KR20170030639A - Formation method for organic semiconductor thin film, organic semiconductor device using formation method for organic semiconductor thin film, and production method for organic semiconductor device using formation method for organic semiconductor thin film - Google Patents

Abstract

A method of forming an organic semiconductor thin film capable of forming an organic semiconductor thin film by a short processing time and an organic semiconductor device using the organic semiconductor thin film and a method of manufacturing an organic semiconductor device having high throughput. In the method of forming the organic semiconductor thin film 4 made of the organic semiconductor material 7, the organic semiconductor material 7 is thinned by applying ultrasonic vibration while applying pressure to the organic semiconductor material 7. A manufacturing method of an organic semiconductor device is a manufacturing method of an organic semiconductor device including an organic semiconductor thin film, and the organic semiconductor thin film is formed by the above-described forming method. The organic semiconductor device is manufactured by the above manufacturing method.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of forming an organic semiconductor thin film, and an organic semiconductor device using the organic semiconductor thin film and a method of manufacturing the organic semiconductor device. SEMICONDUCTOR THIN FILM}

The present invention relates to a method for forming an organic semiconductor thin film, an organic semiconductor device using the method for forming the organic semiconductor thin film, and a method for manufacturing an organic semiconductor device using the method for forming the organic semiconductor device.

A method of forming an organic semiconductor material thin film between electrodes to obtain an organic semiconductor device has recently been studied vigorously in that a device which can be manufactured by a low temperature process and which is more flexible, .

However, since most of the organic semiconductor materials used in the organic semiconductor device are difficult to be dissolved in the organic solvent, the thin film can not be formed using a technique such as coating or printing, It has been common to form the thin film on a substrate by such an expensive vacuum deposition method or the like. Recently, studies for obtaining an organic semiconductor device by forming an organic semiconductor thin film by a method of applying inkjet, flexo printing, coating, or printing have been actively carried out, and a relatively high carrier mobility , Simply referred to as " mobility "). It is expected that the method using coating or printing described above can produce a field effect transistor having a high throughput and a large area at a low cost in a manufacturing process of the field effect transistor.

However, a field effect transistor using an organic semiconductor having high mobility and excellent durability using a coating process or a printing process has not yet been put to practical use. In general, the organic semiconductor thin film is formed by a vacuum process including a vacuum evaporation process, or a coating process such as a spin coating process or a blade coating process using a solvent. However, in the method of forming an organic semiconductor thin film by a vacuum process, equipment for performing a vacuum process is required, and there is a drawback that loss of the organic semiconductor material increases. Also in the method of forming an organic semiconductor thin film by a coating process, since the organic semiconductor solution is applied to the entire substrate, the loss of the organic semiconductor material increases in the same manner as in the vacuum process.

As another method for forming an organic semiconductor thin film, a printing method such as an ink-jet method is known. In the printing method, it is possible to apply a necessary amount of the organic semiconductor material to the target position. However, in order to control the orientation direction of crystals produced from the solution, as in other application or printing methods, It is necessary to slowly form the organic semiconductor thin film while performing fine process control, or to perform firing for several minutes to several tens of minutes for crystal growth after crystal formation. For this reason, in the method of forming an organic semiconductor thin film by these coating or printing methods, it takes a long time for film formation of the organic semiconductor thin film and firing for crystal growth, and there is a drawback that the throughput is not high. Further, in actuality, the conventional method of manufacturing an organic semiconductor device by a method of forming an organic semiconductor thin film such as a coating or printing method is insufficient for practical use of the performance of an organic semiconductor device such as mobility.

One of the reasons why the conventional method of manufacturing an organic semiconductor device by a method of forming an organic semiconductor thin film such as a coating method or a printing method is insufficient for practical use is that the organic semiconductor thin film state of polycrystals of an organic semiconductor material, The characteristics of an organic semiconductor device such as an organic thin film transistor are greatly changed.

As a method of forming a single crystal organic semiconductor thin film in which crystal grain boundaries do not exist, a method of forming a single crystal organic semiconductor thin film by a vapor phase method (physical vapor phase growth) described in Non-Patent Document 1, (A droplet) of an organic semiconductor solution is formed on a substrate by tilting the organic semiconductor solution to evaporate the solvent and grow crystals in a certain direction (direction of inclination) from the organic semiconductor solution, A method of producing a single crystal organic semiconductor thin film by an inkjet method, and the like.

However, the method of forming the organic semiconductor thin film by the vapor-phase method as described in the non-patent document 1 involves a difficulty in application to the production of an actual organic semiconductor device. Further, in the method of inclining the substrate in the solution method described in Patent Document 1, it is very difficult to tilt the substrate itself. In addition, in the method for producing an organic semiconductor thin film by the double ink jet method described in Patent Document 2, it is difficult to select a solvent and control of drying property is required. As a result, there is a problem that it is necessary to use a solvent having a negative influence on the environment, or a method of forming an organic semiconductor thin film having a high throughput can not be realized.

As a method for aligning crystals other than a single crystal of an organic semiconductor, a method of applying a liquid crystalline organic semiconductor material on an alignment film and orienting crystals using liquid crystal transition is disclosed in, for example, Patent Document 3. However, in the above method, there is a possibility that cracks may enter the crystals due to the phase change during the cooling process, so that it is necessary to control the temperature of the cooling process in a precise manner.

Non-Patent Document 2 discloses a method of promoting the redistribution of crystals by forming a polycrystalline organic semiconductor thin film and then exposing it to solvent vapor. However, in order to redirect the crystal by the above-described method, it is necessary to expose the organic semiconductor thin film of the crystal to the solvent for a long time, which is not suitable for application to a manufacturing method of an organic semiconductor having a high throughput.

On the other hand, ultrasonic welding is known as a processing technique of a thermoplastic resin or the like. Ultrasonic welding is a joining / processing technique using ultrasonic vibration and friction heat generated by pressure, and is known as a processing technique with a short processing time. Ultrasonic welding is mainly used in many fields such as spot welding, sealing of film, sealing of non-woven cloth, and insert of metal. However, a technology for thinning an organic semiconductor material by ultrasonic vibration and pressure has heretofore not been known.

Patent Document 4 describes a method of irradiating ultrasonic waves to a coating film containing an organic semiconductor material or the like as a main component as an example using ultrasonic waves to form an organic semiconductor thin film. However, the method described in Patent Document 4 is a technique of modifying the coating film to lower resistance by irradiating ultrasonic waves to the coating film. Therefore, the irradiation of the ultrasonic wave in Patent Document 4 is merely a substitute for the thermo-plasticizing process and the drying process performed by an ordinary oven or the like after the formation of the organic semiconductor thin film, The semiconductor thin film is not formed.

International Publication No. 2011/040155 Japanese Laid-Open Patent Publication No. 2012-49291 Japanese Patent Publication No. 4867168 Japanese Laid-Open Patent Publication No. 2013-74065

 Science and Technology of Advanced Materials, 2009, 10, 024314  APPLIED PHYSICS LETTERS, 94, 093307, 2009

The present invention provides a method of forming an organic semiconductor thin film capable of forming an organic semiconductor thin film by a short-time process, and also provides an organic semiconductor device using the organic semiconductor thin film and a method of manufacturing an organic semiconductor device having high throughput .

Means for Solving the Problems As a result of intensive investigations to solve the above problems, the present inventors have found that a method for forming an organic semiconductor thin film, in which an organic semiconductor material is thinned by applying ultrasonic vibration while applying pressure to the organic semiconductor material, And that the organic semiconductor device using the organic semiconductor thin film can be manufactured with high throughput by using the method of forming the organic semiconductor thin film, and the present invention has been accomplished.

That is, the method for forming an organic semiconductor thin film of the present invention is a method for forming an organic semiconductor thin film made of an organic semiconductor material, characterized in that the organic semiconductor material is thinned by applying ultrasonic vibration while applying pressure to the organic semiconductor material .

A method of manufacturing an organic semiconductor device of the present invention is a method of manufacturing an organic semiconductor device including an organic semiconductor thin film, characterized in that an organic semiconductor thin film is formed by the method of forming an organic semiconductor thin film of the present invention.

The organic semiconductor device of the present invention is characterized by being manufactured by the above-described manufacturing method.

According to the present invention, it is possible to provide a method of forming an organic semiconductor thin film capable of forming an organic semiconductor thin film in a short time, an organic semiconductor device using the organic semiconductor thin film, and a method of manufacturing an organic semiconductor device having high throughput.

