KR20100016892A - Manufacturing method for organic solar cell - Google Patents

Abstract

PURPOSE: A manufacturing method for organic solar cell is provided to increase the effectiveness of a organic solar cell by increasing the mobility of an electron by irradiating an ion beam on one of top layers after forming a bottom electrode, and a hole collect layer and a semiconductor film layer. CONSTITUTION: A Bottom Electrode(200) is formed on a substrate(100). A hole collect layer(300) is formed on the top of the bottom electrode for helping the movement of a hole. A semiconductor film layer(400) is formed on the top of the hole collect layer for dividing the free electron and the hole. A upper electrode(500) is formed on the top of the semiconductor film layer. The ion beam is irradiated to the top side of one of the bottom electrode, the hole collect layer, and the semiconductor film layer, and the top electrode. The top electrode includes the conductive metal like aluminum.

Description

Manufacturing method for organic solar cell

The present invention relates to a method for manufacturing an organic solar cell.

More specifically, in the organic solar cell manufacturing process of forming a lower electrode, a hole collecting layer, a semiconductor thin film layer on the substrate, after the step of forming the layer, the ion beam irradiation step of irradiating the ion beam to the top of the layer further It relates to an organic solar cell manufacturing method comprising.

As the industry develops, the amount of energy used is rapidly increasing, but the resources are limited. Therefore, problems due to the increase in energy demand are expected. Therefore, there is a growing need to develop technologies that produce economical and high performance new energy sources without destroying the environment.

Solar cells are attracting attention as one of such new energy sources, and most of the solar cells that are currently in practical use are inorganic solar cells using single crystal silicon, polycrystalline silicon, and amorphous silicon. However, these inorganic solar cells have a high manufacturing cost due to the complicated manufacturing process, so it is difficult to spread to general households. In order to solve these difficulties, researches on organic solar cells having low manufacturing costs are being actively conducted through simple manufacturing processes.

In particular, the organic solar cell can be made into a thin film having a thickness of several hundred nm or less, and has the advantage that it can be applied in a structure that can be bent, so that the application is possible for various purposes such as presenting a possibility as a future energy source. It is expected.

In researching such an organic solar cell, a lot of research is required about a method of increasing the efficiency of the organic solar cell.

The organic solar cell manufacturing method of the present invention according to the above requirements, after forming a lower electrode, a hole collecting layer, a semiconductor thin film layer on the substrate, by increasing the mobility of electrons by irradiating the ion beam on the upper layer of the organic solar cell To increase the efficiency of the purpose.

In addition, the purpose is to enhance the adhesion between the layers by irradiating the ion beam on the layer.

In order to achieve the above object, the organic solar cell manufacturing method according to the present invention includes a lower electrode forming step of forming a lower electrode on the upper surface of the substrate; A hole collecting layer forming step formed on the lower electrode and forming a hole collecting layer which helps hole movement; An organic solar cell manufacturing process comprising a semiconductor thin film layer forming step formed on the hole collecting layer and forming a semiconductor thin film layer separating free electrons and holes and an upper electrode forming step forming an upper electrode located on the semiconductor thin film layer. In at least one of the lower electrode forming step, the hole collecting layer forming step, the semiconductor thin film layer forming step and the upper electrode forming step, at least one of the lower electrode formed in the step, the hole collecting layer and the semiconductor thin film layer It characterized in that it further comprises an ion beam irradiation step of irradiating the ion beam to the layer upper surface.

In a method of manufacturing an organic solar cell according to a preferred aspect of the present invention, at least one of the lower electrode, the hole collecting layer, and the semiconductor thin film layer formed on the upper surface of the substrate using at least one of hydrogen, nitrogen, oxygen, and fluorine ions as an ion beam. And an ion beam irradiation step of irradiating the ion beam on the upper surface of the layer.

More preferred organic solar cell manufacturing method according to the characteristics of the present invention P3HT poly (3-hexylthiophene) and PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)], poly (9,9-di-n -octylfluorene-alt-benzothiadiazole) and a hole collecting layer forming step of forming a hole collecting layer using at least one of F8BT.

More preferred organic solar cell manufacturing method according to the characteristics of the present invention P3HT: PCBM [poly (3-hexylthiophene): Phenyl-C61-Butyric-Acid-Methyl-Ester] and poly (3-hexylthiophene) (P3HT) and poly ( 9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) is characterized in that it comprises a semiconductor thin film layer forming step of forming a semiconductor thin film layer.

