KR20170078346A - Method for preparing organic thin film including organic semiconductor and dielectric polymer using zone casting process and organic thin film transistor comprising organic thin film prepared thereby - Google Patents
Method for preparing organic thin film including organic semiconductor and dielectric polymer using zone casting process and organic thin film transistor comprising organic thin film prepared thereby Download PDFInfo
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- KR20170078346A KR20170078346A KR1020150188775A KR20150188775A KR20170078346A KR 20170078346 A KR20170078346 A KR 20170078346A KR 1020150188775 A KR1020150188775 A KR 1020150188775A KR 20150188775 A KR20150188775 A KR 20150188775A KR 20170078346 A KR20170078346 A KR 20170078346A
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Abstract
(A) preparing a mixed solution by mixing 20 to 40% by weight of an organic semiconductor and 60 to 80% by weight of a polymeric insulator having a molecular weight of 3 to 40 kDa in a solvent; (b) coating the mixed solution on the substrate using zone casting to form a coating layer; And (c) drying the coating layer.
According to the method of manufacturing an organic thin film according to the present invention, a mixed solution obtained by mixing a polymer insulator and an organic semiconductor on a substrate is coated by a zone casting method to reduce the use amount of an organic semiconductor, which is a costly material, And an organic thin film having excellent electrical characteristics of a large area can be produced.
In addition, since the electrical characteristics of the organic thin film can be controlled by controlling the mixing ratio of the polymer insulator and the organic semiconductor, the organic thin film transistor can be utilized for manufacturing an organic thin film transistor that can be used for various applications.
Description
The present invention relates to a method of manufacturing an organic thin film including an organic semiconductor and a polymer insulator by using a zone casting process, and an organic thin film transistor including the organic thin film produced thereby.
A thin film transistor (TFT) is used as a driving element for controlling the operation of each pixel in various display devices and is expected to be used in a plastic chip for a smart card or an inventory tag .
Conventionally, an inorganic semiconductor material such as silicon (Si) has been generally used as a channel layer of a thin film transistor. However, in recent years, due to the large size, low cost and flexibility of a display, Semiconducting materials, and recently organic thin film transistors (OTFTs) using organic thin films as semiconductor layers have been actively studied.
The organic thin film transistor uses an organic thin film instead of a silicon film as a semiconductor layer. The organic thin film transistor includes a low-molecular organic thin film transistor using a low molecular material such as oligothiophene or pentacene and a polythiophene (polythiophene) series, and the like.
The organic thin film transistor generally includes a dielectric layer, an organic semiconductor layer, and a protective layer formed on the substrate by a method such as drop coating or spin casting, And is manufactured in the form of a multilayer thin film.
However, the solution process using the above-mentioned drop coating or spin casting is difficult to apply to the manufacture of a large-area thin film, and it is disadvantageous in that it is economically disadvantageous because it is manufactured using a large amount of expensive organic semiconductors.
Therefore, in order to solve the above-mentioned problems, there is a need for research on a method which can provide an organic semiconductor having a low content, an excellent electrical characteristic, and a method capable of effectively utilizing a large-area thin film in a single process.
Disclosure of the Invention The present invention has been devised to solve the problems of the prior art as described above, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, which comprises a step of casting a mixed solution containing an organic semiconductor and a polymer insulator on a substrate, The present invention is directed to a method for manufacturing an organic thin film which is capable of performing a large-scale process which can not be performed, and which has a low content of an organic semiconductor but is excellent in electrical characteristics.
According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) preparing a mixed solution by mixing 20 to 40% by weight of an organic semiconductor and 60 to 80% by weight of a polymeric insulator having a molecular weight of 3 to 40 kDa in a solvent; (b) coating the mixed solution on the substrate using zone casting to form a coating layer; And (c) drying the coating layer.
In addition, the organic semiconductor may be formed by using triisopropylsilylethynyl pentacene (TIPS-PEN), triethylsilylethynyl anthradithiophene (TES-ADT), and fluorinated triethylsilylethynyl anthra And at least one selected from the group consisting of fluorinated triethylsilylethynyl anthradithiophene (diF TES-ADT).