1 is a schematic view showing a configuration of an ultrasonic welder used for carrying out a method of forming an organic semiconductor thin film according to an embodiment of the present invention.
FIG. 2 is a schematic view showing a process of a manufacturing method for manufacturing an organic semiconductor device according to an embodiment of the present invention. An organic semiconductor material is sandwiched between a source / drain substrate and a gate substrate, (A state at the completion of the process) provided on the heating stage of Fig.
3 is a schematic view showing another process of a manufacturing method for manufacturing an organic semiconductor device according to an embodiment of the present invention and is a schematic view showing a process of applying a pressure to an organic semiconductor material by lowering a horn of an ultrasonic welding machine to be.
4 is a schematic view showing another process of a manufacturing method for manufacturing an organic semiconductor device according to an embodiment of the present invention, in which ultrasonic vibration is applied to an organic semiconductor material in a state where a pressure is applied to the organic semiconductor material, Fig.
5 is a schematic view showing another process of a manufacturing method for manufacturing an organic semiconductor device according to an embodiment of the present invention and showing a process for forming an organic semiconductor thin film by terminating the application of ultrasonic vibration to an organic semiconductor material Fig.
6 is a schematic view showing another process of a manufacturing method for manufacturing an embodiment of the organic semiconductor device of the present invention, and is a schematic view showing a process of raising the horn of an ultrasonic welder to obtain an organic semiconductor device.
7 is a schematic view showing a structural embodiment of an organic thin film transistor as an example of the organic semiconductor device of the present invention.
8 is a graph showing the history of the temperature of the organic semiconductor material in the method of forming the organic semiconductor thin film according to the embodiment of the present invention.
Fig. 9 is a polarization microscope photograph of an organic semiconductor material at the time when an organic semiconductor material is placed on a heating stage in an embodiment of the present invention. Fig.
10 is a polarized microscope photograph of an organic semiconductor material after heating the organic semiconductor material in a heating stage at 100 캜 according to an embodiment of the present invention.
11 is a polarized microscope photograph of an organic semiconductor thin film formed by the method of forming an organic semiconductor thin film according to an embodiment of the present invention.
12 is a polarization microscope photograph of an organic semiconductor material at the time when an organic semiconductor material is placed on a heating stage in another embodiment of the present invention.
13 is a polarized microscope photograph of an organic semiconductor thin film formed by a method of forming an organic semiconductor thin film according to another embodiment of the present invention.
Fig. 14 is a polarized microscope photograph of an organic semiconductor material at the time when an organic semiconductor material is placed on a heating stage in another embodiment of the present invention. Fig.
15 is a polarized microscope photograph of an organic semiconductor thin film formed by a method of forming an organic semiconductor thin film according to another embodiment of the present invention.

(Mode for carrying out the invention)

The present invention will be described in detail.

A first object of the present invention is to provide a method of forming an organic semiconductor thin film which can form an organic semiconductor thin film made of an organic semiconductor material in a short time.

The method for forming an organic semiconductor thin film according to the present invention is characterized by forming an organic semiconductor thin film made of an organic semiconductor material by thinning an organic semiconductor material by applying ultrasonic vibration while applying pressure to the organic semiconductor material. According to the above method, the organic semiconductor thin film can be formed in a short time. In addition, in the above method, when pressure is applied to the organic semiconductor material during the cooling process after the end of ultrasonic vibration is applied, it is difficult for cracks to enter the organic semiconductor thin film due to a phase change during the cooling process or the like.

In the treatment of imparting ultrasonic vibration while applying pressure to the organic semiconductor material, the organic semiconductor material may be used alone as the material to be subjected to the treatment. However, the material obtained by disposing the organic semiconductor material on the substrate is used as the material to be treated , And it is more preferable that the organic semiconductor material on the substrate is subjected to the above treatment. In the method of the present invention, it is considered that the above-mentioned treatment is applied to the organic semiconductor material on the substrate to induce crystal rearrangement and to make the orientation of the crystals uniform. Therefore, when arranging the organic semiconductor material on the substrate, (For example, a baking treatment after the arrangement of the organic semiconductor material by a solution process) is unnecessary. Further, when the organic semiconductor material is placed on the substrate, it is preferable that the arrangement position of the organic semiconductor material be at a desired position where the organic semiconductor thin film is to be formed (for example, in the case of manufacturing an organic thin film transistor, The organic semiconductor material is spread in the direction of the substrate surface by the above-described process, so that the organic semiconductor thin film can be formed at a desired position. Therefore, high precision is not required for the arrangement of the organic semiconductor material.

In the process of applying ultrasonic vibration while applying pressure to an organic semiconductor material, it is possible to use an organic semiconductor material sandwiched between a pair of substrates as an object to be processed, and to use an organic semiconductor material sandwiched between a pair of substrates It is more preferable to perform the above process. Accordingly, it is possible to avoid the organic semiconductor material from adhering to the horn, stage, or the like of the ultrasonic welding apparatus at the time of the processing, and to prevent cracks from entering the organic semiconductor thin film due to a phase change or the like during the cooling process . As the above substrate, an inorganic substrate such as glass or the like, which is an example of the substrates 1 and 1 'constituting the organic thin film transistors 10A and 10B, or various resin films, and electrodes and / And the like. The pair of substrates is preferably a resin film.

When the organic semiconductor material is disposed on the substrate, the organic semiconductor material may be placed on the substrate in a solid state or a molten state. Further, the method of disposing the organic semiconductor material on the substrate in the solid state or the molten state has merits such that the organic semiconductor material can be disposed on the substrate without using an organic solvent having a high environmental load. Examples of the method of disposing the organic semiconductor material on the substrate in a solid state or in a molten state include a method in which an organic semiconductor material in a solid state such as a bulk powder or a fine powder is directly placed on a substrate, a method in which a solid material such as a bulk powder, A method in which an organic semiconductor material in a state of being melted is arranged on a member such as a sufficiently warmed metal rod and the organic semiconductor material in a molten state is dripped from the member onto the substrate.

As a method of disposing the organic semiconductor material on the substrate, a solution process such as a drop cast method (for example, a process of applying or printing a solution formed by dissolving an organic semiconductor material in an organic solvent, a drying process, etc.) ) May be used. In the method for forming an organic semiconductor thin film according to the present invention, ultrasonic vibration is applied while applying pressure to an organic semiconductor material, and after the generation of frictional heat to raise the temperature of the organic semiconductor material, the organic semiconductor material is cooled do. It is believed that in this cooling process, crystals of the organic semiconductor material are reoriented to make the orientation of the crystals uniform. Therefore, when the organic semiconductor material is placed on the substrate using the solution process, the orientation of the crystal may be random in the step of crystallizing the organic semiconductor material from the organic solvent solution containing the organic semiconductor material. Therefore, in the solution process for disposing the organic semiconductor material on the substrate in the method of forming the organic semiconductor thin film of the present invention, after coating or printing the solution formed by dissolving the organic semiconductor material in the organic solvent, It is only necessary to evaporate the organic solvent. Therefore, after applying or printing a solution obtained by dissolving the organic semiconductor material in an organic solvent, a process such as control of crystal orientation by baking for a long time or rearrangement of crystals by post treatment is carried out in order to make the orientation of crystals uniform You do not have to. The organic semiconductor material disposed on the substrate in this way is thinned to form an organic semiconductor thin film by applying ultrasonic vibration while applying pressure to the organic semiconductor material.

The method of applying pressure to the organic semiconductor material is not particularly limited, but a method of pressing the pressing member directly against the organic semiconductor material or through a protective film or protective layer is suitable. In the case of pressing the pressing member against the organic semiconductor material through the protective film or the protective layer, the organic semiconductive material sandwiched between the substrate and the protective film or protective layer is used as the object to be treated, It is more preferable to press the pressing member through the protective film or the protective layer. The method of applying ultrasonic vibration while applying pressure to the organic semiconductor material is not particularly limited, but an organic semiconductor material may be disposed on the substrate, and the organic semiconductor material may be directly applied to the organic semiconductor material, The pressing member is ultrasonically vibrated while pressing the pressing member. The pressing member is not particularly limited as long as it can apply pressure to the entire organic semiconductor material. In the case where the substrate is a flat plate, it is preferable that the pressing member has a flat surface contacting the organic semiconductor material. Thus, an organic semiconductor thin film having a uniform thickness can be formed. The protective film or protective layer will be described later.

As a method of forming the organic semiconductor thin film of the present invention, there is a method using a general ultrasonic welding machine (ultrasonic welder) used for pressing a packaging film or the like. In the case of using a general ultrasonic welding machine, a material to be processed (including an organic semiconductor material alone, a combination of an organic semiconductor material and a substrate, a combination of an organic semiconductor material and a protective film or a protective layer, A combination of a protective film or a protective layer) is applied to the organic semiconductor material by an ultrasonic welding machine while applying ultrasonic vibration to the organic semiconductor material, and the organic semiconductor material is thinned by using the frictional heat and pressure generated by the ultrasonic vibration, An organic semiconductor thin film is formed. A general ultrasonic welder is provided with a horn as a pressing member which is pressed against a material to be processed, applies pressure to the material to be processed, and applies ultrasonic vibration.

One embodiment of an ultrasonic welding machine suitably used in the method of forming an organic semiconductor thin film of the present invention will be described below with reference to Fig. In addition, members having the same functions in the drawings are denoted by the same reference numerals, and a description thereof will be omitted.

1, the ultrasonic welder 20 includes an ultrasonic oscillator (generator) 21, an ultrasonic oscillator (converter) 22, a booster 23, a horn 24, a pressurizing mechanism (press unit) 25 And a heating stage 26, as shown in Fig. The horn 24 has a flat surface in contact with the object to be processed.

In the heating stage 26, the object to be processed is arranged thereon. The heating stage 26 is provided with a heater 26a for heating the upper surface of the heating stage 26 to a predetermined temperature. Further, the upper surface of the heating stage 26 may not be heated. Therefore, instead of the heating stage 26, a simple stage without the heater 26a may be used.

The pressing mechanism 25 includes an arm portion 25a to which the ultrasonic vibrator 22, the booster 23 and the horn 24 are attached, and a support (not shown) supporting the arm portion 25a so as to be vertically movable up and down The arm portion 25a is moved up and down in the vertical direction and the horn 24 is pressed downward in the vertical direction with respect to the object to be processed placed on the heating stage 26 to apply pressure (Not shown) (for example, an air cylinder).

In the ultrasonic welder 20, an electric signal inputted from a commercial power source (not shown) is amplified by an ultrasonic oscillator 21 into an electric signal of high frequency, and the amplified electric signal is converted into mechanical vibration energy And the mechanical vibration (ultrasonic vibration) is generated from the ultrasonic vibrator 22. [ The mechanical vibration (ultrasonic vibration) emitted from the ultrasonic transducer 22 is transmitted to the horn 24 after the amplitude thereof is increased or decreased in the booster 23. The ultrasonic vibration transmitted to the horn 24 is transmitted to the object including the organic semiconductor material when the horn 24 is pushed downward in the vertical direction with respect to the organic semiconductor material by the pressurizing mechanism 25 do.

