KR102259399B1 - Method For Manufacturing Organic Solar Cells And Organic Solar Cells Thereby - Google Patents

Abstract

The present invention is a method of manufacturing an organic solar cell comprising a base film, a lower electrode layer, an upper electrode layer, and an organic material layer including a photoactive layer positioned between the lower electrode layer and the upper electrode layer,
(A) patterning the organic material layer by irradiating laser light;
(B) placing a heat-sealed film on the pattern formed in step (A);
(C) bonding the impurities by fusing the heat-sealed film; And
It provides a method of manufacturing an organic solar cell comprising; (D) removing the heat-sealed film to which the impurities are bonded, and an organic solar cell manufactured thereby.

Description

Method For Manufacturing Organic Solar Cells And Organic Solar Cells Thereby {Method For Manufacturing Organic Solar Cells And Organic Solar Cells Thereby}}

The present invention relates to a method of manufacturing an organic solar cell and an organic solar cell manufactured thereby.

In the case of organic solar cells, donor-type and acceptor-type organic semiconductor materials are used as photoactive layers between the transparent electrode and the anode. The possibility is very high, and it is expected to be able to manufacture organic solar cells with superior efficiency through this.

According to a report by NREL, a 12% efficient silicon solar cell produces a unit area (m ² ), which consumes 420 kWh of energy and has a payback time of 4 years, whereas an organic solar cell with 5% efficiency is 20 kWh. It is reported that only energy is consumed, and the payback time can be reduced to 0.5 years. Moreover, it is known that silicon solar cells require 8,000 tons of photoactive layer material for 1 GW-class power generation, but only 3.4 tons of material are required for organic solar cells as ultra-thin photoactive layers. Therefore, ultimately, when implementing a roll-to-roll process using a flexible substrate, it is expected that significant cost reductions that cannot be imagined in the existing inorganic solar cells will be possible, and recently, large companies are also participating in technology development.

In the case of such an organic solar cell, research on the scale of a unit cell (device) to improve efficiency is mainly made. In the end, from the viewpoint of mass production considering commercialization, the development of various technologies of the module scale is urgent reality. However, most of the conventional patterning methods employ a lithography process of a semiconductor process, and thus act as a factor that offsets the biggest advantage of mass production of organic solar cells in terms of process efficiency and price competition.

Furthermore, since conventional organic solar cells are manufactured by a combination of discontinuous processes, the need for continuous process development is increasing for early realization of process efficiency and mass production systems. In addition, even if a continuous process is performed, only a simple pattern of a stripe pattern can be realized, and thus various patterns required to improve the efficiency of an organic solar cell cannot be realized. Therefore, technology development is required to overcome these problems.

Republic of Korea Patent Publication No. 10-2011-0063372

In order to solve the above problems, the present inventors have focused on a process of forming a pattern of an organic material layer including a photoactive layer by irradiating laser light. In the process, in the case of forming the pattern of the organic material layer as described above, it was found that the carbide generated as the organic material layer was carbonized remains on the substrate as impurities, causing a problem of increasing the contact resistance when connecting the lower electrode and the upper electrode. Was done.

Therefore, the present invention relates to a method of manufacturing an organic solar cell including a method for efficiently removing impurities such as carbides generated when patterning an organic material layer using laser light, and the like. An object of the present invention is to provide an organic solar cell with excellent efficiency manufactured by the method.

To achieve the above object,

The present invention is a method for manufacturing an organic solar cell comprising a base film, a lower electrode layer, an upper electrode layer, and an organic material layer including a photoactive layer positioned between the lower electrode layer and the upper electrode layer,

(A) patterning the organic material layer by irradiating laser light;

(B) placing a heat-sealed film on the pattern formed in step (A);

(C) bonding the impurities by fusing the heat-sealed film; And

It provides a method for manufacturing an organic solar cell comprising; (D) removing the heat-sealed film to which the impurities are bound.

