CN113258006B

CN113258006B - Perovskite battery structure containing grid lines and preparation method thereof

Info

Publication number: CN113258006B
Application number: CN202110519044.5A
Authority: CN
Inventors: 李卫东; 李新连; 赵志国; 赵东明; 秦校军; 熊继光; 张赟; 李梦洁; 董超
Original assignee: Huaneng Clean Energy Research Institute; Huaneng Renewables Corp Ltd
Current assignee: Huaneng Clean Energy Research Institute; Huaneng Renewables Corp Ltd
Priority date: 2021-05-12
Filing date: 2021-05-12
Publication date: 2022-12-09
Anticipated expiration: 2041-05-12
Also published as: CN113258006A

Abstract

The invention discloses a perovskite cell structure containing grid lines, which belongs to the field of perovskite solar thin film electrical components. The technical problems of uneven subsequent coating and difficult blade coating caused by the conventional preparation of the surface bulge of the grid line are solved by etching the surface of the glass substrate to form the groove and embedding the metal grid line. By embedding the grid lines into the glass, the unevenness of the glass substrate caused by the height of the grid lines is avoided, and the uniform film layer is formed in the subsequent processes of blade coating, magnetic control, evaporation and the like.

Description

Perovskite battery structure containing grid lines and preparation method thereof

Technical Field

The invention belongs to the field of perovskite solar thin film electrical components, and relates to a perovskite cell structure containing a grid line and a preparation method thereof.

Background

In recent years, the perovskite solar cell has been receiving more and more attention due to the advantages of high conversion efficiency, low cost, environmental friendliness and the like, and the photoelectric conversion efficiency of the perovskite solar cell is improved by several times in a short few years and shows very excellent photoelectric properties. The film layer structure of the perovskite thin film solar cell and the conventional preparation method are as follows: preparing a layer of transparent conductive film on a glass substrate, wherein the transparent conductive film is used for an electrode layer on a light receiving side; then preparing a carrier transmission layer on the transparent electrode; preparing a perovskite layer above the carrier transport layer as a light absorption layer; then preparing a carrier transport layer on the other side of the substrate; and finally, preparing a metal layer as a conductive electrode on the other side.

The light-receiving side electrode layer is usually made of a transparent conductive oxide thin film material (TCO), which is required to have both high permeability and high conductivity from the viewpoint of functional requirements of the film layer. The film layer serves on the one hand for collecting charges and transporting them in the plane, so that it is required to have as high an electrical conductivity as possible; on the other hand, the electrode film on the light receiving side is also required to have a high transmittance in order to let more light enter the absorption layer to excite the photogenerated carriers. However, in terms of technology, the conductivity and the transmittance of the transparent conductive film layer are restricted to each other, and the maximum conductivity and the maximum transmittance cannot be obtained at the same time. In order to effectively collect carriers, a metal grid line can be prepared on the surface of the transparent conductive film so as to improve the carrier collection capability, and meanwhile, the thickness of the TCO layer can be reduced to the greatest extent, and the light transmittance is improved. Typically the height of the grid lines is about 10-30 μm. Because the height of the grid line is higher (far greater than the thickness of a subsequent film layer), an obvious bulge can be formed on the surface of the substrate, the shadow effect at the edge of the grid line can cause the uneven film layer at the edge of the grid line and other positions, and the bulge on the surface of the grid line is uneven due to the higher grid line, so that the perovskite and other related film layers are difficult to prepare by adopting blade coating and other modes.

Disclosure of Invention

In order to overcome the defects that in the prior art, a substrate is protruded due to the high height of a grid line, and the film layers at the edge of the grid line and other positions are not uniform due to the shadow effect at the edge of the grid line, the invention aims to provide a perovskite battery structure containing the grid line and a preparation method thereof.

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

a perovskite battery structure containing grid lines sequentially comprises a glass substrate, a transparent conductive film, a first transmission layer, a perovskite absorption layer, a second transmission layer and a metal electrode layer from bottom to top, wherein a groove is formed in one surface, which is in contact with the transparent conductive film, of the glass substrate, and the grid lines are deposited in the groove;

the depth of the groove is 0.1-50 μm, and the width of the groove is 1-50 μm.