As parameters for controlling the ultrasonic vibration while applying the pressure to the organic semiconductor material, there are mainly used parameters such as the oscillation time of the ultrasonic vibration, the amplitude of the ultrasonic vibration, the pressing force, the shape of the horn of the ultrasonic welder (using an ultrasonic welder equipped with a horn ) And the like. The oscillation time of ultrasonic vibration is a time for applying ultrasonic vibration to the organic semiconductor material. The longer the time is, the larger the amount of heat to be applied to the organic semiconductor material. However, it is necessary to adjust the oscillation time appropriately in accordance with the physical properties of the organic semiconductor material. In consideration of the tact time of the organic semiconductor thin film forming process, it is preferable to perform appropriate processing in a short time, and it is usually set to be within 1 minute, preferably within 10 seconds, particularly preferably within 1 second do.

The amplitude of the ultrasonic vibration indicates the magnitude of the ultrasonic vibration applied to the organic semiconductor material (the size of the ultrasonic vibration transmitted from the tip of the horn to the organic semiconductor material when using the ultrasonic welding machine equipped with the horn). In the case of using an ultrasonic welder, it is possible to change the amount of heat applied to the organic semiconductor material by changing the amplitude of the ultrasonic vibration even if an ultrasonic welder with the same output is used. The higher the amplitude of the ultrasonic vibration is, the greater the amount of heat can be imparted to the organic semiconductor material. However, when the organic semiconductor material is used in combination with other materials such as a substrate, It is necessary to set the amplitude of the ultrasonic vibration so as not to be excessively high. The amplitude of the ultrasonic vibration varies depending on the output of the ultrasonic welding machine (in the case of using an ultrasonic welder) and the frequency (frequency) of ultrasonic vibration. Therefore, it is necessary to control the type of the organic semiconductor material used and the organic semiconductor material, if necessary, to have an appropriate amplitude in accordance with the kind of the member to which the frictional heat is applied during the ultrasonic vibration application. Examples of the member to which the frictional heat is applied in applying the ultrasonic vibration include a substrate, an electrode (a gate electrode, a source electrode, a drain electrode, etc.), an insulating layer (e.g. a gate insulating layer) (A protective film or a protective layer, etc.) in contact with a pressing member such as a horn when a pressing member such as a horn is pressed against another semiconductor material through another member to impart ultrasonic vibration. That is, in the method of forming an organic semiconductor thin film of the present invention, it is preferable to control the amplitude of the ultrasonic vibration to an appropriate amplitude so that the temperature of the organic semiconductor material is controlled to an appropriate temperature.

The pressing force is a mechanical energy imparted to the object including the organic semiconductor material (mechanical energy transmitted from the horn to the organic semiconductor material when an ultrasonic welding machine having a horn is used) and its size is determined by ultrasonic vibration The amount of heat generated in the semiconductor material and the processing time (time taken for the organic semiconductor material to become thin). Applying an excessively strong pressure to the object to be processed including the organic semiconductor material may damage the organic semiconductor material in the same manner as when the amplitude of the ultrasonic vibration is excessively large. When used in combination with a material, there is a possibility of damaging other materials such as a substrate. Therefore, it is necessary to set the pressing force so as not to become too strong in consideration of these damages. These parameters (the oscillation time of the ultrasonic vibration, the amplitude of the ultrasonic vibration, and the pressing force) affect each other, and they are used in combination with the kind of the organic semiconductor material to be used and the organic semiconductor material as required, It is necessary to make an appropriate combination according to the kind of the member to be applied.

The shape of the horn of the ultrasonic welder requires an appropriate structure to transmit the transmitted ultrasonic vibration to the organic semiconductor material, and the amplitude of the ultrasonic vibration may change depending on the shape. In addition, since the amount of heat applied to the organic semiconductor material also varies depending on the size (processing area) of the horn surface, it is necessary to individually control the shape of the horn and the size of the horn surface.

The temperature of the organic semiconductor material at the time of applying the ultrasonic vibration while applying pressure to the organic semiconductor material (hereinafter referred to as " pressure and ultrasonic vibration application time ", as appropriate) is set according to the kind of the organic semiconductor material . When the organic semiconductor material has a phase transition point (phase transition temperature), it is preferable to adjust the temperature of the organic semiconductor material at the time of applying pressure and ultrasonic vibration within a range of 0 to + 80 DEG C with respect to the phase transition point of the organic semiconductor material . When the organic semiconductor material is used in combination with the substrate, it is preferable to set the temperature of the organic semiconductor material at the time of applying pressure and ultrasonic vibration to a temperature lower than the glass transition point (glass transition temperature) of the substrate to be used, The optimum temperature range of the temperature of the organic semiconductor material at the time of pressing and ultrasonic oscillation is set by the combination of the phase transition point of the organic semiconductor material and the glass transition point of the substrate. Here, the " temperature of the organic semiconductor material at the time of applying pressure and ultrasonic vibration " as used herein means the temperature at which the heat conduction sheet is disposed in place of the organic semiconductor material and pressure and ultrasonic vibration are applied Quot; means the temperature of the conductive sheet.

If necessary, the organic semiconductor material may be conduction-heated at the same time as the ultrasonic vibration is applied to the organic semiconductor material. When the organic semiconductor material is used in combination with the base material, the base material may be conduction-heated at the same time as the application of the ultrasonic vibration, if necessary. In this case, the heating temperature of the substrate may be changed according to the heating temperature of the organic semiconductor material at the time of applying pressure and ultrasonic vibration, but it is preferable to change the heating temperature of the organic semiconductor material (In the case of using in combination), it is set as low as possible.

In order to thin the organic semiconductor material, the temperature of the organic semiconductor material at the time of applying pressure and ultrasonic vibration is preferably set to a temperature exceeding the phase transition point (that is, liquid crystal transition point, glass transition point, melting point, etc.) Do. In this case, under such conditions, the organic semiconductor material undergoes a phase transition (phase change) from a solid phase to a liquid crystal phase, a glass phase, and a liquid phase at the time of applying pressure and ultrasonic vibration, Thinned. In this case, the organic semiconductor material is recrystallized in the cooling process after finishing the application of the ultrasonic vibration, and an organic semiconductor thin film is obtained. That is, in the method for forming an organic semiconductor thin film of the present invention, ultrasonic vibration is applied while applying pressure to an organic semiconductor material, thereby phase-transitioning the solid phase organic semiconductor material and then recrystallizing the organic semiconductor material, . Accordingly, since the fluidity of the organic semiconductor material is increased by phase-transferring the solid phase organic semiconductor material, the organic semiconductor material becomes easier to be thinned. Further, even when phase transition of the organic semiconductor material does not occur at the time of applying pressure and ultrasonic vibration, the organic semiconductor material may be subjected to sufficient pressure in a state of being heated by ultrasonic vibration, so that thinning may occur.

When the supply of the ultrasonic vibration is started while applying the pressure to the organic semiconductor material, the temperature of the organic semiconductor material sharply drops and the orientation and recrystallization of the organic semiconductor material occur. The pressing of the organic semiconductor material may be continued in order to obtain a uniform organic semiconductor thin film in the thickness direction after finishing the application of the ultrasonic vibration and the time for continuing the pressing after the termination of the ultrasonic vibration application is, The temperature difference between the temperature of the organic semiconductor material and the room temperature at the end of the ultrasonic vibration application (after cooling) and the surface energy of the substrate (when the organic semiconductor material is used in combination with the substrate) . The organic semiconductor thin film thus obtained is less likely to generate cracks among crystal grains than an organic semiconductor thin film obtained by a general solution process.

In the application of pressure and ultrasonic vibration using an ultrasonic welding machine having a horn, since the horn is not directly brought into contact with the semiconductor material, a protective film or a protective layer is formed on the organic semiconductor material, The horn may be pressed through the protective layer. When a protective film or a protective layer is formed on an organic semiconductor material formed on a substrate, the protective film or protective layer used here may be the same as or different from the substrate. Further, in order to separate the organic semiconductor thin film from the protective layer after formation, a film in which a protective layer is laminated on the release material may be formed on the organic semiconductor material so that the release material contacts the organic semiconductor material.

The liquid crystal transition point, glass transition point and melting point of the organic semiconductor material can be measured by observing the phase transition behavior using a differential scanning calorimeter (DSC), a polarizing microscope (POM) observation, an automatic melting point measuring device, have. Further, with respect to the higher order structure of the organic semiconductor material, it is possible to grasp the relationship between the molecular structure, liquid crystallinity, and crystallinity of the organic semiconductor material by using X-ray diffraction (XRD).

As the organic semiconductor material, a low molecular organic compound (low molecular weight organic semiconductor compound) showing a semiconductor property, a high molecular compound (a polymer organic semiconductor compound) showing a semiconductor property (particularly a high molecular weight compound having a number average molecular weight of 1000 or more) (Oligomer organic semiconductor compound) having a molecular weight of 2 to 20 can be used. Among the organic semiconductor materials, an organic semiconductor material having a phase transition point such as a liquid crystal transition point, a glass transition point, and a melting point at a maximum attainable temperature or less at the time of applying pressure and ultrasonic vibration is preferable. Further, when the organic semiconductor material is used in combination with a substrate having a glass transition point (in particular, a resin substrate such as a resin film), it is preferable that the organic semiconductor material has a phase transfer point lower than the glass transition point of the substrate More preferably not more than the maximum attainable temperature at the time of applying pressure and ultrasonic vibration, and has a phase transition point lower than the glass transition point of the substrate. When the organic semiconductor material is used in combination with the resin substrate, it is preferable that the phase transition point of the organic semiconductor material is within the range of 70 占 폚 to 280 占 폚, and the phase transition point of the organic semiconductor material is within the range of 100 占 폚 to 280 占 폚 desirable.