The manufacturing method of the organic solar cell of the present invention is partially fused by irradiating laser light on the top of the heat-sealed film located at the portion where the laser was irradiated during the patterning of step (A) in the fusion bonding of the heat-sealed film in step (C). It may have features that allow it to be implemented in a manner.

In addition, the method may have a characteristic of cooling after combining impurities.

In addition, the method may have a characteristic that the organic material layer includes an electron transport layer (ETL), a photoactive layer, and a hole transport layer (HTL).

In addition, the method may have a feature of using a melting temperature of 50 ~ 250 ℃ as the heat-sealed film.

In addition, the method may further include depositing an organic material layer on the lower electrode layer before the organic material layer patterning step of step (A).

In addition, the method may further include forming a lower electrode layer before the step of laminating the organic material layer.

In addition, the method may have a feature that the lower electrode layer is formed of ITO.

In addition, the present invention provides an organic solar cell manufactured by the manufacturing method of the present invention.

The present invention includes a method for efficiently removing impurities such as carbides generated when patterning an organic material layer using laser light in manufacturing an organic solar cell without damaging the lower electrode or the base film. It provides a method of manufacturing an organic solar cell.

According to the manufacturing method of the organic solar cell, when connecting the lower electrode and the upper electrode, it is possible to prevent an increase in contact resistance caused by carbides, thereby providing an organic solar cell having excellent efficiency.

1 is a perspective view schematically showing the configuration of a general organic solar cell.
2 is a diagram showing a process of forming a lower electrode that can be carried out in the method of manufacturing an organic solar cell of the present invention.
3 is a diagram showing a lamination process of an organic material layer that can be carried out in the method of manufacturing an organic solar cell of the present invention.
FIG. 4 is a diagram schematically showing a process of laser patterning, fusion bonding of a thermally fused film, and removal thereof that can be performed in the method of manufacturing an organic solar cell of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to describing the present invention, when it is determined that a detailed description of related known functions and configurations may unnecessarily obscure the subject matter of the present invention, a description thereof will be omitted.

The description and drawings below illustrate specific embodiments to facilitate those skilled in the art to implement the described apparatus and methods. Other embodiments may include structurally and logically different variations. Individual components and functions may generally be selected unless explicitly required, and the sequence of processes may vary. Parts and features of some embodiments may be included in or replaced by other embodiments.

Hereinafter, a method of manufacturing an organic solar cell of the present invention will be described with reference to FIGS. 1 to 4.

In the present invention, as illustrated in FIG. 1, an organic material layer including a base film 10, a lower electrode layer 20, an upper electrode layer 60, and a photoactive layer 40 positioned between the lower electrode layer and the upper electrode layer ( 30 to 50), as illustrated in FIG. 4,

(A) patterning the organic material layers 30 to 50 by irradiating laser light;

(B) placing the heat-sealed film 70 on the pattern formed in step (A);

(C) bonding the impurities by fusing the heat-sealed film 70; And

It relates to a method for manufacturing an organic solar cell comprising; (D) removing the heat-sealed film 70 to which the impurities are bound.

The step of patterning the organic material layers 30 to 50 by irradiating laser light in step (A) is performed by scribing a part of the organic material layer in a predetermined pattern by irradiating laser light. At this time, organic matter may be carbonized to form a residue. In the step (C), the impurity mainly refers to the carbide remaining on the substrate after being carbonized. The residual carbide is the main cause of increasing the contact resistance when connecting the lower electrode and the upper electrode formed by the lower electrode layer 20 and the upper electrode layer 60, so the removal process of the residual carbide is an efficiency of the organic solar cell. Has a very important effect on

In order to combine the heat-sealed film 70 melted in step (C) with impurities, it may be cooled. Cooling at this time can be carried out by various methods known in the art. For example, the cooling may be performed by air cooling at room temperature.

In the above, as an apparatus for irradiating laser light, a laser irradiation apparatus commonly used in this field may be used. The laser light irradiated by the laser irradiation device considers the material and thickness of the organic material layer to be patterned, and the wavelength, irradiation time, frequency, and output in consideration of damage to the lower electrode layer 20 and the base film 10 under the organic material layer. You should use it with precise control of your back.