The polymer insulator may include at least one selected from the group consisting of polystyrene (PS) -based polymers, polyacrylate-based polymers, and polyethylene (PE) -based polymers.
The solvent may be at least one selected from the group consisting of toluene, chlorobenzene, chloroform and dichloroethane.
Further, the substrate is an SiO 2 substrate.
The present invention also provides an organic thin film transistor comprising an organic thin film produced by the above-described method.
The organic thin film has a thickness of 10 to 50 nm.
Also, the organic thin film transistor includes an organic thin film containing 60 to 70% by weight of a 4 kDa polymer insulator and 30 to 40% by weight of an organic semiconductor, and has a charge mobility of 0.9 to 1.35 (cm 2 / Vs) .
According to the method of manufacturing an organic thin film according to the present invention, a mixed solution obtained by mixing a polymer insulator and an organic semiconductor on a substrate is coated by a zone casting method to reduce the use amount of an organic semiconductor, which is a costly material, And an organic thin film having excellent electrical characteristics of a large area can be produced.
In addition, since the electrical characteristics of the organic thin film can be controlled by controlling the mixing ratio of the polymer insulator and the organic semiconductor, the organic thin film transistor can be utilized for manufacturing an organic thin film transistor that can be used for various applications.
1 is a conceptual view showing a method of manufacturing an organic thin film according to Embodiment 1. FIG.
FIG. 2 is an optical microscope (OM) image and atomic force microscope (AFM) image of the organic thin film layer prepared by the method according to Example 1 at different mixing ratios of the polymer insulator and the organic semiconductor.
FIG. 3 is an optical microscope (OM) image and atomic force microscope (AFM) image of the organic thin film layer prepared by the method according to Example 2 at different mixing ratios of the polymer insulator and the organic semiconductor.
FIG. 4 is a graph showing changes in electrical characteristics of the organic thin film transistor according to the mixing ratio of the polymer insulator and the organic semiconductor prepared by (a) Example 1 and (b) Example 2.
The present invention relates to a method for fabricating an organic thin film on a substrate by controlling the electrical characteristics of the organic thin film by controlling the mixing ratio of the organic semiconductor and the polymer insulator, coating the mixed solution containing the organic semiconductor and the polymer insulator by a zone casting process, .
Hereinafter, the present invention will be described in detail.
(A) preparing a mixed solution by mixing 20 to 40% by weight of an organic semiconductor and 60 to 80% by weight of a polymeric insulator having a molecular weight of 3 to 40 kDa in a solvent; (b) coating the mixed solution on the substrate using zone casting to form a coating layer; And (c) drying the coating layer.
The step (a) is a step of preparing a mixed solution including an organic semiconductor and a polymer insulator. In this step, a mixed solution for preparing an organic thin film is prepared by a solution process using a zone casting method.
The organic semiconductor may be a variety of organic semiconductor materials that can be mixed with the polymer insulator to form an organic thin film by a solution process, and a polymer, an oligomer having a low molecular weight, or an organic semiconductor in the form of a single molecule may be used. In addition, the organic semiconductor may be crystallized by moving the organic semiconductor material remaining in the polymer insulator thin film to the organic semiconductor thin film through a drying process.
Such organic semiconductors include triisopropylsilylethynyl pentacene (TIPS-PEN), triethylsilylethynyl anthradithiophene (TES-ADT), florinated triethylsilylethynyltetradecyl (Fluorinated triethylsilylethynyl anthradithiophene, diF TES-ADT), or a mixture thereof. Typical examples include TIPS-PEN.
In addition, the polymer insulator can use various polymer materials that can be mixed with the organic semiconductor and form an organic thin film through a solution process. Any crystalline or amorphous polymer insulator can be used, It is possible to use a noncrystalline polymer insulator which can maintain electrical characteristics even when the content is reduced. Particularly, it is preferable to use a material having a relatively large surface energy as compared with the organic semiconductor material so as to form a film below the organic semiconductor thin film when the polymeric insulating material is coated on the substrate, and a polyacrylate- Polymer, polystyrene (PS) based polymer, polyethylene (PE) based polymer, or a mixture thereof, and more preferably, amorphous polystyrene based polymer can be used.