In the method for forming an organic semiconductor thin film of the present invention, it is a feature that crystals of the organic semiconductor material are considered to be oriented uniformly in crystal orientation. Therefore, among these organic semiconductor materials, particularly when an organic semiconductor material having crystallinity is used, an organic semiconductor device having excellent semiconductor characteristics such as mobility can be easily obtained in a short time.

Examples of the low-molecular organic semiconductor compound include a compound in which a part of the carbon atoms of the polyacene or polyacene is substituted with a polyfunctional group such as a nitrogen atom, a sulfur atom, an oxygen atom, or a carbonyl group, (Triphenodioxazine derivatives, triphenodithiazine derivatives, thienothiophen derivatives represented by the following general formula (1), etc.) substituted with monovalent functional groups such as an aryl group, an acyl group, an alkyl group and an alkoxyl group . In addition, as the above-mentioned low molecular weight organic semiconductor compound, a colorant such as a styrylbenzene derivative, a metal phthalocyanine derivative, a condensed ring tetracarboxylic acid diimide, a merocyanine colorant or a hemicyanine colorant, a tetrakis (octadecylthio ) And tetrathiafulvalene, and the like. Examples of the condensed ring tetracarboxylic acid diimide include naphthalene-1,4,5,8-tetracarboxylic diimide, N, N'-bis (4-trifluoromethylbenzyl) naphthalene- N, N'-bis (1H, 1H-perfluorooctyl) -1,4,5,8-tetracarboxylic acid diimide, N, Perfluorobutyl) -1,4,5,8-tetracarboxylic acid diimide, N, N'-dioctylnaphthalene-1,4,5,8-tetracarboxylic acid diimide, naphthalene-2,3,6 , 7-tetracarboxylic acid diimide, and other naphthalenetetracarboxylic acid diimides; And anthracene tetracarboxylic acid diimides such as anthracene-2,3,6,7-tetracarboxylic acid diimide.

Examples of the polymer organic semiconductor compound include polypyrroles such as polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole) and poly (3,4-2 substituted pyrrole); Polythiophenes such as polythiophene, poly (3-substituted thiophene), poly (3,4-2 substituted thiophene) and polybenzothiophene; Polyisothianaphthenes such as polyisothianaphthene; Polythienylene vinylene such as polythienylene vinylene; Poly (p-phenylenevinylene) s such as poly (p-phenylenevinylene); Polyanilines such as polyaniline, poly (N-substituted aniline), poly (3-substituted aniline) and poly (2,3-2 substituted aniline); Polyacetylenes such as polyacetylene; Polydiacetylenes such as polydiacetylene; Polyazulenes such as polyazulene; Polypyranes such as polypyrylene; Polycarbazoles such as polycarbazole and poly (N-substituted carbazole); Polyselenopens such as polyselenophene; Polyfurans such as polyfuran and polybenzofuran; Poly (p-phenylene) such as poly (p-phenylene); Polyindoles such as polyindole; Polypyridazines such as polypyridazine; And polysulfides such as polyphenylene sulfide and polyvinylene sulfide.

Examples of the oligomer organic semiconductor compound include oligomers having the same repeating unit as the above-mentioned polymer, for example, oligomers such as α-sexy thiophene, α, ω-dihexyl-α-sexy thiophene, α, Dihexyl-α-quinquiethiophene, and α, ω-bis (3-butoxypropyl) -α-sexy thiophene.

As an example of a particularly preferable organic semiconductor material in the practice of the present invention,

(In the formula, R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group, the substituent may have an aryl group, the substituent represents a good heterocyclic group, an alkoxyl group, an alkoxyalkyl group, each other R ₁ and R ₂ And m and n each independently represent 0 or 1,

Thienothiophene derivatives represented by the following formulas.

The alkyl group is a straight chain, branched chain or cyclic aliphatic hydrocarbon group, preferably a straight chain or branched chain aliphatic hydrocarbon group, more preferably a straight chain aliphatic hydrocarbon group. The number of carbon atoms of the alkyl group is usually 1 to 36, preferably 2 to 24, more preferably 4 to 20, and still more preferably 6 to 12.

The aryl group is preferably a phenyl group, a biphenyl group, a pyrene group, a xylyl group, a mesityl group, a cumenyl group, a benzyl group, a phenylethyl group, 2-naphthyl group, anthryl group, phenanthryl group, and other aromatic hydrocarbon groups. The heterocyclic group is a 2-thienyl group, a benzothienyl group, a thienothienyl group, or the like. Each of the aryl group and the heterocyclic group may have a substituent such as the above-mentioned alkyl group or the like. When plural substituents are present, plural substituents may be the same or different.

In order that the thienothiophene derivative represented by the general formula (1) has the phase transfer point within the above-mentioned range (the range of 70 ° C to 280 ° C), it is preferable that at least one of R ₁ and R ₂ is an alkyl group, The length of the chain is preferably 4 or more carbon atoms.

The thienothiophene derivative represented by the above general formula (1) can be prepared according to the method described in Journal of the American Chemical Society, 2007, Vol. 129, No.51, p.15732-15733 and Advance Materials, 2011, 23, p.1222-1225 Can be synthesized by a known method described. The method for purifying the thienothiophene derivative represented by the general formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography and vacuum sublimation purification can be employed. In addition, these methods may be used in combination if necessary.

A second object of the present invention is to provide an organic semiconductor device using the organic semiconductor thin film, and a third object of the present invention is to provide a method of manufacturing an organic semiconductor device using the same.

The method for manufacturing an organic semiconductor device of the present invention is a method for manufacturing an organic semiconductor device including an organic semiconductor thin film, which is a method for forming an organic semiconductor thin film by the method for forming an organic semiconductor thin film of the present invention. Further, the organic semiconductor device of the present invention is manufactured by the manufacturing method of the present invention. The organic semiconductor device manufactured by the manufacturing method of the present invention is not particularly limited as long as the semiconductor layer including the organic semiconductor thin film is sandwiched between the electrodes, but is preferably an organic thin film transistor. In the organic semiconductor device manufactured by the manufacturing method of the present invention, the two electrodes of the source electrode and the drain electrode are in contact with the semiconductor layer including the organic semiconductor thin film, and the current flowing between the source electrode and the drain electrode is applied to the gate insulating It is more preferable that the organic thin film transistor is controlled to a voltage applied to another electrode called a gate electrode through a layer. That is, the organic semiconductor device manufactured by the manufacturing method of the present invention includes a source electrode and a drain electrode arranged to be spaced apart from each other, and an organic semiconductor thin film made of an organic semiconductor material disposed between the source electrode and the drain electrode An organic thin film transistor which is an organic field effect transistor having a semiconductor layer, a gate electrode arranged to face the semiconductor layer, and an insulating layer (gate insulating layer) disposed between the semiconductor layer and the gate electrode is more preferable . It is more preferable that the organic field effect transistor has the source electrode, the drain electrode, the semiconductor layer, the gate electrode, and the insulating layer on the substrate.

Examples of embodiments of the organic thin film transistor of the present invention are shown in Figs. 7 (a) and 7 (b).

The organic thin film transistor 10A shown in Fig. 7 (a) is called a bottom gate type organic field effect transistor. The organic thin film transistor 10A includes a substrate 1, a gate electrode 2 laminated on the substrate 1, and a gate electrode 2 formed on the top surface (the backside of the surface facing the substrate 1) A source electrode 5 and a drain electrode 6 disposed so as to be spaced apart from each other on a part of the upper surface of the gate insulating layer 3; And a semiconductor layer 4 including an organic semiconductor thin film made of an organic semiconductor material disposed on a substrate (excluding a portion where the source electrode 5 and the drain electrode 6 are disposed).

The organic thin film transistor 10B shown in Fig. 7 (b) is an organic field effect transistor and includes a substrate 1 ', a gate insulating layer 3' laminated on the substrate 1 ' A source electrode 5 and a drain electrode 6 arranged so as to be spaced apart from each other on a part of an upper surface (a back surface of the surface facing the substrate 1 ') of the gate insulating layer 3' A semiconductor layer 4 including an organic semiconductor thin film made of an organic semiconductor material disposed on a top surface of the semiconductor layer 4 (except for a portion where the source electrode 5 and the drain electrode 6 are disposed) A gate electrode 2 laminated on the upper surface of the gate insulating layer 3 and a substrate 1 laminated on the upper surface of the gate electrode 2 . In the organic thin film transistor 10B, one of the substrate 1 'and the gate insulating layer 3' may be omitted. The organic thin film transistor of the present invention is an organic thin film transistor having a structure in which both the substrate 1 'and the gate insulating layer 3' are removed from the organic thin film transistor 10B (referred to as top gate type organic field effect transistor) .

Next, each component in the embodiment of the organic thin film transistor of the present invention shown in Figs. 7 (a) and 7 (b) will be described.

As the substrates 1 and 1 ', besides inorganic substrates such as glass, resin films can be used. The substrates 1 and 1 'are preferably resin films in consideration of the flexibility of the organic thin film transistors 10A and 10B. Examples of the resin constituting the resin film include polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, polyetherimide and the like. The kinds of the substrates 1 and 1 'are selected in accordance with the process temperature at the time of pressure application and ultrasonic vibration application. In addition, a planarization layer may be provided on the substrates 1 and 1 'to improve the smoothness of the surfaces of the substrates 1 and 1'. In order to improve metal adhesion and durability, inorganic oxide particles (for example, silica particles) having an average particle size of nano order (for example, 5 nm) may be dispersed in the resin constituting the resin film. As the base materials (1 and 1 '), a glass transition temperature of 100 ° C or higher is preferable, and a glass transition temperature of 150 ° C or higher is more preferable. The thicknesses of the substrates 1 and 1 'are usually 1 to 10 mm, preferably 5 to 3 mm.