In particular, the organic solar cell manufacturing method according to the characteristics of the present invention is a ratio of poly (3-hexylthiophene) (P3HT): poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) to 6: 4 It characterized by including a semiconductor thin film layer forming step of forming a semiconductor thin film layer.

As described above, in the method of manufacturing the organic solar cell of the present invention, after forming the lower electrode, the hole collecting layer, and the semiconductor thin film layer on the substrate, the mobility of electrons increases as the ion beam is irradiated on the upper layer of the organic solar cell. It can increase the efficiency of.

Moreover, by irradiating an ion beam on the said layer, the adhesive force between the said layers can be strengthened.

Examples of the method for manufacturing the organic solar cell according to the present invention can be variously applied, and the following will describe a preferred embodiment with reference to the accompanying drawings.

1 is a side structural view of an organic solar cell according to an embodiment of the present invention, Figure 2 is a flow chart of a method of manufacturing an organic solar cell according to an embodiment of the present invention.

As shown in FIG. 1 and FIG. 2, the lower electrode 200 made transparent is formed on one side of the upper portion of the substrate 100 (S601). In this case, it is preferable to use a transparent electrode such as indium tin oxide (ITO) as the lower electrode.

A hole collection layer 300 is formed on one side of the substrate 100 on which the lower electrode 200 is formed (S602). It is determined whether the ion beam is irradiated onto the substrate 100 on which the hole collection layer 300 is formed (S603). In accordance with the determination of the ion beam irradiation, irradiating an ion beam onto the substrate 100 (S603), or without irradiating an ion beam onto the substrate 100 on which the hole collecting layer 300 is formed, the hole collecting layer ( The semiconductor thin film layer 400 is formed on one side of the substrate 100 on which the 300 is formed (S605).

As such, it is determined whether the ion beam is irradiated onto the semiconductor thin film layer 400 formed on the substrate 100 (S606). Depending on whether the ion beam is irradiated, the upper electrode 500 is irradiated with an ion beam onto the substrate 100 (S607), or one side of an upper surface of the substrate 100 on which the semiconductor thin film layer 400 is formed without irradiating an ion beam. To form (S608).

In this case, the upper electrode 500 preferably uses a conductive metal such as aluminum.

Hereinafter, the method of manufacturing the organic solar cell of the present invention will be described in detail through various examples.

<First Embodiment>

Indium Tin Oxide (ITO), which is mainly used for transparent electrodes, is coated on one side of the substrate, and poly (3-hexylthiophene) (P3HT) is coated on the ITO-coated substrate to form a hole collecting layer. Coating to a thickness of 60 nm.

The poly (3-hexylthiophene) (P3HT) is a polymer material exhibiting the highest hole mobility among materials reported to date, and has a low band gap, and the chemical formula is as follows.

Subsequently, the poly (3-hexylthiophene) (P3HT) was coated on a substrate coated with a solvent at 50 ° C. for 15 minutes to evaporate.

In this way, the substrate in which the solvent is evaporated is put in a vacuum process chamber to perform heat treatment at 120 ° C. for 30 minutes.

Through the series of processes described above, the ion beam is irradiated onto the substrate on which the hole collection layer is formed.

At this time, the irradiated ion beam may use nitrogen, hydrogen, oxygen, fluorine ions, and in this embodiment, irradiates a low energy nitrogen ion beam.

After irradiating the nitrogen ion beam on the substrate, the absorbance is measured to obtain a graph as shown in FIG. 3A.

As shown in FIG. 3A, the graph indicated by the dotted line is the result of measuring the absorbance after irradiation with the nitrogen ion beam, and the graph indicated by the solid line is the result of measurement of the absorbance without irradiation with the nitrogen ion beam.

Absorption is almost zero for light having a wavelength in the range of 700 to 1100 nm when irradiated with a nitrogen ion beam, but absorbance for light with a wavelength in the range of 700 to 1100 nm when irradiated with a nitrogen ion beam. ) Is 0.1 or more. Considering that the light absorption rate between 400 and 600 nm, which is the highest light absorption rate, is 0.25, it can be seen that the light absorption rate in the 700 to 1100 nm band is high.

In other words, it can be seen that light absorption of a predetermined level or more is possible even when visible light as well as light corresponding to the near infrared range is irradiated to the organic solar cell.

In addition, it can be seen that the energy for removing electrons increases as the nitrogen ion beam is irradiated.

As shown in FIG. 3B, the bar graph shown on the left is a result of measuring the amount of energy when no nitrogen ion beam is irradiated, and the bar graph on the right is a result of measuring the amount of energy after the nitrogen ion beam is irradiated.

The difference in the bar graph shows that the energy increases even with the naked eye.