For example, the patterning of the organic material layer of the present invention may be performed by irradiating laser light having an output of 1 to 30 W, a wavelength of 1064 nm, and a frequency of 200 to 800 KHz at a rate of 1000 to 3000 mm/sec. However, it is not limited thereto.

The fusion bonding of the heat-sealing film 70 in step (C) may be performed by applying heat to the heat-sealing film to melt the film. In the above, the heat source is not particularly limited, and any heat source known in this field may be used.

In the step of bonding the impurities by fusing the thermally fused film 70 of step (C), the impurity, for example, a carbide formed by scribing the organic material layers 30 to 50 by laser light, is lifted off. -off).

The fusion bonding of the heat-sealing film 70 in the step (C) is performed by a laser on the top of the heat-sealing film located at the portion where the laser was irradiated during the patterning of step (A), as shown in FIG. 4(c). It is more preferable that it is carried out in a partial fusion method by irradiating light. This is because, if the heat-sealable film 70 is fused to all areas on which the pattern is formed, there is a fear that the patterns of the organic material layers 30 to 50 may be removed together when the heat-sealable film is removed.

As the laser device used in the above, the above-described laser device can be used, and in this case, wavelength, irradiation time, frequency, output, considering the melting temperature of the heat-sealed film, damage to the lower electrode layer 20, damage to the base film, etc. You should use it with precise control of your back. .

For example, the melting of the heat-sealed film may be performed by irradiating laser light having an output of 10 to 30 W, power (intensity) 3 to 20%, a wavelength of 1064 nm, and a frequency of 100 to 500 KHz at a rate of 1000 to 4000 mm/sec. . However, it is not limited thereto.

The organic material layers 30 to 50 may include an electron transport layer 10, a photoactive layer 20, and a hole transport layer 30, as illustrated in FIGS. 1 and 3.

As a material constituting the electron transport layer 10, the photoactive layer 20, and the hole transport layer 30, components known in the art may be used without limitation.

The heat-sealed film may have a melting temperature of 50 to 250°C. If the melting temperature is less than 50°C, the possibility of fusion occurs at room temperature, and if it exceeds 250°C, it is not preferable because it may damage the lower electrode layer 20. For example, ITO has a crystallization temperature of 270°C. A specific example of the heat-sealed film may include ethylene vinyl acetate (EVA).

In the method of manufacturing an organic solar cell of the present invention, before the organic material layer patterning step of step (A), as illustrated in FIG. 3, a step of laminating an organic material layer on the lower electrode layer may be performed. In this case, the electron transport layer 10, the photoactive layer 20, and the hole transport layer 30 may be stacked in this order, but the present invention is not limited thereto. The formation of the electron transport layer 10 and the hole transport layer 30 is not necessarily required, but is formed to improve the efficiency of the organic solar cell. An organic compound is used as a material for the electron transport layer 10 and the hole transport layer 30, and components known in the art may be used without limitation.

The material forming the photoactive layer 20 is not particularly limited, but representatively, PEDOT:PSS, or the like may be used.

Before the step of laminating the organic material layer, as illustrated in FIG. 2, a step of forming the lower electrode layer 20 may be further performed. That is, the formation of the lower electrode layer 20 may be performed by various methods known in the art. For example, a thin film for forming the lower electrode layer 20 may be formed on the base film 10 and an electrode pattern may be formed by a wet process using a photolithography process.

The lower electrode layer 20 may be formed of a material such as ITO or IZO, but is not limited thereto.

As the base film 10, a film known in this field may be used without limitation. In the case of a flexible organic solar cell, a polyethylene terephthalate (PET) film or the like may be used.

In the method of manufacturing an organic solar cell of the present invention, the (D) removing the thermally bonded film 70 to which the impurities are bonded; after completion, an upper electrode layer 60 is formed on the organic material layer 30-50. Can be formed. The formation of the upper electrode layer 60 may be performed by a method known in the art. The material of the upper electrode layer 60 is not particularly limited, and Ag, Au, Al, Cu, or the like may be used.