When a resin film is used as the substrate 1, the semiconductor layer 4 may be sandwiched between the substrates 1 and 1 'like the organic thin film transistor 10B in consideration of the bending resistance of the organic thin film transistor . In this configuration, it is preferable that the materials of the two kinds of base materials 1 and 1 'are made the same. By using the substrates 1 and 1 'made of such a resin film, it is possible to realize an organic thin film transistor having flexibility, a flexible and lightweight organic thin film transistor having high bending resistance, and the practicality of the organic thin film transistor .

A conductive material (material having conductivity) is used for the source electrode 5, the drain electrode 6, and the gate electrode 2. Examples of the conductive material include a metal such as platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, , Metals such as potassium, sodium, and alloys thereof; Conductive inorganic oxides such as InO ₂ , ZnO ₂ , SnO ₂ and ITO (indium tin oxide); Conductive polymers such as polyaniline, polypyrrole, polythiophene (PEDOT 占 P ss), polyacetylene, polyparaphenylene vinylene, polydiacetylene; Carbon materials such as carbon nanotubes and graphite, and the like can be used. In order to lower the contact resistance between the source electrode 5, the drain electrode 6, and the gate electrode 2, molybdenum oxide may be doped to the above various materials, or the metal may be treated with thiol or the like. In addition, as the conductive material, a conductive composite material in which carbon black is dispersed in various materials as described above, and various kinds of materials such as gold, platinum, silver, copper, ) Can also be used. Wiring is connected to the gate electrode 2, the source electrode 5, and the drain electrode 6 when the organic thin film transistors 10A and 10B are operated. The wiring diagram, the gate electrode 2, the source electrode 5, and the drain electrode 6 are made of the same material. Although the thickness of the source electrode 5, the drain electrode 6 and the gate electrode 2 varies depending on the material thereof, it is usually 1 nm to 10 mu m, preferably 10 nm to 5 mu m, 30 nm to 1 占 퐉.

The gate insulating layers 3 and 3 'are layers of an insulating material (insulating material). Examples of the insulating material include polyacrylate (acrylic resin) such as polyparaxylylene and polymethyl methacrylate, polystyrene, polyvinyl phenol, polyamide, polyimide, polycarbonate, polyester, polyvinyl alcohol , Polyvinyl acetate, polyurethane, polysulfone, fluorine resin, epoxy resin, phenol resin, and the like, and copolymers thereof; Inorganic oxides such as silicon dioxide, aluminum oxide, titanium oxide, and tantalum oxide; Ferroelectric inorganic oxides such as SrTiO ₃ and BaTiO ₃ ; Inorganic nitrides such as silicon nitride and aluminum nitride; Inorganic sulfides; A material in which dielectric particles such as inorganic fluoride are dispersed in a polymer, or the like can be used. It is preferable that the insulating material used for the gate insulating layer 3 is checked beforehand for the presence of damage due to the application of pressure and ultrasonic vibration, and similarly to the substrate 1, thermal stability is required, It is necessary to consider dielectric breakdown after treatment of ultrasonic vibration. The thickness of the gate insulating layers 3 and 3 'differs depending on the insulating material used therein, but is usually 10 nm to 10 mu m, preferably 50 nm to 5 mu m, more preferably 100 nm to 1 mu m to be. In the case of the organic thin film transistor 10B having the structure in which the semiconductor layer 4 as shown in Fig. 7 (b) is sandwiched between two substrates 1 and 1 ', the gate insulating layers 3 and 3' Is preferably made of the same material in consideration of the bending resistance of the organic thin film transistor 10B.

The semiconductor layer 4 includes an organic semiconductor thin film made of the organic semiconductor material described above. As the semiconductor material constituting the semiconductor layer 4, the organic semiconductor material may be used alone, or the organic semiconductor material and at least one other semiconductor material may be used in combination. In order to improve the characteristics of the organic thin film transistors 10A and 10B, various additives may be mixed with the semiconductor material constituting the semiconductor layer 4 as necessary. The thickness of the semiconductor layer 4 is preferably as small as possible as long as necessary functions are not lost. In the organic thin film transistors 10A and 10B, the characteristics of the organic thin film transistors 10A and 10B do not depend on the thickness of the semiconductor layer 4 when the semiconductor layer 4 has a predetermined thickness or more, ) Is thicker, leakage current is often increased. On the other hand, if the thickness of the semiconductor layer 4 is too thin, it is impossible to form a channel of charge in the semiconductor layer 4, so that the semiconductor layer 4 needs to have an appropriate thickness. The thickness of the semiconductor layer 4 for exhibiting the necessary functions of the organic thin film transistors 10A and 10B is usually 1 nm to 5 mu m, preferably 10 nm to 1 mu m, more preferably 10 nm to 500 mu m Nm.

In the organic thin film transistor of the present invention, other layers may be formed on the surface of each of the above-described constituent elements or on the exposed surfaces of the respective constituent elements described above. For example, a thin film transistor protection layer for protecting the organic thin film transistor 10A may be formed directly on the semiconductor layer 4 in the organic thin film transistor 10A or through another layer. Thus, the influence of outside air such as humidity on the electrical characteristics of the organic thin film transistor can be reduced, and the electrical characteristics of the organic thin film transistor can be stabilized. In addition, electrical characteristics such as ON / OFF ratio of the organic thin film transistor can be improved.

The material constituting the thin film transistor protective layer is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin such as polymethyl methacrylate, various kinds of polyurethane, polyimide, polyvinyl alcohol, fluororesin and polyolefin Suzy; Inorganic oxides such as silicon oxide, aluminum oxide and silicon nitride; And a nitride such as a nitride are preferable, and a resin (polymer) having a low transmittance of oxygen, a low transmittance of moisture, and a low absorptance is more preferable. As a material constituting the thin film transistor protective layer, a gas barrier protective material developed for an organic EL display may also be used. The thickness of the thin film transistor protective layer may be any thickness depending on its purpose, but is usually 100 nm to 1 mm.

Next, a method of manufacturing the organic semiconductor device of the present invention will be described in detail.

In the method of manufacturing an organic semiconductor device of the present invention, for example, an organic semiconductor material is disposed on a substrate on which an insulating layer and an electrode are formed, and ultrasonic vibration is applied while applying pressure to the organic semiconductor material, .

A method of manufacturing an organic semiconductor device according to the present invention is characterized in that the organic semiconductor device comprises a source electrode and a drain electrode arranged to be spaced apart from each other and an organic semiconductor thin film made of an organic semiconductor material disposed between the source electrode and the drain electrode In the case of an organic thin film transistor which is an organic field effect transistor provided on a substrate with an insulating layer disposed between the semiconductor layer and the gate electrode and a gate electrode arranged to face the semiconductor layer, It is preferable to include a disposing step of disposing the organic semiconductor material on the substrate before forming the organic semiconductor thin film by the method of forming the organic semiconductor thin film of the invention. In this manufacturing method, the organic thin film transistor 10A shown in Fig. 7 (a) and the organic thin film transistor 10B shown in Fig. 7 (b) can be manufactured.

In the arranging step, the organic semiconductor material may be formed in a region between the source electrode and the drain electrode on the substrate in a solid state or in a molten state with respect to the substrate on which the source electrode and the drain electrode are disposed, Or a solution containing an organic semiconductor material may be applied to the substrate on which the source electrode and the drain electrode are disposed and then dried so that the source An organic semiconductor material may be arranged in a region between the electrode and the drain electrode or in the vicinity thereof.

Here, the method of manufacturing the organic semiconductor device of the present invention will be described in detail based on the organic thin film transistor 10B of the embodiment of Fig. 7 (b) using two kinds of substrates. The first substrate (referred to as "gate substrate 9") is obtained by laminating a gate electrode 2 and a gate insulating layer 3 on a base material 1. The other substrate (referred to as a source / drain substrate 8) is obtained by laminating a gate insulating layer 3 ', a source electrode 5 and a drain electrode 6 on a substrate 1'. In the following description, the case where the semiconductor layer 4 is composed of only the organic semiconductor thin film will be described.

(Preparation of Gate Substrate 9)

[Treatment of substrate (1)] [

The gate substrate 9 is manufactured by forming the gate electrode 2 and the gate insulating layer 3 on the substrate 1 described above. Surface treatment (cleaning treatment) may be performed on the surface of the base material 1 in order to improve the wettability (ease of lamination) of the respective layers to be laminated on the base material 1. Examples of the surface treatment include acid treatment with hydrochloric acid, sulfuric acid, acetic acid or the like; Alkali treatment with sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia or the like; Ozone treatment; Fluorination treatment; Plasma treatment by plasma such as oxygen or argon; Formation treatment of Langmuir-Blodgett film; And electrical treatment such as corona discharge.

[Formation of gate electrode 2]

The gate electrode 2 is formed on the base material 1 by using the above-mentioned conductive material (electrode material). As a method of forming the gate electrode 2, for example, a vacuum deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method and the like can be given. It is preferable that patterning is performed as necessary when the conductive material is formed or after film formation so that the conductive material has a desired shape. As a method of patterning, various methods can be used. For example, a photolithography method in which patterning and etching of a photoresist are combined. As a method of patterning, it is also possible to use a printing method such as inkjet printing, screen printing, offset printing, and relief printing, a soft lithography method such as a micro contact printing method, or a combination of a plurality of these methods. The electrode formed by the printing method is baked by applying energy such as heat or light until the desired conductivity is reached.