Second Embodiment

In the second embodiment, in the same process as in the first embodiment, the low energy hydrogen ion beam is irradiated on the substrate on which the hole collection layer is formed instead of the low energy nitrogen ion beam. After irradiating the hydrogen ion beam on the substrate, the absorbance is measured to obtain a graph as shown in FIG. 4.

As shown in FIG. 4, the graph indicated by the dotted line is the result of measuring the absorbance after irradiating the hydrogen ion beam, and the graph indicated by the solid line is the result of measuring the absorbance without irradiating the hydrogen ion beam.

Absorption is close to zero for light having a wavelength in the range of 700 to 1100 nm without irradiation of the hydrogen ion beam, but for light with a wavelength in the range of 700 to 1100 nm when irradiating the hydrogen ion beam. It can be seen that the water absorption is 0.15 or more. Considering that the light absorption rate between 400 and 600 nm, which is the highest light absorption rate, is 0.35 to 0.45, it can be seen that the light absorption rate is high in the 700 to 1100 nm band.

In other words, it can be seen that light absorption of a predetermined level or more is possible even when visible light as well as light corresponding to the near infrared range is irradiated to the organic solar cell.

Third Embodiment

ITO (Indium Tin Oxide), which is mainly used for transparent electrodes, is coated on one side of the substrate, and PEDOT: PSS [Poly (3,4-) is coated on the ITO-coated substrate to form a hole collecting layer. ethylenedioxythiophene): poly (styrenesulfonate)] is coated to a thickness of 70 nm.

At this time, the chemical formula of the PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)] is as follows.

Thereafter, the PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)] coated substrate is subjected to a heat treatment at 230 ℃ for 15 minutes.

P3HT: PCBM [poly (3-hexylthiophene): Phenyl-C61 for forming a semiconductor thin film on one side of the substrate coated with PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)] -Butyric-Acid-Methyl-Ester] is coated to a thickness of 60 nm.

At this time, the chemical formula of the P3HT: PCBM [poly (3-hexylthiophene): Phenyl-C61-Butyric-Acid-Methyl-Ester] is as follows.

Subsequently, the solvent is evaporated at 50 ° C. for the substrate coated with P3HT: PCB [poly (3-hexylthiophene): Phenyl-C61-Butyric-Acid-Methyl-Ester].

In this manner, the substrate in which the solvent is evaporated is put in a vacuum process chamber and heat-treated at 140 ° C. for 30 minutes.

Through a series of processes described above, the ion beam is irradiated onto the substrate on which the semiconductor thin film layer is formed. In this embodiment, a low energy nitrogen ion beam is irradiated.

In the process of irradiating the nitrogen ion beam on the substrate, the irradiation is performed by varying the concentration of the nitrogen ion beam irradiated onto the substrate.

As such, the substrate irradiated with different concentrations of the nitrogen ion beam is placed in a vacuum process chamber, and the upper electrode is coated on one side of the upper substrate to complete the organic solar cell.

In this embodiment, the concentration of the irradiated nitrogen ion beam is divided into four types of 1x10 ¹⁶ , 5x10 ¹⁶ , 1x10 ¹⁷ , and 5x10 ¹⁷ (ions / cm ² ).

As such, after irradiating the nitrogen ion beam onto the substrate, the absorbance is measured to obtain a graph as shown in FIG. 5A.

As shown in FIG. 5A, graphs labeled as 1 are the results of measuring absorbance without irradiating a nitrogen ion beam on the substrate, and the results of measuring absorbance according to concentrations of nitrogen ion beams, respectively.

As shown in FIG. 5A, other graphs except for the first graph may have an absorbance of 0.1 when irradiated with light in the range of 700 to 110 nm.

On the other hand, in the case of one graph not irradiating a nitrogen ion beam, it can be seen that when light in the range of 700 to 1100 nm is irradiated, it has an absorbance near zero.

Therefore, even if the light corresponding to the near infrared range is irradiated to the organic solar cell it can be confirmed that the light absorption of a certain level or more.

In addition, as the nitrogen ion beam is irradiated at different concentrations, it can be seen from FIG. 5B that the power conversion efficiency varies.

As shown in FIG. 5B, the power change efficiency when the nitrogen ion beam is not irradiated on the substrate is 4.4%, and when the nitrogen ion beam is irradiated at a concentration of ¹ × 10 ¹⁶ (ions / cm ² ), the power change efficiency is 5.0%. Seems. When irradiating nitrogen ion beam at the concentration of 5x10 ¹⁶ (ions / cm ² ), the power change efficiency is 5.6%, and when irradiating the nitrogen ion beam at the concentration of 1x10 ¹⁷ (ions / cm ² ), the power change efficiency is 6.0%. In the case of irradiating nitrogen ion beam at a concentration of 5 × 10 ¹⁷ (ions / cm ² ), it can be seen that it has a power change efficiency of 5.1%.