After the formation of the upper electrode layer 60, a short circuit is checked for each cell, and then necessary measures are taken and a current collecting pattern is formed. The current collecting pattern may be formed in series or in parallel according to a method of connecting the upper electrode and the lower electrode between each module.

Finally, a protective layer is formed on the surface of the substrate on which the upper electrode is formed.

In addition, the present invention relates to an organic solar cell manufactured by the method for manufacturing the organic solar cell. In the organic solar cell as described above, since carbides, which are impurities, are efficiently removed by the fusing process of the thermally fused film, the contact between the lower electrode and the upper electrode is excellent, thereby providing excellent durability and excellent efficiency.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will include such modifications or variations as long as they fall within the gist of the present invention.

Example

[Example 1]

A laminate for an organic solar cell including a base film (PET, 125㎛), a lower electrode layer (ITO), an upper electrode layer (Ag), and an organic material layer (P3TH: PCBM) including a photoactive layer positioned between the lower electrode layer and the upper electrode layer Prepared.

Patterning was performed on the laminate at an output of 5W using a fiber laser (IPG). After placing the EVA film on the carbonized active layer present on the patterned substrate, it was irradiated with a power of 5% at an output of 20W using a fiber laser. After cooling the EVA film for 1 minute, an organic solar cell was manufactured by removing the EVA film to which impurities on the carbonized active layer were bound.

[Example 2]

An organic solar cell was manufactured in the same manner as in Example 1, except that the fiber laser was irradiated with an intensity of 8%.

[Example 3]

An organic solar cell was manufactured in the same manner as in Example 1, except that the fiber laser was irradiated with an intensity of 15%.

Experimental example

1. Check visibility

It was observed whether impurities in the carbonized active layer layer remaining in the patterned portions of the prepared organic solar cells of Examples 1 to 3 were present.

As a result of observation, in the case of Examples 1 to 3, it was found that the impurities in the carbonized active layer layer were removed, and in particular, in the case of Examples 2 to 3, it was found that the impurities were removed well compared to Example 1. .

2. ITO/ Ag Reduction of contact resistance

For the organic solar cells of Examples 1 to 3, an actual module (100*100mm*10Series) was manufactured and the series resistance of the module was measured.

resistance Example 1 150Ω Example 2 42Ω Example 3 45Ω

As in the contact resistance measurement results of Examples 1 to 3, it was found that a contact resistance value suitable for use in an organic solar cell was displayed.

10: base film 20: lower electrode layer
30: electron transport layer (ETL) 40: photoactive layer
50: hole transport layer (HTL) 60: upper electrode layer
70: heat-sealing film 80: carbide produced by the organic material layer
90: laser light

Claims (7)

A method for manufacturing an organic solar cell comprising a base film, a lower electrode layer, an upper electrode layer, and an organic material layer including a photoactive layer positioned between the lower electrode layer and the upper electrode layer,
(A) patterning the organic material layer by irradiating laser light;
(B) placing a heat-sealed film on the pattern formed in step (A);
(C) bonding the impurities by fusing the heat-sealed film; And
(D) removing the heat-sealed film to which the impurities are bound; Including,
Organic solar, characterized in that the fusion bonding of the thermally fused film in step (C) is carried out in a partial fusion method by irradiating laser light on the top of the thermally fused film located at the portion where the laser was irradiated during the patterning in step (A). Method of manufacturing a battery. delete The method of claim 1,
The method of manufacturing an organic solar cell, characterized in that the impurities are combined in the step (C) and then cooled. The method of claim 1,
The organic material layer comprises an electron transport layer (ETL), a photoactive layer, and a hole transport layer (HTL). The method of claim 1,
The method of manufacturing an organic solar cell, wherein the heat-sealed film has a melting temperature of 50 to 250°C. The method of claim 1,
The method of manufacturing an organic solar cell, wherein the lower electrode layer is formed of ITO. An organic solar cell manufactured by the method of manufacturing an organic solar cell according to any one of claims 1 and 3 to 6.

Images