CN109728170B

CN109728170B - Perovskite solar cell and preparation method thereof, perovskite solar cell pack and preparation method thereof

Info

Publication number: CN109728170B
Application number: CN201811633229.3A
Authority: CN
Inventors: 辛明俊
Original assignee: Wuxi Utmolight Technology Co Ltd
Current assignee: Wuxi Utmolight Technology Co Ltd
Priority date: 2018-12-29
Filing date: 2018-12-29
Publication date: 2022-04-29
Anticipated expiration: 2038-12-29
Also published as: CN109728170A

Abstract

The invention discloses a perovskite solar cell and a preparation method thereof, and a perovskite solar cell group and a preparation method thereof. The method for preparing the perovskite solar cell comprises the following steps: (1) providing a plurality of substrates with transparent conductive oxide layers formed in advance, sequentially overlapping the substrates so as to cover the substrates on the transparent conductive oxide layers as masks, and forming overlapped areas on the transparent conductive oxide layers; (2) an electron transport layer, a photoactive layer, and a hole transport layer are sequentially formed on the transparent conductive oxide layer not covered by the substrate. According to the method, the plurality of substrates are overlapped, the substrates are used as masks, thin film layers can be formed on the plurality of upper substrates at the same time, and the production efficiency of the perovskite solar cell is remarkably improved.

Description

Perovskite solar cell and preparation method thereof, perovskite solar cell pack and preparation method thereof

Technical Field

The invention relates to the field of photovoltaic devices, in particular to a perovskite solar cell and a preparation method thereof, and a perovskite solar cell group and a preparation method thereof.

Background

The perovskite solar cell is a type of solar cell which is rapidly developed at present, and has the characteristics of high efficiency, low cost, simple preparation and the like. The perovskite solar cell is divided into a planar structure and a mesoporous structure according to the structure, and mainly comprises a transparent electrode, an electron transport layer, a perovskite light absorption material, a hole transport layer, a counter electrode and the like. The perovskite material generates light to generate electrons and holes after absorbing the light, the electrons and the holes are respectively transmitted to the electron transmission layer and the hole transmission layer and are connected with an external circuit to form a loop, and the loop outputs electric energy.

For the production method of perovskite solar cells, processes such as printing, spraying, slit coating, and inkjet are generally applied. However, in the existing perovskite solar cell preparation method, only a single cell can be processed in each process flow, and the process cost is high and the efficiency is low. And for large-scale production processes such as roll-to-roll printing and slit coating, although the efficiency is improved, the control is difficult. In addition, perovskite solar cells generally suffer from a reduction in efficiency due to their large area, even though

Thus, existing methods of fabricating perovskite solar cells remain to be improved.

Disclosure of Invention

In view of the above, the present invention is directed to a perovskite solar cell and a method for manufacturing the same, and a perovskite solar cell and a method for manufacturing the same. According to the method, the plurality of substrates are overlapped, the substrates are used as masks, thin film layers can be formed on the plurality of upper substrates at the same time, and the production efficiency of the perovskite solar cell is remarkably improved.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

according to one aspect of the invention, a method of fabricating a perovskite solar cell is presented. According to an embodiment of the invention, the method comprises: (1) providing a plurality of substrates with transparent conductive oxide layers formed in advance, sequentially overlapping the substrates so as to cover the substrates on the transparent conductive oxide layers as masks, and forming overlapped areas on the transparent conductive oxide layers; (2) an electron transport layer, a photoactive layer, and a hole transport layer are sequentially formed on the transparent conductive oxide layer not covered by the substrate.

Compared with the prior art, the perovskite solar cell provided by the embodiment of the invention has the following advantages:

according to the method for preparing the perovskite solar cell, the transparent conductive oxide layer is formed on the substrate in advance, the substrates are sequentially overlapped, one substrate is overlapped on the transparent conductive oxide layer of the other substrate to serve as the mask, the use of the mask in the prior art is avoided, and meanwhile the process of removing the mask in the subsequent treatment is omitted. Further, an electron transport layer, a photoactive layer, and a hole transport layer are simultaneously formed in this order on a plurality of substrates stacked in this order. The self-masking process with the overlapped part between the substrates as the mask can reduce the process cost and improve the production efficiency by avoiding the use of the traditional mask, and can effectively solve the defect that the mask setting and removing processes can possibly cause the battery per se, thereby improving the battery performance.