Preferably, the number of the grooves is several;

the distance between the centers of two adjacent grooves is 100-10000 μm.

Preferably, the thickness of the transparent conductive film is 100 to 2000nm; the thickness of the first transmission layer is 10-50 nm; the thickness of the perovskite absorption layer is 200-800 nm; the thickness of the second transmission layer is 10-100 nm; the thickness of the metal electrode layer is 50-500 nm.

Preferably, the grid line is any one of Cu, ag, au, al, ni, fe, metal alloy, graphene, and carbon nanowire.

Preferably, the transparent conductive film is any one of ITO, FTO, AZO, IWO and graphene materials.

A preparation method of the perovskite battery structure containing the grid line comprises the following steps:

step 1) coating a layer of protective film on a glass substrate;

step 2) etching the glass substrate coated with the protective film to form a groove with the depth of 0.1-50 mu m and the width of 1-50 mu m on the glass substrate;

step 3) plating a conductive material on the glass substrate containing the groove to form a conductive film, and filling the conductive material into the groove (9) to obtain a substrate;

step 4) placing the substrate in a solvent, stripping the protective film on the substrate and the conductive film on the protective film, and obtaining a substrate containing the grid line after complete stripping;

step 5) plating a transparent conductive film on the substrate containing the grid line;

and 6) sequentially plating a first transmission layer, a perovskite absorption layer, a second transmission layer and a metal electrode layer on the transparent conductive film to obtain the perovskite battery structure containing the grid line.

Preferably, the thickness of the protective film is 0.3 to 20 μm;

the protective film is photoresist or PMMA;

the thickness of the conductive film is 0.1-50 μm;

the conductive film is prepared from any one of Cu, ag, au, al, ni, fe, metal alloy, graphene and carbon nanowires;

a plurality of grooves are arranged;

the distance between the centers of two adjacent grooves is 100-10000 μm.

Preferably, the solvent in step 4) is an organic solvent such as DMSO, toluene and DMF;

preferably, the etching in step 2) is laser etching, chemical etching or ion bombardment etching.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a perovskite battery structure containing grid lines, which solves the technical problems of uneven subsequent coating and difficult blade coating caused by the conventional preparation of grid line surface bulges in a mode of etching grooves on the surface of a glass substrate and embedding metal grid lines. By embedding the grid lines into the glass, the unevenness of the glass substrate caused by the height of the grid lines is avoided, and the uniform film layer is formed in the subsequent processes of blade coating, magnetic control, evaporation and the like.

The invention discloses a preparation method of a perovskite battery structure containing grid lines.

Drawings

FIG. 1 is a structural diagram of a perovskite battery of the present invention;

FIG. 2 is a schematic structural diagram of a perovskite battery of the present invention after a protective film is coated on the surface of a glass substrate during the preparation process;

FIG. 3 is a schematic cross-sectional view of a perovskite cell of the present invention etched to form grooves during fabrication;

FIG. 4 is a schematic structural diagram of a perovskite battery of the present invention plated with a conductive film after etching in the manufacturing process;

FIG. 5 is a schematic diagram of the perovskite battery of the present invention after the protective film is dissolved during the preparation process;

fig. 6 is a schematic structural diagram of the perovskite cell of the present invention after plating a transparent conductive thin film during the preparation process.

Wherein: 1-a glass substrate; 2-a gate line; 3-a transparent conductive film; 4-a first transport layer; a 5-perovskite absorption layer; 6-a second transport layer; 7-a metal electrode layer; 8-protective film; 9-a groove; 10-a conductive film.

Detailed Description

In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

The invention is described in further detail below with reference to the accompanying drawings:

a perovskite battery structure containing metal grid lines is shown in figure 1 and sequentially comprises a glass substrate 1, a transparent conductive film 3, a first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 from bottom to top, wherein a groove 9 is formed in one surface, which is in contact with the transparent conductive film 3, of the glass substrate 1, and the grid lines 2 are deposited in the groove 9;

the depth of the groove 9 is 0.1 to 50 μm, and the width of the groove 9 is 1 to 50 μm.

Example 1

A method for manufacturing a perovskite cell structure including metal grid lines, as shown in fig. 2-6, includes the steps of:

step 1) as shown in fig. 2, a protective film 8 is coated on the surface of the glass substrate 1: a thin film, i.e., the protective film 8, may be applied by means of knife coating or the like.