According to the method for producing an organic thin film according to the present invention, the polymeric insulator can control the crystallinity of the organic thin film according to the molecular weight, thereby controlling the electrical characteristics of the organic thin film. For this purpose, the polymeric insulator preferably has a molecular weight of 3 to 40 kDa. When the molecular weight of the polymeric insulator is less than 1 kDa or more than 40 kDa, the electrical characteristics of the organic thin film to be produced are excellent The polymer insulator having a molecular weight within the above range can be used. More preferably, the polymer insulator having a molecular weight of 3 to 5 kDa can be used.
The mixed solution may be prepared by mixing 20 to 40% by weight of the organic semiconductor and 60 to 80% by weight of a polymeric insulator having a molecular weight of 3 to 40 kDa with a solvent to form a mixed solution. The crystallinity can be controlled by controlling the mixing ratio, and the electrical characteristics of the organic thin film formed in the step described later can be controlled.
The solvent may be any material capable of simultaneously dissolving the organic semiconductor material and the polymer insulator, and examples thereof include toluene, chlorobenzene, chloroform, dichloroethane, and mixtures thereof.
In the step (b), the mixed solution is coated on the substrate using a zone casting method to form a coating layer.
The substrate has a hydrophilic substrate having a large surface energy such that a polymer insulating layer having a large surface energy is formed at the bottom and an organic semiconductor layer is formed at an upper portion when the organic semiconductor and the polymer insulator are coated by a single process by a zone casting method And a SiO 2 substrate is a typical example.
In this step, a coating layer for forming an organic thin film can be prepared by coating the mixed solution prepared as described above on a substrate by a zone casting method, and a large-area process which can not be realized by spin casting and drop coating in a single process This is possible.
In the step (c), the coating layer may be dried to form an organic thin film including a polymer insulator and crystals of an organic semiconductor on the substrate. Such drying can be carried out by various methods such as room temperature drying or hot air drying.
According to the method of manufacturing an organic thin film according to the present invention as described above, the content of an organic semiconductor, which is an expensive material, is low through a single process of coating a mixed solution of a polymer insulator and an organic semiconductor on a substrate by a zone casting method A large-area organic thin film having excellent electrical characteristics can be produced.
In addition, since the electrical characteristics of the organic thin film can be controlled by controlling the mixing ratio of the polymer insulator and the organic semiconductor, the organic thin film transistor can be utilized for manufacturing an organic thin film transistor that can be used for various applications.
The present invention also provides an organic thin film transistor fabricated by the above-described method.
The organic thin film transistor may be formed by forming an organic thin film on the substrate on which the gate electrode is formed through the method of forming the organic thin film, and then forming a drain and a source electrode connected to the organic thin film.
The organic thin film transistor exhibits excellent electrical characteristics by forming an organic thin film through a zone casting process. Particularly, a mixed solution containing 60 to 70 wt% of a 4 kDa polymer insulator and 30 to 40 wt% as the organic thin film comprising an organic thin film of 10 to 50 nm thickness was formed on a substrate transistor exhibits excellent electric characteristics as a charge mobility of 0.4 to 1.35 μ (cm 2 / Vs) .
Therefore, the organic thin film transistor described above can be effectively utilized as an organic thin film transistor suitable for various applications.
Hereinafter, the present invention will be described in more detail with reference to examples.
The embodiments presented are only a concrete example of the present invention and are not intended to limit the scope of the present invention.
≪ Example 1 >
n-doped silicon was used as a gate electrode, and a gate insulating layer made of SiO 2 was formed thereon. And 30 wt% and 100 wt% of TIPS-pentacene as an organic semiconductor on the gate insulating layer, and each of the mixed solutions containing 0 to 70 wt% of amorphous polystyrene having a molecular weight of 4 kDa as a
≪ Example 2 >
A mixed solution was prepared in the same manner and in the same manner as in Example 1, except that amorphous polystyrene having a molecular weight of 35 kDa was used as a polymer insulator and 20 wt% and 100 wt% of TIPS-pentacene were mixed. To prepare an organic thin film transistor.