Further, the length of the substrate is 1-20 cm, and the width of the substrate is 1-5 cm.

Further, the length of the overlapping area is 1-5 mm.

Further, the method for preparing the perovskite solar cell may further comprise: (3) an electrode is disposed on the overlapping region.

Further, in the step (1), a first electrode may be formed on the transparent conductive oxide layer in advance, and the substrates may be sequentially placed one on another so as to cover the first electrode with the substrates as a mask and form an overlapping region on the first electrode; in the step (2), an electron transport layer, a photoactive layer and a hole transport layer are sequentially formed on the first electrode not covered with the substrate.

Further, the first electrode comprises a grid line electrode, and the width of a grid line in the grid line electrode is 5-100 μm.

Further, the aspect ratio of the first electrode is 0.1 to 1.5.

Further, the method for preparing the perovskite solar cell may further comprise: a second electrode is formed on the hole transport layer.

According to another aspect of the invention, a perovskite solar cell is presented. According to an embodiment of the present invention, the perovskite solar cell is prepared by the method for preparing a perovskite solar cell of the above embodiment. Thus, the perovskite solar cell has high production efficiency and correspondingly lower production cost.

According to yet another aspect of the invention, a method of fabricating a perovskite solar cell is presented. According to an embodiment of the invention, the method comprises: (1) providing a plurality of the perovskite solar cells of the above embodiments; (2) connecting a plurality of perovskite solar cells by connecting a first electrode and a second electrode of any two perovskite solar cells to obtain the perovskite solar cell set.

According to the method for preparing the perovskite solar cell, the problem that the efficiency of the perovskite solar cell is reduced due to overlarge area can be effectively solved by connecting a plurality of small-area sub-cells to form the cell. In addition, the sub-cell adopted in the method is prepared by the method for preparing the perovskite solar cell in the previous embodiment, and the production efficiency and the production cost of the sub-cell are high.

According to yet another aspect of the invention, a perovskite solar cell is presented. According to an embodiment of the present invention, the perovskite solar cell is prepared by the method for preparing a perovskite solar cell of the above embodiment. Thus, the perovskite solar cell has high production efficiency, correspondingly lower production cost and high battery efficiency.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

FIG. 1 is a schematic illustration of multiple substrates placed one over another according to one embodiment of the present invention;

FIG. 2 is a schematic structural diagram of a perovskite solar cell according to one embodiment of the invention;

FIG. 3 is a schematic structural diagram of a perovskite solar cell according to yet another embodiment of the invention;

FIG. 4 is a schematic structural diagram of a perovskite solar cell set according to one embodiment of the invention;

FIG. 5 is a schematic structural diagram of a perovskite solar cell set according to yet another embodiment of the invention;

fig. 6 is a schematic structural diagram of a perovskite solar cell according to yet another embodiment of the present invention.

Reference numerals:

100: a substrate; 200: a transparent conductive oxide layer; 300: an electron transport layer; 400: a photoactive layer;

500: a hole transport layer; 610: a first electrode; 620: a second electrode; 700: and (5) a connecting structure.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.

According to one aspect of the invention, a method of fabricating a perovskite solar cell is presented. According to an embodiment of the invention, the method comprises: (1) providing a plurality of substrates on which transparent conductive oxide layers are formed in advance, sequentially overlapping the substrates so as to cover the substrates on the transparent conductive oxide layers as masks, and forming overlapping regions on the transparent conductive oxide layers; (2) an electron transport layer, a photoactive layer, and a hole transport layer are sequentially formed on the transparent conductive oxide layer not covered by the substrate.

According to the embodiment of the present invention, the overlapping arrangement of the plurality of substrates can be specifically described with reference to fig. 1, and since no mask is disposed on the first substrate (the leftmost substrate in fig. 1) of the plurality of substrates, the first substrate can be recycled in the process of forming the thin film layers (i.e., the electron transport layer, the photoactive layer and the hole transport layer) without further preparing the battery product; in order to ensure that the inclination angle of the last substrate (the rightmost substrate in fig. 1) among the plurality of substrates is the same as that of the other substrates, an auxiliary mechanism such as a pad or a cushion may be provided under the last substrate. In addition, in fig. 1, a transparent conductive oxide layer and/or a first electrode is formed on each substrate surface in advance, and the transparent conductive oxide layer and/or the first electrode are not shown in fig. 1.