And 2) as shown in FIG. 3, performing laser etching to form grooves 9 with a depth d (the distance from the glass surface to the bottom of the groove) of 0.1 μm, a width w of 1 μm and a pitch p (the central distance between two adjacent grooves) of 100 μm on the glass surface. As shown in fig. 2 and 3.

Step 3) as shown in fig. 4, a conductive film 10 is plated on the etched protective film 8. The material of the conductive film 10 may be copper having good conductivity.

And 4) as shown in fig. 5, immersing the substrate into a special solvent which can dissolve the protective film 8 on the substrate without damaging the grid lines 2 in the grooves 9, and stripping off the protective film 8 and the conductive film 10 on the protective film to obtain the substrate.

Step 5) as shown in fig. 6, a transparent conductive film 3 with the thickness of 100nm is plated on the substrate.

And 6) sequentially plating an electronic first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 on the transparent conductive film 3 to obtain the perovskite battery structure containing the grid lines.

Example 2

A preparation method of a perovskite battery structure containing metal grid lines comprises the following steps:

step 1) coating a layer of protective film 8 on the surface of a glass substrate 1: a thin film, i.e., the protective film 8, may be applied by means of knife coating or the like.

And 2) adopting chemical etching to etch and form grooves 9 with the depth d (the distance from the glass surface to the bottom of the groove) of 10 mu m, the width w of 5 mu m and the distance p (the central distance between two adjacent grooves) of 500 mu m on the glass surface.

And 3) plating a layer of conductive film 10 on the etched protective film 8 to obtain the substrate. The conductive film material can be silver with good conductivity.

And 4) immersing the substrate into a special solvent, wherein the solvent can dissolve the protective film 8 on the substrate, and meanwhile, the grid lines 2 in the grooves 9 can not be damaged, and the protective film 8 and the conductive film 10 on the protective film are stripped off to obtain the substrate.

And 5) plating a layer of transparent conductive film 3 with the thickness of 200nm on the substrate.

And 6) sequentially plating a first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 on the transparent conductive film 3 to obtain the perovskite battery structure containing the grid lines.

Example 3

step 1) coating a layer of protective film 8 on the surface of a glass substrate 1: a film, i.e. the protective film 8, can be applied by means of knife coating or the like.

And 2) etching by adopting ion bombardment to form grooves 7 with the depth d (the distance from the glass surface to the bottom of the groove) of 50 microns, the width w of 50 microns and the distance p (the distance between the centers of two adjacent grooves) of 10000 microns on the glass surface.

And 3) plating a layer of conductive film 10 on the etched protective film 8 to obtain the substrate. The conductive film material can be gold with good conductivity.

And 4) immersing the substrate into a special solvent, wherein the solvent can dissolve the protective film 8 on the substrate, meanwhile, the grid lines 2 in the grooves cannot be damaged, and stripping off the protective film 8 and the conductive film 10 on the protective film to obtain the substrate.

And 5) plating a transparent conductive film 3 with the thickness of 2000nm on the substrate.

And 6) sequentially plating a first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 on the transparent conductive film 3 to obtain a second transmission layer of the perovskite cell structure containing the grid lines.

Example 5

And 2) etching by adopting laser to form grooves 9 with the depth d (the distance from the glass surface to the bottom of the groove) of 30 mu m, the width w of 20 mu m and the pitch p (the central distance between two adjacent grooves) of 1000 mu m on the glass surface.

And 3) plating a layer of conductive film 10 on the etched protective film 8 to obtain the substrate. The conductive film 10 can be made of gold with good conductivity.

And 5) plating a transparent conductive film 3 with the thickness of 1000nm on the substrate.

And 6) sequentially plating a first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 on the transparent conductive film 3 to obtain the perovskite battery structure containing the grid line. Second transport layer

Example 6

And 2) etching by adopting ion bombardment to form grooves 9 with the depth d (the distance from the glass surface to the bottom of the groove) of 45 mu m, the width w of 40 mu m and the pitch p (the central distance between two adjacent grooves) of 5000 mu m on the glass surface.