Experimental Example 1 Morphological Characterization of Organic Thin Films Prepared by the Method According to Examples 1 and 2
In order to analyze the morphological characteristics of the organic thin film layer formed on the prepared organic thin film transistor, crystals formed on the organic thin film layer prepared by using optical microscope (OM) and atomic force microscope (AFM) were analyzed , And the results of the analysis are shown in Fig. 2 and Fig.
As shown in FIG. 2 and FIG. 3, it was confirmed that organic thin film layers of different crystals were prepared according to the contents of the polymer insulator and the organic semiconductor, and the molecular weight of the polymer insulator increased in the production of the organic thin film transistor As the crystal grain size decreases, the crystallinity increases. As the content of the polymer insulator increases, the grain boundaries decrease and the crystallinity increases. Thus, it is possible to control the crystallinity of the organic thin film layer by controlling the molecular weight and content of the polymer insulator. .
<Experimental Example 2> Electrical characteristics of the organic thin film transistor fabricated by the method according to Examples 1 and 2
The charge mobility in the parallel direction of the organic thin film transistor manufactured by the method according to Examples 1 and 2 was measured and the results are shown in FIG.
As shown in FIG. 4, it was confirmed that the organic thin film device manufactured by the method according to Example 1 exhibits excellent characteristics with a charge mobility exceeding 0.1 μ (cm 2 / Vs) And the polymeric insulator, the charge mobility was found to be different.
It was confirmed that the organic thin film device manufactured by the method according to Example 2 exhibits excellent characteristics with a charge mobility exceeding 0.1 μ (cm 2 / Vs) It was confirmed that the charge mobility was different.
In particular, the embodiment, when depending on one of the organic thin film transistor made of a mixed solution containing 60% by weight of the polymer insulator has a molecular weight of the
According to Example 2, in the case of an organic thin film transistor manufactured from a mixed solution containing 80 wt% of a polymer insulator having a molecular weight of 20 kWa and an organic semiconductor of 20 wt%, the charge mobility was the most excellent and 0.5 mu m (cm 2 / Vs ). However, it can be confirmed that the charge transport mobility is drastically lowered in the organic thin film transistor made of the mixed solution containing the organic semiconductor at a ratio exceeding 40% by weight there was.
Claims (8)
(b) coating the mixed solution on the substrate using zone casting to form a coating layer; And
(c) drying the coating layer.
The organic semiconductor may be selected from the group consisting of triisopropylsilylethynyl pentacene (TIPS-PEN), triethylsilylethynyl anthradithiophene (TES-ADT) and fluorinated triethylsilylethynyl anthradydiophene (fluorinated triethylsilylethynyl anthradithiopene, diF TES-ADT).
Wherein the polymeric insulator comprises at least one selected from the group consisting of polystyrene (PS) -based polymers, polyacrylate-based polymers, and polyethylene (PE) -based polymers. Gt;
Wherein the solvent is at least one selected from the group consisting of toluene, chlorobenzene, chloroform, and dichloroethane.
Wherein the substrate is a Group 5 element doped n-type silicon substrate.
Wherein the organic thin film has a thickness of 10 to 50 nm.
Wherein the organic thin film comprises an organic thin film containing 60 to 70 wt% of a 4 kDa polymer insulator and 30 to 40 wt% of an organic semiconductor, and has a charge mobility of 0.9 to 1.35 mu (cm 2 / Vs).
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| KR102231942B1 (en) | 2019-10-29 | 2021-03-25 | 한밭대학교 산학협력단 | Apparatus having patterned solution shearing coater of roll to roll type for forming a thin film of organic semiconductor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102231942B1 (en) | 2019-10-29 | 2021-03-25 | 한밭대학교 산학협력단 | Apparatus having patterned solution shearing coater of roll to roll type for forming a thin film of organic semiconductor |
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