the first covering layer, and the second covering layer made of the inorganic material is arranged on the first covering layer.
One embodiment of the present invention provides a film comprising: the coating comprises a resin film layer, a first covering layer and a second covering layer made of inorganic materials. The first covering layer covers the surface hole of the resin film layer, and the second covering layer made of inorganic materials is arranged on the first covering layer.
The second covering layer, the first covering layer and the resin film layer of the inorganic material are sequentially overlapped, the surface hole of the surface of the resin film layer of the first covering layer is covered by the first covering layer, and in the prior art, due to high shape retention (high step coverage rate) of the atomic layer deposition process, the surface hole of the resin film layer can not be completely covered by the inorganic film layer, so that the water resistance of the finally surface-modified resin film layer is poor.
The resin film layer is made of polyethylene terephthalate (PET) or polynaphthaleneEthylene glycol Propionate (PEN) or Polymethylmethacrylate (PMMA) or polypropylene (PP) or Polyamide (PA) or polytetramethylene terephthalate (PBT) or Polyimide (PI) or nylon; the first covering layer is made of SiO 2Etc.; the inorganic material is Al 2O 3Or TiN or TiO 2. The thickness of the first covering layer is 10-1000 nm; the thickness of the second covering layer is 10-100 nm. The film in this embodiment can be prepared by the preparation method of the film in the above embodiment.
One embodiment of the present invention provides a surface film layer of a thin film solar cell, including: fluorine-containing films and thin films. The film is attached to the fluorine-containing film. The film includes a resin film layer, a first cover layer, and a second cover layer of an inorganic material. The first covering layer covers the surface hole of the resin film layer, and the second covering layer made of inorganic materials is arranged on the first covering layer.
The fluorine-containing film mainly has the characteristics of transparency, ultraviolet resistance, moisture resistance, low dielectric constant, high breakdown voltage and the like. The fluorine-containing film and the film may be bonded to each other by an adhesive. Specifically, the material of the fluorine-containing film is ethylene-tetrafluoroethylene copolymer (ETFE), polyvinyl fluoride (PVF), or polyvinylidene fluoride (PVDF), but is not limited thereto. The resin film layer is made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polytetramethylene terephthalate (PBT), Polyimide (PI) or nylon; the first covering layer is made of SiO 2Etc.; the inorganic material is Al 2O 3Or TiN or TiO 2. The thickness of the first covering layer is 10-1000 nm; the thickness of the second covering layer is 10-100 nm. The film in this embodiment can be prepared by the preparation method of the film in the above embodiment.
Fig. 5 is a schematic diagram of an embodiment of a thin film solar cell provided in the present invention, and referring to fig. 5, the thin film solar cell provided in an embodiment of the present invention includes: the thin-film solar cell comprises a thin-film solar cell
The substrate layer can be made of stainless steel, aluminum conductive material or the like, and the photoelectric conversion layer can be made of Copper Indium Gallium Selenide (CIGS) compound material, Copper Indium Selenide (CIS), gallium arsenide (GaAS), cadmium telluride (CdTe), perovskite or the like, but is not limited thereto.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
It will be appreciated that the relevant features of the devices described above may be referred to one another. In addition, "first", "second", and the like in the above embodiments are for distinguishing the embodiments, and do not represent merits of the embodiments.
In the description provided herein, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some instances, well-known structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the disclosed apparatus should not be construed to reflect the intent as follows: that the invention as claimed requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
Those skilled in the art will appreciate that the components of the apparatus of the embodiments may be adapted and arranged in one or more arrangements different from the embodiments. The components of the embodiments may be combined into one component and, in addition, they may be divided into a plurality of sub-components. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and all of the components of any apparatus so disclosed, may be combined in any combination, except combinations where at least some of such features are mutually exclusive. Each feature disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise.
Furthermore, those skilled in the art will appreciate that while some embodiments described herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the following claims, any of the claimed embodiments may be used in any combination. The various component embodiments of the present invention may be implemented in hardware, or in a combination thereof.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or components not listed in a claim. The word "a" or "an" preceding a component or element does not exclude the presence of a plurality of such components or elements. The invention may be implemented by means of an apparatus comprising several distinct elements. In the claims enumerating several means, several of these means may be embodied by one and the same item. The usage of the words first, second and third, etcetera do not indicate any ordering. These words may be interpreted as names.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.