The specific kind of the substrate according to the embodiment of the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs. For example, a glass substrate, a polymer substrate, a stainless steel substrate, or a transparent film substrate, which are commonly used in the art, may be used.

According to an embodiment of the present invention, the substrate may be cut into a rectangular parallelepiped shape in advance, and the thickness of the cut rectangular parallelepiped substrate is not particularly limited, and the length is preferably 1 to 20cm, and the width is preferably 1 to 5 cm. Therefore, the formation of the thin film layer in the subsequent process can be more convenient.

According to the preferred embodiment of the invention, the length of the overlapping area of two adjacent substrates is 1-5 mm. The length of the overlap region is a length d as shown in fig. 1. By controlling the length of the overlapping area to be 1-5 mm, the stability of the overlapping structure between the substrates can be guaranteed, so that the smooth operation of the subsequent thin film layer forming process is guaranteed, and enough space can be reserved for the formation of the thin film layer. In some embodiments, controlling the length of the overlapping region to 1-5 mm can ensure that the region has enough space to dispose the electrodes in the subsequent process.

Further, a thin film layer including an electron transport layer, a photoactive layer, and a hole transport layer is formed on the transparent conductive oxide layer not covered with the substrate. The method for forming the thin film layer is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, thermal deposition, chemical vapor deposition, spray coating, slit coating, roll-to-roll printing, which are conventional in the art, may be used. The self-masking process of the overlapped substrate of the present invention has no strict requirement on the formation mode of the thin film layer, and the conventional methods as described above can be adapted to the self-masking process.

According to a specific example of the present invention, the transparent conductive oxide layer may be formed of at least one of aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), gallium-doped zinc oxide (GZO), gallium-doped aluminum zinc oxide (GAZO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), tungsten-doped indium oxide (IWO), and titanium-doped indium oxide (ITIO); the electron transport layer may be formed of fullerene derivative PCBM, self-assembled titanium oxide, or the like; the hole transport layer may be formed of poly (3, 4-ethylenedioxythiophene) -polystyrenesulfonic acid (PEDOT: PSS), polytriarylamine hole transport material (PTAA), or the like; the electrode can be a metal electrode (such as an Ag electrode, a Cu electrode, an Au electrode, etc.), an oxide electrode, a carbon material electrode or a composite electrode.

Further, according to an embodiment of the present invention, after forming a thin film layer on a transparent conductive oxide layer not covered by a substrate, the substrates may be moved away from each other, exposing the original overlapping area, and disposing an electrode on the overlapping area.

According to an embodiment of the present invention, after the first electrode is provided over the substrate, a thin film layer may be formed by stacking a plurality of substrates. In other words, in some embodiments of the present invention, in step (1), the first electrode may be formed on the transparent conductive oxide layer in advance, that is, before the substrates are overlapped, the transparent conductive oxide layer and the first electrode are formed on the substrates in advance in sequence, and then the substrates are placed in sequence to be overlapped, so that the substrate is covered on the first electrode as a mask, and an overlapped region is formed on the first electrode; in the step (2), an electron transport layer, a photoactive layer, and a hole transport layer are sequentially formed on the first electrode not covered with the substrate. The inventors have found in experiments that the cell can be operated without the first electrode if the cell is small in size (e.g. less than 10 mm). For larger size batteries, the first electrode is preferably provided because of the greater resistance of the battery.

According to an embodiment of the present invention, the first electrode preferably includes a grid line electrode, and a width of a grid line in the grid line electrode is 5 to 100 μm, so that performance of the battery can be further improved.

According to an embodiment of the present invention, an aspect ratio (or referred to as an aspect ratio) of the first electrode is 0.1 to 1.5. If the aspect ratio is too large, subsequent processes are not facilitated.