Fourth Example

Indium Tin Oxide (ITO), which is mainly used for transparent electrodes, is coated on one side of the upper surface of the substrate, and poly (9,9-di-n) is coated on the ITO-coated substrate to form a hole collecting layer. -octylfluorene-alt-benzothiadiazole) (F8BT) is coated to a thickness of 100 nm.

At this time, the chemistry of the poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) is as follows.

Thereafter, the poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) coated substrate is evaporated at 50 ° C. for 30 minutes.

In this way, the substrate in which the solvent is evaporated is put in a vacuum process chamber to perform heat treatment at 120 ° C. for 30 minutes.

Through the series of processes described above, the ion beam is irradiated onto the substrate on which the hole collection layer is formed.

In this embodiment, a low energy nitrogen ion beam is irradiated.

After irradiating the nitrogen ion beam onto the substrate and measuring the absorbance, a graph as shown in FIG. 6 may be obtained.

As shown in FIG. 6, the graph indicated by the dotted line is the result of measuring the absorbance after irradiation with the nitrogen ion beam, and the graph indicated by the solid line is the result of measurement of the absorbance without irradiation with the nitrogen ion beam.

Absorption for light having a wavelength in the range of 550 to 1100 nm when not irradiated with nitrogen ion beam is 0 to 0.1. Absorption for light having a wavelength in the range of 550 to 1100 nm when irradiating with nitrogen ion beam. It can be seen that the 0.1 ~ 0.15 or more.

As with the other embodiments described above, it can be seen that light absorption for a wider range of light is possible.

Fifth Embodiment

Indium Tin Oxide (ITO), which is mainly used for transparent electrodes, is coated on one side of the substrate, and poly (9,9-di-n) is coated on the substrate coated with ITO to form a hole collection layer. -octylfluorene-alt-benzothiadiazole) (F8BT) is coated to a thickness of 100 nm and the solvent for the substrate is evaporated at 50 ° C. for 30 minutes.

Through the series of processes described above, the ion beam is irradiated onto the substrate on which the hole collection layer is formed.

In this embodiment, a low energy hydrogen ion beam is irradiated at a concentration of ¹ × 10 ¹⁶ (ions / cm ² ).

After irradiating the hydrogen ion beam on the substrate, the absorbance is measured to obtain a graph as shown in FIG. 7.

As shown in FIG. 7, the graph indicated by the dotted line is the result of measuring the absorbance after irradiating the hydrogen ion beam, and the graph indicated by the solid line is the result of measuring the absorbance without irradiating the hydrogen ion beam.

When not irradiating a hydrogen ion beam, it can be seen that the light absorption rate when irradiating a hydrogen ion beam to light having a wavelength in the range of 700 to 1100 nm is between 0.05 and 0.1.

As with the other embodiments described above, it can be seen that light absorption for a wider range of light is possible.

Sixth Example

Indium Tin Oxide (ITO), which is mainly used for transparent electrodes, is coated on one side of the substrate, and PEDOT: PSS [Poly (3,4-) is coated on the ITO-coated substrate to form a hole collecting layer. ethylenedioxythiophene): poly (styrenesulfonate)] is coated to a thickness of 70 nm, and the solvent is evaporated at 230 ° C. for 15 minutes.

Poly (3-hexylthiophene) (P3HT) and poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) for the formation of a semiconductor thin film were mixed in a ratio of 6: 4 to 50 nm in thickness of the substrate. Coating on top, evaporate solvent at 50 ° C. for 30 minutes. The concentration of the low energy nitrogen ion beam is irradiated on top of the substrate on which the solvent is evaporated. In this embodiment, the concentration of the nitrogen ion beam is divided into two types, 1x10 ¹⁶ and 1x10 ¹⁷ (ions / cm ² ).

In addition, it can be seen from FIG. 8 that the power conversion efficiency varies as the nitrogen ion beams are irradiated at different concentrations.

As shown in FIG. 8, the power change efficiency when the nitrogen ion beam is not irradiated on the substrate is 0.13%, and when the nitrogen ion beam is irradiated at a concentration of ¹ × 10 ¹⁶ (ions / cm ² ), the power change efficiency is 1.5%. Seems. In the case of irradiation with nitrogen ion beam at the concentration of 1x10 ¹⁷ (ions / cm ² ), it can be seen that the efficiency of power change is 2.0%.