[Formation of gate insulating layer 3]

Next, the gate insulating layer 3 is formed on the gate electrode 2 formed on the substrate 1 by using the above-described insulating material (see Fig. 7 (b)). Examples of the method of forming the gate insulating layer 3 include coating methods such as spin coating, spray coating, dip coating, casting, bar coating, and blade coating; A printing method such as a screen printing method, an offset printing method, and an ink jet method; A vacuum evaporation method, a molecular beam epitaxial growth method, an ion cluster beam method, an ion plating method, a sputtering method, an atmospheric pressure plasma method, and a CVD (chemical vapor deposition) method. The gate insulating layer 3 may be subjected to a surface treatment. The surface of the gate insulating layer 3 is subjected to surface treatment to facilitate control of the molecular orientation and crystallinity at the interface between the semiconductor layer 4 and the gate insulating layer 3 to be formed thereafter, 1) or the portion of the trap on the gate insulating layer 3 is reduced, it is considered that the characteristics such as the carrier mobility of the organic thin film transistor 10B are improved. The trap portion refers to a functional group such as a hydroxyl group present in the untreated substrate 1 or the gate insulating layer 3. When such a functional group exists in the substrate 1 or the gate insulating layer 3, So that the carrier mobility of the organic thin film transistor 10B is lowered as a result. Therefore, it is also effective to reduce the traps in the substrate 1 or the gate insulating layer 3 in improving the characteristics such as the carrier mobility of the organic thin film transistor 10B.

(Fabrication of source / drain substrate 8)

[Treatment of substrate (1 ')]

The gate substrate 9 is fabricated by forming the gate insulating layer 3 ', the source electrode 5 and the drain electrode 6 on the substrate 1' described above. The surface of the substrate 1 'may be subjected to the same surface treatment as the surface of the substrate 1.

[Formation of gate insulating layer 3 '] [

Next, a gate insulating layer 3 'is formed on the substrate 1' using the above-described insulating material (see FIG. 7 (b)). As a method of forming the gate insulating layer 3 ', the same method as the method of forming the gate insulating layer 3 can be used. The gate insulating layer 3 'may also be subjected to a surface treatment in the same manner as the gate insulating layer 3.

[Formation of the source electrode 5 and the drain electrode 6]

Next, the source electrode 5 and the drain electrode 6 are formed on the gate insulating layer 3 'using the above-described conductive material. The materials of the source electrode 5 and the drain electrode 6 may be the same or different. As the method of forming the source electrode 5 and the drain electrode 6, the same method as the method of forming the gate electrode 2 can be used. The conductive material constituting the source electrode 5 and the drain electrode 6 may be doped with molybdenum oxide or the like in order to lower the contact resistance between the source electrode 5 and the drain electrode 6. [ When the source electrode 5 and the drain electrode 6 are made of metal, the metal may be treated with thiol or the like. Molybdenum oxide, thiol, and the like can be laminated on the source electrode 5 and / or the drain electrode 6 by the same method as the method of forming the conductive material.

[Arrangement of organic semiconductor material on source / drain substrate 8]

Next, the organic semiconductor material is disposed on the source / drain substrate 8 formed by the above-described method. The organic semiconductor material is directly deposited in a solid state or in a molten state such as a bulk state directly in the region between the source electrode 5 and the drain electrode 6 on the source / drain substrate 8 or in the vicinity thereof Drain substrate 8 on the source / drain substrate 8 by a process (solution process) in which a solution containing an organic semiconductor material is applied or printed onto the source / drain substrate 8 and then dried And the drain electrode 6, or in the vicinity thereof. As the solution process, a printing method such as an inkjet method, a screen printing method, an offset printing method, a micro contact printing method, or a coating method such as a drop casting method can be used. Although it is possible to arrange the organic semiconductor material on the source / drain substrate 8 in other solution processes, a method capable of arranging a necessary amount of the organic semiconductor material in a required place is desirable in order to increase the utilization efficiency of the organic semiconductor material . Hereinafter, a method of arranging the organic semiconductor material will be described in detail.

First, when the organic semiconductor material in the solid state or the molten state is directly placed on the source / drain substrate 8, the organic semiconductor material of the solid powder in the form of bulk or the organic semiconductor material in the form of fine powder is directly supplied to the source / The organic semiconductor material which has been placed or dispersed in the region between the source electrode 5 and the drain electrode 6 on the drain substrate 8 or heated to a temperature not lower than the melting point, It can be applied to the region between the source electrode 5 and the drain electrode 6 on the source / drain substrate 8 or in the vicinity thereof by various means such as a dispenser. Simultaneously, the organic semiconductor material is taken in the molten state at the tip of the sufficiently heated metal rod, and the semiconductor material in the molten state at the tip of the metal rod is directly introduced into the source electrode 5 and the drain Or may be applied to a region between the electrodes 6 or in the vicinity thereof.

Next, a method of disposing an organic semiconductor material on the source / drain substrate 8 by a solution process will be described. The solution process is a process in which an organic semiconductor material having solvent solubility, for example, a compound represented by the above-mentioned general formula (1) is dissolved in an organic solvent in advance, a solution of the obtained organic semiconductor material is applied or printed, Is placed at a desired location. The method of arranging the organic semiconductor material by application of the solution or by printing and drying, that is, the solution process, does not require the environment at the time of manufacturing the organic thin film transistor 10B to be in a vacuum or high temperature state, 10B can be manufactured at low cost, which is industrially advantageous. Further, in the case where the solution process is used for the arrangement of the organic semiconductor material on the source / drain substrate 8 in the manufacturing method of the organic semiconductor device of the present invention, in the process of cooling the organic semiconductor material after the end of the ultrasonic vibration application, The orientation of crystals may be random in the step of crystallizing the organic semiconductor material from the solution and the organic solvent contained in the solution may be evaporated after application or printing of the solution, It is good just to let. Therefore, after application of the solution or printing, there is no need to carry out a process of crystal orientation control by baking for a long time or rearrangement of crystals by post treatment in order to uniformize the crystal orientation.

The organic semiconductor material is formed on the region (channel) between the source electrode 5 and the drain electrode 6 on the source / drain substrate 8 or in the vicinity of the region (channel) As shown in FIG. In the case where the organic semiconductor layer is formed only by a method of applying or printing a solution such as a droplet method or an inkjet method, the distance between the source electrode 5 and the drain electrode 6 on the source / drain substrate 8 It is necessary to consider the positional accuracy of the organic semiconductor material such as the inkjet landing accuracy of the organic semiconductor material in order to cover the region (channel) of the organic semiconductor material with the organic semiconductor layer. On the other hand, according to this method, the region (channel) between the source electrode 5 and the drain electrode 6 on the source / drain substrate 8 in the step of disposing the organic semiconductor material is set as the organic semiconductor material And there is no need to demand high positional accuracy for the apparatus used for coating or printing. In order to obtain a good organic semiconductor thin film, it is preferable to arrange the organic semiconductor material in the vicinity of the channel other than the channel, and the source electrode 5 It is preferable to dispose the organic semiconductor material within a range of 5 mm or less.

[Formation of semiconductor layer 4 and preparation of organic thin film transistor 10B]

Next, the gate substrate 9 is overlapped with the source / drain substrate 8 on which the organic semiconductor material is disposed. Using the organic semiconductor material sandwiched between the source / drain substrate 8 and the gate substrate 9 thus obtained, ultrasonic vibration is applied to the organic semiconductor material while applying pressure through the gate substrate 9 Thereby imparting energy to the organic semiconductor material. As a result, the organic semiconductor material becomes thinner and the semiconductor layer 4 made of the organic semiconductor thin film is formed as a channel, and the source / drain substrate 8 and the gate substrate 9 are pressed together to form the organic thin film transistor 10B Is completed. The organic thin film transistor 10B is manufactured under the same conditions as the above-described formation method of the organic semiconductor thin film as the conditions of the pressure application and the ultrasonic vibration application. Depending on the properties of the organic semiconductor material, the conditions of application of the oscillation time (deposition time), amplitude, pressing force, and ultrasonic vibration are optimized. The substrate 1 may be subjected to conduction heating (stage heating) by heating the stage (heating stage 26) on which the substrate 1 is placed with a conduction heating means (heater 26a or the like) . When the method of forming an organic semiconductor thin film of the present invention is used, optimization of the conditions for applying pressure and ultrasonic vibration without requiring a long-time baking step as in the prior art can form an organic semiconductor thin film in a very short time of 1 second or less can do.

Next, a method of forming the semiconductor layer 4 using the ultrasonic welding machine 20 shown in Fig. 1 as one embodiment of a method of forming the semiconductor layer 4 made of an organic semiconductor thin film will be described with reference to Figs. 2 to 6 As shown in Fig.

2, the organic semiconductor material 7 sandwiched between the source / drain substrate 8 and the gate substrate 9 is placed on the heating stage 26 of the ultrasonic welding apparatus 20 . Next, as shown in Fig. 3, the horn 24 is lowered to apply pressure to the article to be treated (that is, to the organic semiconductor material 7). Next, as shown in Fig. 4, the organic semiconductor material 7 is transferred from the horn 24 to the gate substrate 9 with the pressure applied to the article to be processed (i.e., with respect to the organic semiconductor material 7) Thereby imparting ultrasonic vibration to the organic semiconductor material 7 (to impart energy to the organic semiconductor material 7). As a result, the thickness of the organic semiconductor material 7 becomes thin. Next, as shown in Fig. 5, the application of the ultrasonic vibration to the organic semiconductor material 7 is terminated with the pressure applied to the article to be treated (that is, with respect to the organic semiconductor material 7) (7). As a result, a thin film of an organic semiconductor material (organic semiconductor thin film) thinner than the original thickness of the organic semiconductor material 7 is formed as the semiconductor layer 4. Finally, as shown in Fig. 6, the horn 24 is raised to terminate the application of the pressure, thereby completing the organic thin film transistor 10B.