According to a preferred embodiment of the present invention, the first electrode is formed using a material that can improve the conductivity of the transparent conductive oxide layer, such as Ag, Au, Al, C (graphene, carbon nanotube), Cu, or the like.

In addition, according to the embodiment of the present invention, the area of the photoactive layer is preferably 1 to 10% of the area of the electron transport layer, and is preferably linear, whereby the performance of the battery can be further improved.

Further, according to an embodiment of the present invention, a second electrode is formed on the hole transport layer.

Further, the solar cell may be packaged or provided with a back plate, an insulating layer and other conventional processes, which are not described herein again.

As described above, the perovskite solar cell may be fabricated using a substrate on which a transparent conductive oxide layer is previously formed or a substrate on which a transparent conductive oxide layer and a first electrode are previously formed to be overlapped, and thus, the perovskite solar cell may have two structures. Specifically, fig. 2 shows a perovskite solar cell structure prepared by using a substrate on which a transparent conductive oxide layer is previously formed, and fig. 3 shows a perovskite solar cell structure prepared by using a substrate on which a transparent conductive oxide layer and a first electrode are previously formed. As shown in fig. 2 and 3, the perovskite solar cell includes: substrate 100, transparent conductive oxide layer 200, electron transport layer 300, photoactive layer 400, hole transport layer 500, first electrode 610, and second electrode 620.

Specifically, referring to fig. 4 to 6, for example, two adjacent sub-cells are taken as an example, the first electrode of one sub-cell may be connected to the second electrode of the other sub-cell through a conventional welding process or by using a low-temperature conductive adhesive material. In addition, the manner of connecting the first electrode and the second electrode may be selected according to the shape of the electrodes. For example, if the surface to be connected of at least one of the first electrode and the second electrode is linear, the first electrode and the second electrode may be continuously welded or connected with an adhesive material (as shown in fig. 5); if the surfaces to be connected of the first electrode and the second electrode are both planar, the first electrode and the second electrode may be welded or connected with an adhesive material intermittently (as shown in fig. 6). In some embodiments, it may be more suitable to connect the plurality of sub-cells using a low temperature conductive adhesive material than high temperature soldering. In fig. 4 to 6, 700 shows a bonding structure formed by a bonding tape or an adhesive material formed by welding.

It should be noted that the perovskite solar cell set has all the features and advantages of the perovskite solar cell set described above, and the description thereof is omitted.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A method of making a perovskite solar cell, comprising:

(1) providing a plurality of substrates with transparent conductive oxide layers formed in advance, sequentially overlapping the substrates so as to cover the substrates on the transparent conductive oxide layers as masks, and forming overlapped areas on the transparent conductive oxide layers;

(2) an electron transport layer, a photoactive layer, and a hole transport layer are sequentially formed on the transparent conductive oxide layer not covered by the substrate.

2. The method of claim 1, wherein the substrate has a length of 1 to 20cm and a width of 1 to 5 cm.

3. The method of claim 1, wherein the length of the overlap region is 1-5 mm.

4. The method of claim 1, further comprising:

(3) an electrode is disposed on the overlapping region.

5. The method according to claim 1, wherein in step (1), a first electrode is formed on the transparent conductive oxide layer in advance, the substrates are placed one on top of another in order to cover the substrates as a mask on the first electrode, and an overlap region is formed on the first electrode; in the step (2), an electron transport layer, a photoactive layer and a hole transport layer are sequentially formed on the first electrode not covered with the substrate.

6. The method of claim 5, wherein the first electrode comprises a gate line electrode, and a width of a gate line in the gate line electrode is 5 to 100 μm;

optionally, the aspect ratio of the first electrode is 0.1 to 1.5.

7. The method of any one of claims 1 to 6, further comprising: a second electrode is formed on the hole transport layer.

8. A perovskite solar cell, characterized in that the perovskite solar cell is prepared by the method of any one of claims 1 to 7.

9. A method of making a perovskite solar cell, comprising:

(1) providing a plurality of perovskite solar cells of claim 8;

(2) connecting a plurality of perovskite solar cells by connecting a first electrode and a second electrode of any two perovskite solar cells to obtain the perovskite solar cell set.

10. A perovskite solar cell, characterized in that the perovskite solar cell is prepared by the method of claim 9.