When the nitrogen ion beam is irradiated onto the substrate, the LiF layer is coated with a thickness of 1 nm on one side of the substrate, and the aluminum electrode for forming the upper electrode is 150 nm on one side of the substrate on which the LiF layer is coated. The deposition of a thickness of to complete the organic solar cell manufacturing.

As described above, in the method of manufacturing the organic solar cell of the present invention, by irradiating an ion beam to at least one layer of a hole collecting layer and a semiconductor thin film layer composed of an organic material, the organic material is ionically bonded or crosslinked around the irradiated ions. As it is formed there is an advantage to increase the efficiency of the organic solar cell by increasing the mobility of electrons during light irradiation.

In addition, by irradiating an ion beam to the upper surface of at least one layer of the hole collecting layer and the semiconductor thin film layer, there is an advantage to strengthen the adhesion between the layers.

The organic solar cell manufacturing method according to the present invention has been described above. Such a technical configuration of the present invention will be understood by those skilled in the art that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention.

Therefore, the above-described embodiments are to be understood in all respects as illustrative and not restrictive, and the scope of the present invention is indicated by the following claims rather than the foregoing description, and the meanings of the claims and All changes or modifications derived from the scope and the equivalent concept should be construed as being included in the scope of the present invention.

1 is a side structure diagram of an organic solar cell according to an embodiment of the present invention,

2 is a flow chart of an organic solar cell manufacturing method according to an embodiment of the present invention,

Figure 3a is a graph showing the change in absorbance of the organic solar cell according to an embodiment of the present invention,

3B is a graph showing the amount of energy to remove electrons from the organic solar cell according to an embodiment of the present invention,

4 is a graph showing the absorbance change rate of the organic solar cell according to another embodiment of the present invention,

5A is a graph showing the absorbance change rate of an organic solar cell according to another exemplary embodiment of the present disclosure, in which an ion beam concentration to be irradiated is changed.

5B is a table showing power conversion efficiency of an organic solar cell according to another embodiment of the present invention, in which the ion beam concentration to be irradiated is changed.

6 is a graph showing the absorbance change rate of the organic solar cell according to another embodiment of the present invention,

7 is a graph showing the absorbance change rate of the organic solar cell according to another embodiment of the present invention,

8 is a table showing the power conversion efficiency of the organic solar cell according to another embodiment of the present invention.

*** Explanation of symbols for main parts of drawing ***

100: substrate 200: lower electrode

300: hole collecting layer 400: semiconductor thin film layer

500: upper electrode

Claims (5)

A lower electrode forming step of forming a lower electrode on an upper surface of the substrate; A hole collecting layer forming step formed on the lower electrode and forming a hole collecting layer which helps hole movement; An organic solar cell manufacturing process including a semiconductor thin film layer forming step formed on the hole collecting layer and forming a semiconductor thin film layer separating free electrons and holes, and an upper electrode forming step forming an upper electrode located on the semiconductor thin film layer. To After at least one of the lower electrode forming step, the hole collecting layer forming step, the semiconductor thin film layer forming step and the upper electrode forming step, the lower electrode formed in the step, at least one layer of the hole collecting layer and the semiconductor thin film layer An organic solar cell manufacturing method further comprises an ion beam irradiation step of irradiating the ion beam to the surface. The method of claim 1, In the ion beam irradiation step, at least one of hydrogen, nitrogen, oxygen, and fluorine ions is used as the ion beam, and the ion beam is irradiated onto at least one layer of the lower electrode, the hole collecting layer, and the semiconductor thin film layer formed on the upper surface of the substrate. Organic solar cell manufacturing method characterized in that. The method of claim 2, The hole collecting layer forming step includes P3HT poly (3-hexylthiophene) and PEDOT: PSS [Poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)], poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) And forming a hole collecting layer using at least one of F8BT. The method of claim 2, The semiconductor thin film forming step is P3HT: PCBM [poly (3-hexylthiophene): Phenyl-C61-Butyric-Acid-Methyl-Ester] and poly (3-hexylthiophene) (P3HT) and poly (9,9-di-n- An organic solar cell manufacturing method comprising forming a semiconductor thin film layer using at least one of octylfluorene-alt-benzothiadiazole (F8BT). The method of claim 2, The forming of the semiconductor thin film layer is characterized by forming a semiconductor thin film layer with a ratio of poly (3-hexylthiophene) (P3HT): poly (9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) 6: 4. Organic solar cell manufacturing method.

Images