In general, the operating characteristics of the organic thin film transistor are affected by the carrier mobility and conductivity of the semiconductor layer, the capacitance of the insulating layer, the device configuration (the distance between the source electrode and the drain electrode, the width of the source electrode and the drain electrode, Thickness, etc.). In order to obtain the semiconductor layer 4 made of an organic semiconductor material having a high carrier mobility, it is preferable that the organic semiconductor material has an alignment in a certain direction (the orientation of the crystal becomes uniform and more crystals are oriented in a certain direction) . In the method of manufacturing an organic semiconductor device of the present invention, the crystal of the organic semiconductor material is reoriented in the process of cooling the organic semiconductor material after the end of ultrasonic vibration application, so that the semiconductor layer 4 ) Can be obtained. In the organic thin film transistor 10B having the two substrates 1 and 1 'and the two gate insulating layers 3 and 3', the same material is used for the substrates 1 and 1 ' When the same material is used for the insulating layers 3 and 3 ', the structure of the organic thin film transistor 10B can be a symmetrical sandwich structure with the semiconductor layer 4 as the center. As a result, it is possible to obtain the organic thin film transistor 10B which is less susceptible to deformation and the like due to different materials and has high bending resistance.

In addition, since the organic semiconductor device of the present invention can form an organic semiconductor thin film by a short-time process, it is possible to use a conventional manufacturing method for forming an organic semiconductor thin film by a vacuum deposition process, The present invention can be applied to the manufacture of an organic semiconductor device for a large area display with a high throughput and a very low cost as compared with a conventional manufacturing method of forming an organic semiconductor thin film by a solution process (solution process). In addition, the method of manufacturing an organic semiconductor device of the present invention can realize a manufacturing method of a sheet-to-sheet system or a roll-to-roll system in that an organic semiconductor thin film can be formed by a short- .

The organic semiconductor device of the present invention can be used as a switching element of an active matrix of a display or the like. Examples of the display include a liquid crystal display, a polymer dispersed liquid crystal display, an electrophoretic display, an electroluminescence (EL) display, an electrochromic display, a particle rotating display, and the like. The organic semiconductor device of the present invention can also be used as a digital device or an analog device, such as a device of a memory circuit, a device of a signal driver circuit, a device of a signal processing circuit, It is possible to manufacture IC tags. Furthermore, the organic semiconductor device of the present invention can be expected to be used as a FET (Field Effect Transistor) sensor because it can cause a change in its characteristics due to external stimuli such as chemical substances.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for the purpose of facilitating understanding of the present invention only, and the present invention is not limited to these examples.

[Example 1]

(2) as an organic semiconductor material,

(Melting point: 127 占 폚) of 2,7-dioctyl [1] benzothieno [3,2-b] [1] benzothiophene) (hereinafter referred to as " Was placed on the tip of the heated metal rod to be melted, and a semiconductor material in a molten state at the tip of the metal rod was laminated on a polyimide film (product name: "POMYRAN (registered trademark)", manufactured by Arakawa Chemical Industries, Ltd.) A silica hybrid polyimide film having a structure in which nanosilica particles having an average particle size of 5 nm were dispersed in a polyimide matrix, manufactured by Taiyo Kagaku Co., Ltd.). The thickness of the semiconductor material at this time was several 占 퐉. Thereafter, another one identical polyimide film was overlapped on the polyimide film through the compound (2).

The organic semiconductor material 7 was sandwiched between the source / drain substrate 8 and the gate substrate 9 shown in Fig. 2 by sandwiching the compound 2 between the two polyimide films thus obtained. The organic semiconductor thin film was formed in the same manner as in the manufacturing method shown in Figs. 2 to 6 except that it was used as the object to be processed instead.

2, a press body of a commercially available ultrasonic welder (product name "? P-30B ", product name " 裡 G-620B ", which is an example of the ultrasonic welding machine 20 of Fig. 1 having the heating stage 26) (Amplitude) 25 占 퐉, frequency (frequency) 28.5 kHz, horn shape: rectangular column shape (chamfer), size of horn surface (processing) (The compound (2) sandwiched between two polyimide films) was provided on the heating stage 26 in the area (area: 64 mm 2)

Next, the heating stage 26 is heated by the heater 26a (heating for conducting the conduction heating of the compound 2) so that the temperature (surface temperature) of the heating stage 26 becomes 100 deg. C, And the horn 24 was lowered to apply a pressure of 0.15 MPa to the article to be treated (that is, to the compound (2)). Thereafter, in the same manner as in Fig. 4, the pressure of 0.15 MPa is applied to the article to be processed (i.e., to the compound (2)) and the ultrasonic vibration amplitude 25%, 30%, or 35% And ultrasonic vibration was applied to the compound (2) by ultrasonic welding the ultrasonic welder under the condition of the oscillation time of 1 second to heat the compound (2).

Next, in the same manner as in Fig. 5, the ultrasonic wave oscillation of the ultrasonic welding machine is terminated and the organic semiconductor material is cooled while the pressure is applied to the article to be processed (i.e., to the organic semiconductor material) (Organic semiconductor thin film) of the compound (2) thinner than the thickness of the semiconductor layer (4) was formed as the semiconductor layer (4). Finally, in the same manner as in Fig. 6, the horn 24 was raised to terminate the application of pressure to obtain an organic semiconductor thin film.

The change in the temperature of the organic semiconductor material (compound (2)) at this time was as shown in Fig. From this result, it was confirmed that the temperature of the organic semiconductor material can be controlled by the change of the amplitude of the ultrasonic vibration, and the temperature of the organic semiconductor material is quickly lowered with the end of the ultrasonic oscillation.

From these, it was confirmed that the organic semiconductor material can be thinned, that is, the organic semiconductor thin film can be formed by applying ultrasonic vibration while applying pressure to the organic semiconductor material. Table 1 shows the maximum attained temperature of the organic semiconductor material under each amplitude condition and whether or not the organic semiconductor material is thinned. As can be seen from the results of Table 1, the organic semiconductor material was thinned under any condition, and an organic semiconductor thin film of several tens nm was formed.

The temperature of the organic semiconductor material was measured by the following method. That is, the same process as that for forming the organic semiconductor thin film described above was performed, except that the sheet-like temperature sensor was disposed in place of the organic semiconductor material (compound (2)) on the polyimide film, And the change of the temperature (the temperature of the portion between the two polyimide films) was measured.

[Example 2]

In this embodiment, an example of the organic thin film transistor 10B shown in Fig. 7 (b) was produced. First, "Parylene (registered trademark) C" (Nippon Pyrrole (registered trademark)) as a gate insulating layer 3 'was formed on a polyimide film (product name " A gold electrode was formed as a source electrode 5 and a drain electrode 6 having a channel length of 20 mu m and a channel width of 5 mm on the parylene film, Whereby a substrate 8 was obtained. On the other hand, a gold electrode was formed as a gate electrode 2 on a polyimide film (trade name: "POMILAN (registered trademark) N") having a thickness of 12 μm as the base material 1 and a gate insulating layer 3) was formed to a thickness of 900 nm to obtain a gate substrate 9.

Next, as shown in Fig. 9, the distance from the source electrode 5 and the drain electrode 6 (and the region between them) on the source / drain substrate 8 to the side of the source / drain substrate 8 (Melting point: 127 占 폚) of the compound (2) as an organic semiconductor material was disposed at a position of about 200 占 퐉 away from the substrate (the right end side in Fig. 9). Next, the gate substrate 9 was overlapped on the source / drain substrate 8 on which the solid of the compound (2) was disposed.

Next, the compound 2 sandwiched between the source / drain substrate 8 and the gate substrate 9 thus obtained was evaluated as the compound 2 between the two polyimide films in Example 1 ) Was used as the object to be processed, the temperature of the heating stage was changed to 95 캜, and the amplitude of the ultrasonic vibration was changed to 45%. In the same manner as in Example 1, The organic semiconductor thin film made of the compound (2) was formed. At this time, the maximum reaching temperature of the organic semiconductor material was 230 占 폚.

Figs. 9 to 11 show the results of observing changes in the organic semiconductor material in Example 2 with a polarization microscope. 9 shows a state in which the organic semiconductor material (compound (2)) sandwiched between the source / drain substrate 8 and the gate substrate 9 is placed on the heating stage 26 Shape. 10 shows the shape of the organic semiconductor material after the organic semiconductor material is heated by the heating stage 26 at 100 캜. Fig. 11 is a graph showing the relationship between the amount of the organic semiconductor (organic semiconductor) in the sample (the organic semiconductor thin film is formed between the source / drain substrate 8 and the gate substrate 9) taken out from the ultrasonic welding machine after the application of the ultrasonic vibration and the application of the pressure are finished And the shape of the material is confirmed by a polarization microscope. A semiconductor layer 4 made of an organic semiconductor thin film is formed between the source electrode 5 and the drain electrode 6 (two vertical lines at the center) as shown in Fig. 11, and the organic thin film transistor 10B I knew I could make it.