And 4) immersing the substrate into a special solvent, wherein the solvent can dissolve the protective film 8 on the substrate, meanwhile, the grid lines 2 in the grooves 9 can not be damaged, and stripping off the protective film 8 and the conductive film 10 on the protective film to obtain the substrate.

And 6) sequentially plating a first transmission layer 4, a perovskite absorption layer 5, a second transmission layer 6 and a metal electrode layer 7 on the transparent conductive film 3 to obtain the perovskite battery structure containing the grid lines. Second transport layer

Example 7

And 2) etching by adopting ion bombardment to form grooves 9 with the depth d (the distance from the glass surface to the bottom of the groove) of 15 microns, the width w of 10 microns and the distance p (the central distance between two adjacent grooves) of 3000 microns on the glass surface.

And 5) plating a layer of transparent conductive film 3 with the thickness of 800nm on the substrate.

It should be noted that the above preparation method is also applicable to other types of thin film batteries. The glass substrate is not limited to a commonly used glass substrate, but may be a flexible transparent substrate such as PET or the like. The material of the grid line can adopt: metal materials having good conductivity such as Cu, ag, and Au, and carbon materials such as graphene and carbon nanowires.

The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims

1. The preparation method of the perovskite battery structure containing the grid lines is characterized in that the perovskite battery structure containing the grid lines sequentially comprises a glass substrate (1), a transparent conductive film (3), a first transmission layer (4), a perovskite absorption layer (5), a second transmission layer (6) and a metal electrode layer (7) from bottom to top, a groove (9) is formed in one surface, which is in contact with the transparent conductive film (3), of the glass substrate (1), and the grid lines (2) are deposited in the groove (9);

the depth of the groove (9) is 0.1 to 50 μm, and the width of the groove (9) is 1 to 50 μm; a plurality of grooves (9) are arranged; the distance between the centers of two adjacent grooves (9) is 100 to 10000 mu m; the thickness of the transparent conductive film (3) is 100 to 2000nm; the thickness of the first transmission layer (4) is 10 to 50nm; the thickness of the perovskite absorption layer (5) is 200 to 800nm; the thickness of the second transmission layer (6) is 10 to 100nm; the thickness of the metal electrode layer is 50 to 500nm, and the method comprises the following steps:

step 1) coating a layer of protective film (8) on a glass substrate (1);

step 2) etching the glass substrate coated with the protective film (8) to form a groove (9) with the depth of 0.1 to 50 mu m and the width of 1 to 50 mu m on the glass substrate (1);

step 3), plating a conductive material on the glass substrate (1) containing the groove (9) to form a conductive film (10), and filling the conductive material into the groove (9) to obtain a substrate;

step 4), placing the substrate in a solvent, stripping the protective film (8) on the substrate and the conductive film (10) on the protective film (8), and obtaining a substrate with the grid line (2) laid on the surface after complete stripping;

step 5), plating a transparent conductive film (3) on the substrate with the grid line (2) laid on the surface;

and 6) sequentially plating a first transmission layer (4), a perovskite absorption layer (5), a second transmission layer (6) and a metal electrode layer (7) on the transparent conductive film (3) to obtain the perovskite battery structure containing the grid lines.

2. The method for preparing the perovskite battery structure containing the grid line as claimed in claim 1, wherein the thickness of the protective film (8) is 0.3 to 20 μm;

the protective film (8) is photoresist or PMMA;

the thickness of the conductive film (10) is 0.1 to 50 μm;

the conductive film (10) is prepared from any one of Cu, ag, au, al, ni, fe, metal alloy, graphene and carbon nanowires.

3. The method for preparing a perovskite battery structure containing grid lines as claimed in claim 1, wherein the solvent in step 4) is DMSO, toluene or DMF organic solvent.

4. The method for preparing the perovskite battery structure containing the grid lines as claimed in claim 1, wherein the etching in the step 2) is a laser etching method, a chemical etching method or an ion bombardment etching method.

5. The method for preparing the perovskite battery structure containing the grid line as claimed in claim 1, wherein the grid line (2) is any one of Cu, ag, au, al, ni, fe, metal alloy, graphene and carbon nano-wire.

6. The method for preparing a perovskite battery structure containing grid lines as claimed in claim 1, wherein the transparent conductive thin film (3) is any one of ITO, FTO, AZO, IWO and graphene materials.