Next, the semiconductor characteristics of the organic thin film transistor 10B obtained in Example 2 were measured. Application of the gate voltage and measurement of the gate current of the organic thin film transistor 10B were performed using a KEITHLEY 2635A SYSTEM Source Meter and the application of the source and drain voltages of the organic thin film transistor 10B and the measurement of the drain current were performed by KEITHLEY 6430 SUBFEMTO AMP REMOTE Source Meter. The current-voltage characteristic of the organic thin film transistor 10B was measured under the condition that the drain voltage of the organic thin film transistor 10B was set to -30 V and the gate voltage Vg of the organic thin film transistor 10B was changed to 30 to -30 V . The mobility and the threshold voltage of the organic thin film transistor 10B were calculated from the current-voltage characteristics of the obtained organic thin film transistor 10B. The calculated mobility was 0.038 cm 2 / V · s, the calculated threshold voltage was 1.2 V, and the organic thin film transistor 10B in which the semiconductor layer 4 had the characteristics of a p-type semiconductor was obtained.

In order to confirm resistance of the parylene film having a thickness of 900 nm used for the gate insulating layers 3 and 3 'to the application of pressure and ultrasonic vibration, under the same conditions as in the formation of the organic semiconductor thin film in this example Pressurization and ultrasonic vibration imparting by an ultrasonic welder were performed on the parylene film. As a result, it was confirmed that there was no substantial change in the leakage current density before and after the treatment, and that the insulating property of the parylene film was not deteriorated by the application of the ultrasonic welding machine and the ultrasonic vibration.

[Example 3]

The same procedures as in Example 2 were carried out except that the source electrode 5 and the drain electrode 6 of Example 2 were subjected to electrode treatment using pentafluorothiophenol before the application of pressure and ultrasonic vibration, (10B). The mobility and the threshold voltage of the organic thin film transistor 10B obtained in this example were measured in the same manner as in the measurement method in Example 2. The mobility and the threshold of the organic thin film transistor 10B obtained in this example Value voltage was calculated. Table 2 shows the calculation results of mobility and threshold voltage. In addition, the semiconductor layer 4 of the organic thin film transistor 10B obtained in the present example exhibited the characteristics of the p-type semiconductor.

[Example 4]

An organic thin film transistor 10B was obtained in the same manner as in Example 3 except that the channel length of the source electrode 5 and the drain electrode 6 in Example 3 was changed to 100 mu m. The semiconductor characteristics of the organic thin film transistor 10B obtained in this example were measured in the same manner as in the measurement method in Example 2 and the mobility and the threshold voltage of the organic thin film transistor 10B obtained in this example were calculated did. Table 2 shows the calculation results of mobility and threshold voltage. In addition, the semiconductor layer 4 of the organic thin film transistor 10B obtained in the present example exhibited the characteristics of the p-type semiconductor.

[Example 5]

(2) of Compound (2) was laminated on a polyimide film (trade name: "POMILAN (registered trademark)") having a thickness of 12 μm using an inkjet apparatus (model No. DMP-2831 manufactured by Fuji Film Co., An organic semiconductor material was disposed on the polyimide film by printing an organic semiconductor material composed of a weight% tetrahydronaphthalene solution and naturally drying the solution to remove the solvent (tetrahydronaphthalene). As shown in Fig. 12, the shape of the organic semiconductor layer (the layer of the organic semiconductor material) immediately after printing was highly irregular, and the film thickness of the organic semiconductor layer was 450 nm at the maximum. Thereafter, another one identical polyimide film was overlapped on the polyimide film through the organic semiconductor material (compound (2)).

Next, the temperature of the heating stage 26 (surface temperature) was 100 ° C, the pressure of the object (organic semiconductor material) was 0.15 MPa, the amplitude of the ultrasonic vibration was 50%, and the oscillation time of the ultrasonic vibration was 1 second. The ultrasonic welder was ultrasonically oscillated. It was confirmed that the maximum reaching temperature of the organic semiconductor material (compound (2)) was 180 캜, and after the ultrasonic welding treatment, the organic semiconductor thin film shown in Fig. 13 was formed.

[Example 6]

A 2 wt% solution of the compound (2) in tetrahydro-naphthalene was added between the source electrode 5 and the drain electrode 6 of the source / drain substrate 8 used in Example 2 using the inkjet apparatus used in Example 5 The organic semiconductor material was printed, and the solution was naturally dried to remove the solvent (tetrahydronaphthalene). A linear pattern is drawn along the source electrode 5 by printing of the organic semiconductor material. However, as the solution dries, the organic semiconductor layer (the layer of the organic semiconductor material) is divided in the channel, Thereby forming a discontinuous organic semiconductor layer (Fig. 14). Thereafter, the gate substrate 9 used in Example 2 is superimposed on the source / drain substrate 8 via the organic semiconductor material (compound 2) to form an organic semiconductor material on the source / drain substrate 8 and the gate substrate 9 (9), and the ultrasonic welding machine was ultrasonically oscillated under the same conditions as in Example 5 to obtain an organic semiconductor thin film. Thus, the organic thin film transistor 10B was obtained. The polarized microscopic image of the obtained organic semiconductor thin film is shown in Fig. From this image, it was confirmed that an organic semiconductor thin film having a uniform channel was obtained by the ultrasonic welding treatment.

[Comparative Example 1]

First, the compound 2 was sandwiched between the source / drain substrate 8 and the gate substrate 9 in the same manner as in Example 2 to obtain an object to be processed. Next, in accordance with a non-patent document (Physica Status Solidi, Volume 210, Issue 7, p.1353-1357 (2013)), Compound (2) was thinned by the method (Fig. 1 (b) of the above non-patent document). The time taken for thinning was 2 minutes. After the thinning, the object to be processed was cooled at a cooling rate of 1.5 캜 / min, whereby an organic thin film transistor for comparison was obtained in the same manner as in Example 2 (the semiconductor characteristics were different from those in Example 2).

The semiconductor characteristics of the obtained organic thin film transistor for comparison were measured in the same manner as in Example 2. As a result, the mobility of the organic thin film transistor for comparison was 0.052 cm 2 / Vs and the threshold voltage was -15.8 V, It was almost equivalent to the semiconductor characteristics of the thin film transistor 10B. However, in this comparative example, the time required for thinning (tact time) is 2 minutes as described above, which is far behind the time (1 second) required for thinning in Example 2, and the pressure required for thinning , 1.6 MPa as described above, and was significantly inferior to the pressure (0.15 MPa) required for thinning in Example 2.

From the results described in each of the Examples, not only is it possible to form an organic semiconductor thin film by thinning an organic semiconductor material by applying ultrasonic vibration while applying pressure to the organic semiconductor material, Organic semiconductor devices have been found to have high semiconductor properties. Further, it has been confirmed that when forming the organic semiconductor thin film, it is not necessary to carry out complicated and stationary process control for the vacuum deposition or crystal growth, and the organic semiconductor thin film can be formed in a very short time. Therefore, it was confirmed that the manufacturing method of the organic semiconductor device of each of the embodiments is a manufacturing method of high throughput.

1, 1 ': substrate
2: gate electrode
3, 3 ': Gate insulating layer (insulating layer)
4: semiconductor layer (organic semiconductor thin film)
5: source electrode
6: drain electrode
7: Organic semiconductor material
8: source / drain substrate
9: gate substrate
10A: organic thin film transistor (organic semiconductor device)
10B: organic thin film transistor
20: Ultrasonic welder
21: Ultrasonic Oscillator
22: Ultrasonic vibrator
23: Booster
24: Hon
25: Pressurizing device
26: Heating stage
26a: Heater

Claims (11)

A method of forming an organic semiconductor thin film comprising an organic semiconductor material,
Wherein the organic semiconductor material is thinned by applying ultrasonic vibration while applying pressure to the organic semiconductor material. The method according to claim 1,
Characterized in that the organic semiconductor material is thinned by recrystallizing the organic semiconductor material after phase transition of the solid phase organic semiconductor material by applying ultrasonic vibration while applying pressure to the organic semiconductor material / RTI > 3. The method according to claim 1 or 2,
Wherein the organic semiconductor material is subjected to conduction heating simultaneously with application of ultrasonic vibration to the organic semiconductor material. 4. The method according to any one of claims 1 to 3,
Wherein ultrasonic vibration is applied while applying pressure to the organic semiconductor material sandwiched between the pair of substrates. 5. The method of claim 4,
Wherein the pair of substrates is a resin film. A method of manufacturing an organic semiconductor device comprising an organic semiconductor thin film,
A method for manufacturing an organic semiconductor device, characterized by forming an organic semiconductor thin film by the forming method according to any one of claims 1 to 5. The method according to claim 6,
Wherein the organic semiconductor device is an organic thin film transistor. 8. The method of claim 7,
Wherein the organic thin film transistor comprises: a semiconductor layer including a source electrode and a drain electrode arranged to be spaced apart from each other; and an organic semiconductor thin film made of an organic semiconductor material disposed between the source electrode and the drain electrode; And an insulating layer disposed between the semiconductor layer and the gate electrode, the organic field effect transistor comprising:
In the above manufacturing method,
And a disposing step of disposing an organic semiconductor material on the substrate before forming the organic semiconductor thin film. 9. The method of claim 8,
In the arranging step, the organic semiconductor material may be formed in a region between the source electrode and the drain electrode on the substrate in a solid state or in a molten state with respect to the substrate on which the source electrode and the drain electrode are disposed, Wherein the organic semiconductor layer is disposed in the vicinity thereof. 9. The method of claim 8,
In the arranging step, a solution containing the organic semiconductor material is applied to the substrate on which the source electrode and the drain electrode are disposed, and then the substrate is dried to form the source electrode and the drain electrode, Wherein an organic semiconductor material is disposed in a region between or in the vicinity of the drain electrode. 11. An organic semiconductor device manufactured by the manufacturing method according to any one of claims 6 to 10.

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